Synthesis, Characterization and Photobiological Studies of Ru(II) Dyads Derived from alpha-Oligothiophene Derivatives of 1,10-Phenanthroline

Three new bis(2,2 '-bipyridine)-heteroleptic Ru(II) dyads incorporating thienyl groups (n = 1-3, compounds 1, 2 and 3, respectively) appended to 1,10-phenanthroline were synthesized and characterized to investigate the impact of n on the photophysical and photobiological properties within the series. All three complexes showed unstructured emission near 618 nm from a triplet metal-to-ligand charge transfer ((MLCT)-M-3) state with a lifetime (tau(em)) of approximately 1 mu s. Transient absorption measurements revealed an additional excited state that was nonemissive and long-lived (tau(TA) = 43 mu s for 2 and 27 mu s for 3), assigned as a triplet intraligand ((IL)-I-3) state that was accessible only in 2 and 3. All three complexes were strong singlet oxygen (O-1(2)) sensitizers, with quantum yields (phi (increment) ) for 2 and 3 being the largest (74-78%), and all three were photocytotoxic to cancer cells with visible light activation in the order: 3 > 2 > 1. Cell-free DNA photodamage followed the same trend, where potency increased with decreasing (IL)-I-3 energy. Compounds 2 and 3 also showed in vitro photobiological effects with red light (625 nm), where their molar absorptivities were m(-1) cm(-1). These findings highlight that Ru(II) dyads derived from alpha-oligothiophenes directly appended to 1,10-phenanthroline-namely 2 and 3-possess low-lying (IL)-I-3 states that are highly photosensitizing, and they may therefore be of interest for photobiological applications such as photodynamic therapy (PDT).