Pyromellitamide gelators: Exponential rate of aggregation, hierarchical assembly, and their viscoelastic response to anions

The gelation and aggregation properties of a newly synthesized structurally simplified tetrahexyl pyromellitamide 2 have been studied and compared to the previously reported tetra(cthylhcxanoate) pyromellitide 1, indicating that the ester groups in the latter significantly impede its aggregation. Morphology studies (AFM and TEM) on the aggregates formed by tetrahexyl pyromellitamide 2 in cyclohexane revealed highly uniform, aggregates with different dimensions at different starting concentrations, suggesting that this molecule aggregates in a hierarchical fashion from a one-dimensional supramolecular polymer through hollow tubes or compressed helices to a network structure and then to a gel. This hypothesis is further supported, by viscosity measurements that indicate a crossover point where individual supramolecular fibers get entangled at concentrations above ca. 3 mM in cyclohexane. Addition of 1 equiv of tetraalkylarnmonium salts of chloride or bromide, however, caused the viscosities of these pyromellitamide solutions to drop by a factor of 2-3 orders of magnitude, demonstrating the sensitivity of these aggregates to the presence of small anions. The sensitivity to anions does depend on the solubility of the salts used as small anion salts with little solubility in cyclohexane did not show this effect. Time-dependent viscosity studies showed that the aggregation of pyromellitamide 2 follows an exponential rate law, possibly related to the columnar rearrangements that are associated with the observed 6 Å contraction in d spacing in the XRD pattern of these gels. These results, particularly on the importance of kinetics of aggregation of self-assembled pyromellitamide gels, will be useful for future development of related materials for a number of applications, including tissue engineering and drug delivery.