Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex

Paul Raithby; Ludmila Leroy; Thiago Francisco; Helena Shepherd; Mark Warren; Lucy Saunders; David Shultz; Carlos Pinheiro

doi:10.1021/acs.inorgchem.1c00638

Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex

Paul Raithby, Ludmila Leroy, Thiago Francisco, Helena Shepherd, Mark Warren, Lucy Saunders, David Shultz, Carlos Pinheiro

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Abstract

The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine is a very versatile compound that displays valence tautomerism (VT) in the solid-state which is induced by temperature, light and hard X-rays and modulated by solvent in the crystal lattice. Here, we demonstrate the photo-induced valence tautomerism in benzene solvated crystals of such complex with a very high yield of metastable states using 450nm light, and also show evidence of the de-excitation of these photo-induced metastable states using red 660nm light. In our work we use single crystal X-ray diffraction as a probe for the VT and demonstrate the controlled use of hard X-rays using attenuated X-ray beams in order to control the X-ray induced VT interconversion. Our results point to a larger efficiency in the VT interconversion when d-d transitions are excited in comparison with charge transfer promotion.

Original language	English
Article number	ic-2021-006388
Pages (from-to)	8665–8671
Journal	Inorganic Chemistry
Volume	60
Issue number	12
Early online date	4 Jun 2021
DOIs	https://doi.org/10.1021/acs.inorgchem.1c00638
Publication status	Published - 21 Jun 2021

Bibliographical note

Funding Information:
This study was financed in part by Brazilian agencies Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) grant 432542/2018-3, Fundação de Amparo à Pesquisa de Minas Gerais (FAPEMIG) grant APQ-01939-16 and the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001; in part by the United Kingdom Engineering and Physical Sciences Research Council (EPSRC) grants EP/K004956, EP/I01974X and EP/K012576, Diamond Light Source Ltd, grant MT9635; and in part by United States National Science Foundation (NSF), grant CHE-1464085. CBP thanks CNPq for continued support. LL and TMF thank CAPES and CNPq for their scholarship. PRR is grateful to the Engineering and Physical Sciences Research Council (EPSRC) UK for continued support. We would also like to thank Dr. David Allan for providing access to beamline I19 and the Diamond Light Source Ltd for the support for the synchrotron experiment and Dr. Leonardo Calazans for support with Python scripts that recruit data reduction and structure refinement software.

Funding Information:
This study was financed in part by Brazilian agencies Conselho Nacional de Desenvolvimento Cienti?fico e Tecnolo?gico (CNPq) grant 432542/2018-3, Fundac?a?o de Amparo a? Pesquisa de Minas Gerais (FAPEMIG) grant APQ-01939-16 and the Coordenac?a?o de Aperfeic?oamento de Pessoal de Ni?vel Superior ? Brasil (CAPES) ? Finance Code 001; in part by the United Kingdom Engineering and Physical Sciences Research Council (EPSRC) grants EP/K004956, EP/I01974X and EP/K012576, Diamond Light Source Ltd, grant MT9635; and in part by United States National Science Foundation (NSF) grant CHE-1464085. CBP thanks CNPq for continued support. LL and TMF thank CAPES and CNPq for their scholarship. PRR is grateful to the Engineering and Physical Sciences Research Council (EPSRC) UK for continued support. We would also like to thank Dr. David Allan for providing access to beamline I19 and the Diamond Light Source Ltd for the support for the synchrotron experiment and Dr. Leonardo Calazans for support with Python scripts that recruit data reduction and structure refinement software.

Publisher Copyright:
© 2021 American Chemical Society.

Funding

This study was financed in part by Brazilian agencies Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) grant 432542/2018-3, Fundação de Amparo à Pesquisa de Minas Gerais (FAPEMIG) grant APQ-01939-16 and the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001; in part by the United Kingdom Engineering and Physical Sciences Research Council (EPSRC) grants EP/K004956, EP/I01974X and EP/K012576, Diamond Light Source Ltd, grant MT9635; and in part by United States National Science Foundation (NSF), grant CHE-1464085. CBP thanks CNPq for continued support. LL and TMF thank CAPES and CNPq for their scholarship. PRR is grateful to the Engineering and Physical Sciences Research Council (EPSRC) UK for continued support. We would also like to thank Dr. David Allan for providing access to beamline I19 and the Diamond Light Source Ltd for the support for the synchrotron experiment and Dr. Leonardo Calazans for support with Python scripts that recruit data reduction and structure refinement software.

Keywords

Valence tautomerism
Cobalt o-semiquinone
Single-crystal
X-ray diffraction

ASJC Scopus subject areas

Inorganic Chemistry
Spectroscopy

Access to Document

10.1021/acs.inorgchem.1c00638

Author Accepted Version Inorg Chem.PDF
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorg. Chem, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00638#
Accepted author manuscript, 552 KB

Cite this

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title = "Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex",

abstract = "The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine is a very versatile compound that displays valence tautomerism (VT) in the solid-state which is induced by temperature, light and hard X-rays and modulated by solvent in the crystal lattice. Here, we demonstrate the photo-induced valence tautomerism in benzene solvated crystals of such complex with a very high yield of metastable states using 450nm light, and also show evidence of the de-excitation of these photo-induced metastable states using red 660nm light. In our work we use single crystal X-ray diffraction as a probe for the VT and demonstrate the controlled use of hard X-rays using attenuated X-ray beams in order to control the X-ray induced VT interconversion. Our results point to a larger efficiency in the VT interconversion when d-d transitions are excited in comparison with charge transfer promotion.",

keywords = "Valence tautomerism, Cobalt o-semiquinone, Single-crystal, X-ray diffraction",

author = "Paul Raithby and Ludmila Leroy and Thiago Francisco and Helena Shepherd and Mark Warren and Lucy Saunders and David Shultz and Carlos Pinheiro",

note = "Funding Information: This study was financed in part by Brazilian agencies Conselho Nacional de Desenvolvimento Cient{\'i}fico e Tecnol{\'o}gico (CNPq) grant 432542/2018-3, Funda{\c c}{\~a}o de Amparo {\`a} Pesquisa de Minas Gerais (FAPEMIG) grant APQ-01939-16 and the Coordena{\c c}{\~a}o de Aperfei{\c c}oamento de Pessoal de N{\'i}vel Superior – Brasil (CAPES) – Finance Code 001; in part by the United Kingdom Engineering and Physical Sciences Research Council (EPSRC) grants EP/K004956, EP/I01974X and EP/K012576, Diamond Light Source Ltd, grant MT9635; and in part by United States National Science Foundation (NSF), grant CHE-1464085. CBP thanks CNPq for continued support. LL and TMF thank CAPES and CNPq for their scholarship. PRR is grateful to the Engineering and Physical Sciences Research Council (EPSRC) UK for continued support. We would also like to thank Dr. David Allan for providing access to beamline I19 and the Diamond Light Source Ltd for the support for the synchrotron experiment and Dr. Leonardo Calazans for support with Python scripts that recruit data reduction and structure refinement software. Funding Information: This study was financed in part by Brazilian agencies Conselho Nacional de Desenvolvimento Cienti?fico e Tecnolo?gico (CNPq) grant 432542/2018-3, Fundac?a?o de Amparo a? Pesquisa de Minas Gerais (FAPEMIG) grant APQ-01939-16 and the Coordenac?a?o de Aperfeic?oamento de Pessoal de Ni?vel Superior ? Brasil (CAPES) ? Finance Code 001; in part by the United Kingdom Engineering and Physical Sciences Research Council (EPSRC) grants EP/K004956, EP/I01974X and EP/K012576, Diamond Light Source Ltd, grant MT9635; and in part by United States National Science Foundation (NSF) grant CHE-1464085. CBP thanks CNPq for continued support. LL and TMF thank CAPES and CNPq for their scholarship. PRR is grateful to the Engineering and Physical Sciences Research Council (EPSRC) UK for continued support. We would also like to thank Dr. David Allan for providing access to beamline I19 and the Diamond Light Source Ltd for the support for the synchrotron experiment and Dr. Leonardo Calazans for support with Python scripts that recruit data reduction and structure refinement software. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

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AU - Warren, Mark

AU - Saunders, Lucy

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N2 - The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine is a very versatile compound that displays valence tautomerism (VT) in the solid-state which is induced by temperature, light and hard X-rays and modulated by solvent in the crystal lattice. Here, we demonstrate the photo-induced valence tautomerism in benzene solvated crystals of such complex with a very high yield of metastable states using 450nm light, and also show evidence of the de-excitation of these photo-induced metastable states using red 660nm light. In our work we use single crystal X-ray diffraction as a probe for the VT and demonstrate the controlled use of hard X-rays using attenuated X-ray beams in order to control the X-ray induced VT interconversion. Our results point to a larger efficiency in the VT interconversion when d-d transitions are excited in comparison with charge transfer promotion.

AB - The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine is a very versatile compound that displays valence tautomerism (VT) in the solid-state which is induced by temperature, light and hard X-rays and modulated by solvent in the crystal lattice. Here, we demonstrate the photo-induced valence tautomerism in benzene solvated crystals of such complex with a very high yield of metastable states using 450nm light, and also show evidence of the de-excitation of these photo-induced metastable states using red 660nm light. In our work we use single crystal X-ray diffraction as a probe for the VT and demonstrate the controlled use of hard X-rays using attenuated X-ray beams in order to control the X-ray induced VT interconversion. Our results point to a larger efficiency in the VT interconversion when d-d transitions are excited in comparison with charge transfer promotion.

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Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex

Abstract

Bibliographical note

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Keywords

ASJC Scopus subject areas

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Understanding and Engineering Function in Switchable Molecular Crystals

Understanding and Engineering Function in Switchable Molecular Crystals

Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Cite this

Controlled Light and Temperature Induced Valence Tautomerism in a Cobalt-o-Dioxolene Complex

Abstract

Bibliographical note

Funding

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Projects

Understanding and Engineering Function in Switchable Molecular Crystals

Understanding and Engineering Function in Switchable Molecular Crystals

Applying Long-Lived Metastable States in Switchable Functionality via Kinetic Control of Molecular Assembly

Cite this