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Title: Sterically controlled mechanochemistry under hydrostatic pressure

Abstract

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. Furthermore, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain.

Authors:
 [1];  [1];  [2];  [3];  [4];  [5];  [1];  [3];  [3];  [6];  [7];  [6];  [8];  [1];  [1];  [1]
+ Show Author Affiliations
  1. SLAC National Accelerator Lab., Menlo Park, CA (United States); Stanford Univ., Stanford, CA (United States)
  2. Hong Kong Univ. of Science and Technology, Hong Kong (China); HKUST Fok Ying Tung Research Institute, Guangzhou (China)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Univ. Nacional Autonoma de Mexico, Coyoacan (Mexico)
  6. Justus-Liebig Univ., Giessen (Germany)
  7. Justus-Liebig Univ., Giessen (Germany); Igo Sikorsky Kiev Polytechnic Institute, Kiev (Ukraine)
  8. Univ. of Chicago, Chicago, IL (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1437554
Report Number(s):
SLAC-PUB-17189
Journal ID: ISSN 0028-0836; nature25765; TRN: US1900334
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 554; Journal Issue: 7693; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemical bonding; Electron transfer; Mechanical properties

Citation Formats

Yan, Hao, Yang, Fan, Pan, Ding, Lin, Yu, Hohman, J. Nathan, Solis-Ibarra, Diego, Li, Fei Hua, Dahl, Jeremy E. P., Carlson, Robert M. K., Tkachenko, Boryslav A., Fokin, Andrey A., Schreiner, Peter R., Galli, Giulia, Mao, Wendy L., Shen, Zhi -Xun, and Melosh, Nicholas A.. Sterically controlled mechanochemistry under hydrostatic pressure. United States: N. p., 2018. Web. doi:10.1038/nature25765.
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Yan, Hao, Yang, Fan, Pan, Ding, Lin, Yu, Hohman, J. Nathan, Solis-Ibarra, Diego, Li, Fei Hua, Dahl, Jeremy E. P., Carlson, Robert M. K., Tkachenko, Boryslav A., Fokin, Andrey A., Schreiner, Peter R., Galli, Giulia, Mao, Wendy L., Shen, Zhi -Xun, & Melosh, Nicholas A.. Sterically controlled mechanochemistry under hydrostatic pressure. United States. https://doi.org/10.1038/nature25765
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Yan, Hao, Yang, Fan, Pan, Ding, Lin, Yu, Hohman, J. Nathan, Solis-Ibarra, Diego, Li, Fei Hua, Dahl, Jeremy E. P., Carlson, Robert M. K., Tkachenko, Boryslav A., Fokin, Andrey A., Schreiner, Peter R., Galli, Giulia, Mao, Wendy L., Shen, Zhi -Xun, and Melosh, Nicholas A.. Wed . "Sterically controlled mechanochemistry under hydrostatic pressure". United States. https://doi.org/10.1038/nature25765. https://www.osti.gov/servlets/purl/1437554.
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@article{osti_1437554,
title = {Sterically controlled mechanochemistry under hydrostatic pressure},
author = {Yan, Hao and Yang, Fan and Pan, Ding and Lin, Yu and Hohman, J. Nathan and Solis-Ibarra, Diego and Li, Fei Hua and Dahl, Jeremy E. P. and Carlson, Robert M. K. and Tkachenko, Boryslav A. and Fokin, Andrey A. and Schreiner, Peter R. and Galli, Giulia and Mao, Wendy L. and Shen, Zhi -Xun and Melosh, Nicholas A.},
abstractNote = {Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress using ring-opening and reorganization, polymer unzipping and disulfide reduction as model reactions. In these systems, the pulling force stretches chemical bonds, initiating the reaction. Additionally, it has been shown that forces orthogonal to the chemical bonds can alter the rate of bond dissociation. Furthermore, these bond activation mechanisms have not been possible under isotropic, compressive stress (that is, hydrostatic pressure). Here we show that mechanochemistry through isotropic compression is possible by molecularly engineering structures that can translate macroscopic isotropic stress into molecular-level anisotropic strain.},
doi = {10.1038/nature25765},
journal = {Nature (London)},
number = 7693,
volume = 554,
place = {United States},
year = {2018},
month = {2}
}
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Journal Article:
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https://doi.org/10.1038/nature25765
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Cited by: 51 works
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Figures / Tables:

Figure 1 Figure 1: Redox reaction in Cu-S-M9 under hydrostatic pressure. a, Unit cell of Cu-S-M9. Atoms are represented by their 50%-probability ellipsoids. Copper, sulfur, carbon and boron are represented by red, yellow, grey and pink, respectively. Hydrogen atoms and interstitial solvent (toluene) molecules are omitted for clarity. b, Cu-S-M9 molecule showingmore » the Cu4S4 mechanophore surrounded by M9 ligands, represented by polyhedra. c, TEM image of nanoclusters formed after compression to 12 GPa. Scale bar, 100 nm. Inset, Scanning electron microscopy (SEM) image of Cu-S-M9 crystals before compression. Scale bar, 50 μm. d, High-resolution TEM image of a single copper nanocluster. Scale bar, 2 nm. Inset, Fourier transform pattern. e, EDS of the clusters shown in (c) and (d). The arrow points to the position of S K-edge. The asterisk marks Ni peaks from the TEM grid. f, In situ XRD patterns of Cu-S-M9 from 0.4 to 12 GPa and back to 0.3 GPa. λ = 0.4959 Å. The bottom dashed line shows the ambient XRD pattern calculated from its crystal structure. The vertical dashed lines mark the positions of six selected peaks. g, Unit cell volume (red, left axis) and total energy change (blue, right axis) as functions of pressure. Open circles and solid lines represent experimentally-derived data and fitting to a third-order Birch-Murnaghan equation of state, respectively. h, In situ XAS at different pressures. The dashed line marks the position of the Cu(I) peak.« less
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      Figure 1 (p. 15)figure
      Figure 2 (p. 16)figure
      Figure 3 (p. 17)figure
      Figure 4 (p. 18)figure
      Extended Data Figure 1 (p. 19)figure
      Extended Data Figure 2 (p. 20)figure
      Extended Data Figure 3 (p. 21)figure
      Extended Data Figure 4 (p. 22)figure
      Extended Data Figure 5 (p. 23)figure
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      Extended Data Figure 9 (p. 27)figure
      Extended Data Figure 10 (p. 28)figure
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