Dithiolenes conductivity

Dithiolene complexes with the maleonitriledithiolate (mnt) ligand form highly delocalized systems and are widespread in studies of conducting and magnetic materials. The electronic properties have been extensively studied with various computational methods including Hiickel and extended Hiickel approaches to identify the nature of the orbitals involved in intramolecular and intermolecular interactions. These structural properties allow the complexes to interact in the solid state via short stacking S, S and short interstack S---S contacts.10 4-1048... 

The solid-state conducting and magnetic properties of 1,2-dithiolene and... 

The complex TBA2[Ni(dmit)2]7 2MeCN was the first reported conducting dmit2- salt.210 A 2D-structure was present in a-(Et2Me2N)[Ni(dmit)2]2,211 while the first superconductor containing a dithiolene system, (TTF)[Ni (dmit)2],212 was reported in 1986. To date, nine other compounds based on... 

Over the past decade a number of new covalently bonded TTF/ferrocene adducts have been reported [77, 78]. The crystal structure of the l,l -bis(l,3-dithiole-2-ylidine)-substituted ferrocene derivative has been published [77]. In this complex, ferrocene has essentially been incorporated as a molecular spacer between the two l,3-dithole-2-ylidene rings forming a stretched TTF molecule. This adduct, and its methyl-substituted derivative, have been combined with TCNQ to form charge-transfer complexes with room temperature powder conductivities of 0.2 S cm-1. Similar diferrocenyl complexes have been prepared with bis (dithiolene) metal complexes [79, 80]. 

New Molecular Architecture for Electrically Conducting Materials Based on Unsymmetrical Organometallic-Dithiolene Complexes... 

The anionic dithiolene complexes will form salts with tetrathiafulvalene. Expectations were that the solids would be highly conducting, but the products are insulators or semiconductors.1853... 

A few years after these events, a review article by McCleverty4 in 1968 provided (in over 170 pages) the first thorough overview of this field. This review contains a multitude of details which still merits its mention as a valuable source of information on this class of compounds. Several other reviews dealing with different aspects of dithiolene chemistry have appeared in the meantime.5"11 The field has expanded in different directions, spurred by the synthesis of several structurally unique compounds and of materials of particular use in quite diverse areas such as highly conducting molecular crystals and as infrared dyes for various applications. Dithiolenes thus represent a class of materials which are not only of significance on their own, but which also find some applications in which their unique electronic properties can be employed. 

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