One-dimensional hydrogen-bonded infinite chains composed of nickel(II) and copper(II) tetraaza macrocyclic complexes with cyclopropane-1-carboxylic acid-1-carboxylate ligand

Abstract

The reaction of [M(L)]Cl 2 Á 2H 2 O (M = Ni 2+ and Cu 2+ , L = 3, 14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,0 1.18 ,0 7.12 ]docosane) with 1,1-cyclopropanedicarboxylic acid (H 2 -cpdc) generates one-dimensional hydrogen-bonded infinite chains [Ni(L)(H-cpdc) 2 ] (1) and [Cu(L)(H-cpdc) 2 ] (2) (H-cpdc = cyclopropane-1-carboxylic acid-1-carboxylate). These complexes have been characterized by X-ray crystallography, spectroscopy, and cyclic voltammetry. The crystal structures of (1) and (2) show a distorted octahedral coordination geometry around the metal ion, with four secondary amines and two oxygen atoms of the H-cpdc ligand at the trans position. Complexes (1) and (2) display the one-dimensional hydrogenbonded infinite chains. The cyclic voltammogram of the complexes display 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 H-cpdc ligand.

Self-assembly of metal(II) tetraaza macrocyclic complexes with cyclobutane-1-carboxylic acid-1-carboxylate ligand linked by hydrogen bond

“…Macrocyclic complexes with aromatic and aliphatic polycarboxylate ligands have been proved to be good building blocks for the construction of coordination polymers and multi-dimensional supramolecular networks [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. For example, the reaction of [Ni(L)]Cl 2 Á 2H 2 O with 1,3,5-benzenetricarboxylic acid (H 3 btc) yields 2D nickel(II) complex via covalent and hydrogen bonds {[Ni(L)] 3 [l-btc] 2 Á 8H 2 O} n [12], which reveals a geometrically symmetric core with a {4/6}coordination number set.…”