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Solvothermal Syntheses of High‐Nuclearity Vanadium( III ) Clusters
Author(s) -
Laye Rebecca H.,
Murrie Mark,
Ochsenbein Stefan,
Bell Aidan R.,
Teat Simon J.,
Raftery James,
Güdel HansUlrich,
McInnes Eric J. L.
Publication year - 2003
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.200305641
Subject(s) - vanadium , solvothermal synthesis , crystallography , materials science , chemistry , metallurgy
Superheating alcohol solutions of simple trimetallic vanadium( III ) precursors gives the octa‐ and decametallic vanadium( III ) clusters [V 8 (OEt) 8 (OH) 4 (O 2 CPh) 12 ] ( 1 ) and [V 10 (OMe) 20 (O 2 CMe) 10 ] ( 2 ). Cluster 2 is the largest vanadium( III ) cluster synthesised to date. Thus solvothermal synthetic techniques are an excellent route to high‐nuclearity vanadium( III ) clusters. Both 1 and 2 consist of a planar or near‐planar array of V III ions. The metal ions in 1 are bridged by either a μ 2 ‐hydroxide and two μ 2 ‐benzoate groups or two μ 2 ‐ethoxides and a μ 2 ‐benzoate groups, the two bridging arrangements alternating around the ring. In 2 each pair of neighbouring metal ions is bridged by two μ 2 ‐methoxides and a μ 2 ‐acetate, and this molecule is the V III analogue of Lippard's famous “ferric wheel”. Preliminary magnetic susceptibility studies show the exchange coupling in both complexes to be antiferromagnetic in nature, with the coupling stronger in 1 than in 2 .