九州大学-研究者情報 [金川慎治 (助教) 先導物質化学研究所物質基盤化学部門]

1.	P. Sadhukhan, S. Q. Wu, S. Kanegawa, S. Q. Su, X. P. Zhang, T. Nakanishi, J. I. Long, K. G. Gao, R. Shimada, H. Okajima, A. Sakamoto, J. G. Chiappella, M. S. Huzan,T. Kroll, D. Sokaras, M. L. Baker, O. Sato, Energy conversion and storage via photoinduced polarization change in non-ferroelectric molecular [CoGa] crystals, NATURE COMMUNICATIONS, 10.1038/s41467-023-39127-8, 14, 1, 3394, 2023.06, To alleviate the energy and environmental crisis, in the last decades, energy harvesting by utilizing optical control has emerged as a promising solution. Here we report a polar crystal that exhibits photoenergy conversion and energy storage upon light irradiation. The polar crystal consists of dinuclear [CoGa] molecules, which are oriented in a uniform direction inside the crystal lattice. Irradiation with green light induces a directional intramolecular electron transfer from the ligand to a low-spin Co-III centre, and the resultant light-induced high-spin Co-II excited state is trapped at low temperature, realizing energy storage. Additionally, electric current release is observed during relaxation from the trapped light-induced metastable state to the ground state, because the intramolecular electron transfer in the relaxation process is accompanied with macroscopic polarization switching at the single-crystal level. It demonstrates that energy storage and conversion to electrical energy is realized in the [CoGa] crystals, which is different from typical polar pyroelectric compounds that exhibit the conversion of thermal energy into electricity. Energy harvesting by utilizing optical control has emerged as a promising solution to alleviate energy and environmental crisis. However, it is challenging to realise nano-scale energy storage and conversion in the same material. Here the authors report a nonferroelectric molecular [CoGa] crystal that uses light as an external stimulus to exhibit photoenergy conversion and energy storage properties..
2.	Sadhukhan, Pritam; Wu, Shu-Qi; Long, Jeremy Ian; Nakanishi, Takumi; Kanegawa, Shinji; Gao, Kaige; Yamamoto, Kaoru; Okajima, Hajime; Sakamoto, Akira; Baker, Michael L.; Kroll, Thomas; Sokaras, Dimosthenis; Okazawa, Atsushi; Kojima, Norimichi; Shiota, Yoshihito; Yoshizawa, Kazunari; Sato, Osamu, Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals, NATURE COMMUNICATIONS, 10.1038/s41467-021-25041-4, 12, 1, 2021.08.
3.	Shu Qi Wu, Meijiao Liu, Kaige Gao, Shinji Kanegawa, Yusuke Horie, Genki Aoyama, Hajime Okajima, Akira Sakamoto, Michael L. Baker, Myron S. Huzan, Peter Bencok, Tsukasa Abe, Yoshihito Shiota, Kazunari Yoshizawa, Wenhuang Xu, Hui Zhong Kou, Osamu Sato, Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex, Nature communications, 10.1038/s41467-020-15988-1, 11, 1, 2020.12, [URL], Polarization change induced by directional electron transfer attracts considerable attention owing to its fast switching rate and potential light control. Here, we investigate electronic pyroelectricity in the crystal of a mononuclear complex, [Co(phendiox)(rac-cth)](ClO<sub>4</sub>)·0.5EtOH (1·0.5EtOH, H<sub>2</sub>phendiox = 9, 10-dihydroxyphenanthrene, rac-cth = racemic 5, 5, 7, 12, 12, 14-hexamethyl-1, 4, 8, 11-tetraazacyclotetradecane), which undergoes a two-step valence tautomerism (VT). Correspondingly, pyroelectric current exhibits double peaks in the same temperature domain with the polarization change consistent with the change in dipole moments during the VT process. Time-resolved Infrared (IR) spectroscopy shows that the photo-induced metastable state can be generated within 150 ps at 190 K. Such state can be trapped for tens of minutes at 7 K, showing that photo-induced polarization change can be realized in this system. These results directly demonstrate that a change in the molecular dipole moments induced by intramolecular electron transfer can introduce a macroscopic polarization change in VT compounds..
4.	金川慎治, 塩田淑仁, KANG SOONCHUL, Takahashi, Kazuyuki, Okajima, Hajime, Sakamoto, Akira, Iwata, Tatsuya, Kandori, Hideki, 吉澤一成, 佐藤治, Directional Electron Transfer in Crystals of [CrCo] Dinuclear Complexes Achieved by Chirality-Assisted Preparative Method, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 10.1021/jacs.6b05089, 138, 43, 14170-14173, 2016.11.
5.	Li, Guo-Ling, 金川慎治, Yao, Zi-Shuo, Su, Sheng-Qun, Wu, Shu-Qi, Huang, You-Gui, KANG SOONCHUL, 佐藤治, Influence of Intermolecular Interactions on Valence Tautomeric Behaviors in Two Polymorphic Dinuclear Cobalt Complexes, CHEMISTRY-A EUROPEAN JOURNAL, 10.1002/chem.201603817, 22, 48, 17130-17135, 2016.11.
6.	Shinji Kanegawa, KANG SOONCHUL, Osamu Sato, Preparation and Valence Tautomeric Behavior of a Cobalt-Dioxolene Complex with a New TTF-functionalized Phenanthroline Ligand, CHEMISTRY LETTERS, 10.1246/cl.130118, 42, 7, 700-702, 2013.07.
7.	Liu, T; Zhang, YJ; Kanegawa, S; Sato, O, Photoinduced Metal-to-Metal Charge Transfer toward Single-Chain Magnet, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 10.1021/ja1027953, 132, 24, 8250, 2010.06.
8.	Shinji Kanegawa, Satoru Karasawa, Masataka Maeyama, Motohiro Nakano, and Noboru Koga, Crystal Design of Monometallic Single-Molecule Magnets Consisting of Cobalt-Aminoxyl Heterospins, Journal of the American Chemical Society, 10.1021/ja0767579, 130, 10, 3079-3094, 2008.03.

主要学会発表等

全てを見る→

1.	金川慎治・佐藤　治, 酸化還元能を有する架橋型配位子を用いたコバルト複核錯体の構造及び磁気挙動, 錯体化学討論会, 2009.09.
2.	S. Kanegawa, S. Karasawa and N. Koga, Preparation of N,N-bis(4-pyridyl)aminoxyl as a Nobel Bridging Ligand Carrying Organic Radical, and Formation of 1D- and 2D- Coordination Polymers in Co(II)-Aminoxyl Heterospin System, The 11th International Conference on Molecule-based Magnets, 2008.09.

学会活動

所属学会名

分子科学会

光化学協会

錯体化学会

アメリカ化学会

日本化学会

学会大会・会議・シンポジウム等における役割

2018.09.10～2018.09.13, 第12回分子科学討論会2018, 講演座長.

2013.03.22～2013.03.25, 日本化学会第93春季年会(2013), 座長（Chairmanship）.

2012.03.25～2012.03.28, 日本化学会第92春季年会(2012), 座長（Chairmanship）.

2010.03～2010.03, 日本化学会第９０回春季年会, 座長（Chairmanship）.

学術論文等の審査

年度	外国語雑誌査読論文数	合計
2022年度	1	1
2021年度	1	1
2017年度	2	2
2015年度	1	1

研究資金

科学研究費補助金の採択状況(文部科学省、日本学術振興会)

2021年度～2023年度, 基盤研究(C), 代表, 分子内電子移動を起源とする新機構焦電・強誘電物質の開発と特性解明.

2015年度～2017年度, 基盤研究(C), 代表, ラセミ化で駆動する新合成戦略を用いた系統的・網羅的な新奇機能性錯体開発.

2015年度～2016年度, 新学術領域研究（研究領域提案型）, 代表, 外場による協同的磁性-電導性物性変換を示す新規ハイブリッド分子材料の研究.

2013年度～2014年度, 新学術領域研究, 代表, ダイナミックな複合的電子物性変換を示す新規機能性錯体分子の開発.

2011年度～2013年度, 若手研究(B), 代表, 原子価互変異性現象を用いた分子性磁性・誘電体の研究.

九大関連コンテンツ

pure2017年10月2日から、「九州大学研究者情報」を補完するデータベースとして、Elsevier社の「Pure」による研究業績の公開を開始しました。

QIR　九州大学学術情報リポジトリシステム情報科学研究院

先導物質化学研究所


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