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Title: The cascade unzipping of ladderane reveals dynamic effects in mechanochemistry

Abstract

Force can induce remarkable non-destructive transformations along a polymer, but we have a limited understanding of the energy transduction and product distribution in tandem mechanochemical reactions. Ladderanes consist of multiple fused cyclobutane rings and have recently been used as monomeric motifs to develop polymers that drastically change their properties in response to force. Here we show that [4]-ladderane always exhibits ‘all-or-none’ cascade mechanoactivations and the same stereochemical distribution of the generated dienes under various conditions and within different polymer backbones. Transition state theory fails to capture the reaction kinetics and explain the observed stereochemical distributions. Ab initio steered molecular dynamics reveals unique non-equilibrium dynamic effects: energy transduction from the first cycloreversion substantially accelerates the second cycloreversion, and bifurcation on the force-modified potential energy surface leads to the product distributions. Our findings illustrate the rich chemistry in closely coupled multi-mechanophores and an exciting potential for effective energy transduction in tandem mechanochemical reactions.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Stanford Univ., CA (United States). Dept. of Chemistry
  2. Stanford Univ., CA (United States). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1605279
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 12; Journal Issue: 3; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chen, Zhixing, Zhu, Xiaolei, Yang, Jinghui, Mercer, Jaron A. M., Burns, Noah Z., Martinez, Todd J., and Xia, Yan. The cascade unzipping of ladderane reveals dynamic effects in mechanochemistry. United States: N. p., 2020. Web. doi:10.1038/s41557-019-0396-5.
Chen, Zhixing, Zhu, Xiaolei, Yang, Jinghui, Mercer, Jaron A. M., Burns, Noah Z., Martinez, Todd J., & Xia, Yan. The cascade unzipping of ladderane reveals dynamic effects in mechanochemistry. United States. doi:https://doi.org/10.1038/s41557-019-0396-5
Chen, Zhixing, Zhu, Xiaolei, Yang, Jinghui, Mercer, Jaron A. M., Burns, Noah Z., Martinez, Todd J., and Xia, Yan. Mon . "The cascade unzipping of ladderane reveals dynamic effects in mechanochemistry". United States. doi:https://doi.org/10.1038/s41557-019-0396-5. https://www.osti.gov/servlets/purl/1605279.
@article{osti_1605279,
title = {The cascade unzipping of ladderane reveals dynamic effects in mechanochemistry},
author = {Chen, Zhixing and Zhu, Xiaolei and Yang, Jinghui and Mercer, Jaron A. M. and Burns, Noah Z. and Martinez, Todd J. and Xia, Yan},
abstractNote = {Force can induce remarkable non-destructive transformations along a polymer, but we have a limited understanding of the energy transduction and product distribution in tandem mechanochemical reactions. Ladderanes consist of multiple fused cyclobutane rings and have recently been used as monomeric motifs to develop polymers that drastically change their properties in response to force. Here we show that [4]-ladderane always exhibits ‘all-or-none’ cascade mechanoactivations and the same stereochemical distribution of the generated dienes under various conditions and within different polymer backbones. Transition state theory fails to capture the reaction kinetics and explain the observed stereochemical distributions. Ab initio steered molecular dynamics reveals unique non-equilibrium dynamic effects: energy transduction from the first cycloreversion substantially accelerates the second cycloreversion, and bifurcation on the force-modified potential energy surface leads to the product distributions. Our findings illustrate the rich chemistry in closely coupled multi-mechanophores and an exciting potential for effective energy transduction in tandem mechanochemical reactions.},
doi = {10.1038/s41557-019-0396-5},
journal = {Nature Chemistry},
number = 3,
volume = 12,
place = {United States},
year = {2020},
month = {1}
}

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