Controlled light and temperature induced valence tautomerism in a cobalt-o-dioxolene complex

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dc.creatorLudmila Maria Diniz Leroy
dc.creatorThiago Martins Francisco
dc.creatorHelena J. Shepherd
dc.creatorMark R. Warren
dc.creatorLucy K. Saunders
dc.creatorDavid A. Shultz
dc.creatorPaul R. Raithby
dc.creatorCarlos Basílio Pinheiro
dc.date.accessioned2023-08-10T14:53:41Z
dc.date.accessioned2025-09-09T00:03:34Z
dc.date.available2023-08-10T14:53:41Z
dc.date.issued2021
dc.description.sponsorshipCNPq - Conselho Nacional de Desenvolvimento Científico e Tecnológico
dc.description.sponsorshipFAPEMIG - Fundação de Amparo à Pesquisa do Estado de Minas Gerais
dc.description.sponsorshipCAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
dc.identifier.doihttps://doi.org/10.1021/acs.inorgchem.1c00638
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/1843/57687
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.relation.ispartofInorganic Chemistry
dc.rightsAcesso Restrito
dc.subjectTautomeria
dc.subjectCobalto
dc.subject.otherValence tautomerism
dc.subject.otherBistability
dc.subject.otherCobalt complexes
dc.titleControlled light and temperature induced valence tautomerism in a cobalt-o-dioxolene complex
dc.typeArtigo de periódico
local.citation.epage8671
local.citation.issue12
local.citation.spage8665
local.citation.volume60
local.description.resumoThe 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.
local.identifier.orcidhttps://orcid.org/0000-0002-4272-0298
local.identifier.orcidhttps://orcid.org/0000-0001-8722-4127
local.identifier.orcidhttps://orcid.org/0000-0003-0832-4475
local.identifier.orcidhttps://orcid.org/0000-0003-1326-0744
local.identifier.orcidhttps://orcid.org/0000-0001-5689-8129
local.identifier.orcidhttps://orcid.org/0000-0001-8121-6812
local.identifier.orcidhttps://orcid.org/0000-0002-2944-0662
local.identifier.orcidhttps://orcid.org/0000-0002-8674-1779
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE FÍSICA
local.publisher.initialsUFMG
local.url.externahttps://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00638

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