The internal free volume of porous materials diminishes upon mechanical compression, and such volume collapse can have chemical consequences. We report here the endothermic bond breakage in a metal-organic framework (MOF) during compression-induced collapse. Upon bulk compression at 1.9 GPa, the effective number for Zr-O bonds between Zr(iv) ions and carboxylate groups in UiO-66 decreased from 4.0 to 1.9, as determined by EXAFS, and the internal free volume was synchronously collapsed. Consistent with the EXAFS data, IR spectra confirmed conversion of syn-syn bridging carboxylates to monodentate ligation, thus establishing mechanochemical reactions induced by external compression of MOFs. Substantial mechanical energy (∼4 kJ g-1) was absorbed by UiO-66 nanocrystals during compression, as demonstrated from nanocompression of single crystals (600 nm) in situ during scanning electron microscopy, which establishes the potential application of MOFs as mechanical energy absorbers for hydrostatic and shock compression.
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