Syntheses, Structure And Properties Of Tetrathiafuvalene Derivatives And Their Coordination-Polymers

The Sulfur-rich organic ligands, tetrathiafulvalene (TTF) and it's derivatives, are excellent functional molecular materials. So far the donors with sulfur have shorter π -conjugated systems and non-plane molecular structures; hence, it's necessary to expend the π-conjugated systems and numbers of peripheral ladder-like sulfur atoms in these ligands. On the one hand, more closely S...S contacts can be formed between supramolecular chains, and the electron-flowing between polymer chains and the conductivity of molecules can also be enhanced. On the other hand, more S...S contacts are available for building 2-0 or 3-D supramolecular networks by supramolecular interactions. At the same time, the extended conductive dimensions could avoid Peierls Phase Transfer at low temperature.For the purpose of the above, main contents of this paper are as follows:(1)By using carbon disulfide, trimethylphosphite etc. as raw materials, two compounds of bi-fused TTF derivatives,2-(4I,5'-bis(methylthio)-1',3'-dithiol -2'-ylidene)-5-(4', 5'-bis(cyanoethylsulfanyl)-1', 3'-dithiole-2'-ylidene)-1,3,4,6-tetrathiapentalene(l) and 2, 5-bis(4',5'-bis(methylthio)-1', 3'-dithiol-2'-ylidene)-1,3,4,6-tetrathiapentalene(ll), were synthesized by Wittig cross-coupling reaction, and the compound(l) is a novel one which is not reported in literatures. The two bi-fused TTF derivatives are potential excellent electron donors because of their extended π-conjugated systems. The effects of substituted groups on their syntheses and the mechanics of coupling reaction were also discussed.(2)The coordinating reactions of five TTF derivatives with different silver(l), copper(l) and nickel(ll) were studied systemically under the conditions of changing reaction- solvent, reaction-ratio and diffusion-solvent.Four single crystals of novel complexes and three conductive complexes with five TTF derivatives and silver(l), copper(l) and nickel(ll) were obtained.(3)The products including some intermediates were analyzed by IR and elementary analyses. Two single-crystal complexes were resolved by X-Ray diffraction; five complexes' conductivities were determined, three of them were semiconductors and the other were insulators.