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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Dalton Trans., 2009, 9402 - 9409, DOI: 10.1039/b911586b

Tri-, tetra- and octa-metallic vanadium(III) clusters from new, simple starting materials: interplay of exchange and anisotropy effects

Ian S. Tidmarsh, Luke J. Batchelor, Emma Scales, Rebecca H. Laye, Lorenzo Sorace, Andrea Caneschi, Jürgen Schnack and Eric J. L. McInnes

The crystal structure of the monomeric vanadium(III) species mer-[V(bipy)Cl3(MeCN)] ( 1; bipy = 2,2-bipyridine) is reported. The solvothermal reaction of [V(bipy)Cl3(MeCN)]with Na(O2CPh) yields the T-shaped cluster [V3(O)Cl3(O2CPh)2(bipy)2(OEt)2], magnetic studies of which show strong intramolecular antiferromagnetic coupling giving a well isolated S = 1 ground state. Solvothermal treatment of 1 with triols yields a series of polymetallic clusters [V4Cl6(thme)2(bipy)3], [V3Cl4(Hcht)2(bipy)2]Cl and [V8(OH)2Cl4(cht)4(O2CPh)6(bipy)2], structurally related to previously reported {M4} centred triangles. Magnetic studies of this series reveal very weak intramolecular antiferromagnetic exchange and very strong local zero-field splitting effects.

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