Summary: | Due to their highly interesting electroactive properties, complexes based on the sulphur heterocycle DMIT have been studied extensively for several decades. The literature is abundant with materials exhibiting semiconducting and metallic properties and up to early 2000 there are eight examples of DMIT based superconductors. In the case of the DMIT complexes, previous work has been constrained to the variation of the transition metal and/or the counter-anion. The work herein concerns the synthesis of a novel series of electroactive ligands, similar to the well-known DMIT species. In contrast to the DMIT ligand, our target derivatives incorporate two thioether and two dithiolate environments as the overall chelating entity. The thioether functionalities are linked via suitable spacer groups and this feature should present a major advantage over traditional DMIT complexes, by adding solubility and synthetic versatility to the overall nature of the complex. In addition to the metal complexes based on DMIT ligands, charge transfer (CT) halogen adducts of these DMIT ligands and their synthetic intermediates are described, providing highly interesting and novel solid state structures and atom-to-atom inter- and intra-molecular interactions.
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