Abstract
Irradiation of mono(2,9-dimethyl-1, 10-phenanthroline)copper(II) in methanol solution in the 26,000–40,000 cm −1 frequency range produces the corresponding copper(I) complex. The primary photoprocess is postulated to be homolytic cleavage of a Cu(II)-methanol coordinate bond. The reactive excited state is concluded to be a “spin-allowed” (doublet) ligand-to-metal charge-transfer state. Ligand-field ( d− d) excited states in this complex are photochemically inert. Rates of radiationless conversion from higher-lying ligand-localized excited states to the reactive charge-transfer state appear to be extremely rapid. Apparent overall quantum yields for the photoreduction are affected by secondary reactions of the alcohol free radicals formed in the primary step.
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