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  • Title: Versatile coordinative abilities of a new hybrid pteridine-thiosemicarbazone ligand: crystal structure, spectroscopic characterization, and luminescent properties.
    Author: Jiménez-Pulido SB, Linares-Ordóñez FM, Moreno-Carretero MN, Quirós-Olozábal M.
    Journal: Inorg Chem; 2008 Feb 04; 47(3):1096-106. PubMed ID: 18186630.
    Abstract:
    The synthesis and characterization of the first thiosemicarbazone-lumazine (TSCLMH=the thiosemicarbazone of 6-acetyl-1,3,7-trimethyllumazine) hybrid ligand is reported. The influence of the conformation of this compound on its energy and the atomic contribution to the molecular orbitals have been theoretically investigated. Ni(II), Cu(I), Zn(II), and Cd(II) complexes of this ligand have been synthesized and characterized by elemental analysis, thermogravimetric studies, IR, 1H, 13C, and 15N NMR, and UV-vis-NIR spectroscopy, magnetic measurements, and X-ray crystallography. Four types of coordination modes for the ligand may be predicted: (a) double bidentate; (b) tetradentate; (c) tridentate; (d) bidentate. Structures of representative complexes of types a, b, and d have been determined by X-ray crystallography. In the [Cu(TSCLMH)]2(ClO4)2 complex, TSCLMH acts as a doubly bidentate bridging ligand forming a dimer with a Cu...Cu distance of 2.876 A. The geometry around the metal ion is trigonally distorted tetrahedral with a relatively long (four-atom) bridge between the metal centers instead of the shorter, mainly single atom, bridges present in other thiosemicarbazone derivatives complexes. In the [Cd(NO3)2(TSCLMH)(EtOH)] complex, the metal ion displays eight-coordinated geometry with the TSCLMH ligand acting in a tetradentate planar fashion and two nitrate anions, one monodentate and the other bidentate. The coordination polyhedron in [Cd(TSCLM)2(H2O)].MeOH.2H2O is a square pyramid with two monoanionic ligands acting as bidentate NS donors and a water molecule completing the coordination sphere. Fluorescence spectroscopic properties of TSCLMH have been studied as well as the changes in position and intensity of fluorescence bands caused by the complexation with different metal ions (Ni2+, Cu+, Zn2+, Cd2+).
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