Search

The ultrafast processes caused by photoexcitation of (n-Bu4N)2[Pt(NO3)6] complex in acetonitrile were studied by means of transient absorption (TA) pump-probe spectroscopy and verified by quantum chemical calculations. The primary photochemical process was found to be an inner-sphere electron transfer followed by an escape of an •NO3 radical to the bulk solution. The reaction occurs via the dissociative triplet excited LMCT state of the initial complex. Based on the experimental data and quantum chemical calculations, the mechanism of ultrafast photophysical and photochemical processes is proposed. [ABSTRACT FROM AUTHOR]

It is known that trans,cis,cis-[RuCl2(DMSO)2(H2O)2] (1a) complexes, which are formed upon dissolution of trans-[RuCl2(DMSO)4] in water, demonstrate light-induced cytotoxicity. The mechanistic study of 1a photochemistry has been performed using ultrafast pump–probe spectroscopy, laser flash photolysis and stationary photolysis. The first stage of 1a photochemistry is the photoexchange of a DMSO ligand to a water molecule; its quantum yield is wavelength-dependent (estimating by values 0.3 and 0.04 upon irradiation at 308 and 430 nm, respectively). The mechanism of photoexchange is complicated involving at least four Ru(II) intermediates. Two tentative mechanisms of the process are proposed. [ABSTRACT FROM AUTHOR]

It is known that both cis,fac-[RuCl2(DMSO)3(H2O)] (1a) and trans,cis,cis-[RuCl2(DMSO)2(H2O)2] (2a) complexes, which are formed on the dissolution of trans and cis-isomers of [RuCl2(DMSO)4] in water, demonstrate light-induced anticancer activity. The first stage of 1a photochemistry is its transformation to 2a occurring with a rather high quantum yield, 0.64 ± 0.17. The mechanism of the 1a→2a phototransformation was studied by means of nanosecond laser flash photolysis and ultrafast pump–probe spectroscopy. The reaction occurs in the picosecond time range via the formation and decay of two successive intermediates interpreted as Ru(ii) complexes with different sets of ligands. A tentative mechanism of phototransformation is proposed. [ABSTRACT FROM AUTHOR]