TY - JOUR
T1 - Advancing the Mechanosensitivity of Atropisomeric Diarylethene Mechanophores through a Lever-Arm Effect
AU - Zhang, Cijun
AU - Kouznetsova, Tatiana B.
AU - Zhu, Boyu
AU - Sweeney, Liam
AU - Lancer, Max
AU - Gitsov, Ivan
AU - Craig, Stephen L.
AU - Hu, Xiaoran
N1 - Publisher Copyright:
© 2025 The Authors. Published by American Chemical Society.
PY - 2025/1/22
Y1 - 2025/1/22
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85214572430&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85214572430&partnerID=8YFLogxK
U2 - 10.1021/jacs.4c13480
DO - 10.1021/jacs.4c13480
M3 - Article
C2 - 39793028
AN - SCOPUS:85214572430
SN - 0002-7863
VL - 147
SP - 2502
EP - 2509
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 3
ER -