Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex

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 and Osamu Sato ()
Additional contact information
Shu-Qi Wu: Kyushu University
Meijiao Liu: Kyushu University
Kaige Gao: Kyushu University
Shinji Kanegawa: Kyushu University
Yusuke Horie: Aoyama Gakuin University
Genki Aoyama: Aoyama Gakuin University
Hajime Okajima: Aoyama Gakuin University
Akira Sakamoto: Aoyama Gakuin University
Michael L. Baker: The University of Manchester
Myron S. Huzan: The University of Manchester
Peter Bencok: Diamond Light Source
Tsukasa Abe: Kyushu University
Yoshihito Shiota: Kyushu University
Kazunari Yoshizawa: Kyushu University
Wenhuang Xu: Kyushu University
Hui-Zhong Kou: Tsinghua University
Osamu Sato: Kyushu University

Nature Communications, 2020, vol. 11, issue 1, 1-8

Abstract: Abstract 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)](ClO4)·0.5EtOH (1·0.5EtOH, H2phendiox = 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.

Date: 2020
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DOI: 10.1038/s41467-020-15988-1

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