Issue 35, 2023

Dynamic self-assembly of supramolecular catalysts from precision macromolecules

Abstract

We show the emergence of strong catalytic activity at low concentrations in dynamic libraries of complementary sequence-defined oligomeric chains comprising pendant functional catalytic groups and terminal recognition units. In solution, the dynamic constitutional library created from pairs of such complementary oligomers comprises free oligomers, self-assembled di(oligomeric) macrocycles, and a virtually infinite collection of linear poly(oligomeric) chains. We demonstrate, on an exemplary catalytic system requiring the cooperation of no less than five chemical groups, that supramolecular di(oligomeric) macrocycles exhibit a catalytic turnover frequency ca. 20 times larger than the whole collection of linear poly(oligomers) and free chains. Molecular dynamics simulations and network analysis indicate that self-assembled supramolecular di(oligomeric) macrocycles are stabilized by different interactions, among which chain end pairing. We mathematically model the catalytic properties of such complex dynamic libraries with a small set of physically relevant parameters, which provides guidelines for the synthesis of oligomers capable to self-assemble into functionally-active supramolecular macrocycles over a larger range of concentrations.

Graphical abstract: Dynamic self-assembly of supramolecular catalysts from precision macromolecules

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Article information

Article type
Edge Article
Submitted
20 jun 2023
Accepted
15 aug 2023
First published
16 aug 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 9283-9292

Dynamic self-assembly of supramolecular catalysts from precision macromolecules

Q. Qin, J. Li, D. Dellemme, M. Fossépré, G. Barozzino-Consiglio, I. Nekkaa, A. Boborodea, A. E. Fernandes, K. Glinel, M. Surin and A. M. Jonas, Chem. Sci., 2023, 14, 9283 DOI: 10.1039/D3SC03133K

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