Letter | Published:

Sterically controlled mechanochemistry under hydrostatic pressure

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


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.

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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.


  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


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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.

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