Reinforced self-assembly of hexa-peri-hexabenzocoronenes by hydrogen bonds: from microscopic aggregates to macroscopic fluorescent organogels

Abstract

Hexa-peri-hexabenzocoronene derivatives (HBCs) that have hydrogen-bonding functionalities (either amido or ureido groups) adjacent to the aromatic cores have been synthesized to study the effects of intracolumnar hydrogen bonds on the self-assembly behavior of HBCs. The hydrogen bonds effectively increased the aggregation tendency of these compounds in solution. In the bulk state, the typical columnar supramolecular arrangement of HBCs was either stabilized substantially (1 a, 1 b, 2 a, and 2 b), or suppressed by dominant hydrogen-bonding interactions (3). For some of the compounds (1 a, 2 a, and 2 b), the supramolecular arrangement adopted in the liquid-crystalline state was even retained after annealing, presumably owing to the reinforcement of the pi-stacking interactions by the hydrogen bonds. Additionally, the combined effect of the hydrogen bonds and pi-stacking of the aromatic moieties led to the formation of fluorescent organogels, whereby some derivatives were further investigated as novel low molecular-mass organic gelators (LMOGs).