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Tripodal Thiols as Ligands for Molecular Magnets: Very Strong Antiferromagnetic Exchange Interactions in Vanadium(III) Clusters
Author(s) -
Batchelor Luke J.,
Fitzgerald Emma,
Wolowska Joanna,
McDouall Joseph J. W.,
McInnes Eric J. L.
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201000823
Subject(s) - diimine , antiferromagnetism , hydroxymethyl , chemistry , tris , crystallography , metal , vanadium , vanadium oxide , oxide , electrochemistry , stereochemistry , inorganic chemistry , organic chemistry , catalysis , physics , biochemistry , electrode , condensed matter physics
The synthesis, structural and magnetic characterisation of [V III 3 O(tmme) 2 (diimine) 2 Cl] [diimine=2,2′‐bipyridine ( 1 ) or 1,10‐phenanthroline ( 2 )] and (HNEt 3 ) 2 [V III 4 O(tmme) 4 ] ( 3 ) is reported, in which H 3 tmme is tris(mercaptomethyl)ethane, MeC(CH 2 SH) 3 , the thiol analogue of the famous tripodal alcohol ligands typified by H 3 thme [tris(hydroxymethyl)ethane, MeC(CH 2 OH) 3 ]. Complexes 1 and 3 have “T‐shaped” and square topologies, respectively, and the latter is centred on a rare example of a square‐planar oxide. The tri‐thiolate ligands bind the periphery of the clusters and provide such strong antiferromagnetic exchange pathways that in both cases only a single total spin state is occupied up to room temperature, in the absence of metal–metal bonding. Magnetic data, electronic structure calculations and electrochemical data are reported.