Issue 4, 2020

Competitive hydrogen bonding in supramolecular polymerizations of tribenzylbenzene-1,3,5-tricarboxamides

Abstract

Despite numerous reports on nucleated supramolecular polymerization, the molecular origin of the properties of these supramolecular polymers remains overlooked. Here, the formation of fibers formed by self-assembly of N,N′,N′′-tris(alkoxybenzyl)benzene-1,3,5-tricarboxamides (benzyl-BTAs) has been studied using both simulations and experimental techniques. The simulations show that the fibers exhibit a dynamic behavior with stacking defects that appear and propagate differently depending on the BTA molecular structure. To validate theoretical results, a library of eight benzyl-BTAs has been synthesized to compare their supramolecular polymerizations both in the bulk and in apolar solvents. We show that the molecular organization of monomers and dynamics of supramolecular polymers strongly depend on the number and position of the alkoxy substituents on peripheral phenyl rings. By combining theoretical results with experimental measurements, we elucidate the likely role of competitive hydrogen bonding between the central amides and peripheral ether moieties on the stacking behavior of BTAs and the dynamics of structural defects in supramolecular polymers. Our findings open up new design rules for these dynamic materials.

Graphical abstract: Competitive hydrogen bonding in supramolecular polymerizations of tribenzylbenzene-1,3,5-tricarboxamides

Supplementary files

Article information

Article type
Paper
Submitted
19 Mar 2020
Accepted
16 Apr 2020
First published
16 Apr 2020

Mol. Syst. Des. Eng., 2020,5, 820-828

Competitive hydrogen bonding in supramolecular polymerizations of tribenzylbenzene-1,3,5-tricarboxamides

M. F. J. Mabesoone, S. Kardas, H. Soria-Carrera, J. Barberá, J. M. de la Fuente, A. R. A. Palmans, M. Fossépré, M. Surin and R. Martín-Rapún, Mol. Syst. Des. Eng., 2020, 5, 820 DOI: 10.1039/D0ME00030B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements