| Tetrathiafulvalene (TTF) derivatives and dithiolen compounds are regarded as excellent donors because of their particular structures and properties. They can be easily oxidized to stable radical cations and are the major components of numerous electrocunductive materials named after "synthetic metals" or "organic metals" which exhibit electronic conductivities from semiconductor to superconductor. In the past two decades, the synthesis and design of supramolecular coordination polymeric networks with TTF derivatives has been a hightlight topic, because these coordination polymers have extended space frameworks and extensive S…S contacts, and their conductive dimensionalities are also expanded.In this study, 4,5-bis(cyanoethylsulfanyl)-1,3-dithiol-2-thione (bcdt) and its Ag(â… ) coordination polymer [Ag4(bcdt)4(CF3SO3)2]·(CF3SO3)2·acetone (â… ) have been synthesized. The single crystals of the title compounds were obtained by a solvent diffusion method. X-ray single crystal analysis reveals that the S…S contacts in the ligand (bcdt) lead to a 1-D wavy chain, while complexâ… exhibits a novel 3-D open coordination network in which intra-molecular face-to-face and side-by-side S…S contacts exist. The ligand bcdt is an insulator at RT, however complexâ… exhibits a semiconducting behavior with aσvalue of 6.45×10-8s·cm-1 at RT. The relationship between the property and structure of these compounds is also discussed.In addition, 6 ,7 - dialkylthio tetrathiafulvalene - 2 ,3 - dithiolate salts were treated with metal(â…¡) cations to afford six new bis(6 ,7 -dialkylthio tetrathiafulvalene - 2 ,3 - dithio) metal complexes with methyl quinolines as anti-cations: [(C8H6S8)Ni(C8H6S8)] (C10H10N)·CsI (â…¡), [(C10H10S8)Ni(C10H10S8)] (C10H10N)·CsI(â…¢), [(C10H10S8)Zn(C10H10S8)] (C10H10N)·CsI(â…£), [(C12H14S8)Ni(C12H14S8)] (C10H10N)·CsI(â…¤), [(C14H18S8)Ni(C14H18S8)] (C10H10N)·CsI(â…¥), [(C14H18S8)Zn(C14H18S8)] (C10H10N)·CsI (â…¦) . The products were characterized by IR and elementary analysis. The conductivities and electrochemical properties of final compoundsâ…¡-â…¦were also investigated. Cyclic voltammetry studies show that all compounds exhibit irreversible charge transfer reactions in the form of one stage, and a two electrons transfer process. The measurement of electrical conductivities for these compounds indicates that complexesâ…£andâ…¦are insulators, while compoundsâ…¡,â…¢,â…¤,â…¥are semiconductors with theσrt alues of 2.706×10-3,1.995×10-3,1.492×10-3,1.031×10-3 s·cm-1, respectively. The coordination modes of metal ions and the lengthes of the ligand substitute groups play an important role in the conductive behaviors of these complexes.
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