Spin-orbit TDDFT electronic structure of diplatinum(II,II) complexes.

[Pt2(μ-P2O5H2)4](4-) (Pt(pop)) and its perfluoroborated derivative [Pt2(μ-P2O5(BF2)2)4](4-) (Pt(pop-BF2)) are d(8)-d(8) complexes whose electronic excited states can drive reductions and oxidations of relatively inert substrates. We performed spin-orbit (SO) TDDFT calculations on these complexes that account for their absorption spectra across the entire UV-vis spectral region. The complexes exhibit both fluorescence and phosphorescence attributable, respectively, to singlet and triplet excited states of dσ*pσ origin. These features are energetically isolated from each other (∼7000 cm(-1) for (Pt(pop-BF2)) as well as from higher-lying states (5800 cm(-1)). The lowest (3)dσ*pσ state is split into three SO states by interactions with higher-lying singlet states with dπpσ and, to a lesser extent, pπpσ contributions. The spectroscopically allowed dσ*pσ SO state has ∼96% singlet character with small admixtures of higher triplets of partial dπpσ and pπpσ characters that also mix with (3)dσ*pσ, resulting in a second-order (1)dσ*pσ-(3)dσ*pσ SO interaction that facilitates intersystem crossing (ISC). All SO interactions involving the dσ*pσ states are weak because of large energy gaps to higher interacting states. The spectroscopically allowed dσ*pσ SO state is followed by a dense manifold of ligand-to-metal-metal charge transfer states, some with pπpσ (at lower energies) or dπpσ contributions (at higher energies). Spectroscopically active higher states are strongly spin-mixed. The electronic structure, state ordering, and relative energies are minimally perturbed when the calculation is performed at the optimized geometries of the (1)dσ*pσ and (3)dσ*pσ excited states (rather than the ground state). Results obtained for Pt(pop) are very similar, showing slightly smaller energy gaps and, possibly, an additional (1)dσ*pσ - (3)dσ*pσ second order SO interaction involving higher (1)dπpσ* states that could account in part for the much faster ISC. It also appears that (1)dσ*pσ → (3)dσ*pσ ISC requires a structural distortion that has a lower barrier for Pt(pop) than for the more rigid Pt(pop-BF2).