1D Hydrogen-Bonded Polymers Assembled by Tetraaza Macrocyclic Metal(II) Complexes and Inorganic Salts

The self-assembly of [M(L)]Cl-2 center dot 2H(2)O (M = Ni2+ and Cu2+, L = 3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0(1.18),0(7.12)]docosane) with sodium 1,2,4-benzenetricarboxylate (Na(3)btcb) and KNO3 generates the 1D hydrogen-bonded polymers with formulas [Ni(L)(H(2)btcb(-))(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 H(2)btcb(-) 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 M-II/M-III and M-II/M-I processes. The electronic spectra and electrochemical behavior of the complexes are significantly affected by the nature of the axial ligands.