Comprehensive Picture of the Excited State Dynamics of Cu(I)- and Ru(II)-Based Photosensitizers with Long-Lived Triplet States

Ru­(II)- and Cu­(I)-based photosensitizers featuring the recently developed biipo ligand (16H-benzo-[4′,5′]-isoquinolino-[2′,1′,:1,2]-imidazo-[4,5-f]-[1,10]-phenanthrolin-16-one) were comprehensively investigated by X-ray crystallography, electrochemistry, and especially several time-resolved spectroscopic methods covering all time scales from femto- to milliseconds. The analysis of the experimental results is supported by density functional theory (DFT) calculations. The biipo ligand consists of a coordinating 1,10-phenanthroline moiety fused with a 1,8-naphthalimide unit, which results in an extended π-system with an incorporated electron acceptor moiety. In a previous study, it was shown that this ligand enabled a Ru­(II) complex that is an efficient singlet oxygen producer and of potential use for other light-driven applications due to its long emission lifetime. The goal of our here presented research is to provide a full spectroscopic picture of the processes that follow optical excitation. Interestingly, the Ru­(II) and Cu­(I) complexes differ in their characteristics even though the lowest electronically excited states involve in both cases the biipo ligand. The combined spectroscopic results indicate that an emissive 3MLCT state and a rather dark 3LC state are populated, each to some extent. For the Cu­(I) complex, most of the excited population ends up in the 3LC state with an extraordinary lifetime of 439 μs in the solid state at 20 K, while a significant population of the 3MLCT state causes luminescence for the Ru­(II) complex. Hence, there is a balance between these two states, which can be tuned by altering the metal center or even by thermal energy, as suggested by the temperature-dependent experiments.