Repozytorium publikacji - Politechnika Gdańska

The light-induced relaxation pathways in the molecular photocatalyst [(tbbpy)2Ru(tpphz)PtCl2]2+ are investigated with time-dependent density functional theory calculations together with the Marcus theory of electron transfer (ET). The calculations show that metal (Ru) to ligand (tpphz) charge transfer (MLCT) triplet states are populated following an excitation in the longer wavelength range of the absorption spectrum, but that an ET toward the catalytic center (PtCl2) from these states is thermodynamically unfavorable, implying that charge separation can only occur via higher energy states in this system. Moreover, low-lying Pt-centered states can be populated and the calculations predict that they can form an excited state equilibrium with MLCT states localized on the tpphz ligand. A comparison with previously reported results for the photocatalyst [(tbbpy)2Ru- (tpphz)PdCl2]2+, based on a PdCl2 catalytic center, is provided in order to decipher the effect of the catalytic center on their respective photochemistry (Staniszewska, M.; Kupfer, S.; Guthmuller, J. Chem.Eur. J. 2018, 24, 11166−11176).

Autorzy

• Magdalena Staniszewska link otwiera się w nowej karcie ,
• Stephan Kupfer,
• prof. dr hab. Julien Guthmuller link otwiera się w nowej karcie