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)(H 2 O)] 2 {[Cu(dien)(H 2 O)] 2 ‐[Cu(dien)(H 2 O) 2 ] 2 [Cu 4 (SiW 9 O 34 ) 2 ]}⋅ 5H 2 O ( 1 ; dien=diethylenetriamine), [Zn(enMe) 2 (H 2 O)] 2 {[Zn(enMe) 2 ] 2 [Zn 4 ‐ (HenMe) 2 (PW 9 O 34 ) 2 ]}⋅8H 2 O ( 2 ; enMe =1,2‐diaminopropane), and [Zn(enMe) 2 ‐(H 2 O)] 4 [Zn(enMe) 2 ] 2 {(enMe) 2 {[Zn‐ (enMe) 2 ] 2 [Zn 4 (HSiW 9 O 34 ) 2 ]}{[Zn‐ (enMe) 2 (H 2 O)] 2 [Zn 4 (HSiW 9 O 34 ) 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 (SiW 9 O 34 ) 2 ] 12− linked by copper complexes into a 2D structure, whereas 2 is constructed from novel inorganic–organic hybrid anions [Zn 4 (HenMe) 2 (PW 9 O 34 ) 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 (PW 9 O 34 ) 2 ] 10− with two types of bridging groups: zinc complexes and enMe ligands.