Extended Architectures constructed from sandwich tetra-metal-substituted polyoxotungstates and transition-metal complexes

Three unprecedented 2D architectures made up of sandwich-type tetra-metal-substituted polyoxotung-states and transition-metal complexes, [Cu(dien)(H2O)](2){[Cu(dien)(H2O)](2)-[Cu(dien)(H2O)(2)](2)[Cu-4(SiW9O34)2]}. 5H(2)O (1; then = diethylenetriamine), [Zn(enMe)(2)(H2O)](2){[Zn(enMe)(2)](2)[Zn-4-(HenMe)(2)(PW9O34)(2)]}center dot 8H(2)O (2; enMe =1,2-diaminopropane), and [Zn(enMe)(2)-(H2O)](4)[Zn(enMe)(2)](2){(enMe)(2){[Zn-(enMe)(2)](2)[Zn-4(HSiW9O34)(2)]}{[Zn-(enMe)(2)(H2O)](2)[Zn-4(HSiW9O34)2]}}. 13H(2)O (3) were hydrothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis, and single-crystal X-ray diffraction. Compound 1 consists of anions [Cu-4(SiW9O34)(2)](12-)linked by copper complexes into a 2D structure, whereas 2 is constructed from novel inorganic-organic hybrid anions [Zn-4(HenMe)(2)(PW9O34)(2)](8-)linked by zinc complexes into a 2D structure. The most interesting is the unique 2D network 3, which consists of anions [Zn-4(PW9O34)(2)](10-) with two types of bridging groups: zinc complexes and enMe ligands.