Two new transition-metal complexes (TMCs)-templated three-dimensional supramolecular networks based on tungstovanadophosphates

Two new polyoxometalates [Ni(phen)3][Ni(en)3][Ni(en)2(H2O)2][Ni(en)2]0.5[PWVI7WV2VIV3O40(VIVO)2]·6H2O[Ni(phen)3][Ni(en)3][Ni(en)2(H2O)2][Ni(en)2]0.5[PWVI7WV2VIV3O40(VIVO)2]·6H2O (1) and [Ni(phen)3]2[Ni(en)2]Na[PWVI7WV2VIV3O40(VIVO)2]·8H2O[Ni(phen)3]2[Ni(en)2]Na[PWVI7WV2VIV3O40(VIVO)2]·8H2O (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.