Issue 45, 2022

Unexpected chirality transition and inversion mediated by dissolution–aggregation and the odd–even effect

Abstract

The evolution of hierarchical chirality at macromolecular and supramolecular levels in biological systems is ubiquitous; however, achieving precise control over transitions between them in polymer systems is still challenging. Here, we reported multiple chiroptical transitions and inversion phenomena in side-chain azobenzene (Azo) polymers, PAzo-L/D-m (m = 3, 6, 7, 8, 9, and 10, where m is the total number of atoms from the chiral stereocenter to the Azo unit), with different distances from the chiral stereocenter to the Azo unit. In the case of m = 3, an unexpected macromolecular-to-supramolecular chirality transition and inversion occurred in situ when the Azo-polymer underwent from a macromolecular-dissolved state to a supramolecular-aggregated state. To our surprise, an exciton-coupling induced multiple chiroptical inversion was observed upon the heating-assisted reassembly treatment, which was demonstrated to be driven by H- to J-aggregation transition. Furthermore, the odd–even effect was first established to regulate the supramolecular helical orientations (left- or right-handedness) in side-chain Azo-polymer assemblies.

Graphical abstract: Unexpected chirality transition and inversion mediated by dissolution–aggregation and the odd–even effect

Supplementary files

Article information

Article type
Edge Article
Submitted
21 sep. 2022
Accepted
25 okt. 2022
First published
25 okt. 2022
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., 2022,13, 13623-13630

Unexpected chirality transition and inversion mediated by dissolution–aggregation and the odd–even effect

Y. Ma, X. Cheng, H. Ma, Z. He, Z. Zhang and W. Zhang, Chem. Sci., 2022, 13, 13623 DOI: 10.1039/D2SC05255E

This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. You can use material from this article in other publications, without requesting further permission from the RSC, provided that the correct acknowledgement is given and it is not used for commercial purposes.

To request permission to reproduce material from this article in a commercial publication, 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 commercial 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