TTF单元与苯单元构建的新型TTF环蕃的合成和性质

以4,5-二(2'-氰乙基硫基)-1,3-二硫杂环戊烯-2-硫酮为原料经甲醇钠消除一个氰乙基生成4-(2'-氰乙基硫基)-1,3-二硫杂环戊烯-2-硫酮的单钠盐, 生成的单钠盐再与1,4-二(氯甲基)苯反应生成4,4'-二(2-氰乙基硫基)-5,5'-(1,4-二亚甲基苯)-二(1,3-二硫杂环戊烯-2-硫酮). 接着在乙酸汞的作用下生成4,4'-二(2-氰乙基硫基)-5,5'-(1,4-二亚甲基苯)-二(1,3-二硫杂环戊烯-2-酮), 此化合物在亚磷酸三乙酯的作用下发生偶联反应, 生成由TTF单元和苯单元构建的新型四硫富瓦烯环蕃和另一种四硫富瓦烯衍生物. 并分别通过循环伏安法和化学氧化法对它们及其导电复合物的电化学性质和紫外光谱进行了研究. 还研究了这种新型四硫富瓦烯环蕃在金纳米颗粒表面自组装行为.

Synthesis and Properties of New Type of Tetrathiafulvalene Cyclo-phane Based on Tetrathiafulvalene Units and Phenyl Units

4,5-Bis(2'-cyanoethylthio)-1,3-dithiole-2-thione was treated with sodium methoxide to deprotect one 2-cyanoethyl group,affording 4-(2'-cyanoethylthio)-1,3-dithiole-2-thione monothiolate.The generated monothiolate was trapped by 1,4-bis(chlommethylene)benzene to yield the corresponding singly bridged 4,4'-bis(2-cyanoethylthio)-5,5'-methylene benzene-bis(1,3-dithiole-2-thione).The thione reacted with mer- curic acetate to yield 4,4'-bis-(2-cyanoethylthio)-5,5'-methylene benzene-bis(1,3-dithiole-2-one).Such com- pound was treated with triethyl phosphite to afford new type of tetrathiafulvalene cyclophane and another tetrathiafulvalene derivative.Electrochemical properties and UV spectra of the two tetrathiafulvalene deriva- tives and their complexes were studied by cyclic voltammetry and chemical oxidation,respectively.The tetrathiafulvalene cyclophanes assembled on the surfaces of gold nanoparticles was discussed,too.