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Exploring proton-electron cooperative properties in bistable coordination compounds

Research Project

Project/Area Number 17K05800
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionUniversity of Tsukuba

Principal Investigator

SHIGA Takuya  筑波大学, 数理物質系, 准教授 (00375411)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords双安定性 / 磁性 / プロトン / 電子 / 誘電性 / 分子エレクトロニクス / 鉄錯体 / 水素結合 / プロトン応答 / スピン平衡
Outline of Final Research Achievements

As for bistable molecules, which have multiple stable states, their various electronic states can be designed by modification of ligands and control of the structure of molecular assemblies. In this work, we aimed an achievement of control of permittivity by magnetic field and conversion of magnetism by electric field by the introduction of proton responsive properties into bistable coordination complexes. An iron(II) mononuclear complex with asymmetric planar tridentate ligand with dissociative protons which have different pKa. Five kinds of iron complexes, which have different proton- and electronic states, were synthesized by trial-and-error of synthetic conditions, and their structures, magnetic properties, and electronic states were investigated.

Academic Significance and Societal Importance of the Research Achievements

熱や光による物性変換は数多く報告されているが、プロトンに起因した双安定性の発現や電場応答性の研究は皆無であり、本研究の成果をもとに適切な分子選択・分子修飾を行うことで、プロトンの変位と連動した新しい外場応答性を持つ機能性分子材料を開発できると考えられる。これらの分子材料は、ナノサイエンス分野・分子エレクトロニクス分野におけるスイッチング素子や電子ペーパー、メモリ材料などへの応用が期待でき、近未来の高機能分子デバイス開発研究において重要な知見を与えるものと考えられる。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (42 results)

All 2020 2019 2018 2017 Other

All Int'l Joint Research (3 results) Journal Article (18 results) (of which Int'l Joint Research: 16 results,  Peer Reviewed: 18 results,  Open Access: 2 results) Presentation (19 results) Remarks (2 results)

  • [Int'l Joint Research] Nottingham大学(英国)

    • Related Report
      2018 Research-status Report
  • [Int'l Joint Research] Hannover大学(ドイツ)

    • Related Report
      2018 Research-status Report
  • [Int'l Joint Research] University of Nottingham/University of Glasgow(英国)

    • Related Report
      2017 Research-status Report
  • [Journal Article] Synthesis of novel Cl2Co4L6 clusterusing 1-hydroxymethyl-3,5-dimethylpyrazole (LH) ligand: Crystal structure, spectral, thermal, Hirschfeld surface analysis and catalytic oxidation evaluation2020

    • Author(s)
      Titi Abderrahim、Shiga Takuya、Oshio Hiroki、Touzani Rachid、Hammouti Belkheir、Mouslim Messali、Warad Ismail
    • Journal Title

      Journal of Molecular Structure

      Volume: 1199 Pages: 126995-126995

    • DOI

      10.1016/j.molstruc.2019.126995

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis, characterization, X-Ray crystal study and bioctivities of pyrazole derivatives: Identification of antitumor, antifungal and antibacterial pharmacophore sites2020

    • Author(s)
      Titi Abderrahim、Messali Mouslim、Alqurashy Bakhet A.、Touzani Rachid、Shiga Takuya、Oshio Hiroki、Fettouhi Mohammed、Rajabi Mehdi、Almalki Faisal A.、Ben Hadda Taibi
    • Journal Title

      Journal of Molecular Structure

      Volume: 1205 Pages: 127625-127625

    • DOI

      10.1016/j.molstruc.2019.127625

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Heteroleptic Iron(II) Complexes with Naphthoquinone-Type Ligands2020

    • Author(s)
      Takuya Shiga,* Rina Kumamaru, Graham N. Newton, Hiroki Oshio
    • Journal Title

      Dalton Trans.

      Volume: 49 Issue: 5 Pages: 1485-1491

    • DOI

      10.1039/c9dt03946e

    • NAID

      120007132599

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Ferromagnetically Coupled Octanuclear Manganese(III) Cluster: A Single-Molecule Magnet with a Spin Ground State of S = 16”2020

    • Author(s)
      Takuya Shiga,* Hiroyuki Nojiri, Hiroki Oshio
    • Journal Title

      Inorg. Chem.

      Volume: 59 Issue: 7 Pages: 4163-4166

    • DOI

      10.1021/acs.inorgchem.9b03343

    • NAID

      120007132598

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Spin crossover behavior of a tetranuclear iron(II) grid complex with a hydroxyl-group functionalized multidentate ligand2019

    • Author(s)
      Shiga Takuya、Ishikawa Daisuke、Tachibana Minami、Saiki Ryo、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Journal of Magnetism and Magnetic Materials

      Volume: 485 Pages: 16-20

    • DOI

      10.1016/j.jmmm.2019.03.101

    • NAID

      120007133435

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A triple-triangle cluster derived from a simple tridentate ligand2019

    • Author(s)
      Shiga Takuya、Okawa Natsumi、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 47 Pages: 17437-17440

    • DOI

      10.1039/c9dt03232k

    • NAID

      120007132600

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structure Switching and Modulation of the Magnetic Properties in Diarylethene-Bridged Metallosupramolecular Compounds by Controlled Coordination-Driven Self-Assembly2019

    • Author(s)
      Li Zhao-Yang、Dai Jing-Wei、Damjanovic Marko、Shiga Takuya、Wang Jin-Hua、Zhao Jia、Oshio Hiroki、Yamashita Masahiro、Bu Xian-He
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 13 Pages: 4339-4344

    • DOI

      10.1002/anie.201900789

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Substituent dependence on the spin crossover behaviour of mononuclear Fe(ii) complexes with asymmetric tridentate ligands2019

    • Author(s)
      Saiki Ryo、Miyamoto Haruka、Sagayama Hajime、Kumai Reiji、Newton Graham N.、Shiga Takuya、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 10 Pages: 3231-3236

    • DOI

      10.1039/c9dt00204a

    • NAID

      120007133433

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Bronsted-Ligand-Based Iron Complex as a Molecular Switch with Five Accessible States2019

    • Author(s)
      Shiga Takuya、Saiki Ryo、Akiyama Lisa、Kumai Reiji、Natke Dominik、Renz Franz、Cameron Jamie M.、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 58 Issue: 17 Pages: 5658-5662

    • DOI

      10.1002/anie.201900909

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Intermediate-Spin Iron(III) Complexes Having a Redox-Noninnocent Macrocyclic Tetraamido Ligand2018

    • Author(s)
      Kojima Takahiko、Ogishima Fumiya、Nishibu Takahisa、Kotani Hiroaki、Ishizuka Tomoya、Okajima Toshihiro、Nozawa Shunsuke、Shiota Yoshihito、Yoshizawa Kazunari、Ohtsu Hiroyoshi、Kawano Masaki、Shiga Takuya、Oshio Hiroki
    • Journal Title

      Inorganic Chemistry

      Volume: NA Issue: 16 Pages: 9683-9695

    • DOI

      10.1021/acs.inorgchem.8b00037

    • Related Report
      2018 Research-status Report 2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Pre-programmed self-assembly of polynuclear clusters2018

    • Author(s)
      Shiga Takuya、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 22 Pages: 7384-7394

    • DOI

      10.1039/c8dt00822a

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Cobalt complexes with redox-active anthraquinone-type ligands2018

    • Author(s)
      Shiga Takuya、Kumamaru Rina、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 23 Pages: 7804-7811

    • DOI

      10.1039/c8dt00586a

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Two-electron redox-active tricyano iron(ii) complex with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine as a building block for coordination polymers2018

    • Author(s)
      Shiga Takuya、Miyamoto Haruka、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 38 Pages: 13402-13407

    • DOI

      10.1039/c8dt02315h

    • NAID

      120007133434

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Carboxylic Acid Functionalized Spin-Crossover Iron(II) Grids for Tunable Switching and Hybrid Electrode Fabrication2018

    • Author(s)
      Shiga Takuya、Sato Yamato、Tachibana Minami、Sato Hiroki、Matsumoto Takuto、Sagayama Hajime、Kumai Reiji、Murakami Youichi、Newton Graham N.、Oshio Hiroki
    • Journal Title

      Inorganic Chemistry

      Volume: 57 Issue: 22 Pages: 14013-14017

    • DOI

      10.1021/acs.inorgchem.8b01856

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Ferrihydrite Particle Encapsulated within a Molecular Organic Cage2018

    • Author(s)
      Nihei Masayuki、Ida Hiromichi、Nibe Takayuki、Moeljadi Adhitya Mangala Putra、Trinh Quang Thang、Hirao Hajime、Ishizaki Manabu、Kurihara Masato、Shiga Takuya、Oshio Hiroki
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 50 Pages: 17753-17759

    • DOI

      10.1021/jacs.8b10957

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] An Antiferromagnetically Coupled Heterometal Cu6Fe Wheel2017

    • Author(s)
      Saiki Ryo、Yoshida Norifumi、Hoshino Norihisa、Newton Graham N.、Shiga Takuya、Oshio Hiroki
    • Journal Title

      Chem. Lett.

      Volume: 46 Issue: 8 Pages: 1197-1199

    • DOI

      10.1246/cl.170365

    • NAID

      130005906975

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis, Crystal Structures and Magnetic Properties of Composites Incorporating an Fe(II) Spin Crossover Complex and Polyoxometalates2017

    • Author(s)
      Kuramochi Satoshi、Shiga Takuya、Cameron Jamie、Newton Graham、Oshio Hiroki
    • Journal Title

      Inorganics

      Volume: 5 Issue: 3 Pages: 48-48

    • DOI

      10.3390/inorganics5030048

    • NAID

      120007134730

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Ligand-directed synthesis of {MnIII5} twisted bow-ties2017

    • Author(s)
      Maria Jose Heras Ojea、Moya A. Hay、Giacomo Cioncoloni、Gavin A. Craig、Claire Wilson、Takuya Shiga、Hiroki Oshio、Mark D. Symes、 Mark Murrie
    • Journal Title

      Dalton Trans.

      Volume: 46 Issue: 34 Pages: 11201-11207

    • DOI

      10.1039/c7dt02430d

    • NAID

      120007134866

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Self-assembly of polynuclear clusters with rigid multidentate bridging ligands2020

    • Author(s)
      Takuya Shiga, Graham N. Newton, and Hiroki Oshio
    • Organizer
      The 1st Asian Conference on Molecular Magnetism (ACMM 2020)
    • Related Report
      2019 Annual Research Report
  • [Presentation] グリッド型スピン平衡錯体の集積化を目指した新規鉄錯体の合成と物性2018

    • Author(s)
      立花 美奈水、志賀 拓也、大塩 寛紀
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Spin Crossover Iron(II) Grid Complexes2018

    • Author(s)
      Takuya SHIGA, Hiroki OSHIO
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Research-status Report
  • [Presentation] Multi-Response Bistability in Chiral Metal Complexes2018

    • Author(s)
      Rong-Jia Wei, Takuya Shiga, Hiroki Oshio
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Research-status Report
  • [Presentation] Electronic state conversions of iron complexes with Bronsted acid and base2018

    • Author(s)
      Ryo SAIKI, Lisa AKIYAMA, Takuya SHIGA, Franz RENZ, Hiroki OSHIO
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Research-status Report
  • [Presentation] A redox-active tricyano iron(II) complex with 2,4,6-tris(2-pyrimidyl)-1,3,5-triazine as a building block for coordination polymers2018

    • Author(s)
      Haruka MIYAMOTO, Takuya SHIGA, Graham N. NEWTON, Hiroki OSHIO
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Research-status Report
  • [Presentation] Spin crossover iron complexes with Bronsted acid/base2018

    • Author(s)
      Ryo SAIKI, Haruka MIYAMOTO, Takuya SHIGA, Hiroki OSHIO
    • Organizer
      第98日本化学会春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 酸性プロトンをもつスピン平衡鉄(II)錯体の電子状態に関する研究2017

    • Author(s)
      大川 夏実、志賀 拓也、大塩 寛紀
    • Organizer
      2017日本放射化学会年会 第61回放射化学会討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] ブレンステッド酸配位子を持つ鉄錯体の脱プロトンによる電子状態制御2017

    • Author(s)
      佐伯 亮、秋山 リサ、志賀 拓也、大塩 寛紀
    • Organizer
      2017日本放射化学会年会 第61回放射化学会討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 有機ナノケージ分子に包接されたフェリハイドライト粒子の合成2017

    • Author(s)
      仁部 孝行、井田 博道、二瓶 雅之、志賀 拓也、大塩 寛紀
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Electronic state conversions of iron complexes with Bronsted acid and base2017

    • Author(s)
      Ryo Saiki, Lisa Akiyama, Takuya Shiga, Hiroki Oshio
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Self-assembly of heterometallic coordination cages based on a tripodic metalloligand2017

    • Author(s)
      Xiaoli Lin, Rong-Jia Wei, Takuya Shiga, Hiroki Oshio
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] メリディオナルな配位様式をもつトリシアノ錯体の合成と集積化2017

    • Author(s)
      宮本 晴佳、佐伯 亮、志賀 拓也、大塩 寛紀
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] プロトン応答性を持つシアン化物イオン架橋多核錯体に関する研究2017

    • Author(s)
      中原 涼平、WEI Rong-Jia、志賀 拓也、大塩 寛紀
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] A Cyanide-bridged Hexagonal Prism [FeCo] Cage with an Encapsulated DABCO Molecule2017

    • Author(s)
      Rong-Jia Wei, Takuya Shiga, Hiroki Oshio
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] オキソ架橋鉄二核錯体の磁気的相互作用に関する研究2017

    • Author(s)
      立花 美奈水、添田 皓輝、志賀 拓也、大塩 寛紀
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 二塩基酸三座配位子をもつスピン平衡鉄(II)錯体の電子状態に関する研究2017

    • Author(s)
      大川 夏実、志賀 拓也、大塩 寛紀
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] メリディオナルな配位様式をもつトリシアノ錯体の合成と集積化2017

    • Author(s)
      宮本 晴佳、佐伯 亮、志賀 拓也、大塩 寛紀
    • Organizer
      「第3回TIA光・量子計測シンポジウム」光・量子が繋ぐTIA計測連携 ~新しい科学と産業の創成をめざして~
    • Related Report
      2017 Research-status Report
  • [Presentation] オキソ架橋鉄二核錯体の磁気的相互作用に関する研究2017

    • Author(s)
      立花 美奈水、添田 皓輝、志賀 拓也、大塩 寛紀
    • Organizer
      「第3回TIA光・量子計測シンポジウム」光・量子が繋ぐTIA計測連携 ~新しい科学と産業の創成をめざして~
    • Related Report
      2017 Research-status Report
  • [Remarks] 筑波大学 大学院数理物質科学研究科 化学専攻 無機合成化学研究室 (二瓶研究室)

    • URL

      http://www.chem.tsukuba.ac.jp/~nihei_lab/

    • Related Report
      2019 Annual Research Report
  • [Remarks] 筑波大学大学院数理物質科学研究科 錯体分子化学(大塩)研究室

    • URL

      http://www.chem.tsukuba.ac.jp/~oshio_lab/index.html

    • Related Report
      2017 Research-status Report

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Published: 2017-04-28   Modified: 2021-02-19  

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