IRCCS,
Integrated ResearchConsortium on
Chemical Sciences
統合物質創製化学研究推進機構
平成30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
平成30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

1‑1 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25

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．平成３０年度事業報告
3‑1 第２回 統合物質若手の会
3‑2 第４回 統合物質国内シンポジウム
3‑3 第２回 統合物質国際シンポジウム

35

1
統合物質創製化学研究推進機構について
統
合物
物質創製

1-1
本機構の背景㸯Ѹ㸯. ᮏᶵᵓࡢ⫼ᬒ 㠉᪂ⓗ࡞ᶵ⬟ᛶ≀㉁ࡢⓎぢ࡜๰㐀ࡀࠊ⛉Ꮫ࡜⛉Ꮫᢏ⾡࡟㣕㌍ⓗ࡞Ⓨᒎࢆࡶࡓࡽࡋ࡚
ࡁࡓࠋࡑࡢ᰿ᖿࢆᢸࡗ࡚ࡁࡓࡢࡀࠊཎᏊ࣭ศᏊ࡛ࣞ࣋ࣝ≀㉁ࢆ᥈ồࡋࠊ๰㐀ࡋࡘ࡙ࡅ࡚ࡁࡓࠕࡶࡢ࡙ࡃࡾࠖࡢ໬Ꮫࠊࡍ࡞ࢃࡕ≀㉁๰〇໬Ꮫ࡛࠶ࡿࠋ㇏࠿࡞≀㉁࡟ᙬࡽࢀࡓ
⌧௦♫఍ࡢᜏᖖⓗⓎᒎࢆ⥔ᣢࡋࠊᡃࡀᅜࡢ⛉Ꮫᢏ⾡❧ᅜ࡜ࡋ࡚ࡢᆅ఩ࢆᦂࡿࡂ࡞࠸ࡶ
ࡢ࡜ࡍࡿࡓࡵ࡟ࡶࠊḟୡ௦ࡢ㣕㌍ࢆ⣙᮰ࡍࡿ᪂ࡓ࡞ᶵ⬟ᛶ≀㉁⩌ࢆ๰㐀ࡋ࡚࠸࠿ࡡࡤ
࡞ࡽ࡞࠸ࠋ≉࡟ࠊ⥭㏕ࡍࡿ࢚ࢿࣝࢠ࣮࣭⎔ቃၥ㢟ࡢゎỴࡸ᭱ඛ➃ࣂ࢖࣭࢜᝟ሗᢏ⾡ࡢ㐍ᒎࢆᅗࡾࠊ⛉Ꮫᢏ⾡඲⯡ࡢᅜ㝿ⓗ➇தຊࢆ㧗ࡵࡿࡓࡵ࡟ࡶࠊ㠉᪂ⓗ࡞ᶵ⬟ᛶ≀㉁⩌ࡢ๰㐀࡜ࠊࡑࢀࡽࡢྜ⌮ྜᡂἲࡢ㛤ᣅ࡟ྥࡅࡓ᪂Ꮫ⾡ᇶ┙ࡢᵓ⠏ࡀᛴົ࡛࠶ࡿࠋ໬Ꮫ
⪅࡟ㄢࡏࡽࢀࡓ௵ົࡣᴟࡵ࡚㔜࠸ࠋ ḟୡ௦ࡢᶵ⬟ᛶ≀㉁๰〇ࡢ㘽ࢆᥱࡿࡢࡀࠊ≀㉁ࢆᵓᡂࡍࡿඖ⣲ࠊศᏊࠊศᏊ㞟ྜయ࡜࠸࠺㝵ᒙᛶࡢ⌮ゎ࡜ไᚚ࡛࠶ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋඖ⣲࡟ࡼࡾ≉ᚩ࡙ࡅࡽࢀࡿከ✀㢮ࡢཎᏊࡀ⤖ྜࢆసࡿࡇ࡜࡟ࡼࡾศᏊࡀᙧᡂࡉࢀࠊࡉࡽ࡟ศᏊࡀ㞟✚ࡍࡿࡇ࡜࡟ࡼࡾ
ศᏊ㞟ྜయ࡬࡜⤌⧊໬ࡉࢀࠊࡑࢀࡒࢀࡢ㝵ᒙ࡟≉᭷ࡢᛶ㉁ࡸᶵ⬟ࡀ࠶ࡿࠋ⏕య≀㉁ࡢ
ᵓ㐀࡟౛࠼ࡿ࡜ࠊಶࠎࡢཎᏊࡢ≉ᛶࢆᇶ♏࡜ࡋ㸦ඖ⣲㸧ࠊࡑࡢᶵ⬟ࢆⓎ᥹ࡍࡿ᭱ᑠ༢
఩࡜࡞ࡿࢱࣥࣃࢡ㉁ࡸ᰾㓟ࡀᵓᡂࡉࢀ㸦ศᏊ㸧ࠊࡇࢀࡽࡀࡉࡽ࡟㞟✚ࡋ࡚࢘࢖ࣝࢫࡸ
⣽⬊ෆ⤌⧊࡛࠶ࡿ࣑ࢺࢥࣥࢻࣜ࢔㸦ศᏊ㞟ྜయ㸧࡜࡞ࡿࠋ㧗ᗘ࡟ᶵ⬟໬ࡉࢀࡓ㠉᪂ⓗ࡞≀㉁ࢆ๰〇ࡍࡿࡓࡵ࡟ࡣࠊ඲࡚ࡢ㝵ᒙ࡟࠾ࡅࡿᵓᡂ༢఩ࢆ๰〇ࡍࡿ⾡ࢆᏛࡧࠊࡑࡢ
ᶵ⬟ࢆゎ᫂ࡋ࡞ࡅࢀࡤ࡞ࡽ࡞࠸ࠋ ᮏ஦ᴗ࡟ཧ⏬ࡍࡿி㒔኱Ꮫ࣭ྡྂᒇ኱Ꮫ࣭஑ᕞ኱Ꮫ࣭໭ᾏ㐨኱Ꮫࡢ㸲◊✲⤌⧊ࡣࠊࡑࢀࡒࢀࠕඖ⣲ࠖࠕศᏊࠖࠕ㞟ྜయࠖࠕゐ፹ࠖࢆ࣮࣮࢟࣡ࢻ࡜ࡋࡓᙉຊ࡞୰᰾ⓗᅜ㝿◊✲ᣐⅬ࡜ࡋ࡚ㄆ▱ࡉࢀ࡚࠸ࡿࠋᮏ஦ᴗࡢ๓㌟࡜࡞ࡿࠕ⤫ྜ≀㉁๰〇໬Ꮫ᥎㐍஦ᴗ Ѹ ඛᑟⓗྜᡂࡢ᪂Ꮫ⾡ᇶ┙ᵓ⠏࡜ḟୡ௦୰᰾◊✲⪅ࡢ⫱ᡂ㸦H22ࠥ27 ᖺᗘ㸧ࠖ࡟࠾࠸࡚ࡣࠊ
㸲◊✲⤌⧊ࡢࡑࢀࡒࢀࡀࢫࢺࣟࣥࢢ࣭࣏࢖ࣥࢺࢆࡶࡘྛ≀㉁㝵ᒙࢆ୰ᚰ࡟ࠊಶู࡟⵳
✚ࡉࢀ࡚ࡁࡓ≀㉁ྜᡂ࡟࠾ࡅࡿ▱㆑࡜▱ᜨࢆ⼥ྜ࣭῝໬ࡉࡏࡿ࡜࡜ࡶ࡟ࠊ≀㉁ྜᡂᴫ
ᛕࡢ⤫ྜ࡟ࡶྲྀࡾ⤌ࢇࡔࠋࡍ࡞ࢃࡕࠊྂ඾ⓗ࡞໬Ꮫ཯ᛂࢆ฼⏝ࡋࡓࠕ໬Ꮫⓗ≀㉁ྜᡂࠖ
࡜ࡶ࡟ࠊ㧗㉸ఏᑟయࡸⓎගᮦᩱࠊ༙ᑟయ࡞࡝ࡢ㛤Ⓨ࡟฼⏝ࡉࢀ࡚ࡁࡓࠕ≀⌮ⓗ≀㉁

ྜᡂࠖࡸࠊ⏕࿨యࡀ✜࿴࡞᮲௳ୗ࡟᪥ᖖⓗ࡟⾜ࡗ࡚࠸ࡿ⢭ᕦ࠿ࡘ㧗ຠ⋡࡞ࠕ⏕࿨≀㉁ྜᡂࠖ࡟ࡶᏛࡪࡇ࡜࡟ࡼࡗ࡚ࠊᣢ⥆ᆺ⤒῭♫఍ࢆᐇ⌧ࡍࡿࠊ⎔ቃ࡟ㄪ࿴ࡋࡓ᪂ࡓ࡞ࠕ≀㉁๰〇ᴫᛕࠖࡢ๰ฟࢆᐇ㊶ࡋࡓࠋࠕ≀㉁㝵ᒙࡢ⤫ྜࠖ࡜ࠕ≀㉁ྜᡂᴫᛕࡢ⤫ྜࠖࢆྜ4ゝⴥ࡜ࡋ࡚ࠊྛ◊✲ᶵ㛵ࡢ▱㆑࡜⤒㦂ࢆ⼥ྜ࣭῝໬ࡉࡏ࡚᪂ࡓ࡞≀㉁๰〇໬Ꮫࢆ㐙⾜ࡋࡓ⤖ᯝࠊኳ↛❅⣲㑏ඖ㓝⣲࡟࠾ࡅࡿᶵ⬟୰ᚰᵓ㐀ࡢ඲ྜᡂࠊ࣮࢝࣎ࣥࢼࣀࢳ࣮ࣗࣈ
ᵓ㐀ࡢ໬Ꮫྜᡂࠊప⎔ቃ㈇Ⲵࡢ㕲ゐ፹࡟ࡼࡿᾮᬗᮦᩱࡢྜᡂࠊᙉㄏ㟁ᛶ࡜ᙉ☢ᛶࡀඹᏑࡍࡿ࣐ࣝࢳࣇ࢙ࣟ࢖ࢵࢡ≀㉁ࡢ㛤Ⓨ࡞࡝ࠊ㠉᪂ⓗ࡞◊✲ᡂᯝࡀ⏕ࡲࢀࡓࠋࡉࡽ࡟ࠊ
ⱝᡭ◊✲⪅࡟⮬⏤㜏㐩࡞◊✲⎔ቃ࡜ࠊ኱Ꮫࡢᇉ᰿ࢆ㉺࠼ࡓඹྠ◊✲ࡸ᝟ሗ஺᥮ࡢᶵ఍
ࢆ୚࠼ࡓࡇ࡜࡟ࡼࡗ࡚ࠊ≀㉁๰〇໬Ꮫࡢᮍ᮶ࢆษࡾ㛤ࡃຊ㔞࠶ࡿḟୡ௦୰᰾◊✲⪅ࡢ⫱ᡂࢆᐇ⌧ࡋࡓࠋᮏ஦ᴗࡣࠊࡇࡢ 4 ኱Ꮫ㛫㐃ᦠ஦ᴗࢆࡉࡽ࡟⤌⧊໬࣭ࢩࢫࢸ࣒໬ࡋࡓ
ࠕ᪂ᶵᵓࠖࢆタ❧ࡋࠊ♫఍ࡢࢽ࣮ࢬ࡟ᛂ࠼ࡿࠕ⤫ྜ≀㉁๰〇໬Ꮫࠖࢆ᥎㐍ࡍࡿࠋ

5

1-2
本機構の目的㸯㸫㸰㸬ᮏᶵᵓࡢ┠ⓗ᪂≀㉁๰〇ࡣࠊ໬Ꮫ⤖ྜࡢᙧᡂࡢࡓࡵࡢ᪂ࡋ࠸᪉ἲㄽࡸࠊᶵ⬟ࡢⓎ⌧ࡢࡓࡵࡢ≀㉁ᵓ⠏ㄽ࡞࡝ࢆ᥈ồࡍࡿᴟࡵ࡚ᇶ♏ⓗ࡞ᇶ┙Ꮫ⾡࡛࠶ࡿ୍᪉ࠊࡑࡢᡂᯝࡣࠊ᪂ゐ፹ࡸ᪂ᮦᩱ㛤Ⓨࡣࡶࡕࢁࢇࠊ࢖ࣀ࣮࣋ࢩࣙࣥ๰ᡂࢆ㏻ࡌ࡚࢚ࢿࣝࢠ࣮࣭㈨※࠿ࡽ⎔ቃ࣭๰⸆࡟⮳ࡿᴟࡵ࡚ᗈ࠸⠊ᅖ࡟㐺⏝ࡉࢀࡿࠋࡇࡇ࡛ࡣࠊᇶ♏࡜ᛂ⏝ࡀ┤⤖ࡋ㸦⦪⣒㸧ࠊࡲࡓ໬Ꮫࢆ୰ᚰ࡜ࡋ࡚≀⌮࠿ࡽ⏕࿨⛉Ꮫࡲ࡛ࡢከࡃࡢ◊✲ศ㔝ࡢ༠ຊࡀᚲ㡲࡛࠶ࡿ㸦ᶓ⣒㸧ࠋࡍ࡞ࢃࡕࠊ≀㉁࡜᝟ሗࡑࡋ࡚ேࡀ㞟⤖ࡍࡿࡇ࡜ࡀఱࡼࡾ㔜せ࡞ศ㔝࡜ゝ࠼ࡼ࠺ࠋࡋ࠿ࡋ࡞ࡀࡽࠊᡃࡀᅜࡢ≀㉁๰〇◊✲ࡣᴟࡵ࡚㧗࠸ᅜ㝿➇தຊࢆࡶࡘ࡟ࡶ࠿࠿ࢃࡽࡎࠊ᪂≀㉁๰〇ࢆ⥲ྜⓗ࠿ࡘᡓ␎ⓗ࡟㐍ࡵࡿᶵ㛵࣭⤌⧊ࡣࠊṧᛕ࡞ࡀࡽᡃࡀᅜ࡟ࡣᏑᅾࡋ
࡞࠸ࠋᇶ♏࡜ᛂ⏝ࢆ⤖ࡪ⦪⣒࡜ከᵝ࡞ศ㔝ࢆ⤖ࡪᶓ⣒ࢆ⤌ࡳྜࡏࠊ㏆ᖺ㛗㊊ࡢ㐍Ṍࢆ㐙ࡆࡓࢼࣀィ

ࡸィ⟬໬Ꮫࢆྲྀࡾ㎸ࢇࡔ⤫ྜⓗ࡞◊✲⤌⧊ࡢᵓ⠏ࡀᛴົ࡛࠶ࡿࠋࡑࡢ

୍᪉࡛ࠊ⌧ᅾࡢࡦࡗ㏕ࡋࡓ㈈ᨻࡢୗ࡛ࡣࠊከࡃࡢ㠃✚࡜࣏ࢫࢺࢆᚲせ࡜ࡍࡿ᪂◊✲ᡤタ❧ࡢࡼ࠺࡞஦ᴗࡣ⌧ᐇⓗ࡛ࡣ࡞࠸ࠋ≀㉁๰〇ࡢᏛ⾡ࢆ⥅ᢎ࣭Ⓨᒎࡉࡏࠊ㏕ࡾࡃࡿ⎔ቃၥ㢟࡞࡝ࡢ㔜Ⅼㄢ㢟ࢆゎỴࡋࠊࡲࡓ᪂⏘ᴗ๰ฟࢆᡂࡍࡓࡵ࡟ࡣࠊ⏘ᐁᏛ㐃ᦠࡸᅜ㝿ᅗ㸯8㐃ᦠࢆ๓㠃࡟ฟࡋࠊ㈐௵࠶ࡿ࣐ࢿ࣮ࢪ࣓ࣥࢺయไࢆᣢࡕ࡞ࡀࡽࡶࠊ᭱ᑠ㝈ࡢ㠃✚࡜࣏ࢫࢺࡢ⋓ᚓ࡛㐙⾜࡛ࡁࡿࠊ኱Ꮫ㛫㐃ᦠࢆᇶ┙࡜ࡋࡓࠕ⤫ྜ≀㉁๰〇໬Ꮫ◊✲᥎㐍ᶵᵓࠖࡣࠊᚲせ࠿ࡘࢱ࢖࣒࣮ࣜ࡞஦ᴗ࡛࠶ࡿࠋ ᅗ㸯࡟⤫ྜ≀㉁๰〇໬Ꮫ◊✲᥎㐍ᶵᵓࡢᴫᛕᅗࢆ♧ࡍࠋᮏᶵᵓ஦ᴗ࡟ཧ⏬ࡍࡿྡྂᒇ኱Ꮫ࣭ி㒔኱Ꮫ࣭஑ᕞ኱Ꮫ࣭໭ᾏ㐨኱Ꮫࡢ㸲◊✲⤌⧊ࡣࠊࠕศᏊࠖࠊࠕඖ⣲ࠖࠊࠕ㞟ྜయࠖࠊࠕゐ፹ࠖࡢ໬Ꮫ◊✲࡟࠾࠸࡚ࠊࡑࢀࡒࢀ࡟≉Ⰽ࠶ࡿᙉຊ࡞୰᰾ⓗᅜ㝿◊✲ᣐⅬ࡜ࡋ࡚ㄆ▱ࡉࢀ࡚࠸ࡿࡀࠊ௨ୗ࡟♧ࡍࡑࢀࡒࢀࡢࢫࢺࣟࣥࢢ࣭࣏࢖ࣥࢺࢆά࠿ࡋ࡞ࡀࡽࠊ≀㉁ࡢ㝵ᒙᵓ㐀ࢆ⦪᩿ࡍࡿ◊✲㐃ᦠࢆᐇ⌧ࡍࡿࠋྡྂᒇ኱Ꮫ㸸↓ᶵ໬Ꮫ࠿ࡽ᭷ᶵ໬Ꮫ࡟ࢃࡓࡿศᏊᛶ≀㉁ࡢྜᡂ࡜ᶵ⬟ࡢⓎ⌧ࠊࡉࡽ࡟ࡣ୙ᩧ཯ᛂࢆྵࡴศᏊゐ፹ࡢ㛤Ⓨ◊✲࡟࠾࠸࡚༟㉺ࡋࡓᡂᯝࢆ࠶ࡆ࡚ࡁࡓࠋ᭱㏆࡛ࡣࠊ⏕≀↓ᶵ໬ᏛࡸࢼࣀⅣ⣲⛉Ꮫศ㔝࡟࠾࠸࡚ࡶୡ⏺ࢆ࣮ࣜࢻࡍࡿࠋ
ி㒔኱Ꮫ㸸ඖ⣲ࡢ≉ᛶࡢゎ᫂࡜ࠊࡑࢀ࡟ᇶ࡙ࡃᶵ⬟๰ฟࡢ໬Ꮫ࡟࠾࠸࡚ඛᑟⓗ࡞◊✲ᡂᯝࢆ࠶ࡆ࡚࠸ࡿࠋᶵ⬟ᛶඖ⣲⛉Ꮫ࡜࠸࠺᪂ࡋ࠸◊✲ࣃࣛࢲ࢖࣒ࢆᥦၐࡋࠊศᏊ
ᛶ≀㉁࠿ࡽจ⦰⣔≀㉁࡟⮳ࡿᵝࠎ࡞㠉᪂ⓗ᪂≀㉁⩌ࡢฟ⌧ࢆಁࡋ࡚ࡁࡓࠋ
஑ᕞ኱Ꮫ㸸」㞧࡞ศᏊ㞟ྜయ࣭㞟✚యࢆᵓ⠏ࡍࡿ᪂ᴫᛕࢆᥦฟࡋࠊከࡃࡢᶵ⬟ᛶ㞟✚యࡢྜᡂ◊✲ࢆ㏻ࡋ࡚ࢼࣀࢧ࢖࢚ࣥࢫ࣭ࢸࢡࣀࣟࢪ࣮◊✲࡟ඛ㠴ࢆࡘࡅࡓࠋ᭱㏆࡛ࡣࠊ᰾㓟ࢼࣀ࣐ࢩࣥࡸࢼࣀࣁ࢖ࣈࣜࢵࢻᮦᩱࡢ๰ฟ࡞࡝࡛㢧ⴭ࡞ᡂᯝࢆᣲࡆࡿࠋ
໭ᾏ㐨኱Ꮫ㸸ゐ፹໬Ꮫ࡟࠾࠸࡚ୡ⏺ࢆඛᑟࡍࡿ୰᰾ⓗ◊✲ᣐⅬ࡛࠶ࡿࠋゐ፹ඖ⣲࣭ศᏊࡢࢼࣀ࣭࣑ࢡࣟ㞟✚࣭㞟ྜ໬Ꮫࡢ◊✲ࢆ᥎㐍ࡋࠊ㈨※㧗ᗘ฼⏝ゐ፹ࠊ⎔ቃゐ፹ࠊࣂ࢖࢜฼⏝ゐ፹ࠊ⇞ᩱ㟁ụ࣭㟁ᴟゐ፹ࠊගゐ፹࡞࡝࡛ከࡃࡢᡂᯝࢆᣲࡆࡿࠋ
ࡉࡽ࡟ᮏ◊✲᥎㐍ᶵᵓ࡛ࡣࠊᇶ♏◊✲ࢆ୰ᚰ࡜ࡍࡿ୍᪉ࠊࠕ᪂཯ᛂ࣭᪂ゐ፹ࠖࠊࠕ࣐ࢸ
ࣜ࢔ࣝࠖࠊࠕ࢚ࢿࣝࢠ࣮࣭㈨※ࠖࠊࠕࢣ࣒ࣂ࢖࢜ࠖ࡜࠸࠺ࠊᛂ⏝ᒎ㛤ࢆព㆑ࡋࡓ 4 ࡘࡢฟཱྀࢆタᐃࡋ࡚ᇶ♏࡜ᛂ⏝ࢆ┤⤖ࡉࡏࡿࠋࡑࡢୖ࡛ࠊ⏘ᐁᏛ㐃ᦠࡸᅜ㝿㐃ᦠࢆ⤌⧊ⓗ࡟ྲྀࡾ㎸ࡳࠊ᪂ࡋ࠸◊✲ࢩࢫࢸ࣒ࡸ◊✲ᨭ᥼యไࠊேᮦ⫱ᡂࢩࢫࢸ࣒ࢆྲྀࡾධࢀࡓࠊ♫఍࡟㛤࠿ࢀࡓ᪂⤌⧊࡛࠶ࡿࠋ≀㉁๰〇࡟࠾ࡅࡿᡃࡀᅜࡢ◊✲ࡢཌࡳࢆ⥅ᢎࡋࠊ᪂Ꮫ
⾡࣭᪂⏘ᴗࡢ๰ฟ࡜ᚋ⥅ேᮦࡢ⫱ᡂࢆ୧❧ࡉࡏ࡞ࡀࡽࠊᣢ⥆ྍ⬟࡞♫఍ࡢⓎᒎࢆᑟࡃࠋ

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本機構の組織㸯㸫㸱㸬ᮏᶵᵓࡢ⤌⧊ ᮏᶵᵓ஦ᴗ࡛ࡣࠊ㸯㸫㸰࡛ㄝ᫂ࡋࡓᶵᵓ◊✲ࡢᴫᛕࢆᐇ⌧ࡍࡿࡓࡵࠊ඲ࡃ᪂ࡋ࠸኱
Ꮫ㛫㐃ᦠࡢࣇ࣮࣒࣮ࣞ࣡ࢡࢆᵓ⠏ࡍࡿࠋ୍⯡ㄽࡔࡀࠊࡇࢀࡲ࡛ࡢ኱Ꮫ㛫ࢿࢵࢺ࣮࣡ࢡ
஦ᴗࡀᢪ࠼ࡿၥ㢟Ⅼ࡜ࡋࡣࠊձ 㧗࠸኱Ꮫ㛫ࡢቨղ ฟཱྀタᐃࡀ㞴ࡋࡃࠊ◊✲┠ᶆࢆ❧࡚࡟ࡃ࠸ճ ᖹ➼୺⩏࡟ࡼࡿ࢞ࣂࢼࣥࢫ୙㊊մ ⦪๭ࡾ㸦኱Ꮫู㸧ࡢ◊✲ᨭ᥼࡜ேᮦ⫱ᡂᨭ᥼յ እ㒊ពぢࡀ཯ᫎࡉࢀ࡟ࡃ࠸ն 㐃ᦠࡢ࣓ࣜࢵࢺࡀࢿࢵࢺ࣮࣡ࢡෆ࡟㛢ࡌࡿ࡞࡝ࡀᣲࡆࡽࢀࡿ㸦ᅗ㸰(a)㸧ࠋ᭱኱ࡢၥ㢟Ⅼࡣն࡛ࠊ㐃ᦠࡢ࣓ࣜࢵࢺࡀ♫఍Ⓨಙࡉࢀࡎࠊࡲࡓ♫఍ࡢせㄳ࡟ࡼࡿ஦ᴗ࡜࠸࠺ព㆑ࡶᕼ࡛ⷧ࠶ࡗࡓࠋࢿࢵࢺ࣮࣡ࢡᙧᡂࡢࡼ࠺
࡞኱Ꮫᙉ໬஦ᴗࡣࠊ♫఍࠿ࡽࡢㄆ▱࡟ࡼࡗ࡚ࡣࡌࡵ࡚㐩ᡂࡉࢀࡿࡶࡢ࡛ࠊᮏ◊✲᥎㐍ᶵᵓ஦ᴗ࡟࠾࠸࡚ࡣࠊᡂᯝࠊ᝟ሗࠊேᮦࡀࢿࢵࢺ࣮࣡ࢡࡢእഃ࡟㍮ฟࡉࢀࡿእ㒊Ⓨಙᆺࡢ㐃ᦠࢆ┠ᣦࡋ࡚࠸ࡿࠋ◊✲᥎㐍ᶵᵓࡢ⤌⧊ᅗࢆᅗ㸱࡟♧ࡍࡀࠊ௨ୗࠊ㐠Ⴀయไࠊ⤫ᣓ◊✲㒊㛛ࠊ◊✲ᨭ᥼㒊㛛࡟ࡘ࠸࡚ࡑࡢᴫせࢆㄝ᫂ࡍࡿࠋ
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ᅗ㸰
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12

㐠Ⴀయไ ᮏ஦ᴗ᥎㐍࡟඲㈐௵ࢆ㈇࠺ᶵᵓ㛗ࢆ⨨ࡃࠋᶵᵓ㛗ࡣࠊᅜෆࡢᏛ㆑⤒㦂⪅㸦4ࠥ6 ྡ㸧ࡸ⌮໬Ꮫ◊✲ᡤ࡞࡝ࡢ㐃ᦠᶵ㛵࠿ࡽὴ㐵ࡉࢀࡓጤဨࠊᮏ஦ᴗࡢᐇ⾜ጤဨ࠿ࡽᵓᡂࡉࢀ
ࡿ㐠Ⴀጤဨ఍ࢆ⤌⧊ࡍࡿࠋ㐠Ⴀጤဨ఍ࡣࠊ㐃ᦠ஦ᴗィ⏬ࡢ⟇ᐃ࡜ᡂᯝࡢྲྀ⧳ࡵࢆ⾜࠺ࠋ㐠Ⴀጤဨ఍࡛ไᐃࡉࢀࡓ஦ᴗィ⏬ࡣࠊ◊✲⤫ᣓ㒊㛛ࡢ◊✲ࣉࣛࢵࢺ࣮࣒࣭࣮࣍ࣜࢲ࣮
࠿ࡽᵓᡂࡉࢀࡿᐇ⾜ጤဨ఍࡟ࡼࡗ࡚㐙⾜ࡉࢀࡿࠋ⤫ྜ◊✲㒊㛛 ᶵᵓ㛗࠾ࡼࡧ㐠Ⴀጤဨ఍ࡢ࣮ࣜࢲ࣮ࢩࢵࣉࡢୗࠊᛂ⏝࡜࠸࠺◊✲ࡢฟཱྀࢆព㆑ࡋࡓ
⤫ྜ◊✲㒊㛛㸦᪂཯ᛂ࣭᪂ゐ፹ࠊ࣐ࢸࣜ࢔ࣝࠊ࢚ࢿࣝࢠ࣮࣭㈨※ࠊࢣ࣒ࣂ࢖࢜ࡢ㸲◊✲ࣉࣛࢵࢺ࣮࣒࣍㸧ࢆタ⨨ࡍࡿࠋྛࣉࣛࢵࢺ࣮࣒࣍࡟ࡣࠊ㐃ᦠ኱Ꮫ࠿ࡽ㸯◊✲ᐊࡎࡘ㑅ᢤࡋࡓ㸲◊✲ᐊ࡜ࠊ⏘ᐁᏛ࣭ᾏእ࠿ࡽᣍ⪸ࡋࡓ㐃ᦠᐈဨ◊✲ᐊࢆタ⨨ࡋ࡚ඹྠ◊✲ࢆᐇ᪋ࡍࡿࠋྛࣉࣛࢵࢺ࣮࣒࣍࡟࠾ࡅࡿ◊✲ෆᐜࡣ௨ୗࡢ㏻ࡾ࡛࠶ࡿࠋ
᪂཯ᛂ࣭᪂ゐ፹◊✲㸸㐃ᦠ㸲኱Ꮫࡢᅛయゐ፹㸦໭኱㸧ࠊศᏊゐ፹㸦ྡ኱㸧ࠊඖ⣲ゐ፹㸦ி኱㸧ࠊศᏊ㞟ྜయゐ፹㸦஑኱㸧ࡢ◊✲ࢳ࣮࣒ࡢඹྠ◊✲࡟ࡼࡗ࡚ࠊࢮ࢚࣑ࣟ
ࢵࢩ࣭ࣙࣥ࢝ࢵࣉࣜࣥࢢ཯ᛂࡢ㛤Ⓨ࡞࡝ࠊᚲせ࡞ࡶࡢࢆᚲせ࡞ࡔࡅࢢ࣮ࣜࣥ࡟ࡘࡃ
ࡾࡔࡍ໬ᏛࢆⓎᒎࡉࡏࠊⅣ⣲ࢼࣀᮦᩱࡸ་⸆ရࡢ㠉᪂ⓗྜᡂ࡟ᒎ㛤ࡍࡿࠋ࣐ࢸࣜ࢔ࣝ◊✲㸸Ⅳ⣲ᮦᩱࠊࢼࣀ⢏Ꮚࠊ᭷ᶵ≀ࠊ↓ᶵᅛయࠊ㔠ᒓ㘒యࠊ㧗ศᏊ࡟⮳ࡿ≀㉁⩌ࡢ㛤Ⓨࡣࠊᶵᵓ㸲኱Ꮫࡀୡ⏺ࢆඛᑟࡋ࡚࠸ࡿศ㔝࡛࠶ࡿࠋࡑࡢ◊✲ࡣከᒱ࡟ࢃࡓࡿࡀࠊ౛࠼ࡤ㸲኱Ꮫࡀ㛤Ⓨࡍࡿ᪂つගᶵ⬟ᛶศᏊࢆ㉸ศᏊ໬ࡍࡿࡇ࡜࡟ࡼࡗ
࡚ࠊ᪤Ꮡࡢ⣽⬊࢖࣓࣮ࢪࣥࢢ࠿ࡽࠊศᏊ࢖࣓࣮ࢪࣥࢢࡸ᭦࡟ࡣᶵ⬟࢖࣓࣮ࢪࣥࢢ࡬
࡜Ⓨᒎࡉࡏࡿࠋ
࢚ࢿࣝࢠ࣮࣭㈨※◊✲㸸࢚ࢿࣝࢠ࣮࣭㈨※ၥ㢟ࡣ໬Ꮫࡀྲྀࡾ⤌ࡴ࡭ࡁ⥭ᛴㄢ㢟࡛࠶ࡿࠋ㔠ᒓࢼࣀ⢏Ꮚ࣭⏺㠃ࡢᶵ⬟໬㸦໭኱ࠊྡ኱㸧ࡸ㠉᪂ⓗࢼࣀ࣮࢝࣎ࣥᮦᩱ㛤Ⓨ㸦ྡ኱㸧ࢆ㏻ࡌ࡚ࠊ᪂ࡋ࠸⇞ᩱ㟁ụࡸኴ㝧㟁ụࢆ㛤Ⓨࡍࡿ㸦໭኱ࠊி኱ࠊ஑኱㸧ࠋ; ⥺྾཰ࢫ࣌ࢡࢺࣝィ 㸦໭኱ࠊྡ኱㸧࡞࡝࡟ࡼࡗ࡚཯ᛂᶵᵓࢆᢲࡉ࠼࡞ࡀࡽࠊࣘࣅ࢟
ࢱࢫඖ⣲ࡀ⏕ࡳฟࡍࢢ࣮࢚ࣜࣥࢿࣝࢠ࣮ࢆ๰〇ࡍࡿࠋࢣ࣒ࣂ࢖࢜◊✲㸸ேᕤ㓝⣲ࢆᐇ⌧ࡍࡿࡓࡵࡢᇶᮏタィࡢ☜❧ࡣࠊ⏕࿨⛉Ꮫ࡟࠾ࡅࡿ
୺㢟ࡢ୍ࡘ࡛࠶ࡿࠋ⏕యศᏊྜᡂ㸦஑኱㸧࡜ࢼࣀࢡࣛࢫࢱ࣮ᑟධᢏ⾡㸦ி኱㸧ࠊ࣑࣮ࣗࢸ࣮ࢩࣙࣥᢏ⾡㸦ྡ኱㸧ࢆ⤌ࡳྜࢃࡏࠊィ⟬ࢩ࣑࣮ࣗࣞࢩࣙࣥ㸦஑኱㸧ࢆ㐨ࡋࡿ࡭࡜ࡋ࡞ࡀࡽࠊᶵ⬟ࢆࡘࡃࡾࡇࢇࡔேᕤ㓝⣲ࡢྜᡂ࡟ࡲ࡛Ⓨᒎࡉࡏࡿࠋ

13ྛ◊✲ࣉࣛࢵࢺ࣮࣒࣍ࡢᵓᡂࡣ௨ୗࡢ㏻ࡾ࡛࠶ࡿࠋ
ࣉࣛࢵࢺ࣮࣒࣍ྡ

࣮ࣜࢲ࣮ࢥ࢔◊✲ᐊ࣓ࣥࣂ࣮

᪂཯ᛂ࣭᪂ゐ፹୰㔝⎔㸦໭኱㸧၏⨾ὠᮌ࣭ఀ୹೺୍㑻㸦ྡ኱㸧ࠊ୰ᮧṇ἞㸦ி኱㸧ࠊỌᓥⱥኵ࣭ᅧಙὒ୍㑻㸦஑኱࣐ࢸࣜ࢔ࣝ

ᓥᕝ♸୍㸦ி኱㸧 ΎỈ◊୍㸦໭኱㸧ࠊᒣཱྀⱱᘯ㸦ྡ኱㸧ࠊ㧗ཎ῟࣭཭ᒸඞᙪ㸦஑኱㸧࢚ࢿࣝࢠ࣮࣭㈨※ 㜿 Ἴ ㈡ 㑥 ኵ 㸦 ྡ ⚟ᒸ῟㸦໭኱㸧ࠊᑠ⃝ᩥᖾ࣭ᮧ⏣㟹ḟ㑻㸦ி኱㸧ࢣ࣒ࣂ࢖࢜

኱㸧ࠊబ⸨἞㸦஑኱㸧ྜྷ⃝୍ᡂ㸦஑኱㸧 㛗㇂ᕝ῟ஓ㸦໭኱㸧ࠊ㜿㒊ὒ㸦ྡ኱㸧ࠊ஧ᮌྐᮁ㸦ி኱㸧ྛࣉࣛࢵࢺ࣮࣒࣍࡟ࢢ࣮ࣝࣉ࣮ࣜࢲ࣮ࢆ⨨ࡁࠊྛศ㔝ࡢ㐃ᦠ◊✲ࡢ᥎㐍࡟㈐௵ࢆࡶࡘࠋ
ࡉࡽ࡟ࠊྛࣉࣛࢵࢺ࣮࣒࡛࣍ࡣⱝᡭ◊✲⪅ࢆ≉௵ຓᩍࡸ༤ኈ◊✲ဨ࡜ࡋ࡚㞠⏝ࡍࡿࠋࡇࢀࡽࡢⱝᡭ◊✲ࡣࠊඹ㏻ⱝᡭ࢚࣮ࢫே஦ࢩࢫࢸ࣒࡟ࡼࡾ᥇⏝ࡉࢀࡿࠋⱝᡭ◊✲⪅ࡢ
Ⓩ❳㛛࡜ࡋ࡚ᶵᵓࢆ఩⨨࡙ࡅࠊษ☩⌶☻࡟ࡼࡿேᮦ⫱ᡂ࡟ࡼࡗ࡚እ㒊ࡢࣃ࣮࣐ࢿࣥ
ࢺ࣭࣏ࢪࢩࣙࣥ࡟㏦ࡾฟࡍࠋ ᮏᶵᵓෆ࡟㝈ᐃࡏࡎࠊ⤫ྜⓗ࡞ඹྠ◊✲ࢆಁ㐍ࡍࡿࡓࡵࠊ⼥ྜ๰Ⓨ◊✲ࢆᐇ᪋ࡍࡿࠋ
ඹྠ◊✲ᥦ᱌ࢆ⾜࠸ࠊ㐠Ⴀጤဨ఍ࡢᑂᰝࢆ⤒࡚᥇ᢥㄢ㢟ࢆỴᐃࡋࠊᐇ᪋ࡍࡿࠋࡲࡓࠊ
ᖺᗘᮎ࡟◊✲ᡂᯝ࡟ࡘ࠸࡚ሗ࿌᭩ࢆసᡂࡋࠊ㐠Ⴀጤဨࡢࣞࣅ࣮ࣗࢆཷࡅࡿࡶࡢ࡜ࡍࡿࠋ
ᴫࡡẖᖺ 10 ௳⛬ᗘࢆᐇ᪋ࡍࡿࠋ
⤫ᣓᨭ᥼㒊㛛 ྡྂᒇ኱Ꮫ≀㉁⛉Ꮫᅜ㝿◊✲ࢭࣥࢱ࣮ෆ࡟タ⨨ࡋࠊࢭࣥࢱ࣮࡟௜タࡢ໬Ꮫᐃᶵჾᐊࢆ⏝࠸࡚ᮏ஦ᴗࡢ◊✲ࢆᨭ᥼ࡍࡿ࡜࡜ࡶ࡟ࠊᅜ㝿ࢩ࣏ࣥࢪ࣒࢘➼ࡢ㛤ദ࡟ᚲせ࡞እᅜே◊✲⪅ᣍ⪸࡟㛵ࢃࡿ஦ົᡭ⥆ࡁࠊᮏ஦ᴗࡢ◊✲ᡂᯝࡢྲྀ⧳ࡵࠊ࣏ࢫࢱ࣮ࡢసᡂࠊ
࣮࣒࣮࣍࣌ࢪࡢ⟶⌮࡞࡝ࡢᗈሗάືࢆᢸᙜࡍࡿࠋලయⓗ࡟ࡣࠊ௨ୗࡢᨭ᥼ࢆ⾜࠺ࠋձ እ㒊Ⓨಙ࣭ᅜ㝿Ⓨಙ㸸ᶵᵓࡢ◊✲ᡂᯝࢆࠊHP ࡸ✀ࠎࡢ࣓ࢹ࢕࢔࡞࡝ࢆ㏻ࡌ࡚
ᅜ㝿ⓗ࡟ᗈሗࡍࡿࠋղ ඹྠ◊✲ࢥ࣮ࢹ࢕ࢿࢺ㸸ᶵᵓ◊✲඲యࢆぢΏࡋ࡚ࠊ᪂ࡋ࠸ඹྠ◊✲ࢆⴌⱆࡉࡏࡿࠋճ ▱㈈Ⓨ᥀࡜⟶⌮㸸ᶵᵓ◊✲඲యࢆぢΏࡋ࡚ࠊ▱㈈⋓ᚓࢆᨭ᥼ࡍࡿࠋմ ⱝᡭ࢟ࣕࣜ࢔ࣃࢫᨭ᥼㸸ồ⫋᝟ሗࢆⱝᡭ࡟ὶᕸࡋࠊ࢟ࣕࣜ࢔ࣃࢫࢭ࣑ࢼ࣮ࢆᐇ᪋ࡍࡿࠋյ ఍㆟࣭ࢩ࣏ࣥࢪ࣒࢘㛤ദᨭ᥼㸸࣮࢜ࣉࣥཧຍᆺࢩ࣏ࣥ࡞࡝ࢆᗈሗࠊᨭ᥼ࡍࡿࠋ

14

1-4
本機構の組織㸯㸫㸲㸬ᮏᶵᵓࡢ≉㛗 ♫఍࡟㛤࠿ࢀࡓ᪂ᶵᵓࡣࠊ௨ୗࡢ㸳ࡘࡢ≉㛗ࢆᣢࡘࠋձ ᡓ␎ⓗ࡞࢞ࣂࢼࣥࢫ࡟ᇶ࡙ࡃ⼥ྜ◊✲㸸ᶵᵓ㛗ࡢ࣮ࣜࢲ࣮ࢩࢵࣉࡢୗࠊᛂ⏝࡜࠸࠺◊✲ࡢฟཱྀࢆព㆑ࡋࡓ⤫ྜ◊✲㒊㛛㸦᪂཯ᛂ࣭᪂ゐ፹ࠊ࣐ࢸࣜ࢔ࣝࠊ࢚ࢿ
ࣝࢠ࣮࣭㈨※ࠊࢣ࣒ࣂ࢖࢜ࡢ㸲◊✲ࣉࣛࢵࢺ࣮࣒࣍㸧ࢆタ⨨ࡋࠊྛࣉࣛࢵࢺ࣍
࣮࣒࡟ࡣࠊ㐃ᦠ኱Ꮫ࠿ࡽ㸯◊✲ᐊࡎࡘ㑅ᢤࡋࡓ㸲◊✲ᐊ࡜ࠊ⏘ᐁᏛ࣭ᾏእ࠿ࡽ
ᣍ⪸ࡋࡓ㐃ᦠᐈဨ◊✲ᐊࢆタ⨨ࡋ࡚ඹྠ◊✲ࢆᐇ᪋ࡍࡿࠋ᭦࡟⼥ྜ◊✲㒊㛛ࢆタ⨨ࡋࠊ⏘ᐁᏛࡸᅜ㝿㐃ᦠࡢሙ࡜ࡍࡿࠋ኱Ꮫ㛫ࡢቨࢆ஌ࡾ㉺࠼ࠊ࠿ࡘ㛤࠿ࢀࡓ◊✲⤌⧊ࢆᵓ⠏ࡍࡿࠋղ ࢖ࣀ࣮࣋ࢩࣙࣥ๰ฟ࡜ࢢ࣮ࣟࣂࣝ໬㸦ᅗ㸲㸧㸸◊✲㒊㛛ࢆᶓ᩿ⓗ࡟ᨭ᥼ࡍࡿࡓ
ࡵ⤫ᣓᨭ᥼㒊㛛ࢆタ⨨ࡋࠊ࣐ࢿ࣮ࢪ࣓ࣥࢺᩍဨࠊࣉࣟࢪ࢙ࢡࢺᨭ᥼ဨ࡞࡝ࢆ㓄⨨ࡍࡿࠋඹྠ◊✲ࢥ࣮ࢹ࢕ࢿ࣮ࢺࠊ▱㈈⋓ᚓࠊᅜ㝿Ⓨಙࠊⱝᡭேᮦ⫱ᡂ࡞࡝ࢆࠊ
኱Ꮫ㛫ࡢቨࢆྲྀࡾᡶࡗ࡚⾜࠺ࠋ⌮໬Ꮫ◊✲ᡤ࡞࡝ࢆ㐃ᦠᶵ㛵࡜ࡋ࡚ຍ࠼ࠊ࢖ࣀ
࣮࣋ࢩࣙࣥ๰ฟ࡞࡝ࢆά
ᛶ໬ࡍࡿࠋճ እ㒊Ⓨಙᆺ㐃ᦠ㸸᪂ࡋ࠸⏘ᐁᏛ㐃ᦠ࡜ᅜ㝿㐃ᦠࡢࣃࣛࢲ࢖࣒ࢆᵓ⠏ࡍࡿࠋ࣮࢜
ࣉࣥཧຍᆺࡢᡂᯝሗ࿌఍
࡞࡝ࢆ㛤ദࡍࡿࡇ࡜࡟ࡼ

ᅗ㸳ࡗ࡚ࠊ◊✲ᡂᯝ࣭◊✲᝟ሗ࣭ேᮦࢆࠊ⏘ᴗ⏺ࠊᐁ⏺ࠊᏛ⏺ࠊᾏእ࡟ᑐࡋ࡚እྥࡁ
࡟Ⓨಙ࣭㍮ฟࡍࡿࠋ
մ ඹ㏻ⱝᡭ࢚࣮ࢫே஦ࢩࢫ
ࢸ࣒㸦ᅗ㸳㸧㸸኱Ꮫ㝔⏕࠿ࡽⱝᡭ◊✲⪅ࡲ࡛ࠊྛ㝵ᒙࡢࢽ࣮ࢬ࡟ྜࢃࡏࡓேᮦ
⫱ᡂࢆ⾜࠺ࠋ≉௵ຓᩍࡸ◊

16

ᅗ㸲

✲ဨࡢே஦ࡘ࠸࡚ࡣࠊඹ㏻ⱝᡭ࢚࣮ࢫே஦ࢩࢫࢸ࣒ࢆ᥇⏝ࡍࡿࠋࡍ࡞ࢃࡕࠊ㐃
ᦠ኱Ꮫඹ㏻ࡢ㑅⪃ጤဨ఍ࢆタ⨨ࡋ࡚ே㑅ࡍࡿࠋᶵᵓࡢ◊✲άືࢆேᮦࢩ࣮ࣙࢣ
࣮ࢫ࡜ࡋ࡚฼⏝ࡋ࡚ⱝᡭࡢ࢟ࣕࣜ࢔ࣃࢫᙧᡂࢆᨭ᥼ࡍࡿ࡜ඹ࡟ࠊࣞࢡࢳ࣮ࣕࢩ
ࢵࣉὴ㐵ࡸᣍ⪸࡟ࡼࡾᅜ㝿ⓗே⬦ᙧᡂࢆಁࡍࠋⱝᡭ◊✲⪅ࡢⓏ❳㛛࡜ࡋ࡚ᶵᵓ
ࢆ఩⨨࡙ࡅࠊษ☩⌶☻࡟ࡼࡿேᮦ⫱ᡂ࡟ࡼࡗ࡚እ㒊ࡢࣃ࣮࣐ࢿࣥࢺ࣭࣏ࢪࢩࣙ
ࣥ࡟㏦ࡾฟࡍࡇ࡜࡟ࡼࡾࠊ≀㉁๰〇ศ㔝࡟࠾ࡅࡿ᪂ࡓ࡞ேᮦ⫱ᡂࣔࢹࣝࢆᐇ⌧
ࡍࡿࠋ
յ ࢼࣀィ

࡜ィ⟬໬Ꮫࡢᨭ᥼㸸ࢼࣀィ࡜ィ⟬໬Ꮫࡢᨭ᥼ࡢୗࠊྜ⌮ⓗ࡞≀㉁๰

〇◊✲ࢆᒎ㛤ࡍࡿࠋ௨ୖࠊᇶ♏◊✲ࢆ㔜どࡋ࡞ࡀࡽࡶࠊᛂ⏝࡜࠸࠺◊✲ࡢฟཱྀࢆព㆑ࡋࡓ㸲ࢸ࣮࣐࡟ྛ
኱Ꮫ࠿ࡽ㸯◊✲ᐊࢆ㏦ࡾ㎸ࡴᙧ࡛⤫ྜ◊✲㒊㛛ࢆᙧᡂࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ஫࠸ࡢ◊✲ࡢᙉࡳࢆ⿵᏶ࡍࡿ◊✲యไࢆᩜࡃࠋ࢞ࣂࢼࣥࢫࢆຠ࠿ࡋࡓᶵᵓ㐠Ⴀ࡟ࡼࡗ࡚ᣍ⪸ࡉࢀࡿࠊ⌮໬Ꮫ◊✲ᡤ࡞࡝࠿ࡽࡢᐈဨ◊✲ᐊࡢᏑᅾࡣࠊ⏘ᐁᏛ࡜ࡢ⤖ࡧࡘࡁࢆᙉ໬ࡍࡿ࡜
ඹ࡟ࠊᶵᵓ⤌⧊ࡢὶືᛶࢆ㧗ࡵࡿࡔࢁ࠺ࠋࡇࡢୖ࡛ࠊ኱Ꮫࡢቨࢆ㉺࠼ࡓ⤫ᣓᨭ᥼㒊㛛࡟ࡼࡿຠ⋡ⓗ࡞▱㈈Ⓨ᥀ࡸᅜ㝿Ⓨಙ࡟ࡼࡗ࡚ࠊ᪂ᶵᵓࡢࣅࢪࣅࣜࢸ࢕ࡣᚲ↛ⓗ࡟㧗ࡲࡿࠋࡇࡢࡼ࠺࡟ࠊ♫఍ࢆព㆑ࡋࡓᶵᵓࡢ◊✲άືࡣࠊ㝔⏕ࡸⱝᡭ◊✲⪅ࡢேᮦࢩ࣮ࣙ
ࢣ࣮ࢫ࡜ࡋ࡚స⏝ࡋࠊ๓㏙ࡋࡓඹ㏻ⱝᡭ࢚࣮ࢫே஦ࢩࢫࢸ࣒ࡣேᮦࡢὶືᛶࢆᚲ↛ⓗ࡟⏕ࡳฟࡍࠋ

17

1-5
事業計画

㸯㸫㸳㸬஦ᴗィ⏬ ᮏ஦ᴗࡢ࣮ࣟࢻ࣐ࢵࣉࢆᅗ㸴࡟♧ࡍࠋ

ᅗ㸴

20

1-6
本機構の期待される成果と波及効果㸯㸫㸴㸬ᮏ஦ᴗࡢᮇᚅࡉࢀࡿᡂᯝ࡜Ἴཬຠᯝ
㸯㸧ᮏ஦ᴗࡀࡵࡊࡍ≀㉁㝵ᒙࡢ⤫ྜ࡜≀㉁ྜᡂᴫᛕࡢ⤫ྜ࡟ࡼࡾࠊ⥲ྜⓗ࡞≀㉁ほ࡟ᇶ࡙ࡃከᙬ࡞≀㉁๰〇ἲࡀ๰ฟࡉࢀࡿࠋࡑࢀࡽࡣࠊ⏕యᶵ⬟ࠊ㟁Ꮚᶵ⬟ࠊගᶵ⬟ࠊゐ፹ᶵ⬟࡞࡝ࡢ᭷⏝ᶵ⬟ࢆࡶࡘᶵ⬟ᛶ≀㉁⩌ࢆ๰㐀ࡍࡿࡓࡵࡢ᪂Ꮫ⾡ᇶ┙ࡢᵓ⠏࡬࡜ᒎ㛤ࡉࢀࡿࠋ
㸰㸧㠉᪂ⓗ࡞ᶵ⬟ᛶ≀㉁⩌ࡢ๰〇ࡣࠊᮦᩱ⛉Ꮫศ㔝࡟㠉᪂ࢆࡶࡓࡽࡍࠋࡇࢀࡲ࡛ࡢ≀㉁ྜᡂ࡛ࡣࠊࢼࣀࢸࢡࣀࣟࢪ࣮࡛ከ⏝ࡉࢀࡿ⇕ຊᏛᨭ㓄࡟ࡼࡿ⮬ᕫ⤌⧊໬ࡀᣦᑟཎ⌮࡜ࡋ࡚⏝࠸ࡽࢀ࡚ࡁࡓࠋࡇࢀ࡟ᑐࡋ࡚ࠊᮏ஦ᴗ࡛ࡣࠊ‽Ᏻᐃ≀㉁ࡢྜᡂἲࡢ㛤ᣅ࡟ࡼࡾࠊ⮬ᕫ⤌⧊໬ࢆ㉸࠼ࡓ᪂つᶵ⬟ᛶ≀㉁⩌ࡢ๰〇ἲࡀ㛤Ⓨࡉࢀࡿࡶࡢ࡜ᮇᚅࡉࢀࡿࠋ
ࡇࢀ࡟ࡼࡾࠊ㧗ᅽྜᡂ࡜ⷧ⭷ᢏ⾡ࡢ⼥ྜ࡟ࡼࡿ㠀ᖹ⾮≀㉁⩌ࡢ๰〇ࠊேᕤ㉸᱁Ꮚࢆࡶࡘ≉␗࡞㧗ḟᵓ㐀యࡢྜᡂࠊග☢Ẽ≉ᛶࢆ♧ࡍ᪂つ㘒యࡸ᭷ᶵⓎග⣲Ꮚࡢ㛤Ⓨࠊ㓝⣲཯ᛂࡢゎ᫂࡜⏕࿨ᶵ⬟ࡢ⌮ゎ࡟㈨ࡍࡿேᕤ㓝⣲ࡢྜᡂ࡞࡝ࡀ㐩ᡂࡉࢀࠊ᭱ඛ➃ࡢࣂ࢖࣭࢜᝟ሗᢏ⾡࡬࡜ᛂ⏝࣭ᒎ㛤ࡉࢀࡿࠋ㸱㸧⦪⣒㸦ᇶ♏࡜ᛂ⏝㸧࡜ᶓ⣒㸦ከᵝ࡞ศ㔝㸧ࡀ⤖ࡤࢀࠊ⏘ᐁᏛཬࡧᅜ㝿ⓗ࡟㛤࠿ࢀࡓ≀㉁๰〇໬Ꮫ◊✲ࡀᐇ᪋ࡉࢀࠊ≀㉁๰〇໬Ꮫࡢ᪂ࡋ࠸Ꮫ⾡ᇶ┙ࡀᵓ⠏ࡉࢀࡿࠋࡑࡢ
⤖ᯝࠊ⎔ቃ࡟ඃࡋ࠸᪂ゐ፹㛤ᣅࠊ᪂つᶵ⬟㟁Ꮚ≀㉁࡟ᇶ࡙ࡃ㦵ኴ࢖ࣀ࣮࣋ࢩࣙࣥࠊ᭦
࡟ࡣ᪂་⸆ရࡸ⏕యάᛶ≀㉁㛤Ⓨࡀᡂࡉࢀࡿࠋࡇࢀࡽࡣᣢ⥆ྍ⬟࡞ᩥ᫂♫఍ࡢᵓ⠏࡟኱ࡁࡃ㈉⊩ࡍࡿࠋ
㸲㸧㧗ᗘ࡞◊✲ᶵ⬟ࢆࡶࡘᅜ㝿◊✲ᣐⅬࡢ᭷ᶵⓗ㐃ᦠ࡟ࡼࡾࠊከࡃࡢⱝᡭ◊✲⪅࡟ᗈ⠊࡞Ꮫၥ㡿ᇦࢆ⤫ྜࡋࡓ༟㉺ࡋࡓ◊✲⎔ቃࢆᥦ౪ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡇࡢࡼ࠺࡞⎔ቃࡣࠊᖜᗈ࠸▱㆑࡜」║ⓗᛮ⪃ຊࢆഛ࠼ࡓ୰᰾◊✲⪅ࡢ㣴ᡂ࡟ᚲせ୙ྍḞ࡞せ௳࡛࠶ࡿࠋ
ᮏ஦ᴗ࡛ࡣࠊⱝᡭ◊✲⪅ࢆ⤫ྜ◊✲ࣇ࢙࣮ࣟ࡜ࡋ࡚ฎ㐝ࡋࠊ⮬⏤࡛๰㐀ⓗ࡞◊✲⎔ቃࢆᥦ౪ࡍࡿࠋࡇࢀ࡟ࡼࡾࠊ≀㉁๰〇໬Ꮫࡢᑗ᮶ࢆᢸ࠺୰᰾◊✲⪅ࢆከᩘ⫱ᡂ࡛ࡁࡿࡶ
ࡢ࡜ᮇᚅࡉࢀࡿࠋࡲࡓࠊᅜ㝿◊✲ᣐⅬࡢ㐃ᦠࡣࠊᡃࡀᅜࡢᏛ⾡ⓗඛ㐍ᛶ࡜ᅜ㝿➇தຊࢆ☜ಖࡍࡿࡓࡵ࡟ࡶ㔜せ࡛࠶ࡾࠊከࡃࡢⱝ⪅࡟ࠊᾏእࡢ୍ὶ◊✲⪅࡜ษ☩⌶☻ࡍࡿᶵ఍ࢆᥦ౪ࡋࠊᅜ㝿ⓗ࡞◊✲⪅࡜ࡋ࡚ᡂ㛗ࡍࡿࡓࡵࡢ࢖ࣥࢭࣥࢸ࢕ࣈࢆ୚࠼ࡿࠋ
㸳㸧ᮏ⏦ㄳࡀᥦ᱌ࡍࡿ᪂ᶵᵓࡢࢫ࣮࣒࢟ࡢ᭷ຠᛶࡣࠊ≀㉁๰〇໬Ꮫศ㔝࡟ࡔࡅ㝈ᐃࡉࢀ࡞࠸ࠋࡇࡢࢫ࣮࣒࢟࡟ࡼࡾࠊཧຍ኱Ꮫࡢᙉࡳࢆ⏕࠿ࡋ࡚ᡃࡀᅜࡢᏛ⾡ࢆ⤖㞟࡛ࡁࡿ࡯࠿ࠊ኱Ꮫ㛫㐃ᦠࡢ࣓ࣜࢵࢺࡀ⏘ᐁᏛ㐃ᦠࡸᅜ㝿㐃ᦠࢆ㏻ࡌ࡚እྥࡁ࡟Ⓨಙࡉࢀࡿࡇ
࡜࡟ࡼࡾࠊ♫఍࠿ࡽࡢᨭᣢࡶᚓࡽࢀࡿࠋࡇࡢຠᯝࡣࠊ᪂ᅜ❧◊✲ᡤࡢタ❧࡟ࡶ༉ᩛࡍ

22ࡿࠋࡇࡢࡼ࠺࡞እྥࡁࣜࣥࢡࡢ኱Ꮫ㛫㐃ᦠ஦ᴗࡢࣃ࢖ࣟࢵࢺࣉࣟࢢ࣒ࣛ࡜ࡋ࡚ࠊ௚ศ
㔝࡬ࡢἼཬຠᯝࡸ࢖ࣥࣃࢡࢺࡶ኱ࡁ࠸ࠋ
㸴㸧஦ᴗィ⏬⤊஢ᚋࡣࠊ᪂≀㉁๰〇ࢆ⥲ྜⓗ࠿ࡘᡓ␎ⓗ࡟㐍ࡵࡿ◊✲ࢩࢫࢸ࣒࡜࠸࠺
ᯟ⤌ࡳࡣṧࡋ࡞ࡀࡽࡶࠊ⤫ᣓ◊✲㒊㛛࡟࠾ࡅࡿ◊✲ࢸ࣮࣐ࡸཧຍ◊✲ᐊࢆ඲㠃ⓗ࡟ぢ┤ࡋࠊࡲࡓ⌧ᅾࡢ㐃ᦠ 4 ኱Ꮫ௨እ࠿ࡽࡢཧຍࢆಁࡋ࡚࣮࢜ࣝࢪࣕࣃࣥయไࢆࡘࡃࡾࠊ
᭦࡟㐍ࢇࡔ≀㉁๰〇᭱ඛ➃◊✲ࢆ㐍ࡵࡿࠋ

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ᕴ࿴⾜ ྡྂᒇ኱Ꮫ≀㉁⛉Ꮫᅜ㝿◊✲ࢭࣥࢱ࣮≉௵ᩍᤵ

28

● 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

㸺ࢥ࢔࣭㐃ᦠ◊✲ᐊ㸼ᮅ಴Ύ㧗 ᩍᤵ㸦ᇶ♏◊✲⣔࣭ゐ፹⾲㠃◊✲㒊㛛㸧㛗㇂ᕝ῟ஓ ᩍᤵ㸦ᇶ♏◊✲⣔࣭ゐ፹⌮ㄽ◊✲㒊㛛㸧⚟ᒸ ῟ ᩍᤵ㸦ᇶ♏◊✲⣔࣭≀㉁ኚ᥮◊✲㒊㛛㸧ΎỈ◊୍ ᩍᤵ㸦ᇶ♏◊✲⣔࣭ゐ፹ᮦᩱ◊✲㒊㛛㸧኱㇂ᩥ❶ ᩍᤵ㸦ᇶ♏◊✲⣔࣭ගゐ፹⛉Ꮫ◊✲㒊㛛㸧㧗ᶫ ಖ ᩍᤵ㸦ᇶ♏◊✲⣔࣭ศᏊゐ፹◊✲㒊㛛㸧୰㔝 ⎔ ᩍᤵ㸦ᇶ♏◊✲⣔࣭㧗ศᏊᶵ⬟⛉Ꮫ◊✲㒊㛛㸧す⏣ࡲࡺࡳ ᩍᤵ㸦ᐇ⏝໬᥎㐍⣔࣭◊✲㛤Ⓨ㒊㛛㸧㸺ࣜࢧ࣮ࢳࣇ࢙࣮ࣟ㸼͐ᖹᡂ  ᖺ  ᭶ᮎ⌧ᅾ
SIDDIKI, S. M. A. Hakim ≉௵ຓᩍ㸦ᇶ♏◊✲⣔࣭ゐ፹ᮦᩱ◊✲㒊㛛㸧బᕝᣅ▮ ◊✲ဨ㸦ᇶ♏◊✲⣔࣭≀㉁ኚ᥮◊✲㒊㛛㸧

29

● 名古屋大学
エネルギー・資源研究プラットホーム メンバー一覧

㸺ࢥ࢔࣭㐃ᦠ◊✲ᐊ㸼㜿Ἴ㈡㑥ኵᩍᤵ㸦≀ᛶ໬Ꮫ㸧ᒣཱྀⱱᘯᩍᤵ㸦ᶵ⬟᭷ᶵ໬Ꮫ㸧ఀ୹೺୍㑻ᩍᤵ㸦᭷ᶵ໬Ꮫ㸧၏⨾ὠᮌᩍᤵ㸦↓ᶵ໬Ꮫ㸧㜿㒊ὒᩍᤵ㸦⏕≀᭷ᶵ໬Ꮫ㸧㔝౫Ⰻ἞≉ูᩍᤵ࣭ᩪ⸨㐍ᩍᤵ㸦ศᏊゐ፹໬Ꮫ㸧⏣୰೺ኴ㑻ᩍᤵ㸦ศᏊ⤌⧊໬Ꮫ㸧⳻ᕝ᫂ᰤᩍᤵ㸦ග≀⌮໬Ꮫ㸧⠛ཎஂ඾ᩍᤵ㸦≀⌮໬Ꮫ㸧Ώ㎶ⰾேᩍᤵ㸦⏕≀↓ᶵ໬Ꮫ㸧㸺ࣜࢧ࣮ࢳࣇ࢙࣮ࣟ㸼͐ᖹᡂ  ᖺ  ᭶ᮎ⌧ᅾ
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● 京都大学
マテリアル研究プラットホーム メンバー一覧

㸺ࢥ࢔࣭㐃ᦠ◊✲ᐊ㸼୰ᮧṇ἞ᩍᤵ㸦᭷ᶵศᏊኚ᥮໬Ꮫ㸧ᓥᕝ♸୍ᩍᤵ㸦ඛ➃↓ᶵᅛయ໬Ꮫ㸧ᑠ⃝ᩥᖾᩍᤵ㸦㘒యゐ፹ኚ᥮໬Ꮫ㸧㔠ග⩏ᙪᩍᤵ㸦ගࢼࣀ㔞Ꮚ≀ᛶ໬Ꮫ㸧ᮧ⏣㟹ḟ㑻ᩍᤵ㸦ᵓ㐀᭷ᶵ໬Ꮫ㸧஧ᮌྐᮁᩍᤵ㸦⏕యᶵ⬟タィ໬Ꮫ㸧᫬௵ᐉ༤ ᩍᤵ㸦᭷ᶵඖ⣲໬Ꮫ㸧ⱝᐑ῟ᚿ ᩍᤵ㸦ศᏊ㞟ྜゎᯒ㸧㸺ࣜࢧ࣮ࢳࣇ࢙࣮ࣟ㸼͐ᖹᡂ  ᖺ  ᭶ᮎ⌧ᅾGELDSETZER, Jan ≉ᐃ◊✲ဨ㸦᭷ᶵศᏊኚ᥮໬Ꮫ㸧ᚋ⸨┿ே◊✲ဨ㸦ඛ➃↓ᶵᅛయ໬Ꮫ㸧㜿Ἴ㐃▱Ꮚ◊✲ဨ㸦ගࢼࣀ㔞Ꮚ≀ᛶ⛉Ꮫ㸧GUO, Jing-Dong ◊✲ဨ㸦᭷ᶵඖ⣲໬Ꮫ㸧
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31

● 九州大学
ケムバイオ研究プラットホーム メンバー一覧

㸺ࢥ࢔࣭㐃ᦠ◊✲ᐊ㸼ྜྷ⃝ ୍ᡂ ᩍᤵ㸦཯ᛂ࣭≀ᛶ⌮ㄽศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧బ⸨ ἞ ᩍᤵ㸦ศᏊ≀㉁໬Ꮫศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧ᅧಙ ὒ୍㑻 ᩍᤵ㸦ᶵ⬟ศᏊ໬Ꮫศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧཭ᒸ ඞᙪ ᩍᤵ㸦㞟✚ศᏊᶵ⬟ศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧Ọᓥ ⱥኵ ᩍᤵ㸦ࢡࣛࢫࢱ࣮ศᏊ໬Ꮫศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧㧗ཎ ῟ ᩍᤵ㸦」ྜศᏊࢩࢫࢸ࣒ศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧㸺ࣜࢧ࣮ࢳࣇ࢙࣮ࣟ㸼͐ᖹᡂ  ᖺ  ᭶ᮎ⌧ᅾሷ⏣ ῄோ ෸ᩍᤵ㸦཯ᛂ࣭≀ᛶ⌮ㄽศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧㔠ᕝ ៅ἞ ຓᩍ㸦ศᏊ≀㉁໬Ꮫศ㔝࣭ඛᑟ≀㉁໬Ꮫ◊✲ᡤ㸧
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34

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統合物質創製化学研究推進機構
第4回国内シンポジウム

物質創製化学の多様化と深化

北海道大学

触媒科学研究所

名古屋大学

物質科学国際研究センター

京都大学

化学研究所

九州大学

先導物質化学研究所

日時： 2018 年 10 月 29 日（月）13:00~18:20
2018 年 10 月 30 日（火） 9:30~15:00
会場： 九州大学 筑紫キャンパス
総合研究棟（C-CUBE）1F 筑紫ホール

47

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General Method for the Synthesis ofTransition-metal Dichalcogenide Nanoribbons Inside Carbon Nanotubesǧİ ­ĸʤEllne ParkʤZheng LiuʤƉƬ çǪʤɂ Æʤ
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Activation of methane at metal-support interface of Ni4-CeO2 (111) catalyst:
A Theoretical study
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Kazunari Yoshizawa
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52

Electronic Structure Origin of
Mechanochemically Activated Chitin Depolymerization
Danjo De ChavezʤAtsushi FukuokaʤJun-ya Hasegawa

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Development of Transparent Organic Hole-Transporting Materials Containing
Partially Oxygen-bridged Triphenylamine Skeletons
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P-40

Preparation and Redox Behavior of Ce-Cr-Rh Mixed Oxides
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DFT Exploration of Active Site Motifs in Methane Hydroxylation by
Ni-ZSM-5 ZeoliteMuhammad Haris MahyuddinʤKazunari Yoshizawa
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Synthesis and properties of phenanthroline polymers having a pi-stackedʤ
helical conformation
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56

Oxidation of Trace Ethylene at 0 ºC overPlatinum Nanoparticles Supported on Silica
Shazia Sharmin SatterʤJun HirayamaʤKiyotaka NakajimaʤAtsushi Fukuoka,/ǀnP\|vßŘ

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Photocatalytic CO2 reduction using an iridium complex with
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Kenji KamadaʤManami MurakiʤJieun JungʤKieta Sekizawaʤ
Shunsuke SatoʤTakeshi MorikawaʤShunichi Fukuzumiʤ
Ryoji Noyori
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P-63

Efficient and Reproducible Lead-free Perovskite Solar Cells Based on
Purified Precursor Materials and Modified Solution Process
Jiewei LiuʤMasashi OzakiʤShinya YakumaruʤTaketo Handaʤ
Yoshihiko KanemitsuʤTakashi SaitoʤYuichi ShimakawaʤYasujiro Murataʤ
Tomoya NakamuraʤRichard MurdeyʤAtsushi Wakamiya
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P-64

Metal-loaded TiO2 photocatalysts for dehydrogenation of methanol underflow conditions
Kensuke KobayashiʤRyoko NagataʤRyoji NoyoriʤSusumu Saito,
Hiroshi Naka
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57

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Synthesis of gold-nanoparticle/silica colloidal crystal to form highly orderedtitania inverse-opal structures
Tharishinny Raja Mogan1,Mai Takashima1,2,Ewa Kowalska1,2 and Bunsho Ohtani1,2*
1Graduate School of Environmental Science, Hokkaido University, Sapporo 060-0810, Japan
2Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan*Corresponding author: ohtani@cat.hokudai.ac.jp
Titania (TiO2) as photocatalyst

Our proposed idea

¾Lack of photochemical
activity under visible light¾Only 3-5% of sunlight is UVTITANIA INVERSE OPAL (TIO2-IO)
CONTAINING SINGLE GOLDNANOPARTICLE (AU-NP)
PER VOID

Theories behind the proposed idea

Schematic procedure to synthesize
TiO2-IO containing Au-NP per void

TiO2
void
Au-NP

optical stop-band effect of
TIO2-IO structure

localized surface plasmon resonance(LSPR) of Au-NP

give rise to visible light absorption

Synthesis of Au/SiO2 colloidal crystal is VITAL STEP to form
highly ordered TiO2-IO structure as the desired photocatalyst!

ACS Appl.Mater.Interfaces 2016,8, 31738-31745

Formation of Au/SiO2 core-shellSelf-assembly of Au/SiO2 core-shell
Formation of coreless
SiO2 particles

Amount of catalyst
used (NH3)Amount of
SiO2 precursor)

affects the self-assembly process
prevents the formation of highly ordered
colloidal crystal structure

no coreless particles observed

Thickness of SiO2 shell formed (nm)

FACTORS AFFECTING FORMATION OF Au/SiO2
CORE-SHELL PARTICLES

Number ofparticles present
in Au/thinSiO2

Au/SiO2 colloidal crystal

high TEOS
molecules
low TEOS
molecules

Increasing number of Au/thinSiO2 particles
in the presence of large amount of catalyst (NH3)

SELF-ASSEMBLY BY Au/SiO2 CORE-SHELLPARTICLES TO FORM COLLOIDAL CRYSTAL

Au/SiO2 core-shell particles
Sedimentation assisted
via centrifugation

Vertical
deposition

Highly ordered arrangement by self-assembled
Au/SiO2 particles

FUTURE WORK/IN PROGRESS

Centrifuge at 4000rpm, 30 minutes

Multilayers arrangement of
Au/SiO2 colloidal crystal

Infiltration of TiO2 onto theself-assembled particles
Selective etching of the SiO2
template to form void79

Development of a Simple but Reliable Method for Photocatalytic-activity Evaluation
Fitri Rizki Amalia,1 Mai Takashima,1,2 and Bunsho Ohtani1,2
1Grad. School of Env. Science, Hokkaido University
2Institute for Catalysis, Hokkaido University

Introduction

Formaldehyde detection

Evaluation of Photocatalytic-activity test
1.Gas chromatography (GC)andliquid chromatography (LC)9accurate
9reliable

HCHO

2.Spectrophotometer

9 affordable
9 simple

9expensive
9complicated+Nash reagent(ammonium acetate,acetylacetone, andacetic acid )Diacetyldihydrolutidine (DDL)

9 unreliable for someanalysis(photodecomposition)

Developing simple and reliable method without dye by
only using spectrophotometer

spectrophotometer
T. Nash, Biochem J., 55, 416-421 (1953)

Future plan

Conclusion
1. Spectrophotometer as the only instrument forphotocatalyrtic activity
2. Formaldehyde as the main compound in photocatalytic
activity-test

Methanol dehydrogenation procedureamount of e- or h+/Pmol

3000

CentrifugationGC[H2 & CO2]

extracted

HPLC[HCOOH]

Pt
H2

j

2000

e

1500

b

1000

i

CO2
HCOOH

d

a

f

500

g

HCHO

h

0
1.4

GC
[CO2]

production of CO2/Pmol

amount of HCHO/H2

Nashreagent

centrifugati
onextracted

Spectromet
er[HCHO]HPLC[HCOOH]

50

b

40

c

d

h
HCHO

i

30

e

20

a

f

HCOOH
g

10

CO2

0

1.2
1
0.8
0.6
0.4
0.2

40
35
30

y = 0.6044x
R² = 0.6745

25
20
15
10
5

0
0

200

400

600

800

0

CH3OH + 2h+ Æ HCHO + 2H+

decomposition of HCHO/Pmol
020
40
HCHO + H2O + 2h+Æ HCOOH + 2H+

CH3OH + 4h+ + H2O Æ HCOOH + 4H+½ O2 + 2 ++ 2 - Æ H2O

amount of HCHO/Pmol

CH3OH + H2O + 6h+ Æ CO2 + 6H+
2H++ 2e- Æ H2

80

TiO2
UV light+(60 min.)
HCHO
*
*from
paraformaldehydeSpectrometer[HCHO]

c

2500

Oxidative decomposition of formaldehyde procedure

decomposition or production
amount/Pmol

UV light
TiO2(60 min.)+
CH3OH+
H2PtCl6

Nashreagent

1. Shorten irradiation time
2. Check dissolved CO2
3. Checking the possibility of other compound

HCHO + 4h+Æ CO2 + 4H+
O2 + 4 + + 4e-Æ 2H2O

60

Light intensity-dependence study for titania photocatalysis withmultielectron transfer process
Pradudnet Ketwong, Shugo Takeuchi, Mai Takashima, and Bunsho Ohtani
Institute for Catalysis, Hokkaido University, Japan
Experimental

Photocatalytic oxygen evolution

Photocatalyst :Small anatase titania (Ishihara ST01)
Electron acceptor: Iodate ion (sodium iodate solution 0.05 mol L-1)
Lamp:
High-intense UV-LED NS Lighting ULEDN-101
Wavelength:
365 nmIO3¯CB

Light power = 500.4 mW
Area95 = 0.15 cm2Light intensity (IL) = 0.95 u 500.4 / 0.15
= 3.17 W cm-2

e-

I¯

Lamp

H2O

StirrerVB

2H2O + 4h+ ĺ O2 + 4H+(+ 1.23 V)

TiO2

2H2O + 2h+ ĺ H2O2 + 2H+(+ 1.76 V)

H2O + h+ ĺ •OH + H+(+ 2.8 V)

Scheme of experiment set up
Light-intensity distribution of a UV-LED lamp

Results and Discussion
60

Order of reaction rate was changed
1

4

Ö

Ö

1

20
1

40

4

20

1

0
0

1

2

3

4

TiO2
(h+)

I Lȥ2 ‫׋‬

1/Ĳ3
TiO2
(2h+)

1/Ĳ4

I Lȥ3 ‫׋‬

k2

TiO2
(3h+)

ILȥ4 ‫׋‬

0

2 2.2

1

3

1

0

1

Fig. 2 Double logarithmic plot of light intensity
and oxygen evolution rate

Based on steady-state approximation,
the model suggests that photocatalytic
oxygen evolution is strongly depended on
photoabsorption of each particle
andaccumulation of generated holes

Four-electron transfer processO2

low light-intensity limit : second order

low light-intensity limit : fourth orderr = ȥ1ȥ2‫׋‬2 Ĳ1IL2

r = k4ȥ1ȥ2ȥ3ȥ4‫׋‬4 Ĳ1Ĳ2Ĳ3IL4 /(k4 + 1/Ĳ4)high light-intensity limit : first orderhigh light-intensity limit : first orderr = k4 ȥ1‫׋‬IL /(k4 + 1/Ĳ4)

4

3ln(IL / W cm-2)

k4

H2O2

1

2

Multielectron-transfer model for photocatalytic oxygen evolutionr = ȥ1‫׋‬IL

0

7

IL / W cm-2

TiO2
(4h+)

O2

Two-electron transfer process6ln(r / μmol h-1 cm-2)

1/Ĳ2

5

Fig. 1 Light-intensity dependence of photocatalytic oxygen evolution rate

TiO2

I Lȥ1 ‫׋‬

4

IL / W cm-2

by increasing Light Intensity

1/Ĳ1

Singularity!

r / μmol h-1 cm-2

h+1 cm2 apertureO2

r / μmol h-1 cm-2

Energy

4h+
2h+
1h+

H2O
H2O2

H2O

h+

Where
r = Reaction rate

O2

h+ h+

h+

h+ h+

IL = Light intensityȌ = Photoabsorption efficiency
ĭ = Quantum efficiency of electron capture
Ĳ= Lifetimek = Rate constanth+Hole accumulation as Light intensity increases

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ĂĐŝĚ ƌĞƐŝĚƵĞ (ĨŝŐ͘ϭ͘)͘ /Ŷ ƚŚŝƐ ǁŽƌŬ͕ ϮͲŵĞƚŚŽǆǇĐĂƌďŽŶǇůͲϯͲ;ϯ͕ϰͲĚŝŵĞƚŚŽǆǇƉŚĞŶǇůͿŽǆŝƌĂŶĞ ;DDWKͿ ĂƐ ĂŶ ƵŶƐǇŵŵĞƚƌŝĐĂůůǇ Ϯ͕ϯͲĚŝƐƵďƐƚŝƚƵƚĞĚ ŽǆŝƌĂŶĞ ŵŽŶŽŵĞƌ ǁĂƐ ƐǇŶƚŚĞƐŝǌĞĚ ĂŶĚ ƉŽůǇŵĞƌŝǌĞĚ ƵƐŝŶŐ Ă ĐĂƚŝŽŶŝĐ ŝŶŝƚŝĂƚŽƌ ƵŶĚĞƌ ǀĂƌŝŽƵƐ ĐŽŶĚŝƚŝŽŶƐ͘ hŶĚĞƌ ĂůůĐŽŶĚŝƚŝŽŶƐ ĞǆĂŵŝŶĞĚ͕ ƚŚĞ ŵŽŶŽŵĞƌ ǁĂƐ ĂůŵŽƐƚ ĐŽŵƉůĞƚĞůǇ ĐŽŶƐƵŵĞĚ ƚŽ ĂīŽƌĚ ŵĞƚŚǇůĂƚĞĚ ĂŶĂůŽŐƵĞ ŽĨ WW' ͲƉŽůǇ;DDWKͿ ;DŶ ϮϵϬϬͲϭϮϴϬϬͿ͘^ĐŚĞŵĞϭ͘ĂƚŝŽŶŝĐƉŽůǇŵĞƌŝǌĂƚŝŽŶŽĨDDWK&ŝŐ͘ϭ͘ WW'͘dĂďůĞϭ͘WŽůǇŵĞƌŝǌĂƚŝŽŶŽĨDDWKǁŝƚŚ&ϯͼKƚϮ ŝŶ,ϮůϮ ĨŽƌϱŚ Ă͕ďĂ DŽŶŽŵĞƌ ϮϬϬ ŵŐ͕ ΀ŵŽŶŽŵĞƌ΁ϭʹϯ͕ ϱʹϴͿ Žƌ Ϭ͘ϲϬ D ;ƌƵŶ ϰͿ͘ŵŽŶŽŵĞƌ ĐŽŶǀĞƌƐŝŽŶ ƌĂƚŝŽ хϵϵй ĂƐ ĚĞƚĞƌŵŝŶĞĚ ĨƌŽŵ ϭ, EDZ
ĐƐƉĞĐƚƌĂ ŽĨ ƚŚĞ ĐƌƵĚĞ ŵŝǆƚƵƌĞ͘ dŚĞ ǇŝĞůĚ ŽĨ ƚŚĞ ŚĞǆĂŶĞͲŝŶƐŽůƵďůĞ ƉĂƌƚ͘ ĚƐƚŝŵĂƚĞĚ ďǇ ^ ǁŝƚŚ ƌŝŐŚƚͲĂŶŐůĞ ůĂƐĞƌ ůŝŐŚƚ ƐĐĂƚƚĞƌŝŶŐ ĂŶĚ ǀŝƐĐŽŵĞƚƌŝĐ
ĚĞƚĞĐƚŽƌƐ͘ Ğ ƐƚŝŵĂƚĞĚ ďǇ ^ ƵƐŝŶŐ ƐƚĂŶĚĂƌĚ ƉŽůǇƐƚǇƌĞŶĞƐ͘ Ĩ DĂƌŬʹ,ŽƵǁŝŶŬʹ^ĂŬƵƌĂĚĂ ĐŽĞĸĐŝĞŶƚƐ͘ď dŚĞŽ Ϭ͘ϴϰ D ;ƌƵŶƐ

ϭ,EDZĂŶĚD>/ͲdK&ŵĂƐƐƐƉĞĐƚƌĂŽĨƉŽůǇ;DDWKͿ&ŝŐ͘ ϯ͘ hs ƐƉĞĐƚƌĂ ŽĨ ƚŚĞ DDWK ŵŽŶŽŵĞƌ ;ĂͿ ĂŶĚ ƉŽůǇ;DDWKͿƐŽĨ DŶ ϱϳϬϬ ;ďͿ͕ ϴϳϬϬ ;ĐͿ͕ ĂŶĚ ϭϮ ϴϬϬ ;ĚͿ ;Ϳ ĂŶĚ Ă ƉůŽƚ ŽĨ ƚŚĞ ƌĂƚŝŽ ŽĨĂďƐŽƌďĂŶĐĞ Ăƚ ϯϯϬ Ŷŵ ;/dͿ ƚŽ ƚŚĂƚ Ăƚ ϮϴϬ Ŷŵ ;ʋʹʋΎͿ ŽĨ ƚŚĞ ƉŽůǇŵĞƌ ŽĨDŶ ϭϮ ϴϬϬ ĂŐĂŝŶƐƚ ƚŚĞ ĚŝĞůĞĐƚƌŝĐ ĐŽŶƐƚĂŶƚ ;ɸƌͿ ĂŶĚ ZŽŚƌƐĐŚŶĞŝĚĞƌ ƉŽůĂƌŝƚǇ
ƉĂƌĂŵĞƚĞƌ ;W͛Ϳ ŽĨ ƚŚĞ ƐŽůǀĞŶƚ ƵƐĞĚ ĨŽƌ ŵĞĂƐƵƌĞŵĞŶƚƐ ;Ϳ͘ dŚĞ ƐƉĞĐƚƌĂ ŝŶ ǁĞƌĞ ŽďƚĂŝŶĞĚ ŝŶ ,ůϯ Ăƚ ϭ͘ϳ 㽢 ϭϬоϰ D ;ĂͿ͕ Ϯ͘ϰ 㽢 ϭϬоϰ D ;ďͿ͕ Ϯ͘ϰ 㽢ϭϬоϰD ;ĐͿ͕ ĂŶĚ Ϯ͘Ϭ 㽢 ϭϬоϰ D ;ĚͿ Ăƚ Ϯϯ 㼻 ŝŶ Ă ϭ ŵŵ ƋƵĂƌƚǌ ĐĞůů͕ ĂŶĚƚŚĞ ĚĂƚĂ ƉŽŝŶƚƐ ŝŶ  ǁĞƌĞ ŽďƚĂŝŶĞĚ ĨƌŽŵ ,ůϯ ;ɸ ϰ͘ϱ͖ W͛ ϰ͘ϭͿ͕ ƚKĐ ;ɸ ϲ͖W͛ ϰ͘ϰͿ͕ d,& ;ɸ ϳ͘ϴ͖ W͛ ϰ͘ϬͿ͕ ĂŶĚ D& ;ɸ ϯϴ͕ W͛ ϲ͘ϰͿ ƐŽůƵƚŝŽŶƐ Ăƚ ϭ͘Ϭ 㽢ϭϬоϱ D Ăƚ Ϯϯ Ϭ ͘^ĐŚĞŵĞ Ϯ͘ ,ĞĂĚͲƚŽͲƚĂŝů ŐƌŽǁƚŚ ǁŝƚŚ ŝŶǀĞƌƐŝŽŶ ;ůĞĨƚͿ ĂŶĚ;ƌŝŐŚƚͿ ŽĨ ƚŚĞ ;ϮͿ ĐŽŶĮŐƵƌĂƚŝŽŶ ŝŶ DDWK ƉŽůǇŵĞƌŝǌĂƚŝŽŶ͘ƌĞƚĞŶƚŝŽŶ

&ŝŐ͘ ϰ͘ ^ƚƌƵĐƚƵƌĞƐ ŽďƚĂŝŶĞĚ ƚŚƌŽƵŐŚ D ƐŝŵƵůĂƚŝŽŶƐ ĨŽƌ ϱ ŶƐ Ăƚ Ϯϵϳ < ;^͕^ͿͲϮϬͲŵĞƌ ;Ϳ͕ ;^͕^Ϳͬ;Z͕ZͿͲϮϬͲŵĞƌ ;Ϳ͕ ĂŶĚ Ă ƐĐŚĞŵĂƚŝĐ ĚƌĂǁŝŶŐ ŽĨ Ă ĐŚĂŝŶ ;Ϳ͘ /Ŷ ĂŶĚ ͕ ǁŚŝƚĞ͕ ŐƌĂǇ͕ ĂŶĚ ƌĞĚ ĐŽƌƌĞƐƉŽŶĚ ƚŽ ,͕ ͕ ĂŶĚ K͕ ƌĞƐƉĞĐƚŝǀĞůǇ͕ ĂŶĚƉŝŶŬ ĐŽƌƌĞƐƉŽŶĚƐ ƚŽ ƚŚĞ ŵĂŝŶ ĐŚĂŝŶ͘ ůƵĞ ĂƌƌŽǁƐ ŝŶĚŝĐĂƚĞ ĐĂƌďŽŶǇůʹĂƌŽŵĂƚŝĐ
ĐŽŵďŝŶĂƚŝŽŶƐ ƚŚĂƚ ŵĂǇ ĐŽŶƚƌŝďƵƚĞ ƚŽ /d ŝŶƚĞƌĂĐƚŝŽŶƐ

&ŝŐ͘Ϯ͘ϭ,EDZƐƉĞĐƚƌƵŵŽĨƉŽůǇ;DDWKͿ;ƌƵŶϳŝŶdĂďůĞϭͿ;ϰϬϬD,ǌ͕ůϯ͕ĂƚϮϯ㼻Ϳ;ƚŽƉͿĂŶĚƚŚĞD>/ͲdK&ŵĂƐƐƐƉĞĐƚƌƵŵŽĨƚŚĞƉŽůǇŵĞƌƵƐŝŶŐɲͲĐǇĂŶŽͲϰͲŚǇĚƌŽǆǇĐŝŶŶĂŵŝĐĂĐŝĚĂůŽŶŐǁŝƚŚĂĐŚĞŵŝĐĂůƐƚƌƵĐƚƵƌĞĚĞĚƵĐĞĚĨƌŽŵƚŚĞƐƉĞĐƚƌƵŵĂŶĚƚĂďƵůĂƚĞĚƚŚĞŽƌĞƚŝĐĂůĂŶĚŽďƐĞƌǀĞĚŵĂƐƐŶƵŵďĞƌƐĐŽƌƌĞƐƉŽŶĚŝŶŐƚŽƚŚĞƐƚƌƵĐƚƵƌĞ;ďŽƚƚŽŵͿ͘ŽŶĐůƵƐŝŽŶƐ
ϮͲDĞƚŚŽǆǇĐĂƌďŽŶǇůͲϯͲ;ϯ͕ϰͲĚŝŵĞƚŚŽǆǇƉŚĞŶǇůͿŽǆŝƌĂŶĞ ǁĂƐ ƐǇŶƚŚĞƐŝǌĞĚ ĂŶĚ ƉŽůǇŵĞƌŝǌĞĚ ƵƐŝŶŐ Ă ĐĂƚŝŽŶŝĐ ŝŶŝƚŝĂƚŽƌ ƚŽ ĂīŽƌĚ Ă ƉŽůǇŵĞƌ ŚĂǀŝŶŐĂ ƌĂƚŚĞƌ Ɛƚŝī͕ ƐƚƌĞƚĐŚĞĚ ĐŽŶĨŽƌŵĂƚŝŽŶ͘ dŚĞ ƐŝĚĞͲĐŚĂŝŶ ŵĞƚŚŽǆǇĐĂƌďŽŶǇů ŐƌŽƵƉ ĂŶĚ ϯ͕ϰͲĚŝŵĞƚŚŽǆǇƉŚĞŶǇů ŐƌŽƵƉ ŽĨ ŶĞŝŐŚďŽƌŝŶŐ ŵŽŶŽŵĞƌŝĐ
ƵŶŝƚǇ ĨŽƌŵ Ă ŚĞƚĞƌŽ ʋͲƐƚĂĐŬĞĚ ƐƚƌƵĐƚƵƌĞ ďĞƚǁĞĞŶ ƐŝĚĞͲĐŚĂŝŶ ĐĂƌďŽŶǇů ĂŶĚ ĂƌŽŵĂƚŝĐ ŐƌŽƵƉƐ ǁŚŝĐŚ ůĞĂĚƐ ƚŽ ŝŶƚƌĂŵŽůĞĐƵůĂƌ ĐŚĂƌŐĞ ƚƌĂŶƐĨĞƌ
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85

86

Reaction Mechanism of the direct synthesis of dimethyl carbonate from
CO2 and methanol over metal-oxide catalysis : a theoretical study
Toshiyuki Sugiyama, Akira Nakayama, and Jun-ya Hasegawa
Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan

BackgroundCO2 + 2CH3OH

Computational details

catalyst

DFT+U (PBE functional)
NVT ensemble (T = 360 K)
Blue-moon ensemble approach(Free energy calculation)
Slab model for CeO2(111) surfacep(3 3) with 3 O-C-O tri-layers (27 CeO2 units)
11.56
11.56

+ H2O
DMC

CeO2 or ZrO2 catalyst(acid-base bifunctional catalyst)

CO2

Adsorption structures of the reactants(CH3O)2COIntermediate of polycarbonates
Electrolytes for lithium ion batteries
Alkylating and carbonylating reagents

COCl2(Toxicity)

CH3OH

A green and sustainable process to replace conventional methods
CeO2 catalyst

CO2
Monodentate

EB = 52 kJ/mol EB =Acid-base sites (Lewis acid-base pairs)
Redox properties
O

Ce4+

O

Ce4+

kJ/molEB =kJ/mol

Mol

EB =

Dis

kJ/molEB =kJ/mol

STEP1
H2O

STEP2

O

Ce4+

CH3OH

LinearBidentate

Ce4+

Adsorption structures of CO2
Surface carbonate species
Monodentate / Bidentate
MMCS
Molecular adsorption
Linear
MMC
Adsorption structures of CH3OH
Dissociated adsorption
Molecular adsorption
Both structures exhibit similar EB

CH3OC(O)OH
MMC

MMCS

In this work
We investigate reaction mechanisms of DMC formation
over CeO2 and clarify the role of active sites.
Ref : Tomishige, K.; Sakaihori, T.; Ikeda, Y.; Fujimoto, K. Catal. Letters 1999, 58, 225 229.
Yoshida, Y.; Arai, Y.; Kado, S.; Kunimori, K.; Tomishige, K. Catal. Today 2006, 115, 95 101.

EB =kJ/molReaction mechanism

EB =kJ/molAnalysis : Free energy profile
Problems of conventional first-principle calculations (T = 0, P = 0)
Numerous local minima on the potential energy surface due to thecomplex interactions between molecules and metal-oxide surface.
Neglects of the thermal (entropic) effects.

First-principle molecular dynamics simulations at finite temperature
Integration of the mean force leads tothe free energy profile along a reaction
coordinate.
Conformational
sampling by fixing rCO
at certain distancesBlue moon ensemble approach

free energy
mean force

Obtaining the mean
force acting on rCO.

160

Relative Free Energy / kJ·mol

140

Reaction mechanism

Red Path A
Blue:Path B
Attack of methoxy species
TS_B1

120
(101)
TS_B1

100

(82)
TSB A

(63)

0
-20

(72)
MMCS

(85)
TS_A3

(22)
MMC
(0)
CO2(m)
CO2 adsorption Attack of methoxy species
TS_A1
TS_A2

TS_B1

(62)
Product

O

TS_A3
TS_A4
INT_A2

Reactant(24)
INT_A1

MMC

Attack of methoxy species
TS_B2
H2O formation
TS_A4
TS_B3
H2O formation
TS_A3

C

MMCS

(63)
(59)
INT_A2

TS_B3

TS_A5
TS_A2

TS_A1

(73)
TS_A4

(56)
Reactant

20

TS_B2

INT_B1(111)(120) TS_A5
INT_B1

(77)
TS_A2

60

(139)
TS_B3

TSB A

Attack of surface O
TSB A

(77)
TS_A1

80

40

(139)
TS_B2

Product

INT_A1CO2(m)

DMC desorption
TS_A5

C
O

Conclusion
The reaction mechanisms of DMC formation over CeO2 were theoretically investigated.
The reaction mechanism via a stable intermediate accompanying an oxygen vacancy is a preferable pathway.

87

88

Development of Columnar Liquid Crystals of Macrocycles toward Anisotropic Transport of Lithium Ion
Kyohei TOMITA, Shin-ichiro KAWANO, Kentaro TANAKA
Department of Chemistry, Graduate School of Science, Nagoya University, Nagoya 464-8601, Japankentaro@chem.nagoya-u.ac.jp

1. Introduction

R'
N

RO
RO

H25C12O

O
OH

HO

N

OR
N
OH

N

HO

OH

O
Li+
O
O
O
N
S
S
CF3
OO

O

1 nm

F3C

+

OR

N
HO

N

NC
CN

H25C12O
H25C12O

OH

HO

N

105 ℃

nanospace

Our liquid-crystalline macrocycle

Lithium ion transport in 1-D pores or liquid crystal

N R'

R' N

Mg(NO3)2･6H2O

100 μm
HO

OH
N

Li+

HO
N

T. Kato, et al., J. Mater. Chem. A., 3, 11232 (2015)• Lithium ion transport in• Lithium ion transport in liquid

1-D honeycomb-type
pores in MOF.

crystal formed by self-assembly of
wedge-shaped zwitterions.

R1
N

OR2

R1
N

R2O
OR2

R2O

N

N
HO

N

O

N

HO

OH

HO

N

N

R2O

Compound

R 2O

Iso
150

Ion transport in
1-D nanospaceof columnar LC
macrocycles

OR2

N R1

Colr

4Li+•H414-

M

8Li+•18-

M

N

O
N

R2O

OR2

2Li+•H612-

O
O

R2O

GIXRD

OR2

N
R1

OR2

150 ℃
270 ℃
300 ℃

Iso
Dec
Dec

CuKα, 45 kV, 45 mA

50 Å

Table 2. Observed XRD data of liquid crystal
phase of 2Li+•H612- and H81

nLi+•H8-n1n-

H 81

Phase

O

N

N
R1

Colr

Structural Analysis by GIXRD

Table 1. Thermal properties

OR2

O
N

OH

N

Colr

• Liquid-Crystalline behavior of the conjugate.

N

nLi+ (8-n)H+

R1 N

HO

OH

100
Temperature / ℃• Formation of a conjugate of the macrocycle and lithium ions.

CHCl3 / EtOH
N

Colr

50

This work

OR2

O

O

nLiOH
n = 2, 4, 8
N R1

R1 N

Colr

OR

N

N

OH

Colr: Rectangular columnar phase
Iso: Isotropic liquid

4. Liquid-Crystalline Properties of 2Li+•H612-

2. Synthesis of nLi+•H8-n1n-

N

OR

N
R'

H 81
K. Tanaka, et. al., J. Am. Chem. Soc., 137, 2295 (2015)

J. R. Long, et. al.,J. Am. Chem. Soc., 133, 14522 (2011)

R 2O

Phase Diagram

N

RO
RO

R 2O

N

OH

OC12H25
R2 :OC122H25
OC12H2255

O

O
O

O

OC6H13CompoundPhase

2D cell parameters

2Li+•H612-

Colr

a = 50 Å

b = 37 Å

H8 1

Colr

a = 45 Å

b = 36 Å

OC6H13POM

3. 1H NMR and 7Li NMR of nLi+•H8-n1n1H NMR (400 MHz, CDCl3, TMS)

7Li NMR (400 MHz, CDCl3)[H81] = 4 mM

[H81] = 4 mM

37 Å

R2O
R2 O

R1
N
N
OH N
HO

N
N HO
OH

OR2
OR2

DSC

105 ℃

N R1

N

OH N
N
N
R1

OR2
OR2

N

N

N
HO

O

N R1

OH N
N

O
N

R2O
R2 O

N
R1

88 ℃

A fan-shaped texture
was observed.

Colr

Colr

40 μm
50

100 ℃

Colr

100
Temperature / ℃

Orientation of columnar structure by Shearing S: shear

2Li+•H612-

150
129 ℃

or
OR2
OR2

2Li+•H612-

2Li+•H612-

Iso

HO

OH
N

Colr Colr

110 ℃

2nd heat

N

2Li+

R1 N

4Li+•H414-

100
Temperature / ℃

100 ℃

HO

OH

4Li+•H414-

OR2
OR2

Colr

50

endo

8Li+•18-

8Li+•18-

R1
N

Colr
100 μm

H 81
R2 O
R2O

72 ℃

HO

OH
HO
N

R2 O
R2O

94 ℃
108 ℃
119 ℃

LiCl
R1 N

scan rate: 10 ℃/min

2nd heat
endo

R1 :

95 ℃

Iso
150

95 ℃

S
a

c

b

e

d

S

shearing

H 81
N

N

OH HO

13

12

11

10

8

9

7

R 2O

e

b

R 2O

40 μm

[Li2(salphen)] = 4 mM

ppm

R1
N

d

O

[LiNTf2] = 4 mM
[DME] = 0.2 M

O
Li+

O

N
N

a

HO

c

O

O

S

100 μm2Li+•H612-

100 μm

CF3
O
O

N
O

S

CF3

OH
4.0

2.0

0.0

-2.0

-4.0

ppm

1H

Glass

POM, DSC and GIXRD measurements demonstrated the formation of rectangular columnar phase.

+

NMR spectrum of 8Li •1

8-

was different from that of H81.

However, in the spectra of 2Li+•H612- and 4Li+•H414-, the set ofsignals derived from H 8 1 were still observed, indicating
disproportionation of the conjugates and H81 in the solutions. On
the other hand, in the 7Li NMR spectra, the signals indicate lithium
ions interact with salphen moieties inside the macrocycle rather
than with ethers outside the macrocycle.

5 Summary and Perspectives
5.
• Lithium ions were conjugated with the columnar liquid-crystalline macrocycle in its hollow.

• POM, DSC and GIXRD measurements revealed the complex 2Li+•H612- showed arectangular columnar liquid-crystalline phase.

• Ionic conductivity will be investigated..
Li+

heat
or

or
cool

89

90

○Ryosuke Y. Shimizu1, Takeshi Yanai1,2,3, Yuki Kurashige4, Daisuke Yokogawa5/"#%

%!$%#)*#&%!!! * 0 $%%&%!# $!#%'!+ !&$,+ -* !) '#$%)* !)242+54.0
1 "    !!) )* * (& 110+../0
2"#% %!$%#)*#&%!!! * )!%! '#$%)* )!%!4.4+53.0
3"#% %!$ *#&%!!!#%$  $* '#$%)!!)!*!)!/31+..2/

I. Advances in Bio-Imaging
Fluorescent molecules are powerful tools forvisualizing biological events.
Optical images of SKH mice injected with hyaluronananalogs modified with IR-783 dye.

 Which is important?
 Electronic structure vs. solvation effect Computational Details

Electronic Structure

Solvatochromism in
Absorption

Error from experimental value (eV)



 
   Heart and Lungs

III. Assessment











Modeled indocarbocyanine
in DMSO (20e,19o) (CY3)













Number of aromatic rings

Liver

Long π-Conjugated Systems

S. Grimme and M. Parac, ChemPhysChem 4, 292 (2003).
Y. Kurashige and T. Yanai, Bull. Chem. Soc. Jpn. 87, 1071 (2014).
G. P. C. Drummen, Molecules 17, 14067-14090 (2012)

N-methyl-6hydroxyquinolinium(12e,11o) (6HQ)In DMSO, acetonitrile,methanol, waterSolvation EffectComparing calculated Stokes shifts
1.4





Modeled indocyanine green
in water (32e,31o) (ICG)

Basis sets: aug-cc-pVDZ (N,O) and cc-pVDZ (other atoms)

IR-783
Stokes shift (eV)

1.2With near-infrared (NIR) light, we are able tostudy ”deeper” into biological systems.

 Why NIR?

1.0

 Results and Discussion

0.8

Solvatochromism in Absorption

0.6
0.4
AN MeOH Water AN MeOH Water

NIR light has high permeability.

: PCM-TD-DFT

: RISM-TD-DFT

μs(mm-1)

 






■: Exp.

D. Yokogawa, J. Chem. Phys. 145, 094101 (2016).

Reduced Scattering Coefficients

Improving accuracy of electronic structure andsolvation effect is essential.

0.5 eV

G. Hong, A. L. Antaris, H. Dai, Nat.
Biomed. Eng. 1, 0010 (2017).






    

The “second NIR window” has been gaining attention
for improving the performance of bio-imaging.
To study theoretically, must consider excitedstate electronic structure and solvation effect.

II. New Method: RISM-CASPT2

Long π-Conjugated Systems Formalization
We defined the Helmholtz free energy calculated with
the CASPT2 method as:
ACASPT2 ≡ Ψ| Ĥ |Ψ + Δμ + E2 .

0.6

subjected to the orthonormalization constraint.
Ĥ solv is the solvated Hamiltonian defined as:

0.4
0.2

where
We checked the absorption energies with aconventional method (PCM-TD-DFT).

Error in Absorption Energy (eV)1.0
0.8

The free energy is minimized by solvingδΨ| Ĥ solv − E |Ψ = 0

 Can we theoretically predict
photochemical properties?

RISM successfully illustrated solvatochromism inabsorption.

Vi = −



 
qs ρs

s

0.0
hαs (r)fi (r )drdr
|r − r |(i ∈ α).

CY3ICG

New method reduces error to within 0.2 eV.

Absorption Wavelength (nm)Molecules with absorption in visible and NIR region

 Program Development

800
NIR Region
700
600

 Conclusion

Flowchart of calculation
START

START

(DMRG-)CASCI(DMRG-)CASCIExp. Value

V[G]

500
Orbital Optimization

PCM-TD-DFT
400

Orbital Optimization

ΨΨ, V

RISM Calculation

Ψ RISM and CASPT2 have been successfully
combined.
 RISM-CASPT2 and its extension with the DMRG
improved computed absorption energies.
R. Y. Shimizu, T. Yanai, Y. Kurashige, D. Yokogawa, J.
Chem. Theory Comput. 14, 5672 (2018).

Update V---Ψconverged?

The accuracy of the widely used PCM-TD-DFT
method was insufficient.
A new method is required for studying thesemolecules.

Ĥ solvΨ

converged?
Ĥ solv(DMRG-)CASPT2(DMRG-)CASPT2

END

END

Ground State

Excited State

Acknowledgement This work was supported by Grant-in-Aid for
Scientific Research (C) and Fusion Emergent
Research.

91

92

93

Synthesis of novel plant-growth stimulants
by functionalization of 2-azahypoxanthine
Ayaka Ueda1; Hiroyuki Kitano2; Jaehoon Choi3; Hideto Ito1,4; Shinya Hagihara1,2,5;
Toshiyuki Kan6; Hirokazu Kawagishi3; Kenichiro Itami1,2,4

ITAMI GROUPRGANIC CHEMISTRY

1)Grad. Sch. Sci., Nagoya Univ.; 2)WPI-ITbM, Nagoya Univ.; 3)Grad. Sch. Sci. Technol.,Shizuoka Univ.; 4)ERATO, JST.; 5)RIKEN CSRS; 6) Sch. Pharm. Sci., Univ. Shizuoka.

HN
N

2-Azahypoxanthine (AHX) is a plant growth stimulator isolated from the fairy-ring-forming fungus Lepista sordida. Since
plant growth regulators that enhance the crop production are in great demand, AHX has attracted considerable attention
from agricultural and horticultural researchers. Herein, we report the synthesis of new AHX derivatives by Pd-catalyzed C–
H functionalization of AHX. Their rice growth-promoting activity was evaluated in vivo. Among the synthesizedcompounds, C8 phenyl-substituted AHX showed remarkable growth-promoting activity on rice. The present study shows
the power and significant opportunity of C–H functionalization chemistry to rapidly transform biologically active natural
products into more active compounds.

O

O
HN
N

N
N
H

N

C–H arylation

N

Ar
N
H

N

AHX

C6-arylated AHX

natural productHigher activity

Growth-promoting activity(“Discovery of Novel Plant Growth Stimulants by C–H Arylation of 2-Azahypoxanthine” Org. Lett. 2018, 20, 5684.)

Results & Discussion

1. Background

Optimized condition of C–H arylation

A story of fairy rings

O
DMB

O
HN
N

N
N
H

N

Characteristics of 2-Azahypoxanthine (AHX)
HN
N
2

8

N

H

1

O
H 2N
H2N

N

HN
N

HN
N

N
H

43%

Na2CO346%

PCy3·HBF4 (10 mol%) 52%

1,4-dioxane

17%

K2CO3

21%

PtBu3·HBF4 (10 mol%) 49%

toluene17%

Cs2CO3

44%

50%

BINAP (5 mol%)43%

71% (Isolated yield)

C–H arylation and deprotection
O
DMB

N
N

Plant growth

?

N
H

N

Additive
None

Miura, M. Bull. Chem. Soc. Jpn. 1998, 71, 467. Rossi, R. Eur. J. Org. Chem. 2006, 1379.

N
H

N

N

DMA

N
N

N

50%

O

O

NOS

(2.0 eq.)

1.1 mmol scale, reaction time 15 h

Kawagishi. H. et al. Chem. Bio. Chem. 2010, 11, 1373.

Biosynthesis of AHX

DMBN+ isomer
NMR yield

Base

Very rare 1,2,3-triazine core as a natural productNew plant hormone…?

O

K3PO4

Structural feature

9 N

DMF, 140 °C
12 h

N
N

50%

Growth promotion activity among varieties of plants

N

DMB

Br

DMF

Biological activity
7+

Solvent

Fairy rings : naturally occurring rings of mushrooms
or necrotic or stimulated growth of grasses.

ON+ isomer
0.2 mmol

2-Azahypoxanthine
(AHX)

3

N
N

Pd(OAc)2 (5 mol%)CuI (2.0 eq.)
K3PO4 (2.5 eq.)

DMB
N
H
N

N

(1) C–H arylation(2) Deprotection

DMB
N
H
N

O
HN
N

N

Ar
N

N
H

2 steps yield+ isomer

Receptor of AHX?
OKawagishi. H. et al. Angew. Chem., Int. Ed. 2014, 53, 1552. Kawagishi. H. et al. Sci. Rep. 2016, 6, 39087.

HN
N

2. N–H functionalization
O
H 3
N
N

O
N

HN
N

N

O
Si

N

O

HN
N

N

OMe

N

N

MeO

N

HN
N

N
H

N

4

5

6

21%

31%

O

F

HN
N

N
H

HN
N

N
H

9

10%

N
N

7
18%

HN
N

N
N
H

N

N
N

10

24%

N
H

O

O

Cl
N

N

HN
N

N
H

N

9%

N
H

11

9%

24%

6. Plant growth assay
N
N

N

Rice growth assay

OMe

No activity

N

O

O
N

8

O
N
N

N
N

N
H

N
N

No activity
O

MeO

N
N

O

Growth inhibition

N
N

HN
N

O

N
9
H

N

N

N

Si

7

O
N

No activity
AHX derivatives (0.1 mM)

Functionalization of N–H bond decreases plant growth activity

Incubated for a week

3. C–H arylation of AHX
Germinatedrice seeds

Strategy of arylationO

Direct C–H arylation

N

HN
N

H
N

N
H

Protection of N–H

PG

N
N

O

PG
N

N

N

controlN

C–H arylation

PG

N
N

4

10

11

N
H

Deprotection

H

AHX

80

Ar
N

Elongation (mm)O
HN
N

Measured
the length of root

O

PG
N

N

N

Ar

60

40

20

Protection of N–H bond
O
HN
N

N
N

N
H

DMBCl (4.0 eq.)
Cs2CO3 (5.0 eq.)
DMF, 100 °C

O
DMB

N
N

N

DMB
N
N

37%
(4.2 : 1)

94

0

O
DMB

+

N
N

O

N
N

N
DMB

control

AHX

O

O
DMB

HN
N

R
N

4

5

6

7

8
F

N
N
H

R=

H

9
Cl

Solid-phase Synthesis of Unsubstituted Poly(para-phenylene)
Shusei Fujiki,a Akiko Yagi,ab Kenichiro Itamiabc

ITAMI GROUPRGANIC CHEMISTRY

aGraduate School of Science, Nagoya University, Japan

bJST, ERATO, Itami Molecular Nanocarbon Project, Nagoya University, Japan

cInstitute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, JapanO
Br

Solid-phase
Synthesis

Br

UnsubstitutedPoly(para-phenylene)Br        
                     $                     
  "   #          
               !                         RESULTSRESULT
4S
Strategy toward Unsubstituted PPP

1 Introduction

Introduction

Br
Ar
Br
Suzuki–Miyaura
cross-couplingBr
B(pin)2

Ar

Ar

Poly(para-phenylenethiophene)

Ar

Poly(para-phenylene)
Miyaura Borylation

Polynaphthylene

5 Solid-phase Synthesis of PPP  

   
        
     2!  ! 

    

!! "  !  ! Suzuki–Miyaura
cross-couplingΔ!
" "

 



Müllen, K. et al. J. Am. Chem. Soc. 2016, 138, 16208.

Elongation of phenylene chain

3 New Synthetic Methodology

OO"  !  ! "" !O

Borylation 

B(pin)Ar
Ar

B(pin)

Br

Ar

O

Ar

O

              

Cross-coupling O#

Solid-phase Synthesis

1. Borylation

1. Borylation

2. Cross-coupling

2. Cross-coupling     " 

 
BrBr

! !

Br

95

Palladium
umm-CatalyzedyTransfer Hydration of Cyanohydrins
Asuka
uka
a Naraoka
okkaa, Tomoyaoyaya Kanda and Hiroshi Naka
Graduate School of Science and Research Center for Materials Science, Nagoya University

+

C N

O

Pd catalyst

H 2N
H2O Donor

HO

NH2

Transfer Hydration[Pdn] (n = 1 or 2)Ohydroxyamides by using carboxamides. This method enables
selective hydration of various aldehyde- and ketone-derived
cyanohydrins to afforded a series of α-mono- and α,αdisubstituted-α-hydroxyamides under mild conditions (50 ºC, 10min). The 18O-labeling study revealed that the carboxamides

O

HO

O

HO

pre
es
se
sen
en
encce
e
work as water donors. The kinetic study indicated the presenceof two mechanistic periods in the

NH2 N
[Pdn]

N
N
H [Pd ] H
n

NH2
[Pdn]

1. Backgroundcatalytic profile.

HO CN

+

HO CN

HCN

R2

R1

HO CONH2

H 2O
catalyst

R2

R1

R1

R2

catalyst poison

European Patent EP 0412310 B1.; United States Patent US 8519187 B2.; Commeyras Tetrahedron Lett.
1989, 30, 563.; Tyler Inrog. Chem. 2009, 48, 7828.; Tyler Organometallics 2012, 31, 2941. Tyler
Organometallics 2013, 32, 824.;Tyler Organometallics 2013, 32, 3744.; Cadierno Chem. Commun. 2014, 50,
9661.; Tyler ACS Catal. 2014, 4, 3096.; Tyler Inorg. Organomet. Polym. 2015, 25, 73.; Grubbs J. Am. Chem.
Soc. 2018, 140, 17782.

Issue: decomposition of cyanohydrins

H

HO CN

H

+

R2

HO CN

H

HO CN

HO CN

Ph

Ph

CONH2

98%
(2 mol% Pd)

HO

CONH2

2. This WorkR2

H2O Donor

cat Pd(NO3)2

HO CONH2AcOH
50 ºC, 10 min

R196%(2 mol% Pd)

O
R CN +
NH2

H 2O

R2

R3CN

HO CN

CN

O
+ CH3CN
conv. 53%

[1 mmol, CH3CONH2 (4 mmol),
10 mol% PdCl2,
THF/H2O (3:1, 4 mL), rt, 22 h]

HO CONH2

CH3COOH (2 mL)
50 °C, 10 min

4 equiv– n-C5H11CN

94% (NMR yield)

H2O donor (4 equiv)[1 mmol, 1 mol% Pd(NO3)2, 50 °C, 10 min]Catalyst

n-C3H7CONH273%

n-C5H11CONH275%

Pd(NO3)2
94%

Pd(O2CCF3)2
66%

CH3CONH2
46%

n-C7H15CONH2
65%

Pd(O2CCH3)2
47%

PdSO4
44%

CF3CONH2< 1%(CH3)2CCONH2< 1%

Solvent

H 2O< 1%

CH3CH=NOH< 1%

Pd(NO3)2 (2 mol%)

NH2

AcOH
50 ºC, 10 min

4 equiv, 90%18O– n-C5H11CN

77%(10 mol% Pd)

18O (16O)HONH2

98% yield, 90%18O
18O/16O ratio determined by

ESI-MS and 13C{1H} NMR.

+ CH3CONH2

ACH, 0.50 M

2.0 M

ACH

Pd(NO3)2 (2 mol%)Cl

Pd(NO3)2 (0.010 M)
CH3COOH (2 mL)
40 °C

HO CONH2+CH3CNFirst order in [ACH]

HO CONH2

conc. (M)n-C5H11CONH2

HO CONH271%(10 mol% Pd)

18O (16O)

+

HO CN

[CH3CONH2]t (min)

PdCl2
< 1%

[CH3CONH2, 2–5 mol% Pd(NO3)2]
CH3COOH> 99%

CH3COOH/H2O
25%

CH3CN/H2O
83%

C2H5COOH
74%

kobs (t ≦ 1 min) (min–1)

1 mmol+Cl

Kinetics

3. Optimization
HO CN

98%
(4 mol% Pd)

18O-Labeling Experimet

Maffioli Org. Lett. 2005, 7, 5237.

NH2

93%
(3 mol% Pd)

HO CONH290%(5 mol% Pd)

n-C5H11R

94%(2 mol% Pd)

5. Mechanistic Studies+

71–98% yield

PdCl2

HO CONH2 HO CONH2
CO2C2H5

HO CONH2

R1, R2 = H, alkyl, aryl; R3 = CH3, alkyl

Mild and Reversible Dehydration

71–98% yield
16 samples

ln[ACH]/[ACH]0

R1

R3CONH2

R2

R3 = CH3

OH

+

R1

– R3CN

4 equiv

HO CONH2

HO CONH2HO

Cf. Miller J. Am. Chem. Soc. 1973, 95, 3729.

HO CN

CH3COOH (2 mL)
50 °C, 10 min

R3 = n-C5H11- difficult to hydrate- unstablePh

Pd(NO3)2 (2–10 mol%)

R3CONH2

1 mmolcatalyst = MnO2, borates
Pt, Mo, Ru complexes
Pt, Ag nanoparticles
enzymes (nitrile hydratase)

HO CN

J. Am. Chem. Soc. 2019 ASAP.

4. Substrate ScopeO
R1

Abstract: We reported the palladium(II)-catalyzed transfer
hydrationof
α-hydroxynitriles(cyanohydrins)
to
α-

N C

[Pdn]

HO
N

+

First order in [Pd]0in the first 1 min[Pd]0 (mM)t (min)kobs (t ≧ 1 min) (min–1)

O

HO

Second order in [Pd]0later than 1 min[Pd]02 (10–6 M2)

Acknowledgements: We sincerely thank Prof. J. Shimokawa (Kyoto U.) for his suggestions. We are grateful to support from Profs. R. Noyori and S. Saito.

96

97

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Chemically -Modified Peptide Nucleic Acids forਫYuichiro Aib a a , Ma sa ki Hib in o a , Ge ra rd o Urb in a a , Yu u ki Och ia ia , Na o m i Ko ch ia , Ma sa n a ri Sh ib a ta a , Osa m i Sh o jia , Yo sh ih ito Wa ta n a b e b
aDepartment of Chemistry, Graduate School of Science, Nagoya University,bReserchCenter for Materials Science, Nagoya University

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103

104

䕿Yoshiaki Shuku䠈Kunio Awaga

Honeycomb crystal structures formed by 3-fold symmetric triptycene derivatives

Department of Chemistry, Nagoya University

Previous work
Highly symmetriccarbon allotropes

HybridorbitalPhysicalproperty•C

sp2

Graphene

This work

Electronic band structure

NDI-'

sp2 carbon
A. H. Castro Neto, et al. Rev. Mod. Phys. 2016, 81, 109-162.

sp3

DiamondSynthesis of NDI-': S. T. Schneebeli et al. Angew. Chem. Int. Ed. 2013, 52, 13100-13104.

Highly symmetric 3D crystal structure
formed by triangle S molecule NDI-'

Insulator

Triptycene=
p- and o-Benzoquinone (BQ)

D. J. Chadi, et al. Phys. Stat. Sol. 1975, 68, 405-419.

Electron acceptor

Variety of functional groups

Reversible two step reduction

Few example ofhoneycomb lattice formation

Strong S-S interactions orcoordination bonds

Unique structure
named assingle gyroid,srs-net etc.

Metallic???
*computational
model

A. Mizuno, Y. Shuku, R. Suizu, M.M. Matsushita, M. Tsuchiizu, D. Reta Maneru, F. Illas, V.
Robert, K. Awaga, J. Am. Chem. Soc. 2015, 137, 7612-7616
M. Itoh, Phys. Rev. Lett, 2009, 102, 055703.

M. Tsuchiizu, Phys. Rev. B, 2016, 94, 195426.

p-TT

p-TT

Rigid paddlewheel like skeleton

Radical anion salt of
NDI-'

sp2

K4 carbon+−•

Conductor

Left: P. Kissel, et al. Nature Chem. 2014, 6, 774-778.
Right: M. R. Talipov, et al. Angew. Chem. Int. Ed. 2015, 54, 14468-14472.

BQ

+e−

+e−

−e−

−e−
SQ•−

o-TT
Electron accepting multidimensional Ssystem

HQ2−

Synthesis of TT: H. Brockmann, et al. Chem. Ber. 1953, 86, 432-443.
Radical detection: G. A. Russell, et al. J. Am. Chem. Soc. 1981, 103, 1560-1561.

A. Mizuno, Y. Shuku, M.M. Matsushita, M. Tsuchiizu, Y Hara, N. Wada, Y. Shimizu, K.
Awaga, Phys. Rev. Lett. 2017, 119, 057201.

Crystallization of p- and o-TT
radical anion species

Cyclic voltammogram

o-TT

Electrochemical reduction of p-TT
using RbClO4 as an electrolyte

p-TT

p-TT + 3e- +3Rb+→ Rb3(p-TT)
Shiny red & air stable
crystals of p-TT anion salto-TTOptimized structure
B3LYP 6-31g*

Chemical reduction of o-TTusing Co2(CO)8 as reductant

o-TT + 1/2Co2(CO)8 → Co(o-TT)
Linear combination of benzoquinone MOs
Electron acceptor
Degenerated LUMOs

Black & air stable
crystals of TT aniontransition metal complex

1 mM solution of p-TT or o-TT
in DMF solution of 0.1 M TBAClO4

multi-step reduction processes

Rb3(p-TT)Co(o-TT)
Valence of BQ moieties

Rb+

Parameters
Valence of BQ moieties

t0: intramolecular transfer integral
t1: intermolecular transfer integral

Electronic band structure(tight binding approx.)

estimated by DFT calculation (B3LYP 6-31+g*)

6-fold inversion axis

HQ

HQ

Trigonal Prism
Co-O: 2.066~2.147 Å
CoII(HS)

Mirror plane
TT3-

SQ

SQ

t0

SQ−•

HF

BQ0

t1
Highly symmetric

BQ

BQ
SQ− •

Coordination bonds between TT and Rb
Hexagonal, P6/m(#175)
a = b = 11.6406(19), c = 8.6575(14) ÅV = 1016.0(3) Å3
R1 (I > 2s(I)) = 0.0249, wR2 (all) = 0.0621, GOF = 1.119
Residual electron density in pore was removed by SQUEEZE
T = 123 K

Exotic band structures
Dirac cones:
Expected for honeycomb structure
Flat bands:
Due to intramolecular interaction

Orthorhombic, Cmcm (#63)
a = 11.743(8), b = 19.128(13), c = 11.588(8) ÅV = 2603(3) Å3
R1 (I > 2V(I)) = 0.0682, wR2 (all) = 0.1841, GOF = 1.094
T = 123 K
SQUEEZE

Rb3(p-TT)Co(o-TT)
Ideal honeycomb
Structure of TT3Strong S dimers
3.02 Å

Hexagonal, P63/m (#176)
a = 12.332(11), c = 12.167(12) Å; V = 1602(3) Å3
R1 (I > 2V(I)) = 0.1243, wR2 (all) = 0.3829, GOF = 1.217
T = 123 K, SQUEEZE~6Å cavity occupied
by fully disordered
solvent molecules

Hexagonal, P63/m (#176)
a = 9.083(4), c = 11.885(5) Å; V = 849.1(6) Å3
R1 (I > 2V(I)) = 0.0629, wR2 (all) = 0.1229, GOF = 1.126
T = 123 K, SQUEEZE

2D MOFCo2+
o-TT2-~8 Å pores

Honeycomb structures of p- and o-TT
radical anion species
Dirac cones and flat bands in the electronic
band structure of Rb3(p-TT)

1D columnar cavity

Rb+
p-TT3-

Charge doping into the honeycomb lattice of TT radical anion→ Band filling control
More variety of building blocks→ Molecular design and synthesis

105

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114

Crystallization of phase-change materials induced by strong THz pulses
Yasuyuki Sanari1, Takehiro Tachizaki2, Yuta Saito3, Kotaro Makino3, Paul Fons3, Alexander V. Kolobov3, Junji Tominaga3, Koichiro Tanaka1
Yoshihiko Kanemitsu1, Muneaki Hase4, and Hideki Hirori1
1Kyoto University, 2Tokai University, 3National Institute of Advanced Industrial Science and Technology, 4University of Tsukuba

We have systematically investigated the spatial and temporal dynamics of crystallization that occurs in the phasechange material Ge2Sb2Te5 upon irradiation with an intense terahertz (THz) pulse. The electric field causes atemperature increase via Joule heating, which in turn leads to nanometer-scale crystal growth parallel to the field
and the formation of filamentary conductive domains across the sample.

Light/electric induced structural change

What happens in the crystalized area?

Pulse duration

Transient reflectivity change measurement

Voltage
geElectrode

Voltage'W>10ns

E

time
Thermal diffusion
length >100 nm

Amorphous

Crystalline[1]M. Boniardi et al., Solid State Electron. 58, 11 (2011).
[2]F. Rao et al., Science 358, 1423 (2017).

• Obscuring the complex mechanisms of resistive switching, where theeffects of both heating and electrical fields contribute to the phasechange.
Joule Heat σE2• The use of ultrashort THz pulses helps to suppress heat diffusion
and may enable the study of crystallization mechanisms in which
the lattice temperature exceeds the crystallization temperatureon picosecond time scales.

ΔT

ߪ:Electrical conductivity

Experiment
Simulation

5μm
630μm
60nm

2 μm

Ei

Ei /EoTHz• Si(630μm)• GST-amorphous+ZnS-SiO2cap(40+20nm)

80μm
10μm

Tunneling electron number n underelectric field E

Allowing field induced phase change with the extremely short time
duration (1 ps=0.001 ns).

ଵ ଷଵ݊ሺ‫ܧ‬ሻ ൌ‫ ܧ‬ଶ ݉௥ଶଵ ሺെͳͺߨ԰ଶ ‫ܧ‬௚ଶ

ʹ԰‫ܧ‬

ሻ

Drude modelߪ ‫ ݐ‬ൌ ߪ଴ ൅ ߪ௭௘௡௘௥ ‫ݐ‬ǡ ߱ߪ௭௘௡௘௥ ‫ݐ‬ǡ ߱ ൌ௡ ௧ ௤మభഓ௠ೝ ఛሺఠమ ା మ ሻ‫ܧ‬௚ :bandgap energy, ݉௥ :effective mass, ߬:relaxation time,ߪ0:Initial conductivity

THz induced phase change
Visible reflectivity changeߨ݉௥ଶ ‫ܧ‬௚ଶ

High electric field causes Zener-tunneling
Mechanism

Eo =175 kV/cm
Raman spectra

1. Crystallization occurs at the edge of Au antenna
2. Nonlinear increase of conductivity induced by Zenertunneling
3. Preferential crystallization at the edge of crystalized
area• Crystal growth along the electric field direction• One dimensional crystal growth• Crystallization speed: nm/pulse
Y. Sanari, HH et al., Phys. Rev. Lett. 121, 165702 (2018)

The observed nonlinear increase in the conductivity of thecrystalized region is a result of Zener tunneling; the tunnelingleads to local heating which causes a one-dimensional crystal
growth.

115

116

Synthesis and Propertiespof 2,5,,55-Digermaselenophene
g
Tomoh
moh
hiro
o Su
ugahargra,raa,,1 TakahiroaTo Sa
asamori,2 ananddN
orihirrihirroo To
Tokitohh1
Tomohiro
Sugahara
Sasamori,andNorihiro
Tokitoh1 Institutee for Chemical Research, Kyoto University,y Ujiy,Uji, Kyoto
o 611
11-0011,
Japan.
2Graduate School of Natural Sciences, Nagoya City Univ., Yamanohata 1, Mizuho-ku Nagoya, Aichi 467-8501, Japan.

1. IntroductionFunctional material
Polythiophene / selenophene

2. IntroductionHeavier triply bonded compounds
R

Physical properties (Ch = S, Se…)

$

M

Ge

 
 

heavier triply bonded
d compounds bearing bulky
y substituents

π
Ch

Mes

Ch

Ch

Ch

π

Oligomer type

Ch

Dsi

Si

Mes

Ch

n

Mes
Si

Ch

Mes

Dsi

Ge

Dsi

disileneWest (1981)

Ladder type

Dsi
Ge

Dsi

C
H



,

  



Sn

Dsi

$$

Dsi

distannene
Lappert (1973)

Si New π-bonded speicies
 Highly reactive
 Small HOMO-LUMO gap

Si



Ph

Ge

Ph
Chalcogenation

Ge

Tbb

Tbb

 

$#+%

  

Tbb

Ge
Ch

Ge

Tbb Tbb

Ph

Ph

Ph
Ch

Ge

Tbb GeGe Tbb
Ch
Ch Ch

Tbb

Ch

Ph

Ph

Chem. Lett. 2018, 47, 7139.; J. Am. Chem. Soc. 2018, 140, 11206.

4. Chalcogenation of 1,2-Digermacyclobutadiene I
Ph

Ph

Ph
S8 or Se
(excess)
THF, r.t.

Ge Ge
Tbb
Tbb

P(NMe2)3
Solvent, T ºC

Ge

Ph

Tbb

+

Tbb

2a: Ch = S (38%)*
2b: Ch = Se (75%)*

Me3Si
Me3Si

SiMe3
SiMe3
Me

&  
&  $
&  $

Me
Me '##

'##

!& $$!% 
$!% 

Ph

Ge

Ch Ch

1

Tbb :

Ch

Ch

Ge

Ch

Tbb

3a: Ch = S (29%)*
3b: Ch = Se (21%)*((
((

Selected Structural Parameters (Side View)

C

117.54°

C

Se1

Ge

125.39°



 


 




120.33° Tbb Ge1

CGe

119.44˚

2btriclinic, P-1,
R1 [I > 2(I)]= 0.0509,wR2 (all data)= 0.1436,
T = –170 ˚C

Ge2

Tbb

Ch2
3a

140.44˚
Se1

triclinic, P-1,
R1 [I > 2(I)]= 0.0313,
wR2 (all data)= 0.0838,
T = –170 ˚C

C2

Ch1

Se2
Compound 2b138.63˚

2a

Ph
C1

Ge

123.67°

S2
Compound 2aS1

Ph

116.00°117.07°

PhC2

Ge

101.92˚

117.79˚

101.77˚ Tbb Ge1 Ch1 Ge2 Tbb 3b

Ge

Tbb

Tbb

Ge

Tbb

Ge

Ph

Tbb : TMS
TMS

Tbb

TMS
TMS

tBu

Ge

Ph

Ph

Tbb GeGe TbbCompound 3b

triclinic, P-1,
R1 [I > 2(I)]= 0.0387,wR2 (all data)= 0.1024,
T = –170 ˚C

C1

Ch

Ge1

C2
Ge2

Se

4a: Ch = S (Not isolated)
4b: Ch = Se (quant.)**1** Isolated yield.

Me'"
2.3176(14)2.2730(14)
2.325
2.325

Ge–C [Å]1.919(7)1.910(8)

1.918
1.918

C1–C2 [Å]Ge–Se–Ge [º]α [º]"$ , $
"$ ," ,         $

1.363(10)91.57(5)
8.8





 

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  
-----

1.390
92.48
7.0
    ,  , ,

 

Me Ge

Ge Me
Se
3’
(Simple model)

-----

1.922
1.366
90.08
6.8
 


 , ,

 

Me

1.443
88.55
----   ,
 


Me
Me

Me

C Me
Se
4
(Tetramethylselenophene)C

Flatness
C
Ge

Ge

Se
C

a B3PW91/6-311G(3df)<Ge,Si,Se>, 6-311G(d)<C,H>, b B3PW91/6-311G(3df)<Se>, 6-311G(d)<C,H>α

7. Molecular Orbitals (Compounds 3’ and 4)
Compoundp3’

Compound 4
Me

Me

Me

Me

Me

triclinic, P-1,
R1 [I > 2(I)]= 0.0457,wR2 (alldata)= 0.1084,
T = –170 ˚C

Ch2 Ch3

Se2, Se3

S2, S3Compound 3a

Ch=P(NMe2)3(1 equiv.)
C6D6, r.t.

Ge Ge
Tbb
Tbb

monoclinic, P21/n,
R1 [I > 2(I)]= 0.0495,wR2 (all data)= 0.1359,–170 ˚C

Ph
C1

C

Ph

Large Contribution

Ph

Ge–Se [Å]* Estimated by 1H-NMR spectroscopy.

S1

Ph

Structural Parameters

Ph

Ge

Tbb

Ri
Ring St
Straini Trans-bent Geometry

Bull. Chem. Soc. Jpn. 2017, 89, 1375.

Ph

Ge

Structural features 

$,#+%

6. Chalcogenation of 1,2-Digermacyclobutadiene II

3. This Work Chalcogenation of 1,2-Digermacyclobutadiene
Ph

Tbb

Mes =

Dsi =

Ge

  
 

$,

Ph

Building blocks for organic optoelectronic materials
Modifying thiophenes via extension of π-conjugatedsystem and introduction of π-conjugated functional
substituents in order to diminish the HOMO-LUMO
gap.

Ge
Tbb

Dsi
Sn

digermene
Lappert (1976)

Ph

Selected Structural
Parameters
$,$Examples
Ch

Ge
Tbb

 

Ph

Ph C C Ph(1 equiv.)
hexane, r.t.

Tbb

R
R
M = Si, Ge, Sn, Pb
Highly reactive

R

Stable)'*( 

R
M

C

R

!
!$

Ch

R

R
C

 Low LUMO level
 High HOMO level Corresponding small
HOMO-LUMO gap

Cyclicc digermene

Dimetallenes

Alkenes

LUMO(–2.63 eV)

Me

Me

Me

LUMO
(–0.21 eV)

HOMO(–5.02 eV)

HOMO(–5.76 eV)

HOMO-1(–6.69 eV)

HOMO-1(–6.10 eV)

5. Theoretical Calculations (Compound 1)
Me

HOMO-2(–7.33 eV)

140.78˚
Se1
117.95˚Side View
C

Ge

101.27˚

Se2, Se3  $ $  $ $  $ $  $ $  $7.3 kcal/mol

15.0 kcal/mol$  $

     

  

$  $
$  $
$  $






 



 
  

$  $





 

Tbb
Se1
Ge1
Ge2
Tbb

Se2
Se3

C1

Ph

Ph

Ph

Ph

Se1
Ge1

C1

Ph

Tbb

Ge

Ge
Se

C2

Ge2
Tbb

Se2
Se3

C2

Ge Tbb

Se Se

Ph

Tbb
H2
(1 atm)hexane, r.t.

Tbb Ge* 1H-NMR yield, ** Isolated yield.

Ph
Se

Tbb

Ge

Ge

Tbb

Se

21%*
Ph

Se
H

Ph

Ph

Se
Tbb Ge

75%*

3

Ph

Se
(excess)
C6D6, 60 ºC

Tbb
Ph

HOMO-3(–8.88 eV)

8. Reactions of 2,5-Digermaselenophene (Compound 3)

  

Selected Structural ParametersMe3’: B3PW91/6-311G(3df)<Ge,Si,Se>, 6-311G(d)<C,H>
4 : B3PW91/6-311G(3df)<Se>, 6-311G(d)<C,H>

Small HOMO
MOO-LUMO gap
NBO6.0: B3PW91/6-311G(3d)<Ge,Si,Se>, 6-31G(d)<C,H>Me

Me

Ge Tbb
H

39%**

Ge

Ge
Se

monoclinic,
P21/n,
R1 [I > 2(I)]= 0.0263,
wR2 (all data)= 0.0683,
T = –170 ˚C

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118

119

120

IRCCS The 2nd International Symposium @ Kyoto University, Uji campus on 25th௅26th, January, 2019

Cage-Expansion of Fullerene
from C60 to C65N and C64N Skeletons

Sheng Zhang, Yoshifumi Hashikawa, Yasujiro Murata*
Institute for Chemistry Research, Kyoto University, Uji, Kyoto 611-0011, JapanINTRODUCTION

THIS WORK & CONCLUSION

A cage expanded derivative

Novel method for synthesis of C65N and C64N cages

Restoration of open-cage fullerene derivatives

X-ray structures
N

N

N

Side view

Triclinic, P1
R1 = 0.0499, wR2 = 0.1334
C65N skeleton

Monoclinic, P21/n
R1 = 0.0449, wR2 = 0.1227
8mr

Enlargement of opening by PMI

75

Top view

88mr

Monoclinic, P21/n
R1 = 0.0823, wR2 = 0.2029
C64N skeloton

6

5

7

6

C65N skeleton

C64N skeleton(The sutured regions are highlighted in red. Thermal ellipsoids are set in 50% probability levels. Allof the substituents are omitted for clarify.)

Insertion of C5N and C4N units
Formation of pentagonal, hexagonal, and heptagonal rings

Plausible mechanism

Construction of C65N and C64N skeletons

Formation of C65N skeleton (M06-2X/6-31G(d,p))
Py N

H

Py N

Py

H

Py N

Py

H
60ʌ

56ʌ
O

all [5,6]-open(Bisfulleroid)ǻG(kcal/mol)

O

N
O
Ph
all [6,6]-closed

all [6,6]-closed

Py

H

H

N
Ph

O 60ʌ

C65N
skeletonall [5,6]-open

+8.7

–29.9
ǻG‡ +23.1

Formation of C60
Ar

O

54ʌ

O

N
Ph

H

Py N

Py
H

Stepwise

0

H

Ar

Ar

Ph

O
Ar

N

Ar

O

O
Ar

Ar

Ph
N

O
Ar

O

Ph
N O

Ar

Ar
C60

60ʌ

56ʌ
58ʌ
Whitby, R. J. et al., Chem. Commun. 2014, 50, 13037.

58ʌ

60ʌ

m, 1H
m, 1H

d 1H

m, 3H

s, 1H

d, 1H

d, 1H

Cage-expansion to C70N2 skeletons
H
NN

H on C beside N

N

H on C from PMI

d 1H
d 1H

N

d 1H

H

N

d 1H

H

d 1H

s, 1H
N
H
p-TsO
H

d 1H

m, 2H
m, 4H
m, 1H
m, 1H

m, 3H

m, 1H
m, 2H
m, 1H
d, 2H
m, 1H
d, 1H

d, 1H
d, 1H

m, 2H

m, 2H

8mr

H

N
O

N

H

N

H

N
O

H

8.0

7.0

6.0

Alteration of cyclized reagents

5.0

4.0

3.0
į (ppm)ON

N

O

C64N-aN
H

H

N
Chemical Formula: C106H32N8O4Exact Mass: 1480.2547
Molecular Weight: 1481.4740

121

Dynamic Behavior of aSinglebutHydrogenͲbondedWaterMolecule
insideaHydroxy OpenͲCageFullereneC60 Derivative
䚽ShotaHasegawa,YoshifumiHashikawa,YasujiroMurata
InstituteforChemicalResearch,KyotoUniversity,Uji,Kyoto611Ͳ0011,Japan

IntroductionThiswork&Summary

H2OmoleculeStudiesonHͲbondedH2OareimportantͲ proteinfoldings,drugdelivery,catalyst…

HͲbondɷ– acceptorHͲbondɷ+ donor

Theoreticalstudiesonly,duetomultipleHͲbondsHͲbondsmediateddimerization

OurapproachesHͲbondwithwitothers

H2Omoleculeinsidehydrophobicfullerenecage

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

Ͳ HͲbondedsingleH2Omolecule
IsolatedH2OmoleculeorHͲbond Ͳ DynamicsoftheencapsulatedH2O
Murata, Y. et al.,Ͳ LessacidicandlessbasicH2O
withoutanyinteraction
Nat. Chem. 2016, 8, 435–441.

SwitchableHͲbondedH2Omolecule

Resultsanddiscussion
Dimerizationbehavior

Synthesis...

1HNMR(CDCl ,500MHz,300K)
3
...

K

3

3

...

1

.
....

CHCl3

0.50mM
3:(3)2 =99:1

2

(3)2

K = 9.63 ± 0.72 M–1
H(2)

H(1)

H(3)

20.0mM
3:(3)2 =77:23

8.0

7.5

7.0

6.5

6.0

5.5

5.0

4.5

4.0

3.5

į (ppm)HͲbondedH2Ointhesolidstate

Dynamicbehavior

XͲraycrystal(H2O)1.38(C82H32N2O4S)2•NiOEP•(C6H6)2
PͲ1,triclinic,R1 =6.22%,wR2=18.04%

1HNMR(ODCBͲd ,500MHz,260Ͳ360K)
4

RestrictedrotationviaHͲbond

O
OO

HͲbondO
2.796(3)Å

DFTcalculations(B3LYPͲD3/6Ͳ31G(d,P))HͲdonor (3.78Å)S
StrongintramolecularHͲbonds
XͲraycrystal(H2O)2.01(C82H32N2O4S)2•(CDCl3)5
P21/c,monoclinic,R1 =15.77%,wR2=45.34%

O
O
S

O

O

S

ȴG298K(kacl/mol)

0HͲacceptor (3.31Å)SO
2.809(4)Å

O
0.87(6)Å
Dimerizationvia
HͲbondings

1220HͲDexchange

O

O

O

O
O

3.81(6)Å

4.66(1)ÅO

0.11(2)0.81(2)PositionaldisorderofH2O

TheencapsulatedH2O:lessacidicandlessbasicthanbulkwater

123

124

125

126

127

128

Directional electron transfer coupled spin-crossover in the crystals of [FeCo]
di-nuclear complexes facilitating ultrafast polarization switching
Pritam Sadhukhan, Shengqun Su, Shinji kanegawa, Osamu Sato *Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, Japan.

Research Motive

Introduction
Polarization switching

To develop functional magnetic materials to
obtain thermally induced phase transition from
nonpolar to polar structure via electron transfer
resulting polarization switching at a crystalline
level which can be widely used in pyroelectric
sensors & memory devices.

Ion displacement

Non-polar

Charge transfer in moleculesBa

Non-polar

polar

polar

D. Fu et al. Intech DOI: 10.5772/61017
Ferroelectric materials – Synthesis & characterization

S. Kanegawa, J. Am. Chem. Soc. 2016, 138, 14170-14173.

Result & discussion

Background

Synthesis of [(Fe(RR-cth))(Co(SS-cth))( P-dhbq)](PF6)3

Valance tautomerism

Polarization direction control: chiral methodology
RR

RR

SSRR
SSRR

RR

SS RR

RR

cth

RR
SSRR
SS
RR
SS
RR

SS

SSRR

SS

SSRR

SS

SSRR

RR

RR
Metal elemental analysis table:
1st analysis

Unit: mass%

Co

Fe

4.72

4.49

2nd analysis

4.71

4.47

Average value

4.72

4.48

Co

Fe

Angew. Chem. Int. Ed. 2004, 43, 3136 –3138

The composition ratio:
Angew. Chem. Int. Ed. 2004, 43, 3136-3138

1st analysis

0.998

2nd analysis

0.999

1

Average value

0.998

1

1

Crystal data:[(Fe(SS-cth))(Co(RR-cth))(dhbq)](PF 6)3Empirical FormulaC 38H74CoF18FeN8O4P3Formula Weight1256.73

temp(K)

40

130

Crystal System

monoclinic

monoclinic

Lattice TypePrimitive

Primitive

Space groupP2 1(#4)

P2 1(#4)

1256.73a(Å)

8.8092(5)b(Å)

29.7189(16)30.327(2)c(Å)

10.1576(6)10.1858(8)8.8881(7)α(deg.)90

90

β(deg.)

110.121(8)110.125(8)γ(deg.)90

90

V (Å3)

2497.0(3)2578.0(4)Z value2

2

Dcalc(g/cm3)

1.671

1.619

radiation

Sr(l = 0.70070 Å)

Sr(l = 0.70070 Å)

R1 (I>2.00σ(I))

0.05570.0868wR2 (all)Magnetic susceptibility data

C38H74CoF18FeN8O4P3

0.14570.2321

GOF

1.073

1.066

Frack parameter0.05(3)0.02(3)•CO stretching vibrations
for dhbq2- :1470 cm-1 & 1290 cm-1•

CO stretching vibrations
for dhbq3- :1525 cm-1

Mass spectroscopy data in acetone

Circular dichromism spectra in acetone∆δTransmittance (%)

Variable temperature FT-IR spectrum

Wavenumber(cm-1)

Freshly prepared solution

Variable temperature Raman spectrum

After 24 hours
After 48 hours• [FeII –O] stretching frequency band :567 cm-1•

Shift of 500 cm-1 band (FeII-O)
to 490 cm-1 band (FeIII-O)
with increasing temperature

Thermally Induced Current (arb. u.)

Fe pre-edge XAS data

Selected bond length table
heatingcooling60[(Fe(SS-cth))(Co(RR-cth))(dhbq)](PF6)340 K

50
Fe-O(Å)40
Fe-N(Å)30
20
Co-O(Å)10
Co-N(Å)

0
80

85

90

95

100

105

m/z

Wavelength (nm)Temperature dependent X-ray absorption spectroscopy data

Pyroelectric data
70

75

1111 (molecular peak)

110

115

120

125

130 K

40 K

2.015(7)1.886(16)1.900(7)2.013(6)1.848(15)2.011(8)2.058(8)2.158(9)2.028(17)2.148(11)2.032(8)2.147(9)2.014(19)2.131(10)2.054(9)2.168(9)1.950(18)2.147(11)2.005(8)2.139(8)2.062(18)

2.138(11)1.897(7)1.889(7)1.878(16)1.892(7)1.892(7)1.908(16)1.888(8)2.025(9)2.030(10)1.99(2)2.016(12)2.024(8)1.964(8)2.059(18)1.987(12)2.012(9)2.026(10)1.996(18)1.972(10)1.986(8)2.005(9)2.00(2)2.027(12)1.898(7)Fe K-edge & Co K-edge XAS data[(Fe(RR-cth))(Co(SS-cth))(dhbq)](PF6)3
130 K
2.017(9)1.894(9)Temperature (K)Conclusion
 A dinuclear complex [{Fe(RR-cth)}{Co(SS-cth)}(dhbq)](PF6)3 is synthesized by chirality-assisted methodology that played an important role in the polarization switching at the crystalline level.
 Charge transfer coupled gradual thermal spin-crossover was found at 85 K with thermal hysteresis.
 There is certain possibility to obtain valence tautomeric transition by substituting the metal ion with another paramagnetic metal (3d or 4d) to achieve switching with different electronic ground state.

129

Tetrahydrofuran-Triggered Magnetic Coupled with Vapochromism
Switching in a Cobalt(II)-Based Single-Ion Magnet
Sheng-Qun Su, Shu-Qi Wu, Shinji Kanegawa, Osamu Sato
Institute for Materials Chemistry and Engineering, Kyushu University, and IRCCS
Control of Magnetic Property

orbital …… coordination number …… spin

+T-T

Su S.-Q. et.al

Angew Chem Int Ed. 52, 4568-4671 (2013)

Results and Discussion+ THF

Complex 1- THF

Complex 1

Complex 1-THF

Complex 1-THF

The variable temperature powder X-ray diffraction data

UV-Vis spectra of solution samples

IR spectrum

TGA curves

The static magnetic properties

Energy level of the d-orbitals

Conclusion
Key words

䕺 single-ion magnet
䕺coordination number䕺 magnetic momentum
䕺 orbital angularmomentum䕺 relaxation time
䕺vaporchromism

The dynamic magnetic properties of complexes 1 (left) and complex 1-THF (right).

130

+ THF

- THF
C.N. = 5

C.N. = 6

131

N3

Mol

Click!

N

Development and Application ofMulti-molecule Connectable DACN

N

Yuuya Kawasaki, Yuuki Seto, Shintarou Kawahara, Kazunobu Igawa, Katsuhiko TomookaInstitute for Materials Chemistry and Engineering, and IRCCS Kyushu University

Background
DACN Derived Multi-Molecule Connector

[C
u]
ca
Bio taly
st
or
th
og
on
nc
ali
tio
ty
n
Sy
nth al D
ive
es
rs
is
Sta
ity
bil

ity


Evolution of Huisgen Reaction DeviceProblems

Mol2

N3

Mol2

N

N

N

Mol1

[Cu] catalyst

Mol2
Mol2

N

N

Introduction of biological properties· peptide· sugar etc.

N

DACN-MMC

N

N3 ×

8[Cu] freeMol1

N× × 

Mol1

2nd generation: cyclooctyne

8Introduction of physical properties· water solubility· fluorescence etc.

Fu

1st generation: terminal alkyne

Mol1

Mol2

Mol3
Mol4

Mol1

Mol4

3rd generation: 4,8-diazacyclononynes (DACN)
Mol3
Mol3
Mol1

9

N

Mol2

N

N

N

Mol1

N

N

Mol1

9

N

Mol1

Mol2

N

N

N

Mol2

N

[Cu] freeclick reaction

N3[Cu] free

N3

N

N

Mol2

N



Mol3

Mol3

DACN
a R. Ni, N. Mitsuda, T. Kashiwagi, K. Igawa, K. Tomooka, Angew. Chem. Int. Ed. 2015, 54, 1190.

ResultSynthesis of DACNReactivity of DACN(OC)3Co

Co(CO)3BF3·OEt2

Co2(CO)8

3 stepsynthesis

HO(OC)3Co

OH

Co(CO)3+(OC)3Co

Co(CO)3

X N

N Y

HN Y

8

double Nicholas reaction

HO

F

RO

CAN

+

+

X NH

X N

OH

N Y

9

Ts N

–1 –1

DACN
one-pot
synthesis

X NH

π orbital

CAN

Thermal Stability
80 °C in toluene
for 2 weeks

pyridine

BF3·OEt2

double Nicholas reaction

N Ts

Ts N

N Ns

Ts N

88%
up to 3.1 g

Ts N

N Ns

Ms N

N Ts
OH
69%

73%

79%
up to 6.3 g

Ns N

O
4

OEt

R NN Na NBO calculation at B3LYP/6-311G(d,p) level of theory.

DACN-NHS ester
N3

Mol

X N

Ms N

N Ns

Ms N

O

H2NBn
1)

N

Ms N

N

N3

Bn N N N

N3

O
Huisgen reaction

Ms N

N

L

N

Fmoc N

n

O

HO2C

SH

n

amidationHSpeptide2

HS
peptideDACN-NHS-ester

L

NH2

CH3CN
97%

O

O
Ms N

N Ns

O O
S

Ns N

N

N

DACN-maleimide Ms N

COOH

O O

MeOH, rtHOOC

N-Fmoc-amino-acid-DACN
PhHN

PBS (pH = 7.4)
DMF, rt

O
3

O O
S
N
H

O
3

N

N

H
N

COOH

O

HO
HO
HO

N

H
N

N

O

HO
HO
HO

O
N3
OH
H2N

Ph
H
N

O
N
H
SH

O

O

O
N
H

O

H
N

O

O

H
N

OH
O

N

N

H
N

N
H

O

HOOC
NH2

S
N
H

H
N

X N

O O
S

H
N

N

O

O

O
N
H

H
N

O
N
H

O

H
N
O
NH2

+ regioisomerO+ regioisomer

N X
O

O
O

O
n

O

O

N

O

OH

NH2

N

N

X N

N X

COOH

O

O

In ProgressN

N

O
DACN-OH-NHS-ester

132

O O
S

O

O O
exact mass [M + H+ : 1126.39
observed mass [M + H]+ : 1126.33

O

exact mass [M + H]+ : 1214.49
observed mass [M + H]+ :1214.44

N

N3
Ms N

H
N

N
H
SH

S

MeOH, rtN

O

exact mass [M + Na]+ : 1031.41
observed mass [M + Na]+ : 1031.48

N
H

NH2

OH

N

O

N

N

O

Fmoc N

O

O
H
N

O O
S

5 steps

O

N

98%

O

H2N

O O
S
N
H

PBS (pH = 7.4)
DMF

OEt

N

O

NH2

O
+ regioisomerO

DACN-maleimide

N
H

N

N-Fmoc Amino Acid DACN

2 steps

HOOC

H2NBn

O

N

N-Fmoc-amino-acid-DACN

DACN-maleimide+ regioisomerOO

peptide1

DACN-maleimide

HS
O

O

BnN3

OH

H
N

N

N

Ms N

thia-Michael reaction

peptide

N

N

Bn N

O
X N

O
NH2

amidation

Ms N

DACN-NHS-ester

O

N

O

n

N3

Mol

Huisgen reaction

O

L

93%

97%

: COOH

Mol

Huisgen reaction

N

BnN3
CH3CN

O

: amino acid

O
X N

H
N

N

PBS (pH = 7.4)
DMF

2)

Mol

N

O

O

N

: NH2

2

DACN-NHS-ester

N3

Mol

,

N

: amino acid

O

O

O

3 stepsN

N

N

stabilization by orbital interaction
low distortion energy

YX

K. Igawa, S. Aoyama, Y. Kawasaki, T. Kashiwagi, Y. Seto, R. Ni, N. Mitsuda, K. Tomooka, Synlett 2017, 28, 2110.

: NH2, SH

Y = CH2: 3.76 kcal·mol–1
Y = NTs: 4.88 kcal·mol–1
Y = O: 5.81 kcal·mol–1

Origin of High Huisgen Reactivity

61%

Design and Concept of DACN-MMC

X N

π-σ* interaction energy a
σ* orbital

Y

X

Tolerance for Thiol
Tol-SH (1.0 eq, 10 mM)
25 °C in toluene
for 2 weeks

Example
E
Examp
xamp
ple
le
O O
S
N

8

N
R
DIBAC
3.1 x 10–1

RODIFO
7.6 x 10–2

Origin of High Thermal Stability

HN Y

Co2(CO)8F

8O

NTs-AOCN
1.9x10–2

NTs, NTs-DACN
5.5x10–3

OCT
k (M s ) = 2.4 x 10–3

9

Ts N

N Ts



nN

O

O
DACN-OH-maleimide

X N

N X
O

SH
O

DACN-SH

O
OH

133

134

135

136

137

138

Regioselective Trifluoromethylthiolation of N-Heteroaromatic Compounds
Takeru Torigoe, Ryuhei Muta, Yoichiro Kuninobu
Institute for Materials Chemistry and Engineering,
Kyushu University, 6-1 Kasugakoen, Kasuga-shi, Fukuoka 816-8580, Japan
Introduction
Fluorine

An Example of Pharmaceuticals
Containing -SCF3 group• The Second Smallest Atom
• The Highest Electronegativity• Strong C–F Bond

Me

Previous Work
R

H
N

O

Triflorex(anorectic drug)

CF3

I

CF3

SCF3 / Pd cat.

JOC 1985, 50, 4047.

ACIE 2015, 54, 6809.

This Work
R

SCF3

N

DG
SCF3

SCF3 / Pd cat.

ACIE 2014, 53, 9316.

OL 2014, 16, 2046.

R

ArSO2ClAgSCF3Ar

HO

N

BF2CF3

Nishida, T.; Ida, H.; Kuninobu, Y.; Kanai, M. Nat. Commun. 2014, 5, 3387.

Representative Method to Prepare Ar–SCF3

H

R

EtOAc

N

Me

· Mimic effect, block effect· Repellency, heatresistanceS

Me3SiCF3 (3.0 equiv)CsF (3.0 equiv)

SCF3

N

MeCN
25-50 ºC, 16 h

O

H

SCF3

Selectivity: >20:1
up to 90 % yield

DG: directing group

Scope of Substrate

Reaction of Quinoline N-Oxide
SCF3

AgSCF3 (1.05 equiv)

SCF3

ArSO2Cl (1.1 equiv)
solvent
25 ºC, 16 h

N

O

entry

solvent

1
2
3

N

N

SCF3

2-

O

total yield (%)

EtOAc

-

<5

-

-

-

EtOAc

o-NsCl

63

68

11

21

DMF

o-NsCl

33

>99

0

<1

R

4

CH2Cl2o-NsCl

38

87

8

5

5

Tolueneo-NsCl

28

68

14

18

6

THF

o-NsCl

27

74

<1

26

7

MeCN

o-NsCl

82

66

11

23

8

MeCN

p-NsCl

68

63

13

24

Me
F
Cl
Br
I
CO2Me

9

MeCN

TsCl

41

24

37

39

10

MeCN

TfCl

<5

-

-

SCF3

O2N

-

SO2Cl

94

96

<1

4

SO2Cl

64

36

19

45

4R

Me
N

N

SCF3

N

SCF3
Me

63%

yield
73%
75%
82%
77%
71%
58%

68%

SCF3

N

Me

OMe

N

N

SCF3

83%

N

81%

SCF3

43%

33%
N

i-Pr

MeCN
i-Pr

SCF3

SCF3

O2N

12

SCF3

50%

N

NO2

MeCN

SO2Cl
N

Product / isolated yield

ArSO2Cl

11

NO2

MeCN
25-50 ºC, 16 h

N

4-

ratio
3-

ArSO2ClR

ArSO2Cl (1.1 equiv)

N

3-

2-

AgSCF3 (1.05 equiv)

R

N

N

SCF3

SCF3

N

75%

i-Pr

Gram-scale reaction

N

SCF3

13%

42%

Reaction of Qunidine Derivative

AgSCF3 (1.05 equiv)ArSO2Cl (1.1 equiv)
N

O

N

BnO

MeCN
25 ºC, 16 h

N

7.2 mmol
1.05 gSCF3

AgSCF3 (1.05 equiv)ArSO2Cl (1.1 equiv) MeO

MeO

1.02 g62%

N
O

Conversion into -SO2CF3

N

BnO

MeCN
50 ºC, 16 h

N

SCF3

90%

Possible Mechanism
AgSCF3 + ArSO2ClAgSCF3 (1.05 equiv)ArSO2Cl (1.1 equiv)
N

O

MeCN
25 ºC, 16 h

SCF3

without isolation

MeO2C

N

N

S

CF3

O O

62%

Ar

H

Me

RuCl3 • 3H2O (2.4 mol%)
NaIO4 (3 equiv)
MeCN, CCl4, H2Ort, 16 h

O O
S
SCF3

O O
S

F3C

CO2Me
N
H

SCF3

N

N

O

O

S

Ar

N

or

O

O O

Me

SCF3

S O
Ar O

H

Nifedipin analog(hypotensive agent)

N

O

S

SCF3
Ar

O O

– ArSO2H(basic work-up)

N

SCF3

139

140

141

142

Photochemical Isomerization Approach to 
Planar Chiral Medium-sized Cyclic Molecules
Yuki Yoshida, Kouhei Machida, Mariko Okamoto, Yusuke Ano, Kazunobu Igawa, and Katsuhiko Tomooka
Institute for Materials Chemistry and Engineering, and IRCCS, Kyushu University

Background
Our Chemistry about Planar Chiral Medium-sized Cyclic Molecules
R1

R1
Ts

N
Ts

R2

Synthetic Approach for Planar Chiral Medium-sized Cyclic Molecules

R1

R2

N

N

R2

(R)

Ts

elimination
R1O

Ts N

R1

Ts N

n

Y
MeO

OH

Cope
rearrangement

Z to E
isomerization

X

X

O

R1

Ts N

X

n

stereo specifictransformation

R1

RCM

X

(S)

n
n

Ts N

n

X
n = 0, 1, 2

R2

R2

R1

R2

R1

R1

Ts N

Y

X

X
n

Z

Ts N

Grob
fragmentation

cyclization

X

E-selective
addition

n

Y

R2

Ts N
H

R2

H

R2

R2
X = Br or I

etc.

n

HX

ResultThis Work

Optimization of Photo Isomerization

Ring Closing Metathesis(RCM)

UV (280 nm)
AgNO3/SiO2
DEIP (2.0 eq)

Photochemical
Isomerization

pentane, rt
Z-isomeracyclic diene

Z-isomerE-isomerE-isomer(0.27 mmol)

quartz photo-inlet
adapter

optical fiber

Our Idea: E-Selective Adsorption with AgNO3/SiO2b

Inoue’s Worka photochemical isomerization
Z-isomerE-isomerUV (254 nm)
sensitizer

AgNO3/SiO2
Entry AgNO -content
3[wt%]

cyclohexane
25 °C
Z-isomerE-isomerselective adsorption

64 : 36
sensitizer
3,5-bis(trifluoromethyl)benzoic acid methyl ester

Ag+

weak
interaction

stronginteraction

Ag+

AgNO3/SiO2

X
rt - reflux

X = C(SO2Ph)2(quant)a(yield)a

–

none

42

23 : 77

(87%)

5

400

42

75 : 25

(81%)

3

10

400

42

93 : 7

(81%)

4

20

400

42

77 : 23

(73%)

5

10

500

42

97 : 3

(88%)

6

10

500

24

67 : 33(72%)

UV light

substrate andsensitizer
in solvent

AgNO3/SiO2

sensitizer
CO2R
DMIP (R = Me)
DEIP (R = Et)

CO2Ra) Combined yields of (E) and (Z). Determined by GC analysis.

Synthesis of Planar Chiral Dialkoxysilane

additivepentane-Et2O
rt

CH2Cl2

E/Z

2

UV (280 nm)
DMIP or DEIP

Grubbs’ 1st cat.
X

time [h]1a) N. Yamasaki, Y. Inoue, T. Yokoyama, A. Tai, J. Photochem. Photobiol., A: Chem. 1989, 48, 465.
b) Related report : Fox and colleagues reported the efficient photochemical Z to E isomerization of medium-sized
cyclic molecules with continuous circulation of a reaction mixture pumped through a packed column of AgNO3/SiO2;
M. Royzen, G. P. A. Yap, J. M. Fox, J. Am. Chem. Soc. 2008, 130, 3760.
M. Royzen, M. T. Taylor, A. DeAngelis, J. M. Fox, Chem. Sci. 2011, 2, 2162.

Synthesis of Planar Chiral Orthocyclopheneamount[mg]

additive

UV (280 nm)
DMIP or DEIP

Grubbs’ 1st cat.
O

X

O Si
R

R

O

CH2Cl2, rt

O Si
R

O Si

additivepentane-Et2O
rt

R

O
R

R

E/Z (yield)aE/Z

additive(yield)b

X = CH2

none
AgNO3/SiO2

22 : 78 (quant)c
89 : 11 (88%)c

X = NTs(68%)

none
AgNO3/SiO2

26 : 74 (81%)d
64 : 36 (67%)d

X=O
(21%)

none
AgNO3/SiO2

31 : 69 (79%)
74 : 26 (88%)d

R = t-Bu
(72%)

none
AgNO3/SiO2
none
AgNO3/SiO2

R = Ph(87%)a) Mg, MeOH, rt, 92%. b) Combined yield of (E) + (Z). Determined by 1H NMR analysis.
c) K. Igawa, K. Machida, K. Noguchi, K. Uehara, K. Tomooka, J. Org. Chem. 2016, 81, 11587.
d) K. Machida, Y. Yoshida, K. Igawa, K. Tomooka, Chem. Lett. 2018, 47, 186.

a) Combined isolated yield of (E) + (Z).
b) K. Tomooka, S. Miyasaka, S. Motomura, K. Igawa, Chem. Eur. J. 2014, 20, 7598.
c) K. Machida, Y. Yoshida, K. Igawa, K. Tomooka, Chem. Lett. 2018, 47, 186.

Stereochemical Behavior of Planar Chiral Medium-sized Cyclic Molecules

Summary

25 : 75 (94%)b
89 : 11 (61%)c

33 : 67 (99%)b>98 : <2 (48%)c

CD spectra

Ring Closing Metathesis
(RCM)

10000

Photochemical
Isomerization

5000

N
Ts

0

acyclic diene

5000

10.0

O Si

Ph
t1/2

O

O Si

Ph

Z-isomer

1.9 yearsbRTs
380 hadynamic

1,000 y

2y

1y

500 h

100 h

50 h

10 h
5h
1h
a) at 25 ºC, in n-hexaneb) calculationOR

with AgNO3/SiO2
up to >98 : <2

4.35 ha56.7 hastatic2,000 y

O Si

X

N

O
t-Bu

E-isomertime [min]

O

t-Bu

1,375 yearsb

20.0



143

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