Primary photochemical processes for PtCl62− complex in acetonitrile solutions

• Photosolvation of PtCl62− in CH3CN was studied in the time range 100 fs–10 s.
• Photosolvation is a chain process.
• Primary intermediate was interpreted as Adamson radical pair [PtIIICl52‐(C4v)⋯Cl].
• PtIIICl52− and PtIIICl4− intermediates were recorded in microsecond time domain.
• PtIIICl4− was proposed to be a chain carrier in the chain photosolvation process.

Photosolvation of hexachloroplatinate(IV) in acetonitrile with the formation of the PtIVCl5(CH3CN)− complex was studied in the time range from hundreds of femtoseconds to seconds. The primary Pt(III) intermediate was recorded and interpreted as the primary Adamson radical pair [PtIIICl52‐(C4v)⋯Cl], which then accepts an electron from a solvent molecule. Two successive Pt(III) intermediates recorded in time range from microseconds to tens of milliseconds were interpreted as PtIIICl52−(C4V) and PtIIICl4− complexes. PtIIICl4− was proposed to be a chain carrier in the chain photosolvation process. Dependencies of quantum yield of photosolvation on the initial complex concentration and excited light intensity were fitted in the framework of the proposed chain mechanism. Rate constants of the reactions of intermediates were determined.

Photosolvation of PtCl62− complex in CH3CN is studied in time range from hundreds of femtoseconds to seconds.Figure optionsDownload as PowerPoint slide