Tuning porosity with electric fields: Many metal-organic framework (MOF) compounds exhibit soft porosity—i.e., their lattices can undergo considerable deformation. Knebel et al. formed membrane layers of the MOF ZIF-8 and found that it was converted into a polar polymorph with a stiffer lattice in response to an applied electric field (see the Perspective by Gascon). This change reduced gas transport but, for certain gas mixtures such as propane and propene, also improved their separation factor. Science , this issue p. 347 ; see also p. 303
ZIF-8 is one of the most interesting metal–organic frameworks due to its high stability and unique capabilities for hydrocarbons separation. Its porous network is formed by large almost spherical cavities interconnected by very narrow windows, ∼3.4 Å, which should be too small even for methane. At the same time the direct experimental observations show that ZIF-8 cavities are able to host even such large molecules as benzene. This effect is associated with the flexibility of the cavity widows, arising from dynamical freedom on the 2-methylimidazole (2-mIM) linkers that form the framework. In this work, by means of 2H NMR we show that the 2-mIM linkers of the ZIF-8 are very mobile and their mobility is sensitive to the presence of benzene guest. In contrast with other known MOFs based on linearly bonded carboxylates, in guest-free ZIF-8 the plane of 2-mIM linker exhibits two-site flips within a sector of 2φf = 34° with very low activation barrier (1.5 kJ mol–1) and high rates (∼1012 s–1). Above 380 K the l...
14 May 2012 in The Journal of Physical Chemistry C