Mixed-valence 24-vanadophosphate decorated with six RuII(dmso)(3) groups: [{Ru-3(II)(dmso)(9)(PV11VRuO37)-V-V-Ru-IV-O-III(OH)(3)}(2)](8-)

摘要

The mixed-valence 24-vanadophosphate [{Ru-3(II)(ddmso)(9)(PV11VRuO37)-V-V-Ru-IV-O-III(OH)(3)}(2)](8-) (1) has been synthesized and characterized in the solid state by IR, magnetism, EPR, XPS, and elemental analysis. Single-crystal X-ray analysis was carried out on Na8[{Ru-3(II)(dmso)(9)(PV11VRuO37)-V-V-Ru-IV-O-III(OH)(3)}(2)]center dot 46H(2)O (Na-1), which crystallizes in the triclinic system, space group P1, with a = 17.168(3) angstrom, b = 18.1971(14) angstrom c = 20.1422(13) angstrom alpha = 114.753(3)degrees, beta = 99.390(4)degrees, gamma = 95.124(4)degrees, and Z = 2. Polyanion 1 has an unusual, open structure composed of 2 (RuO6)-O-III octahedra, 2 (VO6)-O-IV octahedra, 14 (VO5)-O-V square-pyramids, 8 V-V O-4 tetrahedra, and 2 PO4 tetrahedra which are all directly linked via edges and corners. The outer surface of 1 is decorated with six Ru-II(dmso)(3) groups. XPS studies on Na-1 confirm the presence of 2 Ru-III and 6 Ru-II as well as 22 V-V and 2 V-IV centers. Magnetic susceptibility data on Na-1 show that the V-IV - Ru-III pairs are coupled antiferromagnetically, with J(1) = -13 K and J(2) similar to -3 K. We did not detect any peak in our EPR measurements on Na-1, thus supporting the conclusion that Na-1 is diamagnetic in its ground state.