Partially Solvated Dinuclear Ruthenium Compounds Bridged by Quinoxaline-Functionalized Ligands as Ru(II) Photocage Architectures for Low-Energy Light Absorption.

Ruthenium compounds with coordinated photolabile molecules that can be selectively released by irradiation with a visible light source are finding increasing applications in photoactivated chemotherapy (PCT) as photocages. Earlier photocages based on mononuclear Ru(II) compounds lack absorption in the therapeutic window (λ > 600 nm). In previous work, we synthesized the first partially solvated tppz bridged (tppz= 2,3,5,6-tetrakis(pyridin-2-yl)pyrazine) dinuclear Ru(II) complex capable of photoinduced ligand exchange at both metal centers. To further explore the effect of the bridging ligand on Ru(II) photocage design, we used quinoxaline-functionalized bridging ligand platforms to prepare [{Ru ^II (NCCH ₃ ) ₄ } ₂ (μ-BL)](PF ₆ ) ₄ [BL = dpq, 2,3-di(pyridin-2-yl)quinoxaline ( 1 ); BL = dpb, 2,3-di(pyridin-2-yl)benzo[ g ]quinoxaline ( 2 )]. The compounds are capable of absorbing green light with tails extending beyond 650 nm which can be exploited for applications as PCT agents. Experimental results were additionally verified by DFT calculations. The use of two Ru(II) centers equipped with quinoxaline-based bridging ligands is a promising design strategy for the synthesis of a new family of dinuclear Ru(II) photocage prototypes with the ability to absorb low-energy visible light.