Synthesis, luminescence, and electrochemical studies of tris(homoleptic) ruthenium(II) and osmium(II) complexes of 6'-tolyl-2,2':4',2''-terpyridine.

The synthesis and photophysical and electrochemical properties of tris(homoleptic) complexes Ru(tpbpy)32 (1) and Os(tpbpy)32 (2) (tpbpy = 6'-tolyl-2,2':4',2' '-terpyridine) are reported. The ligand tpbpy is formed as the side product during the synthesis of 4'-tolyl-2,2':6',2' '-terpyridine (ttpy) and characterized by single-crystal X-ray diffraction: monoclinic, P21/c. The tridentate tpbpy coordinates as a bidentate ligand. The complexes 1 and 2 exhibit two intense absorption bands in the UV region (200-350 nm) assignable to the ligand-centered (1LC) pi-pi* transitions. The ruthenium(II) complex exhibits a broad absorption band at 470 nm while the osmium(II) complex exhibits an intense absorption band at 485 nm and a weak band at 659 nm assignable to the MLCT (dpi-pi*) transitions. A red shifting of the dpi-pi* MLCT transition is observed on going from the Ru(II) to the Os(II) complex as expected from the high-lying dpi Os orbitals. These complexes exhibit ligand-sensitized emission at 732 and 736 nm, respectively, upon light excitation onto their MLCT band through excitation of higher energy LC bands at room temperature. The MLCT transitions and the emission maxima of 1 and 2 are substantially red-shifted compared to that of Ru(bpy)32 and Os(bpy)32. The emission of both the complexes in the presence of acid is completely quenched indicating that the emission is not due to the protonation of the coordinated ligands. Our results indicate the occurrence of intramolecular energy transfer from the ligand to the metal center. Both the complexes undergo quasi-reversible metal-centered oxidation, and the E1/2 values for the M(II)/M(III) redox couples (0.94 and 0.50 V versus Ag/Ag+ for 1 and 2, respectively) are cathodically shifted with respect to that of Ru(bpy)32 and Os(bpy)32 (E1/2 = 1.28 and 1.09 V versus Ag/Ag+, respectively). The tris(homoleptic) Ru(II) and Os(II) complexes 1 and 2 could be used to construct polynuclear complexes by using the modular synthetic approach in coordination compounds by exploiting the coordinating ability of the pyridine substituent. Furthermore, these complexes offer the possibility of studying the influence of electron-withdrawing and electron-donating substituents on the photophysical properties of Ru(II) and Os(II) polypyridine complexes.