Demystifying the Origin of Vibrational Coherence Transfer Between the S1 and T1 States of the Pt-pop Complex.

We demonstrate that spin-vibronic coupling is the most significant mechanism in vibrational coherence transfer (VCT) from the singlet (S1) to the triplet (T1) state of the [Pt2(P2O5H2)4]4- complex. Our time-dependent correlation function-based study shows that the rate of intersystem crossing (kISC) through direct spin-orbit coupling is negligibly small, making VCT vanishingly small due to the ultrashort decoherence time (2.5 ps). However, the inclusion of the spin-vibronic contribution to the net kISC in selective normal modes along the Pt-Pt axis increases the kISC to such an extent that VCT becomes feasible. Our results suggest that kISC for the S1 →T2 (τISC = 1.084 ps) is much faster than the S1 → T1 (τISC = 763.4 ps) and S1 → T3 (τISC = 13.38 ps) in CH3CN solvent, indicating that VCT is possible from the low-lying excited singlet (S1) to the triplet (T1) state through the intermediate T2 state. This is the first example where VCT occurs solely due to spin-vibronic interactions. This finding can pave the way for new types of photocatalysis.