Hybrid inorganic–organic 1-D and 2-D frameworks with {As8V14O42} clusters as building blocks

Three novel hetero-polyoxovanadates, [Cd(2,2′-bpy)3]{[Cd(dien)]As8V14O42(H2O)} (1, 2,2′-bpy=2,2′-bipyridine, and dien=diethylenetriamine), [Zn(2,2′-bpy)2]2[As8V14O42(H2O)]·H2O (2) and [Ni(en)2]3[As8V14O42(HPO3)]·4H2O (3, en=ethlenediamine), were hydrothermally synthesized and characterized by single-crystal X-ray diffraction. Crystal data: 1 monoclinic, P2(1)/n  , a=15.1728(5)a=15.1728(5), b=19.2863(5)b=19.2863(5), c=25.7122(9)Å, β=96.005(2)°β=96.005(2)°, Z=4. 2, orthorhombic, P  2(1)2(1)2(1), a=12.1270(3)a=12.1270(3), b=15.8678(8)b=15.8678(8), c=40.0422(1)Å, Z=4Z=4. 3, triclinic, P1¯, a=12.9340(3)a=12.9340(3), b=13.4130(3)b=13.4130(3), c=21.1820(4)Å, α=87.170(3)°α=87.170(3)°, β=77.517(3)°β=77.517(3)°, γ=68.480(3)°γ=68.480(3)°, Z=2Z=2. Compounds 1–3 are all made of the {As8V14O42} shells linked by corresponding transition metal complexes into extended structures. Compound 1 and 2 present 1-D wave-like and tubular structures, respectively, while compound 3 exhibits a novel 2-D structure containing interwinding puckery layers. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between VIV cations in 1 and 2.

Three inorganic–organic hybrid solid materials based on [As8V14O42(H2O)]4− cluster building blocks bridging by transition metal complexes have been obtained by hydrothermal reaction and characterized by single-crystal X-ray diffraction. These compounds exhibit a wave-like chain, a tube-shaped chain and a rare two-dimensional structure containing interwinding puckery layers. Variable temperature susceptibility measurements demonstrate the presence of antiferromagnetic interaction between VIV cations in two one-dimensional structures.Figure optionsDownload as PowerPoint slide