Synthesis, structural characterization, and DFT investigation of azoimine-ruthenium complexes containing aromatic-nitrogen ligands

Article abstract of DOI:10.1016/j.poly.2008.07.033

Seven ruthenium(II) complexes continuing substituted diimine ligands and the azoimine ligand (Az: C₆H₅N{double bond, long}NC(COCH₃){double bond, long}NC₆H₅) are synthesized and characterized. trans-[Ru(II)(Az)(L)Cl₂] [L = 2,2′-bipyridine (bpy) 1, 4,4′-dimethyl-2,2′-bipyridine (dmb) 2, 4,4′-dimethoxy-2,2′-bipyridine (dmeb) 3, 4,4′-di-tertbutyl-2,2′-bipyridine (dtb) 4, 1,10-phenanthroline (phen) 5, 5-amino-1,10-phenanthroline (NH₂phen) 6, 5-chlorophenanthroline (Clphen) 7, 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) 8] are made by the reaction of RuCl₃ hydrate and the ligands in the presence of LiCl. These complexes have been characterized by cyclic voltammetry, UV-Vis spectroscopy, electrochemical measurements and X-ray diffraction analysis for 2 and 5. The electrochemical parameters (E_L(L)) of the substituted diimine ligands (L) are reported. The absorption spectrum of 5 in acetonitrile has been modeled by time-dependent density functional theory (TD-DFT) using a hybrid functional, B3LYP, as well as the LanL2DZ basis set.