title: Time-Resolved In Situ X-ray Diffraction Reveals Metal-Dependent Metal-Organic Framework Formation.
abstract: Versatility in metal substitution is one of the key aspects of metal-organic framework (MOF) chemistry, allowing properties to be tuned in a rational way. As a result, it important to understand why MOF syntheses involving different metals arrive at or fail to produce the same topological outcome. Frequently, conditions are tuned by trial-and-error to make MOFs with different metal species. We ask: is it possible to adjust synthetic conditions in a systematic way in order to design routes to desired phases? We have used in situ X-ray powder diffraction to study the solvothermal formation of isostructural M2(bdc)2dabco (M=Zn, Co, Ni) pillared-paddlewheel MOFs in real time. The metal ion strongly influences both kinetics and intermediates observed, leading in some cases to multiphase reaction profiles of unprecedented complexity. The standard models used for MOF crystallization break down in these cases; we show that a simple kinetic model describes the data and provides important chemical insights on phase selection.
authors.affiliation: Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Yue
authors.identifier: 0000-0003-2874-8267
authors.initials: Y
authors.lastname: Wu
authors.affiliation: Lehrstuhl für Anorganische Chemie II, Ruhr-Universität Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
authors.forename: Sebastian
authors.initials: S
authors.lastname: Henke
authors.affiliation: Department of Materials Science and Metallurgy, University of Cambridge, 27 Charles Babbage Road, Cambridge, CB3 0FS, UK.
authors.forename: Gregor
authors.initials: G
authors.lastname: Kieslich
authors.affiliation: Lehrstuhl für Anorganische Chemie II, Ruhr-Universität Bochum, Universitätsstraße 150, 44801, Bochum, Germany.
authors.forename: Inke
authors.initials: I
authors.lastname: Schwedler
authors.affiliation: Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.|School of Chemical Engineering, North-east Dianli University, Jilin, 132012, China.
authors.forename: Miaosen
authors.initials: M
authors.lastname: Yang
authors.affiliation: Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK.
authors.forename: Duncan A X
authors.initials: DA
authors.lastname: Fraser
authors.affiliation: Department of Chemistry, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK. dermot.ohare@chem.ox.ac.uk.
authors.forename: Dermot
authors.identifier: 0000-0001-8054-8751
authors.initials: D
authors.lastname: O'Hare
keywords: X-ray diffraction; crystal growth; metal-organic frameworks; metastable compounds; reaction kinetics