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Title: Magneto-Structural Correlation Studies of A Ferromagnetically Coupled Dinuclear Vanadium(IV) Complex. Single-Crystal EPR Study
Authors: Velayutham, M.
Varghese, B.
Subramanian, S.
Issue Date: 1998
Citation: Inorganic Chemistry, 37(6), 1336-1340
Abstract: The dimer potassium dioxo(citrato)vanadate(IV)-6-water. K4{VO[O2CCH2C(O)(CO2)CH 2CO2]}2�6H2O, was prepared by the reaction of citric acid and metavanadate in a neutral solution. The complex crystallizes in the space group P1? with unit cell parameters a = 8.474(5) �, b = 8.902(7) �, c = 9.596(9) �, � = 71.50(6)�, ?= 70.81(9)�, ? = 87.45(2)�, V = 647.l �3, and Z = 1. The dimeric anion contains a centrosymmetric planar four-membered V2O2 ring with the bridging oxygens derived from the hydroxyl groups. The configuration of the anion is anti-coplanar. A frozen solution EPR spectrum with zero-field splitting and 15 line hyperfine patterns on the parallel and perpendicular features characteristic of two equivalent vanadium atoms confirms the presence of a spin triplet. This is further supported by the presence of half-field "forbidden transition" at g � 4. A broad line with half-field forbidden transitions in the powder EPR spectra at X,Q-bands of the neat sample and at different temperatures shows the presence of a spin triplet ground state and a very weak intermolecular dipolar interaction. From anisotropic exchange contributions to D the magnitude of the derived exchange integral Jxy,x2-y2 is 56 cm-1. UV-visible, ESCA, and theoretical BVS studies support the proposed molecular and electronic structure of the complex.
ISSN: 201669
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