Synthetic Study of Oligomeric TTF-Superphanes Expectative to Form Supramolecular Assemblies

设计并合成了三个或四个TTF骨架通过两个亚乙基二硫桥或两个丙二硫桥连接的TTF超芳，它们具有独特的形状，前者为棱柱，后者为方柱，并有望通过面对面的π相互作用分别自组装成六方和四方单元，通过边-边S-S接触形成具有延伸孔道结构的柱状组装体。尽管合成过程中存在许多困难，主要是由于各种中间体的溶解性差，但我们还是制备了两种三聚体的前驱体。在一个中，三个TTF部分通过总共四个丙二硫基连接，并且两侧的两个TTF部分具有两个受保护的硫醇基团。脱保护，然后与1，3-二溴丙烷反应，预期得到三聚体。在另一种情况下，两个TTF和两个1，3-二硫杂环戊烯-2-酮连接在一起，脱氧偶联应该得到目标。这两个反应在各种条件下进行，并且总是在高稀释条件下进行，在某些情况下，只有通过飞行时间质谱才能识别出极少量的目标。对反应条件的进一步研究正在进行中。

TTF superphanes in which three or four TTF skeletons are connected by either two ethylendithio or two propanedithio bridges were designed and their syntheses have been tried.They have unique shapes, the former being a prism, the latter being a square pillar, and are expected to self-assemble hexagonal and tetragonal units, respectively through face-to-face πinteractions, which, in turn, to form columnar assemblies equipped with extended channel Structures through edge-to-edge S-S contacts.In spite of many synthetic difficulties, which were mainly due to poor solubilities of various intermediates, two kinds of precursor to the trimer have been prepared. In one, three TTF moieties are connected by totally four propanedithio groups and the two TTF moieties at both sides have two protected thiol groups. Deprotection followed by the reaction with 1,3-dibromopropane was expected to give the trimer. In the other, two TTFs and two 1,3-dithiole-2-0ne are connected and deoxygenative coupling should give the target.The two reactions have been carried out under various conditions and always under high-dilution conditions to give, in some cases, extremely small amount of the target discernible only through TOFMS. Further elaboration of the reaction conditions are in progress.