Theoretical investigation of [Ru(bpy)2(HAT)]2+ (HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy = 2,2′-bipyridine): photophysics and reactions in excited state

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dc.creatorJosé Geraldo Mendes Castro Júnior
dc.creatorWillian Ricardo Rocha
dc.date.accessioned2024-09-20T17:59:30Z
dc.date.accessioned2025-09-08T23:00:54Z
dc.date.available2024-09-20T17:59:30Z
dc.date.issued2022
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/10.1016/j.saa.2021.120817
dc.identifier.issn1873-3557
dc.identifier.urihttps://hdl.handle.net/1843/76748
dc.languageeng
dc.publisherUniversidade Federal de Minas Gerais
dc.relation.ispartofSpectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
dc.rightsAcesso Restrito
dc.subjectRutênio
dc.subjectFotoquimioterapia
dc.subjectEstados excitados - Química
dc.subjectTermodinâmica
dc.subjectFuncionais de densidade
dc.subject.otherRuthenium(II) polypyridyl complexes
dc.subject.otherPhotosensitizers
dc.subject.otherPhotodynamic therapy
dc.subject.otherExcited state reactions
dc.subject.otherPhotophysical properties
dc.subject.otherDensity functional theory calculations
dc.titleTheoretical investigation of [Ru(bpy)2(HAT)]2+ (HAT = 1,4,5,8,9,12-hexaazatriphenylene; bpy = 2,2′-bipyridine): photophysics and reactions in excited state
dc.typeArtigo de periódico
local.citation.spage120817
local.citation.volume270
local.description.resumoIn this article, Density Functional Theory based calculations, including dispersion corrections, PBE0(D3BJ)/Def2-TZVP(-f), were performed to elucidate the photophysics of the [Ru(bpy)2(HAT)]2+ complex in water. In addition, the thermodynamics of the charge and electron transfer excited state reactions of this complex with oxygen, nitric oxide and Guanosine-5′-monophosphate nucleotide (GMP) were investigated. The first singlet excite state, S1, strongly couples with the second and third triplet excited states (T2 and T3) giving rise to a high intersystem crossing rate of 6.26 × 1011 s−1 which is ∼106 greater than the fluorescence rate decay. The thermodynamics of the excited reactions revealed that all electron transfer reactions investigated are highly favorable, due mainly to the high stability of the triply charged radical cation 2PS•3+ species formed after the electron has been transferred. Excited state electron transfer from the GMP nucleotide to the complex is also highly favorable (ΔGsol = −92.6 kcal/mol), showing that this complex can be involved in the photooxidation of DNA, in line with experimental findings. Therefore, the calculations allow to conclude that the [Ru(bpy)2(HAT)]2+ complex can act in Photodynamic therapy through both mechanisms type I and II, through electron transfer from and to the complex and triplet–triplet energy transfer, generating ROS, RNOS and through DNA photooxidation. In addition, the work also opens a perspective of using this complex for the in-situ generation of the singlet nitroxyl (1NO−) species, which can have important applications for the generation of HNO and may have, therefore, important impact for physiological studies involving HNO.
local.identifier.orcidhttps://orcid.org/0009-0008-1741-4900
local.identifier.orcidhttps://orcid.org/0000-0002-0025-2158
local.publisher.countryBrasil
local.publisher.departmentICX - DEPARTAMENTO DE QUÍMICA
local.publisher.initialsUFMG
local.url.externahttps://www.sciencedirect.com/science/article/pii/S1386142521013949

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