A Theoretical Study of the Exchange Coupling in Hydroxo‐ and Alkoxo‐Bridged Dinuclear Oxovanadium(IV) Compounds

Abstract

AbstractA density functional study of exchange coupling in hydroxo‐ and alkoxo‐bridged dinuclear oxovanadium(IV) compounds is presented. Coupling constants calculated for full unmodeled structures are in good agreement with experimentally reported values, confirming the ability of the computational strategy used in this work to predict the exchange coupling in dinuclear VIV compounds. The influence of the configuration of the [VO(μ‐OR)2VO]2+ core in compounds with two edge‐sharing octahedrally coordinated oxovanadium(IV) centers, of the nature of the terminal ligands and of structural distortions on the coupling constant have been analyzed through model calculations. The results indicate that the coupling constant is less affected by these factors than for hydroxo‐ and alkoxo‐bridged CuII compounds. The calculations support the orbital models usually employed in qualitative interpretations of magneto‐structural correlations, showing good correlations between the calculated coupling constants and the overlap between the two magnetic orbitals or the square of the orbital gap. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)