MOF DEFECT NANOREGIONS

Correlated defect nanoregions in a metal–organic framework
M J Cliffe, W Wan, X Zou, P A Chater, A K Kleppe, M G Tucker, H Wilhelm, N P Funnell, F-X Coudert and A L Goodwin
Nature Communications 5, 4176 (2014)

Throughout much of condensed matter science, correlated disorder is a key to material function. While structural and compositional defects are known to exist within a variety of metal–organic frameworks (MOFs), the prevailing understanding is that these defects are only ever included in a random manner. Here we show—using a combination of diffuse scattering, electron microscopy, anomalous X-ray scattering and pair distribution function measurements—that correlations between defects can in fact be introduced and controlled within a hafnium terephthalate MOF. The nanoscale defect structures that emerge are an analogue of correlated Schottky vacancies in rocksalt-structured transition metal monoxides and have implications for storage, transport, optical and mechanical responses. Our results suggest how the diffraction behaviour of some MOFs might be reinterpreted, and establish a strategy of exploiting correlated nanoscale disorder as a targetable and desirable motif in MOF design.