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A remote stereochemical lever arm effect in polymer mechanochemistry.

Publication ,  Journal Article
Wang, J; Kouznetsova, TB; Kean, ZS; Fan, L; Mar, BD; Martínez, TJ; Craig, SL
Published in: Journal of the American Chemical Society
October 2014

Molecular mechanisms by which to increase the activity of a mechanophore might provide access to new chemical reactions and enhanced stress-responsive behavior in mechanochemically active polymeric materials. Here, single-molecule force spectroscopy reveals that the force-induced acceleration of the electrocyclic ring opening of gem-dichlorocyclopropanes (gDCC) is sensitive to the stereochemistry of an α-alkene substituent on the gDCC. On the ∼0.1 s time scale of the experiment, the force required to open the E-alkene-substituted gDCC was found to be 0.4 nN lower than that required in the corresponding Z-alkene isomer, despite the effectively identical force-free reactivities of the two isomers and the distance between the stereochemical permutation and the scissile bond of the mechanophore. Fitting the experimental data with a cusp model provides force-free activation lengths of 1.67 ± 0.05 and 1.20 ± 0.05 Å for the E and Z isomers, respectively, as compared to 1.65 and 1.24 Å derived from computational modeling.

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Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

October 2014

Volume

136

Issue

43

Start / End Page

15162 / 15165

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

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Wang, J., Kouznetsova, T. B., Kean, Z. S., Fan, L., Mar, B. D., Martínez, T. J., & Craig, S. L. (2014). A remote stereochemical lever arm effect in polymer mechanochemistry. Journal of the American Chemical Society, 136(43), 15162–15165. https://doi.org/10.1021/ja509585g
Wang, Junpeng, Tatiana B. Kouznetsova, Zachary S. Kean, Lin Fan, Brendan D. Mar, Todd J. Martínez, and Stephen L. Craig. “A remote stereochemical lever arm effect in polymer mechanochemistry.Journal of the American Chemical Society 136, no. 43 (October 2014): 15162–65. https://doi.org/10.1021/ja509585g.
Wang J, Kouznetsova TB, Kean ZS, Fan L, Mar BD, Martínez TJ, et al. A remote stereochemical lever arm effect in polymer mechanochemistry. Journal of the American Chemical Society. 2014 Oct;136(43):15162–5.
Wang, Junpeng, et al. “A remote stereochemical lever arm effect in polymer mechanochemistry.Journal of the American Chemical Society, vol. 136, no. 43, Oct. 2014, pp. 15162–65. Epmc, doi:10.1021/ja509585g.
Wang J, Kouznetsova TB, Kean ZS, Fan L, Mar BD, Martínez TJ, Craig SL. A remote stereochemical lever arm effect in polymer mechanochemistry. Journal of the American Chemical Society. 2014 Oct;136(43):15162–15165.
Journal cover image

Published In

Journal of the American Chemical Society

DOI

EISSN

1520-5126

ISSN

0002-7863

Publication Date

October 2014

Volume

136

Issue

43

Start / End Page

15162 / 15165

Related Subject Headings

  • General Chemistry
  • 40 Engineering
  • 34 Chemical sciences
  • 03 Chemical Sciences