Synthesis And Property Of Novel Crown Ether Annulated Tetrathiafulvalene Derivatives

In this paper, first, we introduce some main research branches about tetrathiafulvalene (TTF). Then, under improved high dilution condition, we synthesized a series of 4,5-dithiacrown ether annulated l,3-dithiole-2-thiones 65a-d from readily available 4,5-bis(bromomethyl)-1,3-dithiole-2-thione 60 and 1, w -dimercapto glycol 63a-d. The target derivetives of tetrathiafluvalene(TTF) incoporating crown ether, including novel asymmeric 73a-d and dumbbel-shaped 67a-d, were prepared in fairly good yields via the standard coupling reaction generating TTF from 4,5-dithiacrown ether annulated l,3-dithiole-2-thiones with corresponding transchalogenated product in net triethyl phosphite. "Template effect" in the synthesis couse of 65a-d and yields of the two series of TTF thia-crown ethers were discussed. All the compounds were typed by IR, 1H-NMR, 13C-NMR, LC-MS. Via cyclic voltammograms, UV and 'H-NMR, respectively, with alkali metal ions, ammonium ion and some transation metal ions, we studied the complexing ability of 67a-d and 73a-d. We also synthesized CT complexes, which were typed by IR spectrum using above compounds with TCNQ. Compounds 67c-d were better cation sensor molecules that were superior to those of reported.We also attempted to synthesize 4,5-all-oxygen crown ether annulated 1,3-dithiole-2-thiones derivatives and some azo-liquid crystal compounds coupling 1,3-diazaazulene.