Photosensitizers Based on Bichromophoric Dyads Combining Ru(II)-Polypyridyl Complexes and Dissymmetric Perylene Monoimide Derivatives: The Nontrivial Role of Ligand Substitution

The covalent modification of Ru(II) polypyridyl complexes (RPCs) with organic chromophores is a powerful strategy to obtain metal-based photosensitizer agents (PSs) with improved performance for application in photodynamic therapy (PDT). In this respect, perylene-imides are of particular interest due to their rich chemical-physical repertoire, and it is therefore quite surprising that their combination with RPCs has been poorly considered so far. Herein, we report on the photophysical behavior of two newly synthesized RPCs bearing a perylene monoimide appendant (PMI-Ad). Differently from the majority of RPCs-perylene-imides dyads, these chromophores are dissymmetric and are tethered to the metal centers through a single C-C bond in the 3- or 5-position of 1,10-phenanthroline (Ru-3PMI-Ad and Ru-5PMI-Ad). Both compounds show excellent singlet oxygen photosensitizing activity, with quantum yields reaching >90% in the case of Ru-3PMI-Ad. A combined spectroscopic and theoretical analysis, also involving transient absorption and luminescence lifetime measurements, demonstrates that both compounds undergo intersystem crossing on a very fast time scale (tens of picoseconds) and with high efficiency. Our results further demonstrate that the increased electron delocalization between the metal center and the PMI-Ad chromophore observed for Ru-3PMI-Ad additionally contributes to increase the singlet oxygen quantum yields by prolonging the lifetime of the triplet state.