有機金属複合体など凝縮重電子系複合体の光反応の理論的研究

• Project Area: Science on Function of Soft Molecular Systems by Cooperation of Theory and Experiment
• Project/Area Number: 26104538
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Institute for Molecular Science
• Principal Investigator: 倉重 佑輝 分子科学研究所, 理論・計算分子科学研究領域, 助教 (30510242)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2015: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2014: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 有機金属複合体 / 励起状態計算 / 分子集合体 / 金属錯体 / 光反応 / 電子相関理論 / 多参照理論

Outline of Annual Research Achievements

本研究が対象とする凝縮重電子系複合体のサンドイッチ多核Pd錯体について理論研究を行い、具体的には前年度の一次元π共役分子(カロテノイド分子)の理論解析からの発展によりベンゼンやシクロオクタテトラエンなど環状π共役分子を用いたサンドイッチ多核Pd錯体の理論解析に取り組んだ。特に、ベンゼン分子のみでサンドイッチしたPd錯体が安定に得られないのに対して片方をシクロオクタテトラエンにしたPd錯体は安定に得られる原理を凝縮重電子系複合体における電子論的な考察から説明を与え、これから同様の環状π共役分子を用いた新たなサンドイッチ錯体の分子設計に対し指針を得ることができた。また長波長の光エネルギーを三重項三重項消滅を利用してより短波長の発光に変換するフォトンアップコンバージョン現象のπ共役分子集合体における機構解明について理論研究を行った。具体的には溶液中ではフォトンアップコンバージョン現象が確認されなかった分子を集合化させることにより初めて現象が確認されるという凝縮重電子系複合体ならでわの凝集誘起フォトンアップコンバージョン現象について理論計算から機構を解明する事に成功した。特に分子の置換基効果から三重項の失活機構が大きく異なることが理論的に明らかになり、今後の凝集誘起フォトンアップコンバージョン材料に用いる分子の設計に対する指針を得ることができた。

Research Progress Status

27年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

27年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] A pentanuclear iron catalyst designed for water oxidation (2016)
  • Author(s): Masaya Okamura, Mio Kondo, Reiko Kuga, Yuki Kurashige, Takeshi Yanai, Shinya Hayami, Vijayendran K. K. Praneeth, Masaki Yoshida, Ko Yoneda, Satoshi Kawata, and Shigeyuki Masaoka
  • Journal Title: Nature Volume: 530 Issue: 7591 Pages: 465-468
  • DOI: 10.1038/nature16529
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Multinuclear Metal-Binding Ability of a Carotene (2015)
  • Author(s): T. Murahashi et al.
  • Journal Title: Nature Communications Volume: 6 Issue: 1 Pages: 6742-6749
  • DOI: 10.1038/ncomms7742
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Aggregation-Induced Photon Upconversion through Control of the Triplet Energy Landscapes of the Solution and Solid States (2015)
  • Author(s): Pengfei Duan, Nobuhiro Yanai, Yuki Kurashige, and Nobuo Kimizuka
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54 Issue: 26 Pages: 7544-7549
  • DOI: 10.1002/anie.201501449
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Fully internally contracted multireference configuration interaction theory using density matrix renormalization group: A reduced-scaling implementation derived by computer-aided tensor factorization (2015)
  • Author(s): M. Saitow, Y. Kurashige, and T. Yanai
  • Journal Title: J. Chem. Theo. Comp. Volume: 11 Issue: 11 Pages: 5120-5131
  • DOI: 10.1021/acs.jctc.5b00270
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Acid/Base-Regulated Reversible Electron Transfer Disproportionation of N-N linked Bicarbazole and Biacridine Derivatives (2015)
  • Author(s): Palash Pandit,† Koji Yamamoto,† (†: equally contributed) Toshikazu Nakamura, Katsuyuki Nishimura, Yuki Kurashige, Takeshi Yanai, Go Nakamura, Shigeyuki Masaoka, Ko Furukawa, Yumi Yakiyama, Masaki Kawano and Shuhei Higashibayashi
  • Journal Title: Chemical Science Volume: 印刷中 Issue: 7 Pages: 4160-4173
  • DOI: 10.1039/c5sc00946d
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Modulation of benzene or naphthalene binding to palladium cluster sites by the backside-ligand effect (2015)
  • Author(s): Y. Ishikawa, S. Kimura, K. Takase, K. Yamamoto, Y. Kurashige, T. Yanai, T. Murahashi
  • Journal Title: Angewandte Chemie International Edition Volume: 54 Issue: 8 Pages: 2482-2486
  • DOI: 10.1002/ange.201409499
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of Molecular Wires Strapped by π-Conjugated Side Chains: Integration of Dehydrobenzo[20]annulene Units (2015)
  • Author(s): J. Terao, M. Ohsawa, H. Masai, Y. Kurashige, T. Fujihara, and Y. Tsuji
  • Journal Title: J. Org. Chem. Volume: 80 Issue: 17 Pages: 8874-8880
  • DOI: 10.1021/acs.joc.5b01414
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Scalar relativistic calculations of hyperfine coupling constants using ab initio density matrix renormalization group method in combination with third-order Douglas-Kroll-Hess transformation: case studies of 4d transition metals (2015)
  • Author(s): T. N. Lan, Y. Kurashige, and T. Yanai
  • Journal Title: J. Chem. Theo. Comp. Volume: 11 Issue: 1 Pages: 73-81
  • DOI: 10.1021/ct5007778
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Density matrix renormalization group for ab initio Calculations and associated dynamic correlation methods: A review of theory and applications (2015)
  • Author(s): T. Yanai, Y. Kurashige, J. Chalupsky, T. N. Lan, and M. Saitow
  • Journal Title: Int. J. Quantum Chem. Volume: 115 Issue: 5 Pages: 283-299
  • DOI: 10.1002/qua.24808
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Complete active space second-order perturbation theory with cumulant approximation for large entanglement space from density matrix renormalization group (2014)
  • Author(s): Y. Kurashige, J. Chalupsky, T. N. Lan, and T. Yanai
  • Journal Title: J. Chem. Phys. Volume: 141 Issue: 17
  • DOI: 10.1063/1.4900878
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Reactivity of Binuclear Non-Heme Iron Δ9 Desaturase Studied by Large-scale Multireference Ab Initio Calculations (2014)
  • Author(s): J. Chalupsky, T. A. Rokob, Y. Kurashige, T. Yanai, E. I. Solomon, L. Rulisek, and M. Srnec
  • Journal Title: J. Am. Chem. Soc, Volume: 136 Issue: 45 Pages: 15977-15991
  • DOI: 10.1021/ja506934k
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Theoretical study of the π→π* excited states of oligoacenes: a full π-valance DMRG-CASPT2 study (2014)
  • Author(s): Y. Kurashige and T. Yanai
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 87 Issue: 10 Pages: 1071-1073
  • DOI: 10.1246/bcsj.20140180
  • NAID: 130004153323
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Presentation] Applications of DMRG-based multireference correlation theories (2016)
  • Author(s): Y. Kurashige
  • Organizer: 251st ACS National Meeting
  • Place of Presentation: San Diego Convention Center, California, USA
  • Year and Date: 2016-03-13
  • Int'l Joint Research / Invited
• [Presentation] Applications of DMRG-based multireference correlation theories (2015)
  • Author(s): Y. Kurashige
  • Organizer: The 15th International Congress of Quantum Chemistry (ICQC) Satellite
  • Place of Presentation: AICS, Kobe, Hyogo, Japan
  • Year and Date: 2015-06-18
  • Int'l Joint Research / Invited
• [Presentation] Development of Multireference Electronic -Structure Methods and Application to Multinuclear Complexes and Metalloenzymes (2015)
  • Author(s): Yuki Kurashige
  • Organizer: The 94th Annual Meeting of the Chemical Society of Japan
  • Place of Presentation: 千葉県船橋市日大船橋キャンパス
  • Year and Date: 2015-03-29
  • Invited
• [Presentation] Quantum chemistry meets density matrix renormalization group (DMRG) theory: Theory and applications to π-conjugated systems (2015)
  • Author(s): Yuki Kurashige
  • Organizer: WPI-MANA seminar
  • Place of Presentation: 茨城県つくば市MANAセンター
  • Year and Date: 2015-03-19
  • Invited
• [Presentation] 多参照電子状態理論の最近の進展 (2015)
  • Author(s): 倉重佑輝
  • Organizer: 第２９回九州大学CMSセミナー
  • Place of Presentation: 福岡県福岡市九大伊都キャンパス
  • Year and Date: 2015-01-23
  • Invited
• [Presentation] 多参照電子状態理論によるπ共役分子の励起状態解析 (2014)
  • Author(s): 倉重佑輝
  • Organizer: 新学術領域「柔らかな分子系」第７回ワークショップ
  • Place of Presentation: 愛知県岡崎市岡崎カンファレンスセンター
  • Year and Date: 2014-12-13
  • Invited
• [Presentation] 有機結晶におけるマルチエキシトン生成機構の理論的解明 (2014)
  • Author(s): 倉重佑輝
  • Organizer: 新学術領域「柔らかな分子系」第５回ワークショップ
  • Place of Presentation: 広島県広島市アステールプラザ
  • Year and Date: 2014-09-20
  • Invited