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

Abstract 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 ( 3 MLCT ) state with a lifetime ( τ em ) of approximately 1 μs. Transient absorption measurements revealed an additional excited state that was nonemissive and long‐lived ( τ TA = 43 μs for 2 and 27 μs for 3), assigned as a triplet intraligand ( 3 IL ) state that was accessible only in 2 and 3. All three complexes were strong singlet oxygen ( 1 O 2 ) sensitizers, with quantum yields ( Φ ∆ ) 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 3 IL energy. Compounds 2 and 3 also showed in vitro photobiological effects with red light (625 nm), where their molar absorptivities were <100 m −1 cm −1 . These findings highlight that Ru( II ) dyads derived from α ‐oligothiophenes directly appended to 1,10‐phenanthroline—namely 2 and 3—possess low‐lying 3 IL states that are highly photosensitizing, and they may therefore be of interest for photobiological applications such as photodynamic therapy ( PDT ).