Amphidynamic character of crystalline MOF-5: Rotational dynamics of terephthalate phenylenes in a free-volume, sterically unhindered environment

Metal-organic frameworks (MOFs) have been the focus of much interest within the context of hydrogen storage and other materials applications. With static metal clusters linked by axially substituted organic spacers capable of experiencing internal rotations, MOFs are one of the most promising amphidynamic materials to investigate and exploit the dynamics of crystalline solids. In this communication we report an experimental study of the rotational dynamics of the 1,4-phenylenedicarboxylate bridge of MOF-5, which has no steric contacts that might contribute to the rotational barrier. Highly reproducible H-1 T, relaxation, high-resolution C-13 CPMAS, and variable temperature quadrupolar echo H-2 NMR data were obtained from high quality samples that were sealed at reduced pressure (ca. 3 mTorr), H-2 NMR line shape simulation revealed an activation barrier for rotation of 11.3 +/- 2.0 kcal/mol, which is lower than the 14-16 kcal/mol values reported in theoretical studies of truncated models. While our results suggest that the models used for MOF-5 are insufficient to account for the properties of the extended crystal lattice, they also suggest that the amphidynamic materials with static and dynamic components may reach the friction-free rotational motion characteristic of gas dynamics.