Charge and energy transfer processes in ruthenium(II) phthalocyanine based electron donor-acceptor materials-implications for solar cell performance

Six supramolecular electron donor-acceptor hybrids, based on a ruthenium(II) phthalocyanine [RuPc] coordinating different dendritic oligothiophene (DOT) ligands [Py-nT] (n = 3, 9, 21) in either one [RuPcCO(Py-nT)] or two [RuPc(Py-nT)(2)] axial positions, have been characterized by standard spectroscopic methods and their photophysical behavior has been established by using ultrafast and fast time-resolved techniques. Based on the spectrochemical and radiolytically generated [Py-nT] (i.e., one-electron reduction of [Py-nT]) and [RuPcCO(Py) or RuPc(Py)(2)] (i.e., one-electron oxidation of [RuPcCO(Py) or RuPc(Py)(2)]) features, the deactivation processes were assigned to a solvent independent energy transfer in RuPcCO(Py-3T) and RuPc(Py-3T)(2) and a strongly solvent dependent charge transfer mechanism, which competes with the energy transfer and the intersystem crossing for RuPcCO(Py-9T), RuPc(Py-9T)(2), RuPcCO(Py-21T) and RuPc(Py-21T)(2).