Photochemistry of (n-Bu4N)2[Pt(NO3)6] in acetonitrile.

Photochemistry of the (n-Bu4N)2[Pt(NO3)6] 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 •NO3 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. These intermediates were identified as PtIII(NO3)52- and PtIII(NO3)4- complexes. Disproportionation of Pt(III) species resulted in formation of final Pt(II) products.

Primary processes in photophysics and photochemistry of a potential light-activated anti-cancer dirhodium complex.

Photophysics and photochemistry of a potential light-activated cytotoxic dirhodium complex [Rh2(µ-O2CCH3)2(bpy)(dppz)](O2CCH3)2, 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. Photoexcitation of Complex 1 results in the formation of the lowest triplet electronic excited state, which lifetime is less than 10 ns. This time is too short for diffusion-controlled quenching of the triplet state by dissolved oxygen resulting in 1O2 formation. We proposed that singlet oxygen is produced by photoexcitation of weakly bound van der Waals complexes [Rh2…O2], which are formed in solutions. If this is true, no oxygen-independent light-induced cytotoxicity of Complex 1 exists. Residual cytotoxicity deaerated solutions are caused by the remaining [Rh2…O2] complexes.

Comprehensive Review on g-C3N4-Based Photocatalysts for the Photocatalytic Hydrogen Production under Visible Light.

Currently, the synthesis of active photocatalysts for the evolution of hydrogen, including photocatalysts based on graphite-like carbon nitride, is an acute issue. In this review, a comprehensive analysis of the state-of-the-art studies of graphic carbon nitride as a photocatalyst for hydrogen production under visible light is presented. In this review, various approaches to the synthesis of photocatalysts based on g-C3N4 reported in the literature were considered, including various methods for modifying and improving the structural and photocatalytic properties of this material. A thorough analysis of the literature has shown that the most commonly used methods for improving g-C3N4 properties are alterations of textural characteristics by introducing templates, pore formers or pre-treatment method, doping with heteroatoms, modification with metals, and the creation of composite photocatalysts. Next, the authors considered their own detailed study on the synthesis of graphitic carbon nitride with different pre-treatments and respective photocatalysts that demonstrate high efficiency and stability in photocatalytic production of hydrogen. Particular attention was paid to describing the effect of the state of the platinum cocatalyst on the activity of the resulting photocatalyst. The decisive factors leading to the creation of active materials were discussed.

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. The characteristic time of photosolvation is ca. 40 ps. Photoreduction occurs in the micro- and millisecond time domains via several Os(iii) intermediates. The nature of intermediates and the possible mechanisms of photoreduction are discussed. We believe that the lability of the photochemically produced Os(iv) and Os(iii) intermediates determines the synthetic potential of OsIVCl62- photochemistry.

Rh(III) hydroxocomplexes speciation using HPLC-ESI-MS.

A mixture of rhodium(iii) hydroxocomplexes formed during the polycondensation process in alkaline media has been fully characterized by the hyphenated high performance liquid chromatography with electrospray ionization mass spectrometry (HPLC-ESI-MS). The baseline separation was achieved using reverse phase ion-pair chromatography (RP-IP-HPLC) in gradient elution mode. When using SDS as the ion pair, the formation of all types of its associates with the molecules of acetonitrile, as well as oligomers of rhodium aquahydroxocomplexes, etc. was taken into consideration. As a result, it was shown that the test mixture is presented by [Rh(H2O)6]3+, [Rh2(µ-OH)2(H2O)8]4+, [Rh3(µ-OH)4(H2O)10]5+, [Rh4(µ-OH)6(H2O)12]6+.

Mechanistic study of the trans,cis,cis-[RuCl2(DMSO)2(H2O)2] complex photochemistry in aqueous solutions.

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.

The study of Rh(iii) hydroxocomplexes using capillary zone electrophoresis with a UV-Vis detector: the development of the method.

The expediency of capillary zone electrophoresis application in the study of a mixture of rhodium(iii) hydroxocomplexes is shown for the species formed during the thermal treatment of [Rh(OH)6]3- at 60 °C in alkaline media. As these compounds are unstable in solution because of polycondensation at pH > 10 and the formation of insoluble rhodium(iii) hydroxides at pH 5-10, their acidic derivatives with terminal aqua ligands acted as the objects of the study. Optimal separation conditions were achieved using sodium perchlorate as a background electrolyte, a voltage of +20 kV and pH 2.6. Rhodium(iii) species with different nuclearities were identified in accordance with their UV spectra and the regularities of electrophoretic migration in the capillary. The presence of a dimer was also verified by the spiking of the mixture under investigation with a previously synthesised complex [Rh2(µ-OH)2(H2O)8](NO3)4, which confirms the correct identification.

A cis,fac-[RuCl2(DMSO)3(H2O)] 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 ± 0.17. 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.

Spectroscopic and DFT Study of RhIII Chloro Complex Transformation in Alkaline Solutions.

The hydrolysis of [RhCl6]3- in NaOH-water solutions was studied by spectrophotometric methods. The reaction proceeds via successive substitution of chloride with hydroxide to quantitatively form [Rh(OH)6]3-. Ligand substitution kinetics was studied in an aqueous 0.434-1.085 M NaOH matrix in the temperature range 5.5-15.3 °C. Transformation of [RhCl6]3- into [RhCl5(OH)]3- was found to be the rate-determining step with activation parameters of ΔH† = 105 ± 4 kJ mol-1 and ΔS†= 59 ± 10 J K-1 mol-1. The coordinated hydroxo ligand(s) induces rapid ligand substitution to form [Rh(OH)6]3-. By simulating ligand substitution as a dissociative mechanism, using density functional theory (DFT), we can now explain the relatively fast and slow kinetics of chloride substitution in basic and acidic matrices, respectively. Moreover, the DFT calculated activation energies corroborated experimental data that the kinetic stereochemical sequence of [RhCl6]3- hydrolysis in an acidic solution proceeds as [RhCl6]3- → [RhCl5(H2O)]2- → cis-[RhCl4(H2O)2]-. However, DFT calculations predict in a basic solution the trans route of substitution [RhCl6]3- → [RhCl5(OH)]3- → trans-[RhCl4(OH)2]3- is kinetically favored.

Primary photochemical processes for Pt(iv) diazido complexes prospective in photodynamic therapy of tumors.

Diazide diamino complexes of Pt(iv) are considered as prospective prodrugs in oxygen-free photodynamic therapy (PDT). Primary photophysical and photochemical processes for cis,trans,cis-[Pt(N3)2(OH)2(NH3)2] and trans,trans,trans-[Pt(N3)2(OH)2(NH3)2] complexes were studied by means of stationary photolysis, nanosecond laser flash photolysis and ultrafast kinetic spectroscopy. The process of photolysis is multistage. The first stage is the photosubstitution of an azide ligand to a water molecule. This process was shown to be a chain reaction involving redox stages. Pt(iv) and Pt(iii) intermediates responsible for the chain propagation were recorded using ultrafast kinetic spectroscopy and nanosecond laser flash photolysis. The mechanism of photosubstitution is proposed.