Temperature dependence of spherical electron transfer in a nanosized [Fe14] complex

Wei Huang; Shuqi Wu; Xiangwei Gu; Yao Li; Atsushi Okazawa; Norimichi Kojima; Shinya Hayami; Michael L Baker; Peter Bencok; Mariko Noguchi; Yuji Miyazaki; Motohiro Nakano; Takumi Nakanishi; Shinji Kanegawa; Yuji Inagaki; Tatsuya Kawae; Gui-Lin Zhuang; Yoshihito Shiota; Kazunari Yoshizawa; Dayu Wu; Osamu Sato

doi:10.1038/s41467-019-13279-y

Temperature dependence of spherical electron transfer in a nanosized [Fe₁₄] complex

Nat Commun. 2019 Dec 3;10(1):5510. doi: 10.1038/s41467-019-13279-y.

Authors

Wei Huang¹, Shuqi Wu², Xiangwei Gu¹, Yao Li¹, Atsushi Okazawa³, Norimichi Kojima⁴, Shinya Hayami⁵, Michael L Baker^{6

7}, Peter Bencok⁸, Mariko Noguchi^{9

10}, Yuji Miyazaki⁹, Motohiro Nakano⁹, Takumi Nakanishi², Shinji Kanegawa², Yuji Inagaki¹¹, Tatsuya Kawae¹¹, Gui-Lin Zhuang¹², Yoshihito Shiota², Kazunari Yoshizawa², Dayu Wu¹³, Osamu Sato¹⁴

Affiliations

¹ Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis & Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou, 213164, China.
² Institute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
³ Department of Basic Science, Graduation School of Arts and Sciences, The University of Tokyo, 3-8-1 Komaba, Meguro-ku, Tokyo, 153-8902, Japan.
⁴ Toyota Physical and Chemical Research Institute, Yokomichi, Nagakute, Aichi, 480-1192, Japan.
⁵ Department of Chemistry, Graduate School of Science and Technology and Institute of Pulsed Power Science (IPPS), Kumamoto University, 2-39-1 Kurokami, Chuo-ku, Kumamoto, 860-8555, Japan.
⁶ The School of Chemistry, The University of Manchester, Manchester, M13 9PL, UK.
⁷ The School of Chemistry, The University of Manchester at Harwell, Didcot, OX11 0FA, UK.
⁸ Diamond Light Source, Science Division, Didcot, OX11 0DE, UK.
⁹ Research Center for Structural Thermodynamics, Graduate School of Science, Osaka University, Toyonaka, Osaka, 560-0043, Japan.
¹⁰ Department of Chemistry, College of Humanities and Sciences, Nihon University, 3-25-40 Sakurajosui, Setagaya-ku, Tokyo, 156-8550, Japan.
¹¹ Department of Applied Quantum Physics, Faculty of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan.
¹² Institute of Industrial Catalysis, College of Chemical Engineering, State Key Lab Breeding Base of Green-Chemical Synthesis Technology, Zhejiang University of Technology, Hangzhou, 310032, China.
¹³ Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology, Advanced Catalysis & Green Manufacturing Collaborative Innovation Center, School of Petrochemical Engineering, Changzhou University, Changzhou, 213164, China. wudy@cczu.edu.cn.
¹⁴ Institute for Materials Chemistry and Engineering & IRCCS, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, 819-0395, Japan. sato@cm.kyushu-u.ac.jp.

Abstract

The study of transition metal clusters exhibiting fast electron hopping or delocalization remains challenging, because intermetallic communications mediated through bridging ligands are normally weak. Herein, we report the synthesis of a nanosized complex, [Fe(Tp)(CN)₃]₈[Fe(H₂O)(DMSO)]₆ (abbreviated as [Fe₁₄], Tp^-, hydrotris(pyrazolyl)borate; DMSO, dimethyl sulfoxide), which has a fluctuating valence due to two mobile d-electrons in its atomic layer shell. The rate of electron transfer of [Fe₁₄] complex demonstrates the Arrhenius-type temperature dependence in the nanosized spheric surface, wherein high-spin centers are ferromagnetically coupled, producing an S = 14 ground state. The electron-hopping rate at room temperature is faster than the time scale of Mössbauer measurements (<~10^-8 s). Partial reduction of N-terminal high spin Fe^III sites and electron mediation ability of CN ligands lead to the observation of both an extensive electron transfer and magnetic coupling properties in a precisely atomic layered shell structure of a nanosized [Fe₁₄] complex.

Publication types

Research Support, Non-U.S. Gov't