Issue 33, 2023

A rational design strategy of radical-type mechanophores with thermal tolerance

Abstract

Radical-type mechanophores (RMs) are attractive molecules that undergo homolytic scission of their central C–C bond to afford radical species upon exposure to heat or mechanical stimuli. However, the lack of a rational design concept limits the development of RMs with pre-determined properties. Herein, we report a rational design strategy of RMs with high thermal tolerance while maintaining mechanoresponsiveness. A combined experimental and theoretical analysis revealed that the high thermal tolerance of these RMs is related to the radical-stabilization energy (RSE) as well as the Hammett and modified Swain–Lupton constants at the para-position (σp). The trend of the RSE values is in good agreement with the experimentally evaluated thermal tolerance of a series of mechanoresponsive RMs based on the bisarylcyanoacetate motif. Furthermore, the singly occupied molecular orbital (SOMO) levels clearly exhibit a negative correlation with σp within a series of RMs that are based on the same skeleton, paving the way toward the development of RMs that can be handled under ambient conditions without peroxidation.

Graphical abstract: A rational design strategy of radical-type mechanophores with thermal tolerance

Supplementary files

Article information

Article type
Edge Article
Submitted
12 Jun 2023
Accepted
28 Jul 2023
First published
03 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 license

Chem. Sci., 2023,14, 8792-8797

A rational design strategy of radical-type mechanophores with thermal tolerance

Y. Lu, H. Sugita, K. Mikami, D. Aoki and H. Otsuka, Chem. Sci., 2023, 14, 8792 DOI: 10.1039/D3SC02991C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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