Linear Supramolecular Polymer of Benzene‐1,3,5‐Tricarboxamides Bearing Two‐Armed Amphiphilic Side Chains in the Bulk State and in Aqueous Solution

ABSTRACT Here, we report the characterization of C 3 ‐symmetric benzene‐1,3,5‐tricarboxamide (BTA) derivatives bearing symmetrically two‐armed amphiphilic chains adjacent to the amide, which were designed to inhibit side chain crystallization of supramolecular polymers in the bulk state at ambient temperature. IR spectroscopy confirmed the formation of triple hydrogen‐bonded supramolecular polymer chains, and XRD suggested two‐dimensional hexagonal packing. DSC showed side‐chain melting below room temperature, indicating suppressed crystallization. By contrast, the linear side‐chain analogs displayed multiple amide bands in their IR spectra and multiple reflections in XRD. N , N′ , N″ ‐tris(3,6,20,23‐tetraoxa‐1,25‐dihydroxy‐13‐pentacosyl)‐BTA having two‐armed side chains terminated with hydroxyl groups (THBTA) displayed amorphous structure from −80°C to 220°C, exhibiting a hypsochromic shift in UV–vis and marked 1 H‐NMR signal broadening upon dissolution in (heavy) water, consistent with H‐aggregate supramolecular polymer formation. These results suggest that a branched hydrophobic moiety adjacent to the amide group promotes one‐dimensional supramolecular stacking more effectively than its linear analog during the higher‐order structure formation of BTA derivatives.