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Controlled light and temperature induced valence tautomerism in a cobalt-o-dioxolene complex
DOI:
10.1021/acs.inorgchem.1c00638
Authors:
Ludmila
Leroy
(Universidade Federal de Minas Gerais)
,
Thiago M.
Francisco
(Universidade Federal de Minas Gerais)
,
Helena J.
Shepherd
(University of Kent)
,
Mark R.
Warren
(Diamond Light Source)
,
Lucy K.
Saunders
(Diamond Light Source)
,
David A.
Shultz
(North Carolina State University)
,
Paul R.
Raithby
(University of Bath)
,
Carlos B.
Pinheiro
(Universidade Federal de Minas Gerais)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Inorganic Chemistry
State:
Published (Approved)
Published:
June 2021
Diamond Proposal Number(s):
22161
,
18816
Abstract: The mononuclear cobalt complex of 3,5-di-tert-butylcathecolate and cyan-pyridine (Co(diox)2(4-CN-py)2) 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. In our work, we used single crystal X-ray diffraction as a probe for the light-induced VT in solid state and demonstrate the controlled use of hard X-rays via attenuation to avoid X-ray-induced VT interconversion. We report photoinduced VT in benzene solvated crystals of Co(diox)2(4-CN-py)2 illuminated with blue 450 nm light at 30 K with a very high yield (80%) of metastable hs-CoII states, and we also show evidence of the de-excitation of these photoinduced metastable states using red 660 nm light. Such high-yield light-induced VT had never been experimentally observed in molecular crystals of cobalt tautomers, proving that the 450 nm light illumination is triggering a chain of events that leads to the ls-CoIII to hs-CoII interconversion.
Journal Keywords: Crystals; X-rays; Ligands; Light; Irradiation
Subject Areas:
Chemistry,
Materials
Instruments:
I19-Small Molecule Single Crystal Diffraction
Added On:
07/06/2021 08:45
Discipline Tags:
Molecular Complexes
Physical Chemistry
Chemistry
Materials Science
Inorganic Chemistry
Technical Tags:
Diffraction
Single Crystal X-ray Diffraction (SXRD)