Cerium ammonium nitrate (CAN) is an important photolytic source of NO radicals in aqueous nitric acid solutions and in acetonitrile. In this work we performed the study of primary photochemical processes for CAN in acetonitrile by means of ultrafast TA spectroscopy and quantum chemical calculations. Photoexcitation of CAN is followed by ultrafast (< 100 fs) intersystem crossing; the vibrationally cooled triplet state decays to pentacoordinated Ce(III) intermediate and NO radical with the characteristic time of ca.
View Article and Find Full Text PDFPhotophysics and photochemistry of a potential light-activated cytotoxic dirhodium complex [Rh(µ-OCCH)(bpy)(dppz)](OCCH), where bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine (Complex 1 or Rh2) in aqueous solutions was studied by means of stationary photolysis and time-resolved methods in time range from hundreds of femtoseconds to microseconds. According to the literature, Complex 1 demonstrates both oxygen-dependent (due to singlet oxygen formation) and oxygen-independent cytotoxicity. Photoexchange of an acetate ligand to a water molecule was the only observed photochemical reaction, which rate was increased by oxygen removal from solutions.
View Article and Find Full Text PDFA study of luminescence and photochromic properties of ()-2,3-bis(2,5-dimethylthiophen-3-yl)-5-(4-(pyrrolidin-1-yl)benzylidene)cyclopent-2-en-1-one, which is a diarylethene with a push-pull system between carbonyl and dimethylamino groups, was performed using time-resolved methods. The intramolecular charge transfer (ICT) process as well as 6π-electrocyclization and -/-isomerization contribute to the complex light-induced properties of this molecule. Formation of unexpected short-lived intermediates was detected in the time range from 100 fs to 100 μs.
View Article and Find Full Text PDFIt 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.
View Article and Find Full Text PDFWe report the generation of 30 microJ single-cycle terahertz pulses at 100 Hz repetition rate by phase-matched optical rectification in lithium niobate using 28 mJ femtosecond laser pulses. The phase-matching condition is achieved by tilting the laser pulse intensity front. Temporal, spectral, and propagation properties of the generated terahertz pulses are presented.
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