IRCCS, Integrated ResearchConsortium on Chemical Sciences
統合物質創製化学研究推進機構
令和元年度 事業報告書

IRCCS, Integrated ResearchConsortium on Chemical Sciences
統合物質創製化学研究推進機構
令和元年度 事業報告書

目

次

１．統合物質創製化学研究推進機構について 
1-1

本機構の背景1-2

本機構の目的

1-3

本機構の組織1-4

本機構の特徴

1-5

事業計画

1-6

本機構の期待される成果と波及効果

２．メンバー 
2-1

コア研究室メンバー、連携研究室メンバー、リサーチフェロー

2-2

外部評価委員３．令和元年度事業報告 
3-1

第３回 統合物質若手の会

3-2

第５回 統合物質国内シンポジウム

3-3

第３回 統合物質国際シンポジウム

1

25

35

1
統合物質創製化学研究推進機構について

1-1
本機構の背景１−１. 本機構の背景
革新的な機能性物質の発見と創造が、科学と科学技術に飛躍的な発展をもたらしてきた。その根幹を担ってきたのが、原子・分子レベルで物質を探求し、創造しつづけてきた「ものづくり」の化学、すなわち物質創製化学である。豊かな物質に彩られた現代社会の恒常的発展を維持し、我が国の科学技術立国としての地位を揺るぎないものとするためにも、次世代の飛躍を約束する新たな機能性物質群を創造していかねばならない。特に、緊迫するエネルギー・環境問題の解決や最先端バイオ・情報技術の進展を図り、科学技術全般の国際的競争力を高めるためにも、革新的な機能性物質群の創造と、それらの合理合成法の開拓に向けた新学術基盤の構築が急務である。化学者に課せられた任務は極めて重い。
次世代の機能性物質創製の鍵を握るのが、物質を構成する元素、分子、分子
集合体という階層性の理解と制御であると考えられている。元素により特徴づけられる多種類の原子が結合を作ることにより分子が形成され、さらに分子が集積することにより分子集合体へと組織化され、それぞれの階層に特有の性質や機能がある。生体物質の構造に例えると、個々の原子の特性を基礎とし（元素）、その機能を発揮する最小単位となるタンパク質や核酸が構成され（分子）、これらがさらに集積してウイルスや細胞内組織であるミトコンドリア（分子集合体）となる。高度に機能化された革新的な物質を創製するためには、全ての階層における構成単位を創製する術を学び、その機能を解明しなければならない。
本事業に参画する京都大学・名古屋大学・九州大学・北海道大学の４研究組織
は、それぞれ「元素」
「分子」
「集合体」
「触媒」をキーワードとした強力な中核的国際研究拠点として認知されている。本事業の前身となる「統合物質創製化学推進事業 − 先導的合成の新学術基盤構築と次世代中核研究者の育成（H22〜27
年度）」においては、４研究組織のそれぞれがストロング・ポイントをもつ各物
質階層を中心に、個別に蓄積されてきた物質合成における知識と知恵を融合・深化させるとともに、物質合成概念の統合にも取り組んだ。すなわち、古典的な化学反応を利用した「化学的物質合成」ともに、高温超伝導体や発光材料、半導体などの開発に利用されてきた「物理的物質合成」や、生命体が穏和な条件下に日常的に行っている精巧かつ高効率な「生命物質合成」にも学ぶことによって、持続型経済社会を実現する、環境に調和した新たな「物質創製概念」の創出を実践した。
「物質階層の統合」と「物質合成概念の統合」を合言葉として、各研究機
関の知識と経験を融合・深化させて新たな物質創製化学を遂行した結果、天然窒
素還元酵素における機能中心構造の全合成、カーボンナノチューブ構造の化学
合成、低環境負荷の鉄触媒による液晶材料の合成、強誘電性と強磁性が共存する

4

マルチフェロイック物質の開発など、革新的な研究成果が生まれた。さらに、若手研究者に自由闊達な研究環境と、大学の垣根を越えた共同研究や情報交換の機会を与えたことによって、物質創製化学の未来を切り開く力量ある次世代中
核研究者の育成を実現した。本事業は、この 4 大学間連携事業をさらに組織化・システム化した「新機構」を設立し、社会のニーズに応える「統合物質創製化学」を推進する。

5

1-2
本機構の目的１－２．本機構の目的
新物質創製は、化学結合の形成のための新しい方法論や、機能の発現のための物質構築論などを探求する極めて基礎的な基盤学術である一方、その成果は、新触媒や新材料開発はもちろん、イノベーション創成を通じてエネルギー・資源から環境・創薬に至る極めて広い範囲に適用される。ここでは、基礎と応用が直結
し（縦糸）、また化学を中心として物理から生命科学までの多くの研究分野の協力が必須である（横糸）。すなわち、物質と情報そして人が集結することが何より重要な分野と言えよう。しかしながら、我が国の物質創製研究は極めて高い国
際競争力をもつにもかかわらず、新物質創製を総合的かつ戦略的に進める機関・組織は、残念ながら我が国には存在しない。基礎と応用を結ぶ縦糸と多様な分野を結ぶ横糸を組み合せ、近年長足の進歩を遂げたナノ計測や計算化学を取り込んだ統合的な研究組織の構築が急務である。その一方で、現在のひっ迫した財政の下では、多くの面積とポストを必要とする新研究所設立のような事業は現実的ではない。物質創製の学術を継承・発展させ、迫りくる環境問題などの重点課

図１8

題を解決し、また新産業創出を成すためには、産官学連携や国際連携を前面に出し、責任あるマネージメント体制を持ちながらも、最小限の面積とポストの獲得で遂行できる、大学間連携を基盤とした「統合物質創製化学研究推進機構」は、必要かつタイムリーな事業である。
図１に統合物質創製化学研究推進機構の概念図を示す。本機構事業に参画する名古屋大学・京都大学・九州大学・北海道大学の４研究組織は、
「分子」、
「元
素」、
「集合体」、「触媒」の化学研究において、それぞれに特色ある強力な中核的国際研究拠点として認知されているが、以下に示すそれぞれのストロング・ポイ
ントを活かしながら、物質の階層構造を縦断する研究連携を実現する。
名古屋大学：無機化学から有機化学にわたる分子性物質の合成と機能の発現、さらには不斉反応を含む分子触媒の開発研究において卓越した成果をあげてきた。最近では、生物無機化学やナノ炭素科学分野においても世界をリードする。
京都大学：元素の特性の解明と、それに基づく機能創出の化学において先導的な研究成果をあげている。機能性元素科学という新しい研究パラダイムを提唱し、分子性物質から凝縮系物質に至る様々な革新的新物質群の出現を促してきた。
九州大学：複雑な分子集合体・集積体を構築する新概念を提出し、多くの機能性集積体の合成研究を通してナノサイエンス・テクノロジー研究に先鞭をつけた。最近では、核酸ナノマシンやナノハイブリッド材料の創出などで顕著な成果を挙げる。
北海道大学：触媒化学において世界を先導する中核的研究拠点である。触媒
元素・分子のナノ・ミクロ集積・集合化学の研究を推進し、資源高度利用触媒、環境触媒、バイオ利用触媒、燃料電池・電極触媒、光触媒などで多くの成果を挙げる。
さらに本研究推進機構では、基礎研究を中心とする一方、「新反応・新触媒」、「マテリアル」、「エネルギー・資源」、「ケムバイオ」という、応用展開を意識した 4
つの出口を設定して基礎と応用を直結させる。その上で、産官学連携や国際連携を組織的に取り込み、新しい研究システムや研究支援体制、人材育成システムを取り入れた、社会に開かれた新組織である。物質創製における我が国の研究の厚みを継承し、新学術・新産業の創出と後継人材の育成を両立させながら、持続可能な社会の発展を導く。

9

1-3
本機構の組織１－３．本機構の組織
本機構事業では、１－２で説明した機構研究の概念を実現するため、全く新しい大学間連携のフレームワークを構築する。一般論だが、これまでの大学間ネッ
トワーク事業が抱える問題点としは、① 高い大学間の壁② 出口設定が難しく、研究目標を立てにくい③ 平等主義によるガバナンス不足④ 縦割り（大学別）の研究支援と人材育成支援⑤ 外部意見が反映されにくい⑥ 連携のメリットがネットワーク内に閉じるなどが挙げられる（図２(a)）。最大の問題点は⑥で、連携のメリットが社会発信されず、また社会の要請による事業という意識も希薄であった。ネットワーク形
成のような大学強化事業は、社会からの認知によってはじめて達成されるもの
で、本研究推進機構事業においては、成果、情報、人材がネットワークの外側に輩出される外部発信型の連携を目指している。研究推進機構の組織図を図３に示すが、以下、運営体制、統括研究部門、研究支援部門についてその概要を説明
する。

図２

12

運営体制
本事業推進に全責任を負う機構長を置く。機構長は、国内の学識経験者（4〜6 名）や理化学研究所などの連携機関から派遣された委員、本事業の実行委員から構成される運営委員会を組織する。運営委員会は、連携事業計画の策定と成果の取纏めを行う。運営委員会で制定された事業計画は、研究統括部門の研究プラットホーム・リーダーから構成される実行委員会によって遂行される。
統合研究部門
機構長および運営委員会のリーダーシップの下、応用という研究の出口を意識した統合研究部門（新反応・新触媒、マテリアル、エネルギー・資源、ケムバ
イオの４研究プラットホーム）を設置する。各プラットホームには、連携大学から１研究室ずつ選抜した４研究室と、産官学・海外から招聘した連携客員研究室を設置して共同研究を実施する。各プラットホームにおける研究内容は以下の通りである。
新反応・新触媒研究：連携４大学の固体触媒（北大）、分子触媒（名大）、元素触媒（京大）、分子集合体触媒（九大）の研究チームの共同研究によって、ゼ
ロエミッション・カップリング反応の開発など、必要なものを必要なだけグ
リーンにつくりだす化学を発展させ、炭素ナノ材料や医薬品の革新的合成に展開する。
マテリアル研究：炭素材料、ナノ粒子、有機物、無機固体、金属錯体、高分子に至る物質群の開発は、機構４大学が世界を先導している分野である。その研究は多岐にわたるが、例えば４大学が開発する新規光機能性分子を超分子化することによって、既存の細胞イメージングから、分子イメージングや更には機能イメージングへと発展させる。
エネルギー・資源研究：エネルギー・資源問題は化学が取り組むべき緊急課
題である。金属ナノ粒子・界面の機能化（北大、名大）や革新的ナノカーボン
材料開発（名大）を通じて、新しい燃料電池や太陽電池を開発する（北大、京大、九大）。X 線吸収スペクトル計測（北大、名大）などによって反応機構を押さえながら、ユビキタス元素が生み出すグリーンエネルギーを創製する。
ケムバイオ研究：人工酵素を実現するための基本設計の確立は、生命科学における主題の一つである。生体分子合成（九大）とナノクラスター導入技術（京大）、ミューテーション技術（名大）を組み合わせ、計算シミュレーショ
ン（九大）を道しるべとしながら、機能をつくりこんだ人工酵素の合成にまで発展させる。

13

各研究プラットホームの構成は以下の通りである。
プラットホーム名リーダー

コア研究室メンバー

新反応・新触媒

中野環（北大）唯美津木・伊丹健一郎（名大）、中村正
治（京大）、永島英夫・國信洋一郎（九
大

マテリアル

島川祐一（京大） 清水研一（北大）、山口茂弘（名大）、
高原淳・友岡克彦（九大）

エネルギー・資源 阿波賀邦夫（名 福岡淳（北大）、村田靖次郎（京大）、
大）佐藤治（九大）ケムバイオ

吉澤一成（九大） 長谷川淳也（北大）、阿部洋（名大）、二木史朗（京大）

各プラットホームにグループリーダーを置き、各分野の連携研究の推進に責任をもつ。さらに、各プラットホームでは若手研究者を特任助教や博士研究員として雇用する。これらの若手研究は、共通若手エース人事システムにより採用される。若手研究者の登竜門として機構を位置づけ、切磋琢磨による人材育成によって外部のパーマネント・ポジションに送り出す。
本機構内に限定せず、統合的な共同研究を促進するため、融合創発研究を実施する。共同研究提案を行い、運営委員会の審査を経て採択課題を決定し、実施する。また、年度末に研究成果について報告書を作成し、運営委員のレビューを受けるものとする。概ね毎年 10 件程度を実施する。
統括支援部門名古屋大学物質科学国際研究センター内に設置し、センターに付設の化学測定機器室を用いて本事業の研究を支援するとともに、国際シンポジウム等の開催に必要な外国人研究者招聘に関わる事務手続き、本事業の研究成果の取纏め、ポスターの作成、ホームページの管理などの広報活動を担当する。具体的には、以下の支援を行う。
① 外部発信・国際発信：機構の研究成果を、HP や種々のメディアなどを通じて国際的に広報する。
② 共同研究コーディネ-ト：機構研究全体を見渡して、新しい共同研究を萌芽させる。
③ 知財発掘と管理：機構研究全体を見渡して、知財獲得を支援する。
④ 若手キャリアパス支援：求職情報を若手に流布し、キャリアパスセミナーを実施する。
⑤ 会議・シンポジウム開催支援：オープン参加型シンポなどを広報、支援する。

14

1-4
本機構の特徴１－４．本機構の特長
社会に開かれた新機構は、以下の５つの特長を持つ。
① 戦略的なガバナンスに基づく融合研究：機構長のリーダーシップの下、応用という研究の出口を意識した統合研究部門（新反応・新触媒、マテリア
ル、エネルギー・資源、ケムバイオの４研究プラットホーム）を設置し、各プラットホームには、連携大学から１研究室ずつ選抜した４研究室と、産官学・海外から招聘した連携客員研究室を設置して共同研究を実施する。更に融合研究部門を設置し、産官学や国際連携の場とする。大学間の壁を乗り越え、かつ開かれた研究組織を構築する。
② イノベーション創出とグローバル化（図４）：研究部門を横断的に支援するため統括支援部門を設置し、マネージメント教員、プロジェクト支援員などを配置する。共同研究コーディネート、知財獲得、国際発信、若手人材育成などを、大学間の壁を取り払って行う。理化学研究所などを連携機関として加え、イノベーシ
ョン創出などを活性化する。
③ 外部発信型連携：新しい産官学連携と国際連携のパラダイムを構築する。オープン参加型の成果報告会などを開催することによって、研究成果・研究情報・
人材を、産業界、官界、学界、海外に対して外向きに発信・輩出する。
図５④ 共通若手エース人事シス
テム（図５）：大学院生から
若手研究者まで、各階層のニーズに合わせた人材育成を行う。特任助教や研究員の人事ついては、共通若手エース人事システムを採用する。すなわち、連携
大学共通の選考委員会を設置して人選する。機構の
図４16

研究活動を人材ショーケースとして利用して若手のキャリアパス形成を支援すると共に、レクチャーシップ派遣や招聘により国際的人脈形成を促す。若手研究者の登竜門として機構を位置づけ、切磋琢磨による人材育成によって外部のパーマネント・ポジションに送り出すことにより、物質創製分野における新たな人材育成モデルを実現する。
⑤ ナノ計測と計算化学の支援：ナノ計測と計算化学の支援の下、合理的な物
質創製研究を展開する。
以上、基礎研究を重視しながらも、応用という研究の出口を意識した４テーマに各大学から１研究室を送り込む形で統合研究部門を形成することによって、互いの研究の強みを補完する研究体制を敷く。ガバナンスを効かした機構運営
によって招聘される、理化学研究所などからの客員研究室の存在は、産官学との結びつきを強化すると共に、機構組織の流動性を高めるだろう。この上で、大学の壁を越えた統括支援部門による効率的な知財発掘や国際発信によって、新機構のビジビリティは必然的に高まる。このように、社会を意識した機構の研究活
動は、院生や若手研究者の人材ショーケースとして作用し、前述した共通若手エース人事システムは人材の流動性を必然的に生み出す。

17

1-5
事業計画

１－５．事業計画

本事業のロードマップを図６に示す。

図６

20

1-6
本機構の期待される成果と波及効果

１－６．本事業の期待される成果と波及効果

１）本事業がめざす物質階層の統合と物質合成概念の統合により、総合的な物質観に基づく多彩な物質創製法が創出される。それらは、生体機能、電子機能、光機能、触媒機能などの有用機能をもつ機能性物質群を創造するための新学術基盤の構築へと展開される。
２）革新的な機能性物質群の創製は、材料科学分野に革新をもたらす。これまでの物質合成では、ナノテクノロジーで多用される熱力学支配による自己組織化が指導原理として用いられてきた。これに対して、本事業では、準安定物質の合成法の開拓により、自己組織化を超えた新規機能性物質群の創製法が開発されるものと期待される。これにより、高圧合成と薄膜技術の融合による非平衡物質
群の創製、人工超格子をもつ特異な高次構造体の合成、光磁気特性を示す新規錯体や有機発光素子の開発、酵素反応の解明と生命機能の理解に資する人工酵素の合成などが達成され、最先端のバイオ・情報技術へと応用・展開される。
３）縦糸（基礎と応用）と横糸（多様な分野）が結ばれ、産官学及び国際的に開かれた物質創製化学研究が実施され、物質創製化学の新しい学術基盤が構築される。その結果、環境に優しい新触媒開拓、新規機能電子物質に基づく骨太イノ
ベーション、更には新医薬品や生体活性物質開発が成される。これらは持続可能な文明社会の構築に大きく貢献する。
４）高度な研究機能をもつ国際研究拠点の有機的連携により、多くの若手研究者に広範な学問領域を統合した卓越した研究環境を提供することができる。このような環境は、幅広い知識と複眼的思考力を備えた中核研究者の養成に必要不可欠な要件である。本事業では、若手研究者を統合研究フェローとして処遇し、自由で創造的な研究環境を提供する。これにより、物質創製化学の将来を担う中核研究者を多数育成できるものと期待される。また、国際研究拠点の連携は、我が国の学術的先進性と国際競争力を確保するためにも重要であり、多くの若者に、海外の一流研究者と切磋琢磨する機会を提供し、国際的な研究者として成長するためのインセンティブを与える。
５）本申請が提案する新機構のスキームの有効性は、物質創製化学分野にだけ限定されない。このスキームにより、参加大学の強みを生かして我が国の学術を結集できるほか、大学間連携のメリットが産官学連携や国際連携を通じて外向きに発信されることにより、社会からの支持も得られる。この効果は、新国立研究所の設立にも匹敵する。このような外向きリンクの大学間連携事業のパイロッ
トプログラムとして、他分野への波及効果やインパクトも大きい。

22

６）事業計画終了後は、新物質創製を総合的かつ戦略的に進める研究システムという枠組みは残しながらも、統括研究部門における研究テーマや参加研究室を全面的に見直し、また現在の連携 4 大学以外からの参加を促してオールジャパ
ン体制をつくり、更に進んだ物質創製最先端研究を進める。

23

2
メンバー

2-1
コア研究室メンバー、連携研究室メンバー
リサーチフェロー

● 機構長
機構長
渡辺芳人
名古屋大学 名誉教授

● 特別顧問巽

和行名古屋大学 名誉教授

28

● 北海道大学
新反応・新触媒研究プラットホーム

北海道大学

新反応・新触媒研究プラットホーム

メンバー一覧

メンバー一覧

＜コア・連携研究室＞
福岡淳

教授（基礎研究系・物質変換研究部門）

高橋保

教授（基礎研究系・分子触媒研究部門）

大谷文章

教授（基礎研究系・光触媒科学研究部門）

朝倉清高

教授（基礎研究系・触媒表面研究部門）

中野

教授（基礎研究系・高分子機能科学研究部門）

環

清水研一

教授（基礎研究系・触媒材料研究部門）

長谷川淳也

教授（基礎研究系・触媒理論研究部門）

西田まゆみ

教授（実用化推進系・研究開発部門）＜リサーチフェロー＞ …令和 2 年 3 月末現在
佐川拓矢

研究員（触媒科学研究所・物質変換研究部門）

29

● 名古屋大学
エネルギー・資源研究プラットホーム

名古屋大学

メンバー一覧

エネルギー・資源研究プラットホーム
名古屋大学

メンバー一覧

エネルギー・資源研究プラットホーム

メンバー一覧

＜コア・連携研究室＞
阿波賀邦夫 教授（物性化学）＜コア・連携研究室＞
山口茂弘 教授（機能有機化学）
阿波賀邦夫
教授（物性化学）
伊丹健一郎教授（機能有機化学）
教授（有機化学）山口茂弘
唯美津木 教授（無機化学）
伊丹健一郎
教授（有機化学）阿部洋 教授（生物有機化学）
唯美津木
教授（無機化学）
野依良治教授（生物有機化学）
特別教授・斎藤進 教授（分子触媒化学）阿部洋
田中健太郎特別教授・斎藤進
教授（分子組織化学）
野依良治
教授（分子触媒化学）
菱川明栄 教授（光物理化学）
田中健太郎
教授（分子組織化学）柳井毅 教授（量子化学）
菱川明栄
教授（光物理化学）
荘司長三教授（量子化学）
教授（生物無機化学）
柳井毅
荘司長三 教授（生物無機化学）＜リサーチフェロー＞ …令和 2 年 3 月末現在
Wu Yang（物性化学） …令和 2 年 3 月末現在
＜リサーチフェロー＞
阿部奈保子（生物有機化学）
Wu
Yang（物性化学）
王晨光（機能有機化学）
阿部奈保子（生物有機化学）
王晨光（機能有機化学）

30

● 京都大学
マテリアル研究プラットホーム

京都大学

マテリアル研究プラットホーム

メンバー一覧

メンバー一覧

＜コア・連携研究室＞
中村 正治 教授（有機分子変換化学・元素科学国際研究センター）
島川 祐一 教授（先端無機固体化学・元素科学国際研究センター）
金光 義彦 教授（光ナノ量子物性化学・元素科学国際研究センター）
村田 靖次郎 教授（構造有機化学・化学研究所）
二木 史朗 教授（生体機能設計化学・化学研究所）
時任 宣博

教授（有機元素化学・化学研究所）

若宮 淳志

教授（分子集合解析・化学研究所）＜リサーチフェロー＞…令和 2 年 3 月末現在
SHARMA, Akhilesh Kumar 特定研究員（有機分子変換化学・元素科学国際研究センター）
INJAC, Sean Dusan Alexander 研究員（先端無機固体化学・元素科学国際研究センター）
RAFIEH, Alwani Imanah Binti 研究員（分子集合解析・化学研究所）

31

● 九州大学
ケムバイオ研究プラットホーム

九州大学

ケムバイオ研究プラットホーム

メンバー一覧

メンバー一覧

＜コア・連携研究室＞
吉澤一成

教授（反応・物性理論分野・先導物質化学研究所）

佐藤

治

國信

洋一郎

友岡

克彦

教授（集積分子機能分野・先導物質化学研究所）

永島英夫

教授（クラスター分子化学分野・先導物質化学研究所）

高原

淳

教授（分子物質化学分野・先導物質化学研究所）
教授（機能分子化学分野・先導物質化学研究所）

教授（複合分子システム分野・先導物質化学研究所）＜リサーチフェロー＞ …令和 2 年 3 月末現在
塩田淑仁

准教授（反応・物性理論分野・先導物質化学研究所）

金川慎治

助教（分子物質化学分野・先導物質化学研究所）

SU, Shengqun
河崎

32

悠也

特任助教（分子物質化学分野・先導物質化学研究所）
特任助教（集積分子機能分野・先導物質化学研究所）

2-2
外部評価委員● 外部評価委員
外部評価委員岩村 秀
東京大学 名誉教授
岩澤康裕
電気通信大学 燃料電池イノベーション研究センター長 特任教授
上村大輔
神奈川大学 特別招聘教授
江崎信芳
鳥取環境大学 学長
大峰 巌
分子科学研究所 名誉教授
新海征治
九州大学高等研究院 特別主幹教授
玉尾皓平
豊田理化学研究所 所長

34

3
令和元年度事業報告

3-1
第３回 統合物質若手の会

統合物質創製化学研究推進機構（IRCCS）
第三回

若⼿の会

開催⽇：令和元（2019）年 7 ⽉ 12 ⽇（⾦）~ 13 ⽇（⼟）

会場：
「久⼭温泉 ホテル夢家」

主催：統合物質創製化学研究推進機構

38

プログラム

令和元年 7 ⽉ 12 ⽇（⾦）
14:00-14:25
14:25-14:30

14:30-14:45

参加登録

開会の挨拶
座⻑

OP1

宋 志毅（北海道⼤学 中野研准教授）
⽥原 淳⼠（九州⼤学 永島研助教）「イリジウム触媒を⽤いたアミドのヒドロシラン還元による D-A 型
p共役エナミン合成およびその物性評価」

14:45-15:00

15:00-15:15

OP2

河野 慎⼀郎（名古屋⼤学 ⽥中研講師）「カラムナー液晶および⼆次元単分⼦膜を構築するサルフェン型⼤環状化合物の開発」

OP3

後藤 真⼈（京都⼤学 島川研助教）「異常⾼原⼦価鉄イオンを含む B サイト層状・無秩序ペロブスカイト
酸化物の酸素脱離」

15:15-15:35

15:35-15:50
15:50-16:05
16:05-16:20

16:20-16:40

16:40-17:30

休憩
座⻑

OP4

⽥中 慎⼆（名古屋⼤学 北村研助教）
⾼ 敏（北海道⼤学 ⻑⾕川研助教 ）「Reactivity of Metal Clusters in the Regime of Structural Fluxionality」
OP5

井川 和宣（九州⼤学 友岡研助教）

OP6

河野 健⼀（京都⼤学 ⼆⽊研助教）「キラル分⼦の新規⽴体化学制御法「DYASIN」の開発と応⽤」「膜曲率誘導によるオクタアルギニンの膜透過促進」
休憩座⻑

⿃越 尊（九州⼤学 國信研助教）

招待講演 1

植村 卓史 先⽣（東京⼤学 教授）「ナノ空間で⾼分⼦を制御する」

18:00-19:00

⼣⾷

20:00-22:00

情報交換会

39

令和元年 7 ⽉ 13 ⽇（⼟）
9:00-9:15

OP7

⾏本

万⾥⼦（京都⼤学 時任研助教）

佐川 拓⽮（北海道⼤学 福岡研博⼠研究員）「キチン由来糖アルコールの脱⽔縮合反応」

9:15-9:30

OP8

阿部 司（九州⼤学 吉澤研特任助教）

9:30-9:45

OP9

有安 真也（名古屋⼤学 荘司研特任助教）

9:45-10:05

10:05-10:20「⼆核銅-酸素錯体の⽣成に及ぼす配位⼦効果に関する理論的研究」「シトクロム P450 による⾼圧条件下ガス状アルカンの直接⽔酸化」
休憩、写真撮影座⻑

OP10

関根 康平（九州⼤学 國信研助教）
縣 亮介（京都⼤学

中村研特定研究員）「鉄触媒クロスカップリング反応の開発と機能性有機化合物合成への応⽤」

10:20-10:35

OP11

⾼島 舞（北海道⼤学 ⼤⾕研助教）

10:35-10:50

OP12

藤本 和宏（名古屋⼤学 柳井研特任准教授）

10:50-11:00

11:00-11:50

11:50-12:00

40

座⻑「光触媒酸素発⽣反応における光強度依存性解析」「励起エネルギー移動理論の開発と応⽤」
休憩座⻑

井川 和宣（九州⼤学 友岡研助教）

招待講演 2

内⽥ ⻯也 先⽣（九州⼤学 准教授）

「効率的酸化反応を⽬指して」
閉会の挨拶
吉澤 ⼀成

先⽣（九州⼤学、オブザーバー）

41

42

43

3-2
第５回 統合物質国内シンポジウム

Integrated Research Consortium on Chemical Sciences
統合物質創製化学研究推進機構
第５回国内シンポジウム

物質創製化学のフロンティア
開催⽇

2019 年 11 ⽉ 18 ⽇（⽉）13:00~18:30
19 ⽇（⽕） 9:30~15:10
会場

北海道⼤学 創成科学研究棟 5F ⼤会議室

特別講演

丸岡 啓⼆ 京都⼤学⼤学院薬学研究科 教授「丸岡触媒®および簡素化丸岡触媒®の創製」
招待講演

井上 克也

広島⼤学 教授

畠⼭ 琢次

関⻄学院⼤学 教授

本倉 健

東京⼯業⼤学 准教授

研究報告

北海道⼤学 福岡 淳
名古屋⼤学 菱川 明栄
三輪 寛⼦
Jung Jieun
京都⼤学
村⽥ 靖次郎 九州⼤学
國信 洋⼀郎
河野 健⼀
⾦川 慎治
融合創発研究成果報告

名古屋⼤学 松井 公佑

九州⼤学

問い合わせ先中野 環
北海道⼤学 触媒科学研究所 ⾼分⼦機能科学研究部⾨
Tel: 011-706-9155 Fax: 011-706-9156
tamaki.nakano@cat.hokudai.ac.jp

46

河崎 悠也

統合物質創製化学研究推進機構 第５回国内シンポジウム「物質創製化学のフロンティア」

平成３１年１１月１８日（月）～１９日（火）（北海道大学

創成科学研究棟

5F 大会議室にて）

１１月１８日（月）13:00-13:10

開会の辞

13:10-13:40

研究報告（A-1）

名古屋大学

菱川 明栄 教授

「位相制御２色強レーザー場による反応の可視化と制御」（ケムバイオ研究
プラットフォーム）13:40-14:00

研究報告（B-1）

京都大学

河野 健一 助教

「膜曲率誘導による膜透過性ペプチドの細胞内送達促進」（ケムバイオ研究
プラットフォーム）14:00-14:40

招待講演（IL-1）

東京工業大学

本倉 健

准教授「協奏効果の発現へ向けた機能集積型触媒の開発」
14:40-15:00

休憩

15:00-15:30

研究報告（A-2）

北海道大学

福岡 淳

教授

「触媒によるバイオマス変換：セルロース・キチンから化学品の合成」（マテ
リアル研究プラットフォーム）
15:30-16:20

特別講演（PL）

京都大学

丸岡 啓二

教授

「丸岡触媒®および簡素化丸岡触媒®の創製」
16:20-16:30

休憩

16:30-17:10

ショートプレゼンテーション

17:10-18:30

ポスターセッション

18:30-20:00

懇親会

47

１１月１９日（火）9:30-9:50

研究報告（B-2）

名古屋大学

Jung Jiuen 助教「A highly efficient iridium photocatalyst for CO2 reduction as a bi-functional
photocatalyst」（新反応・新触媒研究プラットフォーム）
9:50-10:20

研究報告（A-3）

京都大学 村田 靖次郎

教授「内包フラーレンの有機合成による孤立化学種の実現」（エネルギー・資源研
究プラットフォーム）
10:20-10:40

休憩

10:40-11:20

招待講演（IL-2）

関西学院大学畠山 琢次

教授「超高色純度熱活性化遅延蛍光材料の開発」
11:20-11:35

融合創発研究成果報告（C-1）

名古屋大学

松井 公佑

助教

「3D-XAFS イメージングによる固体高分子形燃料電池の劣化機構の可視化」
11:35-11:50

融合創発研究成果報告（C-2）

九州大学

河崎 悠也

特任助教

「多分子連結素子 DACN-MMC の開発とペプチド化学への応用」
11:50-13:20

昼食

13:20-13:40

研究報告（B-3）

北海道大学

三輪 寛子

助教

「ミュオンスピン回転法を用いた触媒構造解析」（エネルギー・資源研究プラットフォーム）13:40-14:10

研究報告（A-4）

九州大学

國信 洋一郎

教授「非共有結合性相互作用を利用する炭素－水素結合変換反応における位置選
択性制御法の開発」（新反応・新触媒研究プラットフォーム）
14:10-14:50

招待講演（IL-3）

広島大学

井上 克也 教授

「キラル物性科学―キラル磁性体の研究を中心に」14:50-15:10

研究報告（B-4）

九州大学

金川 慎治 助教

「分子内電子移動を起源とする電子焦電性発現に向けた極性結晶構築戦略」（マテリアル研究プラットフォーム）
15:10-

48

閉会の辞

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3-3
第３回 統合物質国際シンポジウム

The 3rd IRCCS The 2nd Reaction Infography
Joint International Symposium：“Reaction Imaging
Meets Materials Science”
Nagoya University
Noyori Materials Science Laboratory

January 31 - February 1, 2020
January 31
Keynote Lecture

Kaoru Yamanouchi
François Légaré
Zhi Heng LohJiro Itatani
Hideki Hirori
Shigeki Owada
Mizuho Fushitani
Satoru Takakusagi

February 1
Soo Young Park
Ning Jiao
Iwao Matsuda
Toshiki Sugimoto
Kenichi Shimizu
Takeru Torigoe
Masaharu Nakamura
Hideo Nagashima
Osami Shoji

Hosted byIntegrated Research Consortium on Chemical Sciences (IRCCS)
The World Research Reaction Infography (R-ing)
Contact

Research Center for Materials Science (RCMS) officekihara@os.rcms.nagoya-u.ac.jp

56

The 3rd IRCCS - The 2nd Reaction Infography Joint International
Symposium: “Reaction Imaging Meets Materials Science”
Nagoya University
Noyori Materials Science Laboratory
January 31 - February 1, 2020
January 31 (Friday)
9:30-9:45

Opening Remarks
Yoshihito Watanabe (Nagoya Univ.)
Mizuki Tada (Nagoya Univ.)

Session I
Chair: Akiyoshi Hishikawa
9:45-10:25
François Légaré (INRS-EMT, Canada)“Probing the insulator to metal phase transition in VO2 using
high harmonic spectroscopy”
10:25-10:55

Jiro Itatani (Univ. Tokyo)“Intense infrared and mid-infrared sources for attosecond science:new opportunities at higher energies and in solids”

10:55-11:25

Hideki Hirori (Kyoto Univ.)“Extreme nonlinear optical phenomena caused by strongly driving
electronic states in solids”

11:25-12:05

Zhi Heng Loh (Nanyang Tech. Univ., Singapore)“Ultrafast molecular dynamics of transient ions probed byfemtosecond XUV and soft X-ray radiation”

Lunch @ chez Jiroud
Session II
Chair: Mizuki Tada
13:15-13:45
Shigeki Owada (JASRI / RIKEN)“Current status of SACLA”
13:45-14:15

Mizuho Fushitani (Nagoya Univ.)“Mapping electron correlations in nonlinear ionization of Xe 4d
double-core-hole states by multielectron-ion coincidence
spectroscopy”

14:15-14:45

Satoru Takakusagi (Hokkaido Univ.)“Development of operando PTRF-XAFS technique for elucidating 3D
structure-activity relationship in heterogeneous catalysis”

Break

57

Chair: François Légaré
Keynote Lecture
15:05-16:05
Kaoru Yamanouchi (Univ. Tokyo)“Ultrafast molecular dynamics and ultrahigh resolution spectroscopyusing ultrashort intense laser pulses”
Group Photo
Poster Session
16:30-17:30
Banquet17:45-19:00@ Restaurant “Hananoki”

Februrary 1 (Saturday)
Session III
Chair: Ryotaro Matsuda
9:00-9:30
Iwao Matsuda (Univ. Tokyo)“X-ray optospintronics at SACLA”
9:30-10:00

Toshiki Sugimoto (IMS)“Infrared spectroscopy of water-assisted carrier trapping at TiO2
photocatalyst surfaces with distinct morphologies”

10:00-10:30

Kenichi Shimizu（Hokkaido Univ.）“Machine learning and DFT calculations for catalysis Informatics”

Break
Session IV
Chair: Susumu Saito
10:50-11:20
Takeru Torigoe (Kyushu Univ.)“Iridium-catalyzed ortho-selective C–H borylation of thioanisole
derivatives using simple bipyridine-type ligand”
11:20-11:50

Lunch

58

Masaharu Nakamura (Kyoto Univ.)“Exploring synthetic opportunities of iron catalysis in sustainablechemistry”

Session V
Chair: Shigehiro Yamaguchi
13:10-13:40
Hideo Nagashima (Kyushu Univ.)“Activation of H-H and H-Si bonds by transition metal-silicon
linkage”
13:40-14:10

Osami Shoji (Nagoya Univ.)“Hydroxylation of nonnative substrates catalyzed by cytochrome
P450BM3 exploiting decoy molecules”

14:10-14:50

Soo Young Park (Seoul National Univ., Republic of Korea)“Luminescent organic semiconductor”

Closing Remarks
Kunio Awaga (Nagoya Univ.)59

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The first potential and polarization dependent BCLA+BI-XAFS
studies on the PtAu model catalyst prepared by APD method
B. Hu 1, B. Bharate 1, J. D. Juan 2, K. Dong 1, H. Ariga-Miwa 1, S. Takakusagi 1, K. Asakura 1
1. Institute for Catalysis, Hokkaido University, Hokkaido 001-0021, Japan
2. Department of Chemical Engineering, University of South Carolina, 541 Main St., Columbia, SC 29208, USA

Background•

The PtAu nanoclusters has demonstrated enhanced stability in acidic oxygen
reduction reaction and has become a hot topic in electrocatalytic research.
EXAFS can be used for structural investigation of Pt-Au/C underelectrochemical conditions. However, due to the narrow gap (~350 eV)
between Pt L3 edge and Au L3 edge, it is difficult to obtain EXAFS spectra
on both edges.
BI-XAFS ingeniously reduces the inelastic scattering of electrolyte.
BCLA enables observation of both Pt L3 edge and Au L3 edge EXAFS.

•••BCLA+BI-XAFS Experiment(a)Surface Characterization
(a)

(b)

(a)

Figure.5 XPS spectra of the PtAu/HOPG sample.
(a) Pt 4f spectra and (b) Au 4f spectra.
(b)

(b)

Figure.4 (b) AFM image and (b)particle-height histogram of the
PtAu/HOPG model catalyst
surface.
zz(c)Scan direction

Figure.6 Cyclic voltammogram of PtAu/HOPG in
0.1 M HClO4 with a scanning rate of 50 mV s-1.

CV gives ~0.6ML of exposed Pt and ex-situ AFM shows cluster size of 1~2 nm,
which suggest the Pt total amount is ~1 ML.
XPS shows the Pt : Au is 2.5 : 1.

Anisotropy in local structure
Pt

N

LIII

Fig.1 (a) Illustration of the experimental setup. (b) The real experimental setup. (c) Description ofp-like and s-like polarization measurement (green arrows point polarization direction of X-ray).

XAFS Measurement
(a)

Pt-M
(Å)

dE

DW

R(%)

(eV)

(Å)

p-

7.5

2.78

0.5

0.076

1.7

like

瀟0.5

瀟0.01

瀟2.4

s-

9.7

2.77

0.6

0.076

2.2

like

瀟0.7

瀟0.01

瀟2.4

Fig.7 Analysis of Pt L3 edge EXAFS measured at s-like and p-like conditions at 0.4V vs. RHE.

(b)

Au

N

LIII

Au-M
(Å)

dE

DW

R(%)

(eV)

(Å)

p-

10.0

2.78

-1.4

0.085

6.6

like

瀟1.0

瀟0.02

瀟2.1

s-

9.1

2.78

-1.9

0.085

3.2

like

瀟0.9

瀟0.02

瀟2.0

Fig.8 Analysis of Pt L3 edge EXAFS measured at s-like and p-like conditions at 0.4V vs. RHE.
Pt
Au

Fig.2 Polarization-dependent XAFS measurement of (a) Pt L3 edge and (b) Au L3 edge at 0.4 V vs.
RHE.

(a)

(b)

Fig.9 Coordination environment of Pt and Au basedon polarization dependent EXAFS.

Fig.10 PtAuPt layered structure proposed.

Conclusionsz

Fig.3 s-like XAFS measurement of (a) Pt L3 edge and (b) Au L3 edge at different electrochemical
potentials vs. RHE.
zzz

We have successfully measured EXAFS at both Pt L3 and Au L3 edges.
Results show dependence of EXAFS spectra on the polarization angle of Xray and the electrochemical potential.
Dissolution of Pt at 1.0V vs RHE is evidenced by the large drop of edge step.
Meanwhile, there is no sign of Au dissolution.

z

The BCLA + BI-XAFS setup enables both Pt L3 and Au L3 edges EXAFS
measurement under electrochemical conditions.
Based on the polarization dependence of Pt EXAFS oscillation and less polarization
dependence of Au, a “PtAuPt” layered structure was proposed.

Acknowledgement

This work was finally supported by New Energy and Industrial Technology
Development Organization (NEDO). We would also like to thank SPring-8 for thefacility and staff support in XAFS measurement.

1. Takahashi S, Todoroki N, Myochi R, et al. Effective surface termination with Au on PtCo@ Pt core-shell nanoparticle: Microstructural investigations and oxygen reduction
reaction properties[J]. Journal of Electroanalytical Chemistry, 2019, 842: 1-7.
2. Uehara, Hiromitsu, et al. "In situ back-side illumination fluorescence XAFS (BI-FXAFS) studies on platinum nanoparticles deposited on a HOPG surface as a model fuel cell: a
new approach to the Pt-HOPG electrode/electrolyte interface." Physical Chemistry Chemical Physics 16.27 (2014): 13748-13754.

73

A theoretical study of the factors affecting theCO2 and CO adsorption on Cobalt cluster
Min Gao, Hirokazu Kobayashi, Atsushi Fukuoka, Jun-ya Hasegawa
Institute for Catalysis, Hokkaido University
hasegawa@cat.hokudai.ac.jp gaomin@cat.hokudai.ac.jp

Introduction

Computational Details• Catalyst for Partial oxidation of Methane
Noble metals with high activities and high costBase metals require high temperature above 800• Computational model and Methods
Experimental Condition: mono-atomically dispersed rhodium (0.005 wt%)
Computational Model: Co12Rh, Co13 for comparison• Possible reaction mechanism
Direct Mechanism
CH4 0.5O2 CO + 2H2
Indirect Mechanism
CH4 2O2 CO2 + 2H2O
CH4 H2O CO + 3H2
CH4 CO2 2CO + 3H2

0.0 kJ/mol

Figure. Effect of reduction of catalysts
on the partial oxidation of methane.
Cobalt catalyst modified with rhodium continuously gives 85~86% methane conversion
and 90~91% CO selectivity with an H2/CO ratio of 2.0 without serious coking at 650 .
• Fukuoka & Kobayashi @ICAT[1]• Unsolved Problems

100.5 kJ/mol

0.0 kJ/mol

105.8 kJ/mol
Co12Rh

Co13
Totally 54/113 geometries are obtained for Co13, Co12Rh• Computational procedure

Step 1. Search for all low-lying structures of metal clusters with SC-AFIR
Step 2. Search for geometries of CO/CO2 adsorption on metal clusters at different
environment conditions.

The main factor that influence selectivity of CO molecule is still not clear.

CO/CO2 on Free Metal clusters

Effect of C/H ratio on CO/CO2 adsorption

Eads = ECo13 + ECOx – ETot

• Geometries of Co13 Cluster with Dissociated CH4

3.51 eV

3.43 eV

2.49 eV

1.89 eV

Relative energy in kJ/mol

600
500
400
300
200
100

0
2.33 eV

2.14 eV

1.24 eV

0.92 eV

dis

CH

CH2

CHx+H2

H2• CO/CO2 formation on the most stable Co13-C-4H
900
800

2.30 eV

2.34 eV

1.42 eV

1.41 eVThe doped Rh atom weakens interaction between Metal cluster and CO2/CO

Effect of C/O ratio on CO/CO2 adsorption

Relative energy in kJ/mol

3000
2500

Relative energy in kJ/mol

700
600
500
400
300
200
100

C: O = 1:1
C: O = 1:2
C: O = 1:4

0

2000

OH

OH+CO

CO

CO2

The doped Rh atom weakens interaction between Metal cluster and CO2/COThe CO2 molecule can be formed when C:O is lager than 1:4
The totally dissociated CH4 is energetically favorable on Co13 clusters
The CO molecule and OH species are more easily formed in the C/Henvironment.

1500
1000
500
0

74

Diss

C2

C2, O2

CO

O2

CO2

[1] Y. You, S. Nagamatsu, K. Asakura, A. Fukuoka, H. Kobayashi. Commun. Chem.
2018, 1, 41.

H
Scheme of H2 Binding Reaction on Metallocene (e.g. Molybdocene) [1]

3
4
5

6
7

8

10
5
0

9

10

11

12

13

14

7.77

7.62

4.67

5.27

5.89
5.49
-0.4

-2.35

-3.1

15

-5
-11.0

-10

-11.0
-15

(a)

(b)
50
30.5

25

26.1

6.8
-2.7

0.04

-50

-75

-75

4

0

6
7

0.04

-25

-25.9

-50

3

5

8.1
0

-1.9

-25

26.8

25

10.1
10.2

0

6
50

43.7

8

9

10

11

12

13

14

15

-12

-40.8
-18

Proposed structure and energy profiles of Tungstenocene: original complex(a), ansa-complex(b)

(a)

(b)
50

35.0

25.6

25

23.6

23.3

25

9.29
9.29

0

50

9.1

7.58

0

-1.9

-25

-3.19

0.36
0.35

-25
-38.2

-50
-75

-50

-52.2

-75
(

)

(

)

75

Synthesis and Reactions of poly(naphthalene-1,4-diyl) as a
Precursor of Tailor-made Graphenes
Zhiyi Song, Ka Son, Tamaki Nakano*

Institute for Catalysis (ICAT) and Graduate School of Chemical Sciences and Engineering,
Hokkaido University, N 21, W 10, Kita-ku, Sapporo 001-0021, Japan
E-mail: tamaki.nakano@cat.hokudai.ac.jp

Graphene

Oxidative Structural Modification
4
(B)

0.4

0.3

3

0.2

0.1

2

0.0

Abs

500

1

600

(A)

0

Confined in-plane structure,
Non-zero-gap semiconductor(Controlled by Width (W) and Length (L))

200

oxidation productTHF-insol. >99%
THF-sol. <1%, Mn: 1600

poly(naphthalene-1,4-diyl)
MeOH-insol.
THF-sol. Mn: 1000

Reported works:

A

J. M. Cai, et al. Nature, 2010, 466, 470.

B

100000C

400000Intensity (a. u)

96000

94000

300000

92000

L

n
m

Control over Width and Lengthmn1568, G band

50000

98000

W

Intensity(a. u))

Our Strategies

800

600

wavelength [nm]Raman Spectra

Substrate-controlled growth limits the length while these methods lack versatility

K. Mullen, et al. J. Am. Chem. Soc., 2008, 130, 4216.

400

Figure: UV spectra of poly(naphthalene-1,4diyl)（THF-sol., 1cm, 0.0012 M, all） (A) and its
oxidized product （THF-sol. part only) (B).

Intensity(a. u)

Infinite in-plane structure,zero-gap semiconductor(uncontrollable)

1345, D band

40000

30000

90000
1000

1500

2000

200000
1000

1500

-1

1000

2000

1500

Raman Shift(cm )2000

Raman Shift(cm-1)-1

Raman Shift (cm )Figure: Lasa Raman spectra of poly(naphthalene-1,4-diyl) (A); its oxidized products (wholesolid) (B) and Graphite (C) (λex = 532 nm).

n

Insight into Oxidative Reaction

This Work

Insight into Oxidative Reaction
Polymerization of 1,4-Dibromonaphthalene
BrBr
Ni cat.

Mg
THF
Br

MgBr

m

3.5
90000

3.0

80000

2.5

intensity (a.u)

Abs

1603

70000

2.0
1.5
1.0

1445
60000

1281

50000

40000

30000

0.5

910.242

20000

0.0
10000

200

250

300

350

400

450

500

550

600

650
400

wavelength(nm)

600

800

1000

1200

1400

1600

1800

2000

2200

2400

Raman shfit (cm-1)

Figure: UV spectrum of the oxidized
product （THF-sol., 1cm, 0.00018 M, all）.

Figure: Lasa Raman spectrum ofoxidized product (λex = 532 nm).

Summary

Soluble polymer with average molar mass of ca. 1000 was obtained.

761) Oxidation of poly(naphthalene-1,4-diyl) leads to an ordered
GNR structure.
2) Intra-chain oxidation may not occur at chain terminal.
3) Inter-chain coupling may compete with intra-chain oxidation.

Synthesis and chirality of hyperbranched polyphenylenes
Yuting Wang,1 Zhiyi Song,1 and Tamaki Nakano1,2*

1Institute for Catalysis (ICAT) and Graduate School of Chemical Sciences and Engineering, Hokkaido University, N 21, W 10, Kita‐ku,
Sapporo 001‐0021, Japan; 2Integrated Research Consortium on Chemical Sciences (IRCCS)

E‐mail: tamaki.nakano@cat.hokudai.ac.jp

Abstract: Main‐chain conjugated polymers are an important class of materials that exhibit various photo electronic functions based on
their long electronic conduction. Polyphenylene (poly(benzene‐1,4‐diyl)) is one of the simplest conjugated polymers consisting ofbenzene units directly connected to each other, and properties of polyphenylenes have been tuned mainly introducing side‐chain alkyl
groups. In this work, we introduce new polyphenylene derivatives having regular chain branching leading to hyperbranched, three‐dimensional framework and studied their structures and basic properties as well as chirality induction using chiral external moleculesand circularly polarized light (CPL).

Polymer Synthesis

Table 1. Synthesis of poly(benzene‐1,3,5‐triyl‐alt‐benzene‐1,4‐diyl)[poly(BT‐alt‐BD)] in dimethoxyethane at 80oC using Pd(PPh3)4 for 24 ha

M2
M2

M1

1/1
1.5/1
2/1
3/1
4/1

THF-insol.

M2

Yield (%)

Yield (%)

Mn c

Mw/Mnc

90
>99
>99
>99
>99

0
0
51
44
92

47
45
21
41
15

430
240
580
980
860

1.50
2.04
1.88
1.76
1.47

MeOH-insoluble productM1

THF-sol.

Run

aM = 0.1 mmol, [M ] =0.05 M, [Pd(PPh ) ] = 0.005 M (10 mol% with respect to
2
2
3 4
M2).
bDetermined by 1H NMR analysis of reaction mixture.
cDetermined by SEC using polystyrene standard.

cDetermined by SEC using polystyrene standard.

Surface area and porosity

Absorbance and fluorescence spectra
A. poly(BT‐alt‐BD)

Yield (%)

Mn c

Mw/Mnc

>99
>99
85
>99
>99

35
12
34
23
>99

>99
>99
>99
>99
>99

580
720
660
660
700

3.71
1.88
2.32
2.22
2.66

C. poly(BT‐alt‐TD)

a. Run 3 in Table 2
b. Run 4 in Table 2
c. Run 5 in Table 2

Run 3 in Table 3

Abs

Abs

5 μm

a. Run 3 in Table 2
b. Run 4 in Table 2
c. Run 5 in Table 2

MeOH-insoluble productArbit. Unit

Arbit. Unit

Run 3 in Table 3

THF-sol.

Properties of THF‐soluble polymers

C. poly(BT‐alt‐TD)

A. poly(BT‐alt‐BD)

x 10-4 (L mol-1 cm-1)

Abs
Arbit. Unit

Arbit. Unit

Arbit. Unit

Fig. 4. UV (top) and fluorescence (bottom) spectra in THF solution of THF‐
soluble poly(BT‐alt‐BD) (run 4 in Table 1) (A), poly(BT‐alt‐BPD) (run 3 in Table 2)(B), and poly(BT‐alt‐TD) (C) (run 3 in Table 3) [ r.t.; ex for fluorescence 270 nm].

B. poly(BT‐alt‐BPD)

Abs

B. poly(BT‐alt‐BPD)
x 10-4 (L mol-1 cm-1)

Absorbance and fluorescence spectra in film

A. poly(BT‐alt‐BD)
x 10-4 (L mol-1 cm-1)

Absorbance and fluorescence spectra in THF solution

Fig. 2. UV (top) and fluorescence spectraof THF‐insoluble poly(BT‐alt‐BD)s (A),poly(BT‐alt‐BPD)s (B), and poly(BT‐alt‐TD)s (C) made under different conditions:[suspension in paraffin, r.t; ex for
fluorescence 270 nm].

Arbit. Unit

a. Run 3 in Table 1
b. Run 4 in Table 1
c. Run 5 in Table 1

Arbit. Unit

Yield (%)

B. poly(BT‐alt‐BPD)

a. Run 3 in Table 1
b. Run 4 in Table 1
c. Run 5 in Table 1

Fig. 1. SEM image of poly(BT‐alt‐BPD)(run 3 in Table 2). [3 kV, Pt coating]Fig. 3. 1H NMR spectra of THF‐soluble poly(BT‐alt‐BD) (run 4 in Table 1) (a), poly(BT‐alt‐BPD) (run 3 inTable 2) (b), and poly(BT‐alt‐TD) (run 3 in Table 3)[400 MHz, CDCl3, r.t.].

THF-insol.

M2

Abs

Table 4. BET analysis of poly(BT‐alt‐BD) and poly(BT‐alt‐BPD)

NMR spectra

1/1
1.5/1
2/1
3/1
4/1

Conv. b(%)

aM
2 = 0.1 mmol (runs 1,2,4,5) 1 mmol (run 3), [M2] =0.05 M,[Pd(PPh3)4] = 0.005 M (10 mol% with respect to M2).
bDetermined by 1H NMR analysis of reaction mixture.
cDetermined by SEC using polystyrene standard.

Properties of THF‐insoluble Polymers
Surface morphology[M1]/[M2]in Feed12
345aM = 0.1 mmol, [M ] =0.05 M, [Pd(PPh ) ] = 0.005 M (10 mol% with respect to
2
2
3 4
M2).
bDetermined by 1H NMR analysis of reaction mixture.

M2

C. poly(BT‐alt‐TD)

Abs

1
2
3
4
5

Conv. b(%)

Arbit. Unit

Run

[M1]/[M2]in FeedTable 3. Synthesis of poly(benzene‐1,3,5‐triyl‐alt‐1,1’:4’,1’’‐terphenyl‐4,4’’‐diyl)[poly(BT‐alt‐TD)] in dimethoxyethane at 80oC using Pd(PPh3)4 for 24 ha

Arbit. Unit

M1

Table 2. Synthesis of poly(benzene‐1,3,5‐triyl‐alt‐biphenyl‐4,4’‐diyl)[poly(BT‐alt‐BPD)] in dimethoxyethane at 80oC using Pd(PPh3)4 for 24 ha

Fig. 5. UV (top) and fluorescence (bottom) spectra in film of THF‐soluble poly(BT‐alt‐BD) (run 4 in Table 1) (A), poly(BT‐alt‐BPD) (run 3 in Table 2) (B), and poly(BT‐alt‐TD) (C) (run 3 in Table 3 [film samples coated on a quartz plate, r.t., ex for
fluorescence 270 nm].

Chirality Induction
Chirality induction to THF‐insoluble polymers using ‐pinene

Chirality induction to THF‐soluble polymers using CPL

Fig. 7. CD‐UV (top) spectra (top) observed on L‐CPL irradiation and gCD‐vs.‐irradiation energy plots (bottom) for cast film samples of THF‐soluble poly(BT‐alt‐BD) (run 4 in Table 1) (A), poly(BT‐alt‐BPD) (run 3 in Table 2) (B), andpoly(BT‐alt‐TD) (C) (run 3 in Table 3)

Abs.

Abs.
CD (mdeg)gCD x 104

Abs.
gCD x 104

gCD x 104

gCD x 104

Fig. 6. CD‐UV (top) and gCD‐UV spectra of THF‐insoluble poly(BT‐alt‐BD) (run 4 in Table 1) (A) and poly(BT‐alt‐BPD) (run 3 in Table 2)(B) suspended in ‐pinene enantiomers [(3 mg in 2 mL (pinene)].
The samples were heated at 100 oC for 20 h .

C. poly(BT‐alt‐TD)

CD (mdeg)

B. poly(BT‐alt‐BPD)

A. poly(BT‐alt‐BD)gCD x 104

B. poly(BT‐alt‐BPD)

CD (mdeg)

A. poly(BT‐alt‐BD)

Conclusions: The Suzuki‐Miyaura coupling
polymeriztaions of relevant monomers led to
THF‐insoluble and –soluble polymers which
are expected to possess hyperbranced
structures.
Surface morphology, surface
areas and pore volume of the insoluble
materials as well as photo physical propertiesof the soluble and insoluble materials weredisclosed.
In addition, chirality was
successfully introduced to insoluble polymers
using ‐pinene as an additive and to soluble
polymers in film form using circularly
polarized light (CPL).

77

Unexpected Structural Defects Found in Fluorene‐based
Conjugated Copolymer through Suzuki‐Miyaura Coupling
Yuehui Yuan,1 Zhiyi Song,1 and Tamaki Nakano1,2*

1Institute for Catalysis (ICAT) and Graduate School of Chemical Sciences and Engineering, Hokkaido University, N 21, W 10, Kita‐ku,
Sapporo 001‐0021, Japan; 2Integrated Research Consortium on Chemical Sciences (IRCCS);

E‐mail: tamaki.nakano@cat.hokudai.ac.jp

Abstract: In order to expanded the scope of polymer ligand for catalysis,1 a polymer ligand consisting of alternating 9,9‐dioctylfluorene‐
2,7‐diyl and 1,10‐phenanthroline‐3,8‐diyl units (poly(DOF‐alt‐Phen))2 as well as a polymer consisting of alternating 9,9‐dioctylfluorene‐
2,7‐diyl and benzene‐1,4‐diyl (poly(DOF‐alt‐Bz))3 were synthesized through the Suzuki‐Miyaura coupling method. The reaction was
conducted in a toluene‐ethanol mixture in the presence of Pd(PPh3)4 and K2CO3 at a temperature in the range of 60‐120 oC; theconditions used in this work are consistent with standard methods of the coupling. 4 We found that poly(DOF‐alt‐Phen)s obtained at 80
oC or a higher temperature contained structural defects.

Polymer Synthesis

Table 1. Synthesis of poly(DOF‐alt‐Bz) using Pd(PPh3)4aTable 2. Synthesis of poly(DOF‐alt‐Phen) using Pd(PPh3)4aCHCl3

Polymer Structure
CHCl3

Polym. Temp.
a 80 oC
b 60 oC

C8H17 C8H17

OH

O
N

N

n

defects

100

H2 O

TMS

?

?

O
C

-OH

C8H17-Polymn. Temp.
ab

C8H17-

C8H17

C8H17

80 oC
60 oC

80

T%

n

Aromatic

60

C8H17 C8H17
N

40

N

n

Aromatic

20

10

8

6

4
(ppm)

2

0

4000

2000

1500

1000

500

10

Wavelength (nm)Fig. 2. IR spectrum of poly(DOF‐alt‐Bz) (entry 5 inTable 1). [KBr, rt]

Fig. 1. 400 MHz 1H NMR spectrum of poly(DOF‐alt‐Bz)(entry 1 in Table 1). [CDCl3, rt]

8

6

4
(ppm)

2

4000

0

Fig. 3. 400 MHz 1H NMR spectrum of poly(DOF‐alt‐Phen) (entry 1 andentry 5 in Table 2). [CDCl3, rt]

2000

1500

1000

500

Wavelength (nm)Fig. 4. IR spectrum of poly(DOF‐alt‐Phen) from entry 1(a) and entry 5 (b) in Table 2. [KBr, rt]

Polymer Properties
100

0

160

Td = 140 oC

-10
-20

60

-30

40

-40

20
0

Fig. 5. UV spectrum ofpoly(DOF‐alt‐Bz) (entry 5 inTable 1). [THF, rt, 10‐mm cell].

80

40

-50

400

450
500
Wavelength (nm)

550

600

Fig. 6. Fluorescence spectrumof poly(DOF‐alt‐Bz) (entry 5 inTable 1). [THF, rt, 10‐mm cell,ex = 350 nm].

-60

Polym. Temp.
a 80 oC
b 60 oC120

x 103 [L/(mol·cm)]

x 103 [L/(mol·cm)]

80

100

200
300
Temperature (°C)

400

0

500

Fig. 9. TGA of poly(DOF‐alt‐Bz) (entry 5 in Table 1).
[rate : 10 oC/min].

Fig. 10. DSC profile ofpoly(DOF‐alt‐Bz) (entry 5 inTable 1). [2nd heating scan
at a rate of 10 oC/min.
Intensity of the profile has
been normalized to asample amount of 10.0 mg.]

Fig. 7. UV spectra ofpoly(DOF‐alt‐Phen) fromentry 1 (a) and entry 5 (b)in Table 2. [THF, rt, 10‐mmcell].

400

450
500
Wavelength (nm)

550

600

Fig. 8. Fluorescence spectra ofpoly(DOF‐alt‐Phen) from entry
1 (a) and entry 5 (b) in Table 2.
[THF, rt, 10‐mm cell, ex = 350
nm].

Fig. 11. TGA of poly(DOF‐alt‐Bz) (entry 5 in Table 2). [rate :10 oC/min].

Control Reactions

Fig. 12. DSC profiles ofpoly(DOF‐alt‐Phen)fromentry 1 (a) and entry 5 (b) in
Table 2. [2nd heating scan atoa rate of 10 C/min.
Intensity of all profiles has
been normalized to asample amount of 10.0 mg.]

TMS

CHCl3

a. With Pd(PPh3)4

Conclusions:Poly(DOF‐alt‐Phen)s prepared at 80oC
or a higher temperature appeared tohave defective chemical structures
while the structure of poly(DOF‐alt‐Bz)
was good under all conditions we
examined. The defects may be basedon H2O addition to aromatic systems.

b. Wihout Pd(PPh3)4c. Pristine poly(DOF-alt-Phen)

10

NMR spectra of reaction mixtures of poly(DOF‐alt‐Phen) with H2O
with Pd(PPh3)4 (a) and without Pd(PPh3)4 (b) and that of pristinepoly(DOF‐alt‐Phen) (c). [400MHz, r.t, CDCl3]

8

6

4
(ppm)

2

0

NMR spectra of reaction mixtures of DBrPhen with H2O
with Pd(PPh3)4 (a) and without Pd(PPh3)4 (b) and thatof pristine DBrPhen (c). [400MHz, r.t, CDCl3]

NMR spectra of Poly(DOF‐alt‐Phen) of entry 2 inTable 1(a), products after same reaction without
Pd(PPh3)4 (b). [400MHz, r.t, CDCl3]

1) A. Kimura, H. Hayama, J.‐y. Hasegawa, H. Nageh, Y. Wang, N. Naga, M. Nishida and T. Nakano, Polym. Chem., 2017, 8, 7406‐7415.
2) T. Yasuda and T. Yamamoto, Macromolecules, 2003, 36, 7513‐7519.
3) Bondarev, D. , Zedník, J. , Vohlídal, J. , Podhájecká, K. and Sedláček, J., J. Polym. Sci. A Polym. Chem., 2009, 47, 4532‐4546.
4) (a) N. Miyaura and A. Suzuki, Chem. Rev., 1995, 95, 2457–2483; (b) A. Suzuki, Angew. Chem. Int. Ed., 2011, 50, 6722–6737; (c) N. Miyaura, K. Yamada and A. Suzuki, Tetrahedron Lett., 1979, 20, 3437–3440.

78

A theoretical and spectroscopic study of In-CHA zeolite for activation of light alkanes

Shunsaku Yasumura, Chong Liu, Takashi Toyao, Zen Maeno, Ken-ichi Shimizu
Institute for Catalysis, Hokkaido university, N-21, W-10, Sapporo 001-0021, Japan

Introduction

 Ga-hydride in zeolite

Isolated surface hydrides

ν(Ga−H)

Christophe Copéret et al.,Chem. Rev. 2016,
116, 8463−8505

・Unique hydrogenation catalysis

・Ga-hydrides was
detected in DRIFT IR
measurement.

・Ubiquitous asintermediates incatalytic reactions

Our recent work: CH4 activation by In-oxo cluster in zeolites

 Surface hydride on indium oxides

In K-edge XAFS analysis implied theformation of In-hydrides rather than bare In
cation via reductive solid-state ion exchange.

In2O3 supported on ZrO2 forselective hydrogenation of CO2 to MeOH
J. Pérez-Ramírez et al., ACIE, 2016, 55, 6261-6265

・Stretching mode wastheoretically supported.

Semihydrogenation of acetylene on In2O3This work

J. Pérez-Ramírez et al., ACIE, 2017, 56, 10755-10760

・Characterization of In-hydrides

・Difficulty instructure analysis
of solid surfaces✔Comprehensive characterization of
In-hydrides in CHA zeolites based on
spectroscopic and theoretical studies

H2 activation by frustrated Lewis pairs on In2O3
G. A. Ozin et al., ACIE, 2019, 58, 9501-9505

Characterization and catalysis of surface
In-hydrides have attracted much attention.

R. A. van Santen et al., J. Phys. Chem. A, 2000, 104, 2468-2475
E. J. M. Hensen et al., J. Catal., 2004, 227, 263–269

Zen Maeno, Shunsaku Yasumura and
Ken-ichi Shimizu et al., Phys. Chem. Chem.
Phys., 2019, 21, 13415-13427
Highlighted in Front Cover✔Catalytic application of CHA-supported
In-hydrides for C2H6 dehydrogenation

Synthesis & Characterization

Yellow powder
In2O3/CHA

H2, 773 K

Reductive solid-stateion-exchange

Vacuum at 473 K

ν(C−D)
2170

C 2H4 at 473 K
In-CHA(D2 )0.25

In-CHA(H 2)after C2H4
at 473 K

3000
2500
2000 1900 1800 1700 1600
-1
Wavenumber [cm-1]

2000

1500

Vibrational analysis

Degree of decrease in A1740cm-1 [-]In-CHA(0.2)
In-CHA(0.4)

0
27920

27930 27940 27950
X-ray energy [eV]

27950
28000
X-ray energy [eV]

0

28050

0

1
2
3
4
5
Interatomic distance [Å]6・Scattering peak was hardly
observed after H2 treatment.

・[InH2]+ formation form [InH]2+

0.6
y 2= 1.11 x
R = 0.99

0.4

In/Al = 0.4

In/Al = 0.2

0.2

H

H

ln

ln
H-CHA

0

1800 1700 1600 1500 1400 1300
-10

W avenumber [cm ]0.2
0.4In/Al ratio [-]0.6・ One H+ was exchanged with one In-hydride species.

C2H6 dehydrogenation

Frequency[InH2][InH]

1735.6-

Paired 2Al site

1721.21793.0・ M/Al dependency[10 ] 1.5-1

In-CHA maintained high selectivity.

Reaction mechanism
cf. Proposed mechanism on [GaH]2+ in Ga-zeolites

Al

Si

a
Si

H2

H2

O
Al

O
Si

H

Al

H

ln

O
Si

H

H
O

O
Al

ln

O

O
Al

O
Si

O
Al

[InH2]+ Z- is the most plausible In-hydride species.

・Concerted mechanism[10 ] 1.5

TOF [s ]Temperature：700˚C, Catalyst：0.1 g,
Flow: 10% C2H6/He (Total flow: 10 mL/min)

a
Si

O

O

-3

1

0
0

O

TS calculation for C2H6 dehydrogenation on [InH2]+

・ p(H2) dependency

0.5

2+

Single 1Al site

-3

A. T. Bell et al, J. Am. Chem. Soc. 2019, 141, 1614-1627+

Kinetic study

High durability of In-CHA

H2 poison

2

1
0.5

・H2 elimination from [InH2]+

Rate [mmol・gcat -1・s-1]

Absorbance [a.u.]

H-CHA

0
27900

1.5

TS calculation for feasibility of [InH2]+

NH3 adsorption (FT-IR)
1.0

In 2O3(× 0.5)
In 2O3/H-CHA(× 0.5)
In foil
In-CHA(773 K)
In-CHA(373 K)

4・Absorption edge shifted toward lower
energy than In foil after H2 treatment.

・Stretching mode of In−H bond was observed.
・C−D bond was formed via reaction of In−D with C 2H4.

White powder
In-CHA61

0.5

In-CHA(D 2)after C2H4
at 473 K

FT-EXAFSIn 2O3
In 2O3/CHA
In foil
In-CHA(773 K)|FT|Absorbance [a.u.]

2. Calcination (773 K)

1.5

0.1

In-CHA(H2 )1. Impregnation

In situ XANES

ν(In−H)
1720

Norm.  (E)

In(NO3)3• nH2O

Absorbance [a.u.]

CHA zeolite

Norm.  (E)In situ FT-IR

Synthesis

Reaction order
In-CHA: -0.04
Ga-CHA: -0.34
0.05p(H2) [-]

0.1

In-CHA showed zero-orderkinetics with respect to p(H2).

1

0.5

Ga-CHAIn-CHA00

0.2 0.4 0.6
M/Al ratio [-]0.8

Reaction rate linearly
increased with In/Al ratio.

・ Apparent activation energy: E a = 235 kJ/mol

・Stepwise alkyl mechanism

C2H6 dehydrogenation by In-CHA occurs✔ on [InH2]+ rather than [InH]2+✔ via concerted mechanism
1) H2 does not inhibit the reaction.
2) Reaction rate increased beyond In/Al = 0.5.

Active site3) [InH2]+ is stable in the presence of H2.
4) Calculated Ea for concerted mechanism isin agreement with the experimental value.

79

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aInstitute for Catalysis, Hokkaido university, N-21, W-10, Sapporo 001-0021, Japanb Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, 615-8520, Kyoto, Japanc Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University,N-21, W-10, Sapporo 001-0021, Japan

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0DVD\RVKL%DQGR.L\RKLNR 1DNDMLPD=KL\L 6RQJDQG7DPRWVX7DNDKDVKL1Institute for Catalysis and Graduate School of Life Science, Hokkaido University, Kita-ku, Sapporo 001-0021
2Department of Chemistry, Aichi University of Education, Igaya, Kariya, Aichi 448-8542

Previous ResearchThis Study:H SURSRVHG WZR K\SRWKHVHV IRU WKH WUDYHOOLQJ RI FDUERQ DWRPV LQ RUJDQLF PROHFXOHV :KHQ FRPSRXQGV ZLWK GLIIHUHQW FDUERQ SRVLWLRQV DUH LQ HTXLOLEULXP FDUERQV PRYH WR
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J. Am. Chem. Soc. 129

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J. Am. Chem. Soc. 130

Organometallics

Results and Discussion
Preparation for Starting Material 1

Different Viewpoints on the Reactions
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85

Cation-Distribution-Tuned Perpendicular Magnetic Anisotropy in NiCo2O4
Epitaxial Films
Yufan Shen1, Daisuke Kan1, Zhenhong Tan1, Yusuke Wakabayashi2 and Yuichi Shimakawa1
1 Kyoto Univ. ICR
2 Tohoku Univ. Dep of Physics

ԔԍԡInstitute for Chemical Research

Introduction

Film Deposition and Characterization• NiCo2O4 (NCO), which has the inverse spinel structure, displays various properties.
Above-room temperature Ferrimagnetism withperpendicular anisotropy[1]Out-of-plane

In-plane[1] X. Chen, et al. Adv Mater 2018, 1805260.

Pulse laser deposition:

Our Study

1.We tuned cation distribution in NCO.
2.Cation distribution in NCO films wasdetermined by synchrotron X-ray diffraction
technique.
3.We revealed the impacts of cation distribution
on ferrimagnetism and perpendicular anisotropy.
Co(NiCo)O4

Tunable Conduction [2]Td Co

Substrate on heater• Substrate: MgAl2O4 (001) (8.083 Å)• Target : NiO+Co2O3 (Ni : Co = 1:2)
• Growth conditions: Laser Energy density: 1.2 J/cm2
Substrate Temp. : 350 ℃
Oxygen pressure PO2: 0.03 Torr
0.05 Torr
0.1 Torr• Film Thickness: ~30 nm
0.15 Torr

Excimer Laser
λ= 248 nm

O2Rotating Target

Characterization:• Laboratory source and synchrotron x-ray diffraction for structure analysis of grown films.

Oh Ni/Co• Superconducting quantum interference device (SQUID) magnetometry for magnetic
properties.
• Van der Pauw pattern for electrical conductivity, four-terminal configuration Hall bar fortransverse (Hall) conductivity.

[2] Y. Bitla, et al. Sci. Rep. 2015, 5.15201

Results and Discussion
Structure Analysis

Epitaxyʤ BL-4C Photon Factoryʥ

Cation Distribution(022) reflection originating only from Td cations

PO2 dep. of Ni comp. in
NCO films

Lab-source x-ray

PO2 = 0.15 Torr Film
(222) reflection originating only from Oh cations(00L) Profiles

RSM around (408) MAO
reflection• All films were grown epitaxially on the substrate. Out-of-planelattice constant is about 8.19 Å for all samples (8.128 Å forbulk).
• All NCO films are in fully compressive strained statealong as in-plane direction.

Magnetization
M-H

M-T
(b)

• All NCO films display above-roomtemperature ferrimagnetism withperpendicular magnetic anisotropy.
• Cation Distribution impacts exchange
Ni comp. dep. interaction between cations in Td site
and Oh site.
of M• Both the transition temperature andmagnetization strongly depend on the
Ni comp in Oh site (yOh-Ni).

• Reproducing the incident x-ray energy dependence of the NCO(022) and (222) reflection intensity allows for determining theNi and Co distribution.ʤ BL-4C Photon Factoryʥ
• The cation composition of the film grown under PO2 = 0.15 Torris determined to be (Co0.87Ni0.13)(Co0.98Ni1.02)O4

Resistivity• Higher PO2 introduces more Ni
to the Oh site.
• The cation distribution can becontrolled by simply adjusting
the PO2 during the growth.

Perpendicular Anisotropy

Uxx-T• NCO films with yOh-Ni close to stoichiometricvalue display the enhanced perpendicularanisotropy, highlighting the importance cation
distribution brings to the perpendicular anisotropy.
• Higher yOh-Ni (higher PO2) leads
to lower electrical resistivity

Hk: Anisotropy Field
MAE: Magnetic anisotropy energy
MAE = Ms·Hk/2
Eq.1

Conclusion

NiCo2O4 thin film has been grown epitaxially on MgAl2O4 with thickness around 30 nm. We quantitatively evaluated cation distribution in NCO epitaxial films and elucidated how
it impacts magnetization as well as perpendicular anisotropy:• The Ni concentration in Oh-site (yOh-Ni) can be tuned by simply adjusting the oxygen partial pressure PO2 during the growth of films. Higher PO2 will introduce more Ni to Oh site.
• Films whose cation distribution close to the stoichiometric value show the transition temperature higher than 400K and the enhanced perpendicular magnetic anisotropy.

86Synthesis of π-Conjugated Polymers Containing Benzodithiophene andBenzotriazole Units via Highly Selective Direct Arylation Polymerization (DArP):
Effects of Homocoupling Defects on Photovoltaic Performance
Masayuki Wakioka, Naohiro Torii, and Fumiyuki Ozawa
International Research Center for Elements Science, Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011
2. Previous Work

1. Introduction: π-Conjugated Polymers
Synthetic Routes
Ar'

H

H

– HX
(X = Br, I)

Pd cat.

Ar

Br

+

Br

Ar'

M

Ar'

Ar

Ar

Ar'

Ar

ex)

M

R
N

O

Ar

Ar'

N
R

Ar'

DArP SiPr3(R = 2-hexyldecyl)

S

R
N

Ar

S

S

S

n

H

S

+

BDT-SnMe3

S

F

F

poly(BDT-alt-BTz)

SiPr3

BTz-Br

SiPr3

S

Br

Br

S
S
SiPr3

+

H

S

R
N

F

H

S

+

H

P

S

SiPr3

SiPr3
S

Pd2(dba)3 (1 mol%)
L1 (4 mol%)

N

S
S

S
S

F

S

S

m

n

S

S

BDT-Br (0.80)
+BTz-H (1.00)

S

Pd2(dba)3 (1 mol%)
L1 (4 mol%)N

S

t-BuCO2H (1 eq)+
Cs2CO3 (3 eq)
BTz-Br (0.20) toluene, 100 °C, 96 h
– HBr

S

S
S

F

SiPr3

N

N

F

S

m

SiPr3

SiPr3

S

F

R
N

N

F

N
S

P3
94% yield
Mn = 18,400 (PDI = 3.6)
BTz-BTz homo = 18.5%

S

F

R
N

N

F

S

5. Structures of Poly(BDT-alt-BTz)sS

SiPr3 A4
H
H
S

A1 N

H N

H

S

S
S
SiPr3

BDT-BDT<0.1%

BTz-BTz<0.1%

HA2

1H NMR (800 MHz, o-C D Cl , 150 °C)
6 4 2

R

A3 A5

F

N

F

S

BTz-BTz
18.5%

800

4.0

Main Chain Structures

Terminal Structures

[BDT-BTz cross] A1 – A5
[BDT-BDT homo] B1 – B6
[BTz-BTz homo] C1, C2[BDT-Br end] a1 – a6
[BDT-H end] b1 – b3
[BTz-H end] c1 – c3
[BTz-Me end] d1 – d3

BDT-BTzcross

4.5

5.0
6.0
5.5
photon energy (eV)

6.5

BTz-BTz
homo (%)

λmax (nm)a

Egopt (eV)b

<0.1

<0.1

538, 582

1.99

–5.30

P2

22,800 [3.9]

19.3

<0.1

536, 574

2.01

–5.38 deeper
HOMO

P3

18,400 [3.6]

<0.1

18.5

542, 583

1.97

–5.26

P1*

32,100 [2.2]

1.4

13.1

541, 584

1.98

–5.26EHOMO (eV)cnn-type semiconductor

0

C6H13

P1
P2
P3
P1*

–5
–10

C6H13

BHJ layer 

–15
–20
–0.2

NC

Glass / ITOS

0.2 0.4 0.6
voltage (V)

0.8

1.0

O
C6H13
C6H13

ITIC

Glass/ITO/ZnO/BHJ layer/MoOx/Al

CN

S
S

CN

hv
0

NC

S

O

BHJ Layer: polymer + ITIC (1/1)

BDT-BDT
homo (%)

BTz-BTz
homo (%)

JSC (mA cm–2)aVOC (V)aFFa

PCE (%)a

31,500 [4.1]

<0.1

<0.1

15.6(1) [15.7]

0.909(1) [0.913]

0.66(2) [0.693]

9.5(1) [9.9]

22,800 [3.9]

19.3

<0.1

12.5(2) [12.9]

0.973(2) [0.976]

0.62(2) [0.637]

7.5(3) [8.0]

P3

18,400 [3.6]

<0.1

18.5

16.1(2) [16.3]

0.903(2) [0.905]

0.66(1) [0.678]

9.7(2) [10.0]

P1*

32,100 [2.2]

1.4

13.1

15.2(2) [15.5]

0.909(1) [0.910]

0.683(5) [0.693] 9.4(1) [9.8]

polymerMn [PDI]

P1
P2

aThe values are average values obtained over 6 devices. The values in brackets are for the cell with the highest PCE.

 P1, P3, P1*: almost identical optical properties and comparable dπ (see below)
 comparable photovoltaic parameters (JSC, VOC, FF, PCE) P2: deeper EHOMO and larger dπ (see below)
 higher VOC but lower JSC and FF

GIXD (out-of-plane)

AFM

BDT-BDT
19.3%

P1/ITIC(RMS = 0.89 nm)

P2/ITIC(RMS = 1.00 nm)

BTz-BTz<0.1%

P1*/ITIC(RMS = 0.88 nm)

BDT-BDT
1.4%
BTz-BTz
13.1%

P1*

BDT-BDT
homo (%)

P3/ITIC(RMS = 0.80 nm)

BDT-BDT<0.1%

700
500
600
wavelength (nm)

5

SiPr3
R
N

400

P3

7. Photovoltaic Performance (BHJ OSCs)

SS

P2
91% yield
Mn = 22,800 (PDI = 3.9)
BDT-BDT homo = 19.3%

SiPr3

0.2

P2

 The UV-vis spectra of four kinds of polymer were almost the same.

S
S

S

0.4

P1

aUV-vis (thin lms). bE opt = 1240/λcgonset. Photoemission yield spectra (PYS).

N

F

0.6

Mn [PDI]

SiPr3

SiPr3

R
N

0.8

31,500 [4.1]

L1

BDT-H
(0.20)

S

t-BuCO2H (1 eq)
Cs2CO3 (3 eq)
toluene, 100 °C, 48 h
– HBr

98% yield
Mn = 32,100 (PDI = 2.2)
homo = 14.5%

P1

3

MeO

H

S

BTz-H
(0.80)

BDT-Br
(1.00)

poly(BDT-alt-BTz) (P1)polymer

(R = 2-hexyldecyl)

S

N

F

n

PYS (in lm)
P1
P2
P3
P1*

1.0

0.0
300

current density (mA cm–2)

SiPr3
N

S

F

Mn = 31,500 (PDI = 4.1)
homo < 0.1%

poly(BDT-alt-BTz) (P1*)

toluene, reflux, 24 h

UV-vis (in lm)

4. Synthesis of Poly(BDT-alt-BTz) with Homocoupling Defects
S

F

SiPr3 87% yield

NMe 2

TMEDA

L1

N

6. Optical Properties of Poly(BDT-alt-BTz)s Poly(BDT-alt-BTz) prepared by Migita–Stille cross-coupling
polymerization contains a large amount of BTz-BTz defects.
However, the polymer shows the OSC performance comparable toPoly(BDT-alt-BTz) with well controlled structure (P1),because the deterioration due to BTz-BTz defects is small.

n

S

R
N

 Poly(BDT-alt-BTz) prepared by Migita–Stille polymerization: excellent p-type semiconductor in BHJ OPV BDT-BDT defects signicantly deteriorate the OSC performance,
whereas BTz-BTz defects little affect the performance.
SSS– SnMe3Br*Power conversion efficiency
in bulk-heterojunction organic solar cells (BHJ OSCs)

 Preparation of poly(BDT-alt-BTz) with known amounts of
BDT-BDT and BTz-BTz homocoupling defects via DArP
N

MeO

Me 2N

Pd(PPh3)4 (3.5 mol%)chargeSSR
Nt-BuCO2H (1 eq)
Cs2CO3 (3 eq)
toluene, 100 °C, 48 h
– HBr
3

N

S

cf) Zhang, Li et al., Nat. Commun. 2016, 7, 13651.

absorbance (normalized)NS

Pd2(dba)3 (1 mol%)
L1 (4 mol%)
TMEDA (10 mol%)P

Effects of Homocoupling Defects on Photovoltaic PerformanceS

F

BTz-H

S

Migita–Stille

homo 10%
PCE* = 1.8%

3. This Work and Summary
SiPr3

F

H

S

SiPr3

Sommer et al., Adv. Energy. Mater. 2016, 6, 1601232.

Review on DArP: Leclerc et al., Chem. Rev. 2016, 116, 14225.

+

Br

SiPr3

N

Review for L1-based catalyst:
Asian J. Org. Chem. 2018, 7, 1206. homo <0.1%
PCE* = 5.2%

N

N

S BDT-Brhomo 20%
PCE* = 4.5%

ONR

 DArP realizes shortcut routes
with reduced waste generation.

S

Br

Janssen et al., J. Am. Chem. Soc. 2014, 136, 11128.
S

Ar

Ar

homo <0.1%
PCE* = 7.5%

SnS

Migita-Stille Coupling
Polymerization

Ar'

Synthesis of π-Conjugated Polymers Containing BDT and BTz Units

Ar'

homo

N

Ar'

Ar'

 Homocoupling: deterioration in OSC performance

π-Conjugated Polymers
Ar

Ar

homo

– MX
(M = SnMe3)

Pd cat.

Direct Arylation
Polymerization(DArP)

Ar

Conversion toorganometallic
monomers

P1/ITIC dπ-π = 3.76 Å

P2/ITIC dπ-π = 3.85 Å
P3/ITIC dπ-π = 3.71 Å
P1*/ITIC dπ-π = 3.74 Å
0.5

 Almost no difference (RMS ~ 1 nm)Acknowledgement

1.0
1.5~qz (Å–1)

2.0

face-on orientation
π-stack

charge+Brphotoelectron yield1/2 (a.u.)Arintensity (a.u.)Br

Effects of Homocoupling Defectsdπ-π

 P1, P3, P1*: comparable dπ-π P2: larger dπ-π
(due to steric hindrance of
BDT-BDT units)
 lower JSC & FF

The GIXD experiments were performed on beamline BL19B2 of SPring-8 with the approval of
the Japan Synchrotron Radiation Research Institute (JASRI) (Proposal 2018A1584). We are
grateful to Prof. I. Osaka and Dr. M. Saito (Hiroshima Univ.) for BHJ OPV measurement andProf. A. Wakamiya (ICR, Kyoto Univ.) for analytical GPC, UV-vis, PYS assistance.

87

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Ⴭ୑ৡ॑ஂखथ಍ཝઈ৿॑ාକघॊ૏஡ᄘਙঌউॳॻभ৫৅
┈⏣ಇ༤䚸ᮧᒣ▱䚸஧ᮌྐᮁ䕿Toshihiro
Masuda, Shiroh Futaki
Institute for Chemical Research,
Kyoto University, Kyoto 611-0011, Japanி኱䞉໬◊

INTRODUCTION
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AF594-Dextran10kDa

Relative cellular uptake of
AF594-Dextran10kDa,PSRUWDQFHRIDPSKLSDWKLFVWUXFWXUHZDVLPSOLHG

350
300
250
200
150
100
50
0

400

Ctr siRNA300

CHC siRNA
200

100

No
R6W3 R6W3 R6W3 R6W3
peptide (2.5 μM) (5 μM) (10 μM) (20 μM)ŚĂŽĞƚĂů͕͘EĂƚƵƌĞŶĂŶŽƚĞĐŚŶŽůŽŐǇ͕ϮϬϭϳ΀Ğůů͕,Ğ>ĂĐĞůů͖dƌĞĂƚŵĞŶƚ͕Zϲtϯ͕ůĞǆĂϱϵϰͲĞǆƚƌĂŶϭϬŬĂ;ϱϬђŐͬŵůͿĨŽƌϯϬŵŝŶ΁

5: LQFUHDVHGWKHDPRXQWRIGH[WUDQFHOOXODUXSWDNH

0

no peptide

R6W3΀Ğůů͕,Ğ>ĂĐĞůů͖dƌĞĂƚŵĞŶƚ͕Zϲtϯ;ϮϬʅDͿ͕ůĞǆĂϱϵϰͲĞǆƚƌĂŶϭϬŬĂ;ϱϬђŐͬŵůͿĨŽƌϯϬŵŝŶ΁

&+&NQRFNGRZQGHFUHDVHG5:PHGLDWHGGH[WUDQFHOOXODUXSWDNH

EĂŵĞ ^ĞƋƵĞŶĐĞ
55::55:55
td/ŶǀĞƌƐĞ 55:55::55
Zϲtϯ 55ZZ55Z55

΀Ğůů͕,Ğ>ĂĐĞůů͖dƌĞĂƚŵĞŶƚ͕ZϲtϯĂŶĚĚĞƌŝǀĂƚŝǀĞƐ;ϮϬʅDͿ͕ůĞǆĂϱϵϰͲĞǆƚƌĂŶϭϬŬĂ;ϱϬђŐͬŵůͿĨŽƌϯϬŵŝŶ΁

Relative cellular uptake of
AF594-Dextran10kDa

䞉ZϲtϯĚĞƌŝǀĂƚŝǀĞƐĂďŝůŝƚŝĞƐŽĨĂĨĨĞĐƚŝŶŐĞŶĚŽĐǇƚŽƐŝƐĞǀĞŶƚƐ͘

CONCLUSION

400

300

200

5: VWLPXODWHG HQGRF\WLF HYHQWV

5: LQFUHDVHG WKH QXPEHU RI $PSKLSK\VLQ<)3 SXQFWD
VLJQDOV$PSKLSDWKLF VWUXFWXUH LQ 5: VHTXHQFH ZDV LPSRUWDQW IRU
HQGRF\WRVLV LQGXFWLRQ DQG PHPEUDQH UHPRGHOLQJ DELOLW\&0( LV LQYROYHG LQ 5:PHGLDWHG HQGRF\WRVLV HYHQWV

1000

No peptide

WT

InverseR6DW3,QYHUVH5:LQFUHDVHGGH[WUDQFHOOXODUXSWDNHDV:75:
5':KDUGO\FKDQJHGGH[WUDQFHOOXODUXSWDNH

88

Programmable RNA methylation and demethylation
using PUF RNA binding proteins

Miki Imanishi, Kouki Shinoda, Akiyo Suda, Shiroh Futaki
Institute for Chemical Research, Kyoto University, Kyoto 611-0011, Japan
Concept of the targeted(de)methylation

m6A is an important RNA modification

m6A

METTL3/
METTL14

SAM

Demethylase
DemethylasorMethylase
Methylase

(N6-Methyl
adenosine)

SAH

Pumilio/fem-3 mRNA binding factor (PUF)

Sequequence-s
spec
ecificSequence-specific
A binding domain
dom
main
RNA

R2

R4

R3

R5

R6

R7

R1

R8

N
3′
RNA
RNA

m
m

RNA
nate
2OG,O2
succinate
CO2
HCHO FTO

RRACH
(R=G/A;
H=U/C/A)

5´
5´

mRNA
mRNA

xxxxxxxx
xxxxxxxx
x

A
A

3´
3

m
m

ALKBH5

N 1

ssRNA

3′- AMETTL3/METTL14
heterodimerFTO     #

FTO
FTO
Me
Me
PUFa
PUFa
-AUUGUAUAUAUCUAAGAUUGUAUAUAUCUAAGm6ACAUUUUA-3’
FAM
FAM
RNA[Bm]]
-AUAUCUCUUGGGGUUCUAUUAGm6ACAUUUAG-3’
ACAUUUAG-3’
PUFb
PUFb
TAMRATAMRAMeMeRNA[Am]]

FTO
FTO-PUFa




ex. 488 nm;
em. 500-540 nm(detection of RNA[Am])

 
 

   %

Demethylation (%)

60

***

Uncleaved

ex. 532 nm;
em. 565-595 nm(detection of RNA[Bm])

***     #








RNA[Am]



RNA[Bm]








-1RNA
5’FAMAUUGUAUAUm6ACAUUUUA-3’+2RNA
5’FAMAUUGUAUAUAAGm6ACAUUUUA-3’+6RNA (RNA[Am]) 5’FAM-AUUGUAUAUAUCUAAGm6ACAUUUUA-3’+10RNA
5’FAMAUUGUAUAUAUCGGCUUUAGm6ACAUUUUA-3’

Demethylase
FTO, FTO-PUFa, or FTO-PUFb; 100nM

Buffer
25 mM Tris-HCl (pH7.5)
50 uM alpha-ketoglutarate
35 uM Fe(NH4)2(SO4)2
0.5 mM L-ascorbic acid
50 mM NaCl
50 ug.mL BSA
100 ug/mL yeast tRNA
0.01% Tween20
50 ng/uL competitor RNA

Uncleaved band
fraction)(Methylated fraction)

580
ZF

MTase domain

MazF(-)
MazF(-) MazF(+)
MazF(+)111

RNA[A]

396 456
RGG

37C, for 60 min

SAM

PUFa

-AUUGUAUAUAUCUAAGACAUUUUA-3’
FAM
Me

MTD14
MTD14d-PUFa

His6

MTase domainPUFa

MTD14d-PUFb

His6

MTase domain

PUFb

MTase domain

5’

410

RNA[B]
5’

SummaryPUFb

FTOPUFs demethylated m6A close to the binding site of the PUF
RNA binding domain.
MTD3/MTD14d-PUFs methylated the N6-adenosine in a 5′RRACH-3′ consensus sequence close to the binding site of PUFs.

Me- A U A U C U C U U G G G G U U C U A U U A G A C A U U U A G - 3 ’

TAMRA

Sequence-specic (de)methylation was demonstrated in vitro even in
the presence of an excess amount of non-specic RNA fragments
Summary
derived from mammalian cells.
Chem. Commun. (in press)

Effects of non-specific RNA on targeted RNA methylation Targeted RNA methylation in the presence of HeLa total RNARNA[A] n.s.


nt)

+

-

-

+

uncut

Addition of non-specific RNAs strongly lowered the methylationlevel of RNA[A] by MTD3/MTD14,but not by MTD3/MTD14-PUFa.

MazF (+)

Methylation (%)XXXXXXXXXXXXXXXX


PU
Fa

dPU
Fb


14

RNA
A
RNA

XXXXXXXXXXXXXXXX

A
A
MTase
MTase

PUF
PUF
XXXXXXXXXXXXXXXX

m6A
A

SA
S
AM
A
SAM
A
A

methylation
methylation

d-

14

M
TD

14

a

b

PU
F

PU
F

Even in the presence of non-specific RNAs,
target-specific RNA methylation was achievedby MTD14d-PUFs.



demethylation
demethylation

M
TD

-
+

RNA
RNA
A

Me
M
Me
m6A
A

Me
M
Me

M
TD

+

MTD14d-PUFa (100 nM)  -d-

RNA[A] +RNA[B]

+

5

TD

4

M

+

MTD3 (100 nM) 

3

Methylation (%)

(-)

n.s.

PUF
PUF
XXXXXXXXXXXXXXXX







-

(246 nt, 70-fold excess)

2

(-)

M

Competitor RNA

1

TD

RNA[A]

FTO







14



labeled RNA (100 nM)



M
TD



**
*

** **



d-

(30

nt)
(24
ut
nc
t)
]u
2n
A[A ut (2
RN
]c
[B
A

RN
nt)
(16
ut
]c
A[A
RN



MTD14 (100 nM) 

ut

nc

]u

A[B

RN

14

(merge)

TD

ex. 532 nm
em. 565-595 nm



M



RNA[B]

14

ex. 488 nm
em. 500-540 nm

14

M
T
PUD14
F d
M a TD
PU 14
Fb d

Methylation (%)cleavage

FRET measurement
electrophoresis
or gel electrophoresis

40 mM sodium phosphate (pH7.5)
0.01% Tween20
5 mM EDTA
0.6 U/uL MazF

MTD14dMTD3

Strep-tag

His6

MazF
MazF

MazF-cleaved band
(Non/De-methylated fraction)
fraction)

MTase-PUFs showed sequence-specific RNA methylation activities
MTD3

RRACARRA
R CA
demethylationor
methylation
methylation

MazF reaction



FTO-PUFa showed significant demethylation activity for RNA with PUFa binding site.

255

m6ACAACA
No cleavage
cleavage

MazF
cleavage assay
m6A methylated ssRNA
ssRNA

Denaturingg PAGE
PAGE
PAG

25C, for 30 min
then, heat inactivation



FT
O
FT
FOTOPU
-PF
U(A
Fa)
FT

FOT
-P
O
-UPF
U(B
Fb)




$

$





n.d.



+

RNA
mixture of oligo [Am] and [Bm](24 and 30 nt, 50 nM each)



**

0



+ +

ACA
ACA
A

Demethylase reaction

$6

Simanshu, et al., Mol. Cell 52, 447 (2013)
(2013)

Non/De-methylated
Methylated RNA
RNA
RNA
RNA
Methylation
Methylation
ACA
ACA
m6ACA
ACA
Demethylation
Demethylation
MazF
M
azF
RNase
RN
R
Nase

40



-

- m6A sensitive !!! 

**

20

RNA[A] 
RNA[Am]
FTO - - - - + -
FTO-PUFa - - - - - ++- Part of the toxin-antitoxin system of bacteria / archaea- ACA sequence-specic RNA endonucleaseN6-amino groupgroup

MazF-cleaved(demethylated)

MazF-cleaved(Demethylated)

MazF -

A
U
G
C



Fa Fb
PU PU
O O- OFT FT FT-

Uncleaved(Methylated)

5

Base

MazF endoribonuclease
endoribonuclease+ HeLa cells total RNAFTO (0.1 µM)
FTO-PUFa (0.1 µM)

4

A12A16
(S/C)Q
NQ
SE
SR



PUF binding site (+)3

U A U A U G U -5′Evaluation method of
m6A RNA methylation and demethylation

FTO
FTO



Fusion of the PUF domain did not interfere the FTO demethylase activity.

2

8 C

(Imanishi, et al., Chem. Commun. 53, 12930 (2017))

PUFa
PUFa
Me
Me
-AUUGUAUAUAUCUAAGAUUGUAUAUAUCUAAGm6ACAUUUUA-3’
FAM
FAM

1

7

PUF has great potential as an RNA binding domain
for RNA regulation tools.

Targeted RNA demethylation in the presence of HeLa total RNARNA[Am]]

5’FAMd(CAT)r(GGm6ACA)d(TATGT)-3’BHQ1

6[PDB: 5il0]

FTO-PUFs showed sequence-specific RNA demethylation activities



C

5

- Targets desired 8-nt sequence

Differentiation, Tumorigenesis, Circadian clock, etc.



4

- Each repeat recognizes a single nucleotide[PDB ID: 3LFM]
3LFM]]

PUF binding site (-)5′

3

- Contains 8 repeat and the N- and C-terminal regions

Splicing, mRNA stability, etc.

FTO
FTO

2

Methylation Buffer:
25 mM Tris-HCl (pH7.5)
0.01% Tween-20
1 mM DTT
50 uM ZnCl2
20 uM SAM
0.2U/uL RNasin
50 ng/uL HeLa total RNA89

Development of a Method for Large Scale Synthesis of
H2O@C60 Using a Triazine Derivative○Kazuro Kizaki, Kyusun Kim, Yoshifumi Hashikawa, Takashi Hirose, and Yasujiro Murata
Institute for Chemical Research, Kyoto University

Introduction

This Work

Fullerene C60

Commercially available• Synthesis of H2O@C60

Endohedral C60•

Fast addition reaction•

High yield of opening
closing reaction

using triazine derivative?
• Effects of C=N introduction?

H H

Reactivity, Solubility, Opening size

He

H2@C60
He@C60Komatsu, K. et al. Science
He@C60 / C60 = 3 / 7
2005, 307, 238-240.
Murata, Y. Komatsu, K.
et al. Chem. Commun.
2010, 46, 4532-4534.

CH4@C60
H2O@C60
Murata, Y. et al. Science Whitby, R. J. et al. Angew.
2011, 333, 613-616.
Chem. Int. Ed. 2019, 58,
5038-5043.

Summary

Key of reactivity

Molecular Surgery Methods
Multistep
synthesis

5% overall yield

Murata, Y. et al. Science
2011, 333, 613-616.

Low yield

13% overall yield

Whitby, R. J. et al. Chem. Commun.
2014, 50 13037-13040.

Results and Discussion

Wideropening

Narrower
opening

More reactivewith P

Reactivity

High

Solubility

Low

H2O@:
92%

H2O@:
100%

Low
High

DFT calculation (B3LYP-D3/6-31G(d))

Diels-Alder reaction and opening expanding reaction

26.9 TS2
24.8

ΔG (kcal/mol)Solubility intoluene at r. t.
5.0 mg/mL

19.7 TS1
19.3

TS3 10.6
10.6

5.5
4.6
0.0

S. M.
‐2.3
‐2.3

Komatsu, K. et al. Chem. Eur. J. 2003, 9, 1600-1609.

NMO = O N

O

O

6.4
5.8

H

H O

1.1 mg/mL
Previous method

ΔΔG‡=2.1 kcal/mol

H

O
O

H
O

INT3

‐0.3
‐0.8

INT2

INT4

O

H O

H

H

‐1.2
‐2.7

O

H

O

H
H O

H

O
O

H
O

O

‐10.1
INT5 ‐10.4 INT6

INT1

Product‐7.8‐7.9

34 mg/mL
Murata, Y. et al. Science 2011, 333, 613-616.

Formation of 16mr and encalsulation of H2O

1H NMR, APCI‐MS

3.864 Å4.131 ÅDistance / Å

N=CPh

N=CH

O‐O

3.864

3.969

C‐C

4.070

Narrower opening∆=0.105

4.144

Scale

1
2
3

50 mg, 4.6 mM
50 mg, 4.6 mM
50 mg, 15 mM

4
Pyridazinea

Solvent

Temp.

1ClNp
1ClNp
1ClNp
1ClNp
50 mg, 15 mM+Toluene
340 mg, 30 mM toluene

140 ºC
160 ºC
160 ºC

Yield(encaps. %)56% (36%) 44% (43%)‐
53 % (75%) 47% (53%)‐
35% (39%) 20% (56%) 45% (100%)160 ºC

30% (71%)

33% (72%)

37% (83%)

120 ºC

quant. (100%)

‐

‐

4.159

Ring closing reaction

Mulliken charge and C-C distance(M06-2X/6-31G(d))

Yield and encapsulation ratio were estimated by 1H NMR.
a Murata, Y. et al. Science 2011, 333, 613-616.
1H NMR (CHCl , 500 MHz)
3

-0.40

-0.41
3.32 Å

3.35 Å

More electron-accepting and small opening

H2O@: 82%

Water adduct?

4.010∆=0.041∆=0.015∆=0.074

Entry

CH=CH

Whitby, R. J. et al. Chem. Commun. 2014, 50, 13037-13040.

H2O@: 96%
Retro Diels-Alder reaction proceeded
without any dilution by Al2O3 and solvents.
New 1H

Mechanism

H2O@: 88%
9

7

8

7

8

55

6
6

 ppm

4
4

‐8

‐9

‐10

‐11

δ ppm

Dehydration reaction in ODCB (Preliminary data)
Remaining R-13mr
New compounds?

090

R-13mr
3 h, 160 ºC
5

R-16mr?
10

Retention time / min

150hIntensity

Intensity

0h

0

13mr

Whitby, R. J. et al. Chem. Commun. 2014, 50, 13037-13040.

= H2

Completely converted

1 h, 120 ºC
5

16mr
10

Retention time / min

HPLC, Buckyprep
column, Toluene,
1 mL / min, λ = 326 nm,
50 ºC

Murata, Y. et al. Science 2011, 333, 613-616.

Komatsu, K. et al. Science 2005, 307, 238-616.

Development of "Heavy Aryl Anions"
Yoshiyuki Mizuhata,* Shiori Fujimori, Shingo Tsuji, Ryuto Sasayama, Norihiro Tokitoh*
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011, Japanmizu@boc.kuicr.kyoto-u.ac.jp
Complexation

Introduction

Germabenzenes

η5
η3[RuCp*Cl]4 (0.25 eq.)
LDA

+

THF
r.t.

㽢2

η1

0Υ
dimer

Tbt

monomerJ. Am. Chem. Soc. 2002, 124, 6914.

Märkl, G. et al. Tetrahedron Lett. 1980, 21, 1405.

A kinetic stabilization by a bulky aryl group, Tbt, has been recognized to be efficient tostabilize germabenzene.

Various coordination
modes not observedin the parent phenyl
anion system

Complex A
14%

Complex B
23%

Thermal ellipsoid plots(50% probability)

Heavy Aryl Anions

Ru
Ge

Ge Ru
Ru

Ru Ge

Ge

Ru

Ge
Germabenzenyl Anions

Chem. Commun. 2018,54, 9044. (Back Cover)

Stannabenzenyl Anion

Reducing
agent
KC8, etc.

Tbt
T
bt groupg

Crystal Data (–170 ˚C)triclinic, P-1, GOF = 1.117
R1 [I>2σ(I)] = 0.0442
wR2 (all data) = 0.1289

The First “Metalsubstituted”
Germabenzene

Angew. Chem. Int. Ed. Chem. Lett.
Chem. Eur. J.
2017, 56, 4588. (VIP) 2018, 47, 708. 2018, 24, 17039. (VIP)

Crystal Data (–170 ˚C)triclinic, P-1, GOF = 1.196
R1 [I>2σ(I)] = 0.0312
wR2 (all data) = 0.0821

9-Germaanthracenyl AnionM+

E = GeGe, SnThermally
stablewithout
protecting
group!!

Ge

R = H, CMe3

Mixed polyanion by thetrimerization of anions

extraction withTHF
KC8 (2 eq.)Ge

Organometallics,
2006, 25, 3536.

40% yield
purple crystals

KC8

9-germaanthracenylpotassium
trimerization

Structures of Heavy Phenyl Anions
Nahigh germylene character

K
Na

Ge

Na

Ge
K

Ge

Ge1*

3.095(4) ÅGe2Ge3
2.4740(5) Å
2.5000(5) ÅKorthorhombic, Pbca (#61)
T = –170 °C, Z = 4
R1 [I>2σ(I)] = 0.0149
wR2 (all data) = 0.0375

monoclinic, P21/c (#14)
T = –170 °C, Z = 4
R1 [I>2σ(I)] = 0.0184
wR2 (all data) = 0.0441

K3

K1*

Ge

Na

K2

C4

K

Ge1

3.5490(9) Å
C4*

Ge

Ge

Na

K

monoclinic, P21 (#14)
T = –170 °C, Z = 4
R1 [I>2σ(I)] = 0.0222
wR2 (all data) = 0.0562

K1 contact ion pair

η1 fashion

KC8 (1 eq.)
18-crown-6

Chem. Eur. J.
2019, 25, 6284.

separated ion pairKbenzene, 25 ˚C
GeGeNICS(1)–8.10 (Ge)–7.26 (Sn)1.842(4) Å

Tbt
1.850(3)Å

1.900(2) Å 1.945(2) ÅGeGe

96.40(6)º106.7(2)º– Tbt–

NICS(0)–5.48 (Ge)–5.08 (Sn)The First Radical Anion
Dimer of Heavy Arenes

Korange crystals

2-Germanaphthalenyl Anion
crypt-222(1.1 eq.)KC8(2.5 eq.)
THF–35 ºC

Phenyl anion
negligible
Heavy phenyl anionAti characterht
Aromatic

triclinic, P-1 (#2),
T = –170 °C, Z = 4
R1 [I>2σ(I)] = 0.0540
wR2 (all data) = 0.1320

GeThis work was supported by Grants-in-Aid for
Scientific Research (S) (No. 19H05635), Scientific Research on Innovative Areas (No. 24109013),
Scientific Research (B) (Nos. 18H01963, 16H04110, 25288021), and Scientific Research (C) (No.
26410044) from the Ministry of Education, Culture, Sports, Science and Technology, of Japan. S. F.
thanks Research Fellowships of the Japan Society for the Promotion of Science for Young Scientists.

K

Ge

K

THF
rt

quant.

K

K

Di l t characterht
Divalent

Acknowledgements

monoclinic, C2/c (#15)
T = –170 °C, Z = 4
R1 [I>2σ(I)] = 0.0936
wR2 (all data) = 0.2387

Ge

quant.

monoclinic, P21/c (#14)
T = –170 °C, Z = 4
R1 [I>2σ(I)] = 0.0234
wR2 (all data) = 0.0611

Unpublished

Ge
Ge
Ge

K

K
benzenebenzene91

DFT study on Iron-catalyzed Enantioselective
Carbometalation of Azabicycloalkenes
Akhilesh K. Sharma[1,2], Miho Isegawa[2,3], W. M. C. Sameera[2,4], Masaharu
Nakamura[1][1] Institute for Chemical Research, Kyoto University, Kyoto, Japan[2] Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, Japan.

[3] International Institute for Carbon Neutral Energy Research, Kyushu University, Fukuoka, Japan[4] Institute of low temperature science, Hokkaido University

Introduction
 Asymmetric addition of carbon and heteroatom-nucleophiles to oxa- and azabicyclic
alkenes is an useful strategy for enantioselective synthesis of chiral building blocks of many
natural products.
 Recently, we reported the iron-catalyzed diastereoselective carbometalation of oxa- andazabicyclic alkenes.1
 Currently our group is working on iron-catalyzed enantioselective carbometalation
reactions of azabicycloalkenes with arylzinc reagents.

Objective and Computational Methods
 Computational methods (DFT methods) have nowadays become integral part ofreaction mechanism study.2
 Delineate the mechanistic details of the iron-catalyzed enantioselective
carbometalation reactions using computational (DFT) methods.
 Identify the origin of enantioselectivity in the reaction by DFT method.
h Gaussian 16 program used for all calculations.
Optimization: PCMToluene/B3LYP-D2/SDD(Fe),6-31G*(other atoms)
Free energies (electronic energies) are in kcal/mole at 25 ͦC temperature
with total electronic energy with zpe correction in parenthesis.
AFIR method as implemented in GRRM program with Gaussian 09 was used for
initial TS search for carbometalation step.3

Proposed Mechanism

Free Energy Profile

Spin-crossover occurs before and after carbometalation TS.
n For carbometalation TS and alkene coordinated FeII complex (B) in triplet spinstate is lowest energy.

Origin of Enantioselectivity

Spin-CrossoverSpiin Crossover iinn IIron(II)ron(II(II)) compl
complexlex (5A andd 3A)

 > 45 distinct TSs were obtained and 20 TSs have Gibbs free energy < 3 kcal/mol.
 Due to flexible coordination environment of iron, and sterically bulky chiraphos ligand TSs with
distorted square pyramidal (TS1 & TS3) and trigonal bipyramidal (TS2 & TS4) geometry wereobtained. The TS with SqPy geometry is lowest energy.

MECP

5A

3A

 Spin-crossover before alkene interaction with iron is less likely.

References

Major
enantiomer

Minor
enantiomer

Calculated %ee (TS1 & TS3): 73
Experimental %ee: 77
Energy Decomposition analysis
TS
TS1
TS2
TS3
TS4

ΔEd [Ed(X), Ed(Y)]
0.0 (0.0, 0.0)
-1.1 (0.8, -2.0)-0.1 (-1.2, 1.1)
-4.3 (-0.8, -3.5)

Interaction energy
enantioselectivity.

92

(Ei)

ΔEi
0.0
3.5
1.2
6.7

is

ΔΔE
0.0
2.4
1.1
2.4

controlling(1) S. Ito, T. Itoh, M. Nakamura, Angew. Chem. Int. Ed. 2011, 50, 454–457.
(2) A. K. Sharma, W. M. C. Sameera, M. Jin, L. Adak, C. Okuzono, T.
Iwamoto, M. Kato, M. Nakamura, K. Morokuma, J. Am. Chem. Soc. 2017,
139, 16117–16124; c) T. Iwamoto, C. Okuzono, L. Adak, M. Jin, M.
Nakamura, Chem. Commun. 2019, 55, 1128−1131.
(3) [4] W. M. C. Sameera, A. K. Sharma, S. Maeda, K. Morokuma, Chem. Rec.
2016, 16, 2349-2363.

Acknowledgement
Super-computing resources: Institute of Molecular Science, Japanthe Reaction Development: Experimental group members involved indevelopment of the reaction.
 Prof. Satoshi Maeda for giving access to the developmental version of
GRRM program.

Organic Hole-Transporting Materials with High-Lying HOMO Energy Levels for
Tin-Based Perovskite Solar Cells
Institute for Chemical Research, Kyoto University
Minh Anh Truong, Ruito Hashimoto, Tomoya Nakamura, Richard Murdey, Atsushi Wakamiya

Introduction
Perovskite Solar Cell and Mechanism: A: MA+, FA+…
: B: Pb2+, Sn2+…
: X: I-, Br-…
MA+ = CH3NH3+

Problem:-3.0

Energy Level (eV)ABX3-Type Perovskite

FA+ = (NH2)2CH+

-3.5

–3.74
–4.0

1.28

-4.5

-5.0

–5.02
MASnI3

Progress in Power Conversion Efficiencies
25

50

replace

Pb

Sn

Lead

PCE (%)

82

Tine.g. MAPbI3

e.g. MASnI3

Toxic

Environmentally Friendly

High PCE(a25)

Low PCE(a10)

1.40

㽢
–5.15
PTAA

–5.16
FASnI3

New
HTMs

–5.2
SpiroOMeTAD

Efficient Hole Extraction“Quasiplanar Structure”

15

Donor

10.2%2
6.4%
5.7%

3.8%

5

PTAA

spiro-OMeTAD

20
10

Inefficient Hole Extraction

This Work: HTMs with High-Lying HOMO Levels

25.2%1

Pb PSCs
Sn PSCs

–3.76

TiO2

-4.0

-5.5

30

HOMO Levels of HTMs Lie Below
Valence Bands (VBs) of Perovskite

0
-2
0
2
4
6
8
10
2008
2010
2012
2014
2016
2018
2020

Partially Oxygen-Bridged
Triphenylamine Skeleton1-3

Publication date

HND-NOMe

HND-2NOMe

1.A. Wakamiya, H. Kaji, Y. Murata, et al. Angew. Chem. Int. Ed. 2014, 53, 5800.
2.A. Wakamiya, L. T. Scott, Y. Murata, et al. J. Am. Chem. Soc. 2015, 137, 15656.
3.M. A. Truong, T. Nakamura, R. Murdey, A. Wakamiya, et al. Chem. Eur. J. 2019, 25, 6741.

1. https://www.nrel.gov/pv/assets/pdfs/best-researchcell-efficiencies.20191106.pdf
2. S. Hayase, et al. J. Phys. Chem. Lett. 2019, 10, 5277.

Results and Discussion
DFT Calculations and Energy Diagram (DFT: B3LYP/6-31G(d), TD-DFT: CAM- B3LYP/6-31G(d))

Synthesis and Thermal Properties

Energy Level (eV)

0

0

-1

Amorphous solids with high thermal stability (Td5 > 370 qC)

394

435

2.0

430

1.5
1.0
0.5
0.0

405

422

400

450

CH3CN solution
n
250

300

350

Wavelength (nm)CV in DMF solution

550

HND-NOMe

Current

Eonset = –0.02+0.10 HOMO = –5.08 eV
+0.51

+0.80
1.5

500

1.0

+0.25

0.5

09
–0.09

0.0

HND-2NOMe
Eonset = –0.20

HOMO = –4.90 eV
-0.5

-1.0

Potential (V) vs Fc/Fc+-1.5

UV-Vis360

Vacuumdeposited film

250

300

350

PL

HND-2NOMe
HND-NOMe

405 432 440

422

400

436

450

500

Wavelength (nm)-4

KS–HOMO-5–4.96 eVHND-NOMe
HND-2NOMe

–4.79
–
eV
PTAA

4.0

–5.15 eV
4.5

5.0

5.5

6.0

Photon Energy (eV)

6.5

7.0

2

HOMOfilm–4.74 eV
–5.42 eV2.5

3–0.44 eV
3.5

–2.02 eV

–1.95 eV

–4.35 eV

–4.10 eV

–4.96 eV

–4.79 eV

4

4.5

FASnI3(VB)

PTAA–5.15 eV –5.16 eVfilm were calculated by using HOMOfilm from PYS and optical band gaps obtained from the absorption edges of the films.

1.4 M FASnI3
5 mol% SnF2
1 mol% TM-DHP
in DMSO (45 qC)

HTM + dopant
was spin-coatedfrom PhCl

spin-coating (slope 5 s,
5000 rpm/60 s, slope 1 s)
PhCl dripping (r.t. at 62 s)

Au (80 nm)
thermalevaporation

annealing(45 qC, 65 qC, 100 qC, 10 min)550

PYS under vacuum–0.48 eV

1.5

Tin-Based Perovskite Solar Cells Fabrication and Evaluation

Current density (mA cm–2)

346

2.5

Emission Yield1/3 (cps1/3)

H (u104 M–1 cm–1)

3.0

PL

HND-2NOMe
HND-NOMe

3.5

Normalized Intensity (a.u.)

UV-Vis4.0

Normalized Intensity (a.u.)

4.5

1

-3

*LUMO

In Solid-State
Normalized Intensity (a.u.)

In Solution–0.55 eV

LUMOfilm*-2-6

Photophysical and Electrochemical Properties

0.5

KS–LUMO

28
26
24
22
20
18
16
14
12
10
8
6
4
2
0

Active area: 0.1 cm2

TM-DHPHTMa
HND-NOMeF

R

HND-2NOMe

HND-NOMe

PTAA

HND-2NOMe
PTAA
0.0

0.1

0.2

Voltage (V)Summary

0.3

0.4

Scanb
F
R
F
R
F
R

Voc
Jsc
(mA cm–2) (V)25.34 0.32
25.47 0.33
26.08 0.32
26.11 0.32
25.86 0.33
26.30 0.34

Dopant

FF
0.51
0.56
0.49
0.53
0.50
0.56

PCE
(%)
4.12
4.68
4.04
4.46
4.31
4.93

a) HTM was spin-coated from the solution with additive in PhCl
(HND-NOMe 0.06 M, HND-2NOMe 0.06 M, or PTAA 20 mg/ml
with 7.0 mM dopant). b) F: Forward scan, R: Reverse scanAcknowledgement

 Two thermally stable hole conducting materials were synthesized by connecting the partiallyoxygen-bridged triarylamine structure to one or two 4,4c-dimethoxydiphenylamine throughBuchwald-Hartwig C-N cross coupling reaction.
 The synthesized materials possess high-lying HOMO energy levels of above –5.0 eV. These highlying HOMO energy levels are suitable for efficient hole extraction in tin-based perovskite solar
cells.
 The best power conversion efficiency of the regular structural FASnI3-based Perovskite solar cells
using HND-NOMe, HND-2NONe as HTM is 4.68, and 4.46, respectively; which is comparable
to that of devices using PTAA as HTM (4.93).

Financial supported from IRCCS, NEDO, COI, JSPS, and
ALCA.

93

Preparation of Highly Emissive Perovskite Materials for Light-Emitting Diodes
Alwani Imanah Rafieh, Ai Shimazaki, Yuko Matsushige, Yasuko Iwasaki, Tomoya Nakamura,Richard Murdey, Atsushi Wakamiya
Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan

Introduction
LED Device Structure

Perovskite Nanoparticles

Bulk Perovskite
LigandOptoelectronic property of perovskite nanoparticles is size
dependent. In another words, emission wavelength of theperovskite nanoparticles can be tuned with respect to the size
aside from chemical composition. Varying the size can bedone by changing the ligand.

External Quantum Efficiency (EQE):
Blue = 6% < Green = 20%, Red = 21%

Synthesis of CsPbBr3 Nanoparticles with Ligands
Hot Injection

Ref: L. Protesescu et al. Nano Lett. 2015, 15, 3602..

Ligand Exchange

Ref: T. Chiba et al. ACS Appl. Mater. Interfaces 2017, 9, 18054.

O

Cs-oleate

C sO-

LigandLigand used in this work:
Commonly used ligands

Oleic acid

Oleylamine

n-Butylammonium
bromide (BABr)

Results

BABr Ligand Exchange
Before ligand exchange

DDAB and DDAC Ligand Exchange
PLQY 72%
Emission 515 nm

FWHM 119 meV

FWHM 98 meV

AfterLong chain ligands were successfully replacedwith short ligand

Summary

Didodecyldimethyl
ammonium
chloride (DDAC)

After BABr ligand exchange

PLQY 65%
Emission 516 nm

BeforeDidodecyldimethyl
ammoniumbromide (DDAB)

Halideexchange

DDAB

DDAC

Tuning the emission wavelength through halide exchange issuccessful

 CsPbBr3 nanoparticles with long alkyl chain ligands wereto reduce the distance between nanoparticles and improve charge
synthesized using the hot injection method.
injection in LED devices.
 Long chain ligands were successfully substituted with short ligand  Emission wavelength can be tuned by halide exchange.

94

Investigation of Ru7+ and Os7+ Quantum
Magnets with Scheelite andScheelite-derivative Structures
Sean Injac1,3, Maxim Avdeev2, Brendan J. Kennedy3, Yuichi Shimakawa1
1. Institute for Chemical Research, Kyoto University, Japan
2. Australian Centre for Neutron Scattering, ANSTO, Australia
3. School of Chemistry, University of Sydney, Australia

Introduction

Variable Temperature Structures
I41/amd

Within this work we investigate a number of oxides of the form ABO4 where A = K, Rb, Cs; and B = Ru, Os.
The stabilisation of the Ru7+ and Os7+ cations allows for investigation and comparison between 4d1 and 5d1
S = 1/2 quantum magnets, while the increasing ionic radius of the A cation investigates the effect of structural change and increasing intermetallic distances has on physical properties. These materials were synthesised by the reduction of the associated tetroxide. Structural chacterisation was undertaken using a
combination of X-ray synchrotron (SXRD) and single crystal diffraction (SCXRD) experiments, and neutron
powder diffraction (NPD) measurements undertaken at the ECHIDNA beamline at ANSTO, Australia andthe WISH instrument at ISIS, UK. Variable temperature X-ray diffraction measurements were undertaken at
the powder diffraction beamline of the Australian Synchrotron. The magnetic properties of these oxides
were investigated using temperature dependent, and field dependent magnetisation measurements, heat
capacity measurements and low temperature neutron powder diffraction measurements which allowed forthe determination of the magnetic structures of KOsO4 and RbRuO4.

caRoom Temperature Structures

b

Pnma

I41/a

c

c
a

a

b

P21/c

Pnma

b

c
a

Figure 1: Representations of the I41/a scheelite
structure (a) and Pnma CsRuO4 structure (b).

cbFigure 2: Combined SXRD/NPD refinement profiles for
CsRuO4 (top) and CsOsO4 (bottom) at room temperature.

Magnetic PropertiesaFigure 3: Representations of the ABO4 structures identified in this work. The solid lines represent observed
phase transitions that are allowed to be continuous and Figure 4: Variable temperature SXRD data collected forthe dashed lines observed transitions that must be first
RbOsO4 (top), CsOsO4 (middle), and CsRuO4 (bottom).
order.

P212121

Room temperature structures were determined for all compounds via Rietveld refinement undertaken
against combined SXRD and NPD datasets. At room temperature, KRuO4, KOsO4 and RbOsO4 crystallise in
the scheelite structure in space group I41/a. A representation of this structure is shown in Figure 1(a).
RbRuO4 and CsOsO4 crystallise in a distorted pesudo-scheelite structure in space group Pnma, as a result of
the larger A:B ionic radii ratio for these compounds. A relationship between these two structures is shownin Figure 3, which differ in the axis of rotation of the BO4 tetrahedra. CsRuO4 was determined to crystallise
as a baryte type structure in space group Pnma. This structure is similar to that recently reported for
PbSbO4, and was confirmed through SCXRD measurements.[x] A representation of this structure is shown in
Figure 1(b) and the associated refinement profiles are given in Figure 2. The distinct structural change isevident in diffraction data when compared to the pesudo-scheelite CsOsO4, which also crystallises in apcegroup Pnma, with the associated refinement profiles shown in Figure 2. From these compounds the ionicradius of the Os7+ cation in a tetrahedral coordination environment was determined to be 3.79 Å, it isnoted that no ionic radius for these conditions is given in the Shannon tables.

bbc

Variable temperature SXRD measurements revealed interesting phase behaviour, which is summaried in
Figure 3. The two K containing compounds, KRuO4 and KOsO4 did not undergo any phase transitions uponheating or cooling. RbRuO4 was observed to undergo a 1st order phase transition to the I41/a scheelite
structure upon heating, this transition was also observed for CsOsO4, data for which is shown in Figure 4.
RbOsO4 underwent a continuous phase transition upon heating to a related scheelite structure in spacegroup I4 /amd. This structure can be considered the “undistorted” scheelite structure, as no tetrahedral roa tation is 1present. CsRuO , which crystallises as a baryte-like structure in Pnma at room temperature under4
goes a 1st order phase transition to the scheelite structure in I41/a upon heating, the baryte and scheelite
phase coexist over a large temperature regime, as shown in Figure 4. Upon cooling CsRuO4 underwent a
continuous phase transition to a post-baryte structure in P212121. P212121 is a direct subgroup of Pnma, andthis transition occurs through a softening of the the Γ1− mode. This transition was also observed in variabletemperature SCXRD measurements. CsOsO4 showed unique phase behaviour, upon heating a 1st orderphase transition to the I41/a scheelite structure is observed, consistent with the other Pnma compounds.
Upon cooling at approximately 140 K a 1st order phase transition to a distorted structure in the monoclinic
space group P21/c is observed, with a = 8.22278(11), b = 7.921734(7), c = 8.23025(11), and β =119.0845(6). This structure is similar to the monazite structure, however no relationship between this structure and the scheelite structure could be determined using the ISOTROPY software suite.

Temperature dependent magnetisation, isothermal magnetisation and heat capacity measurements were undertaken on all samples. Temperature dependent DCMS data are shown in Figure 5. All data wereconsistent with long range antiferromagnetism (AFM) for all compounds except for CsOsO4 which remained paramagnetic to 2 K. DCMS and heat capacity data reveals a trend for Os compounds to show higher
ordering temperature compared to their Ru counterparts, and magnetic susceptibilities were observed to decrease with increasing intermetallic distance, as the size of the A cation is increased. These observations suggest that magnetic ordering in these compounds is mediated through direct exchange mechanisms which must result in antiferromagnetic exchange. The higher ordering temperatures for Os compounds are rationalised by consideration of the larger spatial diffusion of the 5d orbitals compared to the Ru 4d orbitals. As orbital overlap is increased the strength of magnetic exchange interactions also increases, resulting in higher magnetic ordering temperatures. In all cases superexchange, which would involve the AO8 polyhedra and entail a long B-O-A-O-B pathway, is expected to be very weak, rather direct
exchange should be dominant. As suggested by Marjerrison et al.[x] nearest neighbour interactions are expected to be the strongest and this suggestion is apparently verified by noting the increase in B-B separation correlates with the decrease in the Néel temperature in both the Ru and Os scheelites. CsOsO4 is an outlier in this series reflecting the different configuration of the OsO4 tetrahedra. Effective magnetic
moments determined from fits to inverse susceptibility were consistent with a S = 1/2 magnetic ground state. A reduction of this moment was observed for the Os compounds compared to their Ru analogues,
this is consistent with the enhanced spin orbit coupling effect of the 5d orbitals. This is due to a 2nd order spin orbital coupling effect, as a 1st order effect does not impact the occupied eg orbitals.

Figure 5: Temperature dependent magnetic susceptibility data for ABO4 compounds where A = K (top), Rb (middle) andCs (bottom). ZFC and FC measurements
are indicated.

Figure 6: NPD data collected at the WISH diffractometer for KOsO4. Temperature dependent
data is shown above-left, with data collected above and below the magnetic transition. The magnetic refinement profile carried out against data collected at 3 K is shown below. A representationof the magnetic structure of KOsO4 is shown to the right.

Figure 7: A refinement profile for RbRuO4 carried out against NPD data collected at ECHIDNA at 3 K. A
magnetic contribution is indicated by magneta tickmarks. A representation of the magnetic structure isshown to the right.

Magnetic structures were determined for KOsO4 and RbRuO4. The magnetic unit cell for KOsO4 was determined by Rietveld refinement carried out against NPD data collected at the WISH instrument at ISIS. A single, weak reflection was observed togain intensity below the magnetic ordering transition and was indexed as hkl = (110) with a k = 0,0,0 magnetic propagation vector in space group I41/a. Group theory analysis, performed with the ISODISTORT software suite, indicated four possible irreducible representations namely Γ1, Γ3, Γ5 and Γ7. Of these only Γ5 allows for intensity in the (110) but not the (002) reflection showing that magnetic structure to be antiferromagnetic with the moments parallel to the c−axis. This is consistent with AFM
ordering of spins along the 001 direction, as represented in Figure 6. A miniscule ordered magnetic moment of 0.46(18) µB was determined. This structure is equivalent to that previously determined for KRuO4, which was reported to have a slightly
larger magnetic moment of 0.57(7) µB.[x] A magnetic structure for RbRuO4 is tentatively proposed. Rietveld refinements carried out against NPD data collected at 3 K for this compound using the ECHIDNA diffractometer at ANSTO show a slight increaseof intensity of several reflections compared to data collected above the magnetic ordering transition temperature. Therefore a magnetic propagation vector of k = 0,0,0 was determined. Eight possible irreps were identified. Of these, Γ2+, Γ3+, and Γ4+show ferromagnetic order, and are therefore inconsistent with the magnetisation data. The remaining representations show AFM ordering. For irreps Γ1+, Γ2−, and Γ3− the moments are required to lie parallel to the b-axis. Irreps Γ1− and Γ4+ show AFM
ordering along the c-axis, with canting of moments within the 100 plane. All AFM irreps resulted in similar quality of Rietveld fits to the NPD data, indicating that better data quality is required in order to unequivocally determine the magnetic structureof RbRuO4. Nevertheless, a magnetic cell is tentatively proposed using Γ1-, as this magnetic structure is effectively equal to that determined for KRuO4 and KOsO4, with a small AFM canting of magnetic moments within the 100 plane. A refinement profile using this model is shown in Figure 7. The magnetic moments were refined to be 0.77(24) µB along the c direction and 0.21(9) µB along the a direction. A representation of this magnetic structure is also shown in Figure 7.

95

Large latent heat by intersite charge transfer transitions
in A-site ordered perovskites
Yoshihisa Kosugi1, Masato Goto1, Takashi Saito1,2, Yuichi Shimakawa1
1 Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan

2 High Energy Accelerator Research Organization (KEK), Tokai, Ibaraki 319-1106, Japan

Introduction
inter-site Charge Transfer (CT) transition in ACu3Fe4O12

A-site ordered perovskite-structure AA’3B4O12
A-site order A : A’ = 1 : 3

BO6octahedron(A = Bi3+, La3+~Tb3+)

Because the structure has A’O4 squareplane, Cu2+ or Mn3+ can occupy A’ site.

A’O4square-plane

Low-T

High-T

ACu3+3Fe3+4O12

ACu2+3Fe3.75+4O12
metal

insulator

A’-B interaction causes various
physical property.

A

antiferromagnetic

paramagnetic

Large volume change (1~2%)
but no symmetry change
Y. Shimakawa. J. Phys. D: Appl. Phys. 48, 504006 (2009).

A-site substitution

This research

A=La~Tb
Inter-site charge transfer(CT) transition
3Cu2+ + 4Fe3.75+ → 3Cu3+ + 4Fe3+

ACu3Fe4O12

We studied heat physical properties at the CT
transition in NdCu3Fe4O12 and found that thetransition is accompanied by large latent heatnear room temperature.

A=Dy~Lucharge disproportionation(CD) transition
8Fe3.75+ → 3Fe5+ + 5Fe3Experimental

We focus on inter-site CT transition because thistunability of transition temperature by A-site
substitution is useful for application.

・synchrotron XRD (SXRD)
・Magnetic measurement
・Electric resistivity measurement
・Neutron diffraction
・Differential scanning calorimetry (DSC)

I. Yamada, et al., Inorg. Chem. 52, 13751-13761 (2013).

Results and Discussion
synthesis and structure

physical properties
Magnetic susceptibility

Electric resistivity

Intensity (a. u. )<Rietveld analysis>
Space group: Im3�a=7.39693 Å
Rwp=4.245%

Neutron diffractionρ (Ω cm)

There are no impurity peaks.

-3

3

NSRRC λ=0.82657 Å

V(Å )

-1

χ (10 emu mol )-1

Volume change

DSC

heat flow (mW g )High pressure synthesis:
9 GPa, 1100 ℃

peak topposition

cooling
process

heating
process302.1 K

316.1 K

entropychange ΔS

84.2 J K-1
kg-1

80.6 J K-1
kg-1

latent heat |Q|

25.5 kJ kg-1

25.1 kJ kg-1

So large entropy change!

All physical properties change in theinter-site CT transition temperature.

In ND pattern, 311, 331 and 333/511 peaks
are observed in LT phase.

DSC curve shows hysteresis loop, indicating intersite CT transition is of a first-order transition.

S=5/2 Brillouin function fitting

Intensity (a. u. )Neel temperature TN=643 K

G-type antiferromagnetic ordering
From temperature evolution of ND pattern,magnetic Bragg peaks 311 abruptly
disappear together with LT phase.

Near 300 K
charge transfer energy ＞ antiferromagnetic interaction

S=5/2
ΔSM = Rln(2S+1) = 79 J K-1 kg-1
⇒ Q = 24 kJ kg-1 (300 K)

An unusual first-order magnetictransition induced by the intersite CT
causes a colossal entropy change.

Conclusions
・NdCu3Fe4O12 was obtained as a single phase by high pressure synthesis and showed inter-site chargetransfer transition near room temperature.
・ The inter-site CT transition is accompanied by a colossal latent heat (25.5 kJ kg-1) near room
temperature. This entropy change is attributed to the unusual first-order magnetic transition induced by
CT transition.
・ The large entropy change is possibly used for a magnetocaloric effect, which provides environmentfriendly and highly-efficient refrigeration systems compared to the widely used conventional vaporcompression cooling systems.

96

Polarization Switching via Electron Transfer in a Valence Tautomeric
Cobalt Complex
Shu-Qi Wu, S. Kanegawa, and O. Sato
Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan

Soft Molecular assemblies

Electron Transfer

Rotation

Electrontransfer

Molecular Transfer

Proton Transfer
C
N
Fe
N N
C
C

C
N

Proton pumpT

N6

Conformation change
Molecular diffusion

UCDAVIS BIOWIKI

P21/n

sp
pin
spin

orbitalx

Molecular Displacement

T
FeII – CN – FeIIIy
Electron
Rotation

DeviceEnergy Saving

H N+

-1

z

e-

Molecular Rotation-3

Proton Transfer

FeIII – CN – FeII

Fm

䠉Co
ChargeTransferH+H+

3mol-1K
FT /Tcm/ cm Kmol

e-

e-

99
88
77
66
55
44
33
22
11
00 0
0

50
50

100
100

150
150

T/K

T/K

200
200

250
250

Angew. Chem. Int. Ed., 55, 6047-6050 (2016)

Results

Polarization Switching

Heating
Cooling{[FeIII(Tp)(CN)3]2FeII(bpe)}·5H2O

O. Sato, Nature Chemistry 8, 644-656 (2016)

Mechanical Property Switching

Magnetization Switching[(H4BPTC)(azpy)2]n

Valence Tautomerism in Cobalt Complexes

Polarization Switching

J. Am. Chem. Soc. 138, 12005-12008 (2016)

Strategy and Potential Advantages

Valence tautomeric transitions involve a stimulated intramolecular electrontransfer between a redox-active metal center and redox-active ligand.

Ion Displacement[H2dabco]·[2CB]2Angew. Chem. Int. Ed., 55, 14628-14632 (2016)

Crystallize valence tautomeric molecules in the polar space group.

Heat

Non
Polar

Ligh
t
Electron Transfer Coupled
Spin Transition

Polar

Energy-economic: Repeatable without polarization field.
Light-controllable: Switching with suitable light excitation.

BaTiO3Magnetic Momentt

D. Fu et al. Intech DOI: 10.5772/61017
Ferroelectric Materials– Synthesis and Characterization

Electric
El t i Dipole Moment

Optical Absorption

Molecular Size

Crystal Packing: Steric Effect and Non-cancelable Polarization

Magnetometry: Two-step Valence Tautomerism

Steric hindrance of the perchlorategroup enhances the T1/2 of Λ motif.

21 screw axis

Heating process:(T1)1/2 = 251 K, (T2)1/2 = 333 K.
Cooling process:(T1)1/2 = 240 K, (T2)1/2 = 312 K.

Pyroelectricity: Two-step Polarization Switching

Calculated orientation ofmolecular dipole moments
Crystal packing viewed along
a-axisLT: 7.27 Debye; HT: 13.15 Debye.

Light-induced Polarization Switching: Magnetometry

Irradiati
onAb-axisLight-induced Polarization Switching: Spectroscopy

Light-induced Polarization Switching: Dynamics

π* excited state

Fast relaxation
Fast
relaxation
CoII-phenSq
CoIII-phenCat
190 K

97

98

Magnetic switching without spin transition in an Iron(II) complex
Sheng-Qun Su, Shu-Qi Wu, Shinji Kanegawa, Osamu Sato
Institute for Materials Chemistry and Engineering, Kyushu University, and IRCCS
Control of Magnetic Property

Multistep transition
In Fe(II) complex

J. Am. Chem. Soc. 2018, 140, 98−101

Control of Spin Angular Momentum

Coord. Chem. Rev. 346 (2017) 176–205

Control of Orbital Angular Momentum
complexes

J. Am. Chem. Soc. 131, 4560–4561 (2009)

Angew. Chem. Int. Ed. 2010, 49, 1410 –1413

Previous work about Co(II) complex

Nature Commun. 6, 8810 (2015)

Current work about Fe(II) complex

gauch conformationtrans

Molecular structures at the low and high temperature phase

303 K
φ (deg.) 155.52
θ (deg.) 88.11

123 K
151.93
78.98

The two components in the angular Jahn–Teller distortion

The propyl group rotated
123 K

303 K

ΔE1 (ev)

0.122

0.049

ΔE2 (ev)

0.204

0.106

151.8380.15

calculated d-orbital splitting

Conclusion

Key words

Jahn- Teller distortion
Alkyl rotation
Magnetic transition
Orbital angular momentum

The magnetic susceptibility depends on the temperature
for the microcrystals (left) and oriented sample (right)

Spin transition◆ Magnetic transition was induced by the variation of coordinationgeometry, which was attained by the rotation of the propyl group.

99

Photoabsorption and Photoluminescence Properties of Donor-Acceptor

S-Conjugated Enamines and Their Additive Effects with B(C6B5)3Atsushi Tahara, Daichi Sakata, Ikumi Kitahara, Yoichiro Kuninobu, Hideo Nagashima
Institute for Materials Chemistry and Engineering ,Kyushu University, 6-1, Kasugakoen, Kasuga-shi, Fukuoka, 816-8580

Introduction

䖃Previous Work : Ir-catalyzed Syntheses of aldenamines

䖃Chemoselective Hydrosilane Reduction of Amides(1) Hydrosilane reduction of N,N-dialkylcarboxamides catalyzed by Vaska’s complex(1) Charette’s work (Hantzsch Ester)䖃Donor-Acceptor (D-A) compounds
5HGOLJKWHPLVVLRQG\H1 2UJDQLF(/HPLVVLRQPDWHULDO2

Non-linear optical material3

Donor
Acceptor‫ٴ‬%OXHVKLIWRIDEVRUEHPLVVLRQ(2) Hydrosilane reduction of N,N-diarylcarboxamides‫ٴ‬/DUJHVWRNHVVKLIWBarde, G.; Charette, A. B., J. Am. Chem. Soc. 2008, 130, 18.

‫ٴ‬VROYDWRFKURPLVP(2) Adolfsson’s work (Mo(CO)6 & TMDS)(1) M. Shimizu, et al., Tetrahedron Lett., 2011, 52, 4084. (2) B. Z. Tang, et al., Phys. Chem. Chem. Phys., 2015, 17, 1134.
(3) W. Rettig, et al, J. Phys. Chem. A, 2007, 111, 2035.

䖃S-Conjugated Enamines as DonorsSKRWRUHFHSWRU+ROHWUDQVSRUWPDWHULDO;HURJUDSK\䖃This Work

(1) Motoyama, Y.; Aoki, M.; Takaoka, N.; Aoto, R.; Nagashima, H. Chem. Commun., 2009, 1574.
(2) Tahara, A.; Miyamoto, Y.; Aoto, R.; Shigeta, K.; Une, Y.; Sunada, Y.; Motoyama, Y.; Nagashima, H. Organometallics, 2015, 34, 4895.
F. Tinnis, A. Volkov, T. Slagbrand, H. Adolfsson, Angew. Chem. Int. Ed. 2016, 55, 4562.

(2) Mashima’s & Okuda’s work (BPh3 & PhMeSiH2)ࢩ࣮ࣕࣉᰴᘧ఍♫≉㛤 2016-184100

J. Jankauskas, et al,
Synthetic Metals, 2008, 158, 993.

ிࢭࣛࢻ࣓࢟ࣗࣥࢺ
ࢯ࣮ࣜࣗࢩࣙࣥࢬ
≉㛤 2016-31474

Mukherjee, D.; Shirase, S.; Mashima, K.; Okuda, J., Angew. Chem. Int. Ed. 2016, 55, 13326.

Results (1)䖃Photoabsorption and photoluminescence properties of 4m (FG = NO2) Unique solvatofluorochromism was observed䖃Hydrosilane Reduction of Amides 2 catalyzed by 1X or 1Y

䖃FL properties of 4f (FG = BTD)
Entry

Chemoselective hydrosilane reduction of amides into enamines

Results (2)Solvent

ET(30)

labs [nm(eV)]aemax [cm1·M-1]

1

Hexane31.0

404 (3.069)

26,000

2
3
4
5
6
7
8
9
10
11
12
13
14
15d

CCl4
Toluene
1,4-Dioxane
THF
o-Dimethoxybenzene
CHCl3
CH2Cl2Acetone
DMF
DMSO
MeCN
EtOH
MeOH
H2O

32.4
33.9
36.0
37.4
38.4
39.1
40.7
42.2
43.2
45.1
45.6
51.9
55.4
62.8

416 (2.981)
424 (2.925)425 (2.918)
431 (2.877)
441 (2.812)
438 (2.831)
439 (2.825)
433 (2.864)446 (2.780)
452 (2.743)
434 (2.857)
429 (2.890)
430 (2.883)–

23,00021,70026,30030,20011,40024,20022,20015,50022,40021,00034,80018,00014,300–lfl [nm (eV)]b458 (2.707)
474 (2.616)
508 (2.441)
525 (2.361)
546 (2.271)
568 (2.183)
595 (2.084)
637 (1.947)
640 (1.937)
623 (1.990)
655 (1.893)
669 (1.854)
671 (1.848)
634 (1.956)
643 (1.928)–

Stokes shift[cm-1]
2918
3655
4353
4537
5214
5596
5869
7132
7154
7043
7154
7176
8138
7537
7703
–

)flc
0.02
0.27
0.54
0.69
0.65
0.38
0.09
0.05
0.08
0.03
0.02
<0.01
<0.01
<0.01
–

HexaneTolueneTHF

CH2Cl2

CHCl3

aMaximum absorption wavelengths of 4m in various solvent at 1.0 㽢 10-5 M were described [nm and eV in the parentheses]. bMaximum fluorescence wavelengths of 4m invarious solvent at 1.0 㽢 10-6 M were described [nm and eV in the parentheses]. cAbsolute fluorescence quantum yield was described. dThe data was not available due tolack of solubility of 4m in H2O.

䖃Treatment of 4k (formyl) with B(C6F5)3(cf.) previous reports<1H NMR experiment>

䖃Additive effect of Lewis acid

<UV-vis (10-5M)>
In CHCl3

9Blue shift of absorption wavelength
9Blue shift of emission wavelength
9Increase of quantum yield for FL.
䖃FG = COMe

䖃FG = CN<UV and FL for 4g (1.0㽢10-5 M)>
Solvent
Oabs [nm]aOfl [nm]b
Hexane䇵䇵
Toluene
370
370
CHCl3
374
370
374
370
CH2Cl2+ 1eq. B(C6F5)3
)flc
䇵
<0.01
<0.01
<0.01

100

+ 1eq. B(C6F5)3
)flc
<0.01
<0.01
0.03
0.04

<UV and FL for 4i + B(C6F5)3 (2.0㽢10-5 M)>
Solvent
Oabs [nm]aOfl [nm]b)flc
Hexane504
544
0.40
Toluene
514
587
0.97
CHCl3
515
601
0.41
CH2Cl2
516
623
0.05

<UV and FL for 4g + B(C6F5)3 (1.0㽢10-5 M)>
Solvent
Oabs [nm]aOfl [nm]b)flc
Hexane422
478
0.01
Toluene
429
502
0.04
CHCl3
427
512
0.08
CH2Cl2426
522
0.11<UV chart for 4g + B(C6F5)3><UV and FL for 4i (1.0㽢10-5 M)>
Solvent
Oabs [nm]aOfl [nm]b
Hexane370
415, 427
Toluene380
440, 465
CHCl3
380
479
CH2Cl2389
485

䖃FG = CHO

<FL chart for 4g + B(C6F5)3><UV chart for 4i + B(C6F5)3><UV and FL for 4k (1.0㽢10-5 M)>
Solvent
Oabs [nm]aOfl [nm]b
Hexane379
428
Toluene
392
450
CHCl3
390
496
CH2Cl2399506+ 1eq. B(C6F5)3
)flc
<0.01
<0.01
0.04
0.05

<UV and FL for 4k + B(C6F5)3 (5.0㽢10-5 M)>
Solvent
Oabs [nm]aOfl [nm]b)flc
Hexane515
569
0.70
Toluene
529
618
0.22
CHCl3
528
642
0.04
CH2Cl2
531
683
<0.01
<FL chart for 4i + B(C6F5)3><UV chart for 4k + B(C6F5)3><FL chart for 4k + B(C6F5)3>

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101

Synthesis of cage-shaped molecules based on
1,8,13-syn-substituted triptycenes

Takayuki Iwata1, Tatsuro Yoshinaga2, Yusuke Maehata2, Mitsuru Shindo1

1Institute for Materials Chemistry and Engineering, Kyushu University 2Interdisciplinary Graduate School of Engineering Sciences, Kyushu University

Introduction

Structural feature of syn-substituted triptycenes

Triptycene
D3h symmetry
Rigid three-dimentional molecule
Firstly synthesized by Bartlett
Usually synthesized by DA reaction
P. D. Bartlett, et al., J. Am. Chem. Soc. 1942, 64, 2649.
G. Wittig, et al., Angew. Chem. 1956, 68, 40.

Ynolate-aryne triple cycloaddition reaction

Umezu, S.; Gomes, G. B.; Yoshinaga, T.; Sakae, M.; Matsumoto, K.; Iwata, T. Alabugin, I.; Shindo, M. Angew. Chem. Int. Ed., 2017, 56, 1298.

Results and Discussions

This work(2) Synthesis of anthrones

Yoshinaga, T.; Fujiwara, T.; Iwata, T.; Shindo, M. Chem. Eur. J . 2019, 25, 13855(1) Synthesis of silyltriptycenes ⇒ distorted benzene/pentacoordinated silicon

Shindo, M. et al.,Tetrahedron. 1998,
54, 2411.

dihedral angle
Si-O distance

21.7° 21.7° 21.7°
3.08 Å 3.08 Å 3.08 Å

19.1° 19.4° 23.6°
3.07 Å 3.19 Å 3.08 Å

X-ray(top view)

12.2° 15.9° 18.2°
3.19 Å 3.14 Å 3.13 Å

18.4° 30.7° 31.9°
3.29 Å 3.19 Å 3.08 Å

29.7° 34.7° 35.4°
3.21 Å 3.27 Å 3.21 ÅSi(i-Pr)3
highly distorted

14.9° 20.2° 32.7°
3.29 Å 3.29 Å 3.29 Å

21.0° 24.4° 26.8°
3.05 Å 3.11 Å 3.12 Å

X-ray(top view)H
less distorted

0.35 °

0.35°

0.35°

Nieger, M.; Konig, A.; Vogtle, F. CSD Communication. 2004.

*Sum of Van der Waals radius 1.52 Å (O) + 2.10 Å (Si)= 3.62 Å(3) Synthesis of cage-shaped molecules
T.; Iwata, Yoshinaga, T.; Shindo, M. Manuscript in preparation

X-ray (side view)
X-ray (top view)

Conclusion ・1,8,13-syn-substituted tris(trialkylsilyl) triptycenes synthesized via triple cycloaddition of ynolates to benzynes.
・Cage-shaped molecules were synthesized based on transformation of the silyl triptycene.

102

Artificial Neural Networks Applied as
Molecular Wave Function Solvers
Nagoya University
Institute of Transformative Bio-Molecules (ITbM)
!(

!!'

!!

!"

!#

Basic ansatz of neural network quantum states

Neural network ansatz with ML technology¡ Quantum entangled form of many-electron wavefunction¡ Boltzmann machines
 ML model of a distribution over the set of their
inputs.

multireference

Takeshi Yanai!)

G30 student
from Taiwan

Data scientists¡ Prof. Mahito Sugiyama(National Institute of Informatics)

!*
ℎ!

ℎ"

ℎ#

ℎ$

!! !"

!#

!$

!%

!&

!%

!$

Acknowledgements
My group (Nagoya WPI-ITbM)¡ Mr. Lester Yang (B4 in my group)
Just graduated→ datascience@berkeley

 Coefficients: P " (")

'!

'"

BM
, #% ='#'$'%'! '" '# '$ '% '&visible variables (input) :'' = {0,1}visible variables (input) :'' = {0,1}1/ 1(2|4). %Strategies to address the observed issues

RBM
hidden variables: ℎ' = {0,1}ℎ! ℎ" ℎ# ℎ$'&

Non-concave

ConcaveΦ # % = ( )/ !/ + ( +0/ !0 !//RBM, #% =

BM

Non-convex

ConvexGenerally hard to
optimize

Should be less hard

Flexibility increased due
to presence of hidden
variables

Fixed flexibility

Extension to deeplearning architecture

Extension to higher order
BM

0/

0

'! '" '# '$ '% '&BMΦ # % = ( )/ !/ + ( +0/ !0 !/
/

'!

'"

'#
'$

'&

'%

/

0/

3-body0/6

our big data

RBM/BM wavefunction
 Minimize state energy ! ", $! ", $ = Ψ ", $ ' Ψ ", $**+! ", $ = 0,*

= ( ) *|" !

*,7! ", $ = 089:*|", $

What is done in machine-learning RBM/BM ….

Given dataset * (<) , * (>) , … , * (?) 〜 big data Maximize log ( #w.r.t. # (or minimize its negative)(+) 1 : log likelihood function
Ö log 0 1 = ∑+,%,…," log 3 %MH implementation for training RBM state

MH sampling loop
after
sampling_4 , _>'', D78?@∗ , _7

F00! = GH I J.0 − J0.

⟹ GH J.-,0 ∗ J.

-! ,0!

∗!

J.- − J-

∗ J0! −
.

J0

!

!

− J.-,0 ∗ J.

CAS(4e,4o) Canonical orbitals (CMO)

Carleo and Troyer (Science 2017)
RBM based theory→ Neural-Network Quantum State (NQS)

P # (#)

distribution→ P #|%

parameterizedÖ Generative model Representability theorem

BM architecture'!

'"Ö Existence of network that can approximate

sufficiently smooth and regular high dimension
functions Question and interests
Ö Feasibility of BM models used as an encoder ofmultireference (CAS-CI) wave function for abinitio QC
Ö Efficacy of information compression of CI
coefficients (' parameterized with occupancies )that act as descriptors.

'!(

'#

')

'$

ℎ! ℎ" ℎ# ℎ$'! '" '# '$ '% '&Formulation of RBM/BM state for QC calcs

Ö ! " # ,! " $

7

*

*

'&

input variables :"& = {0,1}visible variables (input) : '' = {0,1}¡ QC wavefunction expansionΨ = ( 57 |!〉'+RBM architecture

RBM/BM wavefunction

1
) $(
' (

'%

hidden variables: ℎ' = {0,1}¡ Complex RBM/BM wf with real-valued Real-parameterized RBM/BM that can consider phases'**% = %%( , %$( , … , %)( , %% , %$ , … , %)amplitude: RBM/BM distributions

Ö #, $ : RBM/BM params, which are real-valued.

Quantum chemistry Hamiltonian##

Metropolis-Hasting (MH) algorithm

0/

0/68

Non-zero coupling % 4 |"′⟩ arises from only single- and double-excitedconfigurations |" / ⟩ relative to ⟨"|.

local energy* ' |Ψ ", $ ⟩.7∑L) ∈ NOP * ' 0 Q .7)=.7! 89: *|", $ =O(polynomial)

Sequence of distribution approacha limiting equilibrium:
3" 9 ⟼ 301 9
when satisfying the detailedbalanced condition:

Generate n walkers (S< )to initialize1@ = ( B ℎ C D0/ + ( BC|FG {D0/ D68 − J/6 D08 }A
2

Uniformly generate new
set of m walkers (S′)
N iterations

Accepting proposed states (9′)
with probability ;(9′|9),# S ⟼ ,:; Sn configurations (")
has been sampled

R S9 S ≥ 1single and double
excitations

R S9 S < 1accept (S#=! ⟻ S′)
reject (S#=! ⟻ S# )> 9 9 / , uniform probability used
à > 9 9 / = > 9′ 9,:; S 9 V(S|S′),:; (S)V(S′|S),:; S 9,:; (S)R S 9 S = TBU 1,= TBU 1,This does not require the partition function X Y .

Potential energy curve of N2: CAS(6e,6o)Distribution of weights
of configurations (CAS-CI)

 Localized orbitals (LMO)

L(')

L(')

-! ,0!

?( and ?* are the forces

N- = −2GH I P.234 J.- − J- L(').

divide by `BCDE8:B to obtain:
D78?@∗ _7.

derivative of RBM wf withrespect to %, ^ à _74 , _7>#+,-.∗ $+0- +,-∗ , 1>((, and >**, are Hermitian covariancematrices
F--! = GH I J.- − J-local energy D78?@*+" ,'(∗ , ,'(,*+" ,'*∗ , ,'*,

4,>

N configurations (!)
sampledsummationover N loops∗
D8?@

Indocyanine Green: CAS(4e,4o)Updating RBM/BM2/BM3
parameter %, ^ with stochastic
reconfiguration(")¡ Hamiltonian with generators¡ RBM/BM training for quantum state

Update RBM parameters1$; (/0$) = ; (/) − =>((
, ?( ,1$@ (/0$) = @ (/) − =>**
, ?* ,

(#)

!%

phase

2-body0/Φ # % = ( )/ !/ + ( +0/ !0 !/ + ( 30/6 !0 !/ !6

RBM/BM wavefunction

Given %, ^

(#)

!!

"
!! = # # $%& ' $ %Higher order BM’s energy func

0/

(")

parameterizationℎ! ℎ" ℎ# ℎ$

BM’s energy func

Φ #, ℎ % = ( )/ !/ + ( 20 ℎ0 + ( +0/ ℎ0 !/
/

RBM

RBM

1
( / 1(2,5|4)
. %
5

(")

%% , %$ , … , %&¡ Use of probabilistic model of machine learning

Y. Peng-Jian, M. Sugiyama, K. Tsuda, T. Yanai, submitted.

BM(no hidden variables)= $" $ 〜 Probability of configuration " (")(#)!&

Hidden-node free BM versus RBM

! (%)

! ($)

 Occupancies of configuration " (") =杉山麿人先生(国立情報学研)
さきがけ
社会デザイン¡ Prof. Koji Tsuda (Univ of Tokyo)

!&

! (")

configuration
Interaction (CI)

4,> ∗

_7

4 . ,> .

, _7

4,> ∗

_7

4 . ,> .

N0 = −2GH I P.234 J.0 − J0 L(').

⟹ GH P.234∗ J.-,0 − P.234∗ J.-,0

Initial parameters of RBM/BM:
random values (3 seeds)

103Development of A Reduced-Scaling Multireference
Perturbation Theory
Masaaki Saitow and Takeshi Yanai
masa.saitow@chem.nagoya-u.ac.jp

Introduction
Accurate ab initio computation of the electronic wave function in a linear-scaling
scheme opens an unprecedented possibility for modelling chemical reactions forlarge, real-life molecules:• Low costs methods such as semi-empirical theory or DFT often give qualitatively
wrong results. [1]

DEPARTMENT OF CHEMISTRY NAGOYA UNIVERSITY• Use of pair-natural orbitals (PNOs) as a compact set of virtual MOs can be used
to drastically reduce the computational costs for solving accurate many-electron
wave functions.

In the PNO-MR-CEPA model, the residua are obtained by minimizing thefollowing functional:
In the hybrid PNO-CEPT2 model, the MR-CEPA functional is used for the 2external subspaces which are more important for capturing the dynamic
correlation while the CASPT2 functional is used for the rests.

Results
Non-Parallelity Errors by CEPT2 model for N2 dissociation:• Reduced-scaling multireference perturbation theory in the local PNO framework(PNO-CASPT2) for large, strongly-correlated systems.
CAS(6e,6o) / def2-QZVPP• A simple, yet higher-order extension to PNO-CASPT2 method as a hybrid ofhighly accurate Multireference Coupled-Electron Pair Approximation (MRCEPA) and CASPT2 models formulated in the PNO basis (PNO-CEPT2). [2]

CASPT2 (NPE: 10.0 kcal/mol)Figure 1: Quinone-Iron cluster (593
atoms) and oxygen evolving complex(243 atoms) active site models which
are the large, real-life open-shell
systems and are possible to treat withthe accurate PNO-based CoupledCluster method. [3,4]TheoryCompaction of Wave Function by Pair-Natural Orbitals:
In PNO-CASPT2/CEPT2 theory, the pair-natural orbitals (PNOs) are first
constructed for each of the 2-exteral subspaces by diagonalizing the pairdensity:

CEPT2 (NPE: 6.2 kcal/mol)Figure 2: Non-parallelity errors by canonical CASPT2 and CEPT2 models for N2 dissociations
with CAS(6e,6o) treatment using all the 2p orbitals of nitrogen atoms. The def2-QZVPP and def2QZVPP/JK auxiliary basis sets were used.

Singlet-Triplet Gaps for Free-base Porphyrin:
Table 1: The singlet-triplet gap for free-base porphyrin calculated by PNO-CASPT2 and PNOCEPT2 models with various PNO truncation thresholds using CAS(8e,8o) all of which arecomposed of 2pz orbitals of carbon atoms. The def2-SVP and def2-SVP/JK auxiliary basis sets
were used. The threshold for pair-energy-based screening was set to 1.0 x 10-5 Eh.
TCutPNO

Ecorr (S0) / Eh

%Accuracy

Ecorr (T0) / Eh

%Accuracy

S-T Gap / eV

PNO-CASPT2

The PNOs are obtained for each electron pair as eigenfunctions of the pairdensity. Those PNOs with occupation number smaller than a user defined
threshold are discarded. The total number of PNOs is asymptotically linear
scaling with respect to the size of the molecule.

The Reduced-scaling CASPT2/CEPT2 Formalism:
In CASPT2 formalism, the wave function is defined as

Full-3.2332337

100.00-3.2192668

100.001.67

1.00E-09-3.2294806

99.88-3.2149734

99.87

1.69

1.00E-08-3.2283818

99.85-3.2139397

99.83

1.69

5.00E-08-3.2270253

99.81-3.2125440

99.79

1.69

1.00E-09-3.4208555--3.4112125

-

1.55

1.00E-08-3.4195743--3.4100063

-

1.55

5.00E-08-3.4180262--3.4084610

-

1.55

PNO-CEPT2

Exp.

1.58

Benchmark Case: Diketopyrrolopyrrole Supramolecules
where the configurations with ρ indices are the spin-adapted, non-redundantinternally-contracted basis (nr-ICB) which are generated by removing thelinear-dependency of the redundant ICB:
Dimer

Monomer

The orthonormalization matrix is obtained by solving the following equations:TrimerMonomer

The first-order wave function is determined by solving the residual equationsin nr-ICB basis:

The PNO-CASPT2 residua are obtained by taking a derivative of thefollowing energy functional with respect to the amplitude:

Dimer

TrimerTetramer

RI Integral Generations (sec.)

44

425

1,430

4,699

PNO Generations (sec.)

157

3793

26,698Running

PNO-CASPT2 Iterations (sec.)

314

4612

31,556

Running

557

9,308

64,119Running

4e in 4o8e in 8o

12e in 12o

16e in 14o# of AO Functions

538

1,076

1,614

2,152

# of Auxiliary Basis Functions

1,662

3,324

4,986

6,648

Summary
The multireference PNOs are defined for each of nr-ICBs and the residua
are transformed into the following form:

TetramerTable 2: Computational timings for DPP supramolecules using def2-ASVP and def2-SVP/JK
auxiliary basis functions.

Total Timings (sec.)
Size of Active SpaceAn efficient and accurate PNO-CASPT2 program has been developed for
calculating the electronic wave functions of large, real-life systems. The PNOCASPT2 has been extended to higher-order by using MR-CEPA Ansatz.

References[1] F. Neese et al., J. Am. Chem. Soc., DOI: 10.1021/jacs.8b13313.
[2] M. Saitow and T. Yanai, under review.
[3] M. Saitow et al., J. Chem. Phys. 146, 164105 (2017).
[4] M. Saitow and F. Neese, J. Chem. Phys. 149, 034104 (2018).
[5] M. Saitow, Y. Kurashige, T. Yanai, J. Chem. Phys. 139, 044118 (2013).

104

Magnetic properties of electrochemicallydelithiated spinal-LiMn2O4
Qi CHEN, Zhongyue ZHANG and Kunio AWAGA
Department of Chemistry, Graduate School of Science, Nagoya University

Introduction

Geometrical Frustration
Coin cell negative shell
Anode
Separator soak with electrolyte
Cathode?

Coin cell spacer and spring
Coin cell positive shell

Charge delocalized
a=b=c=8.24 ÅSpin Canting

Ex-situ coin cell(This Work)

Susceptibility
Heat Capacity
Neutron Diffraction………

In-situ EXAFS and XRD cell

In-situ cell for magnetic measurement

J. Am. Chem. Soc. 2012, 134, 4918-4924

Angew. Chem. Int. Ed. 2013, 52, 6238 –6241

Using In-situ or Ex-situ
Magnetic measurement toreveal the mechanism ofelectrochemical process⚫ Structure and magnetic phase transition⚫ electronic structures and element distributions⚫ oxide state and Local coordination environments

Jahn-Teller Distortion
High Temperatureത
Cubic Phase(Fd3m)

Triangle Lattice

VerweyTransitionat 290K

eg

Mn3+

t2g
b2g

Low Temperature
Orthorhombic Phase(Fddd)

Charge localized?

?

LiMn2O4

Pyrochlore Lattice

a1g

Mn3+

a=24.74 Å
b=24.84 Å
c=8.20 Å

b2g
eg

Method and structure
0.1C

ResultCharge Capacity
Theoretical Capacityt2gx
Temp. a/Å
Mn-Mn/Å
0.07 300K 8.04(4) 2.84(4)0.50 300K 8.16(1) 2.88(5)0.93 300K 8.24(5) 2.91(5)x value Calculation:
x=1−

eg

Mn4+

x=0.500.1C

1
1
LiMn2 O4 ⟷ Li0.5 Mn2 O4 + Li+ + e− 4.0 V vs. Li/Li+22
1
1
Li0.5 Mn2 O4 ⟷ 2λ − MnO2 + Li+ + e− 4.1 V vs. Li/Li+
2
2

Mn4+

x=1−

Charge Capacity
Disharge Capacity+
Theoretical Capacity Theoretical Capacity

Theoretical Capacity of LiMn2O4−MnO2 redox coupler is 148.226 mAh/g

Antiferromagnetism

Using Large Magnetic field toquench the spin canted state.

LiMn2O4 was synthesized by solid state method, sintered at 700℃.
Electrochemical reversible tuning range: 0.93~0.07

The space group symmetry wasmaintained throughout theelectrochemical process

Discussion
occupied bya Mn(III) ion

S=±2

occupied bya Mn(IV) ion

S=±3/2Spin configurations of LixMn2O4
DC magnetic susceptibility at 500Oe and derivatives of 𝜒𝜒𝑇𝑇

Fitting with Curie-Weiss Law:x=0.50Long range
antiferromagnetic
ordering at 30K

Heat capacity of Li0.07Mn2O4

X
0.07

𝑻𝑻𝒇𝒇
[K]

𝑻𝑻𝒄𝒄
[K]
-

-

𝑻𝑻𝑵𝑵
[K]
60

𝚯𝚯
[K]

-93.4

0.50

16

40

61

-111

0.93

-

38

61

-255

𝑁𝑁𝜇𝜇𝐵𝐵2𝑥𝑥
2 − 𝑥𝑥𝐶𝐶𝑚𝑚𝑚𝑚𝑙𝑙 =4.902 + 3.872
3𝑘𝑘𝐵𝐵
2
2
× 0.04749[𝑚𝑚𝑚𝑚𝑚𝑚/𝑐𝑐𝑐𝑐3 ]𝑪𝑪
𝑪𝑪𝒎𝒎𝒎𝒎𝒎𝒎
𝑪𝑪𝒄𝒄𝒄𝒄𝒄𝒄
𝒎𝒎𝒎𝒎𝒎𝒎
𝝌𝝌 =
[emu
[emu
𝑻𝑻 − 𝜽𝜽
K / mol]

K / mol]

1.80

1.912

1.81

2.155

2.24

2.398

Spin Glass
x=0.50x=0.93A frequency dependent
peak at around 40K

Spin canting induced shortrange AFM phase order

Real part of AC magnetic susceptibility

Frequency range 1k-0.01Hz

Cole-Cole Plot of Li0.5Mn2O4

𝐶𝐶 =2
𝑁𝑁𝜇𝜇𝑒𝑒𝑒𝑒𝑒𝑒

3𝑘𝑘𝐵𝐵

x=0.07

A frequency
independent peakat around 30K

Cole-Cole Equation𝜒𝜒0 − 𝜒𝜒𝑠𝑠
1 + 𝐢𝐢𝜔𝜔𝜏𝜏𝑐𝑐 1−𝛼𝛼The median relaxation time 𝜏𝜏𝑐𝑐 ≈ 0.90s
𝛼𝛼 value close to 1 means a variety of size of
domain are coexist with broad relaxation time

Li content dependence ofthe real part of 𝜒𝜒𝐴𝐴C (f=2
Hz).
A frequency independentintermediate state
appearing anddisappearing at 16K
when x tuned from 0.07
to 0.93

Not completely
saturated bylarge magnetic
field is usually
attributed spin
anisotropy.

Saturation Magnetization

Field dependence of ZFC 𝜒𝜒DC for x=0.50

FM

Mn
(III)

AFM

Mn
(III)

AFM

Mn
(IV)

FM

x=1.00 𝜇𝜇𝑛𝑛𝑛𝑛𝑛𝑛 = 0

FM

Mn
(3.5)

FM

Mn
(3.5)

FM

Mn
(IV)

FM

Ms =0.79 μB
weak coercive force
weak magnetic interaction

Charge Ordering

3

Unbalanced spin moment of Mn(IV) andMn(III) would generate a large and strong
ferrimagnetic ordering with a saturated
magnetization.
Strong Anisotropy!

Mn
(IV)

FM

Mn
(IV)

FM

Mn
(IV)

FM

Mn
(IV)

FM

x=0.00 𝜇𝜇𝑛𝑛𝑛𝑛𝑛𝑛 = 0

6 possible spin configurations for x=0.50

2

Mn
(IV)

x=0.50 𝜇𝜇𝑛𝑛𝑛𝑛𝑛𝑛 = 0𝜒𝜒෤ 𝜔𝜔 = 𝜒𝜒 ′ − 𝐢𝐢𝜒𝜒 ′′ = 𝜒𝜒𝑠𝑠 +Ferrimagnetism

Mn
(IV)

Lang range AFM
ordering
The magnetic structures
will be further verify by
Neutron Diffraction.

Long Range
Antiferromagnet

Magnetic phase diagram of LixMn2O4

Conclusion⚫ We performed the reversible and continuous electrochemical tuning the oxidestate of Mn ion in LixMn2O4 (0.07 ≤ x ≤ 0.93) by electrochemical process.
⚫ A magnetic intermediate state, ferrimagnetic ordering, was observed at x=0.50
below 16k, which was examined by Ex-situ AC/DC susceptibility, fielddependent magnetization, hysteresis loops measurement.
⚫Since the breaking of the symmetry, a considerable strong magnetic anisotropy
was exist in MnIIIMnIV3 tetrahedron, as a consequence, the ferrimagnetic
ground state emerged.

105

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Disulfide‐unit conjugation enables ultrafast cytosolicinternalization of antisense DNA and siRNA○Saki Kawaguchi1, Zhaoma Shu1, Kousuke Nakamoto 1, Naoko Abe1 , Yasuaki Kimura1, Hiroshi Abe1,2
1 Graduate School of Science, Nagoya University , 2 RIKEN Center for Emergent Matter Science

Introduction Poor permeability is the main barrier for oligonucleotides therapeutics.
Oligonucleotides is promising for therapy

Membrane Permeable Oligonucleotides (MPON)

Current delivery method

2-4 hours forreleasews• Antisense DNA inhibits mRNA translation.
• siRNA leads to the cleavage of target mRNA.

0.01%
releaseZ. Shu, H.Abe, et al., , Angew Chem Int Ed Engl, 58, 6611-6615 (2019)

Sci. Rep. 2016, 6, 25879.; Nature Biotech. 2017, 35, 222.

Results
Design and Synthesis of MPON.

Mechanism investigation◼ Phosphoramidite Synthesis◼ Disulfide inhibition experiment*i-Pr Disulfide (i-PrD)

Inhibitory assays for cellular uptake using DTNB and iodoacetate. The cellular uptake of 1 µM 5LD in HeLa cells after 30-min pre-incubation of
1.2mM inhibitors (DTNB or sodium iodoacetate) or no inhibitor. The experiment was performed for three times independently. Data are represented as
mean±SEM, *P < 0.05, **P < 0.01, ***P < 0.001 versus no inhibitors.

◼ Endocytosis inhibition experimentt-Bu Disulfide (t-BuD)f◼ Oligonucleotides Synthesis

The cellular uptake of MPON is via thiol-disulfide exchange reaction.

Gene silencing effect of MPON
◼ Dual Luciferase Assay

ASD(A) The cellular uptake were showed by mean fluorescence Intensity of 1,5,10 repeats of LD-conjugated DNA or CD-conjugated DNA at 1 µM and 100n(i-PrD)

MPON effect depends onn(t-BuD)hydrophobicity, not terminal
structure

Permeability enhancement
(A)

20µm

(B)

DNA concentration: 100 nM, The experiment was performed for three times independently. Data are represented as mean±SEM, n = 3, *P < 0.05,**P < 0.01, ***P < 0.001 versus ASD

Summary
20µm• Disulfide‐unit conjugation enables ultrafast cytosolicinternalization of antisense DNA and siRNA• This unit forms a disulfide bond with the cell membranesurface(A) DNA concentration: 1 μM; Incubation time: 3h The experiment
was performed for three times independently. Data are represented as
mean±SEM, n = 3, *P < 0.05, **P < 0.01, ***P < 0.001 versus ASD(B) DNA Concentration: 1 µM; Incubation time: 10 min.
Endosome/Lysosome were stained with Lysotracker Red following
manufacturer’s protocol. The images was obtained by a confocal
microscope at 10 min. (Green: 488 nm, Red:594 nm)

108

Rapid cytosolic distribution in
Only 10 minutes!
Never been achieved!

• MPON effect depends on hydrophobicity, not terminal
structure• Development of simplified MPON with disulfide ‐unit andhydrophobicity is required

Emissive Radicals Stabilized by a Boron Atom at a Distant Position○Masato Ito1, Shunsuke Shirai1, Yongfa Xie1, Hiroki Soutome1, Naoki Ando1, Shigehiro Yamaguchi1,2(1Grad. Sch. Sci., Nagoya Univ.; 2Institute of Transformative bio-Molecules, Nagoya Univ.)

1. Introduction
Ar
C

Luminescence Properties of Stable Radicals
R

reversible redox character
long λabs and λem
narrow energy gap

ArNstabilityefÞcient
emissionAr

Ambipolar carriertransport materials

Cl

R
Cl

C. Lambert, I. Fisher,
U. Resch-Genger et al.
J. Phys. Chem. C, 2009,
113, 20958.

OLED materials

Nin cyclohexane (R = Cl)
λem = 763 nm, ΦF = 0.38
kr = 1.7×107 [s–1]knr = 3.4×107 [s–1]
Cl Cl

Cl
Cl

Cl
Cl

Cl
Cl

Cl

Cl

Cl

Cl

Cl
Cl

Cl
Cl

Cl

Cl
Cl

Cl

C

Cl

O

F. A. Neugebauer,
D. Hellwinkel et al.
Tetrahedron Lett.,1978, 49, 4871.

M. Ballester et al.
J. Am. Chem. Soc., 1971, 93, 2215.

C

B

C
Br

Cl

Cl

O

C

Cl

i-Pr
i-Pr

B
i-Pr

AcOH

H

DMF

53%

i-Pr
i-Pr

B

i-Pr
i-Pr

0
300

41%

3. Effect of Spin Delocalizationin THF at 195 K
g = 2.0029

exp.

0.141

319

C

320
321
Magnetic Þeld / mT

C

sim.

B

0.429

319

320
321
Magnetic Þeld / mT

i-Pr

0.6

A/A0

Relative absorbance / A/A0

1.0

0.8

0

0

2

i-Pr

i-Pr

i-Pr

i-Pr

i-Pr

0
300

400
500
600
Wavelength / nm700

ε[103·M-1·cm-1]

λem
[nm]

φF

τ
[ns]

kr
[107·s–1]

knr[107·s–1]

596

8.61

612

0.78

34.6

2.1

0.72

586

5.86

600

0.08

14.7

0.54

6.3

i-Pr

C

–0.63 eVE / eV

i-Pr

i-Pr

λabs = 438 nm
f = 0.0037
ΔE = 2.83 eV–4.80 eVC

λabs = 465 nm
f = 0.0031
ΔE = 2.67 eV

C

B

i-Pr
i-Pr

i-Pr

Effective interaction betweenp (boron) and π* (π skeleton).

–0.64 eV

–4.26 eV

B

Introducti
on of
boron

LUMO

–1.57 eVλabs = 566 nm
f = 0.0655
SOMO ΔE = 2.19 eV–4.51 eV

–1.63 eVλabs = 545 nm
f = 0.0559
ΔE = 2.27 eV–4.73 eV

0.99

0.97

0.2

B

Sterically protected derivative did
not show any degraduation.
C

0.98

0.4

i-Pr

0.102

C

1.0

B

B

1.0

700

planarization4. Improvement of Stability
Degradation of toluene solution under ambientcondition monitored by UV-vis spectra

C

C

λabs
[nm]

C

Electron spin density was more delocalized onto
a boron moiety in sterically protected derivative
relative to planarized derivative.

322

B

2.0

Theoretical calculations UB3LYP/6-31+G(d) level
i-Pr

i-Pr

C

Absorption
Emission

3.0

Although both compounds exhibited red emission, the values of ΦF and knr changed
drastically by deplanarization.

0.060

0.144

in THF at 195 K
g = 2.0023

exp.

B

0.447

322

B

400
500
600
Wavelength / nm

Compounds

Spin density UB3LYP/6-31+G(d) level

sim.

C

1.0

i-Pr

B

74%

Absorption
Emission

3.0
2.01) Sc(OTf)3
1) 1,2-DCE
1) reflux2) p-chloranil
1) toluene

i-Pr

66%

Et2O, 0 °C to r.t.

i-Pr

80%

Mg
Et3SiCl

i-Pr

toward morestable and more
emissive

Photophysical properties in toluene

i-Pr
B

O

ε / 104·M-1·cm-1

i-Pr

CrO3

Ar

B

Normalized intensity

2) TipLi
2) toluene

55% (3 steps)
HO

i-Pr

B

Normalized intensity

Br

i-Pr

1) BBr3

C

5. Impacts of Structural Effects

Li
Si

T. Kusamoto, H. Nishihara et al.
Angew. Chem. Int. Ed., 2014, 53,
11845.

B

T. Okamoto, J. Takeya, S.Yamaguchi et al.
J. Am. Chem. Soc., 2017, 139, 14336.

Y. Morita, K. Takui et al.
Nat. Mater., 2011, 10, 947.

2. Synthesis of Sterically Protected DerivativeBrClin cyclohexane
λem = 697 nm, ΦF = 0.020
kr = 0.34×107 [s–1] knr = 1.5×107 [s–1]

F. Li et al.
Angew. Chem. Int. Ed., 2018, 57, 2869.

stable, ambipolar,
emissive

Introduction ofboron atom into

Br

O

ClCl

Cl

New Strategy for Stabilization of Radicals

F. A. Neugebauer, D. Hellwinkel et al.
Tetrahedron Lett,1978, 49, 4871.

Br

Cl

Cl

stable in inert environment

Planarization Spin delocalizationClin CH2Cl2
λem = 585 nm, ΦF = 0.022
kr = 0.50×107 [s–1] knr = 25×107 [s–1]

Cl

Cl
Cl

Cl
Cl

Cl

Elucidation of the correlation between
structures and physical properties (stability,
photophysical property…)
Development of stable and luminescent radicals

C

Steric protection

N

ClCl

Cl

L. Julia et al.Tetrahedron. Lett., 2006, 47, 2305.
F. Li et al. Angew. Chem. Int. Ed., 2015, 54, 7091.

This Work

Conventional Methods for Stabilization

Cl

Cl
Cl

ClCl

in cyclohexane
λem = 628 nm
ΦF = 0.64

Cl

Cl

Cl
Cl

N

ε / 104·M-1·cm-1

Neutral Radical Compounds

40 2

4 6 8 10 12 14 16 18
Time / hour

68 10Time / hour

12

14 16

18

C

Planarizedtrityl radical

B

The introductionof boron atom
drastically
improved thestability.

6. Summary
Spin delocalization and steric protection around boron atom are both essential for
improvement of stability.
The vacant p orbital on the boron atom not only functions to delocalize the spin
density, but also functions as an electron acceptor to generate ICT character.
The rigid structure by planarization and ICT character are important for achieving
highly efÞcient luminescence.

109

Photoreaction of Dithienylborane Derivative
Bearing
Bis(trimethylsilyl)phenyl
Group
.
.

Angewandte
Angewandte
1, Shigehiro Yamaguchi1,2Communications
Communications◯Hirofumi
Kajita1, Naoki Ando
1Graduate School of Science,2
reactswiththeatom to form the borepin
reactswith the University,
other boron atom
to form oftheTransformative
borepin other boronBio-Molecules
NagoyaInstitute(WPI-ITbM), Nagoya University
skeleton.
skeleton.
irradiation with UV light (l = 320 nm), a colorlessUpon irradiation with UV light (l = 320 nm), Upona colorlesssolutionof 2 inin benzene turned to navy blue, as shown insolution of 2 in benzene turned to navy blue,
as shown
Figure 3.of
Intwo
the absorption spectra of 2, the intensity of two
Figure 3. In the absorption spectra of 2, the intensity
and andsharp bands at l = 346 and 387 nm decreased anddistinct and sharp bands at l = 346 and 387 nm distinct
decreased

1. Introduction

Photoreaction of Organoboron Compounds

Ph Ph
B

Ph
Ph B

hν

hν

B

Cf.) Nazarov cyclization
R

R
O

Mes
B

π

Benzylic C–H bond
CF3

S

Absorbance

307 nm0.4

Reaction of Photoproducts with Acetonitrile

ES2
www.angewandte.org

λabs = 308 nm
f = 0.015

270 min

0.2

ES1
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 80.2°
Angew. Chem. Int. Ed. 2013, 52, 3760 –3764
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3762
nm www.angewandte.org
λabs = 313
Σ(∠C)=359.99°
f = 0.047

HOMO–1–6.45 eV

334 nm300
350
400
Wavelength / nmCf.) Examples of BN-allene

HOMO–6.30 eV

Cl
Cl
Cl
Cl

tBu
tBu
B N C
B N C
Ar
BAr2
Ar
BAr2

S

B

hν (302 nm)recrystalization
with pyridine

C6D6

Si

B
N

S

S

B
N

Si
S

110

B

Si
S

CF3
hν

Si
S

B

Si
S

C
180.0°

1.370(3)Å

tBu
tBu
B N C
B N C
Ar
BAr2
Ar
BAr2

Ar
Ar

B

1.266(3)Å

N

C
168.9(2)°

CF3

CF3
Si
S

B

Si

1) hν (Hg lump)Si2) acetone (excess)

S

S

B
O

Si

Triclinic P–1
GOF = 1.079
R1[I>2σ(I)] = 0.0306
wR2(all data) = 0.0876

SiS

10-membered ring formation

Ring-expansion reaction similar toBN-allene formation proceeded
even with reaction with acetone.

Si

B
S

O

S

7. Conclusion

4. Plausible Mechanism
CF3

1.273(5)Å

N

Reaction of Photoproducts with AcetoneS

Not the bora-Nazarov cyclization
but a new type of photoreaction
proceeded upon photo irradiation.

SB

6. Reaction with Acetone

Si

H atom rearrangement fromtrimethylsilyl group to thiophen moiety
C–C bond formation to generatespiro cycle structure

Si

S

CF3

Si

1.302(6)Å

Z. Lin, M.Yamashita et al. Angew. Chem. Int. Ed. 2019, 58, 317.

CF3
Si

Dipp
Dipp
N
N
B N C
B N C
N
Cl
N
Cl
Dipp
Dipp

N
N
Dipp
Dipp

C

∠B–N–C=172.4(2)°

Cl
Cl

Ar
Ar

Crystal Structure of Photoproduct as a Py Complex

Orthorhombic P212121
GOF = 1.194
R1[I>2σ(I)] = 0.0251
wR2(all data) = 0.0832

Dipp
Dipp
N
N

B N C
B N C

N

Angew. Chem. Int. Ed. 2013, 52, 3760 –3764

E. Rivard et al. Chem. Eur. J. 2016, 22, 2134.

450

3. Determination of Photoproduct

Si

Problem¥ TD-DFT Calculation

3762
0 min

0
250

R

a trigonal-planar
geometry
C-B-C angles
Ra thetrigonal-planar
geometry with the sum of the C-B-C angles
R with the sum of
H
A –H
hν
or Δ 360.08. The
B2360.08.
C7bond lengths for the C3B2 and B2C7
bond lengths Ofor the C3
and B2
being
The
being

A
C O

B

0.3

0.1

H

N. TheAndo,
K.Yoshizawa,
H. Ikeda,
S.Yamaguchi
et al.
ization. The sums of the C-C-C and C-C-Bization.
anglesaresums
360.08of the C-C-C
and C-C-B
angles are
360.08for both the C3 and C7 atoms. The boron atom
B2 alsoretainsInt. Ed.
12210.
for boththe Angew.
C3
andChem.
C7 atoms.
The2017,boron56,
atom
B2 also retains

BN-allene

Si

281 nm0.5

AFormal C–H addition

Reversibility

5. BN-allene formation¥ UV-vis Absorption Spectra
0.6

Mes
B

another photoreaction mode.

Photoreaction of DithienylboraneB

πR

Bora-Nazarov Cyclization

),[14]but bonds
still (e.g., Ar3B, 1.57–1.59 ),[14] but still
Csp2B single bonds (e.g., Ar3B, 1.57–1.59
singleCsp2B
comparable or slightly longer than the shortest
examplesof longer than the shortest examples ofcomparable
or slightly[15]
B
singlebonds(1.48–1.52
).
Notably,themethyltheCa new broad band appeared at l = 634 nm witha theisosbestic2
sp at l = 634 nm with the isosbestic
the Csp2B single bonds (1.48–1.52 ).[15] Notably, the methyl
new broad band appeared
CF3
group
C8 and thehydrogenatom at
C4 at
havecisthe hydrogen atom at C4 have a cis
point Bulky
at l = 398
nm.groupThis photochromic behavior
also
aryl
group
C8 aandpoint wasat l =
398 nm.
This atphotochromic
behavior
was also
CF3
No including
other stereoisomer
was observed No
byobserved in other common solvents including
n-pentane,other stereoisomer was observed byCF3
observed
in other configuration.
commonsolvents
n-pentane,CF
CF3 configuration.
3
1¥ Steric
MeOH. Even
NMR3, acetonitrile,
spectroscopy
the reaction
thecyclohexane,
CH2Clprotection
2, CHCl3, acetonitrile, andcyclohexane,, CHClandofMeOH.
Even 1mixture
H NMR after
spectroscopyof the reaction mixture after theCH2Cl2H
a
cast
film
of
2
prepared
fromatoluenesolutionshowedthephotoirradiation,
thus
implying
that
theformation
of
7
a
cast
film
of
2
prepared
fromatoluenesolutionshowedthephotoirradiation,
thus
implying
the formation of 7¥
No
Benzylic
C–H
bonds
Si
1) hν (Hg lump)2) CH3that
CN (excess)Si
SiSi
Si (seephotochromic behavior (see the Supporting photochromic
Information),Si
proceeds
a stereospecificmannerSi Si+
behaviortheSupporting Information),proceeds
in a stereospecificmanner (see below).
Si (see in
Si below).
B
B
whereasits crystals borane
did not show the photochromic
response,
mosthexane
uniquestructuralfeaturein 7Theis theB
B did The
B
whereasits crystals
not showthephotochromic
response,
mostC-B-C
unique structural feature in 7 is the C-B-C
DithienylNprobably because of the immobility of the molecule
substructurein thethe S
number
S
probably inbecausethe immobility
offive-membered
the molecule
the Taking
substructurein theoffive-memberedring. Taking the numberofSthe of
S inring.
S
S
Reactionsiteof¥crystal lattice.
p Selectrons assigned to this moiety intoSconsideration,
the C- to this moiety into consideration, the Ccrystal lattice.
p electrons assigned
S
1is isoelectronic to the allyl cation. To gain
25%
inMonitoringof the reactionby 1H NMR spectroscopy
B-C
skeleton
bora-Nazarov
cyclization
Monitoring of the reaction by H NMR spectroscopy in
B-C skeleton is isoelectronic to the allyl cation. To gain
[16]
that (see2 waswe first theoret[D8]THF (see the Supporting Information) showed
fundamental
insights showed
into thisskeleton,
the Supporting
Information)that
2 was fundamental[D8]THF
insights into this skeleton,[16] we first theoret+=BHCH
cleanly converted into the single product 7 cleanly
by the converted
photoicallythe
comparedthe electronic
CH2compared2 electronic structures of CH =BHCH +intosingle product7 by thestructures
photo- ofically
the
2
2
CF
3
(8)
and
the allyl cation(9) asreverted
model systems.
tocationthe (9) as model systems. According to theirradiation.
Notably, the photoproduct 7 cleanly
revertedNotably,toand the allyl
irradiation.
thephotoproduct7 cleanlyto (8)AccordingCF3
geometry
optimization
at theB3LYP/6-31G*
level oftheory, at the B3LYP/6-31G* level of theory,the initial compound 2 upon storing the solutioningeometry
optimization
theovernight
initial compound2 upon storing
the solution
overnight
in
Monoclinic
P2B1/cbond length in 8 is 1.49 . The naturalbond orbital
theC
a dark at room temperature. Thus, this chromic
reactionisthe C B bond length in 8 is 1.49 . The natural bond orbitala dark at room temperature. Thus, this chromic reaction ishν (Hg lump)Si
GOF =(NBO)
1.156 analysis (MP2/6-31G*//B3LYP/6-31G*)[17] showed
[17]
CF3
CF3
Si
Si reversible.
+
CF3
showed(NBO) analysis (MP2/6-31G*//B3LYP/6-31G*)
reversible.
Si
R1[I>2σ(I)] the= 0.0334
hexane, r.t., 1 hWiberg ofbondof the CB thatbondtheinWiberg
8 is 1.36,
the structure of 7, we successfully
B To characterize Bbond index of the CB bond in 8 is 1.36,
To characterizethat
the structure
7, index
we successfullywR2(alldata)from= 0.1081
while
that
of
the
CCn-pentane
bond in 9solution.
is 1.51.
Thiswhiledifference
implies
obtained singleS crystals froma cooled n-pentane
solution.
S
that
of
the
CC
bond
in
9
is
1.51.
This
difference
implies
obtainedsinglecrystalsacooledS
recrystalization
h
ν
(302
nm)
[11]
[11]
showedthat thethatanalysis
8 hassmallerbondcharactercomparedto thatSi
X-ray
Si a(Figure
S crystal structure analysis (Figure 4)
Si to
SithatSi bond character comparedshowed
that
the
that
8 has a smaller
doubleX-ray crystal
structureSi 4)double
CH3CN
crystal structure contains two crystallographicallyindependof 9. two crystallographicallyB
B
B
crystalstructure contains
independof 9.
61% (mixture)NN
ent molecules, 7 A and 7 B. As their structural parameters
are7 A and 7The
geometry
optimizationof are7 at the The
B3LYP/6-31G*
Sof 7 at the B3LYP/6-31G*S
ent molecules,
B.
As
their
structuralparametersgeometry
optimization
S
C
C
S
Sthe
similar to each other (see the Supporting Information),
we otherlevelof thetheorynicely reproduced
thewecrystalstructure(see
Ssimilar to each(seeSupporting
Information),levelof theory
nicelyreproduced the crystal structure (see the[18]
Sithis structure,Intheoptimized
structure,
theonly discuss the structure of 7 A. In this structure,adiscuss
new CC
Supporting
Information).
[18]
Si
In
the
optimized
structure,
the
only
the
structure
of
7
A.
In
a
new
CC
Supporting
Information).
gas phase]
C3B2
B2C7 bonds
are of1.52
, respectively.
bond is[B3LYP/6-31(d)formed between theinortho-carbon
atombond(C8)isofformed
one ofΣ(∠B)=359.96°
C3B2
and B2C7 bonds are 1.52 and 1.53 , respectively.
betweenthe andortho-carbon
atom (C8)oneandof 1.53
CF3
Accordingto theNBOatomanalysis,bond index
of thethe mesityl groups and the olefinic carbon
atomof groups
theBN-allene
Accordingto theNBO
analysis, themoiety
Wiberg bond index of thethe (C4)
mesitylandthe olefinic
carbon(C4)theof WibergtheB bonds are 1.09 for B2-C7 and 1.22 C
for
B2C3,
borepin moiety to produce a five-membered
ring.
As
a
result,Si
C B bonds
arethus1.09 for B2-C7
for B2C3, thus
borepin moiety to produce a five-membered ring. As a result,
Si
B–N= and 1.22 N–C=
demonstratingthatthesinglebondcharacter
of
the
CB
the mesityl group is transformed intoB a nonaromatic
1,3demonstrating
thatCthe single
bond characterof the CBC
the mesityl group is transformed into a nonaromatic 1,31.369(2)Å
1.251(2)Å
S
moietymore
pronounced
the extended
cyclohexadiene-like structure (1.351–1.380
 for
C=C bonds
B  for
N=C bonds in moiety
S
cyclohexadiene-likestructurebecomes(1.351–1.380
C
S becomes p-more pronounced in the extended pconjugated skeleton of 7, compared to the parent CH2=
and 1.423–1.487  for CC
bonds).
It is important to note
LUMO
–1.77eV
conjugated skeleton of 7, compared to the parent CH2=
and 1.423–1.487  for CC bonds).
It is important to note+in 7 still
BH CH2 skeleton. However, the CBC moiety
to the boron
2.8 × 10–5 M in THF that the carbon atoms, C3 and C7, connectedthat
the carbon atoms, C3 andC7, connected to the boron BHCH2+ skeleton. However, the CBC moiety in 7 still
maintains
the allyl cation-like charge distribution. Thus, theatom in the five-membered ring, still retain the sp2 hybridS
maintains the allyl cation-like charge distribution. Thus, theatom in the five-memberedring, still retain the sp2 hybridλex = 310 nm

Molecular DesignSΔ(l = 320 nm) in benzene. Inset: Photographs of a benzene
solution(l = 320nm) inofbenzene. Inset: Photographs of a benzene solution of[13]Si)light.
[e.g., (Mebondsand[e.g.,ordinary(Me3Si)2C=B(tBu) 1.361(5) ][13] and ordinary
2C=B(tBu) 1.361(5) ]
2 before (left) and after (right) irradiation of UV light. 2 before (left) and afterbonds(right) irradiationof 3UV

2. Photoreaction

Si

π

R

Mes
B

C O
B. G. Ramsey et al.
giverise to Thesebonds are1.527(5)  and1.522(5) , respectively.
TheseC–H
R
bonds Benzylic
are 1.527(5) and bonds
1.522(5) ,
respectively.
R
3. UV-Visabsorption spectra of 2 upon
by 3.
UVUV-Vislight absorption spectra
Figureof 2 upon irradiation by UV lightR
R irradiation
J. Am. Chem. Figure
Soc.1967,
99, 3182.
values are between the bond lengths of typical
double the bond lengths of typical C=B double
values C=B
are between

S. Wang et al.
J. Am. Chem. Soc.2008, 130, 12898.

R

H

hν

Figure 4. ORTEP drawing of 7 A. Thermal ellipsoids
are 4.
shownat drawing
50 % hνFigureORTEP
of 7 A. Thermal ellipsoids are shown at 50 %S.Yamaguchi et al. Angew.probability.
Chem. Int.Hydrogen
Ed. 2013,atoms,
52, 3760.
except H4, are omitted
for clarity.
probability.
Hydrogen atoms, except H4, are omitted for clarity.
π

hν

B

B Mes

Mes
B

B
Mes

B
Mes

Δ

H

H

Drastic color changes

N
B

hν

hν

Photoreaction of BMes2-arenesΔ

M. Tokuda et al.
Chem. Lett. 1976, 209.

G. B. Schuster et al.
J. Am. Chem. Soc.1988, 110, 6252.

N
B

B Mes

+

ether

Ph

Ph

Bora-Nazarov Cyclization

Ligand CouplingDi-π-borate Rearrangement*

CF3
H abstraction

Si
S

H

B
H

Si
S

CF3
C–C bond
formation

Si
S

B

Si
S

A new type of photoreaction proceeds upon UV irradiation.
This reaction suggests that H atom rearrangement proceeds evenat the methyl group on the trimethylsilyl group.
Photoproduct reacts with CH3CN to form a BN-allene derivative.

SSelf-Assembly of Amphiphilic Aromatic Hydrocarbons
into Nanosheets via Multiple CH/π Interactions

YAMAGUCHI

Hiroki Narita,1 Tsuyoshi Nishikawa,1 Soichiro Ogi,1 Yoshikatsu Sato,2 and Shigehiro Yamaguchi1,21Department of Chemistry, Graduate School of Science, 2Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University

1. Introduction

Covalent nanosheets

Two-dimensional assemblies of amphiphilic π-systems in aqueous media

Non-covalent nanosheets

TEM imageself-assembly

R

R

R
O

O

R

O

R=

2

Monomers

2D aggregate

C7H15O

Problem
Structural requirements have notbeen established.

O

C7H15ON

2

O

OC7H15O

CH/π interaction, a type of hydrogen bond

AFM height image
3

O 3

N

O

O

N

O

C8H17

Hydrophobicity&
π-stacking¥ Dispersion force ¥ Cooperative and multiple features ¥High symmetry of PAH
Effective interaction in aqueous media
Enthalpic and entropic advantage

E. Lee, J.-K. Kim, M. Lee, Angew. Chem. Int. Ed. 2009, 48, 3657.

S. Ghosh, D. S. Philips, A. Saeki, A. Ajayaghosh, Adv. Mater. 2017, 29, 1605408.

5. Molecular orientation of aggregates

2. This work
CH/π interaction-driven self-assembly into nanosheets in aqueous media

O

O

R

1-PrOH/H2O

AnthraceneO––– Measured pattern of aggregates––– Simulated pattern from single crystal

O

Terminal substituent
Control of surface property
Triethylene glycol chain
Proper solubility in water

R=O

1-PrOHIntensity / a.u.

CH/π donor and acceptor
High hydrophobicity
Matching length
Orthogonality

XRD patterns

O
OO

Biphenyl group

Aggregate
Single crystal

OH

5

10

15

20
2𝜃𝜃 / ºOut-of-plane XRD pattern

Hydrophilic chain
Hydrophobicity&
CH/π interaction

H2O

Intensity / a.u.

Schematic representation
Hydrophobic
aromatic hydrocarbon

NNO
C7H15OO

3O

GraphenehBN¥ Large anisotropy¥ High surface-to-volume ratio¥ Unique surface charge

O

O

O

O

O 2

0

CH donorπ-acceptor

25

30

35

d010

d010

5

10

15

2𝜃𝜃 / º20

25

Sheet-like aggregates and single crystal have a similar molecular packing.

3. Self-assembly in aqueous media
O

MonomerO

O

Aggregate

H2O

O

O

OH

20 °C

AFM height image

Spectral imaging
Normalized intensity / a.u.

TEM image

nm

4.0

10 µm

0

24 nm
1.6

3.2

X-ray crystal structure

4.8

6.4

µm

Zeta potential––– OMe––– OHB
C
2.5 µm415 450

500
550
600
Wavelength / nm

650

7.6
4.0

3 nm

0.4
0

1.2

5 nm
2.4

3.6

4.8 µm

–100

–50
0
50
Wavelength / nm

100

Terminal substituents affect the surface properties of nanosheets.

4. X-ray crystallographic analysis

7. Possible mechanism of nanosheet formation
1st step: one-dimensional growthO
O

Tuning properties of
the nanosheet surface

A

The sheet-like aggregates were formed in aqueous media.

OterminalmodiÞcation

AFM height imagenm

2.5 µm28.0

tetragonal P42/n
GOF = 1.033, Z = 8
R1 = 0.0543 (l>2𝜎𝜎(l))
wR2 = 0.1454 (all data)

5 µM solutionin 1-PrOH/H2O (1:9, v/v)

50 µM solutionin 1-PrOH

Solvent: 1-PrOH/H2O (1:9, v/v)
Concentration: 5 µM

Presence of terminal
substituents on thenanosheet surface

Intensity / a.u.

O

6. Effect of terminal substituent on aggregates

Sample preparation procedureOO

multiple
CH/π interactions

triclinic P-1
GOF = 1.081, Z = 4
R1 = 0.0440 (l>2𝜎𝜎(l))
wR2 = 0.1457 (all data)

Hydrophobic effect and CH/π interaction drive one-dimensional assembly.

Windmill-shaped packing structure

CH/π interaction

2.41 nm2.75 Å

2.72 Å

lesshydrophilic
Fast growthwater layer

morehydrophilic
Slow growthOne-dimensional aggregates self-assemble into nanosheets.

2.88 Å
multiple
CH/π interactions

2nd step: two-dimensional growth

8. Summary
2.85 Å

Biphenylanthracene is effective for formation of multiple CH/π interactions.

Two-dimensional self-assembly driven by CH/π interaction in aqueous media
Windmill-shpaed packing structure composed of biphenylanthracene units
Versatility of biphenylanthracene-based amphiphiles
Control over the surface property of nanosheets by terminal modiÞcation

111

Synthesis and Catalytic Methane Oxidation Property of μ-NitrideBridged Iron Phthalocyanine Dimer Bearing Eight 12-crown-4 Groups○Junichi Kura1, Yasuyuki Yamada1,2,3, Kentaro Tanaka1

1Graduate School of science, Nagoya University, 2RCMS, Nagoya University, 3PRESTO/JST

kentaro@chem.nagoya-u.ac.jp

1. Introduction

CH4

2. This Work・Major constituent of natural gas

C–H dissociation energy

CH4・Abundant in the sea near Japan104.9 kcal / mol・DifÞculty of direct C-H activation

89.7 kcal / mol

Novel catalysts are desired for direct and efÞcient conversion of CH4.

N

N
N

N

N
FeIII

N
N

N

N

N

N
FeIV
N
N

TTN
TTN2S==tBuO
30 MPa CH4
60 °C, 22 hrs, TON : 492

N

O

1

N

H2O2, H+
–H2O

N

N
N
N
IV
N Fe N
N
N
N
N
N
IV
N Fe N
N

N・+

N

33

N
N
N
III
N FeN
N

N

tBuO S
2
40
40tBuO S
2

TON
20
20

SO2tBuSO2tBu

tBu

N FeN
N

tBu

N

SO2tBu

＜

N

45
45 N

tBu

＜

30
10330

N
N
N
III
N FeN
N

00
00

22

44
Time
Time/ /hr
hr

66

88

11

39
39

H

O

O

Br

O

Br

O

CuCN

O

DMF
82%

O

NC

O

NC

O

O

N

O

N
O

O

N
N

O

N

FeII

N

O

O

I-

N

N

O

Side
View

O

O

N
FeIV N

N

O

O

O

O

N

2+

N

O

O

O

O

O

N

NaN3

N

O

O

O

Cl

N

O

63%

O

N

Molecular Modeling+Electron-Donating
Substituent
O

N

N

O

O

N
N

OH

N

O

O

O

Fe(OAc)2

O

O

tBu

O

N
FeIV N

O
O

tBu

223

O
O

Br2
CCl4,
AcOH
73%

tBu

N
N
N
IV N
N FeN
N

O

O

O
O

O

N

N

O

O
O

Top
View

O

1¥CuTPPS
1¥CuTPPS 1¥NiTPPS
1¥NiTPPS

O

O

O

tBu
N

N

tBu

N
N
N
IV N
N FeN
N

N

32

3. Synthesis of 2+

H

N

OO

N
CC
Cat
Cat
/mM
N /mM
N
III N
N

(c)
(c)

O

O

OH
OH

Electron-donating substituents would enhance
the activity of catalytic methane oxidation.

10
10

Active Species

SO2tBuN

30
30 tBuO2S

CH3OH
HCHO
HCOOH

HH

[O]
[O]

[O]

O

O

HH
OO

N

N
N
N
IV N
N FeN
N

N

CH4

HH

[O]
[O]

CH
CH33ÐOH
ÐOH

11××CCCH
CHCHO
CHCOOH
CHOH
OH/mM/mM++22××C
HCHO/mM/mM++33××C
HCOOH/mM
/mM

(b)
(b)

TTN
TTN

N

N
N

[O]
[O]

CH
CH33–H–H

TTN (8(8 hr)
hr)
TTN

(a)
(a)
µ-Nitrido-Bridged Iron Phthalocyanine Dimer Catalyst
for Oxidation of Methane

CH3OH
HCHO
HCOOH

CH4

101.4 kcal / mol
98.6 kcal / mol

CH3–CH3(CH3)2–CH2
Ph–CH3

as methane hydrate

O

O
O

O

N

O
O

O

O
O

N

O

O
O

O

O

N

O

O

N

N

N
III

FeN

N

N

N

O

O

I2

O
O

O

O

N

O

O
O

O

N
O

O

O

O

O

O

32% in 2 steps

N

O

O

pyridineO

FeNIV N

N

O
O

N

O

N

O
O

O

O

O

O

N

O

O

N
IV

FeN

N

N

N

O
O

+
O

N

O

N

O

N

O

N

N

O
O

O
O

N

O
O

O

FeNIV N

N

O

O
O

I–
I-

O

2+I–

4. Spectra of 2+·I–

5. Electrochemical property of 2+·I–
Cyclic voltammogram

MALDI-TOF-MS
2+

calcd.

N
found.

1600
1600

2316

1800
1800

m/z

2320

I–

2200
2200

O

O
O

O

N

Py
O

Py

O
O

O
O

O

N
O

Py

O
O

H 2O

N

O
O

O

N

O

N

N

N
FeIV N

O
O

N

N

O

N
N

N

O
O

N

FeNIV N

N

O

O
O

I–

O
O

O

+

O

O

O

O
O
N

O

O
O

O
H
H
HH

O
O
N

O

O
O

N

O
O

O

O

O

O

N

O

N
FeIV N

O
O

O

N
N

O
O

O

N

O
O

–2.07 –1.57
–1.81

–0.66

0.22

Fe(III)Fe(IV) / Fe(IV)Fe(IV)

O

O
O

1e–

O

I-

N

O

+

I–

O

N
FeIV N

N

–0.58

1e–

N

N

Fe(III)Fe(IV) / Fe(IV)Fe(IV)1+I– 400 μM in Pyridine containing 0.1 M TBAPF6. scan rate : 100 mV/s, 20℃

NN

4.0 μA–1.74–2.00 –1.52

2400
2400

in Pyridine-d5

1e–

1e–

1e–

N

m/z
1H-NMR

1e–

1+·I–

2324

2000
2000

N

N
N
N
IV
N Fe N
N

N
2312

+

N
N
N
IV
N Fe N
N
N

1e–

1e–

2.0 μA

1e–

O

2+·I–
–2.5

–2.0

–1.5

–1.0

–0.5

0

0.5

Potential / V vs. Fc/Fc+
2+I– 200 μM in Pyridine containing 0.1 M TBAPF6. scan rate : 100 mV/s, 20℃

10

9

8

7

ppm

6

5

4

3

Each redox waves of 2+·I– showed signiÞcant negative shifts by theeffect of the electron-donating character of the 12-crown-4s.

6. Conclusion and Perspective
We synthesized a novel complex 2+·I– having four 12-crown-4 units on each of thephthalocyanines. A cyclic voltammogram of 2+·I– showed four reversible one-electron redox waves

in the range between –2.0 V to 1.0 V (vs. Fc/Fc+) which signiÞcantly shifted to more negative
potentials compared to the corresponding redox waves of 1+·I–. This result clearly demonstrates theeffect of the electron-donating character of the 12-crown-4s. Methane oxidation activity of 2+·I– isunder investigation.

112

Strong Electron Donation
O

O
O
N

CH4

O

O
O

H2O2, H+
CH3OH
HCHO
HCOOH

O
O
N

O
O

N

O
O

O

O

O

O

N

N

N

O
N

O
O

+
O

FeNIV N

N

O

N
N

N

O
O

O
O

N

FeNIV N

N

2+

O

O
O

O
O

O

IO

Synthesis and physical property of Tb(Ⅲ)-phthalocyanine
double-decker complex having planar chirality○Hiroaki Nakajima1, Chisa Kobayashi1, Yasuyuki Yamada1,2,3, Yoshiaki Shuku1, Kunio Awaga1 and Kentaro
Tanaka1*
1Graduate School of science, Nagoya University, 2RCMS, Nagoya University, 3PRESTO/JST

kentaro@chem.nagoya-u.ac.jp

1. Introduction

0

N
N

N

N

O O
OO
O O OO

N
N

N
O

N

N

N

N

N
N

O O
OO
O O OONO O OO O OO

N
N
N
N

O O O
O
O
O O O

N
N

O

N

• Tb(III)-phthalocyanine

double-decker complex
is known as a singlemolecule-magnet.
• Physical property canbe tuned by changing
the environment aroundterbium ion.

0.8
0.6

O O O
O
O
O O O
N

N

O

NH3

H3N

=

O O
O
O

O
OO

×4

O O O
O O O O

O

0 eq.

O

N

NH N
N HN

N

N

O

0.4
π-SOMO

4 eq.

400

800

O

CN

H
N

1200

N
N

N

CN

NH

N

N

HN

O

N

N

Tb3+

N
N

O

N

N

O

O
N
N

N

O

N

O

N

O

O

N
N

N
N

N

N
N

N
N

O

O

N

O

N

N
N

N

O

O

N
N

N

(R,R)

enantiomer

NN(S,S), (R,R), andmeso isomers canbe generated due tothe coordinatingorientation of the twophthalocyanines.

O
N
N

Tb3+

O

N
N

The structuraldifference aroundterbium ion shouldcause the differenceof their physicalproperty.

O
N
N

N

O

Tb3+

Tb3+

O
O

N
N

N

N
N

N

N

O

O

O

N

N

N
N

N

O

meso

O

N
N

N

O

TbCl3 , LiN(SiMe3)2

N

diglyme

N
O

25%

O

O

Isomers were separated by using a chiral column (CHIRAL ART Amylose-SA,
Hexane : MTBE = 95 : 5).
1H-NMR(400 MHz, CHCl3, TMS)

N
N
O

N

O

2000

1600

N

K. Tanaka et. al.

n-pentanol

43%

N

(S,S)

N

O

Wavelength / nm

Li

CN

N

O

4 μM in CH2Cl2

CH3CN

N

N
N
O

IVCT band

SOMO-LUMO

0, K2CO3

OH

N

O

0.2

N
N

O

N

N
H

N
O

N

O

CN

O

O

N

Q band

Soret
band

N

Tb3+

3. Synthesis and Separation
NO2

Planar Chirality
O
O

Modeling

1.0

NN

Absorbance

N
N

N
N

Tb3+

Tb3+
N

N

=

O O
O
O
O
O O
O

N

2. Concept

Our previous work

10%

(S,S)

C4h - Type Pc

O
N

O

N
N

N
N

0
N
N

N

O

O

O

O

Tb3+
O

N

N
N
O

N
N

+

O

N
N

N
N

N

N

O

O

O

(S,S)

N
N

N

N
N

0

O
N
N

N

Tb3+
N
N

N
N

O
O

O

N

+
N

N
N

O

N

N
N

O

N
N

N

(R,R)

O

O

Tb3+

O

O

0

N
N

N

N
N

N

N

O

meso

O

meso

(R,R)

20

0

−20

−40

−60

−80

−100

−120

ppm

5. Magnetic Property

4. Identication of Chiral Complex(S,S)2(S,S)1
21 Helix Axisa(R,R)1(R,R)2

b

c

meso

38.9

Pc-Pc
distance

2.803

2.800

(R,R)1(R,R)2

Twisted
angle

41.4

39.0

Pc-Pc
distance

2.799

2.795

meso

Twisted angle

Twisted
angle

40.9

Pc-Pc
distance

2.778

c
(S,S)
(R,R)
meso

4
0

-4
500

400

600

Wavelength / nm

700

1.5
1.0
0.5

Normalized Absorbance / a. u.

1000

0
10

20

30

40

50

0

10

20

30

40

50

60

70

Temperature / K

36.4 K at 1, 10, 100, and 1000 Hz, respectively.

36.9 K at 1, 10, 100, and 1000 Hz, respectively.

1.0

data for tting was carried out on the basis of athermally activated mechanism, τ = τ0 exp(Ueff / kBT).

1.0
0.0

0.0

−1.0

−1.0

(R,R)

meso

−3.0

Ueff/kB (K)

644

603

−5.0

τ0 (×10-11 s)

1.39

1.12

TB (K)

21.8

21.9

−2.0

−2.0
−3.0

−4.0

−4.0
−5.0

−6.0

−6.0

−7.0

−7.0

2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0

2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0

1 / T × 10-2 / K-1

1 / T × 10-2 / K-1of the enantiomers
were similar.

IVCT band (nm)
1973

(S,S)

1951

(R,R)

1950

• IVCT band of meso wasslightly different fromthat of enantiomers.

IVCT band

Wavelength / nm

70

• These results indicate that the complexes have slow magnetic relaxation.
Arrhenius Plot
• In the high temperature region, the χ” peaks of the
(R,R)
meso

meso

2000

60

• χ” shows a local maximum at 26.2, 28.3, 30.5, and • χ” shows a local maximum at 26.4, 29.9, 33.3, and• UV absorption spectra

1500

0.2
0.1

Temperature / K• (R,R) and (S,S)
showedopposite Cotton
effect, whereas
meso isomer
showed no
Cotton effect.

SOMO→LUMO

500

0

0

Q bandπ→SOMO

0.5

0.3

0.2

1 Hz
10 Hz
100 Hz1000 Hz1.0

00

Pc distance of meso
were slightly different
compared to those ofenantiomers.

(S,S)
(R,R)
meso

1.5

0.3

0.1

6. UV-vis-NIR spectrum
Soret band

meso

1 Hz
10 Hz
100 Hz1000 Hzχ’ / emu mol-1

41.3

ln(τ)

a

[θ] × 105 / deg•cm2•dmol-1

Twistedangle• Twisted angle and Pc-

CD spectrum

300

(R,R)

c

b

(R,R)
R)

(S,S)2χ” / emu mol-1aAlternating current (ac) magnetic susceptibility (powder, dc eld : 0 Oe)(S,S)1ln(τ)

21 Helix Axis

χ’ / emu mol-1

b

(S,S)

χ” / emu mol-1

X-ray Crystal Structure2500(CCl4 solution)• Structural difference of
meso and enantiomer
might have caused
the difference in IVCT
energy.

τ : relaxation time, τ0 :frequency factor Ueff /k : effective energy
barrier, TB : blocking
temperature• Magnetic property of (R,R) isomer was similar to thatof meso isomer in spite of the difference of structure.

7. Summary• We synthesized new chiral Tb(Ⅲ)-phthalocyanine double-decker
complexes based on planar chirality.

• (R,R) and meso complex showed single molecule magnet

character in spite of their lower symmetry compared to nonsubstituted double-decker complex.

• The structural difference between meso and enantiomer did not
result in the difference in their magnetic susceptibility, but it wascaused the difference in IVCT energy.

113

Synthesis of π-Expanded Porphyrin Derived from Tetra(N-carbazolyl)porphyrin○Atsuya Matsubuchi, Shin-ichiro Kawano, and Kentaro Tanaka*

Department of Chemistry, Graduate School of Science, Nagoya University
kentaro@chem.nagoya-u.ac.jp
1. Introduction

Fused Porphyrins

Ar = 2,4,6-trimetylphenyl
OAr

ArO

N

Ni

R

CO2R

N

R

N

Ni

N

OAr

N
N

R

N

ArON

N

N
M N
N
N

H. L. Anderson, et al.,J. Am. Chem. Soc., 2011, 133, 30

A. Osuka, et al.,Angew. Chem. Int. Ed., 2006, 45, 3944

N

R

N

CH2Cl2, MeOH

H
N

40%

R

Zn

N

N

N

R

1. TFA
2. Ni(OAc)2

DDQ/MeSO3H (in CH2Cl2)

N
N
N

R

R

Ni

N

R

R
N

E/V (vs Fc/Fc+)

N

N

R

Ni

N

R

N

DDQ/MeSO3H

N

N

R

N
R

1(Ni)

N
N

CH2Cl2
65%

Ni

N

R

R
N

R

R

2(Ni)

R

found [2(Ni)[2(Ni)]+MALDI-TOF MS(Dithranol, Positive)

0.8
0.4
300

400

0.79 V
0.94 V

1(Ni)2

1(Ni)
10 μA

500

600

700

Wavelength / nm

800

900

1.5

1000

1

0.5

1000

2000

1H NMR

m/z

2520

4000

3000

The aromatic signals are intensied 2.5 times.
t-Bu

N
N

2(Ni)

N

t-Bu

c
i’

q’

p’

Ni

N

j’

t-Bu

2540

N

i

N

k’

b

ah
j

f
g
t-Bu

q

k

r

i

h

t-Bu

e k k’,f

b

c,j

q

o

m
g

i’

j’

N

N

Ni

N

0.11

—1.19

1.30

• π-Expanded porphyrin 2(Ni) was synthesized

E

C

D A

E

C F

B

δ / ppm—1.77 V

1(Ni) 2 μA
0

—0.5

—1.5

—1

—2

Potential / V [Fc/Fc+][1(Ni)] = [2(Ni)] = 400 μM in CH2Cl2,
containing 100 mM Bu4NPF6

R

and small HOMO-LUMO gaps.

R

R
N

R
N

• 2(Ni) has the red-shifted absorption bands

t-Bu
t-Bu

F

• Further oxidation will be investigated.

114—1.34 V

A
B

D

2(Ni)

from the tetra(N-carbazolyl)porphyrin 1(Ni).

N

N

N

2.13

5. Summary and Perspectives
t-Bu

t-Bu

N

—1.34

comparison with porphyrin 1(Ni).

q’

n,
p p’
l

t-Bu

N

0.79

have shifted to long wavelength region.

t-Bu

t-Bu

1(Ni)

—1.34 V
—1.19 V —1.72 V2(Ni)・2(Ni) has small HOMO-LUMO gap in

o

p

a

E1ox — E1red(eV)・Both of Soret band and Q band of 2(Ni)

e

N

N

E1red (V)

t-Bu

l

m

d

d

t-Bu

2535

t-Bu

t-Bu

t-Bu

2530

m/z

The structure of 2(Ni) can be explained by the NMR symmetry.

t-Bu

1(Ni)

2525

Table. Redox potential of 1(Ni) and 2(Ni)E1ox (V)—0.5[1(Ni)] =[2(Ni) = 400 μM in CH2Cl2,
containing 100 mM Bu4NPF6

DPV

compound0

Potential / V [Fc/Fc+][1(Ni)] = [2(Ni)] = 5.0 μM in CHCl3 at 293 K

calcd. [2(Ni)][2(Ni) +0.11 V

0.45 V

2(Ni)

1.2

0

0.97 V2(Ni)1

1.6

N

N

N

R=

R

2.0

N

R

ε / 105 M-1･cm-1

N
N

R

R

ε / 105 M-1･cm-1

N

R

CV

UV-visR

R

DDQ/MeSO3H is suitable foroxidative coupling of 1(Ni).

[1(Ni)] = 400 μM in CH2Cl2
containing 100 mM Bu4NPF6
scan rate: 100 mV/s

R

3. Synthesis of 2(Ni)※R. Rathore, et al. J. Org. Chem. 2010, 75, 4748

Potential / V [Fc/Fc+]

R

N

R

Ered = 1.29 V※

5 μA

1(Ni)

R

1(Ni)

R

R

84%

N

R=

R

R
N

R

Eox1 = 0.79 V

N

PIDA, NaAuCl4･2H2O+

R

0.79 V

0.94 V

R

R

N

N

R

N

Cyclic Voltammetry

H
N

N

Zn

N

N

R = 3,5-di-tert-butylphenyl, M = Ni

96%
R

N

M

Synthesis of novel π-expanded porphyrinby oxidative coupling of tetra(N-carbazolyl)porphyrin.

DME, H2O

B(OH)2

R
N

N

R

2(M)

2. Synthesis of 1(Ni)
+

N

R

R

1(M)

Pd(OAc)2, (o-tol)3P
Ba(OH)2･8H2O

N

R

N

N

R

N

N

R

π-Expanded porphyrins exhibit absorptions in near IR regionand small electrochemical HOMO-LUMO gaps.

Br

M

N

R

R
N

R

λmax = 1136 nm
Eox1 — Ered1 = 1.01 eV

Br

N

R

RO2C

OAr

λmax = 1417 nm
Eox1 — Ered1 = 0.61 eV

H
N

N

CO2R

R

N

oxidation

NR

R
OAr

R

R
R

RO2C

OAr

N

N

ArO

This WorkR = 2,4,6-tert-butylphenyl

OAr

N

M

N

R

R
N

R

N

N

N

N

R

N
R

R
N

R

M

N

R

R
N

N

N

R

N
R

R = 3,5-di-tert-butylphenyl, M = NiR

Pd/TiO2-Photocatalyzed Self-Condensationof Primary Amines to Afford Secondary
Amines at Ambient Temperature
Wang, L.-M.; Kobayashi, K.; Arisawa, M.; Saito, S.; Naka, H.
Grad. Sci., Nagoya Univ.; Grad. Pharm., Osaka Univ.; RCMS, Nagoya Univ.
Symmetric secondary amines were synthesized by the self-condensation of primary amines over a Pd/TiO2

photocatalyst. The reactions afforded a series of secondary amines in moderate to excellent isolated yields atambient temperature in cyclopentyl methyl ether. Applicability for one-pot pharmaceutical synthesis wasdemonstrated by a photocatalytic reaction sequence of self-condensation of an amine followed by N-alkylation of theresulting secondary amine with an alcohol.
Org. Lett. 2019, 21, 341-344.

© Issey Takahashi

1. Background: Intermolecular Self-Condensation
2 R

R

catalyst

NH2N
H

3.3 Substrate Scopehν (UV-LEDs, λ = 365 nm)
2

R

+ NH3

2

¥ atom-economical¥ high selectivity for 2¡ amines¥ high temperature ( > 110 ¡C)
CO
Cy3P COH
H Ru
Ru PCy3
O
OH
Ru H
OC Ru
O
H
H CO PCy3
Cy P
3

nBu

N

OH

+

tBu
OH 130 ¡C
Yi, C. S. et al.
J. Org. Chem. 2018, 83, 4932.

NpP

Cl

Ir

N

Cl

Ir

NH2

R1

0.50 mmol

Cy2P

N
Co

BArF4

Me3Si

BF4

180 ¡C
120 ¡C
Yamashita, M.; Nozaki, K. et al.
Zhang, G. et al.
Inorg. Chim. Acta. 2011, 369, 15. ACS Catal. 2016, 6, 6546.

2
2

[ ]9

NH2
NH
2

0.50
[ ]9mmol
NH2

CPME (3 mL), Ar, 30 °C

N
H
N
67%H(24 h)

67% (24 h)
N
H
81%N
H(15 h)2. This Work: Photocatalytic Self-Condensation
R

R

N
H

CPME, 30 °C

81% (15 h)RhνPt (5 wt %)/TiO2 50 mg

NH2

R

60–120 µmolR

N
H

H2O, 25 °C, 20 hRR

+ amine– NH3

N

3. Result and Discussion
Ph

79% (20 h) moleculesCore structures in functional[1] Fang, Y.-Q.; Jacobsen, E. N. J. Am. Chem. Soc. 2008, 130, 5660.
[2] Schiller, A. et al., J. Am. Chem. Soc. 2017, 139, 4991.

N
H

hν
hν
+ C2H5OH (1 mL)[1]+ C2H5OH (1 mL)[1]30 °C, 5 h
30 °C, 5 h

one-pot

one-potPhminor peak in GC

2e–2[Pd]n-H(2)2e–conduction
band

H

(1)
N + NH3 + H2O
H
87%
N

+

N

1%

imine

N

C 2H 5C2H 5

alverine, 83% overall
alverine, 83% overallO– H2O
Changes from the optimized conditions
Without Pd: < 1% (<1% imine)in the dark: < 1% (<1% imine)
L.-M.;
Morioka,
Jenkinson,
A. E. H.;Naka,
H. Sci.imine)
Rep. 2018, 8, 6931.
Pt (5 wt %)Wang,
in placeof Pd:<1 %Y.;(78%imine)K.; Wheatley,
THF in placeof Saito,
CPME:S.;75% (<1%Cu (5 wt %) in place of Pd: <1 % (20% imine) acetonitrile in place of CPME: 88 % (9% imine)
Ag (4 wt %) in place of Pd: <1 % (<1% imine) ethyl acetate in place of CPME: 88% (4% imine)Au (4 wt %) in place of Pd: <1 % (22% imine) toluene in place of CPME: 90% (3% imine)

R

N
H

R

R

N

R

(5)

2H+

3.2 Optimized Conditions and Controls

98%

N

H

Cf. Mono-Alkylation with Alcohols+ amineN
H

3.5 Mechanistic Hypothesis+ Biomol. Chem.
N2012, 10, 3556.+ NH3
Mitkina, T.; Stanglmair, C.; Setzer, W.; Gruber, M.; Kisch, H.; König, B. Org.
H

N
H

N
H
61%N(72 h)
H
61% (72 h)[1] 17 mmol. see: Wang, L.-M.; Jenkinson, K.; Wheatley, A. E. H.; Kuwata, K.; Saito, S.; Naka, H.
ACS Sustainable Chem. Eng. 2018, 6,15419.

hν[2H+, 2e–]85% (24 h)[2]
+ NH3
N
H
91% (16 h)
N
NH2
N
N
N
H
Boc-protected
75% (30 h)
N
N
N
H
H
Boc-protectedON
N 75%O(30 h)
[ ]4
[ ]4
N
H
H
H
O O N
N O O
[ ]4
[ ]4
N
71%H(23 h)
OO
71% (23 h)

NH2

hν
hν
Pd/TiO2
Pd/TiO2
NH2
CPME
CPME
30 °C, 20 h
30 °C, 20 h
0.50 mmol
0.50 mmolRhν (Xe lamp)hν (UV-LEDs, λ0 = 365 nm)
Pd (5 wt %)/TiO2 (20Au/TiOmg) 2, Cu/TiO2
NH2
NH2 + HO2
CPME (3 mL), Ar hexanes, Ar
25 °C, 50 min
30 °C, 10 h
0.50 mmol
Optimized
0.2 mmol
1 mLconditions

[ ]9
N
H
[ ]91%
N
9(16 h)[ ]9
NH2 H

NH2

NH2

N
Ph + PhN
Ph
2H
CH3CN, 25 °C, 24 hhν (Xe lamp)20%
21%
0.1 mmolAu/TiO2,Cu/TiO2 NH
Ph
2
+ H2O
NH2 +
N
H
Ar, 25 °C,10 h
NH
HO
Ph + Ph+ Ph
HN
major peak in GC
0.2 mmol
1 mL
NH
Ph
2
19%
20%

[ ]9

Cyclohexanamine

Nishimoto, S.-i.; Ohtani, B.; Yoshikawa, T.; Kagiya, T. J. Am. Chem. Soc. 1983, 105, 7180.
Intramolecular versions: Ohtani, B.; Tsuru, S.; Nishimoto, S.-i.; Kagiya, T. J. Org. Chem. 1990, 55, 5551.

CdS 15 mg
3.12 Initial
DiscoveryNH
PhN

3.4 One-pot Photocatalytic Pharma Synthesis+ NH3

R = H: 33%; R = CH3: 22%[2H+, 2e–]

H 2N

N

NH2

N
H
N
79% H
(20 h)

52–96% yield

2

N
H
N
N
H
N85% (24 h)[2]N
+ NH3

NH2

N

Cyclohexanamine+ NH3• Pd/TiO2 photocatalyst selectively promotes the self-condensation of primary amines.
• Various secondary amines were synthesized under mild reaction conditions.
• Cross-condensation and one-pot dialkylation were demonstrated.
Pioneering works

R1hν (UV-LEDs, λ0 = 365 nm)
Pd (5 wt %)/TiO2 (20 mg)hν (UV-LEDs, λ0 = 365 nm)
CPME(3%)/TiOmL), Ar,
30 mg)
°C
Pd
(5 wt
2 (20

NH2

0.50 mmol

NH2

CPME (3 mL), Ar, 30 °C

N
H
+ NH3
N
R1
H
+ NH3
1
R = CH3, 81% (17 h)
R1= CH3O, 93% (20 h)
R1 =
= F,
CH96%
3, 81%(13(17
h) h)
93%
(20
=
52%
(22
h)h)
= CH
CF33,O,=C
F, 96%(13 h)[1]=
6H5, 84% (30 h)
,
52%
(22
=
CF
1
3 with R =h)sluggishCl, Br, NO2= C6H5, 84% (30 h)[1]
sluggish with R1 = Cl, Br, NO2

PCy2

Pd3Pb/Al2O3
Pd@porous graphene oxide
Cu/γ-Al2O3
Pt-Sn/γ-Al2O3
H2 + O2, 90 ¡CO2, 110 ¡C
145 ¡C140 ¡C
Mizuno, N. et al.
Furukawa, S.; Komatsu, T. et al.
Yu, Z. et al.
Loh, C. T. et al.
CEJ 2011, 17, 13308. Catal. S&T 2013, 3, 2397. Chem. Commun. 2014, 50, 3277. J. Am. Chem. Soc. 2015, 137, 685.

2 R

R1

0.50 mmol

PNp2

Nhν (LEDs)
Pd/TiO20

Pd (5 wt %)/TiO2 (20 mg)hν (UV-LEDs, λ0 = 365 nm)
CPME(3%)/TiOmL), Ar,
30 mg)
°C
Pd
(5 wt
2 (20

H

H

nBu

150 ¡C
Peris, E. et al.
CEJ 2008, 14, 11474.

NH2

R1

2 hν
NH3

H

valence
band
2h+
TiO2
Pd/TiO2

2h+

R

(3)
R

NH2

(4)

NH

+ 2H+

H 2N

R

Cf. Nishimoto, S.-i.; Ohtani, B.; Yoshikawa, T.; Kagiya, T. J. Am. Chem. Soc. 1983, 105, 7180.
Ohtani, B.; Tsuru, S.; Nishimoto, S.-i.; Kagiya, T. J. Org. Chem. 1990, 55, 5551.
Acknowledgement: The authors sincerely thank Prof. Ryoji Noyori for his continuous support.

115

Spatio-temporal Control of Formation and Reaction ofFormamide Radicals under Nickel-complexes/TiO2
Cooperative Photocatalysis
Shogo Mori,1 Takahiro Aoki,1 Kaliyamoorthy Selvam2, Jieun Jung1, Susumu Saito*,1,2

The Noyori Laboratory

1Graduate School of Science, 2Research Center for Materials Science , Nagoya University

Abstract

C–C bond formation

O
+

R–X

H

TiO2

R1

N

O

Ni

N

R

R1

O

N

H

R
N
H
(R1 = H, X = Br, I)

R

H(R1 = Me, X = Br)

1. C–C Bond Formation with DMF

1-1. Spatio-temporal transition of DMF radicals

1-3. Scope

distance from TiO2

O

+0.12
more
hydridic

N

O
N

N
Br

R
O

C–H abstraction of DMF by O-centered radicals: DiLabio, G. A.; Bietti, M. et al. J. Org. Chem. 2013, 78, 5909.
Utilization of CO derived from DMF under Pd(II)/TiO2 photocatalysis: Li, Z. et al. J. Photochem. Photobio. A: Chem. 2017, 337, 19.

H

1-2. Ligand Design

O
H

OMe
N

77% (7.3:1)(30 h)

Br

desorption
distance from TiO2

0

R1

Me O

O
H

N

N

adsorption

N
Ni
Br
R

0

TiO2

600
700
Wavelength (nm)

75% (3.5:1)

Br+

64% (1:3.3)(30 h)

46% (4.9:1)

N

O

+

O

H

TEMPO
1 equiv[S]0 = 0.17 M
conv. 50%

800

Ar

+

H

N
H

N

600
700
Wavelength (nm)standard conditions

O

+

O

96%

H

N
H

Pd(dba)2
H bulky P-ligand

1.2 equiv

OMe

O
H

100 °C

800

H

73%

EtO2C
[S]0 = 0.17 M
conv. <1%O

TEMPO
1 equiv

+

H

N
H

H

+

O

17%
O

N

18% (22%)a

N

O
34%

TEMPO–DMF
adducts

H

Hybrid CatalystNstandard conditions

a Without TEMPO

CN

5% (11%)astandard conditions

O

H

>

N

NC

O

N

4%

N

78 equiv

N
H

CN
Ar

H 2N
0%

40%

X

+

[S]0 = 0.17 M

Jursic, B. S. et al. Tetrahedron lett. 2014, 55, 1523.

Ni-catalyzed
coupling products

O
H

N
H
<1% (65%)a

N
H

N

O

N

63% (73%)a

O

N

<1%

CO2Et

O

N
H
65% (X = Br)
81% (X = I)O

13%

Thermodynamically less stable N-centered radical of formamide
would be involved. (ΔG = +19.63 kcal/mol to C-centered radical)

NH2

Ni

H

N

OH

Br

Ar

N
H
isolated yield

K2HPO4 (300 mol %)hν (300–470 nm), 60 °C, 8 h

151 equivN

O

TiO2(P25) (38 mol %), Ni cat.

H

Ni cat. =NiBr2(L1) (5 mol %)Selective C–N Bond Formation

H

N

O

N
H

Br

<1%

O

EtO2C
<1% (4%)a

O

O
H

HO

TEMPO–FA
adducts

CO2Et

NH2

FA
151 equivON

2-2. Scope

CN

H

O

N

O

Hybrid catalysis around TiO2 surface was hardly prevented by TEMPO.

O

N

N

O

Drawbacks✓ only electron rich substrates✓ expensive Pd catalyst

N
H

Zhang, Z. et al. J. Org. Chem. 2012, 77, 5279.

+

NC

a Without TEMPO

2-3. Radical Trapping Experiment

Br

<

N

N

78 equiv

TEMPO
1 equiv[S]0 = 0.17 M
conv. 100%

O
N
H

+

NC

O

solvent
Br

CN

H

O

Solution A
Solution B

H

TEMPO–DMF
adducts

Ni-catalyzed
coupling productsBr

150 °C

33% (1:1.3)

O

7% (61%)aH

Cu salt

57% (1:15.7)

Non-hybrid catalysis in solution was sufficiently prevented by TEMPO.

2-1. Background

H

N

3

N

Non-hybrid Catalyst

a Without TEMPO

Hybrid Catalyst

O

O

N

O

2. C–N Bond Formation with Formamide
Br

OMe O

MeO2C

ΔAbs. = 8%500

Ni cat. =NiBr2(L1) (5 mol %)

N

3

H

Solution A
Solution B

AbsorbanceOH

OH

Ni-catalyzed
coupling products

NC

0.08

N
Br

1-4. Ligand Effect on Radical Trapping (Competition with TEMPO)

ΔAbs. <1%500

Ni

R1 = CN, AMP+ACP = 79% (AMP:ACP = 1:8.1)
R1 = CO2Et, 81% (1:9.0)
R1 = OMe, 61% (1:6.1)

N

Non-hybrid Catalyst

HO

116

O

Measurement method: Majima, T. et al. Langmuir 2004, 20, 2753.

N

ACP

Selective AminoCarbonylation

TiO2 + adsorbed Ni complex

suspension

Absorbance

R

Me
N

Solution B

centrifugation

0.08

Ni

N
Br

R1 = CN, AMP+ACP = 77% (AMP:ACP= 2.7:1)
R1 = CO2Et, 90% (3.8:1)
1
1 R = OMe, 68% (8.1:1)

CO2Me

Solution A
NiBr2(L1) or NiBr2(L2)(0.01 M) in DMF (5 mL)HO

Ni cat. =NiBr2¥glyme (2.5 mol %), L2 (2.5 mol %)

Br

N

H

time

B3LYP/6-31++G(3df,3pd)
Atomic charges were calculated by natural population analysis.

N

N

Ni

O

TiO2

TiO2 (100 mg)
sonication

N

R

R

AMP

Selective AminoMethylation

H
DMF

Ti

N

H

K2HPO4 (300 mol %)hν (300Ð470 nm), 60 ¡C, 20 h

78 equiv

O

O

TiO2(P25) (38 mol %), Ni cat.

H

N

AMR

ΔG =
–1.62 kcal/mol

ACR

H[S]0 = 0.17 M

N

O

H
HO

H

O

+

R–Br

CO
+(0.20–0.24)

We report herein C–C and C–N bond formation reactions between organic
halides and formamides under nickel-complexes/TiO2 cooperative
photocatalysis. The key to selective reactions would be spatio-temporalcontrol of formation and reaction of formamide radicals, where kineticallyfavorable radicals would be formed around TiO2 surface and then theywould be transformed into thermodynamically stable radicals in solution.

C–N bond formation

O

N
H

Me
33% (X = Br, 24 h)

Ac

O
H

N
H
68% (X = Br)
71% (X = I)

CO2Me

O
H

CN

O
H

H

66% (X = I)

O
H

CHO

O

N
H

N
H
28% (X = I)ON
H

29% (X = I)

Cl

H

N
H

OMe

43% (X = I)

Complementary synthetic method with cheap reagents

Molecular-frame momentum imaging of tunneling electrons frommolecular deuterium in circularly polarized intense laser fields
H. Fujise1, M. Takahashi1, D. Ikeya1, T. Nakamura1, A. Matsuda1, M. Fushitani1, A. Hishikawa1, 2
1 Graduate School of Science, Nagoya University, 2 Research Center for Materials Science, Nagoya University

Introduction
Laser Tunneling Ionization Process
Intense laser electric field
F : ~109 V/cm

Molecular orbital
(MO)

e-

Tunneling
electronDistorted
binding potential

THIS STUDY

Observables
1

Tunneling ionization rate

2

Transverse Momentum Dsitribution
Sensitive to molecular orbitals

TMD

Investigation of the effects
of molecules on TMDs
 Electron-ion coincidence imaging

H2 1s

A. Staudte et al., Phys. Rev. Lett. 102 033004 (2009)

Tunneling ionization rate

Transverse Momentum Distribution

 Visualization of excited states of NO Three-dimensional molecular orbital imaging1

T. Endo et al. Phys. Rev. Lett. 116 163002 (2016)

TMD Momenta perpendicular

Circularlypolarizedlaser pulses

to laser polarization

Ultrafast scanningof molecules

Photoelectron momenta distribution
depends on electron wavefunction1, 2
1 V. N. Pham et al., Phys. Rev. A 89 033426 (2014)
2 L. Arissian et al., Phys. Rev. Lett. 105 133002 (2010)

N+ fragment ion distribution with respect to laser polarization portrays MO shapes

Experimental Results

FIG. 1 (color online). (a) Schematic trajectory of the tu

Transverse Momentum Distribution

Molecular Frame Photoelectron Angular Distribution
45

0.04
0.02
0

135

0.5

90

0.0

45

-0.5

-1.0

0.0

0.5

1.0
KER/ eV

1.5

2.0

2

Asymmetric yields observed perpendicular to molecular axis
Observed clear KER dependence in MFPADs

Ions

-2

-1

0
px / a.u.

 / a.u.

Position (xi, yi)
Flight time (ti)

2

pi

50

1

2

0

pi

TDC 2
Focusing mirror
f = 100 mm
Molecular
beamElectrons

SQ window

QWP

Position (xe, ye)
Flight time (te)

4

-2

0

2

-2

0

1



0.1



0

45

90

135

180

 / deg.

pe

-6

-1

x10

100

6

-1

0
px / a.u.

1

2

0

8
6

0

4

-1
-2

2

-2

-1

0
px / a.u.

1

2

0

2

4

6

8

 = 90°

10



0.2

0.0

150

0

0
px / a.u.

2

8

0

10

 = 90°

1

10

0

WFAT

Molecular frame
Recoil approximation

200

1

-1

1

12

-1

1

Position sensitive detector

0.1 event / pulse
pz / a.u.

2

0.3

Electron-ion coincidence momentum imaging

Diff. amp+
Discriminator

3

2

14

 = 45°1

Evaluation of TMD and comparison with WFAT

Experimental

-2

4

0

-2

J. Wu et al. Nat. Commun. 4 2177 (2013)

-2

5

-1

Correlation between ionization process
and dissociation observed from MFPADs

2

6

 = 0°

1py / a.u.

0py / a.u.

WFAT

-90

TDC 1



Asymmetry-45

MFPAD resembles MO

Diff. amp+
Discriminator

electronsintheplaneof laser polarization, summedover p
angles of the ionization f eld, yields a toroidal distribu
momentum where the center of the ring is E=! L . The thof this distribution perpendicular to the laser polarization
width of the momentumdistribution at ionization. (b) Me
momentumspectrumof Ar photo electron incircularly po
light at an intensity of 3:1' 1014 W=cm2, 800 nm. Th
propagates along the z axis. The integrated prof le alo
direction of propagation (top) is in good agreement
Gaussian distribution. The integrated prof le in the plpolarization (side) is used to determinetheintensity.

Three-dimensional momentum distribution: torus
TMD appears in cross section
py / a.u.

-135

D
0.02 0.04

1.0

py / a.u.

D

-180

0 

+

180

/ deg.

90
135

P H Y SI C A L

PRL 105, 133002 (2010)

-1


-2

-1
px / a.u.

0

TMD width in agreement with WFAT prediction
TMD could be utilized for three-dimensional MO imaging
KER dependence is required to explore the similar effects
seen in MFPADs
Weak Field Asymptotic Theory (WFAT)
O. I. Tolstikhin et al., Phys. Rev. A. 84 053423 (2011)

F = 0.049 a.u.
800 nm, 40 fs, 1 kHz

pe

Position sensitive detector

Ionization potential
Tunneling ionization rate

TMD

TMD width,@ F = 0.049 a.u.  = 0.214 a.u.

117

Three-dimensional molecular frame momentum distribution ofphotoelectrons from O2 in circularly polarized intense laser fields
IKEYA, Daimu1; FUJISE, Hikaru1; NAKAMURA, Takeru1; MATSUDA, Akitaka1;
FUSHITANI, Mizuho1; HISHIKAWA, Akiyoshi1,2(1Dept.Chem.,Nagoya Univ.; 2RCMS,Nagoya Univ.)

Laser tunneling imaging

Results
Laboratory-frame 3D fragment ion momentum
Peak assignment: H. Liu et al., Phys. Rev. A 88, 061401(R) (2013).
distribution

Tunneling Ionization
Electric fieldboundpotential

O2 → O2+ + e- → O+ + O + e-

laser intensity~1014 W/cm2

Ip

e-

HOMO
etc.

Tunneling

Molecular Orbital Imaging

ε1. Tunneling ionization rate
Momentum angular
distribution of N+

NO 2π

HIGH

H2 1sσMolecular-frame photoelectron
angular distribution

HOMO-1→ PeakⅠ, Ⅲ

HOMO-2Multiple peaks→ different dissociative pathways

HOMO-1HOMO-2→ PeakⅡ, Ⅳ

HOMO

LOW

ε

Endo et al, Phys. Rev. Lett. 116 163002(2016)

Reflect one-dimensional orbital shape

Molecular-frame 3D photoelectron momentum
distribution
O2 → O2+ + e- → O+ + O + e-

2. Transverse momentum distribution (TMD)
e-

Cross
sectionV. N. T. Pham et al, Phys. Rev. A. 89 033426 (2014)

TMD

e-

Transverse momentum distribution
on a plane perpendicular to thelaser electric field

Reflect two-dimensional
orbital shape
Weak-Field Asymptotic Theory (WFAT)TMD
𝑃𝑃 𝒑𝒑�

Torus-like distribution was obtained

PeakⅡ(0.6-1.2 eV)PeakⅢ(1.2-1.9 eV)

90

90

135

4𝜋𝜋𝜋𝜋
𝜅𝜅𝜅𝜅��
=Γ
exp −
𝐹𝐹
𝐹𝐹

𝜅𝜅 𝜅 2𝐼𝐼�
𝐼𝐼� : ionization energy
𝐹𝐹 : laser electric field

Depends on orbital shape

ε

45

O O+

180

1. Tunneling ionization rate
2. Transverse momentum distribution (TMD)

225

135

0

315
270

225

: Exp.
: MO-ADK

pe- eO+OElectrodes

O+

pO+

pO+ : Molecular axis
pe- : Orbital shape

Concave mirror(f =100 mm)

O2 molecule
X axisPSD( electron )118

Y axise-

Circularly polarized laser pulse• Wavelength 800 nm• Pulse duration 45 fs• Repetition rate 1 kHz• Ellipticity 0.93
• Intensity: 6×1014 W/cm2

e-

=

yz

𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚� )/𝑡𝑡
𝑚𝑚𝑚𝑚𝑚𝑚𝑚𝑚� )/𝑡𝑡
D�+)−𝑞𝑞𝑞𝑞𝑞𝑞𝑞𝑞𝑞𝑞

transform to“Molecular frame”𝑝𝑝�𝑝𝑝�
rotation
𝑝𝑝�
𝑝𝑝�
𝑝𝑝�
𝑝𝑝�

z

O+

 Angular momentum

𝑥𝑥

Electron which has
angular momentum tunnels
with initial momentum

O+

O O+

Shift of final momentume-

TMDs predicted from MOsxyyz

Isotropic

Circle Laser-focus volume

Variation in laser intensity in focal point
broadens longitudinal momentum distribution.

“Laboratory frame”

e-xy: Qualitative agreement with prediction
yz: Nodal structure was not visible
S. Eckart et al., Nat. Phys. 14 , 701 (2018).

Three-dimensional
momentumywith
Coulomb potential

270

e-

① detected position (𝑥𝑥, 𝑦𝑦)② time of flight (𝑡𝑡)
𝑝𝑝�
𝑝𝑝�
𝑝𝑝�

ε

315

xy

Three-dimensional momentum imaging
O2 → O2+ + e- → O+ + O + e- : Dissociative ionization process of O2

X

eTilted

2. Transverse momentum distribution (TMD)

Electron-ion coincidence measurement

Y

without
Coulomb potential
0

TMDs in PeakⅢ

Z

1.1×1014 W/cm2

45

O O+

180

Simulation of Classical electron
trajectory in a circularly pol. field

Angular distributions reflected orbital shapes

in attempt to image three-dimensional molecularorbital structure

Position Sensitive
Detector :PSD
( ion)O O+

1. Tunneling ionization rate

Circularly pol. lightεT. Morishita et al., Phys. Rev. A 75, 023407 (2007).

Summary
Image three-dimensional orbital of O2 in intense laser field
1.Tunneling ionization rate
• Reflected orbital shape
2.Transverse momentum distribution• Obtained transverse momentum
distribution from cross section of torus

Outlooks

Visualization of O2 HOMO
• Promotion of dissociation
by second pulse• Fix molecular axis by alignment෇೫ගᙉ䝺䞊䝄䞊ሙ䛻䜘䜛Ỉ⣲ศᏊ䛾䝖䞁䝛䝹䜲䜸䞁໬䛻䛚䛡䜛ྠ఩యຠᯝ

Isotope effects in tunneling ionization of molecular hydrogen in intense circularly polarized laser fields

䕿㧗ᶫ䜏䛺䜏㻝䠈⸨℩ග㤶㻝䠈௰ᮧṊ⍠㻝䠈⳻ᕝ᫂ᰤ㻝㻘㻞‫س‬M. Takahashi1, H. Fujise1, T. Nakamura1, A. Hishikawa1,2

㻝㻚 ྡ኱㝔⌮䠈㻞㻚㻌ྡ኱㻾㻯㻹㻿

1. Grad. Sch. Science, Nagoya U 2. RCMS, Nagoya U

1 BACKGROUND

3 RESULTS

Tunneling ionization

H2 and D2 in circularly polarized laser fields

F ~ 0.06 [a.u.]

Kinetic energy spectrum

The pathways leading to dissociation

䐟1ω dissociation
䙶 net-2ω dissociation

Wavepacket

Molecular frame photoelectron angular distribution (MFPAD)
Coulomb explosion
H2 ͳ‫ߪݏ‬௚

A. Staudte et al., PRL 102, 033004 (2009).

MFPAD provides molecular structure and ionization rate information.

Molecular frame photoelectron
momentum distribution (KER<3.0 eV )MFPAD (Symmetrized)

Theoretical calculation H2 / D2
Nuclear mass effect on the tunneling ionization
Rate

H2 > D2 experimental confirmation!

X. Wang et al., PRL 117, 083003 (2016).

Angular distribution
yet to be known experimentally
Internuclear distanceAngle
Laser field
between ܴ and ‫ܨ‬Ȟ௩ ߚ ൌ න ‫ܩ‬଴଴ ܴǡ ߚ

Structure factorଶଶܹ଴଴ ‫ܨ‬Ǣ ܴ ߯௩଴ܴ ܴ݀

Field factor

O. I Tolstikhin et al., Phys. Rev. A 87, 041401(R) (2013).

Purpose Clarify effects of nuclear motion on the angular
distribution of ionization rates that reflectmolecular orbitals (electron distribution)

D2 shows a higher ionization rate in the perpendicular direction

But there is a difference from the calculated value
Orientation dependencies of each KER peakPeak1 & Peak 2

2 METHOD
Electron-ion coincidence method
Laboratory frameܻܼ

Position → ሺܺ ǡ ܻ ሻTime of flight → ‫ݐ‬ܺIonሺ ‫݌‬௑ǡ௜௢௡ ǡ ‫݌‬௒ǡ௜௢௡ ǡ ‫݌‬௓ǡ௜௢௡ ሻ‫݌‬௑ ൌ ݉ሺܺ െ ܺ଴ ሻȀ‫ݐ‬‫݌‬௒ ൌ ݉ሺܻ െ ܻ଴ ሻȀ‫ݐ‬‫݌‬௓ ൌ ‫ܧݍ‬ሺ‫ ݐ‬െ ‫ݐ‬଴ ሻElectronሺ ‫݌‬௑ǡ௘ ǡ ‫݌‬௒ǡ௘ ǡ ‫݌‬௓ǡ௘ ሻ

Different orientation dependencies for ߚ ൌ ͻͲι and ʹ͹Ͳι and each peak
䚏 Influence of correlation between ionization and dissociation processes

J. Wu et al., Nature communications 4, 2177 (2013).

4 SUMMARY

Measured MFPAD of H2 / D2

Molecular frame
Electronሺ ‫݌‬Ԣ௫ǡ௘ ǡ ‫݌‬Ԣ௬ǡ௘ ǡ ‫݌‬Ԣ௭ǡ௘ ሻ

D2 has a higher yield in the direction perpendicular to the molecular axis
䚏 Agreement with the trend expected from the WFAT
Asymmetry in the angular distribution
䚏 Need to reduce the correlation between ionization and dissociation process
for accurate reading of MO.

119

Observation of association reaction of C6H14/N2 gas flow system
induced by femtosecond laser filament
Kentaro Tani1, Chiaki Kubo1, Kasumi Hashigaya1, Akitaka Matsuda1, Akiyoshi Hishikawa1,2¹Department of Chemistry, Nagoya University, ²Research Center of Materials Science, Nagoya University

Introduction

Laser field intensity in laser filament

Unimolecular reactions in intense laser fields

Laser field intensity
��
𝐼𝐼 𝐼 �

Plasma diameter mesurement
Femtosecond laser pulse
800 nm, 45 fs, 1 mJ/pulse, 1kHz

�� ��

𝐸𝐸 𝐸 𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸𝐸 𝐸𝐸 : Pulse duration,
𝑑𝑑 : Beam diameter at 1/𝑒𝑒 �

In ultra high vacuum : 𝑑𝑑 𝑑𝑑𝑑𝑑𝑑/𝜋𝜋D

Plano-convex lens
f=200 mm

𝑓𝑓 : Focal length, λ : Laser wavelength, D : Input beam diameter

Intense femto second laser Plasma defocusing

Laser pulse shaping + Closed loop control

Laser filament

Lens

Kerr self focusing

Beam diameter can’t be determinedin laser filament

Multimolecular reactions in intense laser field

Spatial distribution of plasma density

 [AuCl4]⁻

𝑁𝑁𝑁𝑁 𝑟𝑟 𝑟 𝑟𝑟𝑟𝑟𝑟� 𝑒𝑒 �� /� )�

�Gold nanoparticle

Behzad Tangeysh, et al., J. Phys. Chem. C 117, 18719 (2013).

Y. Taguchi et al., Carbon 115, 169 (2017).

��

CnH2 (H-capped polyyne)

 C2H4gold nanoparticles=𝜎𝜎𝜎𝜎� � 𝑒𝑒 �� /(�/ �)�𝑑𝑑������

𝑛𝑛 times

Calibration curve

𝜎𝜎 : Cross section of ionization , n : Nonlinear orderd : Beam diameter at 1/𝑒𝑒 �

𝐼𝐼 𝐼 𝐼𝐼𝐼 𝐼 𝐼𝐼�� {1 − exp −16𝐸𝐸 𝐸

amorphous carbon
A. Matsuda et al., Chem. Lett. 46, 1426 (2017).

・Hydrogenated amorphous carbon
films and nanoparticles were produced

Low intensity

High intensity
sp2 rich

C2H4

sp3 rich・Products depends on laser-field
intensity

C2H3*(+), CH*(+), C2*(+), etc

Batch reaction

CCD camera

Laser filamentation▶ Selective Bond Dissociation

 C6H14

Atmosphere

Multiple laser irradiations

Nano particle

Complex reaction processThis work
Observation of association reaction of gaseous C6H14 in intenselaser fields∝ 𝑰𝑰𝟕𝟕𝟕𝟕𝟕

A Tlebpour, et al., Opt Commun. 163, 29 (1999)𝑑𝑑����� = 7.5𝑑𝑑������

S, Xu, et al., Opt Express, 20, 299(2012)

Results and Discussion
Laser-field intensity dependence Laser-field intensity dependence of multimolecular reaction
 Gas flow system

Simplification of reaction

ExperimentGas flow system
Femtosecond laser pulse
800 nm, 45 fs, 1 mJ/pulse, 1kHz

Total pressure : 1 atm

Reaction chamber

Plano-convex lens
f=200 mm

Cooling trap（~70 ℃）

N2

UV absorption spectrum
C6H14

Pump

Air(Calibration)
O2 0.2 atm
N2 0.8 atm

C6H14/N2flow system
C6H14 0.2 atm (Vapor pressure)N2 0.8 atm

Summary26

m/z=14m/z=2839

1.42 × 10�� W/cm�

m/z=42m/z=56m/z=86𝟓𝟓𝟓𝟓𝟓𝟓𝟓

C6H14
CaHb, CcHd, etc (fragment)[CaHb, CcHd, etc]∝ 𝐼𝐼�

Laser-field intensity dependence of association reaction of gaseous
C6H14

Polyyne production process

 Simplification of reaction by gas flow system
 Calibration of the laser-field intensity using filament plasma diameter

CaHb + CcHd + etc

Nonlinear coefficient (𝒏𝒏) about laser-field intensity~ Fragmentation of C H
C2H4, C3H6 etc
CnH2
C6H14

Hydrogen capped polyyne

C6H14

120

Single molecule dissociation reaction

6

14

Collision between fragments[CnH2] ∝ 𝐼𝐼��CnH2 (polyyne)

disagreement withthe result

Collision between fragment and parent

CaHb + C6H14

CnH2 (polyyne)[CnH2] ∝ 𝐼𝐼�

agreement

Pseudo first-order reaction : [C6H14] = constantAsymmetric Coulomb explosion of CH4 inphase-locked two-color intense laser fields
H. Hasegawa1, H. Fujise1, A. Matsuda1, A. Hishikawa1,2(1Dept. Chem., Nagoya Univ., 2RCMS, Nagoya Univ.)

Results and Discussion

Introduction(1) H+ + CH3+ channel

Spatial phase modulator + machine learning+

Optimally tailored pulse
8

R. J. Levis et al, Science 295, 709 (2001)
A. Assion et al., Science 282, 5390 (1998)

III

6-8 eVH+

3-4 eVH++

Coherent reaction control in intense laser fields

6

E ω cos ( ω t ) + E 2ω cos ( 2 ω t + Φ ) = E ω +2ω
Φ=0

Pulse shape

4

Φ=π/2

changing by Φ3

Φ= πAsymmetry of laser fields altered by phase Φ

A(Φ)

Φ

II

5

I
0

+

Two-color laser fields

+

7

3
yield

Different relative phase dependence on KER→ Suggests different dissociation pathways

Selective breaking of equivalent bonds:
C2H2 : Q. Song et al., J. Phys. B 48, 094007 (2015)

Fragmentation pathways from CH42+

CO2 : T. Endo et al., Phys. Chem. Chem. Phys. 19, 3550 (2017)

1A

Deformation of the potential energy surfaces
Y. Sato et al., J. Am. Chem. Soc. 125, 8019 (2003)[1] R. Flammini et al.,New J. Phys 11, 083006 (2009).

1

1T
2

Excitation energy / eVdemonstrated with linear molecules

Tetrahedral molecule: CH₄
Four equivalent C-H bonds

Coulomb explosion processes(1) CH42+ → CH3+ + H+

50

3T
2
1A
1
1T
2
1

40

E

3A”

3T
1

2

1E’
3E’

30

1A’
1

(CH42+)*(CH42+)eq

Region III via 1T2 and 1A1
Region I via 3T1 and 1E(CH3+)eq + H+

Region I, III : large asymmetry
Direct dissociation from CH42+ ground and excited states(2) CH42+ → CH2+ + H2+

Region II : small asymmetry[2]G. Dujardin etPhys. Rev. A 31,
Predissociation from 3T1 to 1A1 → long lifetime[2] al.,
5 (1985).

Experiment

Origin of opposite asymmetry region for I and III

Orientation dependent excitation?
Potential deformation dependent on electronic state?

mi xi / ti
Pi = mi yi / ti
F q ( ti – t0 )xyz

Kinetic energy release (KER)

EKER =

Σ 2m|p i |²

i=H, CH₃i(2) H2+ + CH2+ channel
3.5-8 eV

8

H2+

7
6

β - BBO

Iris
Concave mirror
f = 75 mm

CH₄molecular beam
Intensity~ 3× 1014 W/cm2

CaF₂
window

DWP α - BBO+

electrodes
Spectrometer

Phase-locked(feedbackloop)
800 nm1 kHz
45 fs

Wedge α - BBO
platesε

A (Φ) =

Y+－ YY+ + Y-

Energy spectrum
yield / arb.u.

Y-

H+ Momentum image

5

Similar phase dependence tothat of Region I of channel (1)40Asymmetry ParameterY++ +momentum+

Position sensitive detector( x, y, t )A(Φ)

Coincidence 3D momentum imaging

β - BBO

2.5
yield

Fragmentation to H2+ + CH2+
via 1T2 state [1]Summary

Coincidence imaging of Coulomb explosion of CH4
in phase-locked two-color intense laser fields(1) CH42+ → CH3+ + H+
Different relative phase dependence on KER→ Suggests different dissociation pathways(2) CH42+ → CH2+ + H2+
Similar relative phase dependence to that of high KER of (1)121Preparation of Oxide-supported Heterobimetallic
Catalysts from Cu-Fe Complex〇Aiko ASAI1, Satoshi MURATSUGU1, Mizuki TADA1,2

Dept. of Chemistry Nagoya University1, RCMS and IRCCS, Nagoya University2, Nagoya, JAPANIntroduction

PurposeSupported metal complex catalyst

Homogeneous catalyst

Preparation and catalytic activity of new
supported heterobimetalic complex〇One of the preferable heterogeneous systems to understandthe relationship between catalytically active structure andreactivityEx.) Ir2/γ-Al2O3IntermediateOHO
H2
structure in the
H H2
C
C H
transfer
Ir
Ir
Ir
hydrogenation
IrO
Homometallic
O
O
O
O
OH
systemAl
Al〇Well-defined structure to
produce high selectivity
×Aggregation and deactivation

Heterogeneous catalyst〇High activity, isolation and reuse
×Difficult to understand therelationship between active structure
and activity due to heterogenity

AlAl

γ-Al2O3Ex.) (NHC)M-M’Cp(CO)2 complex

R
N

Mes
N
N
Mes

Cu Fe
CO

CO

1

Mes
N

Oxide support
Ex.) SiO2• Direct bond
between Cu and FeOHOH OH+• Active for alkynehydrogenation andbenzene borylation

Impregnation

SiO2, γ-Al2O3, TiO2, MgO,
SiO2-Al2O3, K-Al2O3 (Usedafter calcination)

N. P. Mankad, et al. Organometallics
2013, 32, 3986-3992.

COTo understand the roles of each metal
atom in heterogeneous nature

Preparation of oxide-supported heterobimetallic complex
Bimetallic complex
Ex.) (IMes)Cu-FeCp(CO)2(CuFp)CO

N. P. Mankad, et al. Organometallics 2013, 32, 3986-3992.

S. Muratsugu, et al. Phys.
Chem. Chem. Phys.,2012, 14, 16023-16031

γ-Al2O3

M M'

N
R

Mes

N Cu

OH

Toluene, r.t. 30 min
Under N2

Fe CO
CO
OH
OH

2_SiO2 (Expected structure)• Coordination to metal center

Characterization of oxide-supported heterobimetallic complex
FT-IR

ν(C-H)
NHC

ν(CO)

NHC
1736

1892

Cp

1910

Fe complex
precursor

1848

Mes
N

1
1996
0.1

N
Mes

1956

Mes
N

Cu complex
precursor

N
MesK

Fe K-edge XANES

Fe
CO

Cu Fe
CO

Fe complex
1
2_SiO2
2_K-Al2O3

Cu Cl

After the attachment
(1)
NHC
was
maintainedandbridged CO wasdisappeared. (FT-IR)

CO

CO

2_SiO2

0.2(2) Fe was moreoxidized than 1.
(XANES)

SiO2

Catalytic reactions on oxide-supported heterobimetallic complex
Diphenylacetylene hydrogenationPhcatalyst
Ph H (1 atm), Ph2
150 ºC,
Xylene, 24 hCatalyst
1
2_SiO2
2_TiO2
2_γ-Al2O3
2_MgO
2_SiO2-Al2O3
blank

Ph +

Ph
Ph

Conv. /%
28
4
0
20
24
69
~0

Reaction conditions: Fe(Cu) = 5.0 × 10-6 mol, 150 ºC, H2 1 atm,
Fe(Cu)/diphenylacetylene = 1/200, 24 h, xylene 5 mL.

Benzene borylation
+

O
O
B B
O
O

Xanthene oxidation

catalyst
UV, r.t.,Benzene, 24 hCatalyst
1
2_SiO2
2_TiO2
2_γ-Al2O3
2_MgO
2_SiO2-Al2O3
blank

O
B
O

Conv. /%
45
13
30
26
33
0
0

catalyst

O

Oxidant, 60 ºC
Toluene, 24h

Catalyst Oxidant Conv. /%
1
TBHP
40
2_K-Al2O3 TBHP
49
K-Al2O3
TBHP
14
blank
TBHP
~0
1
H2O2
4
2_K-Al2O3
H2O2
14
blank
H2O2
0

O

Catalyst Oxidant Conv. /%
1
PhIO
~0
2_SiO2PhIO
6
2_K-Al2O3
PhIO
7
blank
PhIO
~0
Reaction conditions: Fe(Cu) = 5.0 × 10-6 mol,
60 ºC, Fe(Cu)/xanthene/oxidant= 1/50/25, 24
h, Toluene 5 mL.

Reaction conditions: Fe(Cu) = 5.0 × 10-6 mol, r.t., N2 1 atm,
Fe(Cu)/bis(pinacolato)diboron= 1/25, 24 h, UV: 365 nm, benzene 2 mL.

Summary• Supported heterobimetallic complex catalysts were prepared by the impregnation of (IMes)Cu-FeCp(CO)2 (CuFp, 1)
on several oxide supports (SiO2, γ-Al2O3, TiO2, SiO2-Al2O3, MgO, K-Al2O3).
• After the attachment of 1 on SiO2 (2_SiO2), it was suggested that NHC ligand was maintained and bridged CO wasdisappeared from FT-IR, and that Fe was oxidized from Fe K-edge XANES.
• Catalytic performances (diphenylacetylene hydrogenation, benzene borylation, and xanthene oxidation) on the
prepared supported heterobimetallic complexes (2_support) were investigated.

122

OPreparation and Catalytic Oxidation Performance of
Rutile Type IrO2 Nanoparticles
䚽Takatoshi SUDOH1, Satoru IKEMOTO1, Satoshi MURATSUGU1,2, Mizuki TADA1,3

Dept. of Chemistry Nagoya University1, JST PRESTO2, RCMS and IRCCS, Nagoya University3, Nagoya, JAPANIntroduction and Purpose

Preparation ofIrO2 nanoparticle

An image for C-H activation on
IrO2(110) surface [2]Rutile type Iridium dioxide (IrO2)

Ir(CH3COO)3+ carboxylic acid(110) surface of rutile type IrO2:
C-H bond activation at very low temperature
Methane oxidation (-172 ºC) [1], [2]IrCyclohexane oxidation (-88 ºC) [3]Oxidation of nitric oxide (NO) (r.t.) [4]O

H2O, stirred

Purpose: Preparation of rutile type IrO2
nanoparticles with (110) surface and its
application as catalysts

Only from surface chemistry[1], [3]and theoretical chemistry[2],[4] fields
No application as real catalysts

calcination
IrO2 nanoparticle[1] Z. Liang. et al. Science. 2017, 356, 299-303. [2] Y. Tsuji. et al. J. Phys. Chem. C 2018, 122, 15359-15381.
[3] Martin, R. et al. Phys. Chem. Chem. Phys. 2018, 20, 29264. [4] Yuan, H. et al. ACS Catal. 2018, 8, 10864−10870.

Characterization of IrO2 nanoparticle
XRD

TEM

(110) plane(101) plane

Ir LIII-edge EXAFS
Oscillation

Ir-O

IrO2 nanoparticle
IrO2 (Wako)

FT

Ir…O

Ir…Ir
Ir-O-Ir

ICSD-NO. : 84577(111) plane(211) plane

BET and estimated particle size

0.02

䞉 Rutile type IrO2 nanoparticles with (110) surface
were successfully prepared and characterized.

2.6 x105

Catalytic reactions of rutile type IrO2 nanoparticle

Pretreatment
conditions

Methane oxidation with O2

CH4 + 2O2
CH4 + 1/2O2

IrO2

Reactionconditions

CO2 + 2H2O ('H298
CO + 2H2 ('H298 = -36 kJmol-1)

Catalytic activity on IrO2 nanoparticle= -802 kJmol-1)

䞉Flow gas : He = 100 mL min-1
䞉Pretreatment temp. : 1) 25-300 ºC, 5 ºC min-1, 2) 300 ºC, 2 h䞉Reaction gas : CH4/O2/N2/He = 20/10/3/67(total flow rate = 100 mL min-1)
䞉Reaction temp. : 1) 25-700 ºC, 5 ºC min-1, 2) 200, 300 ºC, 30 min,C, 10 min3) 500, 700 ºC,
䞉Amount of Catalyst : 200 mg

Schematic
image forflow
reactorComparison with bulk IrO2 (Wako)

䞉CO2 was formed at 200 ºC, andCO was emerged at 300 ºC.
䞉IrO2 nanoparticles showed
higher activity than bulk IrO2
(Wako).

Xanthene oxidation with O2

Catalyst
Conversion %IrO2 nanoparticle
82.3
IrO2 (Wako)
4.8
Blank
4.8

IrO2
Xanthene(Reactant)Nonane,60 ºC,
O2 (101.3 kPa)

Xanthone(Product)

Selectivity %
100
100
100

Mass balance
0.98
0.98
1.00

Reaction conditions: IrO2 (75 mg (0.34 mmol)), Xanthene (0.375 mmol), nonane (1.5 mL),
IrO2/xanthene/dodecane (IS) = 1/25/12.5 (molar ratio), 60 ºC, 101.3 kPa of O2, 24 h.

Conversion-Time plot䢳䢲䢲Conversion of Xanthene /%IrO2nanoparticle
IrO2 (Wako)

Specific
Particle size
surface area(nm)
(m2g-1)
21.5
24

XRD: pure rutile type structure and broad peak patternparticle size : 27 nm from Scherrer's equation
TEM: confirmation of (110) plane
average size: ~20 nm
BET: specific surface area: 21.5 m2g-1
estimated average particle size: 24 nm
Ir LIII-edge EXAFS: smaller Ir…O, Ir…Ir, and Ir-O-Ir
contributions→ smaller size than bulk IrO2

䢺䢲䢸䢲

IrO2 nanoparticle
Blank

䢶䢲
䢴䢲

䢲
䢲

䢷

䢳䢲
䢳䢷
Time /h䢴䢲䢴䢷

䞉IrO2 nanoparticles also exhibited higher activity on the xanthene oxidation with O2 than bulk IrO2 (Wako).

Conclusions
䞉We succeeded in preparing pure rutile type IrO2 nanoparticles with (110) planes (ca. 20 nm), which werecharacterized by XRD, TEM, BET, and Ir LIII-edge EXAFS.
䞉The prepared IrO2 nanoparticles exhibited higher catalytic activity to methane oxidation in gas phase andxanthene oxidation in liquid phase with O2 than bulk IrO2.

123

N2 Activation by the Fe Sites of Cubane-type[Mo3S4Fe] Clusters Supported by Cp Ligands(Nagoya Univ,1 Daido Univ,2 Hawaii Univ3 )◯Kenichiro. Munakata,1 Keisuke. Uchida,1 Ryota. Hara,1 Mami. Kachi,1 Mizuki. Tada,1Tsutomu. Takayama,2 Yoichi. Sakai,2 Roger. E. Cramer,3 Yasuhiro. Ohki1

Introduction

N
N

MoFe protein

N2

N2

Metal-Sulfer Cluster
Me2N

S

Ru

Ir

Cp*

Mo-Ti-S Cluster

NH3

H+
e-

Cp*

S
NMe2 Ir
S
S
Mizobe, Y. et al.,Ir
Cp*
Angew. Chem. Int. Ed.,Cp* 2007, 46, 5431.

H+
eNH3

CO2HO

COOH
O

O
O

H+
e-

S
S

Mo

(His)N

S

S

Fe
Fe

S
C

S

Fe

S

Fe

Fe

Fe

Fe

S(Cys)

R

Cp*(1a)R = MeR = SiMe3 CpL (1b)R = SiEt3

S
CpR

CpXL (1c)

S

Mo

Mo

S

Mo

S

2a
Mo S

S Mo
Cp*

15%

CpL

Mo S

S Mo S Fe N
CpL
Mo S
CpL

S

Mo

N

Fe

CpL
S Mo
CpL
Fe S Mo S

CpXL S
Mo

S Mo

S
CpXL

CpL

Mo

S

CpR

S

Mo

Fe

S

Fe

N

1b
75% yield

S

O
OKO
N O O

Fe Cl

Si

Mo

S

triclinic P-1 (#2)
R1/wR2 = 0.0305/0.0800
GOF = 1.021

-0.33

2400

1900

1400

900

monoclinic C2/m (#12)
R1/wR2 = 0.0646/0.1886
GOF = 0.974

N2 + 6 Na + 6 Me3SiCl
1 atm.
2000 eq. for cluster
Entry

Cluster

127.0 ± 28.3

1b
1c
A
B
C

2
3
4
5
6
SiEt3

A

N(SiMe3)3 /eq.

1a1The highest
yield by Fe
reaction site

248.0 ± 12.7
122.9 ± 3.8
21.8 ± 5266.2 (N=1)
9.6 ± 2.2
SiMe3

CpL=

-2.17

0.5

-0.86

0

-0.5

Me3Si

Cp*

Mo

S

Mo

S
Cp*

-1.88

-1

-1.5

S

Fe

Mo

N

B Cp*

SiMe3

S

S
Cp*

Cp*

CpL

Mo S

Mo

Fe

S

Mo

S

S

Fe

Mo
S

Mo
S

Cp*

Mo

S
CpXL

124

Mo

S

Mo

Fe
S

CpXL

Cl

CpL

Mo

S
CpL

S

Mo

S

Mo

Fe
S

CpL

Cl

S Mo S Fe N
CpL
Mo S
CpL

N

-2.5

-3

CpR

Mo
S
Cp*

S

Mo

S

Mo

Fe
S

Cp*

CpL

Mo

S

Mo

S

Mo

Fe
S

CpR

Cl

Me3Si・

S Mo
CpL

CpR

Complex

Mo

S
CpR

S

Mo

S

Mo

CpR
S
Mo
S
CpR

Fe

Mo

S

Mo

Fe

N

N

S

S
CpL

Cp*

[N2(SiMe3)3]– formation suggested by DFT :(1) Y. Nishibayashi, K. Yoshizawa, et al.,J. Am. Chem. Soc. 2011, 133, 3498.
(2) C. C. Lu, et al.
J. Am. Chem. Soc. 2015, 137, 4638.

-N2

S

Me3Si
Na

S

Mo

S

Mo

S

CpL

THF THF

Mo S

Dimerization
-N2
CpR
S
Mo
S
CpR

CpR

Mo

S

Mo

SiMe3
SiMe3

N

M

S

CpR

Me3Si

Me3Si
N
CpR
N
S
SiMe3
CpR
N
S
Fe
Mo
Fe
Mo
S
S
Mo
S
Mo
S
S
S
CpR MoMe3Si・CpR Mo
CpR
CpR

N N

N

Fe

2Me3Si・

CpR

Cl

Mo

Cp*
K
S Mo
Cp*
S Mo S Fe N N Fe S Mo S
Cp*
Mo S
S Mo
K
Cp*
THF THF
Cp*

N2

Cp*

C

Cp*

Me3Si

S

-2

Cp*
S

CpL
S Mo
CpL
Fe S Mo S

Sponteneous
Clevage

Cp*=

Cp*

S

Mo

Na

Mo

-2.15

Expected Scheme of Catalytic Silylation

S
CpR

CpXL

-2.15

-1.94

Potential vs Ag/Ag+ (V)

2 N(SiMe3)3

THF
100h r.t.

-2.02

-1.04

-0.04

1

Catalytic Silylation of N2 by Mo-Fe-S clusters
Cluster
0.01 mmol

-0.94

-2.23

Wavenumbers /cm-1

monoclinic C2/c (#15)
R1/wR2 = 0.0418/0.1178
GOF = 1.024

-2.24

-1.02

-0.08
-0.29

1a

400

Mo

monoclinic P21/n (#14)
R1/wR2 = 0.0357/0.0940
GOF = 1.009

-1.10

-0.30

Cl

Fe

S

Mo

orthorhombic Cmc21 (#36)
R1/wR2 = 0.0446/0.1102
GOF = 0.956

1c(Fe-N2-K)
1922cm-1
2900

3400

Si

Cl

Cyclic Voltammetry

S

CpXL

FT-IR

1c
46% yield

Fe

1b

N
3900

CpXL=

Nature. Commun.
2018, 9, 3200.

1a
66% yield

Cl1) 2.3 eq. KC82) 1.0 eq. 15-crown-5

trace

Mo

N

Fe

S

Mo

NH3

~ 1.2 eq.

-0.15

K

S

S
CpR

Cp*

X-ray

2b
Cp*
S Mo
Cp*
Fe S Mo S

S Mo S Fe N N
Cp*
Mo S
K
Cp*
THF THF

Mo

Mo

N2
activation by
Mo-Fe-S
Cluster

S Mo

K
THF THF

N21) 2.2 eq. KC8

THF THFK

1) 1.0 eq. Na(C10H8)2) 1.0 eq. FeCl2

CpR

1) 2.3 eq. KC8

Cp*

CpR

N

H+
e-

Synthesis and Characterization of Mo-Fe-S clusters
CpR

N

NH3

S

S

Cp*
S Mo
Cp*
Ti S Mo SK

Mo S

S Mo S Ti
Cp*
Mo S
Cp*

N2

Extracted FeMo-cofactor

THF THF

Me3SiCl

N(SiMe3)3

N

SiMe3

P53

The 3rd IRCCS - The 2nd Reaction Infography Joint International Symposium: “Reaction Imaging Meets Materials Science”
Jan. 31, 2020, Noyori Materials Science Laboratory, Nagoya University

Direct monitoring of gas coordination-adsorption on MOFs
with an in situ XAFS system
Hirotoshi Sakamoto, Akihiro Hori, Hirosuke Matsui, Ryotaro Matsuda, Mizuki Tada
Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan
Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
Graduate School of Engineering, Nagoya University, Nagoya 464-8603, Japan
E-mail: sakamotoh@nagoya-u.jp

Backgrounds
MOF for Gas Separation

Self-Accelerating Adsorption Process(1) CO molecules coordinates to Cu2+ in the pore.

Small pore+

Cu(NO3)2·3H2O

MeOH/pyridine
R.T.

5-azidoisophthalic acid(H2aip)N2, 120 K

of [Cu(aip)][Cu(aip)](N3-Kagomé)(2) The pore expands to afford
extra space for CO accommodation.

CO, 120 K(3) CO molecules diffuse
into the depth of the pore.
COcoordination

Coordination Environment of Cu2+
-H2O
Vacuum
363 K

CO gas120 K
CO-coordinatedDried

As-synthesized(H2O-coordinated)

Direct information about the chemical state of Cu in [Cu(aip)]: Unavailable

Selective Adsorption of CO over N2

Objective: In-situ Monitoring of Cu2+ Coordination
Environment during the Gas Adsorption Process by XAFS

H. Sato, R. Matsuda, S. Kitagawa et al. Science, 2014, 343, 167-170

Construction of an In-situ Gas Adsorption-XAFS Measurement System
Cell Design¥¥¥

Prototype Cell

Whole System Setup

Attached on a Cryostat(at BL11S2/AichiSR: Hard X-ray XAFS)Path for gas
Heating
Attached to the cold head

HeaterSample{Gas

SampleHeat-insulating CoverWindow: Kapton
Inside: Vacuum

X-ray-transparent window¥ Inside: gas tight for pressure control¥

Temperature (10~400 K)
Gas pressure (vacuum~100 kPa)

Controllable at the sample position

Experiments, Results and Discussion
Dehydration Process (Temp. control)

CO Gas Introduction (Gas pressure control)[Cu(aip)(H2O)][Cu(aip)]

as-synthesized

298 K

Vacuum373 K

Vacuum298 K

VacuumDehydrated
As-syn
373KvacDehydrated
373 K~130K

298Kvac
130Kvac

0.4

1.6

1.4

1.4

1.2

1.2

1.0
0.8
0.6
0.4
0.2
0.0

As-synthesized
298 K

0.2
0.0

1.6

8960

8980

9000

Energy (eV)

9020

9040

As-synthesized(H2O-coordinated)

Distinct changes due to the change ofthe coordination mode of Cu2+ in [Cu(aip)]

Normalized χµ(E)1.0

Normalized χµ(E)Normalized χµ(E)

1.2

0.6

CO 100 kPa
82 K

Cu K-edge XAFSPlots of 373 K and 298 K are
overlapped on that of 130K

1.4

CO 100 kPa
120 K

130 K

Cu K-edge XANES

1.6

0.8

dehydrated

130 K

CO adsorption isotherm

CO 100 kPa
130 K

Cu K-edge XANES

1.0
0.8

130Kvac

130Kvac

120KCO
100kPa120KCO
100kPa82KCO100kPa

82KCO100kPa

130Kvacdesorpti
on

130Kvacdesorpti
on

0.6
0.4
0.2

8700

9200

Energy (eV)9700

Almost all spectra are overlapped

0.0

8960

8980

9000

Energy (eV)9020

CO-coordinated

?

9040

Dehydrated

Much smaller changes than those of the dehydration process• Small diﬀerence of chemical state between Cu…(CO) and Cu…(O of COO-)?

➡ EXAFS analysis, Theoretical calculation• CO molecules have not diﬀuse into the pore suﬃciently?

➡ In-situ XRD, Machine accuracy improvement

125

>ŝŐĂŶĚͲƉƌŽŵŽƚĞĚWƚEŝEĂŶŽƉĂƌƚŝĐůĞƐŝŶ,ŽůůŽǁWŽƌŽƵƐĂƌďŽŶ^ƉŚĞƌĞƐĂƐ,ŝŐŚůǇĐƚŝǀĞĂŶĚ^ƚĂďůĞKǆǇŐĞŶZĞĚƵĐƚŝŽŶZĞĂĐƚŝŽŶĂƚĂůǇƐƚƐ
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ĂƚĂůǇƐƚƐ^;ŵϮͬŐƉƚͿ/Ŭ;Ϭ͘ϵsͿ
;;ŵͬĐŵϮͿD
;ŵͬʅŐWƚͿ^;ŵͬĐŵϮWƚͿdϭϬϱϬϲϱ͘ϭϵцϯ͘ϲϰϳϯ͘ϱϴцϲ͘ϮϭϭϬϰ͘ϲϱцϳ͘ϴϭϳϰ͘ϰϮцϬ͘ϱϮϯϬ͘ϯϭцϭ͘ϭϵϰ͘ϰϴцϬ͘ϬϬϭϰ͘ϲϮцϭ͘ϲϲϱϵ͘ϮϳцϮ͘ϲϱϭϬ͘ϲϬцϬ͘ϳϯϭϳ͘ϱϲцϬ͘ϴϱϬ͘ϮϰцϬ͘ϬϮϬ͘ϳϬцϬ͘Ϭϴϯ͘ϮϱцϬ͘ϭϰϬ͘ϱϳцϬ͘ϬϯϬ͘ϴϴцϬ͘ϬϰϬ͘ϯϳцϬ͘ϬϯϬ͘ϵϱцϬ͘Ϭϯϯ͘ϭϭцϬ͘ϬϵϬ͘ϳϲцϬ͘ϬϱϮ͘ϵϭцϬ͘Ϭϯ

Wƚ;,ĚƉĂͿͬ,W^dZ
WƚEŝϭ͘ϮϮ;,ĚƉĂͿͬ,W^dZ
WƚEŝϭ͘ϮϮ;,ĚƉĂͿͬdZWƚEŝϭ͘ϮϮͬ,W^dZ^ͬŵϮ ŐͲϭͲϮũͬŵĐŵͲϮͬsǀƐ͘Z,ĂƚĂůǇƐƚƐ

ͬsǀƐ͘Z,ũͬŵĐŵͲϮ

DͬŵȝJ3W

^ͬŵĐŵ3W

ĂƚĂůǇƐƚƐ

126

DͬŵȝJ3W

ͬsǀƐ͘Z,EŽƌŵĂůŝǌĞĚ^ͬй͘ũͬŵĐŵͲϮũͬŵĐŵͲϮͬsǀƐ͘Z,

9 ŽŵďŝŶŝŶŐůŝŐĂŶĚͲƉƌŽƚĞĐƚŝŽŶǁŝƚŚŚŽůůŽǁƉŽƌŽƵƐĐĂƌďŽŶƐƉŚĞƌĞƐůĞĂĚƚŽŚŽŵŽŐĞŶĞŽƵƐůǇĚŝƐƚƌŝďƵƚĞĚƵůƚƌĂͲĨŝŶĞWƚEŝEWǁŝƚŚŚŝŐŚĐĂƚĂůǇƚŝĐĂĐƚŝǀŝƚǇĂŶĚƐƚĂďŝůŝƚǇ
9 DĂǆŝŵƵŵĂĐƚŝǀŝƚǇǁĂƐĨŽƵŶĚĨŽƌWƚEŝϭ͘ϮϮ;,ĚƉĂͿͬ,W^ǁŝƚŚŽŶĞŵĂŐŶŝƚƵĚĞŚŝŐŚĞƌŵĂƐƐĂĐƚŝǀŝƚǇƚŚĂŶƌĞĨĞƌĞŶĐĞWƚͬ;dϭϬϱϬͿ
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22
Topological molecular nanocarbons: all-benzene catenane and trefoil knot
Motonobu Kuwayama1, Yasutomo Segawa1,2,*, Yuh Hijikata2,3,4, Masako Fushimi1,2, Taishi Nishihara1,2,5, Jenny Pirillo3,4, Junya Shirasaki1,
Natsumi Kubota2, Kenichiro Itami1,2,3,*
JST-ERATO, Itami Molecular Nanocarbon Project, Chikusa, Nagoya 464-8602, Japan.
Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602, Japan.
4 Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Hokkaido 001-0021, Japan
5
Institute of Advanced Energy, Kyoto University, Uji, Kyoto 611-0011, Japan
1

2

3

ABSTRACTThe generation of topologically complex nanocarbons can spur developments in science and technology.
However, conventional synthetic routes to interlocked molecules require heteroatoms. We report thesynthesis of catenanes and a molecular trefoil knot consisting solely of para-connected benzene rings.
Characteristic fluorescence of a heterocatenane associated with fast energy transfer between two rings wasobserved, and the topological chirality of the all-benzene knot was confirmed by enantiomer separation andcircular dichroism spectroscopy. The seemingly rigid all-benzene knot has rapid vortex-like motion in solution
even at –95 °C, resulting in averaged nuclear magnetic resonance signals for all hydrogen atoms. This
interesting dynamic behavior of the knot was theoretically predicted and could stimulate deeper
understanding and applications of these previously untapped classes of topological molecular nanocarbons.
Y. Segawa, M. Kuwayama, Y. Hijikata, M. Fushimi, T. Nishihara, J. Pirillo, J. Shirasaki, N. Kubota, K. Itami, Science 2019, 365, 272-276.

RESULTS and DISCUSSION
1. Topological molecular nanocarbons

4. Synthesis of all-benzene catenane and knot
A

Cl
RO

I

OR
pinB

(i)

Br
Br

5

Br
Br

OR

X=I

RO

R = n-butyl
4a (X = Y = I) 56%
4b (X = I, Y = Cl) 15%
4c (X = Y = Cl) 50%

fullerenecarbon nanotube

ORRO

carbon nanotorus

RO
RO

(iv)

RO
RO

B

RO

OR

OR

8a
+ side products(not isolated)(ii)

all-benzene trefoil knot

O
O

O
O
O

O

B

N
N

N

Cu+

O

O

N

O

NH

N
H
NH

O

N
O

O

O

N
H

O

Electrostatic interaction

RO

O

N
H

4c

HN

O

O

H
N

HN

O

O

all-benzene trefoil knot 2

RO

Si

OR

OR

Cl

(vi)

+ [12]CPP
14%
a

OR

[9]CPP(iv)–(vi)

+

Cl

RO

OR

14%
[12]CPP

Cl

13%

RO

OR

OR

RO

1b
1.5% based on 7bOR(v),(vi)

OR

RO

RO
OR

OR

OR

1a + [12]CPP
0.2%
6.1%

c
a

OR

11
+ side products(not isolated)

10
86%

+

Si

5. Properties of all-benzene knot
AB

2
0.3% based on 10

C4

CD (mdeg)

F–, ROH
cycloparaphenyleneÞrst fraction2

left-handed (Ð)

0–2catenanecDsecond fraction

–4
250

b

D

F–, ROHb1a
16% based on 7a

OR

RO

Cl

7a
57%

OR

OR

OR

RO

Si

RO
RO

OR

OR

RO

(iv)

OR

7b
41%

Cl
Cl

OR

(i) 4 steps. (ii) catalytic Pd(PPh 3)4, K 2CO 3, toluene/EtOH/water or THF/DMF/water, reflux. (iii) n-BuLi; then TMEDA, SiHCl3, THF/Et2O. (iv) Ni(cod) 2,2,2'-bipyridyl, DMF. (v) n-Bu 4NF, THF/EtOH. (vi) Sodium naphthalenide, THF; then I2. Abbreviations: THF = tetrahydrofuran, cod = 1,5cyclooctadiene, DMF = N,N-dimethylformamide, TMEDA = N,N,N',N'-tetramethylethylenediamine, Bpin = 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.

C. J. Bruns, J. F. Stoddart, The Nature of the Mechanical Bond: From Molecules to Machines, Wiley-VCH, Weinheim, 2016.

C

RO
RO

RO

Hydrogen bonding

3. Synthetic
strategy for all-benzene catenane and knot
Si
Si

RO
RO

Synthesis of catenanes requires coordinating / polar functional groups.
all-benzene catenane 1a

(iii)

OR

Si
RO

RO

6b
58%

C

O
O

O

O

Cu(phen)2 complexation

O
N

O

O

N
N

O

corannulene

O

O

RO

RO

Cl

RO

OR
OR

RO

OR

Cl
Cl

(iii)

RO

2. Conventional synthesis of catenanes
O

Cl

RO

RO

9a
+ side products(not isolated)

RO

6a

Br
Br

RO

OR
Cl
Cl

Si

OR

RO

OR
OR

5

RO

RO
RO

RO

cycloparaphenylene

RO

OR

RO

4b

OR

OR

RO

RO

(v)

Si
RO

corannulene

OR

OR

OR

RO

OR

RO

OR

RO

Cl
Cl

OR

6a
57%

RO
OR

RO

(iii)

OR
RO

OR

RO

Cl
Cl

Br
Br

Y

RO

RO
OR

RO

(ii)

RO

3

OR

RO

X

RO

I

E

300

350
400
Wavelength (nm)

450

500

right-handed (+)–25 °C1a

all-benzene trefoil knot

–95 °C

trefoil knot

–25 °C–95 °C

2

R4N+F–SiF

CH2Cl2Si

if EtOH99%–25 °C2ßuoride sensor
Lenormand, H.; Goddard, J.; Fensterbank, L. Org. Lett. 2013, 15, 748.

[12]CPP
7.8–95 °C
7.6

7.4
7.2
Chemical shift (ppm)

7.0

6.8

127

Synthesis of a Zigzag Type Carbon Nanobelt
Kwan Yin Cheung1 Yasutomo Segawa2,3,*, Kenichiro Itami1,2,3,*
1 Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Chikusa, Nagoya 464-8602, Japan.
2 JST-ERATO, Itami Molecular Nanocarbon Project, Chikusa, Nagoya 464-8602, Japan.
3 Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.

INTRODUCTION
Carbon nanobelts, the fully fused polyaromatic hydrocarbons resembling sidewall segment of carbon nanotubes, are gaining much attention recently since the synthesis of the firstcarbon nanobelt in 2017.1 Similar to carbon nanotube, carbon nanobelt can be classified into three classes such as armchair, chiral, and zigzag types according to their sidewall
structures. Until now, only armchair2 and chiral3 type carbon nanobelts were reported while zigzag type carbon nanobelt remains a challenging synthetic target.4
Herein we report the synthesis of the first zigzag type carbon nanobelt. The synthesis involves an iterative Diels–Alder reaction sequence followed by reductive aromatization
reactions. Being a benzannulated [18]cyclacene with fully benzenoid structure, this zigzag nanobelt is isolated as a stable compound, in stark contrast to the still elusive parent
cyclacenes. The structure of this nanobelt is fully characterized by X-ray crystallography and its photophysical properties elucidated by UV-vis absorption and fluorescence spectroscopy.

RESULTS and DISCUSSION• Synthesis and crystal structure• Structures of different types of carbon nanobelts
and their synthetic strategies

Armchair Carbon Nanotube

Chiral Carbon Nanotube

Zigzag Carbon Nanotube• Molecular design of the target zigzag-type nanobelt

orthorhombic, Pnnm
R1 = 0.1268 (I>=2σ (I)),
wR2 = 0.3955 (all data)• Structural analysis• Photophysical Properties
1.8• Aromaticity analysis
supports a fullybenzenoid structure

1.4

ε (105 M-1 cm-1)

1.2

ΦF = 10%
τ = 9.25 ns
λex = 320 nm

1

0.8

0.6

(x10)

0.4

normalized fluorescence intensity

1.6

0.2

0

250

300

350

400

450

wavelength (nm)

128

500

550

600

• Reference
(1)
(2)
(3)
(4)

G. Povie, Y. Segawa, T. Nishihara, Y. Miyauchi, K. Itami, Science 2017, 356, 172.
G. Povie, Y. Segawa, T. Nishihara, Y. Miyauchi, K. Itami, J. Am. Chem. Soc. 2018, 140, 10054.
K. Y. Cheung, S. Gui, C. Deng, H. Liang, Z. Xia, Z. Liu, L. Chi, Q. Miao, Chem 2019, 5, 838.
R. Gleiter, B. Esser, S. C. Kornmayer, Acc. Chem. Res. 2009, 42, 1108.

129

130

131

132

133

134

Catalytic C-H Arylation of Cubane
toward Synthesis of Novel 3D Molecules
Ryo Okude1, Genki Mori1, Akiko Yagi1,2, and Kenichiro Itami1, 2, 3

ITAMI GROUP

1) Graduate School of Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan.
2) JST, ERATO, Itami Molecular Nanocarbon Project, Nagoya University , Japan
3) Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, JapanAr
LiTMP,
ZntBu 2Rthen,
Pd cat.
Ar-I

HR'
R = CONiPr

R

2

R' = CONiPr 2 or CN

Ar-I

Ar-I

Ar

R'

Ar

Monoarylcubane

Cubane, which is a cubic alkane rst synthesized by Eaton in 1964, has been
widely utilized as a unique 3D building block. Despite high potential utility of
cubane derivatives, the synthesis has mainly relied on the transformation of the
carboxyl or halogeno groups on cubane. To create novel 3D molecules based on
cubane, we envisioned to establish a universal method for functionalization of
cubane. In this work, identied arylcubane as the rst and high value target, acatalytic C–H arylation of cubane was developed. This arylation allowed to
install a wide variety of aryl groups and realized the synthesis ofmultiarylcubanes as well.

R
Ar

R'

Multiarylcubane· Programmable synthesiss· Chiral arylcubanes
aryl
y cubanes· 16 examples, up to 82%

RGANIC CHEMISTRY

Okude, R.; Mori, G.; Yagi, A.; Itami, K. manuscript preparation

1. Background3. Scope of Aryl Groups for Monoarylcubane
LiTMP 2.0 eq.
ZntBu2 2.0 eq.
THF, rt, 12 hR

1 : 50 μmol

then,
Pd2(dba)3•CHCl3 10 mol%P(OPh)3 80 mol%

R = CONiPr 2I

R

Cubane (C8H8)2015 Senge et al.
Pd cat.
Ar-I or
Ar-B(OH)2R

No ConvertionorO
X = I, ZnCl, B(OH) 2 etc. Decomposition

O

31%

0-58%

O

N iPr 2MeOON iPr 2iPr N
2N iPr 2

iPr N
2

O

O

1999 Uchiyama et al.

I

EtO

O

Scope of Diarylcubanes

O

TMPZntBu 2Li

I

ZntBu 2Li

O

O

F 3C

N iPr 2

D

iPr N
2

O

N.D.

LiTMP 2.0 eq.
ZntBu2 2.0 eq.
THF, –78 ºC→0 ºC, 3 h

NiPr2

NC

CF3
48% (1000 μmol)
442% (5000 μmol)

NLi

3a : 73%

NiPr2

NC

CF3

Diarylcubane
Chiral cubane

EtO2C

Br

O

O

NC

LiTMP

then,
Pd2(dba)3•CHCl3 10 mol%P(OPh)3 80 mol%RI
8.0 eq.

[a] 2 : 0.20 mmol, coupling time = 24 h.
[b] 2 : 0.15 mmol, coupling time = 18 h.
[c] 2 : 1.7 mmol, coupling time = 15 h.

Br

NC

O

R

THF, rt, 12 h

NC

CF3

16%[a]

O

NiPr2

NiPr2

NiPr2

O

O

CF3 8.0 eq.

O
EtO: 54%[d]then,D 2O 30 eq.
THF, rt, 30 min

THF, rt, 12 or 24 h

iPr N
2

Bashir-Hashemi, A. J. Am. Chem. Soc. 1988, 110, 7234.

Pd(PPh 3)4= 1-isoquinolyl

ZntBu 2 2.0 eq.
LiTMP 2.0 eq.
THF, rt, 12 h

N iPr 2
iPr N
2

then,
Pd2(dba)3•CHCl3 10 mol%P(OPh)3 80 mol%O

53%

C–H arylation of arene via directed ortho-metalation: 22%[a],[c],[d][a] 0.05M Pd2(dba)3·CHCl3/P(OPh)3=1/4 THF solution 10 mol%, rt, 24 h.
[b] 1 : 0.10 mmol. [c] 1 : 0.10 mmol, orthometalation : 1 h.
[d] Pd2(dba)3·CHCl3 20 mol%, P(OPh)3 160 mol%O

LiTMP 2.0 eq.
ZntBu2 2.0 eq.
THF, –78 ºC→0 ºC, 3 h

NiPr2

N iPr 2

Limitationof arenes

MgBr

O

Br

excess= 3-thienyl

50 μmol

NC

O

BrMg

LiTMP
MgBr 2•Et 2O

R: 54%[d]Het = 3-pyridyl
Het

Cl

Cl

C–H phenylation of cubaneO: 18%: 19%[a],[c]

R'
R

F 3C

N.D.

Senge, M. O. et al. Organometallics 2015, 34, 1408. Baran, P. S. et al. J. Am. Chem. Soc. 2016, 138, 11132.
Senge, M. O. et al. Chem. Eur. J. 2018, 24, 1026. Uchiyama, M. et al. Chem. Sci 2019, 10, 6107.

1988 Bashir-Hashemi et al.

: 76%
: 82%
: 59%
: 49%
: 48%
: 52%
: 51%
: 37%

then,
PhCHO 8.0 eq.
THF, rt, 5 h

O

O
Cl

Cl

OH

iPr N
2

O
N

ZntBu 2 2.0 eq.
LiTMP 2.0 eq.
THF, rt, 12 h

O

F 3C

O

R' = Me
= CF3

: 57%

4. Synthesis of Diarylcubanes

2018 Senge et al.

Ni cat.
dtbbpyArZnCl•LiCl

O

O
N

O

then Pd cat., SPhos,
2-Iodomesitylene

iPr N
2

O

MeO

· Bioisostere of biarys· Building blockfor 3D materials

tBuLi, CuI

I

18-25%

Arylcubane

2019 Uchiyama et al.

O

R'

O

Fe cat.
dppBz
Ar2Zn

R

MeO

EtO

R

2016 Baran et al.
X

R

R' = CN= CF 3
= tBu
= Me
= Ph
= CO2Et= SO2Et= CONEt2: 55%: 51%[a],[b]= 2-naphthyl

8.0 eq.

R

Novel 3D materials

Synthesis of arylcubane; A cubane derivative promising as a unique material
ArR

R'' = Me
= CF3

R'
R

Ar

THF, rt, 48 h・Unique 3D structure
・Stable under 220 °C
・Bioactive derivatives

Diverse chemical space

Ar

R

R

NC

CF3

NiPr2

NC

CF3

27%[b]

CF3

25%[b]

58%

Uchiyama, M. et al. J. Am. Chem. Soc. 1999, 121, 3539.

O
N iPr 2O

N iPr 2

OH
iPr N
2

O

Plausible intermediate

50 μmolO
N iPr 2

ZntBu 2Li

iPr N
2

O

O
N iPr 2iPr N
2

O

50 μmolthen,
Pd 2(dba) 3·CHCl 3 5.0 mol%
Ligand X mol%
CN 8.0 eq.

I

entry

Metal amide baseX

1H NMR yield

1

iBu Al(TMP)Li
3

5.0

N.D.

2

MeCu(TMP)(CN)Li 2

5.0

N.D.

3

tBu ZnTMPLi
2

5.0

96%

4

tBu ZnTMPLi
2

2.0

92%

5

nBu ZnTMPLi
2

2.0

98%

6

LiTMP + ZnCl2

2.0

N.D.

NC

O

THF, rt, 48 h
X-ray crystal structure
Orthorhombic, Pbca
GOF = 1.017
R1 = 0.0484
wR2 = 0.1094

entry
N iPr 2

iPr N
2

O

CN

LigandX

1H NMR yield

1

PPh 3

40

28%

2

P(2-furyl) 3

40

N.D.

3

dppe

20

2%

4

dppp

20

13%

40

<1%

40

1%

5
6

P

O

CF 3
P(OEt) 3

3

7

P(OPh) 3

40

58%

8[a]

P(OPh) 3

80

84%[a] Pd2(dba)3·CHCl3 10mol%

NC

CF3

27%[a]

CF3

64%[c]

5. Synthesis of Triarylcubanes
NC

3aMonoclinic, P21/n
GOF = 1.106
R1 = 0.0615
wR2 = 0.1466

NC

ZntBu2 2.0 eq.
LiTMP 2.0 eq.
THF, temp., 3 h

O
NiPr2

NC

LiTMP 2.0 eq.
ZntBu 2 2.0 eq.
THF, rt, 12 h

NiPr2

NiPr2

O

Metal amide base X eq.
THF, rt, 12 h
then,
PhCHO 8.0 eq.
THF, rt, 5 h

iPr N
2

O

O

2. Divelopment of C–H Arylation of Cubanediamide

CF33a
50 μmol

Ph
OHO
NiPr2

then,
PhCHO 8.0 eq.
THF, rt, 5 h

NC

CF3

17 %[a] (temp. = –78 ºC)
N.D. (temp. = –20 ºC)
In both condition, all of 3a was comsumed

LiTMP 2.0 eq.
ZntBu2 2.0 eq.
THF, –78 ºC→0 ºC, 2 h

O
NiPr2

NC

0.40 mmol

CF3

then,
Pd2(dba)3•CHCl3 10 mol%P(OPh)3 80 mol%I

8.0 eq.

THF, rt, 12 h[a] 1H NMR yield

O

O

NiPr2

NiPr2
NC

11%

Triarylcubane

CF3

NC

CF3

Enantiomer

Chiral cubane

135Development of a Synthetic Method for Unsubstituted Nanocarbons
Shusei Fujiki,a Akiko Yagi,ab Kenichiro Itamiabc

ITAMI GROUP

aGraduate School of Science, Nagoya University, JapanRGANIC CHEMISTRY

bJST, ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Japan

cInstitute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Japan

Solubility Problem

Nanocarbons are promising candidates for electronic devices. Because of their strong
intermolecular interaction, nanocarbons easily form the aggregates. In order to suppress
the aggregation, long alkyl or alkoxy chains are often installed as substituents in thesynthesis of nanocarbons. Since the substituents cause the change of physicalproperties, a synthetic method for unsubstituted nanocarbons is highly demanded.
Herein, we report new synthetic methodologies circumventing this problem.
Unsubstituted nanocarbons was successfully synthesized with the aid of cross-linked
polystyrene or sterically demanding dendrimer-like molecule. The result implies thatstrong aggregation of nanocarbons are effectively hampered by this strategy.

m-up synthesis

Unsubstituted nanocarbon: promising candidate for electronic devices

Aggregation

Strategies toward Unsubstituted Nanocarbons
polymer chain

dendrimer-like molecule

polymer beads

Segregation of easy-to-aggregate nanocarbons

Segregation by cross-linked polymer

Solid-phase Synthesis

Segregation by dendrimer-like molecule

Dendrimer-supported Synthesis

Solid-phase Synthesis

Conventional Liquid-phase Synthesis
solubilizing groupnOlinear polystyrene

n

OH

HO

linear PEG

O
OH

O

…

n

…

cellulose

poorly soluble molecules
This Work : Developement of solubilizing group optimazed for nanocarbon synthesis
functional group

Synthesis of Dendrimer-like Support

Synthetic Strategy toward Poly(p-phenylene)
Br

Ar

MeO

O
B

Ar

O

OR

RO

unsubstituted poly(p-phenylene)

O

OH

OR

Choi (2018)

HO

HO

Br

B(pin)

1: 1% cross-linked polystyrene (loading: 0.46 mmol/g)

I

NC

B(pin)DME or CPME

OMe

HO

S

borylation

toluene/EtOH/H2O
90 °C, 24 h

OR
O

O

OR

Br

OR
OR

[94%]

OR

R=

S

(RO)2B

NC

Br

NC

S

C6H13

L
Pd I

polymerization

H
n

3 cy
cycles

RO

Br

S

S

Pd
L

S

S

S

Br

S

(15 equiv)S

I

polymerization

S

S

S

S

cleavage

S

S

S

S

OR

=

O

crosscoupling

THF/H2O
50 °C, 45 min
S(RO)2B

O
O

OR

B(pin)

Br

Br

OR

K2CO3
DMF
70 °C, 24 hO
OMe

XPhos Pd G3
XPhos
K3PO4
Br

O

H+
cleavagefrom resin

136

OH O

O

THF/H2O
50 °C, 45 min

O

THF

O

HO

O

RuPhos Pd G3
RuPhos
K3PO4

O

a : Result was determined byy 1H NMR.

Detected by LDI-TOF MS

THF
rt, 1.5 h

OR

OR

OR

2

Elongation of phenylene chain
O

PPh3
NBS

OR

Seo, K.-B.; Lee, I.-H.; Lee, J.; Choi, I.; Choi, T.-L. J. Am. Chem. Soc. 20188, 1400, 4335.

resultta
1
1 : 2 = 10 : 1
2

Br

LiAlH4
THF
0 °C, 10 h
[62%]

OR

OR

cleavagecleavaggefrom resin

B(pin)

cat. Pd(PPh3)4
K2CO3

HO

Dendrimer-supported Synthesis of PolythiopheneH+solvent
80 °C, 24 h

Br

OR

RO

O

Reaction condition of Miyaura borylation

solvent
THF
DME
CPME

OR

O

Solid-phase Synthesis of Poly(p-phenylene)

Br

THF
0 °C, 10 h
[92%]

OR

O

OR

DIBAL-HOR

OH

Miyaura borylation

O

OR
MeO

Br

Ar

B2((p
(pin))2
cat. Pd(OAc)()2
cat.XPhosat.XPhos
KOAc

R-OTs
K2CO3
DMF
70 °C, 14 h
[85%]

OH
OH

O

Suzuki–Miyaura
cross-coupling
Ar

OH

Br

OR
OR

R=

MALDI-TOF MS spectrum of unsubstituted polythiopheneDirect C–H Borylation of Pristine Hexabenzocoronene
Chem Soc Rev

View Article Online

Review ArticleITAMI GROUPRGANIC CHEMISTRY

material (usually by centrifugation). Although van der Waals realized that closer surface energies between graphene andaa forces are classified asaweak attractive interactions, they play aa,bsolvent diminish the mixing enthalpy
a,b,cfavouring exfoliation.
major role in graphite maintaining the graphene layers stacked They tested graphite exfoliation in a wide range of solvents,
following an AB or Bernal-stacked pattern structure (Fig. 1b).50 measuring the resulting concentration of the graphene disperaThus,School
the successful
exfoliationof graphite
towardsJapangraphene sions after ultrasonication and centrifugation using UV-vis
Graduateof Science,
NagoyaUniversity,
should necessarily overcome the van der Waals attraction spectroscopy. The best performances were obtained for lowbJST, ERATO, Itamibetween
Molecular
Nanocarbon
Project,
NagoyaUniversity,
viscosity solvents, with a surface tension (g) of 40–50 mJ m2 atadjacent
layers by applying
external
physicalforces. Japan
cInstitute of Transformative
In this regard,
the mechanicalliquid phase
exfoliationof room
temperature and for short sonication times (long or
Bio-Molecules(WPI-ITbM),
NagoyaUniversity,
Japangraphite combines a liquid immersion that diminishes the intensive sonication periods can cause solvent degradation,
strength of the van der Waals interactions and allows the liquid thus changing its properties).100 The most popular candidates
to slide between sheets favouring their separation, and an for the liquid exfoliation protocol are N-methyl pyrrolidone
The physical and electronic properties of polycyclic aromatic hydrocarbons(PAHs), fused
ultrasonication process, as an exfoliation strategy (Fig. 17a). (NMP, g = 40 mJ m2) (inBpin
a recent report used in combination2
structure.
In that usually exist in the liquid areHBpin
arenes that consist of sp -hybridized carbon atoms, depend strongly on
Thetheirmicroscopic
gas bubbles
with a-functionalized alkanes),103 o-DCB (g = 37 mJ m2), and
pinB
Bpin
Ir cat.
submitted
toanacoustic
field(soundenergyoffrequencies
N,N-dimethylformamide(DMF,
g = 37.1 mJ m2), which allspite of the strong demand of concise and practical methods for the functionalization ofligando20 kHz), oscillating and growing in size until they rapidly
present surface energy values within the previously mentioned
PAHs, there have been few reports on the direct functionalization of largecollapse
PAHs.by a pressure increase. This physical phenomenon, range.102 However, even when the sonication protocol produces
In this study, we have established conditions for Ir-catalyzed six-fold
C–Hcavitation,
borylationof compressive stress to the bulk pristine graphene
calledinducespinB of high quality andBpinin amounts suitable forgraphite, and overcomes the van der Waals forces resulting in laboratory experiments, the concentration of the graphene
pristine hexabenzocoronene (HBC).
exfoliation.100,101
dispersions obtained doesBpin
not exceed 0.01 mg mL1, which ispristine HBC
Acknowledgement: Prof. Dr. Tsuyohiko Fujigaya for fruitful discussion.
It has been demonstrated that the liquid phase exfoliation of unfeasible for applications in the industrial field. Alternativegraphite can only take place through a small energetic cost strategies that have been explored to increase the graphene’s(mixing enthalpy per unit volume).102 Coleman and co-workers concentration, while maintaining the quality of the flakes, arePublished on 12 July 2017. Downloaded by Nagoya Daigaku on 9/14/2019 2:43:09 AM.

Mai Nagase, Kenta Kato, Akiko Yagi, Yasutomo Segawa, Kenichiro Itami,

1. Functionalization of pristine PAHs
- Planar PAHs

pinB

pinB

Bpin

pinB

Bpin

pinB

Bpin

pinB

Bpin

tetraborylated pyrene

RESULTS

3. NMP as a magic solvent for nanocarbons

pinB

Bpin

pinB

Bpin

(1) Coventry, D. N.; Batsanov, A. S.; Goeta, A. E.; Howard, J. A. K.; Marder, T. B.; Perutz R. N. Chem. Commun. 2005,
41, 2172.
(2) Eliseeva, M. N.; Scott, L. T. J. Am. Chem. Soc. 2012, 134, 15169.

Cl
Cl

Cl

ICl, AlCl3

Cl

Cl
Cl

CCl4, 80 ºC

Cl

NMP

graphite(1) Bottari, G.; M. Á. Herranz, Wibmer, L.; Volland, M.; Rodríguez-Pérez; L.; Guldi, D. M.; Hirsch, A.; Martín,N.; D′Souza, F.; Torres, T. Chem. Soc. Rev. 2017, 46, 4464.
(2) Bergin, S. D.; Nicolosi, V.; Streich, P. V. ; Giordani, S. ; Sun, Z.; Windle, A. H.; Ryan, P.; Niraj, N. P. P.;
Wang, Z.-T. T.; Carpenter, L .;Blau, W. J.; Boland, J. J.; Hamilton, J. P.; Coleman, J. N. Adv. Mater. 2008, 20,
1876.

NMP = N-methylpyrrolidone

Cl
Cl

Cl
Cl

exfoliation

O
B
O

Bpin =

hexaborylated coronene

tetraborylated peryleneplots of C/(S – S0) versus C for the known molecular weight(Mw) standards and literature values for B2 to be K0 ¼
1.0325(5) m3 mol kg�1 and K00 ¼ 9.0570(5) m3 mol kg�2.
Subsequent measurement of B2’s and x’s for known
materials were uniformly within a few percent of theliterature values.[31] A plot of CNT/(S – S0) versus CNT for
NMP
SWNT in NMP (Fig. 2B) was fit with Equation 5 giving
B2 ¼ 1.78 � 10�3 m3 mol kg�1. Taking the density[19] of
HiPco nanotubes as 1830 kg m�3 and VS ¼ 96 �
10�6 m3 mol�1 we calculate a value for x ¼ �0.074. Thatx < 0 confirms the solubility of nanotubes in NMP. The small
size of x shows that dissolution in these systems is weakly
SWNT:
single-walled
energydriven and hence does not require mixing entropy
carbonnanotube
whichwould be very small for such large rigid objects. As
such these solutions are reminiscent of athermal solutionsof rigid rod polymers.[32] The assumption of rNT ¼
1830 kg m�3 is the limiting factor in the accuracy of x. In
Heranandez, Y.; Nicolosi, V.; Lotya, M.; Blighe, F. M.; Sun, Z.; De, S.; McGovern, I. T.; Holland, B.;
fact, x, S.;
andGoodhue,
so DHMix
Byrne, M.; Gun’ko, Y. K.; Boland, J. J.; Niraj, P.; Duesberg, G.; Krishnamurthy,
R.; , is negative as long as the nanotube
Hutchison, J. Scardaci, V.; Ferrari, A. C.; Colemen, J. N. Nat. Nanotechnol.density
2008, 3, 563.
is greater than 1700 kg m�3, suggesting that only
nanotubes with diameters less than 1 nm are soluble.[19] Thisis supported by the lack of high-diameter nanotubes observedin the PL.

Bpin– Absorption spectra of HBC at 60 ºC

We can use Equation 3 to calculate the enthalpy of mixing of
nanotubes in NMP, giving an experimentally determined valueof DHMix per mole to be �720 kJ mol�1. Adding the entropic
contribution of �49 kJ mol�1 gives a total Gibbs energy of
mixing of �770 kJ mol�1 (�8 eV/SWNT) in the concentrationCl
HBC
range studied.
Tan, Y.-Z.; Yang, B.; Parvez, K.; Narita, A.; Osella, S.; Beljonne, D.; Feng, X.; Müllen, K. Nat. Commun. 2013, 4, 2646.
Finally, we address the role of the initial sonication, and theaffinity of NMP for the tubes themselves. NMP was evaporated
from nanotube solutions to form a dry powder, which was
Bpin Bpin
transferred to a fiberglass substrate and used in a contactFigure 2. Fraction of nanotubes remaining after centrifuging dispersions
transfer process[33] to deposit tubes on a Si(100)-2 � 1 surface(C ¼ 0.1 mg mL�1) made in a range of solvents as a function of solvent
under ultrahigh vaccum (UHV;3 � 10�11 mbar) conditions.
surface tension (bottom axis). The best 12 solvents were measured 5 times
This sample was then characterized using scanning tunneling
pinB
Bpin
and the mean and standard deviation plotted (Supporting Information).
HBpin
microscopy (STM). Figure 3A shows two bundles on what was
The top axis shows the approximate solvent surface energy. The horizontal
Bpin
Bpin
[Ir(OMe)cod]2
pinB
initially an atomically clean surface. Neither the surface nor thearrow shows the approximate range of measurements of nanotube andtmphengraphite surface energy reported in the literature. The vertical arrows
tubes can be imaged with atomic resolution. Figure 3B shows a
Temperature variable UV/vis spectrometer
indicate four typical literature values. B) The slope of an inverse scattering
similarsample that had been annealedfor 30 min at
cyclopentyl methyl ether (CPME)
pinB
Bpin
intensity plot yields the 2nd virial coefficient usedHBpin
to determine
theFH(18 equiv)
approximately 340 8C in UHV. Both the surface and tubes
120 ºC, 24 hparameter.
[Ir(OMe)cod](15M.;mol%)Solubility of HBC at r.t.: Hughes, J. M.; Hernandez, Y.; Aherne, D.; Doessel, L.; Müllen, K.; Moreton, B.; White,
T. W.; Partridge, C.; Costantini, G.; Shmeliov,
A.; Shannon,
Nicolosi, V.;
are now atomically resolved. Similar results are routinely
Coleman, J. N. J. Am. Chem. Soc. 2012, 134, 12168.
tmphen (31 mol%)
pinB
Bpin
obtained when pristine, non-solvent-treated tubes are used,solventtmphen =indicating that the poor resolution in Figure 3A is due to the
80 °C, 2 dayspresence of NMP molecules on the surface. NMP is expected towarped nanographene
Bpin
pinB
N N
Fig. 17 (a) Schematic representation of the sonication-induced, liquid-phase exfoliation of graphiteusing ratio,
NMPisasrelated
representative(b) Chemical
Rayleigh
to CNT viasolvent.
B2 throughthe Debye chemisorb
pinB on the Si(100) surfaceBpin
through the nitrogen75%
structures of solvents and ionic liquids used in graphene exfoliation and discussed in the text.
light scattering equation,[20,30] which for experimental containing group,[34,35] so that, on contact, the surface
convenience can be expressed as
effectively titrates molecules that are present in the dried
Bpin
bundles. In addition, some NMP remains tenaciously bound toKato, K.; Lin, H. -A.; Kuwayama, M.; Nagase, M.; Segawa, Y.; Scott, L. T.; Itami, K. Chem. Sci. 2019, 10, 9038.
B2
1
CNT
the tubes even under UHV conditions. However, the¼ CNT þ(5)
Bpin
reversibility of the NMP-tube binding interaction is clearly
S � S0 K 0
Mw K 00
4478 | Chem. Soc. Rev., 2017, 46, 4464--4500
This journal is © The Royal Society of Chemistry 2017 evident from the perfection of the bundle surface after
HBpin (18 eq.)
1H NMR(Fig.
where S and
S0 are dimensionlessentry numbers proportional
solvent to annealing
yield3B), indicating that the NMP physisorbs onto
pinB
Bpin
[Ir(OMe)cod]2 (15 mol%)the solution and pure solvent scattering intensities respec- the nanotube surface, a prerequisite for any effective solvent.
tively.[29] The quantities K0 and
1 K00 are instrumental
28% we often find evidence for molecules emerging
CPME con- Remarkably,tmphen (31 mol%)stants unique to our SLS instrument and were obtained from from bundles (circles in Fig. 3B), but which ultimately migrate
X
X

Cl

Cl
Cl

Cl
Cl

Cl

chemdrawもとのサイズ
Bpinいつも青にせず
NMP
THF
Mesitylene
CPME- Nonplanar PAHs

NMP is a good solvent
also for HBC

4. Direct C–H borylation of pristine HBC

Nonplanar structure increases the solubility of PAHs

2. Heteroatom-substituted HBCs
- Halogenated HBCs
X

X

X

X

FeCl3
CH3NO2CH2Cl2X

2solvent
80 ºC, 2 days

X

pinB

Bpin

Bpin

1

X

2

X

(1) Kikuzawa, Y.; Mori, T.; Takeuchi, H. Org. Lett. 2007, 9, 4817.

Bpin ArAr

Bpin Ar

Ar

Bpin
Ar

Ar

Ar pinB
Bpin

Ar

I

I

(i)

dtbpy = 4,4′-tBu2bipy

Bpin

Ar

I

I

www.advmat.de

I

(ii)

I

1

I
I
3

Bpin2 or 3

R3 or 4

Mesitylene / tBuOMeortBuOMe

13%

I

I
2

B2pin2[Ir(OMe)cod]2
dtbpy

R3 or 4I
I(2) Wu, J.; Fechtenkötter, A.; Gauss, J.; Watson, M. D.; Kastler, M.; Fechtenkötter, C.; Wagner, M.; Müllen, K. J. Am.
Chem. Soc. 2004, 126, 11311.

- Borylated HBCs

5.0%

 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

X = F, I

X

X

b

THF

NMP

3

Adv. Mater. 2008, 20, 1876–1881

Ar

tBu

Bpin

tBu

Ar

tBu

tBu

insoluble

Top view

Side view

Packing structure

cubic, Pa-3
GOF = 1.063
R 1 = 0.0705,
wR 2 = 0.2192

Slightly distorted tohave S6 symmetry

No π–π stacking is observed.

– UV/vis absorption and ßuorescence spectraof hexaborylated HBC
353 369Ar =1 in NMPε = 1.65 × 105 M–1·cm–1

2 in CH2Cl2(1) Yamaguchi, R.; Hiroto, S.; Shinokubo, H. Org. Lett. 2012, 14, 2472.

OMe

R

R

R

R
OMe

OMe

R

R
FeCl3
CH3NO2CH2Cl2

R = C12H25

R

R

R

R

normalized intensity(2) Ryuichi Yamaguchi, Ph.D. thesis, 2014, Nagoya University.

Unexpected rearrangement caused by Scholl reaction

400
337 352

O

O

R

300

OMe
70%

384

350

400

509
499

477

(×20)

R

LUMO –1.46 eV

ΦF = 2.5%
τ = 12.4 ns

447

546
534

476

450
wavelength (nm)

500

550

600

Red-shifted from HBC because of the σ-donation of boryl groups

not detected

Dou, X.; Yang, X.; Bodwell, G. J.; Wagner, M.; Enkelmann, V.; Müllen, K. Org. Lett. 2007, 9, 2485.

normalized intensity

353 369

Calculated at B3LYP/6-31G(d)1 in NMPε = 1.65 × 105 M–1·cm–1

2 in CH2Cl2

ΦF = 2.5%
τ = 12.4 ns
400
337 352

477

384

(×20)
300

HOMO –4.89 eV

350

400

499

509

447

450
wavelength (nm)

137

546
534

476

500

550

600

Stereoselective benzylic hydroxylation
catalyzed by cytochrome P450BM3 with Decoy Molecules

Kazuto Suzuki,a Joshua Kyle Stanfield,a Sota Yanagisawa,a Hiroshi Sugimoto,b,c Yoshihito Watanabe,d Osami Shojia,ba Dept. of Chem., Grad. Sch. of Sci., Nagoya Univ., b CREST, Japan Science and Technology Agency, c RIKEN SPring-8, Harima Inst., d Reserch Center for Materials Science, Nagoya Univ.

Background
Cytochrome P450BM3

Non-Native Substrate Hydroxylation by Substrate-Misrecognition System

Native reaction: fatty acid hydroxylation

P450BM3’s stringent substrate-specificity for fatty acids
have prevented the application of the enzyme
to an oxidative catalyst bearing substrate generality.

O2, 2H+, 2eP450BM3

Substrate binding mode

PropaneP450BM3

Propane, which structure is totally different
from fatty acids,
cannot be recognized as a substrateand hydroxylated by P450BM3.

Gln73
Arg47

Ala74
Carboxylate

PFC9-Trp

Decoy Molecules
Native substrate mimics, which can trick
P450BM3 into catalyzing hydroxylationof non-native substrates

PropanolBinding of the decoy molecule
activates P450BM3,
leading to the formation of propanol.

P450BM3

P450BM3

Tyr51

PDB: 1JPZ

Heme
D. C. Haines et al., Biochemistry, 2001

O2, 2H+, 2e-• A monooxygenase, which catalyzes the hydroxylation of long-chain
fatty acids at the sub-terminus

Heme• Fatty acid is bound to P450BM3 through hydrogen-bonding interactions.

Catalytic Cycle
Substrate R-H binding

Activation of molecular oxygen

R-H
Heme

-

S

R-H

O2, 2H+, 2e-

FeIII

- H2O

Axial cysteinCys

In the presence of the decoy molecules, P450BM3 can catalyze hydroxylation of non-native substrates
such as propane and benzene.
Recent studies have demonstrated the potential as decoy molecules of various carboxylic acids
with structural diversity.

Substrate hydroxylation

O
FeIV

- H2O

-

S

Product
Compound I
Oxo-ferryl porphyrin π-cation radical

Cys

Fluorinated Decoy Molecules (Perfluorinated Carboxylic Acids, PFC)

Aim

PFC9-PheControlling Stereoselectivity of hydroxylation using Decoy Molecules
Direct, yet enantioselective C-H bond functionalization
is highly attractive for organic chemists
since it promises substantially streamlined synthetic routes.
In this study, we aimed to control stereoselectivity of
C-H bond hydroxylations of non-native substrates
catalyzed by P450BM3 using decoy molecules.

P450BM3

Gln73

Arg47

PFC9-Trp

Ala74
Heme

PFC9-Trp

Decoy molecule =Fluorine coating prevents the decoy molecule itself frombeing reacted with active species of P450BM3.

Non-fluorinated Decoy Molecules
C9-PheIbuprofen-Phe

C7-Pro-Phe(S)-selective hydroxylation

Arg47

Ala74

Heme
Decoy molecule =Tyr51“Decoy for (S)”Hydroxylation target:
alkylbenzene derivatives

Z. Cong et al., ACS Catal. 2015

PDB : 3WSP

Gln73

Z-Pro-Phe

Z-Pro-Phe

PFC9-Trp: 207 min-1
PFC9-Phe: 251 min-1

Tyr51(R)-selective hydroxylation

P450BM3“Decoy for (R)”O2, 2H+, 2e-C9-Phe: 192 min-1

Ibuprofen-Phe: 236 min-1

C7-Pro-Phe: 259 min-1

Z-Pro-Phe: 229 min-1

PDB : 5XA3

O. Shoji et al., ACIE. 2017

Crystal Structure & Computational Analysis

IndaneResults

Crystal Structures of P450BM3 Bound to Decoy Molecules

Structures of decoy molecules employed

PDB: 5XHJ

5CHVA-Trp

PDB: 5XA3

Gln73

Gln73

Z-Pro-Phe

Ala74
PFC9-Phe

5CHVA-Phe(R)-Ibuprofen-Phe

Benzylic Hydroxylation by P450BM3 with Decoy Molecules
Indane Hydroxylation

Heme

Intensity

40000

None

Si

30000

with 5CHVA-Phe

(R)-

10000

18.0

18.5

5CHVA-Phe

53% (R)(R)-Ibu-Phe

45% (S)

Z-Pro-Phe

56% (S)
10(S)-

with Z-Pro-Phe

19.0

19.5

20.0

20.5

21.0

5CHVA-Trp

Retention time / min

6% (R)

0

Heme

20

30

ee [%]

40

50

60

Ethylbenzene Hydroxylation

Decoy
molecule

Rate

ee

-1

[min ][%] (R/S)

[%]

None

36 ± 216 (S)

8

PFC9-Phe

216 ± 86 (R)

245CHVA-Phe

435 ± 2753 (R)

44(R)-Ibu-Phe

314 ± 545 (S)

39

Z-Pro-Phe

302 ± 1056 (S)

43

CE[%] (R/S)

[%]

Decoy
molecule

Opened
Heme

Decoy

None

147 ± 1145 (R)23

None

PFC9-Phe373 ± 46

52 (R)

31

PFC9-Phe

Rate

ee

CE

[min-1][%] (R/S)[%]

20 ± 155 (S)

7

212 ± 16

69 (S)

17

5CHVA-Phe

447 ± 1385 (R)

47

5CHVA-Phe

320 ± 31

13 (S)

49(R)-Ibu-Phe

321 ± 57 (S)35(R)-Ibu-Phe

332 ± 40

89 (S)

66

Z-Pro-Phe

324 ± 94 (S)43Z-Pro-Phe

260 ± 15

96 (S)

82

Phe87

Phe87

Ala264ee[min-1]Z-Pro-Phe

ClosedTatralin Hydroxylation

Rate

Active site cavities
depicted by surface model.

CE

Phe87
Decoy
molecule

O. Shoji et al., ACIE. 2017

The crystal structures of P450BM3 bound to 5CHVA-Trp and Z-Pro-Phe were successfully solved.

Conformational Change of P450BM3 Induced by Decoy Molecules
P450BM3 with 5CHVA-Trp → Closed conformation
P450BM3 with Z-Pro-Phe → Opened conformation

without decoy molecule

O

20000

0

16% (S)

PFC9-Phe

Tyr51

GCMS Chromatogram

50000

Enantiomeric Excess (ee) of the products

Ala74

Tyr51

Z-Pro-Phe

Heme

Smaller space

Heme

Larger space

5CHVA-Trp induced closed conformation
while Z-Pro-Phe induced open conformation.



The shapes of active site cavity
are different between the two structures.

Phe87 and Ala264, residues near
the active site, are displaced by
the binding of the decoy molecules.

Docking Simulation of Indane to Decoy-bound P450BM3
Software: AutoDockFR (PLoS Comput. Biol., 2015, 11, e1004586.)

 Stereoselectivity of benzylic hydroxylation was improved or inverted
depending upon decoy molecule displayed above.
 5CHVA-Phe improved (R)-selectivity.

 Z-Pro-Phe improved (S)-selectivity.

“Decoy for R”“Decoy for S”

53% (R) ee
435 min-1

OH

13% (S) ee
320 min-1

4% (S) ee
324 min-1

Experimental Procedure
P450BM3
Decoy molecule
Tris-HCl (pH 7.4)
KCl
Substrate
NADPH
DMSO

138

0.5 μM
100 μM
20 mM
100 mM
10 mM
5 mM
1.5%

Reactions were performed
at 25℃ under stiring for 10 min.

Z-Pro-Phe

Reactions were quenched with CH2Cl2
and products were extracted .
For indane hydroxylation, products
were derivatised with BSTFA.
NADPH consumption was monitoredby the absorption at 340 nm.
ε340 = 6.22 mM-1 cm-1

Z-Pro-Phe

56% (S) ee
302 min-1

85% (R) ee
447 min-1

5CHVA-Phe

Indane5CHVA-Trp

OH

Pro-(R) indane was obtained

Phe87

by the docking simulation
into the crystal structure of
P450BM3 with 5CHVA-Trp.

96% (S) ee
260 min-1

Experimental: (R)-selectivity (41% (R) ee)
CE (%)：Coupling efficiency =［Product formation]［NADPH consumption］

×100



Phe87

by the docking simulation
into the crystal structure of
P450BM3 with Z-Pro-Phe.

Heme

Reaction extracts were analysed by GC
and turnover per min (TOF) andenantiomeric excess (ee) were determined.

Pro-(S) indane was obtained

HemeExperimental: (S)-selectivity (56% (S) ee)

The results of each docking simulation were consistent with the experimental stereoselectivity.

Sequence-selective recognition of double-stranded DNA by peptide nucleic acid
˕Masanari Shibata, Masaki Hibino, Yuichiro Aiba*, Osami Shoji*(Department of Chemistry, Graduate School of Science, Nagoya University)

Summary

Introduction
⿑Peptide Nucleic Acid (PNA)‫ ۀ‬We have succeeded in developinga novel PNA invasion method.

Thermal StabilityʀElectrostatically-neutral backbone
ʀPNA forms a stable duplex with DNA.

DNA/DNAʀHigh resistance to enzymatic digestion

No electrostatic൏repulsion
DNA/PNA‫ ۀ‬Parallel invasion does not require
any chemical modification of nucleobase.

Chemically-modified nucleobase

Double-duplex invasion

Pseudo-complementary PNA (pcPNA)‫ ۀ‬We will optimize invasion conditions forin cellulo and in vivo applications.

Us

Complementary PNAs
D
Direct recognition

Target sequences

Steric repulsion destabilizes
PNA/PNA interactions.

Invasion complex

Steric repulsion

D : 2,6-diaminopurine, Us : 2-thiouracil

Invasion proceeds efficiently.

prevents efficient invasion
Lorse, J. et al. Protc. Natl. Acad. Sci. 1999, 96, 11804-11808

However

PNA invasion is applicableto the DNA recognition in cellulo or in vivo.

Problems of pcPNA• Effective pcPNA monomers are only available
for AT pair.
Limitations in recognition sequences

ʀGene expression control
ʀGenome editing• Boc synthesis(not applicable to automatic synthesizers,
limited to manual synthesis)
Time consuming and laborious

Strategy

Research Aim• Binding property of nucleic acid

Development of a novel invasion method
w/o chemical modification of nucleobase

Structure of DNA

3’

5’ endʶ

3’ endD

StableReverseDNA duplex exists stably in anti-parallel orientation.
Us

Anti-parallel

Invasion does not proceed when using unmodified PNAs.
3’
5’

5’

ParallelThermal stability of PNA/PNA duplex is lower
in parallel orientation.

ʶN, C : N terminus, C terminus

䃺Targeting any sequences
NC䃺Fast and automated synthesis of PNA

Useful for molecular biology applications

Anti-parallelC
N

Electrophoresis[DNA (119 bp)] = 100 nM[Each of PNAs] = 100 -1000 nM[HEPES (pH = 7.0)] = 5 mM

Incubation

300

Shift

50 C for 1 h

180
140

1

2

3

2

1

180
140

200

34 %

An
Anti
nti
n
tiiparallelSizemarkerSingle mismatch was introduced in
the center of the target sequence.
Target sequence (single mismatch)

DNA

Full mismatch
match

5’…GTGACTACTCTTAGTCATGGT…3’
CTT
T
GTA
A
TGATGAGTATCAGTACAT
T
ACTACTCATAGTCATGAA
A
3’…CACTGATGAGAATCAGTACCA…5’

⿑ Investigation of Applicable PNA Length

5’…GTGACTACTCTTAGTCATGGT…3’TGATGAGAATCAGTA

Parallel[PNA] / [DNA] = 0
300

ACTACTCTTAGTCAT
3’…CACTGATGAGAATCAGTACCA…5’

180
140
ഓ྽΃͹

㍏Thermal Stability - Tm measurement
PNA/PNA



82.8

82.8




> 27

15.2




conditions[DNA (15 mer)] = 1 μM
[PNA (15 mer)] = 1 μM
[HEPES (pH 7.0)] = 5 mM

67.6
63.2



Fw
AntiRev parallel

Parallel

Antiparallel

Antiparallel

5

5

5

200

PNA length‫ق‬10, 11, 12 mer‫ك‬
5’…GTGACTACTCTTAGTCAT…3’TGATGAGAATCA

160
120
100
80
60
40

DNA
A

10
0 mer
11
1 mer

ACTACTCTTAGT
3’…CACTGATGAGAATCAGTA…5’

20

PNA/DNA> 90

Tm / CC

10

The single base mismatch prevented the formation of invasion complex.

This result is the first achievement of PNA invasion
w/o any chemical modification.

Low

5

20

Target sequence

DNA

60
40
20

Thermalerm
stability

10

Parallel invasion showed high sequence selectivity.

120
100
80

High

5

160
120
100
80
40

Invasionn efficiency

160

0

200

60

3

300

Reversing the orientation of a PNA inhibits
the formation of PNA/PNA duplex.

⿑ Mismatch Sequence Discrimination[PNA] / [DNA] =⿑ Invasion Efficiency - Electrophoretic Mobility Shift Assay[PNA] / [DNA] = 0

ParallelUnstable

Novel Invasion Method

N
N

Wittung, P. et al. Nature 1994, 368, 561-563

Results and Discussion
⿑Invasion Experiment൐CC

Sequence of PNA and DNA (15 mer)Fw: ACTACTCTTAGTCAT|||||||||||||||
Rev: TGATGAGAATCAGTA

Parallel

The longer PNAs formed invasion complex more efficiently.

⿑ Application to other sequence[PNA] / [DNA] = 0
300

10

5

10

80

• The thermal stability of parallel PNA/PNA duplexes was very low.
• PNA/DNA duplex was more stable than parallel PNA/PNA duplex.

20

40

Target : GC-rich sequences
GC content 33%

200
180
160
140
120
100
60

The results of Tm measurement supported that of
the invasion experiment.

567%

Target sequence (GC rich)

5’…AGTGCTTCAGCCGCTACCCCG…3’CGAAGTCGGCGATGG

DNA

Anti
An
nti
n
tiiParallel
parallel

GCTTCAGCCGCTACC
3’…TCACGAAGTCGGCGATGGGGC…5’

Invasion complex was formed even with GC-rich target sequence.

This result suggested that parallel invasion method
covers extensive target sequences.

139

140

141

142

Transfer Hydration of Dinitriles to Dicarboxamides
Asuka Naraoka1 and Hiroshi Naka 2
1Graduate School of Science, Nagoya University; 2RCMS, Nagoya University

trap

CN

+

O

2

CONH2

Pd(CH3CN)4(BF4)2

AcOH
NH2
reduced pressure
H2O donor

CONH2– CH3CN– AcOH+ 2 CH3CN↑

Abstract: We report a robust method for double transfer hydration of dinitriles.
The transfer hydration of 1,n-dinitriles (n = 1–6) proceeds smoothly in thepresence of a palladium(II) catalyst with acetamide as a water donor, affording thecorresponding diamides in high yields without involving significant side reactions.
The equilibrium was shifted in the forward direction by removing coproduced
acetonitrile under reduced pressure.
Naraoka, A.; Naka, H. Synlett 2019, 30, 1977–1980 (Invited Cluster).

4. Pressure Dependence

1. Background
Reported side-products:
CN

H 2O

catalyst

CN

CONH2

CONH2

CONH2

CN

O

NH
O

COOH

COOH

CN

CONH2

hydrolysis

monohydration cyclization
Homogeneous catalysts

Heterogeneous

Me2 Me2
P OH
O P
H
Pt
H
O P
Me2

ex.)

Cl

Me2
Ru P
OH
Cl

CONH2

H2NOC

CONH2

[{Rh(OMe)(cod)}2]/PCy3

74%[1 mol %, 60 ºC, 1 h]

Parkins, A. W. et al.
J. Mol. Catal. A: Chemical
2000, 160, 249.

Cadierno, V. et al.
Dalton Trans.
2016, 45, 13590.

CN

CONH2
99%
[2 mol %, 25 ºC, 48 h]Ley, S. V. et al.
Org. Lett.
2014, 16, 1060.

C N

+

H 2N

Pd(NO3)2R

H2O donor[Pdn] (n = 1 or 2)
HO

O

R

+

CONH2

N
NH2
[Pdn]

H

R = CH3, alkyl

+

N C R

R

NH2 N
[Pdn]

O

R

NH2

+ CH3CN

R CN +H2O

O
NH2

3. Control ExperimentCN
CN

Pd(CH3CN)4(BF4)2 (Pd/1 = 0.01)
AcNH2 (10 mmol)
AcOH (2 mL)
760 mmHg, 50 ºC, 10 min

1, 1.0 mmol

– CH3CN

Changes from the above scheme

55% (32%)
CONH2

CONH2

CONH2

CONH2

CONH2

CONH2

94% (79%)

76%*

CONH2

CONH2

CONH2

H2NOC

CONH2

HO

68% (63%)

79%

91%

CONH2

Cl

Cl

84%*
(Pd/dinitrile = 0.1)

CONH2

91%

Cl
CONH2

CONH2

Maffioli, S. I. et al. Org. Lett. 2005, 7, 5237.
Dai, M. et al. Org. Biomol. Chem. 2014, 12, 9109.
Ebright, R. H. et al. Cell 2017, 169, 1240.
Singh, A. K. et al. Dalton Trans. 2017, 46, 13065.
Croatt, M. P. Org. Lett. 2018, 20, 6046.

H2NOC

O

CONH2

Cl

CONH2

96%*
(70–90 ºC)

76%**Dinitrile (0.7 mmol), AcNH2 (7 mmol), AcOH (1.4 mL), 6–30 min.

6. Decagram-Scale Hydration
CONH2
CONH2

+

CONH2

3

2
yield of 2 (%)ayield of 3 (%)a

none

73

25

29

58

without AcNH2<1<1

H2O instead of AcNH2, 1/H2O = 1:10

<115

without Pd(CH3CN)4(BF4)2<1<1

reduced pressure (0.8–1.2 mmHg)

81

17

1 (10 mmol), reduced pressure, 1 hb

>99

<1

1 (10 mmol), Pd/1 = 0.001, reduced pressure, 1 hb

99

1aDetermined by 1H NMR analysis (internal standard = mesitylene).

Pd(CH3CN)4(BF4)2(Pd/Dinitrile = 0.001)
AcNH2 (1.2 mol)

CN

CN

1/AcNH2 = 1:2

bAcOH (20 mL), 0.8–1.2 mmHg.

CONH2

n = 4: 89% (84%)
n = 5: 82% (74%)
n = 6: 79% (66%)

CONH2

O

Kanda, T.; Naraoka, A.; Naka, H. J. Am. Chem. Soc. 2019, 141, 825.

PdCl2

Yields of products with minor
contamination by acetamiden

83% (54%)

Cf. Pd-Catalyzed Reversible Dehydration of Amides
O

CONH2

– 2 CH3CN

CONH2

HO

N
N
H
[Pdn]

CONH2

CONH2

O

15

AcOH (20 mL)
1–3 mmHg, 50 ºC, 2 h

CONH2n = 1: 77% (43%)
n = 2: 83% (61%)
n = 3: 80% (69%)

71–98% yieldR

10time (min)(Overall yields after recrystallization)
H2NOC

NH2

5

Pd(CH3CN)4(BF4)2(Pd/Dinitrile = 0.001–0.01)

100 mmol[Pdn]
O

2 AcNH2+

CH3CN ↑

O

0

5. Substrate Scope

10 mmol

CONH2

HO

AcOH
50 ºC, 10 min

HO

760 mmHg

The removal of the coproduct (CH3CN) and the solvent (AcOH)
under reduced pressure is highly effective

CN

AcOH
reduced pressure, 50 ºC, 2 h

O

20
0

CN

Previous Work: Rapid Transfer Hydration of Cyanohydrins
HO

40

CONH2

99%
[100 ºC, 30 min]

Saito, S. et al.
Angew. Chem. Int. Ed.
2008, 47, 3607.

cat Pd(CH3CN)4(BF4)2

H2O donor

60

0.8–1.2 mmHg

H2NOC

This Work: Transfer Hydration of Dinitriles
2 AcNH2

2

Reaction appratus

2. Transfer Hydration+– CH3CN1, 1.0 mmol

80

CONH2

– AcOH ↑– CH3CN ↑¥ Efficient route to 1,n-diamides¥ The substrate scope for 1,3-dinitriles remains limited

CN

100

CONH2

AcOH (2 mL)
x mmHg, 50 ºC, t h

CN

MnO2

CONH2

CONH2

97%
[0.2 mol %, 95 ºC, 8 h]Pd(CH3CN)4(BF4)2(Pd/1 = 0.01)
AcNH2 (10 mmol)CNyield of 2 (%)

CN

pump

CONH2

AcOH (240 mL)
0.6–0.7 mmHg, 50 ºC, 12 h

CN

CONH2

– CH3CN

120 mmol

88% (13.7 g)

7. Ongoing Project w/ Profs. Uchiyama and Kamigaito
Pd(CH3CN)4(BF4)2 (0.01 mmol)
AcNH2 (12 mmol)
CN

CN

CN

1.0 mmol

AcOH (2 mL)
0.8–1.2 mmHg, 50 ºC, 20 min

CONH2 CONH2 CONH2
85% yield[+ 0.13 mmol AcNH2]– CH3CN

Hydration of Polyacrylonitrile
n

CN
PAN

catalyst
AcNH2

n–x

CN

x

catalyst
AcNH2

CONH2

PAN-co-PAAm

n

CONH2

PAAm

Acknowledgements: We are grateful to support from Profs. M. Uchiyama, M. Kamigaito, R. Noyori and S. Saito.
We thank Nagoya Univ. (the MEXT’s diversity program) for financial support.

143

Photocatalytic N-Methylation of
Amino Acids with Methanol

Ivven Huang, Yuna Morioka, Susumu Saito, Hiroshi Naka (Grad. Sch. of Sci., & RCMS, Nagoya Univ.)

3.2 Scope and Limitations: Proteogenic Amino Acids
UV-LEDs
R
H 2N

CO2H

AgNO3/TiO2+ 2CH3OH

H 3C

30 ºC
– 2H2OUV-LEDs(λ0 = 365 nm)
AgNO3/TiO2

R
N

CH3

CO2H

H 2N

CO2H

+

2CH3OH

Val, 0.10 mmol

H 3C

30 ºC, 15 h

N

CH3
83%

10 mL

2H2O

+

CO2H

product, isolated yield, dr:

Abstract: A silver-loaded titanium dioxide (AgNO3/TiO2) photocatalyst
promotes N-methylation of amino acids with methanol at ambient temperature
under UV light irradiation. Scope and limitation of this method on proteogenic

H3 C

amino acids have been clarified.

R

H 3C

CO2H

CO2H

H 3C

CO2H

CO2H

2

CH3

Tsarev, Morioka, Caner, Wang, Ushimaru, Kudo, Naka, Saito, OL 2015, 17, 2530.

+ 2CH3OH

H 3C

30 ºC
– 2H2O

CH3

–

CO2H

Val, 0.10 mmol

10 mL
photocatalyst
Ag/TiO2
Ag/TiO2
AgNO3/TiO2
AgNO3/TiO2

cosolvent
30 ºC, 3 h– nH2O

cosolvent
none
H 2O
none
H2O

75%
from Phe+

CO2H+ H 3C

e–

CH3

45%
13%
45%
23%

band
gap

+ H 2O
+ H2

CO2H

N

+ H2O

CO2H

1/2

Ag/TiO2

CO2H

¥
H 3C

N
H

e–

CO2H

O

H

H

O
H

H 2N

generation of Ag-H and HCHO
H+

H 2O

H

H 3C

H 2O

H

Profs. R. Noyori (Nagoya Univ.) for supports; Prof. A. Kudo (Tokyo Univ. of Sci.) for helpful comments.
¥ from JSPS KAKENHI / Iwatani foundation

H+

H

H

1/2

Ag/TiO2

CO2H

OH

1/2 CH3OH

Ag

N

H
hν

h+

+ H+

¥
H

Ag

band
gap

1/2 CH3OH

Acknowledgements

144

CH3

83%

hν

O2p h+

yield (diMe-Val)
33%
<1%
36%
2%

CO2H

N

10 mL

Ag

¥
N

S

H2C

CH3

second methylation
yield (Me-Val)81%
from Met

as above

CH3OH+

first methylation

N
H

CO2H

70%

generation of silver nanoparticles
Ag+

potential

3. Result and Discussion
3.1 Reaction Parameters

H2N

N

CH3

10 mL

Ti4+3dPhotocatalytic Reactions
UV-LEDs 16Wx2 (CCS Ltd.)

H 3C

H 3C

CO2H

3.3 Supposed Reaction Mechanism

Photocatalyst Preparation
AgNO3/TiO2 Impregnation of AgNO3 on TiO2 (P25)
Ag/TiO2 Reduction of AgNO3/TiO2 with NaBH4

UV-LEDs(λ0 = 365 nm)
photocatalyst

CH3Pro, 0.10 mmol

CO2H

2. Method+ nCH3OH

CO2H

N
H

R
N

N

CH3

S

Pro: monomethylation

Scope on other proteogenic amino acids remains unclear.

CO2H

H 3C

CO2H

2

This Work: Photocatalytic Methylation of Amino Acids with AgNO3/TiO2
R

82%
from Leu

94%
from Ala

Cys, 0.10 mmol

88%, S:R = 97:3

Pro, S:R = 98:2

H 2N

CO2H

Complex mixture with: Ser, Thr, Tyr, Asp, Asn, Glu, Gln, Arg, His, Trp.

N

Ar, H2O
25 ºC, 10 h

UV-LEDs
AgNO3/TiO2

N

CH3

Cys: Thiazolidine formation and N-methylation
UV-LEDs(λ0 = 365 nm)
HS
AgNO3/TiO2+ 2CH3OH
35 ºC, 15 h
CO H
H N

Previous Work: Photocatalytic Methylation of Amines with Ag/TiO2

N
H

H 3C

CO2H

CH3

92%, dr >98:2
from Ile+ Atom-economical– Unclear scopehν (Xe, λ = 300–470 nm)
Ag/TiO2

N

CH3

CH3OH as Methylating Reagent
Huang, CC 2010, 46, 7834.
CH3OH, H2, Pd/C, rt, 80 h

+ Well-established– Hazardrous reagents

N

R
N

CH3

Conventional Methods
Bowman, JCS 1950, 1342.
HCHO, NaBH4, CF3CH2OH, rfx, 24 h

+ CH3OH

H 3C

CO2H

CH3
80%
from Gly

1. Introduction
H2N

N

H

¥

H

H

Ag
CO2–

H+
Ag+

H

+ H+

¥
H 3C

Ag+

N+

O

H

H 3C

N
H

CO2H

¥
N
CH3

CO2H

Synthesis of ⍺-Amino Amides by Transfer
Hydration of Nitriles◯Tomoyo Tamura, Taimeng Liang, Ryoji Noyori, and Hiroshi Naka

Graduate School of Science and Research Center for Materials Science, Nagoya University, JAPAN

R1 R2

R

N
CN
H
α-amino nitrilesO+

Pd catalyst

R1 R2

R

NH2
(AcNH2)H2O donor

NH2

N
H

+

We have recently reported PdII-catalyzed transfer

CH3CN

hydration of cyanohydrins with amide-based

Oα-amino amides

extended this method to the catalytic transfer hydration

[Pd]

R

R1
R2
O

H
N

R1 R2

R

N
[Pd]

N
H

NH2

H

N

R1 R2

R

O
N

[Pd]

N
H

H

R

N
CN
H
α-amino nitriles

catalyst

H 2O

+

Me

H

O

P

Me

Me

Me

P

Pt

P
O
Me
Me

OH

P

Fe

H

Ph

Me

Pt
Ph

P

Cl

Ph

Grubbs, R. H.; Virgil, S. C. et al.
J. Am. Chem. Soc.
2018, 140, 17782–17789.

Ghaffar, T.; Parkins, A. W.
Tetrahedron Lett.
1995, 36, 8657–8660.

3.2 Substrate Scope
O

N

N

Ni

N

N
2Cl–

N

N

65% yield
10 mol%, 100 °C, 24 h
TOF = 0.27 h–1

O O
S
N
H

R

N
CN
H
α-amino nitriles+O

Pd catalyst

R

NH2(AcNH2)H2O donor

N
H

NH2

+

CH3CN

PhCN

> 99%
conv.

H2O–THF
rt, 6 h– CH3CN

PhCONH2

Ph Ph

HO

HO

AcOH
50 ºC, 10 min– CH3CN

Kanda, T.; Naraoka, A.; Naka, H.
J. Am. Chem. Soc. 2019, 141, 825–830.

Maffioli, S. I.; Marzorati, E.; Marazzi, A.
Org. Lett. 2005, 7, 5237–5239.

O
O

N
H

CN

1 mmol
Pd catPd(NO3)2
Pd(NO3)2
Pd(NO3)2

Pd(NO3)2
Pd(NO3)2

Pd(CH3CN)4(BF4)2
Pd(O2CCF3)2

Pd(CH3CN)2Cl2

Pd cat (2 mol %)AcNH2 (4 equiv)

solvent (2 mL)temperature, timesolvent

temperature, time

AcOH

50 °C, 10 min

CH3CN/H2O (3:1) 50 °C, 10 min

CH3CN

50 °C, 10 min

AcOH

30 °C, 5 min

AcOH

30 °C, 5 min

CH3OH
AcOH
AcOH

Pd(CH3CN)4(BF4)2a) AcOH

30 °C, 5 min

O
O

N
H

CONH2

Cbz-Gly-NH2
NMR
conv. (%)

NMR
yield (%)

> 99

> 99

54

60

44

36

64

54

31

22

83

69

55

30 °C, 5 min

46

37

25

50 °C, 10 min

> 99

92b)

30 °C, 5 mina) AcNH2 (1 equiv) was used. b) Average of 4 times

O

O
CONH2

N
H

O

N
H

CONH2

92%
(50 °C, 1 h)
w/ Pd(CH3CN)4(BF4)2
w/ AcNH2 (0.5 M)

N
H

CONH2
N
H

CONH2

CONH2

< 1%

base-sensitive
Fmoc-Gly-NH2, 96%
w/ Pd(CH3CN)4(BF4)2

1 mmolO

reagent (4.6 equiv)Osolvent (mL)
75 °C, 2–4 h, N2

N
H

COOH

NMR
NMR
time
(h) conv. (%) yield (%) vessel

reagent

solvent (mL)

TBN

AcOH/H2O (9:1, 3 mL)

TBN

AcOH/TFA (2:1, 3 mL)

AcOH (3 mL)

TBN

3. Result and Discussion
3.1 Effect of Parameters

CONH2

O

N
CONH2
H
acid-sensitive
Boc-Gly-NH2, 76%
w/ Pd(CH3CN)4(BF4)2

highly congested
72% isolated yield(50 °C, 1 h; 70 °C, 3 h)
w/ 10 mol % Pd

CONH2

75%

N
H

Cbz-Ala-NH2, 92%OO

Our previous work
Pd(NO3)2 (5 mol %)Ph Ph
AcNH2 (4 equiv)CN

AcOH, 50 °C, 10 min– CH3CN

3.3 Conversion to Amino Acid

Applicable to highly congested nitriles

PdCl2 (10 mol %)AcNH2 (4 equiv)

O

O
O O
S
N
H

Applicable to acid-/base-sensitive nitriles

Pioneering work

CONH2

Bera, J. K. et al.
Chem. Eur. J.
2017, 23, 7761–7771.

O
α-amino amidesO

Pd(NO3)2 (2 mol %)AcNH2 (2 M)Ohighly congested
69% isolated yieldw/ 10 mol % Pd

2. This Work: Catalytic Transfer Hydration
R1 R2

CN

0.5 M

Issues: Limited substrate scope and long reaction time
R1 R2

N
H

O

2+

OH HO
HO
OTf

single amino nitrile, 61% yield
0.1 mol %, 40 °C, 12 h
TOF = 51 h–1

most widely usedester hydrolysis
as side reactions

disubstituted-α-aminoamides under mild conditions.

N
CO2H
H
α-amino acids

MeP

protected amino nitriles to afford α-mono- and α,α-

NH2 N

R1 R2

R

N
CONH2
H
α-amino amides

Review: Cadierno, V.; Crochet, P. et al. Green Chem. 2013,15, 46–66.

Ph

amides. This method enables rapid conversion of various

[Pd]

R1 R2

R

of α-amino nitriles for the rapid synthesis of α-amino

CH3O

1. Background: Catalytic Hydration of Amino Nitriles
R1 R2

water

donors (J. Am. Chem. Soc. 2019, 141, 825–830.). Here we

2

> 99

5

A

2

87

39

A

2

79

30

A

TBN

AcOH/MeOH (9:1, 3 mL) 2

14

3

AcOH (3 mL)

A

TBN

4

> 99

14

AcOH (2 mL)

A

2

> 99

9

A
A

TBN

isoamyl nitrite

AcOH (3 mL)

hexyl nitrite

2

80

7

AcOH (3 mL)

TBN (5 equiv)

83

4

AcOH (2 mL)

2A

TBN (5 equiv)a)

3

> 99

86

AcOH (2 mL)

B

3

> 99

91

B

a) Under air
ONvessel A

vessel B

O

tert-butyl nitrite
(TBN)
N
O
O
isoamyl nitrite

Ohexyl nitriteNO

Cf. Kandasamy, J. et al. Green Chem. 2016, 18, 2323–2330.

Acknowledgements: Prof. S. Saito for fruitful discussion. Prof. T. Ooi, K. Ohmatsu and T. Ohkuma for providing several aminonitriles. Prof. T. Ohshima and H.
Morimoto for providing method for synthesis of substrates. ¥ from JSPS KAKENHI 15KT0141 & 17K05859 / Toyota Riken / IQCE

145

Direct α-C(sp3)–H arylation of amides
by TiO2/Ni complex cooperative catalysts
Masaki Nomura,1 Shogo Mori,1 Susumu Saito1,2Thee Noyori Laboratory
Labora1Graduate School of Science, 2Research Center of Materials Science, Nagoya UniversityyAbstract
X

Ar

O

R1

+

H

N

R2
Amides

T
TIO2

hν

R3

Ni

N

Ar

R2

R3

-C(sp3)–H arylation

1. Introduction
efficientsynthetic route

This work

mild conditions

Ar

O

R1

H

X

Ar

X = hagogenNR2
catalyst

4. Solvent effect
Br

O

R1

The photocatalyzed direct α-C(sp3)–H arylation of amides with aryl
halides is an attractive synthetic strategy to access to complex molecules.
Our group has developed this transformation using TiO2/Ni complex
cooperative catalysts, where TiO2, an inexpensive and easily removable
heterogeneous photocatalyst provided a practical synthetic protocol.

O

R1

R3
Ar

N

R2

EtO2C

R3

0.25 mmol

Solvent

NH2

Ar

multi steps

multi stepsorharsh conditions

Photocatalyzed direct α-C(sp3)–H arylation provides a short syntheticroute to complex amides. Readily accessible starting material, mild
reaction conditions, and high selectivity make this strategy attractive
for the synthesis of drugs, bioactive molecules and so on.

2. Previous reports

DMA
THF
1,4-dioxane
MTHP
Et2O
iPr O
2
tBuOMe
MeOH
tBuOH
MeCN

+

N
Boc
Amides(2 equiv.)

H

Ni

Ir

N
Boc

R

H

NBoc

Mes

W

Ni

W

hν

Ar

NBoc

TBADT

10 mol%

+

O
H

BA

hν

O

Ni

N

Ar

BA

H

N
N
(dtbbpy)
65%

O

O
EtO2C
27% (from 1,4-dioxane)

N

DMA
1.5 mL(65 equiv.)

O
N
EtO2C

40% 〜 5%

64%

N

49%

N

Me

OH

Mes

N

N

47%

N

Mes

Me

56%

N

HO

Mes

N

33%

〜 5%

29%

N

N

N

HO

47%

N

OH

OH

N

Me
Ph

N

8%

N

OH

HO

Ph

N
HO

3%
N

N
1%

MeO2C

N

N

N

PPh3
<1%

1%

Me
CO2Me

N

OMe

51%

N

N

N
N
(bpy)
42%

Br
EtO2C
0.50 mmol

TiO2 (P25) (38 mol%)
NiBr2(glyme) (2.5 mol%)bpy (2.5 mol%)
K2HPO4 (300 mol%)hν (300–470 nm)
60 ºC, 20 h

+ H

6%

6. Addition pattern of Ni complex

3. Our previous system
O

O

Me

Recently, direct α-C(sp3)–H alkylation/arylation methods withhomogeneous photocatalysts and Ni complexes were reported.

O
N
EtO2C

96%

 An inexpensive and easily removable heterogeneous photocatalyst
 A rare example where simple carboxylic acid amides can be used
DMA as solvent  Limited substrate scope146

butyl formateO

EtO2C
15% (from THF)

50% 〜 40%

N

Hashmi, A. S. K. et al. Org.Lett. 2019, 21, 6329–6332.

EtO2C
0.25 mmol

ethyl formatetBuNbenzaldehyde

+ H

OnBu

H

OEt

Other products

50% 〜

MeO

O

N

Amides(5 equiv.)

Br

O
MTHP

K2HPO4 (300 mol%)
ethyl formate (2.8 mL)hν (300–470 nm)
25 ºC, 20 h

Me

MacMillan, D. W. C. et al. Nature 2018, 560, 70–75.

X

O

O
H

DMA
0.20 mL(4 equiv.)

N

Amides(5 equiv.)

Ar

23
71
68
5
7
9
8
2
0

0.50 mmol

tBu

5 mol%+ H

Yield (%)

N

EtO2C

N
quinuclidine

X

EtOAc
ethyl formate
butyl formate
cyclohexane
tolueneacetone
CH2Cl2
DMSO
H 2O

EtO2C

TiO2 (P25) (38 mol%)
NiBr2(glyme) (2.5 mol%)
Ligand (2.5 mol%)Br

H

MacMillan, D. W. C. et al. Nature 2017, 547, 79–83.

Ar

K2HPO4 (300 mol%)solvent (0.75 mL)hν (300–470 nm)
25 ºC, 20 h

DMA
0.75 mL(32 equiv.)

24
55
43
23
6
13
25
9
18
17

O
N

5. Ligand effect

2 mol%R X

N

Yield (%) Solvent

Irhν

TiO2 (P25) (38 mol%)
NiBr2(glyme) (2.5 mol%)bpy (2.5 mol%)

O
+ H

O
N

TiO2 (P25) (38 mol%)
Ni complex (2.5 mol%)

DMA
0.20 mL(4 equiv.)

K2HPO4 (300 mol%)
ethyl formate (2.8 mL)hν (300–470 nm)
25 ºC, t h+ HAddition pattern
NiBr2(glyme)+
dtbbpypre-synthesized
NiBr2(dtbbpy)
a 20 hb 24 hYield (%)

O
N
EtO2C

tBu

up to 72%

tBu

65a

N

72b

Br

Ni

N
Br

NiBr2(dtbbpy)

Ethyl formate and pre-synthesized NiBr2(dtbbpy) resulted in efficient
α-C(sp3)–H arylation with a small amount of DMA (4 equiv.) at room
temperature.

Photocatalytic CO2 Reduction Using Base Metal
Complexes Bearing PNNP-type Tetradentate Ligand
Taku Wakabayashi1, Kenji Kamada1, Jieun Jung1, Susumu Saito*,1,2The
e NoyoriN
Labor
Laboratory

1Graduate School of Science, 2Research Center for Materials Science, Nagoya University

Abstract

N

Visible light +

+

N

N

BIH
(Sacrificial reagent)

Mes
N

CO
O2

s
Mes

L
M
P
Cy2
L

4. Electrochemical study

N

Cyclic voltammetry measurement

N

Mes-CrPCY2

fac-Ir(ppy)3(Photosensitizer)

e–

N

Ir

Mes-MnPCY2

CO2

CO2

Conditions:
Complex (0.1 mM) in DMA
solution containing 0.1 M
NEt4BF4 as a supporting
electrolyte.
Scan rate: 0.1 V/s.

CO
HCOOH

P
Cy2

Base metal complexes

Mes =(M = Cr, Mn, Fe, Co)

Mes-FePCY2

We have developed new base metal complexes which can catalyze CO2
photoreduction. These catalysts consist of earth-abundant base metals and
PNNP-type tetradentate ligands, showing the ability for reducing CO2
under visible light irradiation to generate CO and HCOOH.

Mes-CoPCY2

CO2Catalytic current wereincreased under CO2
atmosphere.

CO2

1. Introduction

CO2 reduction would
be occurred.

material

All complexes have catalytic ability for CO2 reduction.

combustion
CheapLow-toxic

Platformchemicals

CarbonNeutralCO2

5. Results of CO2 photoreduction

conversion

Effect of metal center
CO2

CO, HCOOH

Catalyst (0.05 mM)
fac-Ir(ppy)3 (0.25 mM), BIH (0.1 M)
DMA/TEOA (4.0 mL, 5:1 v/v)
rt., h𝞶𝞶𝞶(>385 nm)

Mes-CrPCY2
CO
HCOOH
H2

Mes-MnPCY2
Mes-FePCY2
Mes-CoPCY2etc.

CO2 capture &reductionCO
O2 reduction can realize sustainable society.

2
S
t
2. St
Strategy
Mes

Mes +

H
N

N

Ir

P
Cy2

P
Cy2

Cl

Mes
N

BPh4–

Mes +

Cl

Cr
P
Cy2
Cl

N
P
Cy2

Mes
N

Cl–

Mn
P
Cy2 C
O

Mes-CrPCY2

Mes-IrPCY2
 High ability
 High durability
 Noble metal

Metal
Change

Mes

Fe
P
Cy2
Cl

Mes +
N
P
Cy2

Br–

Mes +

Mes
N

N

Co
P
Cy2
Cl

P
Cy2

Mes-FePCY2

N
P
Cy2

Mes-FePCY2 and Mes-CrPCY2 are suitable for
CO and HCOOH production respectively.

Additive effect

Mes-MnPCY2

Mes

Cl
N

O
C

CO2

Mes-FePCY2 (0.05 mM), fac-Ir(ppy)3 (0.25 mM), BIH (0.1 M)
Additive (5.0 mM), DMA (4.0 mL), rt., h𝞶𝞶𝞶(>400 nm), 24 h

CO
HCOOH
H2

Cl–

Mes-CoPCY2

 Base metal complexes

3. Synthesis
Br

Br

N

+

N

Pd(PPh3)4

B(OH)2

81%

Mes

Mes
N

N

Mes

1) MeLi2) MnO2

Mes
N

76%

N

1) LDA, PCy2Cl
2) BH3–THF
48%
Mes

Mes
1) morpholine

N

N

PCy2

Cy2P

BH3

Mes-CrPCY2

BH32) metal source

Mes-MnPCY2
Mes-FePCY2

Mes-CoPCY2

metal sourceyield

CrCl3•(THF)3

73%

Mn(CO)5Br

13%

FeCl2

39%

CoCl2

40%

Mg and Al salts can improve CO and HCOOH production respectively.

147

Ir-catalyzed transformation of bio-renewable evennumbered carboxylic acids into odd-numbered carbon chain
Kazuki Teramoto,1 Shota Yoshioka,1 Susumu Saito*,1,2
1Graduate School of Science, 2Research Center for Materials Science, Nagoya University

AbstractO

H2 (6 MPa)O
SucA (C = 4)

Recently, we have developed multifunctional Ir pre-catalyst, IrPCY2 forhydrogenation of 1,4-dicarboxylic acids (1,4-diCAs) via in-situ formation ofcorresponding anhydrides and lactones. In survey of reaction pathway of thehydrogenation, IrPCY2 was found to convert SucA into spiro-diGBL under Ar
BPh4–
atmosphere as shown the scheme. Aming for the application of this reaction
toward transformation of diCAs or fatty acids to odd numbered carbon chain, weinvestigate herein the optimization of left reaction conditions.

+

HO

OH
1,4-BDO (C = 4)–2H2O
IrPCY2
toluene180 °C Ar (1 atm)
18 h
–H2O
–CO2

OH

HO

O

N H N
Ir

O

P
Cy2

O
O
spiro-diGBL (C = 7)

P
Cy2

Cl
IrPCY2

2. This Work

1. Introduction
q DecarboxylationOOHnq Hydrogenation
H2
OH Pd/Al2O3O

Pd cat.
Ac2O

HO

n

Odd-numberedalpha olefins

Even numbered
Fatty acids

Ex.) Bio-renewable CAs

O

O

OH

HO

OH

O

OH

O

Crystal density

M.p.

Fatty acids

330
310
290

1.100

270

1.000
0.900

250
4

5

6

7

8

OH

9 10 11 12 13

n

HO2C

CO2H

2 HO2C230
Bond, A. D. New. J. Chem. 2004,
28,104–114

n

–H2O

C = n+3

O

n

O

CO

Photoreduction

OH
1,4-BDO (C = 4)

O

O

O
O
spiro-diGBL (C = 7)

n

CO2H

CO2H –CO2 O

n

+

OH

HO

–2H2O
IrPCY2
toluene180 °C Ar (1 atm)
18 h
–H2O
–CO2

Ø Unique change of carbon chain
q Future target

Ceven : Abundant
Codd : Rare

BIH
hν
H

H2 (6 MPa)OH

O
SucA (C = 4)

OH

n

BPh4–

P
Cy2

Multifunctional Catalyst

O

O

Cl

CO2

IrPCY2HO

350

Melting point

Crystal density

1.300
1.200

OH

n

1.400

P
Cy2

Hydrogenation

OHOH

q Odd-Even nunber Effectex.) Correlation between melting point and crystal density

N H N
Ir

H2

HO

Antoine,B; Ceri, H. ACS Sustainable Chem. 2018, 6,
16341–16351

O

OH

FG2

O

OH
Value-added chemicals(C = 3 or 4)

+

FG1 O

HO

HO

HO

O

q Background

O

O

O

Succinic acid
(C = 4)

Vider, J. ACS Catal. 2016, 6, 7784–7789

O

The Noyori Laboratory

H2

CO2H

n

n

CO2H

CO2H
CO2H

n

C = 2(n+3)–1 = 2n+5

3. Synthesis of Ir precatalyst+
1) CH3Li, THF–78 ºC to reflux
NN2) MnO2, r.t.

N1) LDA
0 ºC to r.t.

N2) PClCy2,
0 ºC to r.t.
3) BH3–THF
0 ºC to r.t.

43% yield

H 3B

N

N

PCy2

Cy2P

1) morpholine, 120 °C
2) [IrCl(cod)]2
MeOH, 70 °C
BH3 3) LiBPh4(glyme)3, r.t.

OH
O

SucA, 0.22 M

100

O

Yields (%)

O

50

diGBL

34

0

36

23
0.75

0

1.5

3

IrPCY2 (mol%)O

O

SucA, 0.22 M

SucAn (%)
diGBL (%)

Ø Larger amount of
IrPCY2 leads
increase yield of
diGBL.

HO

OH
O

SucA, 0.22 M

Yields (%)

100
90
80
70
60
50
40
30
20
10
0

IrPCY2 (1.5 mol%)
NaH (0–18.0 mol%)
Ar (1 atm)
toluene180 ºC, 18 h
[Ir]0 = 3.4 mM

O

O

O
O

O

56

24
0.0

37
3.0

diGBL

SucAn

diGBL

26

23

12

22

43

45

49

45

6.0

9.0
12.0
NaH (mol%)

15.0

Ø The formation of diGBL might be promoted by NaH.
Ø The propotion (IrPCY2 : NaH = 1.5 : 12.0) is better.

148

O

O

+

SucAn
50

O

O

O

+

O

diGBL

O

SucAn

diGBL
SucAn

0

3

6

9

12

15

18

21

24

Reaction time (h)

27

30

33

36

Ø The formation of SucAn might be occurred at first.

5. Effect of different amount of NaH
OO

Ar (1 atm)
toluene180 ºC, 3–36 h[Ir]0 = 3.4 mM

O

100
90
80
70
60
50
40
30
20
10
0

O

IrPCY2 (1.5 mol%)

OH

HO

SucAn

48
70

25

O

O

+

7
69

IrPCY260% yield

6. Reaction time and Pathway

O

75

BPh4–

P
Cy2

Cl

triclinic, P-1,
R1 = 0.0684,
wR2 = 0.1754,
GOF = 1.092
H atoms except
hydride wereomitted forclarity.

Yields (%)

HOO

IrPCY2 (0–3.0 mol%)
Ar (1 atm)
toluene180 ºC, 18 h
[Ir]0 = 0–6.7 mMPCy2

35% yield

4. Screening of the amount of IrPCY2
O

N H N
Ir

33
34
18.0

O

Hypothesis
OH

HO
SucA

O

O

Δ
–H2O

O

O

O

O
SucA

O
O

HO2C

O

OH or

O
SucA
(0–0.22 M)

Substrate (mmol)
SucA (0.67)
SucAn(0.67)
SucA (0.335)+
SucAn (0.335)

CO2H
CO2H

HO2C

SucAn
(0–0.22 M)

IrPCY2 (1.5 mol%)
H2O (0 or 100 mol%)
Ar (1 atm)
toluene180 ºC, 18 h
[Ir]0 = 3.4 mM

H2O (mol%)conv. (%)

0

>99

O

O

O

– CO2

O

O

O

diGBL

O
O

yield of diGBL (%)
36

26

100

19

16

0

>99

28

85

8

100

O

diGBL

47

0

O

– H2O

Key Structure

Control Experiment
HO

O

+ H2O

O

Development of Fluoro-phosphoroamidate prodrug for Nucleotide
Analogs
Zheng Ti, Yuki Yoshida, Hirotaka Murase, Yasuaki Kimura, Hiroshi Abe
Research Centre for Materials Science, Nagoya University

Introduction

DesignThe problem of nucleoside analogue : Time of phosphorylation is toolong → long time results in drug convert into inactive form
Polarity form can hardly penetrate the cell memberane

Gemcitabine(anticancer drug )Deoxycytidine

slow

Gemcitabine (dFdC)
Nucleosidetransporter
Deoxycytidine
kinaseCytidinemonophosphate kinase
Diphosphate kinass

Cell membrane
dFdC

CDA

dFdCMP

dFdU

DCTD

fast

d

dFdUMP

5’-NT

dFdU (No drug effect)dFdCDP

5’-NT

dFdCTP

Recognized by DNA polymerase

dFdCTP (active form)

Outside cells

Cell memberane

Didanosine

Development of fluoride type phosphate prodrugs
Advantages ：The use of fluoride group leads to decrease of molecular weight
Side reaction is hard to occur due to the stability of P-F bondStavudine

抗B型肝炎剤
Lamivudine

Entecavir

Inside cells

Hydroxyl group connect to phosphoric acid lead to elevation of hydrophobicity → improvement of cellpermealbility
After being taken up by cells, the reaction to monophosphate by enzyme is fast→increase of efficiency byeliminating detoxified step

抗HIV剤
AZT

d

Sofosbuvir

Experimental Results

1. Synthesis of phosphate prodrugs

2. 殺がん細胞活性評価
HeLa: Cervical cancer cell line

H1299:Lung cancer cell line

3. Synthesis of anti-hepatitis prodrugs

Lamivudine

Sofosbuvir• Selectively react with 5’- hydroxyl group• In addition to Gemcitabine, other nucleoside analogs can also be synthesized under the same
reaction condition.

Conclusion ＆ Prospect
Conclusions• We developed a new type of Fluoride type phosphate prodrug andestablished a synthesis scheme.
• Cell assay shows that it is effective to cancer cells• The synthesis method is also applicable to other nucleotide analogs

Prospects• Make sure that the prodrug itself is not toxic.
• Evaluate anti-hepatitis effect of prodrugs

149

IRCCS

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福岡市西区元岡 744 九州大学先導物質化学研究所
TEL 092-802-2529 FAX 092-802-2528

機構事務室〒464-8602

名古屋市千種区不老町 名古屋大学物質科学国際研究センター
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IRCCS, Integrated Research Consortium on Chemical Sciences