A Novel Chainlike As−V−O Polymer Based on a Transition Metal Complex and a Dimeric Polyoxoanion

The novel polyoxometalate {[As8V13NiClO41][Ni(en)2(H2O)][Ni(en)2]}{[Ni(en)2(H2O)2]0.5}·4H2O (1), which is the first
example of a chainlike inorganic−organic hybrid polymer based on dimeric polyoxoanions linked by nickel complex
fragments, has been synthesized in the system of As2O3−V2O5−H2C2O4−en−NiCl2·6H2O−H2O under hydrothermal
conditions and characterized by IR, TGA, elemental analysis, single crystal X-ray diffraction, XPS, and magnetic
susceptibility studies, respectively. This compound crystallized in the triclinic space group P1̄ with a = 13.358(3)
Å, b = 14.198(3) Å, c = 19.723(4) Å, α = 83.88(3)°, β = 86.04(3)°, γ = 64.66(3)°, V = 3360.2(2) Å3, and Z
= 2. Interestingly, the dimeric polyoxoanion contains two {[Ni(en)2(H2O)][As8V13NiClO41]} cluster units linked by
Ni−O−As bonds and is a Ni-substituted [As8V13NiClO41] cluster supported by [Ni(en)2(H2O)] coordination fragment.
The chainlike structure consists of {[Ni(en)2(H2O)][As8V13NiClO41]}2 dimeric polyoxoanions and [Ni(en)2] groups
which are linked together through vertexes forming a unique one-dimensional polymer. The study of the magnetic
susceptibility of 1 demonstrates the presence of antiferromagnetic interaction in 1.