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.
Extended data figures
This file contains Supplementary Tables S1-S5.