Synthsises, Stuctrues And Properties Of Organic Sulfur-Rich Ligands And Their Metal-Coordinated Complexes

Derivatives of tetrathiafulvalene(TTF) and dithiolen are regarded as one kind offunctional material precursors(donor and acceptor) for their particular structures andproperties. However, these donors with sulfur atoms reported previously have shorterπ-conjugated systems or non-plane molecular structures, hence it is necessary to expend theπ-conjugated systems and increase the numbers of peripheral ladder-like sulfur atoms inthese ligands, for getting more extendingπ-conjugated systems and more closely S…Scontacts.By using carbon disulfide, trimethylphosphite etc. as raw materials, three newcompounds of bi-fused TTF derivatives: 2-(4',5'-bis(alkylthio)-1',3'-dithiol-2'-ylidene)-5-(4',5'-bis(cyanoethylsulfanyl)-1',3'-dithiole-2'-ylidene)- 1,3,4,6-tetrathiapentalene(Ⅶ) weresynthesized by Wittig cross-coupling reaction. The products were characterized by IR,~1H-NMR and elementary analysis, and the route of synthesis was proved to be feasible. Theconductivities and electrochemical properties of final compounds(Ⅶ) and intermediatecompounds 2,3-bis(cyanoethlsulfanyl)-6,7-bis(alkylthio) tetrathiafulvalen(Ⅴ) wereinvestigated. Cyclic voltammetry studies show that the electrochemical behaviors of (Ⅶ) and(Ⅴ) are irreversible. Compounds (Ⅴ) shows a single electron transfer process whereas thecharge transfers of compounds (Ⅶ) occur in the form of two stages and shows a two electronstransfer process. The electrical conductivities of compounds (Ⅶ)were measured. The resultsindicate that all of these compounds, except ethyl and propyl substituted derivatives whichexhibit semiconductive behaviour, are insulators.On the other hand, four single crystals of Ag(Ⅰ) coordination polymers with sulfurcontaining organic ligands were obtained by means of solvent diffusion method. Thestructures of the products were characterized by IR, elementary analysis andⅩ-ray singlecrystal diffraction. The electrical conductivities of four coordination polymers andⅠ-dopedcomplex(Ⅰ) were measured. The results show that both pure andⅠ-doped complex(Ⅰ) aresemiconductor, the pure complex(Ⅱ), (Ⅲ) and (Ⅳ) are insulator. The structures andproperties of the four complexes were preliminary studied.