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Modulation of the Excited States of Ruthenium(II)-perylene Dyad to Access Near-IR Luminescence, Long-Lived Perylene Triplet State and Singlet Oxygen Photosensitization

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Autor(es):
Campos, Isabele S. ; Fermi, Andrea ; Ventura, Barbara ; Moraes, Carlos A. F. ; Ribeiro, Gabriel H. ; Venancio, Tiago ; Ceroni, Paola ; Carlos, Rose M.
Número total de Autores: 8
Tipo de documento: Artigo Científico
Fonte: Inorganic Chemistry; v. 63, n. 10, p. 9-pg., 2024-02-29.
Resumo

Herein, we present a novel ruthenium(II)-perylene dyad (RuPDI-Py) that combines the photophysical properties of pyrrolidine-substituted perylene diimide (PDI-Py) and the ruthenium(II) polypyridine complex [Ru(phen)(3)](2+). A comprehensive study of excited-state dynamics was carried out using time-resolved and steady-state methods in a dimethyl sulfoxide solution. The RuPDI-Py dyad demonstrated excitation wavelength-dependent photophysical behavior. Upon photoexcitation above 600 nm, the dyad exclusively exhibits the near-infrared (NIR) fluorescence of the (PDI)-P-1-Py state at 785 nm (tau(fl) = 1.50 ns). In contrast, upon photoexcitation between 350 and 450 nm, the dyad also exhibits a photoinduced electron transfer from the {[Ru(phen)(3)](2+)} moiety to PDI-Py, generating the charge-separated intermediate state {Ru(III)-(PDI-Py)(center dot-)} (4 mu s). This state subsequently decays to the long-lived triplet excited state (PDI)-P-3-Py (36 mu s), which is able to sensitize singlet oxygen (O-1(2)). Overall, tuning O-1(2) photoactivation or NIR fluorescence makes RuPDI-Py a promising candidate for using absorbed light energy to perform the desired functions in theranostic applications. (AU)

Processo FAPESP: 18/03424-0 - Complexos de Ru(II)-perilenodiimida para ativação do oxigênio singleto: terapia fotodinâmica e imagem celular no tratamento de Câncer Melanoma
Beneficiário:Isabele Aparecida Soares de Campos
Modalidade de apoio: Bolsas no Brasil - Doutorado
Processo FAPESP: 21/10586-9 - Investigação das propriedades dos estados excitados de díades doadoras-receptoras de rutênio(II)-perileno diimida
Beneficiário:Isabele Aparecida Soares de Campos
Modalidade de apoio: Bolsas no Exterior - Estágio de Pesquisa - Doutorado