Creation of the charge bistability and functions based on structural control in halogen-bridged metal complexes

• Project/Area Number: 16K05713
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Tohoku University
• Principal Investigator: Takaishi Shinya 東北大学, 理学研究科, 准教授 (10396418)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: ハロゲン架橋 / 混合原子価 / エネルギー変換 / バンドギャップ / ハイブリッドペロブスカイト / 太陽電池 / 強相関電子系 / 配位高分子 / 擬一次元ハロゲン架橋金属錯体 / 平均原子価 / 固体物性

Outline of Final Research Achievements

We synthesized quqsi-one-dimensional metal complexes and gold halide perovskite complexes to realize the charge bistability. We have succeeded in synthesized bromo-bridged palladium complex with new in-plane ligand 2,3-diaminobutane-1,4-diol(dabdOH). This compound has the shortest Pd-Pd distance (5.18A) and largest electrical conductivity.

Academic Significance and Societal Importance of the Research Achievements

一次元金属錯体については、室温38Scm-1と非常に高い電気伝導度を示したうえ、バンドギャップについても0.5eVと既存のMX錯体中で極めて小さい部類に入る。このようななρギャップの一次元半導体は、近年、高い熱電特性を示すことが予想されており、本錯体のバンドフィリングを制御することができれば、熱電材料としても期待される。また、本錯体系のCT吸収帯を光励起することで超高速光スイッチングを実現できると期待される。

Research Products

• [Journal Article] Correlation between Chemical and Physical Pressures on Charge Bistability in [Pd(en)2Br](Suc-Cn)2・H2O (2018)
  • Author(s): Shohei Kumagai、Shinya Takaishi、Hiroaki Iguchi、Brian K. Breedlove、Takuya Kaneko、Hiroshi Ito、Shin-ichi Kuroda、Masahiro Yamashita
  • Journal Title: Inorg. Chem. Volume: 57 Issue: 1 Pages: 12-15
  • DOI: 10.1021/acs.inorgchem.7b02566
  • Peer Reviewed
• [Journal Article] MX-chain Compounds with ReO4 Counterions: Exploration of the Robin-Day Class I-II Boundary (2018)
  • Author(s): Shohei Kumagai, Shinya Takaishi, Mengqi Gao, Hiroaki Iguchi, Brian K. Breedlove, Masahiro Yamashita
  • Journal Title: Inorg. Chem. Volume: 58 Issue: 7 Pages: 3775-3781
  • DOI: 10.1021/acs.inorgchem.7b03051
  • Peer Reviewed
• [Journal Article] Structural Study of Bromide-Bridged Pd Chain Complex with Weak CH・・・O Hydrogen Bonds (2018)
  • Author(s): Rasel Mian Mohammad、Iguchi Hiroaki、Miyata Momoka、Takaishi Shinya、Yamakawa Hiromichi、Terashige Tsubasa、Miyamoto Tatsuya、Okamoto Hiroshi、Yamashita Masahiro
  • Journal Title: Zeitschrift fur anorganische und allgemeine Chemie Volume: 644 Issue: 14 Pages: 646-651
  • DOI: 10.1002/zaac.201700461
  • Peer Reviewed
• [Journal Article] Multiple Hydrogen-Bond Approach to Uncommon Pd(III) Oxidation State: A Pd-Br Chain with High Conductivity and Thermal Stability (2017)
  • Author(s): Mian M. Rasel, Hiroaki Iguchi, Shinya Takaishi, Hideaki Murasugi, T. Miyamoto, Hiroshi Okamoto, Hisaaki Tanaka, Shin-ichi Kuroda, Brian K. Breedlove, MasahiroYamashita
  • Journal Title: J. Am. Chem. Soc. Volume: 136 Issue: 19 Pages: 6562-6565
  • DOI: 10.1021/jacs.7b02558
  • Peer Reviewed
• [Journal Article] Three dimensional porous Hofmann clathrate [MIIPtII(CN)4] (M = Co, Ni) synthesized by using postsynthetic reductive elimination (2017)
  • Author(s): Takuro Okamura, Bin Wu, Hiroaki Iguchi, Brian K. Breedlove, Masahiro Yamashita, Wataru Kosaka, Hitoshi Miyasaka, Shinya Takaishi
  • Journal Title: ChemComm. Volume: 53 Issue: 48 Pages: 6512-6515
  • DOI: 10.1039/c7cc01766a
  • Peer Reviewed
• [Journal Article] Optically visible phase separation between Mott-Hubbard and charge-density-wave domains in a Pd-Br chain complex (2016)
  • Author(s): T. Yoshida, S. Takaishi, H. Iguchi, H. Okamoto, H. Tanaka, S. Kuroda, Y. Hosomi, S. Yoshida, H. Shigekawa, T. Kojima, H. Ohtsu, M. Kawano, B. K. Breedlove, L. Gué rin, and M. Yamashita
  • Journal Title: ChemistrySelect Volume: 2 Issue: 2 Pages: 259-263
  • DOI: 10.1002/slct.201600065
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] A highly emissive distyrylthieno[3,2-b]thiophene based red luminescent organic single crystal: Aggregation induced emission, optical waveguide edge emission, and balanced ambipolar carrier transport (2016)
  • Author(s): Shuai Mu, Kazuaki Oniwa, Tienan Jin, Naoki Asao, Masahiro Yamashita, Shinya Takaishi
  • Journal Title: Organic Elelctronics Volume: 34 Pages: 23-27
  • DOI: 10.1016/j.orgel.2016.04.001
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structure Insights into the Counterion Effects on the Manganese(lll) Spin Crossover System with Hexadentate Schiff-Base Ligands (2016)
  • Author(s): S. Wang, W. T. Xu, W. R. He, S. Takaishi, Y. H. Li, M. Yamashita amd W. Huang
  • Journal Title: Dalton Trans. Volume: 45 Issue: 13 Pages: 5676-5688
  • DOI: 10.1039/c5dt04824a
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Temperature dependence of Peierls-Hubbard Phase Transition in [Pd(cptn)2Br]Br2 Studied by Scanning Tunneling Microscopy (2016)
  • Author(s): 90Yuka Hosomi, Shoji Yoshida, A. Taninaka, Takefumi Yoshida, Shinya Takaishi, O. Takeuchi, Masahiro Yamashita, Hidemi Shigekawa
  • Journal Title: Japanese Journal of Applied Physics Volume: 55
  • NAID: 120007129519
  • Peer Reviewed
• [Presentation] Continuous Carrier Control in the Electron Conductive Metal-Organic Framework Cu[Cu(pdt)2] (2018)
  • Author(s): Shinya Takaishi, Miyuki Hosoda, Masahiro Yamashita
  • Organizer: International Conference on Coordination Chemistry
  • Int'l Joint Research / Invited
• [Presentation] 有機-無機ハイブリッドペロブスカイト A2[AuI2][AuI4](A=CH3NH3 or NH2=CHNH2)の合成と物性 (2016)
  • Author(s): 村杉 英昭,熊谷翔平,影澤幸一,井口弘章,高石慎也, 山下正廣
  • Organizer: 第6回CSJ 化学フェスタ
  • Place of Presentation: タワーホール船堀
  • Year and Date: 2016-11-14
• [Presentation] Highly selective H2 or O2 sorption over N2 in metal-organic frame-work with dynamic aperture (2016)
  • Author(s): Shinya Takaishi, Bin Wu, Shin-ichiro Noro, Masahiro Yamashita
  • Organizer: 5th International Conference on Metal-Organic Frameworks & Open Framework Compounds (MOF 2016)
  • Place of Presentation: hilton long beach (USA)
  • Year and Date: 2016-09-14