The synthesis, crystal structures, and magnetic properties are reported for a redox family of butllerfly-type tetrametallic vanadium alkoxide clusters, namely [V-2(VO)(2)(acac)(4)(RC{CH2O}(3))(2)] (R = Me 1, Et 2, CH2OH 3), [V-2(VO)(2)(acac)(2)(O2CPh)(2)(MeC{CH2O}(3))(2)] (5), [(VO)(4)(MeOH)(2)(O2CPh)(2)({HOCH2}C{CH2O}(3))(2)] (6), [V4Cl2(dbm)(4)(RC{CH2OH}(3))(2)] (R = Me 7, Et 8, CH2OH 9), and [V4Cl2(dbm)(4)(MeO)(6)] (10). The cluster cores are {V-4(IV)} (6), {(V2V2IV)-V-III} (1-5), and {V(III)4} (7-10), with examples of both isomeric forms of the of the mixed-valence cores (either V-III or V-IV ions forming the butterfly body). Magnetic studies reveal the clusters to be dominated by antiferromagnetic exchange interactions in each case. The magnetic exchange parameters are determined for representative examples of each core type. {V-4(IV)} and {V-4(III)} have diamagnetic ground states. The two isomeric {(V2V2IV)-V-III} types are found to give rise to either an S = 0 ground state with a number of low-lying excited states due to competing antiferromagnetic exchange interactions (V-2(III) butterfly body) or to a well-isolated S = 1 ground state (V-2(IV) butterfly body). ; Tidmarsh, Ian S. Scales, Emma Brearley, Paul R. Wolowska, Joanna Sorace, Lorenzo Caneschi, Andrea Laye, Rebecca H. McInnes, Eric J. L. 38 AMER CHEMICAL SOC WASHINGTON 228LS