Abstract
Supramolecular building blocks assembling into helical aggregates are ubiquitous in the current literature, yet the role of solvents in these supramolecular polymerizations often remains elusive. Here, we present a systematic study that quantifies solvent-supramolecular polymer compatibility using the Hansen solubility parameters (δD, δH, and δP). We first studied the solubility space of the supramolecular building block triazine-1,3,5-tribenzenecarboxamide S-T. Due to its amphiphilic nature, a dual-sphere model based on 58 solvents was applied describing the solubility space of the monomeric state (green sphere) and supramolecular polymer state (blue sphere). To our surprise, further in-depth spectroscopic and morphological studies unveiled a distinct solubility region in-between the two spheres giving rise to the formation of higher-order aggregated structures. This phenomenon occurs due to subtle differences in polarity between the solvent and the side chains and highlights the solvent-induced pathway complexity of supramolecular polymerizations. Subsequent variations in concentration and temperature led to the expansion and contraction of both solubility spheres providing two additional features to tune the monomer and supramolecular polymer solubility. Finally, we applied our dual-sphere model on structurally disparate monomers, such as Zn-porphyrin (S-P) and triphenylamine (S-A), demonstrating the generality of the model and the importance of the supramolecular monomer design in connection with the solvent used. This work unravels the solvent-induced pathway complexity of discotic supramolecular building blocks using a parametrized approach in which interactions between the solvent and solute play a crucial role.
| Original language | English |
|---|---|
| Pages (from-to) | 17987-17994 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 145 |
| Issue number | 32 |
| DOIs | |
| Publication status | Published - 16 Aug 2023 |
Bibliographical note
Funding Information:The authors would like to thank Andy Bänziger for his help in the sample preparation for the solubility studies. They thank the ICMS Animation Studio for creating the representative cartoons. The work received funding from the Dutch Ministry of Education, Culture and Science (Gravity program 024.001.035) and European Research Council for funding (H2020-EU.1.1., SYNMAT project, ID 788618).
Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society.