Fullerene-Filled Liquid-Crystal Stars: A Supramolecular Click Mechanism for the Generation of Tailored Donor-Acceptor Assemblies

摘要

Two shape-persistent star mesogens with oligo(phenylene ethenylene) arms and a phthalocyanine core-one providing free space (2) and one sterically encumbered by four fullerenes attached through spacers (3)-have been successfully synthesized. In contrast to the smaller discotic derivative 1, mesogen 2 forms a columnar liquid crystal (LC), which can only be partially aligned without pi-stacking, while 3 is not an LC. Exceptionally, the 1:1 mixture of 2 and 3 forms an alignable columnar LC with strong pi-stacking and quadruply helically organized fullerenes by an unprecedented click process that is similar to a ball detent mechanism. The C-60 units also interconnect different columns. This is driven by nanosegregation and space-filling of the voids with fullerenes. Photophysical studies confirm the presence of a light-collecting system that generates charge-separated states in solution and in the solid state, which makes such highly organized materials attractive for the study of future photovoltaic devices.