Abstract
The self-assembly of [M(L)]Cl2·2H2O (M = Ni2+ and Cu2+, L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.18,07.12]docosane) with sodium 1,2,4-benzenetricarboxylate (Na3btcb) and KNO3 generates the 1D hydrogen-bonded polymers with formulas [Ni(L)(H2btcb−)2] (1) and [Cu(L)(NO3)2] (2). These polymer complexes have been characterized by X-ray crystallography, spectroscopy and cyclic voltammetry. The crystal structure of 1 shows a distorted octahedral coordination geometry around the nickel(II) ion, with the four secondary amines of the macrocycle and two carboxylate oxygen atoms of the H2btcb− ligand in the trans position. In 2, the coordination environment around the central copper(II) ion reveals an axially elongated octahedron with four Cu–N bonds and two oxygen atoms of the nitrate ligand in the trans position. The cyclic voltammograms of the complexes undergo two one-electron waves corresponding to MII/MIII and MII/MI processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the axial ligands.
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