Twoi somerso fh eteroleptic bis(bidentate) ruthenium(II) complexes with dimethyl sulfoxide (dmso) and chloride ligands, trans(Cl,N bpy )-and trans(Cl,N Hdpa )-[Ru(bpy)Cl-(dmso-S)(Hdpa)] + (bpy:2 ,2'-bipyridine;H dpa:d i-2-pyridylamine), are synthesized. This is the first reporto nt he selective synthesis of ap air of isomers of cis-[Ru(L)(L')XY] n + (L ¼ 6 L':bidentate ligands;X¼ 6 Y: monodentate ligands). The structures of the ruthenium(II) complexes are clarified by means of X-ray crystallography,a nd the signals in the 1 HNMR spectra are assignedb ased on 1 H-1 HC OSY spectra.T he colors of the two isomers arec learly different in both the solids tate and solution:t he trans(Cl,N bpy )i somer has ad eep red color, whereast he trans(Cl,N Hdpa )i somer is yellow.A lthough both complexes have intense absorption bands at l % 440-450 nm, only the trans(Cl,N bpy )i somer hasashoulder band at l % 550 nm. DFT calculations indicate that the LUMOs of both isomers are the p*o rbitals in the bpy ligand, and that the LUMO level of the trans(Cl,N bpy )i somer is lower than that of the trans(Cl,N Hdpa )i somer due to the trans effect of the Cl ligand; thus resulting in the appearance of the shoulder band.T he HOMO levelsa re almost the same in both isomers.T he energy levels are experimentallys upported by cyclic voltammograms, in which these isomers have different reduction potentials and similaroxidation potentials.[a] Dr.M.T oyama Current address:O saka Prefecture University Collegeo fT echnology 26-12 Saiwaicho,
A pair of isomers of heteroleptic bis(bidentate) ruthenium(II) complexes with two different monodentate ligands, cis‐[Ru(L)(L’)XY]n+ (L≠L’: bidentate ligands; X≠Y: monodentate ligands), has been synthesized for the first time. trans(Cl,Nbpy)‐[Ru(bpy)Cl(dmso‐S)(Hdpa)]+ (bpy: 2,2’‐bipyridine; Hdpa: di‐2‐pyridylamine) has a deep red color while the trans(Cl,NHdpa)‐isomer is yellow; these together with the DFT calculations and the CV studies are discussed. More information can be found in the Full Paper by M. Toyama, N. Nagao, H. Ishida et al. on page 16582.
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