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submitted on 08.03.2018 and posted on 08.03.2018by Simon Krause, Jack D. Evans, Volodymyr Bon, Irena Senkovska, Sebastian Ehrling, Ulrich Stoeck, Pascal Yot, Paul Iacomi, Philip Llewellyn, Guillaume Maurin, François-Xavier Coudert, Stefan Kaskel
In this article we report the synthesis and detailed analysis of the highly porous metal-organic framework DUT-48, isoreticular to DUT-49 a material which shows an adsorption-induced structural transition. DUT-48 has impressive porosity and methane storage capacity, however displays conventional adsorption behaviour. The contrasting flexibility of DUT-48 and DUT-49 were analysed and rationalised using a combination of novel experimental and computational techniques. Microcalorimetry measurements, in conjunction with molecular simulations, demonstrate that DUT-48 has a significantly lower adsorption enthalpy difference and a higher framework stiffness which leads to an absence of adsorption-induced transitions and negative gas adsorption (NGA). However, by analysing the mechanical behaviour of both DUT-48 and DUT-49, employing mercury porosimetry experiments, we discovered that both materials exhibit large volume changes under hydrostatic compression, demonstrating noteworthy potential as shock absorbers, and directly linking internal adsorption-induced contraction to external hydrostatic compression.