Mixed-Addenda Lindqvist-Type Polyoxoanion [V(2)W(4)O(19)](4-)-Supported Copper Complexes

作者：Wang Chunling; Weng Linhong; Ren Yuanhang; Du Chengbo; Yue Bin^*; Gu Min; He Heyong

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2011, 637(3-4): 472-477.

DOI：10.1002/zaac.201000332

• Polyoxometalates
• Mixed-addenda compounds
• Lindqvist-type
• Copper
• Cluster compounds

Three mixed-addenda Lindqvist-type polyoxoanion-supported copper 1,10-phenanthroline (phen)or 2,2';-bipyridine (bpy) complexes, [Cu(phen)(H(2)O)(3)](2)[V(2)W(4)O(19)] (1), [Cu(bpy)(2)][H(2)V(2)W(4)O(19)]center dot 6H(2)O (2), and [Cu(bpy)(H(2)O)](2)[V(2)W(4)O(19)]center dot 4H(2)O (3) were synthesized in aqueous solution and characterized by elemental analysis, IR and (51)V NMR spectroscopy, TG as well as X-ray powder and single-crystal X-ray diffraction. The structure of compound 1 is constructed from copper(II)-tri(aqua)-phen complexes and [V(2)W(4)O(19)](4-)clusters. It exhibits a three-dimensional (3D) supramolecular framework due to the abundance of hydrogen bonding interaction between the copper-phen cation and the polyoxoanion. In compound 2 the [V(2)W(4)O(19)](4-) cluster as bidentate ligand coordinates two [Cu(bpy)(2)] units, which leads to a single twist-armed chain. In both 1 and 2, the crystallographical positions of the two vanadium atoms are totally disordered in the whole Lindqvist [V(2)W(4)O(19)](4-) cluster. In compound 3 the [V(2)W(4)O(19)](4-) cluster as a quadridentate ligand connects four [Cu(bpy)] units to form double armed chains, where two vanadium atoms are mainly disordered over four positions around the equatorial belt of the [V(2)W(4)O(19)](4-) cluster. Compounds 2 and 3 are the first examples of the extended structure based on mixed-addenda [V(2)W(4)O(19)](4-) and metal coordination ions. Furthermore, the extensive hydrogen bonding and pi-pi packing interactions between the chains play important roles in the construction of the 3D framework of 1-3.

• 出版日期2011-3
• 单位复旦大学