Dual Luminescence and Long-Lived Charge-Separated States in Donor-Acceptor Assemblies Based on Tetrathiafulvalene-Fused Ruthenium(n)-Polypyridine Complexes

摘要

The creation of long-lived charge-separated states in donor-acceptor assemblies has been the goal of many studies aimed at mimicking the primary processes in photosynthesis. Here we present such assemblies based on tetrathiafulvalene (TTF) as electron donor and a dipyridophenazine (dppz) unit as electron acceptor in the form of a fused ligand (TTF-dppz) coordinated to ruthenium(Ⅱ) via the dipyrido coordination site and with 2,2'-bipyridine (bpy) as auxiliary ligand, namely [Ru(bpy)_(3_x)(TTF-dppz)_x]~(2+) (x = 1-3). For x = 2, irradiation into the metal to dppz charge transfer transition results in electron transfer from TTF to ruthenium, thus creating a charge-separated state best described by [(TTF~+-dppz)Ru(dppz~--TTF)(bpy)]~(2+) with a lifetime of 2.5 μs in dichloromethane.