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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]
  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.
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. doi:10.1038/nature25765.
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. doi:10.1038/nature25765. https://www.osti.gov/servlets/purl/1437554.
@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}
}

Journal Article:
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Cited by: 17 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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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly
journal, December 2016

  • Yan, Hao; Hohman, J. Nathan; Li, Fei Hua
  • Nature Materials, Vol. 16, Issue 3
  • DOI: 10.1038/nmat4823

Tree branch-shaped cupric oxide for highly effective photoelectrochemical water reduction
journal, January 2015

  • Jang, Youn Jeong; Jang, Ji-Wook; Choi, Sun Hee
  • Nanoscale, Vol. 7, Issue 17
  • DOI: 10.1039/C5NR00208G

Die Krystallstruktur von Adamantan (symm. Tri-cyclo-decan)
journal, January 1945


The Janus-faced role of external forces in mechanochemical disulfide bond cleavage
journal, June 2013

  • Dopieralski, Przemyslaw; Ribas-Arino, Jordi; Anjukandi, Padmesh
  • Nature Chemistry, Vol. 5, Issue 8
  • DOI: 10.1038/nchem.1676

Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain
journal, June 2012

  • Chen, Yulan; Spiering, A. J. H.; Karthikeyan, S.
  • Nature Chemistry, Vol. 4, Issue 7
  • DOI: 10.1038/nchem.1358

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

Finite Elastic Strain of Cubic Crystals
journal, June 1947


Force-induced activation of covalent bonds in mechanoresponsive polymeric materials
journal, May 2009

  • Davis, Douglas A.; Hamilton, Andrew; Yang, Jinglei
  • Nature, Vol. 459, Issue 7243
  • DOI: 10.1038/nature07970

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Mechanochemistry
journal, October 1996


X-ray Photoelectron Spectroscopy Sulfur 2p Study of Organic Thiol and Disulfide Binding Interactions with Gold Surfaces
journal, January 1996

  • Castner, David G.; Hinds, Kenneth; Grainger, David W.
  • Langmuir, Vol. 12, Issue 21
  • DOI: 10.1021/la960465w

OLEX2 : a complete structure solution, refinement and analysis program
journal, January 2009

  • Dolomanov, Oleg V.; Bourhis, Luc J.; Gildea, Richard J.
  • Journal of Applied Crystallography, Vol. 42, Issue 2
  • DOI: 10.1107/S0021889808042726

Mechanochemical unzipping of insulating polyladderene to semiconducting polyacetylene
journal, August 2017


Experimentally realized mechanochemistry distinct from force-accelerated scission of loaded bonds
journal, July 2017


Single-Molecule Observation of a Mechanically Activated Cis -to- Trans Cyclopropane Isomerization
journal, August 2016

  • Wang, Junpeng; Kouznetsova, Tatiana B.; Craig, Stephen L.
  • Journal of the American Chemical Society, Vol. 138, Issue 33
  • DOI: 10.1021/jacs.6b06452

The condensed phases of carboranes
journal, August 1996

  • Gamba, Z.; Powell, B. M.
  • The Journal of Chemical Physics, Vol. 105, Issue 6
  • DOI: 10.1063/1.472111

Biasing reaction pathways with mechanical force
journal, March 2007

  • Hickenboth, Charles R.; Moore, Jeffrey S.; White, Scott R.
  • Nature, Vol. 446, Issue 7134
  • DOI: 10.1038/nature05681

Is Molecular Weight or Degree of Polymerization a Better Descriptor of Ultrasound-Induced Mechanochemical Transduction?
journal, January 2016


Copper(I) tert -Butylthiolato Clusters as Single-Source Precursors for High-Quality Chalcocite Thin Films:  Precursor Chemistry in Solution and the Solid State
journal, May 2007

  • Schneider, Sven; Dzudza, Alma; Raudaschl-Sieber, Gabriele
  • Chemistry of Materials, Vol. 19, Issue 11
  • DOI: 10.1021/cm0700504

Polymer mechanochemistry: techniques to generate molecular force via elongational flows
journal, January 2013

  • May, Preston A.; Moore, Jeffrey S.
  • Chemical Society Reviews, Vol. 42, Issue 18
  • DOI: 10.1039/c2cs35463b

Chemomechanics: chemical kinetics for multiscale phenomena
journal, January 2011

  • Huang, Zhen; Boulatov, Roman
  • Chemical Society Reviews, Vol. 40, Issue 5
  • DOI: 10.1039/c0cs00148a

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Higher-accuracy van der Waals density functional
journal, August 2010


Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules
journal, June 2017

  • Berland, Kristian; Jiao, Yang; Lee, Jung-Hoon
  • The Journal of Chemical Physics, Vol. 146, Issue 23
  • DOI: 10.1063/1.4986522

Atomistic Evidence of How Force Dynamically Regulates Thiol/Disulfide Exchange
journal, December 2010

  • Li, Wenjin; Gräter, Frauke
  • Journal of the American Chemical Society, Vol. 132, Issue 47
  • DOI: 10.1021/ja104763q

Diamondoids: functionalization and subsequent applications of perfectly defined molecular cage hydrocarbons
journal, January 2014

  • Gunawan, Maria A.; Hierso, Jean-Cyrille; Poinsot, Didier
  • New J. Chem., Vol. 38, Issue 1
  • DOI: 10.1039/C3NJ00535F

Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer
journal, April 2014

  • Diesendruck, Charles E.; Peterson, Gregory I.; Kulik, Heather J.
  • Nature Chemistry, Vol. 6, Issue 7
  • DOI: 10.1038/nchem.1938

Crystal structure refinement with SHELXL
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section C Structural Chemistry, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053229614024218

Activating catalysts with mechanical force
journal, April 2009

  • Piermattei, Alessio; Karthikeyan, S.; Sijbesma, Rint P.
  • Nature Chemistry, Vol. 1, Issue 2
  • DOI: 10.1038/nchem.167

Mercury : visualization and analysis of crystal structures
journal, May 2006

  • Macrae, Clare F.; Edgington, Paul R.; McCabe, Patrick
  • Journal of Applied Crystallography, Vol. 39, Issue 3
  • DOI: 10.1107/S002188980600731X

A backbone lever-arm effect enhances polymer mechanochemistry
journal, December 2012

  • Klukovich, Hope M.; Kouznetsova, Tatiana B.; Kean, Zachary S.
  • Nature Chemistry, Vol. 5, Issue 2
  • DOI: 10.1038/nchem.1540

Mechanically-Induced Chemical Changes in Polymeric Materials
journal, November 2009

  • Caruso, Mary M.; Davis, Douglas A.; Shen, Qilong
  • Chemical Reviews, Vol. 109, Issue 11
  • DOI: 10.1021/cr9001353

Diamonds are a Chemist's Best Friend: Diamondoid Chemistry Beyond Adamantane
journal, January 2008

  • Schwertfeger, Hartmut; Fokin, Andrey A.; Schreiner, Peter R.
  • Angewandte Chemie International Edition, Vol. 47, Issue 6
  • DOI: 10.1002/anie.200701684

    Works referencing / citing this record:

    Van der Waals Density Functional for General Geometries
    journal, June 2004


    Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules
    journal, June 2017

    • Berland, Kristian; Jiao, Yang; Lee, Jung-Hoon
    • The Journal of Chemical Physics, Vol. 146, Issue 23
    • DOI: 10.1063/1.4986522

    Mechanochemistry
    journal, October 1996


    Atomistic Evidence of How Force Dynamically Regulates Thiol/Disulfide Exchange
    journal, December 2010

    • Li, Wenjin; Gräter, Frauke
    • Journal of the American Chemical Society, Vol. 132, Issue 47
    • DOI: 10.1021/ja104763q

    Biasing reaction pathways with mechanical force
    journal, March 2007

    • Hickenboth, Charles R.; Moore, Jeffrey S.; White, Scott R.
    • Nature, Vol. 446, Issue 7134
    • DOI: 10.1038/nature05681

    Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer
    journal, April 2014

    • Diesendruck, Charles E.; Peterson, Gregory I.; Kulik, Heather J.
    • Nature Chemistry, Vol. 6, Issue 7
    • DOI: 10.1038/nchem.1938

    Single-Molecule Observation of a Mechanically Activated Cis -to- Trans Cyclopropane Isomerization
    journal, August 2016

    • Wang, Junpeng; Kouznetsova, Tatiana B.; Craig, Stephen L.
    • Journal of the American Chemical Society, Vol. 138, Issue 33
    • DOI: 10.1021/jacs.6b06452

    Copper(I) tert -Butylthiolato Clusters as Single-Source Precursors for High-Quality Chalcocite Thin Films:  Precursor Chemistry in Solution and the Solid State
    journal, May 2007

    • Schneider, Sven; Dzudza, Alma; Raudaschl-Sieber, Gabriele
    • Chemistry of Materials, Vol. 19, Issue 11
    • DOI: 10.1021/cm0700504

    Studying weak interactions in crystals at high pressures: when hardware matters
    journal, April 2018

    • Zakharov, Boris A.; Gal, Zoltan; Cruickshank, Dyanne
    • Acta Crystallographica Section E Crystallographic Communications, Vol. 74, Issue 5
    • DOI: 10.1107/s205698901800470x

    A backbone lever-arm effect enhances polymer mechanochemistry
    journal, December 2012

    • Klukovich, Hope M.; Kouznetsova, Tatiana B.; Kean, Zachary S.
    • Nature Chemistry, Vol. 5, Issue 2
    • DOI: 10.1038/nchem.1540

    Chemomechanics: chemical kinetics for multiscale phenomena
    journal, January 2011

    • Huang, Zhen; Boulatov, Roman
    • Chemical Society Reviews, Vol. 40, Issue 5
    • DOI: 10.1039/c0cs00148a

    Polymer mechanochemistry: techniques to generate molecular force via elongational flows
    journal, January 2013

    • May, Preston A.; Moore, Jeffrey S.
    • Chemical Society Reviews, Vol. 42, Issue 18
    • DOI: 10.1039/c2cs35463b

    Force-induced activation of covalent bonds in mechanoresponsive polymeric materials
    journal, May 2009

    • Davis, Douglas A.; Hamilton, Andrew; Yang, Jinglei
    • Nature, Vol. 459, Issue 7243
    • DOI: 10.1038/nature07970

    Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain
    journal, June 2012

    • Chen, Yulan; Spiering, A. J. H.; Karthikeyan, S.
    • Nature Chemistry, Vol. 4, Issue 7
    • DOI: 10.1038/nchem.1358

    Activating catalysts with mechanical force
    journal, April 2009

    • Piermattei, Alessio; Karthikeyan, S.; Sijbesma, Rint P.
    • Nature Chemistry, Vol. 1, Issue 2
    • DOI: 10.1038/nchem.167

    The Janus-faced role of external forces in mechanochemical disulfide bond cleavage
    journal, June 2013

    • Dopieralski, Przemyslaw; Ribas-Arino, Jordi; Anjukandi, Padmesh
    • Nature Chemistry, Vol. 5, Issue 8
    • DOI: 10.1038/nchem.1676

    Diamonds are a Chemist's Best Friend: Diamondoid Chemistry Beyond Adamantane
    journal, January 2008

    • Schwertfeger, Hartmut; Fokin, Andrey A.; Schreiner, Peter R.
    • Angewandte Chemie International Edition, Vol. 47, Issue 6
    • DOI: 10.1002/anie.200701684

    The condensed phases of carboranes
    journal, August 1996

    • Gamba, Z.; Powell, B. M.
    • The Journal of Chemical Physics, Vol. 105, Issue 6
    • DOI: 10.1063/1.472111

    Mechanically-Induced Chemical Changes in Polymeric Materials
    journal, November 2009

    • Caruso, Mary M.; Davis, Douglas A.; Shen, Qilong
    • Chemical Reviews, Vol. 109, Issue 11
    • DOI: 10.1021/cr9001353

    Die Krystallstruktur von Adamantan (symm. Tri-cyclo-decan)
    journal, January 1945


    Switching Chemoselectivity: Using Mechanochemistry to Alter Reaction Kinetics
    journal, November 2018

    • Howard, Joseph L.; Brand, Michael C.; Browne, Duncan L.
    • Angewandte Chemie International Edition, Vol. 57, Issue 49
    • DOI: 10.1002/anie.201810141

    Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly
    journal, December 2016

    • Yan, Hao; Hohman, J. Nathan; Li, Fei Hua
    • Nature Materials, Vol. 16, Issue 3
    • DOI: 10.1038/nmat4823

    Is Molecular Weight or Degree of Polymerization a Better Descriptor of Ultrasound-Induced Mechanochemical Transduction?
    journal, January 2016


    X-ray Photoelectron Spectroscopy Sulfur 2p Study of Organic Thiol and Disulfide Binding Interactions with Gold Surfaces
    journal, January 1996

    • Castner, David G.; Hinds, Kenneth; Grainger, David W.
    • Langmuir, Vol. 12, Issue 21
    • DOI: 10.1021/la960465w

    Experimentally realized mechanochemistry distinct from force-accelerated scission of loaded bonds
    journal, July 2017


    Mechanochemical unzipping of insulating polyladderene to semiconducting polyacetylene
    journal, August 2017


    QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
    journal, September 2009

    • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
    • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
    • DOI: 10.1088/0953-8984/21/39/395502

    Switching Chemoselectivity: Using Mechanochemistry to Alter Reaction Kinetics
    journal, October 2018

    • Howard, Joseph L.; Brand, Michael C.; Browne, Duncan L.
    • Angewandte Chemie, Vol. 130, Issue 49
    • DOI: 10.1002/ange.201810141

    Studying weak interactions in crystals at high pressures: when hardware matters
    journal, April 2018

    • Zakharov, Boris A.; Gal, Zoltan; Cruickshank, Dyanne
    • Acta Crystallographica Section E Crystallographic Communications, Vol. 74, Issue 5
    • DOI: 10.1107/s205698901800470x