Advancing the Mechanosensitivity of Atropisomeric Diarylethene Mechanophores through a Lever-Arm Effect

Cijun Zhang, Tatiana B. Kouznetsova, Boyu Zhu, Liam Sweeney, Max Lancer, Ivan Gitsov, Stephen L. Craig, Xiaoran Hu

Research output: Contribution to journalArticlepeer-review

Abstract

Understanding structure-mechanical activity relationships (SMARs) in polymer mechanochemistry is essential for the rational design of mechanophores with desired properties, yet SMARs in noncovalent mechanical transformations remain relatively underexplored. In this study, we designed a subset of diarylethene mechanophores based on a lever-arm hypothesis and systematically investigated their mechanical activity toward a noncovalent-yet-chemical conversion of atropisomer stereochemistry. Results from Density functional theory (DFT) calculations, single-molecule force spectroscopy (SMFS) measurements, and ultrasonication experiments collectively support the lever-arm hypothesis and confirm the exceptional sensitivity of chemo-mechanical coupling in these atropisomers. Notably, the transition force for the diarylethene M3 featuring extended 5-phenylbenzo[b]thiophene aryl groups is determined to be 131 pN ± 4 pN by SMFS. This value is lower than those typically recorded for other mechanically induced chemical processes, highlighting its exceptional sensitivity to low-magnitude forces. This work contributes a fundamental understanding of chemo-mechanical coupling in atropisomeric configurational mechanophores and paves the way for designing highly sensitive mechanochemical processes that could facilitate the study of nanoscale mechanical behaviors across scientific disciplines.

Original languageEnglish (US)
Pages (from-to)2502-2509
Number of pages8
JournalJournal of the American Chemical Society
Volume147
Issue number3
DOIs
StatePublished - Jan 22 2025

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry

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