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 polyoxotungstates and transition-metal complexes, [Cu(dien)(H2O)]2{[Cu(dien)(H2O)]2[Cu(dien)(H2O)2]2[Cu4(SiW9O34)2]} x 5 H2O (1; dien = diethylenetriamine), [Zn(enMe)2(H2O)]2{[Zn(enMe)2]2[Zn4(HenMe)2(PW9O34)2]} x 8 H2O (2; enMe = 1,2-diaminopropane), and [Zn(enMe)2(H2O)]4[Zn(enMe)2]2{(enMe)2{[Zn(enMe)2]2[Zn4(HSiW9O34)2]}{[Zn(enMe)2(H2O)]2[Zn4(HSiW9O34)2]}} x 13 H2O (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 [Cu4(SiW9O34)2]12- linked by copper complexes into a 2D structure, whereas 2 is constructed from novel inorganic-organic hybrid anions [Zn4(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 [Zn4(PW9O34)2]10- with two types of bridging groups: zinc complexes and enMe ligands.