Abstract: The synthesis of C3- and C2-symmetric benzene-1,3,5-tricarboxamides (BTAs) containing well-defined oligodimethylsiloxane (oDMS) and/or alkyl side chains has been carried out. The influence of the bulkiness of the oDMS chains in the aggregation behavior of dilute solutions of the oDMS-BTAs in methylcyclohexane was studied by temperature-dependent UV spectroscopy. The formation of hierarchically self-assembled aggregates was observed at different BTA concentrations, the tendency of aggregation increases by shortening or removing oDMS chains. Chiral BTAs were investigated with circular dichroism (CD) spectroscopy, showing a stronger tendency to aggregate than the achiral ones. Majority rules experiments show a linear behavior consistent with the existence of a high mismatch penalty energy. The most efficient oDMS-BTAs organogelators have the ability to form stable organogels at 5 mg mL-1 (0.75 wt%) in hexane. Solid-state characterization techniques indicate the formation of an intermolecular threefold hydrogen bonding between adjacent molecules forming thermotropic liquid crystals, exhibiting a hexagonal columnar organization from room temperature to above 150°C. A decrease of the clearing temperatures was observed when increasing the number and length of the oligodimethylsiloxane chains. In addition to the three-fold hydrogen bonding that leads to columnar liquid crystalline phase, segregation between the oDMS and aliphatic chains takes place in the BTA functionalized with two alkyl and one oDMS chain leading to a superlattice within the hexagonal structure with potential applications in lithography.

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