Solvent-dependent energy and charge transfer dynamics in hydroporphyrin-BODIPY arrays

Arrays of hydroporphyrins with boron complexes of dipyrromethene (BODIPY) are a promising platform for biomedical imaging or solar energy conversion, but their photophysical properties have been relatively unexplored. In this paper, we use time-resolved fluorescence, femtosecond transient absorption spectroscopy, and density-functional-theory calculations to elucidate solvent-dependent energy and electron-transfer processes in a series of chlorin- and bacteriochlorin-BODIPY arrays. Excitation of the BODIPY moiety results in ultrafast energy transfer to the hydroporphyrin moiety, regardless of the solvent. In toluene, energy is most likely transferred via the through-space Förster mechanism from the S₁ state of BODIPY to the S₂ state of hydroporphyrin. In DMF, substantially faster energy transfer is observed, which implies a contribution of the through-bond Dexter mechanism. In toluene, excited hydroporphyrin components show bright fluorescence, with quantum yield and fluorescence lifetime comparable to those of the benchmark monomer, whereas in DMF, moderate to significant reduction of both quantum yield and fluorescence lifetime are observed. We attribute this quenching to photoinduced charge transfer from hydroporphyrin to BODIPY. No direct spectral signature of the charge-separated state is observed, which suggests that either (1) the charge-separated state decays very quickly to the ground state or (2) virtual charge-separated states, close in energy to S₁ of hydroporphyrin, promote ultrafast internal conversion.