Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex
Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex
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DOI：
10.1038/s41467-020-15988-1
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发表时间：
2020-04
影响因子：
16.6
通讯作者：
Shu-Qi Wu;Meijiao Liu;K. Gao;Shinji Kanegawa;Yusuke Horie;Genki Aoyama;Hajime Okajima;A. Sakamoto;M. Baker;M. Huzan;P. Bencok;Tsukasa Abe;Y. Shiota;K. Yoshizawa;Wenhuang Xu;H. Kou;O. Sato
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文献类型：
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作者：
Shu-Qi Wu;Meijiao Liu;K. Gao;Shinji Kanegawa;Yusuke Horie;Genki Aoyama;Hajime Okajima;A. Sakamoto;M. Baker;M. Huzan;P. Bencok;Tsukasa Abe;Y. Shiota;K. Yoshizawa;Wenhuang Xu;H. Kou;O. Sato
定向电子转移引起的极化变化由于其快速的开关速率和潜在的光控制能力而受到人们的广泛关注。本文研究了单核配合物[Co（phendiox）（rac-cth）]（ClO 4）·0.5EtOH（1·0.5EtOH，H2 phendiox = 9，10-二羟基菲，rac-cth =外消旋5，5，7，12，12，14-六甲基-1，4，8，11-四氮杂环十四烷）晶体中的电子热释电性，该配合物经历了两步价态互变异构（VT）。相应地，热释电电流在相同的温度范围内呈现双峰，极化变化与VT过程中的偶极矩变化一致。时间分辨红外光谱表明，在190 K时，在150 ps内可以产生光诱导亚稳态。在7 K下，这种态可以被捕获几十分钟，表明在该系统中可以实现光致偏振变化。这些结果直接表明，分子内电子转移引起的分子偶极矩的变化可以在VT化合物中引入宏观极化变化。
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.