Synthesis, structure, and magnetic properties of [(CH3CN)5V-O-V(CH3CN)5][BF4]4 |
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Authors: | Cissell Julie A Kaur Narpinder Nellutla Saritha Dalal Naresh S Vaid Thomas P |
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Institution: | Department of Chemistry and Center for Materials Innovation, Washington University, St. Louis, Missouri 63130, USA. |
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Abstract: | The reaction of vanadium(III) acetylacetonate with HBF4 in acetonitrile yields (CH3CN)5V-O-V(CH3CN)5]BF4]4, a material that serves as a convenient precursor to other V-O-V]4+ species such as (bipy)2(CH3CN)V-O-V(CH3CN)(bipy)2]BF4]4 (bipy=2,2'-bipyridine). Single-crystal X-ray diffraction shows that the V-O-V linkage of (CH3CN)5V-O-V(CH3CN)5]4+ is linear. An Evans method measurement of the solution-phase magnetic susceptibility indicates strong ferromagnetic coupling between the vanadium centers. Magnetic susceptibility (chi) and magnetization (M(H)) data for a powdered sample and for a single crystal oriented with its V-O-V axis parallel to the applied field were measured over 1.8-300 K. The results suggest that the V(III) centers are ferromagnetically coupled with J approximately 72 K (approximately 50 cm(-1)) yielding a ground state with a total spin Stotal=2. Theoretical fit to the M(H) plot for the single crystal yielded g||=2.01+/-0.01 and the zero-field splitting parameter D=0.60+/-0.04 K (0.42+/-0.03 cm(-1)). EPR measurements at 34 and 101.6 GHz are consistent with the Stotal=2 ground state and yield g||=1.9825, g perpendicular=1.9725 and D=0.57+/-0.03 K. |
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