Synthesis Of Thiacalixarene-tetrathiafulvalene Assemblies And The Study Of These Properties

Thiacalixarenes are the new members of the calixarene family. The presence of sulfur atoms in place of the usual CH2 bridges makes thiacalixarenes very interesting molecules,with many features that are not present in "classical calixarene",for example.the larger cavity, different conformational features, special complexation properties and oxidizability of bridging sulfur.With the study continuing thiacalixarenes which are used as building blocks,and molecular platforms display very big potential in the synthesis of more complicated systems.Tetrathiafulvalene and its derivatives are strong electron donors, and they can be reversibly transformed into the corresponding radical cation and dications.Because of special property of the redox, tetrathiafulvalene not only can be used as components of molecular conductors,but aslo molecular switch,molecular sensors,liquids crystal materials,LB film and nonliner optical (NLO) and so on,which exhibits a exciting future. Now, it is widely reported that various fuctional groups were connected to TTF such as crown ether, cyclodextrin, fullerene, cyclophanes, rotaxanes and so no and these systems display unusual electchemistry properties, respectively.Until now, the synthesis of TCA-TTF systems have been a blank. So,we intruced the TTF to the lower rim of the TCA by making use of the click chemistry and four TCA-TTF derivatives was synthesized and these properties was studied.The major work of this paper are as follows:1, First, taking the Zincate salts as raw materials, we got the compound 5a..The compound 5a reacted with ethylene bromohydrin in the dry THF at the presence of cesium hydroxide, which gave the compound 6a in 56% yield. The compound 6a was changed into 8a (77% yield), which reacted with 4-Methylbcnzcncsulfonyl chlfonyl at the presence of triethylamine. Then, the compound 8a was converted to compound 10a, after reacted with with NaN3. As the same method compound 10b, 11a, lib were synthesized. The p-tert-butylthiacalix[4]arene with an excess of iodomethane in the pressene of K2CO3 (1 equiv) in refluxing acetone gave the compound 13. The compound 14 was obtained by compound 13 reacted with Propargyl bromide.At last, thiacalix[4]arene-alkyne derivatives and TTF-azide derivatives were reacted by click chemistry and four TCA-TTF derivatives (TCA-TTF-1, TCA-TTF-2, TCA-TTF-3, TCA-TTF-4) were obstained.All the TCA-TTF derivatives were characterized by 1H NMR,13C NMR, MS.2. The electchemistry properties of the new componds were studied by cyclic voltammetry. Meanwhile, in the solution of all the TCA-TTF derivatives, we observed the behavior of the electron transfer respectively after the addition of the meatal ions with UV absorption spectra.