Organic–inorganic hybrids constructed by Anderson-type polyoxoanions and copper coordination complexes

Four organic-inorganic hybrid compounds based on Anderson-type polyoxoanions, namely, {l_brace}[Cu(2,2'-bpy)(H{sub 2}O){sub 3}]{sub 2}[Cr(OH){sub 6}Mo{sub 6}O{sub 18}]{r_brace}{l_brace}[Cu(2,2'-bpy)(H{sub 2}O)Cl][Cu(2,2'-bpy) (H{sub 2}O)(NO{sub 3})][Cr(OH){sub 6}Mo{sub 6}O{sub 18}]{r_brace}.18H{sub 2}O (1), [Cu(2,2'-bpy)(H{sub 2}O){sub 2}Cl]{l_brace}[Cu(2,2'-bpy)(H{sub 2}O){sub 2}][Cr(OH){sub 6}Mo{sub 6}O{sub 18}]{r_brace}.4H{sub 2}O (2), (H{sub 3}O){l_brace}[Cu(2,2'-bpy)(H{sub 2}O){sub 2}]{sub 2}[Cu(2,2'-bpy)(H{sub 2}O)]{sub 2}{r_brace}[Cr(OH){sub 6}Mo{sub 6}O{sub 18}]{sub 3}.36H{sub 2}O (3), and (H{sub 3}O){l_brace}[Cu(2,2'-bpy)(H{sub 2}O){sub 2}]{sub 2}[Cu(2,2'-bpy)(H{sub 2}O)]{sub 2}{r_brace}[Al(OH){sub 6}Mo{sub 6}O{sub 18}]{sub 3}.33H{sub 2}O (4), were isolated by conventional solution method, and crystal structures have been determined by single-crystal X-ray diffraction. Among them, compound 1 displays a discrete supramolecular structure, compound 2 shows a chainlike structure with chloro-copper complexes as counteranions, and compounds 3 and 4 are isomorphic and exhibit unique 3D open frameworks with lattice water molecules residing in the channels. The compounds 3 and 4 represent the first example of 3D organic-inorganic hybrid compounds in the TMs/2,2'-bpy/POMs system. Investigation of the reaction conditions reveals that the geometry and size of the anions together with its coordinating abilities to the metal centers have a decisive influence on both the composition and the dimensionality of the final compounds. - Graphical Abstract: Four organic-inorganic hybrids based on Anderson-type polyoxoanions have been synthesized. Compound 1 displays a discrete structure, 2 shows a chainlike structure, 3more » and 4 are isomorphic and exhibit unique 3D open frameworks with lattice waters residing in the channels. The different structures suggest that the overall structures of the compounds are influenced by the nature of the acidic anions.« less