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 Baker; Myron Huzan; Peter Bencok; Tsukasa Abe; Yoshihito Shiota; Kazunari Yoshizawa; Wenhuang Xu; Hui-Zhong Kou; Osamu Sato

doi:10.1038/s41467-020-15988-1

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 Baker, Myron Huzan, Peter Bencok, Tsukasa Abe, Yoshihito Shiota, Kazunari Yoshizawa, Wenhuang Xu, Hui-Zhong Kou, Osamu Sato

Research output: Contribution to journal › Article › peer-review

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 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.

Original language	English
Journal	Nature Communications
DOIs	https://doi.org/10.1038/s41467-020-15988-1
Publication status	Published - 24 Apr 2020

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10.1038/s41467-020-15988-1

UoMaH: The University of Manchester at Harwell
Lawrence, J. (PI), Burnett, T. (PI), Baker, M. (Researcher), Eastwood, D. (Researcher), Falkowska, M. (Researcher), Freitas, D. (Researcher), Hunt, S. (Researcher), Khan, A. (Researcher), Lane, H. (Researcher), Lezcano Gonzalez, I. (Researcher), Ma, L. (Researcher), Mirihanage, W. (Researcher), Parlett, C. (Researcher), Xu, S. (Researcher), Yan, K. (Researcher), Reinhard, C. (Support team), Duggins, D. (Technical team), Lewis-Fell, J. (Technical team), Nonni, S. (Technical team), Rollings, B. (Technical team), Sinclair, L. (Technical team) & Batts, S. (Support team)
1/01/18 → …
Project: Other

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@article{6cf0de10896c45caae17a2db72548132,

title = "Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex",

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 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. ",

author = "Shu-Qi Wu and Meijiao Liu and Kaige Gao and Shinji Kanegawa and Yusuke Horie and Genki Aoyama and Hajime Okajima and Akira Sakamoto and Michael Baker and Myron Huzan and Peter Bencok and Tsukasa Abe and Yoshihito Shiota and Kazunari Yoshizawa and Wenhuang Xu and Hui-Zhong Kou and Osamu Sato",

year = "2020",

month = apr,

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doi = "10.1038/s41467-020-15988-1",

language = "English",

journal = "Nature Communications",

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publisher = "Nature Research",

}

TY - JOUR

T1 - Macroscopic Polarization Change via Electron Transfer in a Valence Tautomeric Cobalt Complex

AU - Wu, Shu-Qi

AU - Liu, Meijiao

AU - Gao, Kaige

AU - Kanegawa, Shinji

AU - Horie, Yusuke

AU - Aoyama, Genki

AU - Okajima, Hajime

AU - Sakamoto, Akira

AU - Baker, Michael

AU - Huzan, Myron

AU - Bencok, Peter

AU - Abe, Tsukasa

AU - Shiota, Yoshihito

AU - Yoshizawa, Kazunari

AU - Xu, Wenhuang

AU - Kou, Hui-Zhong

AU - Sato, Osamu

PY - 2020/4/24

Y1 - 2020/4/24

N2 - 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 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.

AB - 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 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.

U2 - 10.1038/s41467-020-15988-1

DO - 10.1038/s41467-020-15988-1

M3 - Article

SN - 2041-1723

JO - Nature Communications

JF - Nature Communications

ER -

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

Abstract

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UoMaH: The University of Manchester at Harwell

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