Elucidating the Supramolecular Copolymerization of N- and C-Centered Benzene-1,3,5-Tricarboxamides: The Role of Parallel and Antiparallel Packing of Amide Groups in the Copolymer Microstructure.

Autor: de Windt LNJ; Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands., Fernández Z; Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares and, Departamento de Química Orgánica, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain., Fernández-Míguez M; Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares and, Departamento de Química Orgánica, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain., Freire F; Centro Singular de Investigación en Química Biolóxica e Materiais Moleculares and, Departamento de Química Orgánica, Universidade de Santiago de Compostela, 15782, Santiago de Compostela, Spain., Palmans ARA; Laboratory of Macromolecular and Organic Chemistry, Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB, Eindhoven, The Netherlands.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2022 Jan 03; Vol. 28 (1), pp. e202103691. Date of Electronic Publication: 2021 Dec 02.
DOI: 10.1002/chem.202103691
Abstrakt: An in-depth study of the supramolecular copolymerization behavior of N- and C-centered benzene-1,3,5-tricarboxamides (N- and C-BTAs) has been conducted in methylcyclohexane and in the solid state. The connectivity of the amide groups in the BTAs differs, and mixing N- and C-BTAs results in supramolecular copolymers with a blocky microstructure in solution. The blocky microstructure results from the formation of weaker and less organized, antiparallel hydrogen bonds between N- and C-BTAs. In methylcyclohexane, the helical threefold hydrogen-bonding network present in C- and N-BTAs is retained in the mixtures. In the solid state, in contrast, the hydrogen bonds of pure BTAs as well as their mixtures organize in a sheet-like pattern, and in the mixtures long-range order is lost. Drop-casting to kinetically trap the solution microstructures shows that C-BTAs retain the helical hydrogen bonds, but N-BTAs immediately adopt the sheet-like pattern, a direct consequence of the lower stabilization energy of the helical hydrogen bonds. In the copolymers, the stability of the helical aggregates depends on the copolymer composition, and helical aggregates are only preserved when a high amount of C-BTAs is present. The method outlined here is generally applicable to elucidate the copolymerization behavior of supramolecular monomers both in solution as well as in the solid state.
(© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz:
Nepřihlášeným uživatelům se plný text nezobrazuje