Abstract
Application of time-resolved near-infrared spectroscopy (TRNIR) to Os ( phen ) 3 2 + in CD 3CN, following visible (450 nm) laser flash excitation, reveals an absorption feature at ν ¯ max = 5460 cm - 1 ( ε max ⩾ 5000 M −1 cm −1, Δ ν ¯ 1 / 2 = 1840 cm - 1 ) for the MLCT excited state Os ( phen ) 3 2 + ∗ . Based on an electronic structure model, including spin–orbit coupling, the absorption is tentatively assigned to three overlapping ligand-to-ligand charge transfer (LLCT) bands two of which have dπ → dπ interconfigurational character. This assignment is consistent with the results of a solvent dependence study and an analysis of predicted band energies.
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