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

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 π‐stacking, while 3 is not an LC. Exceptionally, the 1:1 mixture of 2 and 3 forms an alignable columnar LC with strong π‐stacking and quadruply helically organized fullerenes by an unprecedented click process that is similar to a ball detent mechanism. The C60 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.