Synthesis and characterization of luminescent mixed ligand zinc(II) complexes containing a novel dithiol ligand

• Published in: Inorganica Chimica Acta Vol. 234; no. 1; pp. 13 - 18
• Main Authors: Gronlund, P.J., Burt, J.A., Wacholtz, W.F.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.06.1995
• Subjects: Crystal structures; Dithiol complexes; Luminescence; Mixed ligand complexes; Zinc complexes; Crystal structures; Zinc complexes; Dithiol complexes; Mixed ligand complexes; Luminescence
• ISSN: 0020-1693; 1873-3255
• DOI: 10.1016/0020-1693(95)04470-T

A series of mixed ligand zinc(II) complexes containing the uncommon dithiol ligand dithiosquarate (dtsq) and having the formula Zn(dtsq)(N-N), where N-N is 2,2′-biquinoline (biq), 1,10-phenanthroline (phen) and 1,4-diphenyl-2,9-dimethyl-1,10-phenanthroline (bathocuproine or batho), have been synthesized. The crystal structure of Zn(dtsq)(batho) has been determined by X-ray crystallography. This complex crystallizes in the monoclinic space group P2 1/ n with a = 10.840(4), b = 17.630(7), c = 15.826(6) A ̊ , β = 101.23(2)°, V = 2967(2) A ̊ 3 and Z = 4 . The final refinement of all non-hydrogen atoms converged at R = 0.052 and R w = 0.075 for the 3406 observed reflections. The crystal structure indicates a mononuclear complex with a distorted tetrahedral geometry around the zinc atom and having one ethanol of solvation hydrogen bonded to one of the oxygens on the dtsq ligand. The complexes Zn(dtsq)(phen) and Zn(dtsq)(batho) are emissive in the solid state at room temperature and both complexes exhibit multiple emissions at lower temperature. The two emissions observed are believed to be metal assisted ligand to ligand charge transfer (LLCT) and an intraligand ππ ∗ transitions.