Conductive Soft Crystals Based on Porous Molecular Conductor

• Project Area: Soft Crystals: Science and Photofunctions of Easy-Responsive Systems with Felxibility and Higher-Ordering
• Project/Area Number: 18H04498
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Tohoku University
• Principal Investigator: 井口 弘章 東北大学, 理学研究科, 助教 (30709100)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2019: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2018: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: ソフトクリスタル / 分子性導体 / 多孔性配位高分子 / 一次元電子系 / 分子吸脱着 / 化学ドーピング

Outline of Annual Research Achievements

本研究では、多孔性配位高分子 (MOF) と分子性導体を融合することで、両者の特長を併せ持つ多孔性分子導体 (PMC) を開発し、分子吸脱着や機械的刺激によって、電子状態と電子物性を劇的に変換可能な導電性ソフトクリスタルの創製を目指した。本年度の研究実績は以下の通りである。
（1）様々な配位子を用いたPMCの合成と物性解析
前年度に報告した、ナフタレンジイミド (NDI) 系配位子とCdイオンからなるPMC-1(Cd)とほぼ同等の結晶構造を持つPMC-1(Zn), PMC-1(Co)を合成した。他にも、金属イオン部位が[Co(acac)2]錯体となるPMCや、硫酸イオンが金属イオン間を架橋した、二次元、三次元配位高分子からなるPMCの合成も行った。さらに、テトラチアフルバレン(TTF)系配位子の合成にも成功し、90度配向がずれてπスタックした伝導体の合成にも成功した。これらはいずれも最大で0.01 S/cm 程度の伝導性を示す半導体であった。
2）PMCへの弱い刺激による構造・電子状態・電子物性のスイッチング
PMC-1の各種金属イオンによる刺激応答性の違いについて検討を行った。粉末X線回折パターンより、PMC-1(Co)よりもPMC-1(Zn,Cd)の方が結晶性が高く結晶溶媒脱離の際の安定性が増加していることが明らかとなった。また、熱重量分析より、Co, Zn, Cdの順に溶媒脱離のステップが明確に現れることが明らかとなった。これは、柔らかい配位構造を持つCdイオンでは、堅い配位構造もつCoイオンよりも構造変化に対して耐性があるためと考えられる。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Int'l Joint Research] The University of Sydney(オーストラリア)
• [Int'l Joint Research] The University of Sydney(オーストラリア)
• [Journal Article] Supramolecular self-assembled coordination architecture composed of a doubly bis(2-pyridyl)pyrazolate bridged dinuclear CuII complex and 7,7′,8,8′,-tetracyano-p-quinodimethanide radicals (2020)
  • Author(s): Ishikawa Ryuta、Ueno Shunya、Iguchi Hiroaki、Breedlove Brian K.、Yamashita Masahiro、Kawata Satoshi
  • Journal Title: CrystEngComm Volume: 22 Issue: 2 Pages: 159-163
  • DOI: 10.1039/c9ce01580a
  • Peer Reviewed
• [Journal Article] Porous Molecular Conductor: Electrochemical Fabrication of Through-Space Conduction Pathways among Linear Coordination Polymers (2019)
  • Author(s): Qu Liyuan、Iguchi Hiroaki、Takaishi Shinya、Habib Faiza、Leong Chanel F.、D’Alessandro Deanna M.、Yoshida Takefumi、Abe Hitoshi、Nishibori Eiji、Yamashita Masahiro
  • Journal Title: Journal of the American Chemical Society Volume: 141 Issue: 17 Pages: 6802-6806
  • DOI: 10.1021/jacs.9b01717
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] MX-type single chain complexes with an aromatic in-plane ligand: incorporation of aromatic interactions for stabilizing the chain structure (2019)
  • Author(s): Afrin Unjila、Iguchi Hiroaki、Mian Mohammad Rasel、Takaishi Shinya、Yamakawa Hiromichi、Terashige Tsubasa、Miyamoto Tatsuya、Okamoto Hiroshi、Yamashita Masahiro
  • Journal Title: Dalton Transactions Volume: 48 Issue: 22 Pages: 7828-7834
  • DOI: 10.1039/c9dt00784a
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Formation of Pores and π-Stacked Columns in Benzothienobenzothiophene-based Linear Coordination Polymers (2019)
  • Author(s): Koyama Shohei、Iguchi Hiroaki、Takaishi Shinya、Cosquer Goulven、Kumagai Shohei、Takeya Jun、Okamoto Toshihiro、Yamashita Masahiro
  • Journal Title: Chemistry Letters Volume: 48 Issue: 8 Pages: 756-759
  • DOI: 10.1246/cl.190276
  • NAID: 130007687727
  • Peer Reviewed
• [Journal Article] Simultaneous Spin‐Crossover Transition and Conductivity Switching in a Dinuclear Iron(II) Coordination Compound Based on 7,7′,8,8′‐Tetracyano‐ p ‐quinodimethane (2019)
  • Author(s): Ishikawa Ryuta、Ueno Shuya、Nifuku Shoei、Horii Yoji、Iguchi Hiroaki、Miyazaki Yuji、Nakano Motohiro、Hayami Shinya、Kumagai Shohei、Katoh Keiichi、Li Zhao‐Yang、Yamashita Masahiro、Kawata Satoshi
  • Journal Title: Chemistry - A European Journal Volume: 26 Issue: 6 Pages: 1278-1285
  • DOI: 10.1002/chem.201903934
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Smallest Optical Gap for Pt(II)?Pt(IV) Mixed-Valence Pt?Cl and Pt?Br Chain Complexes Achieved by Using a Multiple-Hydrogen-Bond Approach (2019)
  • Author(s): Mian M. Rasel、Iguchi H.、Takaishi S.、Afrin U.、Miyamoto T.、Okamoto H.、Yamashita M.
  • Journal Title: Inorganic Chemistry Volume: 58 Issue: 1 Pages: 114-120
  • DOI: 10.1021/acs.inorgchem.8b01910
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Development of Porous Molecular Conductors Constructed from Threefold Stack of Linear Coordination Polymers (2020)
  • Author(s): Hiroaki Iguchi, Liyuan Qu, Shohei Koyama, Shinya Takaishi, Masahiro Yamashita
  • Organizer: 日本化学会第100春季年会
• [Presentation] Porous Molecular Conductors: Conductive Soft Crystals Self-Assembled from Coordination Polymers with π-Radicals (2019)
  • Author(s): Hiroaki Iguchi, Liyuan Qu, Shohei Koyama, Shinya Takaishi, Masahiro Yamashita
  • Organizer: The 2nd International Symposium on Soft Crystals
  • Int'l Joint Research
• [Presentation] Porous Molecular Conductors Self-Assembled from Coordination Polymers with π-Radicals (2019)
  • Author(s): Hiroaki Iguchi
  • Organizer: 5th Japan-Taiwan-Singapore-Hong Kong Quadrilateral Symposium on Coordination Chemistry (QSCC)
  • Int'l Joint Research / Invited
• [Presentation] Porous Molecular Conductors Self-Assembled from Coordination Polymers with π-Radicals (2019)
  • Author(s): Hiroaki Iguchi
  • Organizer: 7th Asian Conference on Coordination Chemistry (ACCC7)
  • Int'l Joint Research / Invited
• [Presentation] Naphthalenediimide-based Porous Molecular Conductors Constructed from Linear Coordination Polymers (2019)
  • Author(s): Hiroaki Iguchi
  • Organizer: The 13rd Japan-China Joint Symposium on Conduction and Photoconduction in Organic Solids and Related Phenomena
  • Int'l Joint Research / Invited
• [Presentation] MX-type Single Chain Complexes with Aromatic In-plane Ligands (2019)
  • Author(s): Hiroaki Iguchi, Unjila Afrin, Shinya Takaishi, Masahiro Yamashita
  • Organizer: 錯体化学会第69回討論会
• [Presentation] Syntheses of Porous Molecular Conductors by Electrochemical Self-Assembly of Coordination Polymers (2019)
  • Author(s): 井口弘章、瞿李元、高石慎也、山下正廣
  • Organizer: 第29回日本MRS年次大会 N: 自己組織化材料とその機能XVI
• [Presentation] Highly Conductive and Thermally Stable Pd(III)-Br Chain Complex (2018)
  • Author(s): Hiroaki Iguchi, Mohammad Rasel Mian, Shinya Takaishi, Masahiro Yamashita
  • Organizer: 43rd International Conference on Coordination Chemistry (ICCC2018), S34 session
  • Int'l Joint Research
• [Presentation] ナフタレンジイミド型配位子を用いた多孔性分子導体の開発 (2018)
  • Author(s): 井口弘章、瞿李元、宮田百香、上野健太、高石慎也、山下正廣
  • Organizer: 第12回分子科学討論会
• [Presentation] Porous Molecular Conductors Synthesized by Using π-π Interaction and Coordination to Metal Ion (2018)
  • Author(s): Hiroaki Iguchi, Liyuan Qu, Shohei Koyama, Shinya Takaishi, Masahiro Yamashita
  • Organizer: The 8th TOYOTA RIKEN International Workshop Organic Semiconductors, Conductors, and Electronics
  • Int'l Joint Research
• [Presentation] 高導電性ナノワイヤー金属錯体と多孔性分子導体の開発 (2018)
  • Author(s): 井口弘章
  • Organizer: 第３回有機若手ワークショップ
  • Invited
• [Presentation] 一次元金属錯体の電子状態制御と多孔性分子導体の開発 (2018)
  • Author(s): 井口弘章
  • Organizer: 日本化学会中国四国支部 愛媛地区化学講演会
  • Invited
• [Presentation] Porous Molecular Conductors Self-Assembled by Radical-Radical Interaction among Coordination Polymers (2018)
  • Author(s): Hiroaki Iguchi
  • Organizer: MOF2018 Young Investigator Symposium
  • Int'l Joint Research
• [Presentation] Porous Molecular Conductors Constructed from Coordination Polymers with p-Radicals (2018)
  • Author(s): Hiroaki Iguchi, Liyuan Qu, Shohei Koyama, Shinya Takaishi, Masahiro Yamashita
  • Organizer: 6th International Conference on Metal-Organic Frameworks & Open Framework Compounds (MOF 2018)
  • Int'l Joint Research