• 研究課題をさがす
  • 研究者をさがす
  • KAKENの使い方
  1. 課題ページに戻る

2017 年度 実績報告書

酸化還元活性な錯体格子の開発とホストーゲスト相互作用による物性制御

研究課題

研究課題/領域番号 17J02497
研究機関東北大学

研究代表者

張 俊  東北大学, 理学研究科, 特別研究員(DC1)

研究期間 (年度) 2017-04-26 – 2020-03-31
キーワードmagnetic sponge / Curie temperature (Tc) / electronic state
研究実績の概要

A reversible magnetic change induced by guest molecules is desirable in the fields of both metal-organic frameworks/porous coordination polymers(MOFs/PCPs) and molecule-based magnets. The magnetic sponge behavior via electronic state modulations was achieved in a new D2A-type-layered magnet,[{Ru2(O2CPh-2,3,5-Cl3)4}2(TCNQMe2)]-4DCM (1; 2,3,5-Cl3PhCO2- = 2,3,5-trichlorobenzoate; TCNQMe2 = 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, DCM = dichloromethane), where [Ru2(O2CPh-2,3,5-Cl3)4] ([Ru2II,II]) is an electron-donor (D) and TCNQMe2 is an electron-acceptor (A). Compound 1 had a 1e-I state. Strong intra-layer antiferromagnetic couplings between [Ru2] and TCNQMe2, as well as ferromagnetic interlayer interactions, induced long-range ferrimagnetic ordering at Tc = 101 K. Interstitial DCM molecules were located between layers, and these were gradually eliminated under vacuum at 80 °C to form a solvent-free compound (1-dry) without loss of crystallinity. The electronic state of 1-dry thermally fluctuated and eventually provided a charge-disproportionate disordered state, 1.5e-I. The Tc in 1-dry was 34 K. A large Tc variation with about 70 K was switchable; switching was achieved by charge state modulations accompanied with subtle structural modifications in solvation/desolvation treatments.

現在までの達成度 (区分)
現在までの達成度 (区分)

1: 当初の計画以上に進展している

理由

My research plan is to realize deliberate control of the physical properties such as magnetism and electrical conductivity via guest molecule sorption. Last year, the first compound 1 was synthesized. It showed large Tc variation with about 70 K, which was achieved by charge state modulations accompanied with subtle structural modifications in solvation/desolvation treatments. This is just one example of magnetic sponges, for which the magnetic properties were tuned by solvation/desolvation. Additionally, other compounds were also be prepared. The magnetic phase could be controlled by solvent or a simple, ubiquitous gas such as O2, N2, and CO2. This work is now under way.

今後の研究の推進方策

Electronic-state-sensitive, porous materials are a new class of functional porous materials. Previously, we found examples of magnetic sponges, for which the magnetic properties were tuned by charge state modulations accompanied with subtle structural modifications in solvation/ desolvation treatments. Next, we'd like to focus the guest molecule on a simple, ubiquitous gas such as O2, N2, and CO2 to control the magnetic phase. Because gas molecules are relatively small compared with solvent. So, they are easy to handle. And MOFs always show gate-opening behavior for different gas molecules, which is propitious to adjust physical properties. Besides, the paramagnetic O2 could adjust the inter-layer magnetic interaction in two-dimensional frameworks.

  • 研究成果

    (6件)

すべて 2018 2017

すべて 雑誌論文 (1件) (うち国際共著 1件、 査読あり 1件) 学会発表 (5件) (うち国際学会 1件)

  • [雑誌論文] Magnetic Sponge Behavior via Electronic State Modulations2018

    • 著者名/発表者名
      Jun Zhang, Wataru Kosaka, Kunihisa Sugimoto, and Hitoshi Miyasaka
    • 雑誌名

      Journal of the American Chemical Society

      巻: 140 ページ: 5644-5652

    • DOI

      10.1021/jacs.8b02428

    • 査読あり / 国際共著
  • [学会発表] Magnetic Sponge Behavior via Electronic State Modulations in a Redox-Active [Ru2]2TCNQ Coordination Framework2018

    • 著者名/発表者名
      Jun Zhang
    • 学会等名
      日本化学会第98春季年会
  • [学会発表] Gas Adsorption-Induced Magnetic Modification in a Porous Donor-Acceptor Metal-Organic Framework.2017

    • 著者名/発表者名
      Jun Zhang
    • 学会等名
      第133回東北大学金属材料研究所講演会
  • [学会発表] CO2 Adsorption-Induced Tc switching in a Layered Ferrimagnet Composed of Paddlewheel [Ru2] Units and TCNQ.2017

    • 著者名/発表者名
      Jun Zhang
    • 学会等名
      第2回固体化学フォーラム研究会
  • [学会発表] Solvent-Triggered Electronic State Modulation in a Layered Ferrimagnet Composed of Paddlewheel [Ru2] Units and TCNQ2017

    • 著者名/発表者名
      Jun Zhang
    • 学会等名
      The 6th Asian Conference on Coordination Chemistry
    • 国際学会
  • [学会発表] Magnetic phase control based on gas-induced perturbations in a charge-variable layered magnet composed of paddlewheel-type Ru dimers and TCNQ2017

    • 著者名/発表者名
      Jun Zhang
    • 学会等名
      第67回錯体化学会討論会

URL: 

公開日: 2018-12-17  

サービス概要 検索マニュアル よくある質問 お知らせ 利用規程 科研費による研究の帰属

Powered by NII kakenhi