Nonadiabatic excited-state dynamics of ReCl(CO)3(bpy) in two different solvents

0563307 - ÚFCH JH 2023 RIV GB eng J - Journal Article
Šrut, A. - Mai, S. - Sazanovich, I. - Heyda, Jan - Vlček, Antonín - González, L. - Záliš, Stanislav
Nonadiabatic excited-state dynamics of ReCl(CO)3(bpy) in two different solvents.
Physical Chemistry Chemical Physics. Roč. 24, č. 42 (2022), s. 25864-25877. ISSN 1463-9076. E-ISSN 1463-9084
R&D Projects: GA ČR(CZ) GA21-05180S; GA MŠMT(CZ) EF18_054/0014591
Grant - others:GA MŠk(CZ) CZ.02.2.69/0.0/0.0/18_054/0014591
Research Infrastructure: e-INFRA CZ - 90140
Institutional support: RVO:61388955
Keywords : RESOLVED INFRARED-SPECTROSCOPY * TRANSITION-METAL-COMPLEXES * CARBONYL-DIIMINE-COMPLEXES
OECD category: Physical chemistry
Impact factor: 3.3, year: 2022
Method of publishing: Open access

We present a study of excited-states relaxation of the complex ReCl(CO)3(bpy) (bpy = 2,2-bipyridine) using a nonadiabatic TD-DFT dynamics on spin-mixed potential energy surfaces in explicit acetonitrile (ACN) and dimethylsulfoxide (DMSO) solutions up to 800 fs. ReCl(CO)3(bpy) belongs to a group of important photosensitizers which show ultrafast biexponential subpicosecond fluorescence decay kinetics. The choice of solvents was motivated by the different excited-state relaxation dynamics observed in subpicosecond time-resolved IR (TRIR) experiments. Simulations of intersystem crossing (ISC) showed the development of spin-mixed states in both solvents. Transformation of time-dependent populations of spin-mixed states enabled to monitor the temporal evolution of individual singlet and triplet states, fitting of bi-exponential decay kinetics, and simulating the time-resolved fluorescence spectra that show only minor differences between the two solvents. Analysis of structural relaxation and solvent reorganization employing time-resolved proximal distribution functions pointed to the factors influencing the fluorescence decay time constants. Nonadiabatic dynamics simulations of time-evolution of electronic, molecular, and solvent structures emerge as a powerful technique to interpret time-resolved spectroscopic data and ultrafast photochemical reactivity.

Permanent Link: https://hdl.handle.net/11104/0335304