Abstract

Two new polyoxometalates [ Ni ( phen ) 3 ] [ Ni ( en ) 3 ] [ Ni ( en ) 2 ( H 2 O ) 2 ] [ Ni ( en ) 2 ] 0.5 [ PW VI 7 W V 2 V IV 3 O 40 ( V IV O ) 2 ] · 6 H 2 O ( 1) and [ Ni ( phen ) 3 ] 2 [ Ni ( en ) 2 ] Na [ PW VI 7 W V 2 V IV 3 O 40 ( V IV O ) 2 ] · 8 H 2 O ( 2) (en=ethylenediamine, phen=1,10-phenanthroline) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, IR, EPR, XPS, elemental analysis and thermogravimetry. Their structures exhibit interesting 3D supramolecular networks, and contain new bicapped (pseudo-) Keggin-type tungsten–vanadium cluster and the template transition-metal complexes (TMCs) being generated in situ under mild hydrothermal conditions. Interestingly, compound 1 contains four different kinds of nickel complex countercations.

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