Photophysical and electrochemical properties of Ru(ii) complexes containing tridentate bisphosphino-oligothiophene ligands

Abstract

Nine Ru(II) complexes containing the conjugated oligothiophene ligands 3,3''-bis(diphenylphosphino)-2,2':5',2''-terthiophene (P(2)T(3)) and 4',3'''-bis(diphenylphosphino)-3,3''''-dihexyl- 2,2':5',2'':5'',2''':5''',2''''-pentathiophene (P(2)T(5)) were prepared and characterized. P(2)T(3) and P(2)T(5) bond as tridentate ligands and three of the complexes (1, 2 and 5) form green five-coordinate Ru(II) complexes in solution. Cyclic voltammetry, variable temperature UV-vis spectroscopy and time-resolved transient absorption spectroscopy were used to characterize the electronic properties of the complexes. Increased conjugation in the complexes containing the P(2)T(5) ligand resulted in a lowering of the oxidation potential of the oligothiophene, but electropolymerization was not observed. The electronic spectra were dominated by π-π* transitions. All of the complexes were non-emissive both at room temperature and low temperature, indicating the excited state decays by other, non-radiative pathways. The transient absorption spectrum of complex 7 shows a species with a band at 475 nm and a lifetime of ∼100 ns, assigned to a ligand-based triplet state.