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

摘要

Seven ruthenium(II) complexes continuing substituted diimine ligands and the azoimine ligand (Az: C6H5N=NC(COCH3)=NC6H5) are synthesized and characterized. trans-[Ru(II)(Az)(L)Cl-2] [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 (NH(2)phen) 6, 5-chlorophenanthroline (Clphen) 7, 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) 81 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 Xray 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. (C) 2008 Elsevier Ltd. All rights reserved.