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

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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.