title: Correlated defect nanoregions in a metal-organic framework.
abstract: 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.
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Matthew J
authors.initials: MJ
authors.lastname: Cliffe
authors.affiliation: Berzeli Center EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.
authors.forename: Wei
authors.initials: W
authors.lastname: Wan
authors.affiliation: Berzeli Center EXSELENT on Porous Materials, Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden.
authors.forename: Xiaodong
authors.initials: X
authors.lastname: Zou
authors.affiliation: Diamond Light Source, Chilton, Oxfordshire OX11 0DE, UK.
authors.forename: Philip A
authors.initials: PA
authors.lastname: Chater
authors.affiliation: Diamond Light Source, Chilton, Oxfordshire OX11 0DE, UK.
authors.forename: Annette K
authors.initials: AK
authors.lastname: Kleppe
authors.affiliation: 1] Diamond Light Source, Chilton, Oxfordshire OX11 0DE, UK [2] ISIS Facility, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, Oxfordshire OX11 0QX, UK.
authors.forename: Matthew G
authors.initials: MG
authors.lastname: Tucker
authors.affiliation: Diamond Light Source, Chilton, Oxfordshire OX11 0DE, UK.
authors.forename: Heribert
authors.initials: H
authors.lastname: Wilhelm
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Nicholas P
authors.initials: NP
authors.lastname: Funnell
authors.affiliation: Institut de Recherche de Chimie Paris, CNRS-Chimie ParisTech, 11 rue Pierre et Marie Curie, 75005 Paris, France.
authors.forename: François-Xavier
authors.initials: FX
authors.lastname: Coudert
authors.affiliation: Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QR, UK.
authors.forename: Andrew L
authors.initials: AL
authors.lastname: Goodwin