Force governs product diversity in the mechanochemical reactivity of triprismane

Abstract

Unlike conventional modes of activation of reactivity, mechanochemical force provides facile and unique pathways. Extensive studies have been performed on the thermal and photochemical interconversions between benzene and its valence isomers. In this article, we show that mechanochemical pulling along 1,2- positions of triprismane (TP) can precisely control the outcome, namely, benzene (BZ) and/or Dewar benzene (DB), depending upon the strength of external force. Within the force range of 1.5–1.9 nN, DB is formed exclusively, whereas at forces exceeding ≥2.0 nN, BZ becomes the major product. Also, we report that on pulling across 1,4-sites of TP, BZ is produced exclusively when external force ≥1.8 nN. Ab initio steered molecular dynamics (AISMD) simulations on the force modified potential energy surfaces (FMPESs) for 1,2-pulling of TP reveal that DB becomes the minor product beyond external force ≥2.0 nN. The thermodynamically controlled product, BZ, is obtained as the major and sole product for stronger 1,2-pulling and 1,4-pulling respectively. The constrained geometries simulate external force (CoGEF) calculations fail to locate the kinetically trapped intermediate, DB, revealing the prowess of AISMD in revealing unique intermediates and fleetingly stable products in the course of mechanochemical reactions. Also, we demonstrate that the TPBZ reaction, which demands significant thermal energy, can be induced mechanochemically.

Graphical abstract: Force governs product diversity in the mechanochemical reactivity of triprismane

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Article information

Article type
Paper
Submitted
17 Apr 2025
Accepted
22 Jul 2025
First published
23 Jul 2025
This article is Open Access
Creative Commons BY-NC license

RSC Mechanochem., 2025, Advance Article

Force governs product diversity in the mechanochemical reactivity of triprismane

A. Das, C. Hajra and A. Datta, RSC Mechanochem., 2025, Advance Article , DOI: 10.1039/D5MR00050E

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