The intersystem crossing of a cyclic (alkyl)(amino) carbene gold (i) complex

The intersystem crossing (ISC) mechanism of a cyclic (alkyl)(amino) carbene gold (I) complex (CMA1) is studied using quantum dynamics. Amodel spin-vibronic Hamiltonian is developed, which includes 10 excited states and two important nuclear degrees of freedom. The quantum dynamics reveals that ISC from S-1 -> T-1 occurs on the tens of picosecond time scale, consistent with recent experiments. It is driven by motion along the torsional degree of freedom of the carbazole (Cz) ligand, which causes orthogonality between the donor and acceptor groups closing the gap between the initial (S-1) and final (T-1) states. The role of higher triplet states through spin-vibronic interactions is also discussed. Although previous calculations, evaluated in the Condon approximation, yield large ISC rates, our present dynamical treatment, taking into account the large amplitude torsional motion, increases the calculated rate by an order of magnitude improving the agreement with experiments. The model spin-vibronic Hamiltonian developed can also be used to understand the properties of related linear metal carbene compounds, facilitating molecular design. (C) 2018 Author(s).