Solvent‐Directed Helical Stereomutation Discloses Pathway Complexity on N‐Heterotriangulene‐Based Organogelators

Abstract

The chiroptical features of supramolecular polymers formed from N-heterotriangulenes 1-3 have been investigated by circular dichroism (ECD) and vibrational circular dichroism (VCD) techniques. In solution, the CD spectra demonstrate that the helicity of the aggregates depends on only the stereogenic centres located at the peripheral chains. In the gel state, the chiroptical features are conditioned by the point chirality of the stereogenic centres and by the achiral solvent utilised. Sonication of the gels formed in CCl reveals both kinetic and thermodynamic phases. These findings reveal the presence of pathway complexity in the gel state triggered by sonication. The described solvent-induced helical stereomutation demonstrates that the gel state can be utilised as an outstanding benchmark for investigating uncommon chiroptical effects and to explore the rules of chirality transmission.

Supramolecular assemblies of a 1,8-naphthalimide conjugate and its aggregation-induced emission property

“…The details of gelation of NMI-GW-OMe is given in Table 1. Recently, several emerging properties 26,[36][37][38][39][40][41][42][43] of planar fluorophores have been observed in mixed solvents. One of them is supramolecular gelation [44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] .…”

C3‐Symmetrical π‐Scaffolds: Useful Building Blocks to Construct Helical Supramolecular Polymers

“…These gels unveil an explicit VCD response that, in the case of toluene as solvent, is constant regardless of the experimental conditions applied. This is not the case for the gels formed in CCl 4 , which switch the VCD signal in the gel state upon ultrasound treatment (Figure d) …”

Tunable Energy Landscapes to Control Pathway Complexity in Self‐Assembled N‐Heterotriangulenes: Living and Seeded Supramolecular Polymerization

“…Herein, we present and rationalize the solvent‐dependent energy profiles shown by carbonyl‐bridged triarylamines (CBT, N‐ heterotriangulenes) 1 – 3 to form different supramolecular polymers ( Figure ). Very recently, a pathway complexity in the self‐assembly of referable CBTs, both in solution and in the gel state, has been described. We have decorated the periphery of the N ‐heterotriangulenes 1 – 3 with 3,4,5‐trialkoxy‐ N ‐(alkoxy)benzamide moieties that favor the formation of metastable monomeric units through intramolecular hydrogen‐bonding interactions.…”