Photoinduced electron transfer via nonbuttressed metal-metal bonds. The photochemical study of binuclear complexes with platinum-thallium bonds
2008 (English)In: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 112, no 26, 5786-5793 p.Article in journal (Refereed) Published
The photochemistry of binuclear metal-metal bonded complexes [(NC)(5)Pt-Tl(solv)(x)] (solv is water or dimethylsulfoxide) has been studied in aqueous and dimethylsulfoxide solutions. Both stationary and nanosecond laser flash photolysis have been carried out on the species. The metal-metal bonded complexes have been photolyzed by irradiation into the corresponding intense MMCT absorption bands. Photoexcitation results in the cleavage of the platinum-thalliurn bond and the formation of a solvated thallous ion and a cyano complex of platinum(IV), [Pt(CN)(5)(Solv)](-), in both cases. The species have been characterized by multinuclear NMR and optical spectroscopy. The products of the photoreaction indicate a complementary two-electron transfer occurring between platinum and thallium ions in the binuclear Pt-T1 species. Quantum yield values for the photodecomposition of the species have been determined. The intermediates of the photoinduced metal-to-metal electron transfer have been detected and characterized by optical spectroscopy. The kinetics of transient formation and decomposition have been studied, and mechanisms of the photoactivated redox reaction have been suggested.
Place, publisher, year, edition, pages
2008. Vol. 112, no 26, 5786-5793 p.
IdentifiersURN: urn:nbn:se:kth:diva-17643DOI: 10.1021/jp7121278ISI: 000257155700005ScopusID: 2-s2.0-53349128288OAI: oai:DiVA.org:kth-17643DiVA: diva2:335687
QC 201005252010-08-052010-08-05Bibliographically approved