Alcoholysis/hydrolysis of 1,1′-carbonyldiimidazole as a means of preparing unprecedented, imidazole-containing one-dimensional coordination polymers of copper(II)

The use of 1,1'-carbonyldiimidazole, (im)(2)CO, for the synthesis of imidazolate (im(-)) and/or imidazole (Him)-containing copper(II) coordination polymers is described. The [Cu(2)(O(2)CMe)(4)(H(2)O)(2)]/(im)(2)CO reaction system in EtOH yields the new polymeric species [Cu(O(2)CMe)(im)(Him)(EtOH)](n) () and the known compound [Cu(im)(2)](n) (), depending on the reaction conditions. A mechanism for the alcoholysis/hydrolysis of (im)(2)CO is proposed. Complex comprises neutral, zigzag chains with the eta(1):eta(1):mu im(-) ligand bridging two neighbouring Cu(II) atoms. Each square pyramidal metal centre is coordinated to two imidazolate nitrogen atoms, the pyridine-type nitrogen atom of the terminal imidazole ligand, one acetate oxygen atom and the ethanol oxygen atom. The dc magnetic susceptibility data for have been analysed according to the Bonner-Fisher model for an equally spaced S = 1/2 chain, revealing moderate antiferromagnetic Cu(II)Cu(II) exchange interactions (J = -33.5 cm(-1) using the H = -2J summation operatorS(i)S(i+1) spin Hamiltonian). The reaction system Cu(NO(3))(2).3H(2)O/(im)(2)CO in EtOH leading to the preparation of known trans-[Cu(NO(3))(2)(Him)(4)] () is also described. With terephthalate(-2) (tp(2-)), instead of MeCO(2)(-), in MeOH/H(2)O the product is the new, 1D linear coordination polymer [Cu(tp)(Him)(2)(H(2)O)](n).2nH(2)O (.2nH(2)O). Adjacent square pyramidal Cu(II) atoms are singly bridged by the bis-monodentate tp(2-) ligand, while two monodentate Him groups and one H(2)O molecule complete five-coordination at each metal centre. The chains of and .2nH(2)O form interesting, hydrogen-bonded 3D networks. The combined work demonstrates the usefulness of (im)(2)CO in the preparation of interesting Cu(II) coordination polymers which can not be obtained by the use of Him.