Journal
COORDINATION CHEMISTRY REVIEWS
Volume 254, Issue 13-14, Pages 1534-1548Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2009.12.026
Keywords
Dithiolene coordination compounds; Cluster complexes; Molecular conductors; Molybdenum sulfides
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The present article reviews synthetic approaches to efficiently prepare Mo3S7 clusters coordinated to 1,2-bis-dithiolene ligands of general formula [Mo3S7(dithiolene)(3)](2-) where dithiolene stands for tfd (bis(trifluoromethyl)-1,2-dithiolene), bdt (1,2-benzenedithiolene), mnt (maleonitriledithiolene), tdas (1,2,5-thiadiazole-3,4-dithiolene), dmid (1,3-dithia-2-one-4,5-dithiolene), dmit (1,3-dithia-2-thione-4,5-dithiolene) and the diselenolene dsit (1,3-dithia-2-thione-4,5-diselenolene). These [Mo3S7(dithiolene)(3)](2-) dianions serve as starting materials to access new dithiolene clusters featuring Mo3S7 and Mo2O2S2 cluster cores. The electrochemical and spectroscopic properties as well as solid state structures of Mo3S7/dithiolene compounds are also described. These C-3-symmetry [Mo3S7(dithiolene)(3)](2-) molecules inherently possess degenerate frontier orbitals and display a rich structural diversity due to the electrophilic character of the three sulfur atoms in axial positions. These characteristics make the [Mo3S7(dithiolene)(3)](2-) dianions, versatile targets for the development of new molecular conductors. Several examples of hybrid charge-transfer salts based on TTF-donors and [Mo3S7(dithiolene)(3)](2-)/[Mo3S7X6](2-) dianions (X = Cl, Br) are discussed as well as the preparation of the first family of cluster-based single-component magnetic conductors of formula Mo3S7(dithiolene)(3). (C) 2009 Elsevier B.V. All rights reserved.
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