Photochemistry of (n-BuN)[Pt(NO)] in acetonitrile.

Photochemistry of the (n-BuN)[Pt(NO)] complex in acetonitrile was studied by means of stationary photolysis and nanosecond laser flash photolysis. The primary photochemical process was found to be an intramolecular electron transfer followed by an escape of an NO radical to the solution bulk. The spectra of two successive Pt(III) intermediates were detected in the microsecond time domain, and their spectral and kinetic characteristics were determined.

Photochemistry of hexachloroosmate(IV) in ethanol.

The photochemistry of the OsIVCl62- complex in ethanol was studied by means of stationary photolysis, nanosecond laser flash photolysis, ultrafast pump-probe spectroscopy and quantum chemistry. The direction of the photochemical process was found to be wavelength-dependent. Irradiation in the region of the d-d and LMCT bands results in the photosolvation (with the wavelength-dependent quantum yield) and photoreduction of Os(iv) to Os(iii), correspondingly.

Quantum chemistry of OsCl photoaquation products and the reaction scheme.

Quantum chemical calculations (CASSCF and XMCQDPT level of theory, IMCP-SR1 and SBKJC basis sets) of the structures and electronic absorption spectra of the OsIVCl5(H2O)- and OsIVCl5(OH)2- complexes, which are the products of OsIVCl62- photoaquation, were performed. The satisfactory agreement between the experimental and calculated spectra was achieved using both triplet and quintet manifolds. The dissociation of the aquacomplex with the formation of the hydroxocomplex was explained by the thermochemical data.

A cis,fac-[RuCl(DMSO)(HO)] complex exhibits ultrafast photochemical aquation/rearrangement.

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.