Ru(II) Dyads Derived from 2‑(1-Pyrenyl)‑1<i>H</i>‑imidazo[4,5‑<i>f</i>][1,10]phenanthroline: Versatile Photosensitizers for Photodynamic Applications

Abstract

Combining the best attributes of organic photosensitizers with those of coordination complexes is an elegant way to achieve prolonged excited state lifetimes in Ru­(II) dyads. Not only do their reduced radiative and nonradiative rates provide ample time for photosensitization of reactive oxygen species at low oxygen tension but they also harness the unique properties of ³IL states that can act as discrete units or in concert with ³MLCT states. The imidazo­[4,5-<i>f</i>]­[1,10]­phenanthroline framework provides a convenient tether for linking π-expansive ligands such as pyrene to a Ru­(II) scaffold, and the stabilizing coligands can fine-tune the chemical and biological properties of these bichromophoric systems. The resulting dyads described in this study exhibited nanomolar light cytotoxicities against cancer cells with photocytotoxicity indices exceeding 400 for some coligands employed. This potency extended to bacteria, where concentrations as low as 10 nM destroyed 75% of a bacterial population. Notably, these dyads remained extremely active against biofilm with light photocytotoxicities against these more resistant bacterial populations in the 10–100 nM regime. The results from this study demonstrate the versatility of these highly potent photosensitizers in destroying both cancer and bacterial cells and expand the scope of compounds that utilize low-lying ³IL states for photobiological applications