Demonstration of intramolecular energy transfer in asymmetric bimetallic ruthenium(II) complexes

摘要

A new family of bimetallic Ru(II) complexes derived from an asymmetric bridging ligand (tpy-Hbzim-dipy) consisting of both bipyridine and terpyridine chelating sites covalently connected via phenyl-imidazole spacer were designed in this work to demonstrate intramolecular energy transfer from one component to the other in asymmetric dyads. To fine tune the photo-redox properties, both bidentate and tridentate terminal ligands in the complexes were varied systematically. Both steady state and time-resolved luminescence spectral results indicated photo-induced intramolecular energy transfer from the excited MLCT state of the (bpy/phen) Ru-2(II)(dipy-Hbzim-tpy) component to the MLCT state of the tpy-containing unit (dipy-Hbzim-tpy) Ru-II(tpy-PhCH3/H(2)pbbzim) in dyads with rate constant values on the order of 10(6)-10(7) s(-1). Temperature-dependent luminescence studies indicated an enhancement in the luminescence intensity and excited state lifetimes upon decreasing the temperature.