Zinc and copper complexes of stilbene iminopyridine ligands with eta 2-Olefin binding mode
Abstract
Two stilbene based iminopyridine ligands (L1-L2) synthesized by a condensation reaction between N, N-Dimethyl-4,4'-azodianiline and 2-pyridinecarboxaldehyde or 2,6-pyridinedicarboxaldehyde, with 73% and 65% yield, are described. The two ligands have been characterized by elemental analysis and spectroscopic techniques. The complexation of ligand L1 with ZnCl2 afforded neutral tetrahedral zinc(II) metal complex C1 formulated as [ZnL1Cl(2)] with a 2D supramolecular architecture reinforced by pi center dot center dot center dot pi stacking and hydrogen bonding in the solid state. Interestingly in the case of copper(I) complex C2, ligand L1 acts as a ditopic ligand since it coordinates one Cu(I) with an iminopyridyl fragment and a second metal center with an eta(2)-olefin binding mode giving rise to a 1D-polymeric structure. The coordination sphere is completed with an acetonitrile solvent molecule leading to a distorted tetrahedral geometry around copper cation and the resulting coordination polymer can be formulated as {[Cu(L1)(2)CH3CN] BF4}. In addition complexation of L2 with zinc chloride afforded complex C3 formulated as [ZnL2Cl(2)]. DFT and TDDFT computations permitted to investigate the frontier MOs of all species and to assign their UV-visible absorption bands.
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