Supramolecular Fullerene Materials:  Dendritic Liquid-Crystalline Fulleropyrrolidines

[60]Fullerene-containing liquid-crystalline dendrimers were synthesized from the first to the fourth generation by applying the 1,3-dipolar cycloaddition reaction from a mesomorphic dendritic-type aldehyde derivative, sarcosine (N-methylglycine) or glycine and C<INF>60</INF>. The cyanobiphenyl unit was used as a liquid-crystalline promoter. With the exception of the first-generation fullerene dendrimer, which was found to be nonmesomorphic, all fullerene-based dendrimers gave rise to a smectic A phase. The liquid-crystalline fullerenes led to two different supramolecular organizations within the smectic layers:  for the second-generation dendrimers, the molecules are oriented in a head-to-tail fashion within the layers; for each molecule the cyanobiphenyl units point in the same direction. For the dendrimers of third and fourth generations, the dendritic core extends laterally, parallel to the layer planes; the mesogenic units are oriented above and below the dendritic core. For the aldehyde precursors, only one organization inside the layers was obtained, similar to the one observed for the third and fourth fullerene-based dendrimers. Cyclic voltametry investigations displayed several one-electron and multielectron reduction processes; no significant interaction in the ground state between the fullerene and the dendrimer was noticed. The title compounds showed the typical electrochemical stability of fulleropyrrolidines.