Letter | Published:

Sterically controlled mechanochemistry under hydrostatic pressure

Nature volume 554, pages 505510 (22 February 2018) | Download Citation

Abstract

Mechanical stimuli can modify the energy landscape of chemical reactions and enable reaction pathways, offering a synthetic strategy that complements conventional chemistry1,2,3. These mechanochemical mechanisms have been studied extensively in one-dimensional polymers under tensile stress4,5,6,7,8,9 using ring-opening10 and reorganization11, polymer unzipping6,12 and disulfide reduction13,14 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 dissociation15. However, 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. We engineer molecules with mechanically heterogeneous components—a compressible (‘soft’) mechanophore and incompressible (‘hard’) ligands. In these ‘molecular anvils’, isotropic stress leads to relative motions of the rigid ligands, anisotropically deforming the compressible mechanophore and activating bonds. Conversely, rigid ligands in steric contact impede relative motion, blocking reactivity. We combine experiments and computations to demonstrate hydrostatic-pressure-driven redox reactions in metal–organic chalcogenides that incorporate molecular elements that have heterogeneous compressibility16,17,18,19, in which bending of bond angles or shearing of adjacent chains activates the metal–chalcogen bonds, leading to the formation of the elemental metal. These results reveal an unexplored reaction mechanism and suggest possible strategies for high-specificity mechanosynthesis.

  • Subscribe to Nature for full access:

    $199

    Subscribe

Additional access options:

Already a subscriber?  Log in  now or  Register  for online access.

References

  1. 1.

    Mechanochemistry. Science 274, 65–66 (1996)

  2. 2.

    et al. Mechanically-induced chemical changes in polymeric materials. Chem. Rev. 109, 5755–5798 (2009)

  3. 3.

    et al. Biasing reaction pathways with mechanical force. Nature 446, 423–427 (2007)

  4. 4.

    et al. Polymer mechanochemistry: techniques to generate molecular force via elongational flows. Chem. Soc. Rev. 42, 7497–7506 (2013)

  5. 5.

    & Chemomechanics: chemical kinetics for multiscale phenomena. Chem. Soc. Rev. 40, 2359–2384 (2011)

  6. 6.

    et al. Mechanically triggered heterolytic unzipping of a low-ceiling-temperature polymer. Nat. Chem. 6, 623–628 (2014)

  7. 7.

    , & Activating catalysts with mechanical force. Nat. Chem. 1, 133–137 (2009)

  8. 8.

    et al. A backbone lever-arm effect enhances polymer mechanochemistry. Nat. Chem. 5, 110–114 (2013)

  9. 9.

    et al. Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain. Nat. Chem. 4, 559–562 (2012)

  10. 10.

    et al. Force-induced activation of covalent bonds in mechanoresponsive polymeric materials. Nature 459, 68–72 (2009)

  11. 11.

    , & Single-molecule observation of a mechanically activated cis-to-trans cyclopropane isomerization. J. Am. Chem. Soc. 138, 10410–10412 (2016)

  12. 12.

    et al. Mechanochemical unzipping of insulating polyladderene to semiconducting polyacetylene. Science 357, 475–479 (2017)

  13. 13.

    & Atomistic evidence of how force dynamically regulates thiol/disulfide exchange. J. Am. Chem. Soc. 132, 16790–16795 (2010)

  14. 14.

    et al. The Janus-faced role of external forces in mechanochemical disulfide bond cleavage. Nat. Chem. 5, 685–691 (2013)

  15. 15.

    et al. Experimentally realized mechanochemistry distinct from force-accelerated scission of loaded bonds. Science 357, 299–303 (2017)

  16. 16.

    et al. Hybrid metal–organic chalcogenide nanowires with electrically conductive inorganic core through diamondoid-directed assembly. Nat. Mater. 16, 349 (2017)

  17. 17.

    & The condensed phases of carboranes. J. Chem. Phys. 105, 2436 (1996)

  18. 18.

    , & Diamonds are a chemist’s best friend: diamondoid chemistry beyond adamantane. Angew. Chem. Int. Ed. 47, 1022–1036 (2008)

  19. 19.

    et al. Diamondoids: functionalization and subsequent applications of perfectly defined molecular cage hydrocarbons. New J. Chem. 38, 28–41 (2014)

  20. 20.

    , & X-ray photoelectron spectroscopy sulfur 2p study of organic thiol and disulfide binding interactions with gold surfaces. Langmuir 12, 5083–5086 (1996)

  21. 21.

    , , & Copper(I) tert-butylthiolato clusters as single-source precursors for high-quality chalcocite thin films: precursor chemistry in solution and the solid state. Chem. Mater. 19, 2768–2779 (2007)

  22. 22.

    Finite elastic strain of cubic crystals. Phys. Rev. 71, 809–824 (1947)

  23. 23.

    et al. Tree branch-shaped cupric oxide for highly effective photoelectrochemical water reduction. Nanoscale 7, 7624–7631 (2015)

  24. 24.

    Die Krystallstruktur von Adamantan (symm. Tri-cyclo-decan). Helv. Chim. Acta 28, 1233–1242 (1945)

  25. 25.

    et al. Is molecular weight or degree of polymerization a better descriptor of ultrasound-induced mechanochemical transduction? ACS Macro Lett. 5, 177–180 (2016)

  26. 26.

    APEX2, (Bruker AXS, 2007)

  27. 27.

    et al. Crystal structure refinement with SHELXL. Acta Crystallogr. C. 71, 3–8 (2015)

  28. 28.

    A short history of SHELX. Acta Crystallogr. A 64, 112–122 (2008)

  29. 29.

    et al. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Cryst. 42, 339–341 (2009)

  30. 30.

    & in Treatise on Geophysics 231–267 (Elsevier, 2007)

  31. 31.

    Internal Report, ESRF98HA01T, FIT2D V9.129 Reference Manual V3.1 (European Synchrotron Radiation Facility (ESRF), 1998)

  32. 32.

    , & Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996)

  33. 33.

    et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009)

  34. 34.

    . et al. Mercury: visualization and analysis of crystal structures. J. Appl. Cryst. 39, 453–457 (2006)

  35. 35.

    & VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Cryst. 44, 1272–1276 (2011)

  36. 36.

    et al. Van der Waals density functional for general geometries. Phys. Rev. Lett. 92, 246401 (2004)

  37. 37.

    et al. Higher-accuracy van der Waals density functional. Phys. Rev. B 82, 081101 (2010)

  38. 38.

    et al. Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules. J. Chem. Phys. 146, 234106 (2017)

Download references

Acknowledgements

We thank C. Beavers, J. Yan and S. Teat from the Advanced Light Source for help with XRD measurements, and C. Park and D. Popov from the Advanced Photon Source for XAS measurements. This work was supported by the Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering, under contracts DE-AC02-76SF00515 and DE-FG02-06ER46262. D.P. acknowledges support from Hong Kong Research Grants Council (project number ECS-26305017), the National Natural Science Foundation of China (project number 11774072) and the Alfred P. Sloan Foundation through the Deep Carbon Observatory. D.S.-I. acknowledges support from PAPIIT IA203116/27 and CONACYT FC-2015-2/829. This research used resources of the Advanced Light Source, which is a US Department of Energy (DOE) Office of Science User Facility under contract DE-AC02-05CH11231. This research also used resources of the Advanced Photon Source, a DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under contract DE-AC02-06CH11357. Portions of this work were performed at the Stanford Nano Shared Facilities, supported by the National Science Foundation under award ECCS-1542152. The computational work used resources at the Stanford Research Computing Center, the Research Computing Center at the University of Chicago, and the Deep Carbon Observatory computer cluster.

Author information

Author notes

    • Hao Yan
    • , Fan Yang
    •  & Ding Pan

    These authors contributed equally to this work.

Affiliations

  1. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

    • Hao Yan
    • , Fan Yang
    • , Yu Lin
    • , Fei Hua Li
    • , Jeremy E. P. Dahl
    • , Robert M. K. Carlson
    • , Wendy L. Mao
    • , Zhi-Xun Shen
    •  & Nicholas A. Melosh
  2. Department of Materials Science and Engineering, Stanford University, Stanford, California 94305, USA

    • Hao Yan
    • , Fei Hua Li
    •  & Nicholas A. Melosh
  3. Department of Geological Sciences, Stanford University, Stanford, California 94305, USA

    • Fan Yang
    •  & Wendy L. Mao
  4. Department of Physics, Hong Kong University of Science and Technology, Hong Kong, China

    • Ding Pan
  5. Department of Chemistry, Hong Kong University of Science and Technology, Hong Kong, China

    • Ding Pan
  6. HKUST Fok Ying Tung Research Institute, Guangzhou, China.

    • Ding Pan
  7. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA

    • J. Nathan Hohman
  8. Laboratorio de Fisicoquímica y Reactividad de Superficies (LaFReS), Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Coyoacán, CDMX 04510, México

    • Diego Solis-Ibarra
  9. Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany

    • Boryslav A. Tkachenko
    • , Andrey A. Fokin
    •  & Peter R. Schreiner
  10. Department of Organic Chemistry, Igor Sikorsky Kiev Polytechnic Institute, pr. Pobedy 37, 03056 Kiev, Ukraine

    • Andrey A. Fokin
  11. Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, USA

    • Giulia Galli
  12. Department of Physics, Stanford University, Stanford, California 94305, USA.

    • Zhi-Xun Shen

Authors

  1. Search for Hao Yan in:

  2. Search for Fan Yang in:

  3. Search for Ding Pan in:

  4. Search for Yu Lin in:

  5. Search for J. Nathan Hohman in:

  6. Search for Diego Solis-Ibarra in:

  7. Search for Fei Hua Li in:

  8. Search for Jeremy E. P. Dahl in:

  9. Search for Robert M. K. Carlson in:

  10. Search for Boryslav A. Tkachenko in:

  11. Search for Andrey A. Fokin in:

  12. Search for Peter R. Schreiner in:

  13. Search for Giulia Galli in:

  14. Search for Wendy L. Mao in:

  15. Search for Zhi-Xun Shen in:

  16. Search for Nicholas A. Melosh in:

Contributions

H.Y., W.L.M., Z.-X.S. and N.A.M. conceived the idea. H.Y., J.N.H. and D.S.-I. synthesized the crystals and solved their structures. H.Y., F.Y. and Y.L. carried out the high-pressure experiments. H.Y., D.P. and G.G. performed the DFT computations. H.Y. and F.H.L. performed the ex situ characterizations. J.E.P.D., R.M.K.C., B.A.T., A.A.F. and P.R.S. provided the diamondoids and synthesized their derivatives. H.Y. and N.A.M. wrote the paper. All authors contributed to the discussion and revision of the paper.

Competing interests

The authors declare no competing financial interests.

Corresponding author

Correspondence to Nicholas A. Melosh.

Reviewer Information Nature thanks D. Braga, S. James and L. Yan for their contribution to the peer review of this work.

Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Extended data

Supplementary information

PDF files

  1. 1.

    Supplementary Information

    This file contains Supplementary Tables S1-S5.

About this article

Publication history

Received

Accepted

Published

DOI

https://doi.org/10.1038/nature25765

Rights and permissions

To obtain permission to re-use content from this article visit RightsLink.

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.