Thematic Session on"Asymmetry in materials and properties”

March 15, 2021 Online
Integrated Research Consortium on Chemical Sciences (IRCCS)

The 4th IRCCS International
Symposium:"Multidimensional control overmaterial structure and function"
Thematic Session,"Asymmetry in materials and properties”

March 15, 2021 Online

The 4th IRCCS International Symposium:"Multidimensional control over material structure and function"
With a Thematic Session, "Asymmetry in materials and properties”

March 15, 2021 Online
13:00-13:05

Opening remarks
Jun-ya Hasegawa (Hokkaido Univ.)

Chair: Atsushi Fukuoka
13:05-13:30 Senior talk 1 Kunio Awaga (Nagoya Univ.) Thematic Session“Development of Molecular Mimics of Carbon Allotropes”
13:30-13:50

Younger scientist talk 1

Ewa Kowalska (Hokkaido Univ.) Thematic Session“Morphology design in heterogeneous photocatalysis: Symmetry vs asymmetry”
Chair: Tamaki Nakano
13:50-14:10

Younger scientist talk 2

Masato Goto (Kyoto Univ.)“Structural and magnetic properties of B-site-ordered double perovskites Ln2LiFeO6(Ln: lanthanoid elements) with unusually high valence Fe5+ ion”
14:10-14:45

Keynote Lecture

Xinhua Wan (Peking Univ.)

Thematic Session“From Pasteur Resolution to Controlled Preparation of Chiral Organic Crystals“
14:45-15:50

Poster Session

Chair: Daisuke Uraguchi
15:50-16:15

Senior talk 2 Katsuhiko Tomoomka (Kyushu Univ.)

Thematic Session“New Aspects of Asymmetric Preparation of Chiral Molecules”
16:15-16:35

Younger scientist talk 3

Akiko Yagi (Nagoya Univ.)“Programmable Synthesis of Multiply Arylated Cubanes through C–H Metalation and
Arylation”
16:35-16:55

Younger scientist talk 4

Shu-Qi Wu (Kyushu Univ.)“Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric
Cobalt Complex “
16:55-17:00

Short Break

Chair: Jun-ya Hasegawa
17:00-17:30

Emerging Scientist Lecture Adriana Pietropaolo (Univ. Catanzaro) Thematic Session“Molecular asymmetry from chiral free-energy approaches”

1Chair: Tamaki Nakano
17:30-18:15

Plenary Lecture

Ron Naaman (Weizmann Institute of Science)

Thematic Session“The electron spin and chiral systems-Merging that results in novel properties “
18:15-18:35

Committee members’ comments

18:35-18:40

Closing remarks
Shigehiro Yamaguchi (Nagoya Univ.)

18:40-20:00

Open Baquet in breakout rooms2

Poster Presentations
P-01

Spontaneous Deposition of Pt on Au(111)○Bing Hu, Daiki Kido, Kaiyue Dong, Md. Harun Al Rashid, Hiroko Ariga-Miwa, Satoru
Takakusagi, Kiyotaka Asakura (Hokkaido Univ.)

P-02

Electric-assisted propane dehydrogenation at low temperature: far beyond the equilibrium
conversion○Jianshuo Zhang, Ruoyun Ma, Ken-ichi Shimizu, Shinya Furukawa (Hokkaido Univ.)

P-03

ExploringtheMechanism

of

Novel

Bifunctional

AlIII

Porphyrin

Catalyzed

Copolymerization of CO2 and Cyclohexene Oxide: A DFT Study○Manussada Ratanasak, Jingyuan Deng, Hideki Tokuda, Chihiro Maeda, Tadashi Ema,
Kyoko Nozaki, Jun-ya Hasegawa (Hokkaido Univ.)
P-04

Mechanistic Study on the Selective Catalytic Reduction of NOX Catalyzed by Fe/SO42/CeO2 with NH3〇Kai Oshiro, Min Gao, Jun-ya Hasegawa (Hokkaido Univ.)

P-05

Asymmetric Hyperbranched and Linear Fluorene-vinylene Polymers

Thematic Poster〇Pengfei Wu, Zhiyi Song, Masayoshi Bando, and Tamaki Nakano (Hokkaido Univ.)
P-06

Doping of Rh in In2O3 promotes methanol formation during CO2 hydrogenation〇Nazmul Hasan MD Dostagir, Coogan Thompson, Hirokazu Kobayashi, Ayman M. Karim,
Atsushi Fukuoka and Abhijit Shrotri (Hokkaido Univ.)

P-07

The Variation of Surface/Bulk Structure and Activity of Titania Photocatalyst Particles by
Milling〇Chen, G.; Takashima, M.; Ohtani, B. (Hokkaido Univ.)

P-08

Interparticle Charge-transfer Excitation at Adjoined Anatase and Rutile Interface Proved by
Reversed Double-beam Photoacoustic Spectroscopy〇Shen, Y.; Nitta, A.; Takashima, M.; Ohtani, B. (Hokkaido Univ.)

P-09

Titania Inverse-opal with a Gold Nanoparticle Incorporated per Void Space for
Photoabsorption Amplification〇Raja-Mogan, T.; Kowalska, E.; Takashima, M.; Lehoux, A.; Ohtani, B. (Hokkaido Univ.)

P-10

Solid State Fabrication of Polythienylenevinylene Thin Films via Cis-to-trans Thermal
Isomerization〇 Masayuki Wakioka, Natsumi Yamashita, Hiroki Mori, Richard Murdey, Atsushi
Wakamiya, Yasushi Nishihara, Fumiyuki Ozawa (Kyoto Univ.)

3

P-11

Isolation of Organophosphorus Zwitterions〇Yoshifumi Hashikawa, Shu Okamoto, Yasujiro Murata (Kyoto Univ.)

P-12

Comparative investigation of quadruple perovskite structures AA'3B4O12 containing divalentmanganese, iron, cobalt and nickel square-planar centers at the A' sites〇Midori AMANO,

P-13

Fabio Denis Romero, Masato Goto, Yuichi Shimakawa (Kyoto Univ.)

Stabilisation and characterisation of the polymorphs of BaRhO3 between 7 and 22 Gpa〇Sean INJAC, Romero, Denis. F, Xu Yuanhui, Shimakawa Yuichi (Kyoto Univ.)

P-14

Near-Ultraviolet Transparent Organic Hole-Transporting Materials Containing Partially
Oxygen-Bridged Triphenylamine Skeletons for Efficient Perovskite Solar Cells〇TRUONG Minh Anh, Hayoon Lee, Ai Shimazaki, Richard Murdey, Atsushi Wakamiya(Kyoto Univ.)

P-15

Asymmetric Synthesis of Chiral Silicon Molecules

Thematic Poster〇Kazunobu Igawa, Katsuhiko Tomooka (Kyushu Univ.)
P-16

Synthesis and Transformation of Silylalkene〇Yuuya Kawasaki, Kazunobu Igawa, Katsuhiko Tomooka (Kyushu Univ.)

P-17

Electronic Pyroelectricities of Heterometallic Dinuclear Complexes〇Shinji Kanegawa, SadhuKhan Pritam, Jeremy Ian Long and Osamu Sato (Kyushu Univ.)

P-18

Water-orientated reversible magnetic anisotropy transition〇Shengqun Su, Shuqi Wu, Shinji Kanegawa and Osamu Sato (Kyushu Univ.)

P-19

Observation of Proton Transfer Coupled Spin Transition in Fe(II) Complexes〇Takumi Nakanishi and Osamu Sato (Kyushu Univ.)

P-20

Effect of Urea Additives in the Iridium-Catalyzed C-H Borylation of Aromatic Compounds〇Takeru Torigoe, Jie Wang, Yadong Pang, Koji Kubota, Hajime Ito, Yoichiro Kuninobu(Kyushu Univ.)

P-21

Novel Access to Silacyclic Compounds〇Kohei Sekine, Yafang Dong, Kazuto Fuji, Masashiko Sakai, Yoichiro Kuninobu(Kyushu Univ.)

P-22

Contactless masstransfer between alternating droplets〇Shusaku Asano, Yu takahashi, Taisuke Maki, Yosuke Muranaka, Nikolay Cherkasov,Kazuhiro Mae (Kyushu Univ.)

P-23

Synthesis of macrocyclic compounds using 1,8,13-substituted triptycenes as a foundation〇Takayuki Iwata, Yusuke Maehata, Tatsuro Yoshinaga, Mitsuru Shindo (Kyushu Univ.)

4

P-24

Multiple droplets formation by a simple mixing method with microfabricated channel andtheir mass-transport mechanism〇Kenta Goto, Kyoka Nakanishi, Fumito Tani (Kyushu Univ.)

P-25

Ink-Jet Printable Thermally-Activated Delayed Fluorescence Dendrimers〇 Ken Albrecht, Kenichi Matsuoka, Amruth C., Beata Luszczynska, Jacek Ulanski,
Katsuhiko Fujita, Kimihisa Yamamoto (Kyushu Univ.)

P-26

Syntheses of donor-π-acceptor (D-π-A) conjugated enamines〇Atsushi Tahara, Ikumi Kitahara, Hideo Nagashima (Kyushu Univ.)

P-27

Investigating the Nonradiative Decay Pathway in the Excited State of Silepin Derivatives:
A Study with Second-Order Multireference Perturbation Wavefunction Theory〇Naoto Inai, Daisuke Yokogawa, Takeshi Yanai (Nagoya Univ.)

P-28

Analytical Nuclear Gradients for the State-Averaged Density Matrix Renormalization Group
Complete-Active-Space Self-Consistent-Field Method〇Tsubasa Iino, Toru Shiozaki, Takeshi Yanai (Nagoya Univ.)

P-29

Enzymatic Hydroxylation of Small Alkanes by P450BM3 with Decoy Molecules underHigh Pressure〇Shinya Ariyasu, Yusaku Kodama, Kai Yonemura, Chie Kasai, Joshua Kyle Stanfield,
Yuma Shisaka, Yuichiro Aiba, Yoshihito Watanabe, Osami Shoji (Nagoya Univ.)

P-30

The Building of Rigid Heme Protein Multimers Based on Metal Coordination〇Hiroaki Inaba, Yuma Shisaka, Garyo Ueda, Kazuto Suzuki, Shinya Ariyasu, Yuichiro Aiba,
Hiroshi Sugimoto, Osami Shoji (Nagoya Univ.)

P-31

Directed Evolution of Cytochrome P450BM3 for Responding to Decoy Molecule Producedby Bacteria〇 Yuya Yokoyama, Masayuki Karasawa, Shinya Ariyasu, Yuichiro Aiba, Osami Shoji(Nagoya Univ.)

P-32

Synthesis of zigzag carbon nanobelt〇 Kosuke Watanabe, Kwan Yin Cheung, Yasutomo Segawa, Kenichiro Itami (Nagoya
Univ.)

P-33

Photoredox-catalyzed decarboxylative direct aminomethylation towards aryl bromides:
Straightforward synthesis of primary benzylamine〇Jaehyun Jung, Yota Sakakibara, Kei Murakami, Kenichiro Itami (Nagoya Univ.)

5

P-34

Synthesis and Properties of Non-alternant Aromatic Belts〇Hideya Kono, Yuanming Li, Yasutomo Segawa, Akiko Yagi, Kenichiro Itami (Nagoya
Univ.)

P-35

Phosphorus-Based

OrganocatalysisforDehydrative

Cyclization

of

N-(2-

Hydroxyethyl)amides into 2-Oxazolines〇Farzaneh Soleymani Movahed, Siong Wan Foo, Saeko Ogawa, Susumu Saito (Nagoya
Univ.)
P-36

C–O bond formation between aryl halides and carboxylic acids using titanium dioxide
photocatalyst and a nickel complex〇Riku Hashimoto, Hiroya Tada, Shogo Mori, Jieun Jung, Susumu Saito (Nagoya Univ.)

P-37

Photoreduction of CO2 using molybdenum complexes bearing PNNP-type tetradentate
ligands〇Hiroaki Shibayama, Hiroko Okuwa, Kenji Kamada, Jieun Jung, Susumu Saito (Nagoya
Univ.)

P-38

Crystal structures and physical properties of a triptycene derivative annulated with electron
donating thianthrene moieties〇Takuma Yoshiyuki, Yoshiaki Shuku, Kunio Awaga (Nagoya Univ.)

P-39

A metallomacrocycle tethering eight corannulenes and the host–guest interaction with C60〇Yuta Kobayashi, Shin-ichiro Kawano, Kentaro Tanaka (Nagoya Univ.)

P-40

Template-independent RNA sequential synthesis using modified nucleic acid as substrate〇 Kato Shunichi, Nakamoto Kosuke, Murase Hirotaka, Inagaki Masahito, Hashiya
Fumitaka, Kimura Yasuaki, Abe Hiroshi (Nagoya Univ.)

P-41

Development of post-cleaving PCR primers for genome-scale DNA synthesis〇Kase Mikiya, Inagaki Masahito, Hiraoka Haruka, Abe Naoko, Hashiya Fumitaka, Kimura
Yasuaki, Abe Hiroshi (Nagoya Univ.)

P-42

Tunneling ionization of molecular hydrogen by using a high-repetition-rate pulse laser〇Shinnosuke Inaba, Daimu Ikeya, Hikaru Fujise, and Akiyoshi Hishikawa (Nagoya Univ.)

P-43

Development of momentum imaging apparatus for intense-field dynamics of molecular ions
〇M. Yamada, H. Hasegawa, A. Matsuda, M. Fushitani and A. Hishikawa (Nagoya Univ.)

P-44

Association reaction of gaseous C6H14 in femtosecond laser filament studied by productmass spectrometry〇Y. Okumura, A. Matsuda, and A. Hishikawa (Nagoya Univ.)

6

P-45

Cross–linking gelation of isomaltodextrin for the chromatographic separation ofsemiconducting carbon nanotubes〇Yuki Matsunaga, Jun Hirotani, Yutaka Ohno and Haruka Omachi (Nagoya Univ.)

P-46

Catalytic NO Reduction Performances of Cr and Rh-incorporated Ceria〇Satoru Ikemoto, Satoshi Muratsugu, Mizuki Tada (Nagoya Univ.)

P-47

Preparation and Catalytic Performances of Copper and Ruthenium Incorporated Ceria〇Chaoqi Chen, Satoru Ikemoto, Satoshi Muratsugu, Mizuki Tada (Nagoya Univ.)

P-48

Preparation and Luminescent Properties of Surface-Attached Chiral Tb Complexes
Thematic Poster〇Sora Shirai, Satoshi Muratsugu, Hidetaka Nakai, Mizuki Tada (Nagoya Univ.)

7

LecturesThematic session

9

Thematic session

O-1

10

Thematic session

Ewa Kowalska
Associate Professor,
Institute for Catalysis (ICAT), Hokkaido University
Phone: +81-11-706-9130
Fax: +81-11-706-9133
E-mail: kowalska@cat.hokudai.ac.jp
Education:
1992–1998(B.Sc./M.Sc. Eng.) Faculty of Chemistry,
Gdansk University of Technology (GUT), Poland
Faculty of Chemistry, GUT, Poland
Received a PhD (Supervisor: Prof. Jan Hupka)

1998–2004

Professional Career:
2002–2003
2004-20092005–2007
2007–20092009–20122012–presentMarie Skłodowska-Curie Fellow at Paris-sud University, France
postdoctoral researcher at GUT, Poland
JSPS postdoctoral fellow at Hokkaido University
GCOE fellow at Hokkaido University
Marie Skłodowska-Curie Fellow at FAU/Ulm University, Germany
Associate Professor at Hokkaido University

Research Interests:
1) Heterogenous photocatalysis
2) Environmental protection
3) Plasmonic photocatalysis4) Multi-functional (nano)materials5) Antimicrobial properties
Honors:since 2020
2019
2014
2012
2005

2004

Deputy Editor-in-Chief for Micro & Nano Letters (MNL), IET/Wiley
Hokkaido University President's Award for Excellence in Research and
Education
Global Networking Award, WinGS Project, Hokkaido University
Brigitte Schlieben-Lange-Programme stipend from Ministry of Science,
Research and the Arts of Baden-Württemberg, Germany
Award in STEF-NANO-ACC contest for the best PhD thesis in the field of
nanotechnology, nanoscience and multifunctional materials under theEuropean Commission Sixth Framework Programme
Doctoral dissertation with distinction

11

Thematic session

O-2
Morphology design in heterogeneous photocatalysis:
Symmetry vs asymmetry
Ewa Kowalska
Institute for Catalysis (ICAT), Hokkaido University, Sapporo 001-0021, Japan
Heterogeneous photocatalysis has been considered as the future for humanity,
especially solar photocatalysis (under natural sunlight), solving environmental and energy
problems. However, there are two main problems facing heterogeneous photocatalysis, i.e.,charge carriers’ recombination and low efficiency of light harvesting as the most active
photocatalysts are usually active under UV irradiation only. Accordingly, the proper design ofphotocatalytic materials has been broadly investigated to achieve better photocatalytic
performance. Although, it is well known that all surface properties, e.g., specific surface area,
crystallinity and crystal/particle sizes, have crucial impact on the overall photocatalytic activity,
the resent studies have indicated that the morphology of photocatalysts, including also
symmetry and asymmetry aspects, has governed the photocatalytic performance.
It is thought that symmetry and asymmetry of photocatalysts is highly important fordifferent photocatalytic reaction. Indeed, our studies on the design of photocatalysts haveconfirmed that slight change in the photocatalyst morphology might result in significant changeof photocatalytic activity.1 For example, the polydispersity in gold deposits on titania surface ishighly recommended for activity under visible-light irradiation (plasmonic photocatalysis) due
to enhanced light harvesting efficiency.2 Moreover, even slight increase in the crystallite sizeof gold results in an increase in photocatalytic efficiency because of significant enhancementof plasmonic field.3 The deposition of noble metals on anatase facets with different morphology,
resulting in high or low photocatalytic activity, 4-5 will be also discussed during this presentation
to underline the importance of morphology.
(1) Wei, Z.; Janczarek, M.; Zheng, S.; Wang, K.; Kowalska, E. Catalysts 2020, 10, 1070.
(2) Kowalska, E.; Abe, R.; Ohtani, B. Chem. Commun. 2009, 2, 241.
(3) Wei, Z.; Rosa, L.; Wang, K.; Endo, M.; Juodkazis, S.; Ohtani, B.; Kowalska, E. Appl.
Catal. B-Environ. 2017, 206, 393.
(4) Wei, Z.; Endo, M.; Wang, K.; Charbit, E.; Markowska-Szczupak, A.; Ohtani, B.;
Kowalska, E. Chem. Eng. J. 2017, 318, 121.
(5) Wei, Z.; Janczarek, M.; Endo, M.; Balčytis, A.; Nitta, A.; Mendez Medrano, M. G.;
Colbeau-Justin, C.; Juodkazis, S.; Ohtani, B.; Kowalska, E. Appl. Catal. B-Environ. 2018,
237, 574.

12

Masato Goto
Assistant Professor,
Institute for Chemical Research, Kyoto University
Phone: +81-774-38-3113
Fax: +81-774-38-3118
E-mail: goto.masato.8s@kyoto-u.ac.jp
Education:
2008–20122012–2014
2014–2017

Kyoto University
Graduate School of Science, Kyoto University
Graduate School of Science, Kyoto University
Received a PhD (Supervisor: Prof. Kazuyoshi Yoshimura)

Professional Career:
2017–20192019–present

Postdoctoral researcher at Kyoto University
Assistant Professor at Kyoto University

Research Interests:6) Solid State Chemistry7) Condensed Matter
8) Magnetism
Honors:2018
2014

Inoue Research Award for Young Scientists
Papers of JPSJ Editors’ Choice

13

O-3
Structural and magnetic properties of B-site-ordered double perovskites
Ln2LiFeO6 (Ln: lanthanoid elements) with unusually high valence Fe5+ ion
Masato Goto
Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan
Geometrically frustrated magnets have attracted much attention owing to their exotic magnetic
properties originating from the suppression of antiferromagnetic ordering. We focus on B-siterock-salt-ordered double perovskites A2BB’O6, which belong to one of famous frustrated
systems. In this work, we succeeded in synthesizing double perovskites Ln2LiFeO6 (Ln = Nd,
Sm, Eu) with a frustrated f.c.c. lattice of unusually high valence Fe5+ ions by using a highpressure and high temperature condition, and then investigated their structural and magnetic
properties.
The 57Fe Mossbauer spectra (Figure 1) showed that Ln2LiFeO6 (Ln = Nd, Sm, Eu) had a highly
negative isomer shift (−0.4 mm/s), confirming unusually high valence Fe5+ state. Ln2LiFeO6(Ln = Nd, Sm, Eu) were found to adopt a monoclinic structure (Figure 2) at room temperatureand show magnetic transitions at low temperatures. Interestingly, each magnetic transition
temperature is much lower than the absolute value of Weiss temperature, which could be due
to geometrical spin frustration. Detailed structural and physical properties of the obtained
compounds will be presented and the effects of lanthanoid ions at the A site will be discussed.

Figure 1.Mossbauer spectra of Ln2LiFeO6 (Ln =Figure 2. Crystal structure of

Nd, Sm, Eu) at room temperature.

Ln2LiFeO6 (Ln = Nd, Sm, Eu).

14

Thematic session

Xinhua Wan
Professor,
Beijing National Laboratory for Molecular Sciences, College ofChemistry & Molecular Engineering, Peking University
Phone: +86-10-62754965
E-mail: xhwan@pku.edu.cn
Education:
1981–1985
1985–1988

Hefei University of Technology
Department of Chemical Fiber Engineering, China Textile
University
Department of Chemical Fiber Engineering, China Textile
University
Received a PhD (Supervisor: Prof. Tong Sun)

1988–1991

Professional Career:
1991–1993
1993–1997
1995–1996
1997–present
2001-2001
2004–2005

Fax: +86-10-62751708

Postdoctor at Peking University
Associate Professor at Peking University
Visiting Scholar at the Hong Kong University of Science &Technology
Professor at Peking University
Senior Visiting Scholar at the University of Akron
Senior Visiting Scholar at Harvard University

Research Interests:9) Helical polymers, chiral resolution, circularly polarized luminescence, chiroptical switches;10) Liquid crystalline polymers, high performance polymers;
11) Living/controlled polymerization, helix-sense-selective polymerization;12) Self-assembly of polymers, organic/inorganic hybrid assembly.
Honors:
1997
1999
2003
2010
2017

The National Award for Natural Science, Tier III, the Ministry of Science &Technology of China
Trans-Century Training Programme Foundation for the Talents by the
Ministry of Education of China
National Outstanding Young Investigator Found by Natural Science
Foundation of China
Changjiang Professorship by the Ministry of Education of China
Polymer science innovation award of Chinese Chemical Society

15

Thematic session

O-4
From Pasteur Resolution to Controlled Preparation of Chiral Organic
Crystals
Xinhua Wan
Beijing National Laboratory for Molecular Sciences, College of Chemistry & MolecularEngineering, Peking University, Beijing 100871, China
Since Louis Pasteur separated sodium ammonium tartrate crystals into two sets ofcrystals with mirror images of each other in 1848, selective crystallization has become one of
the most economical and convenient techniques to provide large-scale enantiomerically purechiral compounds. Usually, only one enantiomer can be obtained at a low yield in a single
operation. In the past several years, we have been searching for an efficient method to meetsuch a challenge. First, we design and prepare a novel polymer aggregates that act as the
additives of crystallization to inhibit, enrich, and promote the crystallization of one enantiomer.
By the aid of these “nano-splitters”, the precipitation of second enantiomer is directly read out
from the crystal color and the completely isolation of the crystallization processes of two
enantiomers is realized. Second, we endow the “nano-splitters” with magnetism. The magnetic“nano-splitters” are selectively wrapped into the crystals of the second enantiomer. As a resultof efficient separation under magnetic field, high purity chiral compounds (99.2 ee% for Rcrystals and 95.0 ee% for S-crystals) can be obtained in a simple one-step crystallization process,with an extremely high separation yield (95.1%). Moreover, the nano-splitters show
expandability and excellent recyclability. Herein, we describe a strategy that enables thepreferred formation of one enantiomorph directly from racemic solutions as well as their in-situ
oriented attachment to fabricate macroscopic chiral crystal aggregates, only aided by the “tailormade” polymeric additives with various molar masses. When a L-polymer with a medium molar
mass is used, Plus (P)-type fan-shaped crystal aggregates of D-p-hydroxyphenylglycine ptoluenesulfonate (D-pHpgpTs) are obtained. Changing the molar mass of the polymer canswitch the chirality of the hierarchically ordered structures thus formed on both molecular andsupramolecular levels. The financial support of the National Natural Science Foundation ofChina (No. 51833001) is greatly appreciated.
(1) Li, N., Wang, H., Zhang, J., Wan, X. H. Polym. Chem. 2014, 5, 1702.
(2) Ye, X. C., Zhang, J., Cui, J. X., Wan, X. H. Chem. Commun. 2018, 54, 2785.
(3) Ye, X. C., Cui, J. X., Li, B. W., Li, N., Zhang, J., Wan, X. H. Angew. Chem. Int. Ed. 2018,57, 8120.
(4) Ye, X. C., Cui, J. X., Li, B. W., Li, N., Wang, R., Yan, Z. J., Tan, J. Y., Zhang, J., Wan, X.
H. Nat. Commun. 2019, 10, 1964.

16

Thematic session

Katsuhiko Tomooka

Institute for Materials Chemistry and Engineering, Kyushu University
Address: Kasuga-koen 6-1, Kasuga, Fukuoka 816-8580, JAPAN
Phone: +81-92-583-7806
Fax: +81-92-583-7810
E-mail: ktomooka@cm.kyushu-u.ac.jp
Education:
1983
Bachelor of Engineering, Keio University
1985
Master of Engineering, Keio University
1988
Doctorate of Science, Keio University(SV: Prof. G.-i. Tsuchihashi and Prof. K. Suzuki)
Professional Career:
1988–1998
Assistant Professor at Tokyo Institute of Technology (Prof. T. Nakai group)
1991–1993
Postdoctoral Research Associate at Stanford University (SV: Prof. P. A. Wender)
1998–2006
Associate Professor at Tokyo Institute of Technology
2007–present
Professor at Kyushu University
Research Interests:
1) Development of synthetic methods
2) Synthetic and structural chemistry of natural and unnatural chiral molecules

Honors:1988 The 5th Inoue Research Award for Young Scientists
1996 Eisai Award in Synthetic Organic Chemistry
1996 Incentive Award in Synthetic Organic Chemistry
2001 Thieme Journal Award
2009, 2010, 2014, 2015 and 2016
Asian Core Program Lectureship Award [Korea], [Singapore], [Hong Kong], [China], [Taiwan]
2010 SSOCJ Astellas Award for Organic Chemistry in Life Science2010 The Chemical Society of Japan Award for Creative Work2012 Nagase Foundation Award
2019 Synthetic Organic Chemistry Award

17

Thematic session

O-5
New Aspects of Asymmetric Preparation of Chiral Molecules
Katsuhiko Tomooka
Institute for Materials Chemistry and Engineering, Kyushu University,
Fukuoka 816-8580, Japan
In modern organic chemistry, chemists have put forth considerable efforts in order to obtain
desired enantiomers selectively. Chiral molecules with configurational isomerism of anasymmetric carbon represent a principal motif in this field, because most biologically relevantchiral molecules fall under such category. In general, the chirality of an asymmetric carbon isthermally stable, and hence it can be called “static chirality”. Developed approaches towards
enantioenriched static chiral molecules (STCMs) are generally classified by optical resolution
and asymmetric synthesis. On the other hand, it is well known that molecular chirality canalso be caused by conformational isomerism and many examples are dynamic, i.e., enantiomers
are capable of interconversion via bond rotation, in sharp contrast to STCMs. Dynamic chiralmolecules (DYCMs) have a potential advantage in that the enantioenriched forms can beprepared in a very different way from STCMs. In this regard, recently we have developed a
new approach termed dynamic asymmetric induction (DYASIN) for the preparation ofenantioenriched chiral molecules based on the stereocontrol of DYCMs using an outer chiralsource (OCS). DYASIN makes it possible to obtain the enantioenriched form of dynamic chiralmolecules from their racemic form without bond cleavage or bond formation.
This work

Hitherto developed method

racemate of STCM

racemate of DYCM

achiralat ambient temp

+ outer chiral source(OCS)

bond cleavage

1) optical resolution

separationbond rotation2) asymmetric synthesis3) dynamic asymmetric induction(DYASIN)

stereoselective
bond formation

enantioenriched DYCM
at low temp

stereospecific transformation
enantiomer

enentioenriched
STCM[1] K. Igawa, Y. Kawasaki, Y. Ano, T. Kashiwagi, K. Ogawa, J. Hayashi, R. Morita,
Y. Yoshioka, K. Uehara, K. Tomooka, Chem. Lett. 2019, 48, 726.

18

19

O-6

20

Shu-Qi Wu
Assistant Professor,
Institute for Materials Chemistry and Engineering, Kyushu University
Phone: +81-92-802-6208
E-mail: wu.shuqi.152@m.kyushu-u.ac.jp
Education:
2007. Sept.–2011. Jul.
2011. Sept.–2014. Jul.
2014. Oct.–2018. Mar.

Professional Career:
2018. Apr.–2021. Jan.
2021. Feb.–present

Tsinghua University
Department of Chemistry, Tsinghua University
Department of Chemistry, Kyushu University
Received a Ph. D. (Supervisor: Prof. Osamu Sato)

Researcher at Kyushu University
Assistant Professor at Kyushu University

Research Interests:13) Molecular Magnetism;
14) Electronic Dynamics in Molecular Crystals;15) Magnetoelectric Coupling in Molecular Crystals.

21

O-7
Macroscopic Polarization Change via Electron Transfer in a ValenceTautomeric Cobalt Complex
Shu-Qi Wu, Shinji Kanegawa, Osamu Sato
Institute for Materials Chemistry and Engineering and IRCCS, Kyushu University, Nishi-ku,
Fukuoka 819-0395, Japan
Polarization of materials characterizes the degree of co-alignment of permanentmolecular dipole moments. Switching polarization by different external stimuli provides anefficient way for energy conversion. Herein, we report electronic pyroelectricity in the single
crystal of a mononuclear cobalt complex, [Co(phendiox)(rac-cth)](ClO4)·0.5EtOH(H2phendiox = 9, 10-dihydroxyphenanthrene, rac-cth = racemic 5, 5, 7, 12, 12, 14-hexamethyl1, 4, 8, 11-tetraazacyclotetradecane) crystallized in the polar P21 space group1. The complex
exhibits a two-step valence tautomerism (VT), and the co-alignment of the complex motifs
amplify the change of the molecular dipole moment during the VT process to a macroscopic
level, giving two pyroelectric peak currents in the same temperature domain of the VT transition.
Different from common ferroelectric materials, no pre-polarization process is needed to obtain
the optimized pyroelectric coefficient. The photo-induced metastable state could be trapped at
low temperature, meaning that the Co compound exhibits a photo-tunable polarization
bistability.
(1) S. -Q. Wu, M. Liu, K. Gao, S. Kanegawa, Y. Horie, G. Aoyama, H. Okajima, A. Sakamoto,
M. L. Baker, M. S. Huzan, P. Bencok, T. Abe, Y. Shiota, K. Yoshizawa, W. Xu, H. –Z. Kou, O.
Sato. Nat. Commun. 2020, 11, 1992.

22

Thematic session

Adriana Pietropaolo
Associate Professor,
Dipartimento di Scienze della Salute, Università di Catanzaro
Phone: +39-0961-3694356
E-mail: apietropaolo@unicz.it
Education:
1999–2004
2005–2007
2008

Università di Catania and Scuola Superiore di Catania
Alma Mater Studiorum, Università di Bologna
PhD (Supervisor: Prof. Claudio Zannoni)

Professional Career:
2008–20102010–202020112012/2013
2021 at present

Research Fellow at ETH-Zürich
Assistant Professor at Università di Catanzaro
Visiting Scientist at Forschungszentrum Jülich
Visiting Scientist at Hokkaido University
Associate Professor at Università di Catanzaro

Research Interests:16) Simulations of chiral molecular systems and of the related spectroscopic signatures.
17) Development of free-energy methods for simulating excited state molecular rearrangements.
18) Free-energy predictions of molecular asymmetry and its implication on luminescent
properties.
Honors:2021: Member of Italian Research Evaluation for the chemistry area (GEV03).
2015: “Raffaele Piria” Prize for Chemistry.

23

Thematic session

O-8
Molecular asymmetry from chiral free-energy approaches
Adriana Pietropaolo
Dipartimento di Scienze della Salute, Università di Catanzaro, 88100 Catanzaro, Italy.
Widespread motions in functional nanostructures stem from transforming chemical energy intoa functional activity.1,2 Owing to continuous observations at how nature works and functions,chemists moved from a static molecular design to the synthesis of molecular frameworks
capable of displaying stimuli-based motions.3,4 Light irradiation is a source of induction of thesecollective functional movements that in turn can cause a symmetry breaking in the molecular
structure,5,6 originating inherent stimuli-based chiral switches that can work away from theglobal free-energy minimum.7,8
The realization of à la carte molecules with tunable optical properties can be speeded up
nowadays thanks to the incredible computational resources facing the exascale computing.
In this vein, we recently developed several simulation frameworks7-10 to reconstruct and predict
the free-energetics of the ground and the excited states9 of chiral systems.
A perspective of nanoscale simulations of photoactive chiral transitions will be presented.
References(1) Nakano, T; Okamoto, Y. Chem. Rev. 2001, 101, 12, 4013.
(2) Liu, Z; Wang, H.I.; Narita, A; Chen, Q; Mics, Z; Turchinovich, D; Kläui, M; Bonn, M;
Müllen, K. J. Am. Chem. Soc. 2017, 139, 9443.
(3) Yashima, E; Ousaka, N; Taura, D; Shimomura, K; Ikai, T; Maeda, K. Chem. Rev. 2016,
116, 22, 13752–13990(4) Gon, M; Tanaka, K; Chujo Y. Angew. Chem. Int. Ed. 2018, 57, 6546.
(5) Sakamoto T, Fukuda Y, Sato S, Nakano T. Angew. Chem. Int. Ed. 2009, 48, 9308.
(6) Wang Y, Sakamoto T, Nakano T. Chem. Commun. 2012, 48, 1871.
(7) Pietropaolo, A; Nakano, T. J. Am. Chem. Soc. 2013, 135, 5509.
(8) Pietropaolo, A; Wang, Y; Nakano, T. Angew. Chem. Int. Edit. 2015, 54, 2688.
(9) Cozza, C; Bonomi, M; Pietropaolo, A. J. Chem. Theory Comput. 2018, 14, 5441.
(10) Cozza, C; Raymo, F; Pietropaolo, A. Mol. Sys. Des. Eng. 2021
doi.org/10.1039/D0ME00164C.

24

Thematic session

Ron Naaman
Professor,
Department of Chemical and Biological Physics, Weizmann Institute,IsraelPhone: +972-8-9342367
Fax: +972-9-9344001
E-mail: ron.naaman@weizmann.ac.il
Education:
1970–1973
1973–1978

BSc, Ben Gurion University, Beer Sheba, Israel
PhD, Weizmann Institute, Rehovot, Israel

Professional Career:
1978–19791980
1981–1986
1987–1992
1993–20192019-

Postdoctoral Fellow, Stanford University, USA
Research Associate and Lecturer, Harvard University, USA
Senior Scientist at the Weizmann Institute
Associate Professor at the Weizmann Institute
Professor at the Weizmann Institute
Professor Emeritus

Research Interests:19) Interaction of electrons and their spins with molecules and chiral molecules20) Organic-inorganic interfaces
Honors:Fellow of the American Physical Society
2007- Recipient of the "Lectureship Award of the Division of Colloid and Surface Chemistry"
authorized by The Chemical Society of Japan.
2010 Lectureship of the Chemical Society, Taiwan.
2013-The prize of the Israel Vacuum Society
2014 Kolthof award from the Technion Israel.
2018 Israel Chemical Society Prize for Excellent Scientist
2019 Recipient of the Humboldt-Meitner award.

25

Thematic session

O-9
The electron spin and chiral systemsMerging that results in novel properties
Ron Naaman
Department of Chemical and Biological Physics, Weizmann Institute, Rehovot, Israel
Spin based properties, applications, and devices are commonly related to magnetic effects andto magnetic materials. However, we found that chiral molecules act as spin filters forphotoelectrons transmission, in electron transfer, and in electron transport.
The new effect, termed Chiral Induced Spin Selectivity (CISS), i was found, among others, inbio-molecules and in bio-systems. It has interesting implications for the production of new typesof spintronics devices, ii
in controlling magnetization, iii and on electron transfer andconduction. Recently we also found that charge polarization in chiral molecules is accompaniedby spin polarization. This finding shed new light on spin dependent interaction between chiralmolecules and between them and magnetic surfacesiv and on the ability to control chemical
reactions by controlling the spin polarization.v

Reference(i) Naaman, R., Paltiel, Y., Waldeck, D, H, J. Phys. Chem. Lett., 2020, 11, 3660.
(ii) Michaeli, K., Varade, V., Naaman, R., Waldeck, D. H., J. of Physics: Condensed Matter.
2017, 29, 103002.
(iii) Smolinsky, E. Z. B. et al. J. Phys. Chem. Lett. 2019, 10, 1139.
(iv)Banerjee-Ghosh, K. et. al., Science 2018, 360, 1331.
(v) Naaman, R., Paltiel, Y., Waldeck, D.H. Acc. Chem. Res., 2020, 53, 2659.

26

Thematic session

Poster Presentations

P-01

Spontaneous Deposition of Pt on Au(111)Bing Hu, Daiki Kido, Kaiyue Dong, Md. Harun Al Rashid, Hiroko Ariga-Miwa, Satoru
Takakusagi, Kiyotaka AsakuraInstitute for Catalysis, Hokkaido University, Hokkaido 001-0021, Japan
Abstract Pt-skin electrocatalyst or Pt monolayer catalyst is one major breakthroughs in hydrogen fuel cellresearch in recent years, as it has the potential to afford >100% Pt atom economy due to the complete
exposure of Pt atoms to fuel cell catalysis and the enhanced activity as well as stability compared to Pt metalalone[1, 2]. Meanwhile, the structural investigation of this kind of vital top-layer atoms on heterogeneous solid
catalyst has long remained a challenge[3]. In this work, we explore the phenomenon of spontaneous depositionof monolayer Pt species onto Au(111). We have applied the technique of polarization-dependent totalreflection fluorescent X-ray absorption fine structure (PTRF-XAFS) to study the surface deposited species.
It was found that the Pt L3 XANES and EXAFS spectra of the species both show dependence to thepolarization direction of the X-ray and show enhanced signals when the polarization is parallel to the Au
surface, from which planar structure parallel to Au(111) can be inferred. The EXAFS spectra wererationalized by nearest Cl neighbors at 2.27 Å. From XPS, we also confirmed surface Pt and Cl after
spontaneous deposition. The XANES simulation corroborates the proposal of PtCl42- species. From theseevidences, we conclude that the spontaneous deposition of Pt on Au(111) produces PtCl42- sticking parallelto Au(111) single crystal surface. The mechanism for the reduction of PtCl62- into Pt(II) species is also
discussed. The current work not only provides new insight for the preparation of Pt-skin electrocatalysts, butalso serves as the pilot research for further in situ study of Pt stability and dynamic structural variation underelectrochemical conditions.
(1) Zhang J., et al., Angew. Chem. 2005, 117, 2170. (2)Lopes P. P., et al., Nature Materials 2020, 19, 1207.
(3)Niemantsverdriet, J. W. (2007). Spectroscopy in catalysis: an introduction. John Wiley & Sons.

P-02
Electric-assisted propane dehydrogenation at low temperature: far beyond
the equilibrium conversion
Jianshuo Zhang, Ruoyun Ma, Ken-ichi Shimizu, Shinya Furukawa
Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan
The propane dehydrogenation proceeded at low temperature (300℃), where the equilibrium
conversion is only 0.7%, by using an electric field and Pt-In intermetallic compounds (IMCs)
supported on TiO2. HAADF-STEM, XAFS revealed the formation of Pt3In IMCs, in which Pt
atoms became electron-rich by In atoms. Pt-In/TiO2 showed much higher propylene yieldcompared with Pt/TiO2 (2.5%→6.9%, with 2.0 W of electric power). Electric field plays anessential role on the propane dehydrogenation at low temperature. Kinetic analysis suggested
that the electric field enabled the proton hopping on TiO2 surface and its collision to propane at
the Pt-TiO2 interface was accelerated by the electric field. This electro-assisted uniquemechanism allowed to break the equilibrium limitation of propane conversion at low
temperature.

28

P-03
Exploring the Mechanism of Novel Bifunctional AlIII Porphyrin Catalyzed
Copolymerization of CO2 and Cyclohexene Oxide: A DFT Study
Manussada Ratanasak1, Jingyuan Deng2, Hideki Tokuda3, Chihiro Maeda3, Tadashi Ema3,
Kyoko Nozaki2, Jun-ya Hasegawa1*
1

Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan
Graduate School of Engineering, The University of Tokyo, Tokyo 113-8656, Japan
3
Graduate School of Natural Science and Technology, Okayama University, Okayama 7008530, Japan
2

Abstract: A detailed study on the mechanism for the copolymerization of CO2 and cyclohexene
oxide (CHO) catalyzed by novel bifunctional AlIII porphyrins with quaternary ammonium (QA)
bromide was performed by using DFT calculations. To the best of our knowledge, our catalyst
is the highest TOF (TOF=10,000 h-1) among monometallic catalysts reported so far for the
CHO/CO2 copolymerization. Moreover, the carbonate-linkage selectivity >99%. DFT
calculation results clearly indicated that the high polymerization activity and high selectivity of
the AlIII catalyst originate from the cooperative actions of the metal center and the QA cation,
both of which facilitate the epoxide-ring opening by the nucleophilic carbonate anion in the key
transition state to form the carbonate linkages.
Deng, J.; Ratanasak, M.; Sako, Y.; Tokuda, H.; Maeda, C.; Hasegawa, J.; Nozaki, K.; Ema,
T., Aluminum porphyrins with quaternary ammonium halides as catalysts forcopolymerization of cyclohexene oxide and CO2: metal–ligand cooperative catalysis. Chem.
Sci. 2020, 11, 5669-5675.

P-04
Mechanistic Study on the Selective Catalytic Reduction of NOX
Catalyzed by Fe/SO42-/CeO2 with NH3
Kai Oshiro1, Min Gao2, Jun-ya Hasegawa2
1
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Japan
2
Institute for Catalysis, Hokkaido University, Japan
Selective catalytic reduction (SCR) is one of most efficient method for removing
nitrogen oxides (NOX) in exhaust gases released from factories and power plants. However,alkali metals in the exhaust gases disturb the adsorption of NH3 which is the reducing agent in
SCR, and therefore deactivate the catalyst. Recently, Zhang et al. reported the Fe-decorated
SO42--modified CeO2 (Fe/SO42-/CeO2) catalyst with alkali poisoning resistance.1 The purposeof this study is to clarify the effect of Fe and SO42- on the NH3-SCR reaction by ab initio
calculations. The influence of H2SO4 and Fe on the properties of CeO2 adsorbed molecules were
investigated. The results suggest that Fe works as a Lewis acid site to promote the adsorptionof NH3, while H2SO4 is contributed to the increase in surface acidity.
(1) M. N. Khan, L. Han, P. Wang, D. Zhang, j. iScience., 2020, 23, 101173

29

Thematic Poster

P-05

Asymmetric Hyperbranched and Linear Fluorene-vinylene Polymers
Pengfei Wu, Zhiyi Song, Masayoshi Bando, and Tamaki Nakano
Institute for Catalysis and Graduate School of Chemical Sciences and Engineering, Hokkaido
University, Sapporo 001-0021, Japan
Circularly polarized light (CPL) is expected to find a variety
of application including advanced display devices, andargicultural technologies. While CPL can be created bymodulating non-polarized light (NPL) using proper optics,
ogranic light-emitting diodes (OLED’s) emitting efficient
CPL without the need of modulation would bring benefits.
In this context, we have been developing light-emitting polymers and molecules with chiralstructures,[1-4] and in this work, we synthesized optically active poly(fluorenevinylene) derivatives
having neomenthyl group as the source of chirality with hyperbranched and linear chain structures(poly(TNPF) and poly(BNPF)).
[1] J.-M. Yu, T. Sakamoto, K. Watanabe, S. Furumi, N. Tamaoki, Y. Chen and T. Nakano, Chem.
Commun., 2011, 47, 3799-3801. [2] K. Watanabe, T. Sakamoto, M. Taguchi, M. Fujiki and T. Nakano,
Chem. Commun., 2011, 47, 10996-10998. [3] Y. Wang, T. Harada, L. Q. Phuong, Y. Kanemitsu and T.
Nakano, Macromolecules, 2018, 51, 6865-6877. [4] Z. Zhang, T. Harada, A. Pietropaolo, Y. Wang, Y.
Wang, X. Hu, X. He, H. Chen, Z. Song, M. Bando and T. Nakano, Chem. Commun., 2021,
DOI:10.1039/D0CC07898K.

P-06

Doping of Rh in In2O3 Promotes Methanol Formation During CO2
Hydrogenation

Shaikh Nazmul Hasan Mohammad Dostagir,1,2 Coogan Thompson,3 Hirokazu Kobayashi,1 Ayman M
Karim,3 Atsushi Fukuoka,1 Abhijit Shrotri1
1Institute for Catalysis, Hokkaido University, Sapporo 001-0021, Japan
2
Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo, 060-8628,
Japan
3
Department of Chemical Engineering, Virginia Polytechnic Institute and State University,
Blacksburg, Virginia 24060, USA
CO2 hydrogenation to methanol is important because of the versatile use of methanol in chemicalindustry. Current industrial catalyst, Cu-ZnO/Al2O3, deactivates during the reaction and is unable to handle
CO2 rich feedstocks.[1] Recently, In2O3 with oxygen vacancies on the surface was reported as a selective andstable catalyst.[2] However, space time yield (STY) of methanol was low due to poor CO2 conversion. To
overcome this issue, promotion with a secondary metal such as Pd is required.[3] Herein, we use Rh doped
In2O3 catalyst where the Rh atoms are atomically dispersed in the In2O3 matrix. Catalyst with a 0.96 wt% Rh
loading showed the best activity with a methanol STY of 1.0 g h-1 gcat-1 (Scheme 1), one of the highest
reported so far. Characterization suggested the formation of Rh single atom which were stable under reaction
condition. During reaction, Rh atoms were reduced to create oxygen vacancy. Rh atoms helped in strong CO2
chemisorption and promoted formate formation with the help of the neighboring In atoms.

Scheme 1: CO2 hydrogenation to methanol over Rh-In2O3 catalyst. Conditions: 300 °C, 5 MPa, SV = 60,000mL h-1 gcat-1, H2/CO2 = 4.
References:[1] J. Wu et al. Appl. Catal. A Gen. 2001, 218, 235–240. [2] O. Martin et al. Angew. Chemie - Int.
Ed. 2016, 55, 6261–6265. [3] M. S. Frei et al. Nat. Commun. 2019, 10, 1–11.

30

P-07
The Variation of Surface/Bulk Structure and Activity of Titania
Photocatalyst Particles by Milling
Guangyi Chen,1 Mai Takashima1,2 and Bunsho Ohtani1,21
Environmental Science School, Hokkaido University, Sapporo 060-0810, Japan
2
Institute for Catalyst, Hokkaido University, Sapporo 060-0810, Japan
Solid are sometimes not crystalline, that is, an amorphous part might be included.
Surface structures are indescribable since there is no systematic nomenclature method for solid
surfaces except for single crystals exposing only one type of facet. Amorphous structures are
entirely indescribable; therefore, they are called amorphous. In the majority of materialscience studies, discussions without the description of surface and amorphous structures were
put forward even if those structures are included in them. Recently, we have developed anovel technique, reversed double-beam photoacoustic spectroscopy (RDB-PAS), which enables
characterization of semiconducting metal oxides, to obtain the energy-resolved distribution ofelectron traps (ERDT), predominantly located on the surface of samples [1,2]. In this study,
amorphous titania samples were prepared by braying rutile titania powder in an automatic agate
mortar and post calcination in air at 773 K. Those samples were characterized by RDB-PAS
measurement to elucidate the surface/bulk structure changes by the above-mentioned treatment.
[1] Chem. Commun. 2016, 52, 12096-12099. [2] Electrochim. Acta, 2018, 264, 83.

P-08Interparticle Charge-transfer Excitation at Adjoined Anatase and Rutile
Interface Proved by Reversed Double-beam Photoacoustic Spectroscopy
Y. Shen,1 A. Nitta,1 M. Takashima1,2 and B. Ohtani1,21Graduate School of Environmental 2Science and Institute for Catalysis, Hokkaido University
Herein, we obtain experimental evidence of interparticle spatial overlapping of orbitals
to result in interparticle charge-transfer excitation (ICTE) at an anatase-rutile interface
measured by reversed double-beam photoacoustic spectroscopy (RDB-PAS). The detailedenergy-resolved distribution of electron traps (ERDT) analyses of various anatase-rutile
mixtures revealed that all of the photoexcitation occurred from a high-density part of states (hDOS) in valence band of rutile in a thoroughly mixed sample, and h-DOS of rutile was locatedca. 0.2-eV higher than that of anatase. This is the first experimental results of practical h-DOS,
which enable to cause photoabsorption, of materials. In addition, the ICTE analysis suggested
a new concept, hetero-contact degree, which could be quantitively evaluated by comparison of
ERDT patterns of mixture sample to simulation patterns with thoroughly adjoined mixture
particles and non-contacted particles.
[1] A. Nitta et al. Chem. Commun. 2016,52, 12096–12099. [2] A. Nitta et al. Electrochim.
Acta, 2018, 264, 83–90. [3] Y. Shen et al. Chem. Lett. 2021, 50, 80-83.

31

P-09
Titania Inverse-opal with a Gold Nanoparticle Incorporated per Void Space
for Photoabsorption Amplification
Tharishinny Raja Mogan,1 Ewa Kowalska,1,2 Mai Takashima,1,2 Anais Lehoux,2and Bunsho Ohtani1,2Graduate School of Environmental Science1 and Institute for Catalysis,2 Hokkaido University
Photochemical reactions are initiated by photoabsorption and proceeded by chemical
reactions by utilizing the photoexcited charge carriers, thus the overall efficiency of thereactions could be defined as a product of photoabsorption efficiency and quantum efficiency.
Till date, almost all the studies related to photoreactions have focused only to improve thechemical reactions occurring after photoexcitation of charge carriers, i.e., quantum efficiency
rather than photoabsorption efficiency as it is difficult to alter the photoabsorption coefficientof any photoabsorping materials. Inverse opal (IO) photonic crystals (PCs) are known asperiodic nanostructures that could exhibit photonic band gap (PBG), resulting in photons with
reduced group velocity, namely as slow photons which could be utilized by photoabsorbing
materials. In this regard, a novel photocatalyst design, TiO2 IO PC incorporated with a gold
nanoparticle (Au NP) per void space (Au-NP@TiO2 IO) has been developed as a strategy toamplify the photoabsorption efficiency. Several Au-NP@TiO2 IO photocatalysts have been
prepared in a similar way except in the variance of nanovoid diameter to study on the slow
photons’ effect. The precise wavelengths overlapping of slow photons arising in TiO2-IO
structure, surface plasmon peak from Au NPs and monochromatic irradiation source exhibited
an amplified photocatalytic activity, i.e., enhanced photoabsorption has been evident by thephotoabsorbing material (Au NPs).

P-10

Solid State Fabrication of Polythienylenevinylene Thin Films
via Cis-to-trans Thermal Isomerization

Masayuki Wakioka,1 Natsumi Yamashita,1 Hiroki Mori,2 Richard Murdey,1 Atsushi Wakamiya,1Yasushi Nishihara,2 and Fumiyuki Ozawa1

Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Research Institute for Interdisciplinary Science, Okayama University, 3-1-1 Tsushimanaka, Kitaku, Okayama 700-8530, Japan
1

2

Although trans-polythienylenevinylenes (PTVs) are desirable organic semiconductors, theirlimited solubility necessitates the use of toxic halogenated solvents to process the polymers into thinfilms. In this work, we demonstrate the efficient thermal conversion of thin film of cis-PTV (cisP1), which is readily fabricated from environmentally friendly 2-MeTHF solution, to thin films ofthe trans-polymer (trans-P1iso). In organic field effect transistors (OFETs), the trans-P1iso films
prepared by isomerization are shown to have comparable hole mobility as films prepared from
CHCl3 solutions of the trans-polymer.

32

P-11
Isolation of Organophosphorus Zwitterions
Yoshifumi Hashikawa, Shu Okamoto, Yasujiro Murata
Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan
Organophosphorus zwitterions are one of themost important but elusive intermediates for carbon–
carbon bond formation in synthetic chemistry andbiology. However, a lack of isolated examples due to theirlability has hampered in-depth understanding ofstructures and their reaction mechanisms. In this study, we
crystallographically revealed the solid-state structure of aphosha-Michael adduct engaged in a cage-opened C60
skeleton, which was formed as a kinetic product. From the 1,2-dicarbonyl moiety on the
conjugated orifice, β-oxo-phosphorus ylide was obtained as a thermodynamic product. The
reaction mechanism that has long been disputed was examined by experimental and theoreticalstudies, showing a pathway which includes an SN2 reaction as a key step instead of hitherto
considered carbene pathway.
(1) Hashikawa, Y.; Okamoto, S.; Murata, Y. Commun. Chem. 2020, 3, 90.

P-12Comparative investigation of quadruple perovskite structures AA'3B4O12
containing divalent manganese, iron, cobalt and nickel square-planarcenters at the A' sites
Midori E. Amano Patino1, Fabio Denis Romero1,2, Masato Goto1, Yuichi Shimakawa1
1
Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan. 2Hakubi Center for
Advanced Research, Kyoto University, Kyoto 606-8501, Japan
The A-site-ordered quadruple perovskite structure of general formula AA’3B4O12 canaccommodate transition metal cations at the square-planar A’ site. When A and B are nonmagnetic, the complex interactions between the spins at the A’-sites can provide exotic
magnetic orders.1 We recently found that CaA’3Ti4O12 with A’-site Fe2+ centers, adopts anunusual multi-k antiferromagnetic spin ordering which responds to applied magnetic fields. To
further understand the non-trivial A’-site magnetism in this structural class, we focused on thesynthesis of the series A’ = Mn2+, Co2+, Ni2+. Here we present some insights on the challenging
preparation and the results from characterization of these materials.
(1) Y. Shimakawa and T. Saito, Phys. Status Solidi Basic Res. 2012, 249, 423.

33

P-13
Stabilisation and characterisation of the polymorphs of BaRhO3 between 7
and 22 GPa
Injac, Sean D. A.; Romero, Denis. F.; Xu Yuanhui; Shimakawa Yuichi
Institute for Chemical Research, Kyoto University, Japan
We report the synthesis and characterisation of two phases of BaRhO3 stabilised under highpressure, high temperature (HPHT) synthesis conditions. Synthesis at pressures of 4 to 7 GPa
resulted in stabilisation of the 4H perovskite polymorph.1 Synthesis at higher pressures of 14 to
22 GPa stabilised a novel 6H phase of BaRhO3.
Physical property measurements were carried out for both compounds. The magnetic
susceptibilities include large temperature-independent terms. Metallic conductivity is observed
for the 4H polymorph, while resistivity measurements
indicate the 6H polymorph is a semiconductor due to grain boundary effects. High Wilson ratios
of approximately Rw ≈ 2 indicate both polymorphs are strongly electron correlated systems.
Magnetic ground state and density of state calculations were carried out for both compounds.
These electronic structure calculations give metallic ground states for both structures. All theseresults indicate Pauli paramagnetic ground states for both polymorphs.
(1)

B. L. Chamberland and J. B. Anderson, J. Solid State Chem. 1981, 39(1), 114-119.

P-14
Near-Ultraviolet Transparent Organic Hole-Transporting Materials
Containing Partially Oxygen-Bridged Triphenylamine Skeletons for
Efficient Perovskite Solar Cells
Minh Anh Truong, Hayoon Lee, Ai Shimazaki, Richard Murdey, Atsushi Wakamiya
Institute for Chemical Research, Kyoto University, Uji 611-0011, Japan
In this study, three transparent
organic semiconducting materials were
designedandsynthesized.
The
combination of strong donor oxygenbridged triphenylamine and weaker
electron-donating group at the head
position suppresses the - transition, Fig. 1. The molecular design for transparent organic
hole-transporting materials.
leading to weak absorption in the NUVregion (Fig. 1).1,2 All of three materials were successfully applied as hole-transporting materials
in both conventional and bifacial semitransparent perovskite solar cells.
(1) A. Wakamiya, Y. Murata, H. Kaji, et al. Angew. Chem., Int. Ed. 2014, 53, 5800.
(2) M. A. Truong, Y. Kanemitsu, A. Wakamiya, et al. ACS Appl. Energy Mater. 2021, in press.

34

Thematic Poster

P-15

Asymmetric Synthesis of Chiral Silicon Molecules
Kazunobu Igawa, Katsuhiko Tomooka
Institute for Materials Chemistry and Engineering, Kyushu University,
Kasuga, Fukuoka, 816-8580, Japan
Chiral silicon molecules having asymmetric silicon are non-existence in nature, which havequite different chiral functionality from chiral carbon molecules owing to the structural andelectrical features of silicon. To open up a novel chiral technology with chiral silicon molecules,
we have developed asymmetric synthetic methods to obtain functionalized ones based on theasymmetric desymmetrization of prochiral silicon molecules 1-3) and further stereoselective
transformations.4-6) The detail of this chemistry will be presented.
R1

X

asymmetricdesymmetrization

R1

Si
R2

X

stereoselective
transformation

R1

Si
X

achiral

R2

FG1
Si

Y

chiral enantioenriched

R2

FG2

functionalizedchiral silicon molecules(1) J. Amer. Chem. Soc. 2008, 130, 16132. (2) Angew. Chem. Int. Ed. 2012, 51, 12745. (3) Angew. Chem. Int. Ed. 2016, 55,5814. (4) Angew. Chem. Int. Ed. 2010, 49, 728. (5) Synlett 2017, 28, 2445. (6) J. Org. Chem. 2020, 85, 4165.

P-16
Synthesis and Transformation of Silylalkene
Yuuya Kawasaki, Kazunobu Igawa, Katsuhiko Tomooka
Institute for Materials Chemistry and Engineering,Kyushu University,
6-1 Kasuga-koen, Kasuga, Fukuoka 816-8580, Japan
Silylalkene 1 is a versatile synthetic precursor for a variety of functiional molecules (eg. tri-substituted
alkenes, ketones, acyloin, etc.). For the efficient synthesis and further transformation of silylalkene 1, we
have developed highly regioselective hydrosilylation of unsymmetric alkyne (step 1),1 and addition-typeozone oxidation of silylalkene 1, which provides -silylperoxy carbonyl compounds 2 (step 2).3-4 The detailof the reactions and further transformation of 2 will be presented.

(1) J. Am. Chem. Soc. 2011, 133, 20712. (2) Chemistry Letters 2011, 40, 233. (3) Chem. Eur. J. 2014, 20, 9255. (4) J. Org.
Chem. 2020, 85, 4065.

35

P-17
Electronic Pyroelectricities of Heterometallic Dinuclear Complexes○Shinji Kanegawa, SadhuKhan Pritam, Jeremy Ian Long and Osamu Sato
Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishiku, Fukuoka 819-0395, Japan
Pyroelectricity and ferroelectricity are macroscopic physical properties caused bycharge asymmetry in matter. Classically, these phenomena have been understood by changes in
the position and arrangement of molecules and/or ions throughout the matter. This time, we
focused on the intramolecular electron transfer phenomenon that occurs in one molecule andthe resulting dynamic and microscopic permanent dipole moment, and discovered apyroelectric phenomenon based on a new mechanism.
The directional intramolecular electron transfer in the polar structure was confirmed
by magnetic measurement and crystal structure analysis of various heteronuclear dinuclear
complexes containing 3d metal elements obtained by using chirality. By measuring the
pyroelectricity of these heteronuclear complex single crystals, the relationship between
intramolecular electron transfer and pyroelectric current was investigated.

P-18
Water-orientated reversible magnetic anisotropy transition
Sheng-qun Su, Shu-qi Wu, Shinji Kanegawa, Osamu Sato
Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka Nishi-ku,
Fukuoka, 819-0395, Japan
Magnetic anisotropy greatly affects the hysteresis in ferromagnets, the blocking temperaturein single-molecule magnets, and the operation temperature of quantum computing. However,
the manipulation of magnetic anisotropy remains, especially the effect of subtle structuralvariation. Here, we observed a two-step reversible magnetic anisotropy transition depending on
the orientation of the coordinated water in a cobalt(II) complex. The water molecule rotated ca.
24° in total around the Co-O bond and the magnetic susceptibility changed ca. 30% along thea-axis after a two-step phase transition. The angular-resolved magnetometry studies reveal that
this complex possesses easy plane anisotropy and the direction of the magnetic hard axischanged after structural transition. Theoretical calculations further indicated that the orientationof the coordinated water molecule is the main effect on the magnetic anisotropy. This complex
can be used as a magnetic switch and the discovery of the effect of water orientation will be
useful in the magnetic devices and MRI.

36

P-19
Observation of Proton Transfer Coupled Spin Transition in
Fe(II) Complexes
Takumi Nakanishi and Osamu Sato
Institute for Materials Chemistry and Engineering, Kyushu University, 744 Motooka, Nishiku, Fukuoka, Japan
Proton transfer phenomenon occurring with electron transfer or the change ofelectronic state plays an important role in biological reactions, catalytic reactions, and solidstate materials. In this presentation, we will report Fe(II) hydrazone complexes, where twokinds of protonation state can beswitched via the photo- and thermallyinduced spin transition in crystalline
system (Fig. 1).
(1) T. Nakanishi et al., Angew. Chem.
Int. Ed., 2020, 132, 14891-14897.
Figure 1. Proton transfer coupled spin transition.

P-20
Effect of Urea Additives in the Iridium-Catalyzed C–H Borylation of
Aromatic Compounds
Takeru Torigoe1,2, Jie Wang2, Yadong Pang3, Koji Kubota3,4, Hajime Ito3,4, Yoichiro Kuninobu1,21Institute for Materials Chemistry and Engineering, Kyushu University, Kasuga 816-8580, Japan,2Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering
Sciences, Kyushu University, Kasuga 816-8580, Japan,3Institute for Chemical Reaction Design andDiscovery (WPI-ICReDD), Hokkaido University, Sapporo 060-8628, Japan, 4Division of Applied
Chemistry, Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan

We found iridium-catalyzed 2-position-selective C–H borylation of 1,3-disubsituted
indoles by modifying the structure of a bipyridine-type ligand and the yield could be improvedby addition of urea additives. The results of solid-state reactions, in which the interactions
between substrates and urea additives can be strong, will also be shown.

37

P-21
Novel Access to Silacyclic Compounds
Kohei Sekine1,2, Yafang Dong2, Kazuto Fuji2, Masashiko Sakai2, Yoichiro Kuninobu1,21Institute for Materials Chemistry and Engineering, Kyushu University
6-1 Kasugakoen, Kasuga-shi, Fukuoka 816-8580, Japan and
2Interdisciplinary Graduate School of Engineering Sciences, Kyushu University
Five- or six-membered silacycles are attractive for applications as organic electronicmaterials. Their common synthetic method is the reaction of dichlorosilanes with dilithiatedintermediates prepared form dihalogenated biaryl or diaryl substrates. However, efficient andversatile synthetic methods based on atom and step economy are desirable.
Herein, we report a simple and efficient synthetic method of multi-substituted
silafluorene and phenoxasilin derivatives by double sila-Friedel–Crafts reaction of
dihydrosilanes with amino group-substituted biphenyls, or diaryl ethers.1 A synthesis of othersilacycles will be discussed.
(1) (a) Takata, Y.; Yoshigoe, Y.; Sekine, K.; Kuninobu, Y. Chem. Commun. 2019, 55, 13303. (b)Dong, Y.; Sakai, M.; Fuji, K.; Sekine, K.; Kuninobu, Y. Beilstein J. Org. Chem. 2020, 16, 409.

P-22
Contactless masstransfer between alternating droplets〇Shusaku Asano1, Yu takahashi2, Taisuke Maki, Yosuke Muranaka, Nikolay Cherkasov,Kazuhiro Mae
1. Kyushu University, Japan. 2. Kyoto University, Japan. 3. University of Warwick, UKThis study1 demonstrates the possibility of mass transfer between two aqueous slugs (droplets)
separated by an oil slug in Taylor flow inside milli-channels. Separation of the alternating
aqueous slugs at the outlet was performed by switching a couple of solenoid valves at branchedoutlets according to signals obtained by an optical sensor at the branch. Transfer ofbromothymol blue (BTB) from acidic to basic aqueous slugs was performed for demonstration.
Almost complete (93%) transfer of BTB was achieved within a short residence time of several
minutes under optimized conditions. The presented system opens a way for advanced separation
using minimum amounts of the oil phase and allows concentrating the solute by altering relative
lengths of the sender and receiver slugs.
(1) Asano, S.; Takahashi, Y.; Maki, T.; Muranaka, Y.; Cherkasov, N.; Mae, K. Sci. Rep. 2020,
10 (1), 7685.

38

P-23
Synthesis of macrocyclic compounds using 1,8,13-substituted triptycenes
as a foundation〇Takayuki Iwata,1 Yusuke Maehata,2 Tatsuro Yoshinaga,2 Mitsuru Shindo1
12

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

Triptycenes, which have fixed
three benzene rings, have been utilized inmaterial sciences and so on. We haverecently developed a novel regioselective
synthesis of 1,8,13-substituted triptycenes
using ynolates and 3-methoxy-1 orsilylbenzynes.2 In this presentation, ourrecent study on synthesis of macrocyclic
compounds using 1,8,13-substituted triptycenes as a foundation will be shown.
(1) T. Iwata, M. Shindo, et al., Angew. Chem. Int. Ed., 2017, 56, 1298. (2) T. Iwata, M. Shindo,
et al., Chem. Eur. J., 2019, 25, 13855.

P-24
Multiple droplets formation by a simple mixing method withmicrofabricated channel and their mass-transport mechanism
Kenta Goto, Kyoka Nakanishi, Fumito Tani
Institute for Materials Chemistry and Engineering, Kyushu University, Fukuoka, Japan
Multiple droplets and/or emulsions are defined as dispersed droplets including tiny
droplets in immiscible liquid phases. A couple of methods are present for formation of multiple
droplets. Among them, multiple droplets obtained from phase separation show an attractive
phenomenon including pattern dynamics and mass-transport. On the other hand, fabricatedmicro channel is a promising candidate for droplet formation. We developed multiple dropletsformation by a simple mixing method with microfabricated channel in the diethyl phthalate(DEP)-ethanol-water system in the presence of a polymer surfactant, Pluronic F-127. Formationand mass-transport mechanism on phased-separated multiple droplets will be discussed.

39

P-25
Ink-Jet Printable Thermally-Activated Delayed Fluorescence Dendrimers
Ken Albrecht1, Kenichi Matsuoka1, Amruth C.2, Beata Luszczynska2, Jacek Ulanski2,
Katsuhiko Fujita1, Kimihisa Yamamoto3
1 Institute for Materials Chemistry and Engineering, Kyushu University, 6-1 Kasuga-Koen
Kasuga-shi, 816-8580, Fukuoka, Japan
2 Department of Molecular Physics, Lodz University of Technology, 90924, Lodz, Poland
3 Laboratory for Chemistry and Life Science, Tokyo Institute of Technology, 4259 Nagatsuta
Midori-ku, 226-8503, Yokohama, JapanThe development of emitting materials for OLEDs has started with fluorescence,
moved to phosphorescence, and recently reached thermally-activated delayed-fluorescence(TADF). The important design principle of a TADF material is to spatially separate the HOMO
and LUMO because this reduces the difference in the singlet and triplet energy level. Carbazole
dendrimers have the LUMO at the inner layer and the HOMO at the outer-layer. Attachment ofan acceptor can further separate the HOMO and LUMO and this molecule showed efficient
TADF1. These TADF dendrimers can be used as efficient solution-processable emitting-layer
for printed OLEDs2.
(1) K. Albrecht & K. Matsuoka et al. Chem. Commun. 2017, 53, 2439.
(2) Amruth C et al. Org. Electron. 2019, 74, 218.

P-26
Syntheses of donor--acceptor (D--A) conjugated enamines
Atsushi Tahara1, Ikumi Kitahara2, Daichi Sakata2, Yoichiro Kuninobu1,2, Hideo Nagashima3
1
IMCE, 2Interdisciplinary graduate school of engineering sciences, 3Research Center forGreen Technology, Kyushu University, Fukuoka 816-8580, Japan
Hydrosilane reduction of N,N-diaryl-2-arylacetamides bearing various electronwithdrawing groups (2) with 1,1,3,3-tetramethyldisiloxane (TMDS) was catalyzed by Vaksatype iridium complexes trans-IrCl(CO)(PR3)2 (1X; R = Ph, 1Y; R = OC6F5) to afford donor-acceptor (D--A) conjugated enamines (4). Various types electron- withdrawing groups suchas halogen, carbonyl, cyano, nitro, and 2,1,3-benzothiazol-4-yl (BTD) group were selected as
an acceptor. Some D--A
conjugatedenamines
showedphtotoluminescence properties.1(1) Tahara, A.; Kitahara, I.;
Sakata, D.; Kuninobu, Y.; Nagashima H. J. Org. Chem. 2019, 84(23), 15236.

40

P-27
Investigating the Nonradiative Decay Pathway in the Excited State of
Silepin Derivatives: A Study with Second-Order Multireference
Perturbation Wavefunction Theory
Naoto Inai1, Daisuke Yokogawa2 and Takeshi Yanai1,3
1Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
2
Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku 153-8902, Japan
Institute of Transformative Bio-Molecules, Nagoya University, Nagoya 464-8602, Japan
Computational estimation of the nonradiative decay rate constant has become an
attractive task. Since rate constant of thermally activated decay via conical intersection (CI) is
sensitive to the activation energy to reach CI geometry, the accuracy of the excited-state
potential energies is critical. In this study, we employed a second-order multireference
perturbation theory (MRPT) for studying decay via conical intersection of silepin derivatives.
MRPT-level geometry optimization of the transition state in the pathway triggered by the central
C−C bond twisting resulted in a reasonable estimation of the activation energy.
(1) N. Inai, D. Yokogawa and T. Yanai, J. Phys. Chem. A 2021, 125, 559.

P-28
Analytical Nuclear Gradients for State-Averaged Density Matrix
Renormalization Group Complete-Active-Space Self-Consistent-Field Method
Tsubasa Iino,1 Toru Shiozaki,2 Takeshi Yanai1
1Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
2
Quantum Simulation Technologies, Inc., Cambridge, Massachusetts 02139, United States
The SA-DMRG-CASSCF method1 is a class of multiconfigurational quantum chemical theory,
which has been widely-recognized as an efficient approach to describe ground and excitedstates simultaneously with a qualitatively reliable accuracy, for large systems. However, thismethod cannot be used for molecular geometric search on top of the potential energy surface
calculated at this level of theory because its analytical nuclear gradient method has not been
established so far. To break through the current situation, we present a formalism of the gradientmethod and its implementation by combining Lagrangian approach for SA-CASSCF2 with
DMRG linear response theory.3,4 The illustrative performance of its application to acenes will
be shown. (1) D. Ghosh et al., J. Chem. Phys. 2008, 128, 144117. (2) P. Celani and H.-J. Werner,
J. Chem. Phys. 2003 119, 5044. (3) J. J. Dorando et al., J. Chem. Phys. 2009 130, 184111. (4)N. Nakatani et al., J. Chem. Phys. 2014 140, 024108.

41

P-29
Enzymatic Hydroxylation of Small Alkanes by P450BM3 with Decoy
Molecules under High Pressure○Shinya Ariyasu, Yusaku Kodama, Kai Yonemura, Chie Kasai, Joshua Kyle Stanfield,
Yuma Shisaka, Yuichiro Aiba, Yoshihito Watanabe, Osami Shoji
Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
P450BM3 exhibits promising catalytichydroxylation activity against long fatty acids.
We have previously achieved the hydroxylationof non-native substrates such as propane byutilizing decoy molecules. However, its
turnover frequencies were not as high as fornatural substrate hydroxylation. Recently wehave developed a new type of high-pressure reactor1 and succeeded in drastic improvement ofhydroxylation efficiencies of not only propane but also ethane in the presence of chemically
evolved decoy molecules.2(1) S. Ariyasu, Y. Kodama et al. ChemCatChem, 2019, 11, 4709, (2) K. Yonemura, S. Ariyasu
et al. ACS Catal., 2020, 10, 9136

P-30
The Building of Rigid Heme Protein Multimers
Based on Metal Coordination
Hiroaki Inaba1, Yuma Shisaka1, Garyo Ueda1, Kazuto Suzuki1, Shinya Ariyasu1,
Yuichiro Aiba1, Hiroshi Sugimoto2, Osami Shoji1
1
Graduate School of Science, Nagoya University, 2RIKEN SPring-8 Center
Supramolecular heme protein assemblies undergo great developments in recent years, but it
is not so easy to control defined architectures because reported systems have flexible scaffolds.
On the other hand, when using synthetic small molecules, self-assembled metal complexes suchas MOF achieve control of highly defined architectures by metal coordination. Based on thisknowledge, we have attempted to build rigid heme protein multimers based on metal
coordination for units of rigid supramolecular heme protein assemblies. Thus, we incorporated
Fe-TPP-phen into heme acquisition system protein A (HasA) and obtained HasA dimer byadding Ni2+ to the solution of Fe-TPP-phen HasA
monomer (Figure). Currently, we are investigating
this dimer for the detail and other metal ions arealso under consideration.

42

P-31
Directed Evolution of Cytochrome P450BM3 for Responding to Decoy
Molecule Produced by Bacteria
Yuya Yokoyama, Masayuki Karasawa, Shinya Ariyasu, Yuichiro Aiba, Osami Shoji
Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
Cytochrome P450BM3 (P450BM3) is a heme enzyme that catalyzes the efficient hydroxylation of
long-chain fatty acids. We demonstrated that addition of synthesized dummy substrates called “Decoy
Molecules” enabled hydroxylation of non-native substrates such as benzene.1 In this research, we attempt todevelop the reaction system without synthesis and addition of decoy molecules using C10-acyl homoserine
lactone (C10-AHL), produced by a kind of bacteria, as a decoy molecule (Fig. 1). Herein, we engineered
P450BM3 mutants responding C10-AHL by directed evolution to
improve their catalytic efficiencies. We introduced randommutagenesis to P450BM3 heme domain and obtained a 1.5-fold
active mutant from >1600 mutants screening through benzenehydroxylation in the presence of C10-AHL. The obtained mutant
contains mutagenesis points which are far from heme. Thus, wehypothesize that these residues are essential and examine detaileffects of these residues by saturation mutagenesis.
(1) O. Shoji, et. al., Angew Chem. Int. Ed. 2017, 56, 10324-10329.

Fig. 1 Whole-cell reaction using
bacteria producing C10-AHL.

P-32
Synthesis of a zigzag carbon nanobelt
Kosuke Watanabe,1,2 Kwan Yin Cheung,3 Yasutomo Segawa,2 Kenichiro Itami1,3
1
Graduate School of Science, Nagoya University, Japan
2
Institute for Molecular Science, Japan
3
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Japan
Herein we report the synthesis and isolation of a zigzag carbon nanobelt.1 The
synthesis involves an iterative Diels–Alder reaction sequence followed by reductive
aromatization of oxygen-bridged moieties. The structure of the zigzag carbon nanobelt was
fully characterized by X-ray crystallography, and its wide energy gap with blue fluorescence
properties were revealed by photophysical measurement. As predicted by theoretical
calculations, the carbon nanobelt was isolated as a stable compound.
1) Cheung, K. Y.; Watanabe, K.; Segawa, Y.; Itami, K. Nat. Chem. 2021, DOI: 10.1038/s41557-020-00627-5

43

P-33
Photoredox-catalyzed decarboxylative direct aminomethylation
towards aryl bromides: Straightforward synthesis of primary benzylamine○Jaehyun Jung1, Yota Sakakibara1, Kei Murakami3, Kenichiro Itami1,2
1

Graduate School of Science, Nagoya University, 2Institute of Transformative Bio-Molecules(WPI-ITbM), Nagoya University, 3Department of Chemistry, Kwansei Gakuin University

Primary benzylamines are not only highly important building blocks in pharmaceuticalchemistry, but also useful in the construction of electrophilic fragment libraries such as
chloroacetamide, acrylamide, and cyanide for fragment-based drug discovery in covalent
drugs.[1] Recently, the synthesis of benzylamine derivatives by photoredox-catalyzed
aminoalkylation toward aryl halide has been developed by several groups.[2] However, astraightforward synthesis of primary benzylamines through the direct introduction ofaminomethyl group is limited. Herein, we report the development of photoredox/nickelcatalyzed direct aminomethylation of aryl bromides. This reaction exploits glycine derivativeas aminomethyl source via carbon radical species generated in a decarboxylative process underblue light irradiation. The wide range of aryl bromides, including heteroarenes, polycyclicaromatic hydrocarbons (PAHs) as well as drug precursors could be applied to our procedure.
(1) Keeley, A.; Petri, L.; Ábrányi-Balogh, P.; Keserű, G. M. Drug Discovery Today 2020, 6,
983. (2) (a) Zuo, Z.; Ahneman, D. T.; Chu, L.; Terrett, J.A.; Doyle, A. G.; MacMillan, D. W.
C. Science 2014, 345, 437. (b) Luo, J.; Zhang, J. ACS Catal. 2016. 6. 873.

P-34
Synthesis and properties of non-alternant aromatic belts
Hideya Kono,1 Yuanming Li,2 Yasutomo Segawa,3 Akiko Yagi,1,2 Kenichiro Itami1,2
1
Graduate School of Science, Nagoya University, Japan
2
Institute of Transformative Bio-Molecules (WPI-ITbM), Nagoya University, Japan
3
Institute for Molecular Science, Japan
Herein we report the synthesis of a methylene-bridged [6]cycloparaphenylene([6]MCPP), a non-alternant aromatic belt.1 [6]MCPP was obtained in 18% isolated yield by thearyl–aryl intramolecular coupling reaction using nickel complexes with pillar[6]arene
derivatives. Compared with [6]CPP, the methylene bridges co-planarize neighboring
paraphenylene units and enhance the degree of -conjugation, resulting in a significant decreasein energy gap. Moreover, the incorporation of small molecules in the defined pocket of[6]MCPP makes it an attractive supramolecular architecture.

(1) Li, Y.; Segawa, Y.; Yagi, A.; Itami, K. J. Am. Chem. Soc. 2020, 142, 12850.

44

P-35
Phosphorus-Based Organocatalysis for Dehydrative Cyclization of N-(2Hydroxyethyl)amides into 2-Oxazolines
Farzaneh Soleymani Movahed,1 Siong Wan Foo,1 Saeko Ogawa,1 Susumu Saito1,2
1
Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan
2
Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan
2-Oxazolines posses an extensive range of applications,1-2 and due to the vital potentialof the heterocyclic units in natural products and pharmaceuticals, practical and cost-efficientsynthetic approaches have yet to be developed. In this work, our biomimetic catalytic protocolfeatures the minimum employment of the catalyst and a broad substrate scope (up to 99% yield),along with high chemoselectivity toward 2-oxazolines; furthermore, it can be utilized as a gramscale (4 g) synthetic pathway with high efficiency.
(1) Van Steenberge, P. H. M.; Sedlacek, O.; Hernandez-Ortiz, J. C.; Verbraeken, B.; Reyniers,
M.-F.; Hoogenboom, R.; D’hooge, D. R. Nat. Commun. 2019, 10, 3641. (2) Yang, G.; Zhang,
W. Chem. Soc. Rev. 2018, 47, 1783.

P-36
C–O bond formation between aryl halides and carboxylic acids usingtitanium dioxide photocatalyst and a nickel complex
Riku Hashimoto1, Hiroya Tada1, Shogo Mori1, Jieun Jung1, Susumu Saito1,2
1
Graduate School of Science, Nagoya University, Nagoya 464-8602, Japan, 2Research Center
for Materials Science, Nagoya University, Nagoya 464-8602, Japan
Carboxylic acids are important carbon resources since they are abundant in nature andthey can be synthesized from carbon dioxide. Recently, C–O bond formation between aryl
halides and carboxylic acids has been achieved using photocatalyst/Ni complex systems under
mild conditions for the purpose of effective utilization of carboxylic acids.1 Our group has also
developed this transformation using a cheap, safe, reusable and heterogeneous photocatalyst,
titanium dioxide (TiO2). TiO2 can activate carboxylic acids to carboxyl radicals (RCOO•), mostof which are too unstable to undergo rapid decarboxylation into carbon-centered radicals (R•).2
In our TiO2/Ni complex system, RCOO• may be immediately intercepted by the nickel complex
upon their formation on/near the TiO2 surface, which resulted in the selective and rapid C–O
bond formation.
(1) (a) Welin, E. R.; Le, C.; Arias-Rotond, D. M.; McCusker, J. K.; MacMillan, D. W. C. Science 2017, 355,
380–385. (b) Pieber, B.; Malik, J. A.; Cavedon, C.; Gisbertz, S.; Savateev, A.; Cruz, D.; Heil, T.; Zhang, G.;
Seeberger, P. H. Angew. Chem. Int. Ed. 2019, 58, 9575–9580.
(2) Manley, D. W.; McBurney, R. T.; Miller, P.; Howe, R. F.; Rhydderch, S.; Walton, J. C. J. Am. Chem. Soc.
2012, 134, 13580–13583.

45

P-37
Photoreduction of CO2 using molybdenum complexes
bearing PNNP-type tetradentate ligands
Hiroaki Shibayama1, Kenji Kamada1, Jieun Jung1, Susumu Saito*,1,2
1Graduate School of Science, 2Research Center for Materials Science, Nagoya University,
Nagoya 464-8602, Japan
Photocatalytic CO2 reduction has attracted extensive interest since the photocatalytic
conversion of CO2 to energy-enriched compounds could potentially be achieved under mild
conditions. Herein, we report new molybdenum (Mo) complexes bearing PNNP-type
tetradentate ligands, which has been shown to prevent catalyst deterioration and promote CO2
reduction,1 acting as mononuclear photocatalysts for CO2 photoreduction. These non-precious
metal complexes show selective catalytic activities in photocatalytic conversion of CO2 toHCO2H under visible light irradiation. Nanosecond transient absorption spectrophotometermeasurements and EPR measurements were performed to investigate their reaction
mechanisms.
(1) Kamada, K.; Jung, J.; Wakabayashi, T.; Sekizawa, K.; Sato, S.; Morikawa, T.; Fukuzumi,
S.; Saito, S. J. Am. Chem. Soc. 2020, 142, 10261–10266.

P-38
Crystal structures and physical properties of a triptycene derivative
annulated with electron donating thianthrene moieties.
Takuma Yoshiyuki, Yoshiaki Shuku, Kunio Awaga
Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
Graphene with a honeycomb structure is in the spotlight due to its unique physicalproperties derived from the band structure called Dirac cone. To constructing molecule based
honeycomb structure, we focused on triptycene derivatives, which are paddle-wheel shaped
molecules having a three-fold rotational symmetry. Previously, we have reported ahoneycomb crystal structure of triptycene derivative (p-TT) and its unique band structure,
namely Dirac cone and flat band.1) However, the pore size of the honeycomb structure wastoo small to insert ions on the band filling control. Therefore, we focused on the thianthrene
skeleton as an extended and electron donating π conjugated system. It is known that theradical cation of thianthrene molecules often form a dimer by their strong π-π interaction. We
designed and synthesized a triptycene derivative having thianthrene moieties and prepared its
radical cation salts by chemical oxidation. The details of the crystal structures and physicalproperties will be discussed.
(1) Y. Shuku, et al. Chem. Commun. 2018, 54, 3815-3818.

46

P-39
A metallomacrocycle tethering eight corannulenes
and its host–guest interaction with C60
Yuta KOBAYASHI, Shin-ichiro KAWANO, Kentaro TANAKA
Department of Chemistry, Graduate School of Science, Nagoya University,
Nagoya 464-8602, Japan
Recently, we reported Schiff-base containing macrocycles composed ofdibenzothiophene and metal-salen complexes with a nanometer-sized inner cavity.1 In this paper,
we discuss the macrocycle containing four Co(III) complexes at the salen units withaminomethylcorannulenes as the axial ligands. The metallomacrocycle with eight corannulene
moieties could be a fullerene receptor, because of high affinity between corannulene andfullerene. Single crystallographic analysis of the conjugate of the Co-macrocycle and C60
revealed that the receptor molecule captured four C60, in which each four pair of corannulenes
sandwiches a single C60 through concave-convex interaction.
(1) S. Kawano, T. Hamazaki, A. Suzuki, K. Kurahashi, K. Tanaka, Chem. Eur. J., 2016, 22, 15674.

P-40
Template-independent RNA sequential synthesis using modified nucleic
acid as substrate〇Kato Shunichi1, Nakamoto Kosuke2, Murase Hirotaka3, Inagaki Masahito1, Hashiya
Fumitaka1, Kimura Yasuaki1, Abe Hiroshi1,4,5
1Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan,
2
Department of Chemistry, Brandeis University, America, 3Graduate School of Medicine,
Nagasaki International University, Nagasaki, 859-3298, Japan, 4RIKEN, 5JST CREST
In recent years, oligonucleotide therapeutics including antisense oligonucleotides and short interfering RNA(siRNA) has attracted a great deal of attention as a new type of drug, following small molecule drugs and antibody
therapeutics. These oligonucleotides are prepared by solid-phase synthesis with phosphoramidite-based chemistry
and are widely applied to medicine. On the other hand, the chemical synthesis of long RNA that can be applied formRNA therapeutics has not been achieved. In general, mRNA is synthesized by in vitro transcription (IVT) using
T7 RNA polymerase. However, since the IVT method cannot introduce the modified nucleoside analog site
specifically, it is not suitable to prepare modified mRNA which is highly stable in vivo and efficiently translated forpharmaceutical applications.
In the present work, we have attempted the enzymatic synthesis of long RNA strands using modified nucleic acid.
In general, RNA ligation by ligase proceeds in a three-step reaction. First, RNA ligase and ATP form an enzymeAMP complex. Next, the complex transfers AMP to the phosphate group located on a terminal of RNA to form
adenylated RNA. Finally, the adenylated RNA and the hydroxyl group of another RNA strand react to complete
ligation. The formation of adenylated RNA in the second step is a reversible reaction, and it seems to be the ratedetermining step of ligation reactions. Therefore, we chemically prepared adenylated RNA and developed a new
RNA ligation reaction that circumvents the rate-determining step.

47

P-41
Development of post-cleaving PCR primers for genome-scale DNA synthesis
Mikiya Kase, Masahito Inagaki, Haruka Hiraoka, Hashiya Fumitaka, Naoko Abe, Hiroshi Abe
In order to synthesize genome-scale long DNA strands, DNA assembly techniques are essential toconnect DNA fragments via sticky ends. Since conventional restriction enzyme-based methods such as
golden gate assembly limit the length of sticky end to 4 nt, our group has developed cleavable primer
that can generate site-specific DNA strand cleavage by introducing modified nucleic acids to prepare
any length and sequence sticky ends. In this study, we have developed a new method to create arbitrary
3' overhang sticky ends. This method uses the principle of chemical reactive cleavage of DNA with 3'
modification. So first, we needed to synthesize each nucleoside derivative containing modification at 3'.
We have completed the synthesis and optimization of reaction conditions of cytidine, adenosine andthymidine derivatives, and currently working on the synthesis of guanosine derivatives. We plan tosynthesize PCR primers and measure the cleavage efficiency after the synthesis.

P-42
Tunneling ionization of molecular hydrogen by using a high-repetition-rate
pulse laser
Shinnosuke Inaba1, Daimu Ikeya1, Hikaru Fujise1, Akiyoshi Hishikawa1,2
1
Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
2
Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan
Rates of laser tunneling ionization in intense laser fields (~1014 W/cm2) reflect
electron distributions in a molecule. Therefore, the molecular frame angular distribution ofphotoelectrons (MFPAD) can be used to visualize molecular orbitals and electron dynamics inreaction processes (1). Electron-ion coincidence momentum imaging technique is powerful inmeasuring MFPAD, as it allows us to determine the orientation of the molecular axis from themomenta of fragment ions. However, it requires a long accumulation time to obtain a sufficientamount of data, because the event rate per laser shot should be kept low (≲0.1) to suppress
accidental coincidences. In this work, we use a high-repetition-rate Yb:KGW pulsed laser (<100kHz, 190 fs) to reduce the time required for the electron-ion coincidence measurements. We
constructed a pulse compression system to generate ultrashort pulses for tunneling ionization
imaging, and investigated the field intensity dependence of MFPAD of molecular hydrogen.
(1) A. Staudte et al., Phys. Rev. Lett. 2009, 102, 033004.

48

P-43
Development of momentum imaging apparatus for intense-field dynamics
of molecular ions
M. Yamada1, H. Hasegawa1, A. Matsuda1, M. Fushitani1, A. Hishikawa1,2
1
Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan
2
Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan
Molecules in intense fields show a variety of exotic processes such as Coulomb
explosion and tunneling ionization, which provide unique methods for investigating ultrafast
molecular and electronic dynamics in chemical reactions. So far, studies on intense fieldprocesses have mostly focused on neutral molecules. Molecular ions have different geometricaland electronic structures from neutral molecules, and are therefore interesting targets for a
deeper understanding of intense field dynamics (1). In this study, we developed a threedimensional momentum imaging apparatus equipped with a pulsed ion source for generation ofmolecular ions. Two different ionizers can be used depending on desired ion species. The designof the apparatus and the characteristics are presented.
(1) B. Jochim et al., J. Phys. Chem. Lett. 2019, 10, 2320-2327.

P-44
Association reaction of gaseous C6H14 in femtosecond laser filament studied
by product mass spectrometry
Yuya Okumura1, Akitaka Matsuda1, Akiyoshi Hishikawa1,2¹Department of Chemistry, Nagoya University, Nagoya 464-8602, Japan²Research Center for Materials Science, Nagoya University, Nagoya 464-8602, Japan
Many-body reactions using femtosecond laser filaments has recently attracted attention. For
example, formation of short polyynes, C6H2, C8H2, from gaseous C6H14 in a laser filament has
been confirmed by UV absorption spectroscopy of products recovered by condensation(1). In
this study, we investigate the products from a laser filament of C6H14 by mass-spectrometry,
where the reaction gas cell is connected directly to a time-of-flight mass spectrometer via a
differential pumping stage. In addition to C6H2 and C8H2 observed by the previous UV
spectroscopy, we have identified other hydrocarbons, such as C4H2n, C6H2n (n=1,2,3…), which
could be considered as reaction intermediates in polyyne formation.
(1)N. Takizawa et al., Carbon. 2019, 152, 372-375.

49

P-45
Cross-linking gelation of isomaltodextrin for the chromatographic
separation of semiconducting carbon nanotubes
Yuki Matsunaga,1 Jun Hirotani,2 Yutaka Ohno,2,3 Haruka Omachi1,41Department of Chemistry, Graduate School of Science, 2Department of Electronics,
Graduate School of Engineering, 3Institute of Materials and Systems for Sustainability,
4
Research Center for Materials Science, Nagoya University, Nagoya, Japan
We report the cross-linking gelation of a cost-efficient polysaccharide isomaltodextrin(IMD) for the high-purity separation of semiconducting single-wall carbon nanotubes(SWCNTs) by column chromatography1). The cross-linking reaction with epichlorohydrin
under precisely controlled basic conditions gave the sub-micrometer porous IMD gels, which
was important for achieving gel chromatographic SWCNT separation. Furthermore, the thinfilm transistors prepared from the separated s-SWCNTs exhibited excellent on/off ratios.
(1) Y. Matsunaga, J. Hirotani, Y. Ohno, H. Omachi, Appl. Phys. Express. 2021, 14, 017001.

P-46
Catalytic NO Reduction Performances of Cr and Rh-incorporated Ceria○Satoru Ikemoto, Satoshi Muratsugu, Mizuki Tada
Research Center for Materials Science, Nagoya University, Nagoya 464-8602, JapanCr and Rh-incorporated ceria catalysts (denoted as Cr0.19Rh0.06CeOz) with low-temperature
redox activity1 exhibited superior NO reduction performances over Cr0.17CeOz and Rh0.04CeOz
incorporated with only Cr or Rh, and CeO2 without Cr and Rh; quantitative NO conversion with
100% selectivity to N2 at 473 K using CO as a reductant (Figure 1). Changes in adsorbed specieson the surface of Cr0.19Rh0.06CeOz
from in situ FT-IR and changes in theoxidation states of each metal species
from in situ XAFS analyses suggested
that the NO reduction performance on
Cr0.19Rh0.06CeOz was enhanced by the
co-involvement of CrOx species as anefficient O mediator from NO to COwith Rh species as both NO and CO
adsorption and activation sites.
(1) Ikemoto, S. et al. Phys. Chem.
Chem. Phys. 2019, 21, 20868-20877.
Figure 1. (A) NO conversion and (B) N2 selectivity for NO reduction
with CO on Cr0.19Rh0.06CeOz, Rh0.04CeOz, Cr0.17CeOz, and CeO2.

50

P-47
Preparation and Catalytic Performances of Copper and Ruthenium
Incorporated Ceria
Chaoqi Chen, Satoru Ikemoto, Satoshi Muratsugu, Mizuki Tada
Grad. Sch. Sci., RCMS, and IRCCS, Nagoya University, Nagoya 464-8602, Japan
We prepared a Cu and Ru-incorporated ceria catalyst (denoted as Cu0.17Ru0.05CeOz) which
maintained the fluorite structure of CeO2 from XRD and TEM. Cu0.17Ru0.05CeOz exhibited
highest catalytic activities on ammoxidation of benzyl alcohol over Cu0.18CeOz and Ru0.04CeOz
incorporated with only Cu or Ru, and CeO2 without Cu and Ru. It showed not only the highest
yield
for
benzonitrile(90 %, 24 h) 423 K by using
O2 (1 MPa) as an oxidant
and aqueous NH3 as anitrogensource.
The
recycling
testof
Cu0.17Ru0.05CeOz showedstable catalytic activity.
Figure 1 (A) XRD peak pattern of Cu0.17Ru0.05CeOz. (B) Catalytic
performances for ammoxidation of benzyl alcohol on Cu0.17Ru0.05CeOz.

Thematic Poster

P-48

Preparation and Luminescent Properties of Surface-Attached Chiral Tb
Complexes
Sora Shirai, Satoshi Muratsugu, Hidetaka Nakai, Mizuki Tada
Grad. Sch. Sci., RCMS, and IRCCS, Nagoya University, Nagoya 464-8602, Japan
We investigated a new preparation method of surface-attached chiral metal complex and the inducementof solid-state circularly polarized luminescence (CPL) by using luminescent achiral terbium (Tb) complex
and chiral ligand attached on silica surface. A new chiral benzyl alcohol ligand was synthesized andsuccessfully attached on silica surface. Then, achiral Tb complex (1Tb)(1) was grafted on the prepared surfaceattached chiral ligand (L(R/S)/SiO2), and thecoordination of the Tb complex to the chiralligand moiety was confirmed with UV-vis
spectra and quantification of eliminated ligand.
Luminescent properties of the surface-attached
Tb complexes (1Tb/L(R/S)/SiO2) were evaluatedwith solid-state CPL spectra.
(1) H. Nakai, et al., Chem. Commun., 2014, 50,
Figure 1. Preparation scheme of surface-attached chiral Tb
15737-15739.
complex (1 /L(R/S)/SiO ) by the coordination of 1 to
Tb

L(R/S)/SiO2.

51

2

Tb

The 4th IRCCS International Symposium:"Multidimensional control over material
structure and function"