量子化学計算に基づいた多核金属錯体による分子素子設計指針の構築と物性予測

• Project Area: Coordination Programming - Science of Molecular Superstructures for Chemical Devices
• Project/Area Number: 24108721
• 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: Osaka University
• Principal Investigator: 北河 康隆 大阪大学, 理学(系)研究科(研究院), 助教 (60362612)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥7,540,000 (Direct Cost: ¥5,800,000、Indirect Cost: ¥1,740,000); Fiscal Year 2013: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2012: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
• Keywords: 量子化学 / 多核遷移金属錯体 / 強相関電子系 / 物性 / 分子素子

Research Abstract

本年度は、まず、Niによる１次元多核錯体の磁性と伝導性に関して研究を進めた。磁性に関しては金属―金属結合に由来するdσ並びにdδ軌道が担っており、さらに伝導性に関しては、錯体内のσ軌道のみならず、軸上配位子と金電極の非局在軌道が単分子伝導性に大きく寄与することを明らかにした。加えて、巨大多核金属錯体の電子状態並びに分子構造計算のための新規QM/QM’方の提案を行った。
また、領域内で合成・測定された、錯体の機能発現機構の解明を行った。まず、西原ループのπ共役配位子を使った長距離電子移動錯体と棚瀬グループのAu４核錯体ならびにPd８核１次元錯体、大塩グループのシアン化物イオン架橋擬一次元Fe-Co錯体、オキソバナジウム環状錯体を主たる研究対象とした。まず、西原ループ錯体に関しては、π共役配位子を有する多核錯体の、非常に高い発光特性の原理解明を行った。まず、溶媒環境下でのDFT計算により分子構造を求め、TDDFT計算を実行した。その結果、エネルギー準位の異なる配位子間での電子移動が重要であることが明らかとなった。棚瀬グループの錯体に関しては、まず、様々な構造を有するAu４核錯体における吸収および発光特性をDFT計算とTDDFT計算により調べた。分子構造、発光波長、吸収波長とも実験と一致し、すべてAuの軌道により構成されるHOMO-LUMO間の遷移で説明された。またPd８核錯体に関しては伝導特性を調べるため、電極との接合に適した軸上配位子をDFT計算により探った。大塩グループの錯体に関しては、XMCDスペクトルの帰属をDFT計算により行い、その結果、錯体の電子状態・スピン状態を明らかにした。

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Strongly Luminous Tetranuclear Gold(I) Complexes Supported by Tetraphosphine Ligands, meso- or rac-Bis[(diphenylphosphinomethyl)phenylphosphino]methane (2014)
  • Author(s): T. Tanase, R. Otaki, T. Nishida, H. Takenaka, Y. Takemura, B. Kure, T. Nakajima, Y. Kitagawa, T. Tsubomura
  • Journal Title: Chem. Euro. J. Volume: 20 Issue: 6 Pages: 1577-1596
  • DOI: 10.1002/chem.201303729
  • Peer Reviewed
• [Journal Article] Combination of approximate spin-projection and spin-restricted calculations based on ONIOM method for geometry optimization of large biradical systems (2013)
  • Author(s): Y. Kitagawa, N. Yasuda, H. Hatake, T. Saito, Y. Kataoka, T. Matsui, T. Kawakami, S. Yamanaka, M. Okumura, K. Yamaguchi
  • Journal Title: Int. J. Quant. Chem Volume: 113 Issue: 3 Pages: 290-295
  • DOI: 10.1002/qua.24018
  • Peer Reviewed
• [Journal Article] meso -Alkynyl BODIPYs: Structure, Photoproperties, π-Extension, and Manipulation of Frontier Orbitals (2013)
  • Author(s): Shinpei Kusaka, 他4名
  • Journal Title: Chemistry An Asian Journal Volume: 8 Issue: 4 Pages: 723-727
  • DOI: 10.1002/asia.201201176
  • Peer Reviewed
• [Journal Article] Photophysical Properties of Mono- and Di-nuclear Platinum (II) Complexes with the Tridentate Ligand 2-phenyl-6-(1H-pyrazol-3-y1)-pyridine : A DF T and TDDFT Study (2013)
  • Author(s): Yusuke Kataoka, Yasutaka Kitagawa, Takashi Kawakami, Mitsutaka Okumura
  • Journal Title: Journal of Organometallic Chemistry Volume: 743 Pages: 163-169
  • DOI: 10.1016/j.jorganchem.2013.06.042
  • Peer Reviewed
• [Journal Article] π-Conjugated Trinuclear Group-9 Metalladithiolenes with a Triphenylene Backbone (2013)
  • Author(s): R. Sakamoto, Tetsuya Kambe, S. Tsukada, K. Takada, K. Hoshiko, Y. Kitagawa, M. Okumura, H. Nishihara
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 13 Pages: 7411-7416
  • DOI: 10.1021/ic400110z
  • Peer Reviewed
• [Journal Article] DFT calculations of effective exchange integrals at the complete basis set limit on oxo-vanadium ring complex (2013)
  • Author(s): Y. Kitagawa, T. Matsui, N. Yasuda, H. Hatake, T. Kawakami, S. Yamanaka, M. Nihei, M. Okumura, H. Oshio and K. Yamaguchi
  • Journal Title: Polyhedron Volume: 66 Pages: 97-101
  • DOI: 10.1016/j.poly.2013.02.040
  • Peer Reviewed
• [Journal Article] Theoretical studies of electronic structures, magnetic properties and electron conductivities of one-dimensional Nin (n= 3,5,7) com plexes (2013)
  • Author(s): Y. Kitagawa, T. Matsui, Y. Nakanishi, Y. Shigeta, T. Kawakami, M. Okumura and K. Yamaguchi
  • Journal Title: Dalton Transaction Volume: 42 Issue: 45 Pages: 16200-16208
  • DOI: 10.1039/c3dt51466h
  • Peer Reviewed
• [Journal Article] X-ray Magnetic Circular Dichroism Investigation of the Electron Transfer Phenomena Responsible for Magnetic Switching in a Cyanide-Bridged [CoFe] Chain (2013)
  • Author(s): M. L. Baker, Y. Kitagawa, T. Nakamura, K. Tazoe, Y. Narumi, Y. Kotani, F. Iijima, G. N. Newton, M. Okumura, H. Oshio, H. Noiiri
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 24 Pages: 13956-13962
  • DOI: 10.1021/ic402580n
  • Peer Reviewed
• [Journal Article] Consistent Scheme for Computing Standard Hydrogen Electrode and Redox Potentials (2013)
  • Author(s): Toru Matsui, Yasutaka Kitagawa, Mitsutaka Okumura, Yasuteru Shigeta, and Shigeyoshi Sakaki
  • Journal Title: Journal of Computational Chemistry Volume: 34 Issue: 1 Pages: 21-26
  • DOI: 10.1002/jcc.23100
  • Peer Reviewed
• [Journal Article] Vibrational frequency without spin contamination error- approximately spin projected force constant- (2012)
  • Author(s): Y. Kitagwa, T. Saito, Y. Kataoka, Y. Nakanishi, T. Matsui, T. Kawakami, M. Okumura, K. Yamaguchi
  • Journal Title: AIP Conf. Proc. Volume: 1504 Pages: 879-882
  • DOI: 10.1063/1.4771835
  • Peer Reviewed
• [Journal Article] Fluorescent azadipyrrinato zinc(II) complex: hybridisation with a dipyrrinato ligand (2012)
  • Author(s): Shinpei Kusaka, 他19名
  • Journal Title: Dalton Transactions Volume: 41 Issue: 46 Pages: 14035-14037
  • DOI: 10.1039/c2dt32039h
  • Peer Reviewed
• [Journal Article] Approximate spin projection for geometry optimization of biradical systems: Case studies of through-space and through-bond systems (2012)
  • Author(s): N. Yasuda, Y. Kitagawa, H. Hatake, T. Saito, Y. Kataoka, T. Matsui, T. Kawakami, S. Yamanaka, M.Okumura, K. Yamaguchi
  • Journal Title: Progress in Theoretical Chemistry and Physics Volume: 26 Pages: 345-359
  • DOI: 10.1007/978-94-007-5297-9_18
  • ISBN: 9789400752962, 9789400752979
  • Peer Reviewed
• [Journal Article] An Extremely Bright Heteroleptic Bis(dipyrrinato)zinc(II) Complex (2012)
  • Author(s): Shinpei Kusaka, 他4名
  • Journal Title: Chemistry An Asian Journal Volume: 7 Issue: 5 Pages: 907-910
  • DOI: 10.1002/asia.201200131
  • Peer Reviewed
• [Presentation] Theoretical studies of molecular structures and magnetic properties on polynuclear metal complexes (2013)
  • Author(s): Y. Kitagawa
  • Organizer: 5th JCS International Symposium on Theoretical Chemistry
  • Place of Presentation: 東大寺総合文化センター
  • Invited
• [Presentation] 一次元多核金属錯体の電子状態・電極構造・電気伝導性の関係に関する理論的研究 (2013)
  • Author(s): 北河康隆
  • Organizer: 錯体化学会第６３回討論会
  • Place of Presentation: 琉球大学
• [Presentation] Structure of active site in oxyhemocyanin:Comparative studies of BS and AP DFT methods (2013)
  • Author(s): Y. Kitagawa
  • Organizer: Interna'onal Symposium of Homogeneous Chemical Reac'vity
  • Place of Presentation: 茨城大学
  • Invited
• [Presentation] CuM錯体の有効交換積分値における汎関数および基底関数依存性 (2013)
  • Author(s): 北河康隆
  • Organizer: 第16 回理論化学討論会
  • Place of Presentation: 福岡市健康づくりサポートセンター
• [Presentation] DFT for calculations of di-chromium(II) complex (2012)
  • Author(s): Y. Kitagawa
  • Organizer: Cambodian and Malaysian Chemical Congress
  • Place of Presentation: Siem Reap, Cambodia
  • Year and Date: 2012-10-19
  • Invited
• [Presentation] Which DFT is suitable for calculations of magnetic property and molecular geometry on di-chromium(II) complex ? (2012)
  • Author(s): Y. Kitagawa
  • Organizer: 17th Malaysian Chemical Congress
  • Place of Presentation: Kuala Lumpur, Malaysia
  • Year and Date: 2012-10-15
  • Invited
• [Presentation] DFT studies of weak magnetic interactions between oxovanadiums in (VO)n magnetic rings (2012)
  • Author(s): Y. Kitagawa, N. Yasuda, H. Hatake, T. Matsui, T. Kawakami, S. Yamanaka, M. Nihei, H. Oshio, M. Okumura and K. Yamaguchi
  • Organizer: 13th International Conference on Molecule-based Magnet
  • Place of Presentation: Orland, Florida, USA
  • Year and Date: 2012-10-07
• [Presentation] 量子化学計算に基づいた金属錯体の光機能創出に向けて～構造・電子状態・光物性の関係を中心として～ (2012)
  • Author(s): 北河康隆
  • Organizer: 錯体化学討論会
  • Place of Presentation: 富山大学
  • Year and Date: 2012-09-21
  • Invited
• [Presentation] Cr(II)二核錯体のhybrid DFT計算におけるHF項の混合割合と汎関数の評価 (2012)
  • Author(s): 北河 康隆・松井 亨・宋 鍾元・畑ヶ 宇宙・安田 奈都美・川上 貴資・山中 秀介・奥村 光隆
  • Organizer: 分子科学討論会
  • Place of Presentation: 東京大学
  • Year and Date: 2012-09-18
• [Presentation] ハイブリッドDFT法におけるHF交換項の混合割合と有効交換積分値 (2012)
  • Author(s): 北河康隆・安田奈都美・畑ヶ宇宙・松井亨・川上貴資・山中秀介・奥村光隆
  • Organizer: 理論化学討論会
  • Place of Presentation: 仙台
  • Year and Date: 2012-05-24
• [Presentation] A relation between a molecular electron conductance and a structure of electrodes by DFT calculations (2012)
  • Author(s): Y. Kitagawa, T. Matsui, Y. Shigeta, N. Yasuda, H. Hatake, T. Kawakami, S. Yamanaka, M. Okumura
  • Organizer: Gold2012 post conference
  • Place of Presentation: Kyoto, Japan