Characterization of mechanochemically synthesized imidazolates of Ag+1, Zn+2, Cd+2, and Hg+2 :: Solid state reactivity of nd10 cations

Silver, zinc, cadmium, and mercury imidazolates have been synthesized mechanochemically by milling imidazole and the metal oxides in an agate mortar. The reaction products were characterized by FTIR and XRPD techniques. The results obtained for the mechanochemical imidazolates have been compared with those obtained by precipitation reported in the literature. The mechanochemical Ag imidazolate has the same orthorhombic crystal structure as the precipitated one. The mechanochemical Zn imidazolate has a tetragonal structure with similar crystal parameters to those of Zn(Imz)(2)H2O, but no water molecules are present in the structure. This new anhydrous form is a polymorph of the one obtained by precipitation. The mechanochemical Cd imidazolate has a monoclinic structure which is the polymorph of the precipited orthorombic form. The mechanochemical Hg imidazolate presents a hexagonal structure which is a polymorph of the orthorombic structure obtained by precipitation. The influence of the nd(10) electronic configuration of the cations on the mechanochemical reaction is discussed. (c) 2006 Elsevier Ltd. All rights reserved.