Correlated defect nanoregions in a metal–organic framework

• Published in: Nature communications Vol. 5; no. 1; p. 4176
• Main Authors: Cliffe, Matthew J., Wan, Wei, Zou, Xiaodong, Chater, Philip A., Kleppe, Annette K., Tucker, Matthew G., Wilhelm, Heribert, Funnell, Nicholas P., Coudert, François-Xavier, Goodwin, Andrew L
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 20.06.2014; Nature Publishing Group
• Subjects: 119/118; 639/301/299/921; 639/638/263; Chemical Sciences; Humanities and Social Sciences; Material chemistry; multidisciplinary; or physical chemistry; Science; Science (multidisciplinary); Theoretical and
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/ncomms5176

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. Correlated defects are known to be closely linked to material properties throughout condensed matter research. Here, the authors examine the defects in a canonical metal–organic framework with an array of crystallographic and computational techniques and suggest they are correlated rather than random.