Computational Analysis of Photophysical Properties and Reactivity of a New Phototherapeutic Cyclometalated Au(III)-Hydride Complex.

Gold(III) complexes have recently emerged as new versatile and efficacious metal containing anticancer agents. In an attempt to reconcile the specific affinity of such complexes for target sulfur containing biomolecules with their capability to strongly bind thiol-containing compounds widely distributed in non-tumoral cells, a new series of cyclometalated Au(III)-hydride complexes has been proposed as photoactivatable anticancer prodrugs. Here, the computational exploration of the photophysical properties and reactivity in dark and under light irradiation of the first member of the series, named 1 a, is reported. Complex 1 a low hydricity in dark together with facile hydride substitution leading to H2 elimination under excitation by visible light have been examined by means of DFT and TD-DFT computations. Both singlet and triplet excited states have been characterized, allowing the identification of the active species involved in photoactivation pathways leading to the controlled detachment of the hydride ligand. Also the viable two-photon activation at the ideal phototherapeutic window has been investigated.