Organic-inorganic hybrid materials: hydrothermal syntheses and structural characterization of bimetallic organophosphonate oxides of the type Mo/Cu/O/RPO(3)(2-)/organoimine

The hydrothermal reactions of a Cu(II) starting material, a molybdate source, 2,2'-bipyridine or terpyridine, and the appropriate alkyldiphosphonate ligand yield two series of bimetallic organophosphonate hybrid materials of the general types Cu(n)(bpy)(m)Mo(x)O(y)(H(2)O)(p)O(3)P(CH(2))(n)PO(3)](z)] and Cu(n)(terpy)(m)Mo(x)O(y)(H(2)O)(p)O(3)P(CH(2))(n)PO(3)](z)]. The bipyridyl series includes the one-dimensional materials Cu(bpy)(MoO(2))(H(2)O)(O(3)PCH(2)PO(3))] (1) and Cu(bpy)(2)]Cu(bpy)(H(2)O)](Mo(5)O(15))(O(3)PCH(2)CH(2)CH(2)CH(2)PO(3))].H(2)O (5.H(2)O) and the two-dimensional hybrids Cu(bpy)(Mo(2)O(5))(H(2)O)(O(3)PCH(2)PO(3))].H(2)O (2.H(2)O), Cu(bpy)](2)(Mo(4)O(12))(H(2)O)(2)(O(3)PCH(2)CH(2)PO(3))].2H(2)O (3.2H(2)O), and Cu(bpy)(Mo(2)O(5))(O(3)PCH(2)CH(2)CH(2)PO(3))](4). The terpyridyl series is represented by the one-dimensional Cu(terpy)(H(2)O)](2)(Mo(5)O(15))(O(3)PCH(2)CH(2)PO(3))].3H(2)O (7.3H(2)O) and the two-dimensional composite materials Cu(terpy)(Mo(2)O(5))(O(3)PCH(2)PO(3))] (6) and Cu(terpy)](2)(Mo(5)O(15))(O(3)PCH(2)CH(2)CH(2)PO(3))] (8). The structures exhibit a variety of molybdate building blocks including isolated MoO(6)] octahedra in 1, binuclear subunits in 2, 4, and 6, tetranuclear embedded clusters in 3, and the prototypical Mo(5)O(15)(O(3)PR)(2)](4-) cluster type in 5, 7, and 8. These latter materials exemplify the building block approach to the preparation of extended structures.