A S 6-symmetric triarylamine-based macrocycle (i.e., hexaaza­[16]­paracyclophane), decorated with six lateral amide functions, is synthesized by a convergent and modular strategy. This macrocycle is shown to undergo supramolecular polymerization in o-dichlorobenzene, and its nanotubular structure is elucidated by a combination of spectroscopy and microscopy techniques, together with X-ray scattering and molecular modeling. Upon sequential oxidation, a spectroelectrochemical analysis of the supramolecular polymer suggests an extended electronic delocalization of charge carriers both within the macrocycles (through bond) and between the macrocycles along the stacking direction (through space).

p-Bromo- or p-iodophenylthioacetate can react with trimethylsilylacetylene by simultaneous Sonogashira coupling at the halide function and addition of acetyl and arylthio moieties to the triple bond. Reaction of arylthioacetates with p-OMe, -Me, Ph and -Cl substituents, under the typical conditions of the Sonogashira coupling, leads only to the regio- and stereoselective acetylthiolation of trimethylsilylacetylene affording beta-silylated beta-arylthio-alpha,beta-unsaturated ketones. The carbothiolation of PhSAc is faster than the Sonogashira coupling of Ph-Br andslower than that of Ph-I, implying that the rates of oxidative addition to Pd(0) are in the order (X=I > SAc >Br)