Syntheses and characterization of layered phenyl- and benzylphosphonates of tetravalent vanadium, Ca[(VO)(O3PPh)(2)]center dot 2H(2)O, Cd[(VO)(O3PPh)(2)]center dot 2H(2)O, Ba[(VO)(O3PCH2Ph)(2)]center dot 2H(2)O, Sr[(VO)(3)(O3PPh)(4)]center dot 5H(2)O and Ba[V4O4(OH)(2) (O3PPh)(4)]center dot 5H(2)O

摘要

Five new phenyl- and benzylphosphonates of tetravalent vanadium, Ca(VO)(O3PPh)(2)center dot 2H(2)O(1), Cd(VO)(O3PPh)(2)center dot 2H(2)O(2), Ba(VO)(O3PCH2Ph)(2)center dot 2H(2)O(3), Sr(VO)(3)(O3PPh)(4)center dot 5H(2)O(4) and Ba[V4O4(OH)(2)(O3PPh)(4)]center dot 5H(2)O(5), were synthesized under hydrothermal conditions and structurally characterized by single crystal and powder X-ray diffraction, CHN analyses, infrared spectroscopic, magnetic and thermal studies. They have layered structures, wherein the vanadium and alkaline earth or cadmium metal ions are approximately confined to a crystallographic plane and bonded to oxygen atoms of phenyl/benzylphoshonate moieties and water of crystallization. The structures of compounds 1-3 are of new type, whereas the compounds 4 and 5 have known types of structures. Their magnetic susceptibilities in the 20-300 K regions were found to vary with temperature, according to the Curie-Weiss law. The compounds 1 and 2 showed phase matching second-harmonic-generation responses.