Robust 1D open rack-like architecture in coordination polymers of Anderson POMs [{Na4(H2O)14}{Cu(gly)}2][TeMo6O24] and [{Cu(en)2}3{TeW6O24}]: synthesis, characterization and heterogeneous catalytic epoxidation of olefines.

Two novel organic-inorganic hybrid tungsto- and molybdo-telurates having formula [{Na(4)(H(2)O)(14)}{Cu(gly)}(2)][TeMo(6)O(24)] (1){gly = glycine} and [{Cu(en)(2)}(3){TeW(6)O(24)}]·6H(2)O {en = ethyline-diamine} (2) based on Anderson type heteropolyoxometalates (POMs) have been synthesized and characterized by X-ray crystallography. Common structural feature of both 1 and 2 is the presence of a unique 1D open rack-like architecture, where the disc shaped Anderson POMs act as steps and cationic Cu-organic complexes act as handles of the rack. In 1 the independent structural unit is a 1D coordination polymer with the above mentioned rack type architecture, while in 2, these independent rack-like architectures are further extended to a 2D coordination polymer. Heterogeneous catalysis for the epoxidation of cyclohexene and styrene by complexes 1 and 2 showed very good catalytic efficiency resulting epoxides of 60% yield, with dialcohol formed by the hydrolysis of epoxides, as the other major product (28%). Cyclic voltammetric studies of [{Na(4)(H(2)O)(14)}{Cu(gly)}(2)][TeMo(6)O(24)] (1) in aqueous KCl solution indicates that the redox changes occur only on the copper centers and supported by carrying out parallel experiments on the precursors like (Cu(gly)(2) and TeMo(6)O(24), under the identical experimental conditions. The E(1/2) = 0.662, -0.142 and -0.332 V(vs. SCE) correspond to Cu(III) → Cu(II), Cu(II) → Cu(I) and Cu(I) → Cu(0) reductions, respectively. Thermal analyses reveal identical phase transition reactions with an exothermic peak in the DTA curve at 380 °C for 1 and an endothermic peak appears at comparatively higher temperature (408 °C) for 2 manifesting the higher stability of tungstane based POM over the molybdenum ones. EPR as well as magnetic moment results indicate that both the complexes 1 and 2 are paramagnetic with one unpaired electron per copper(II) ion.