Premium
Time‐Resolved In Situ X‐ray Diffraction Reveals Metal‐Dependent Metal–Organic Framework Formation
Author(s) -
Wu Yue,
Henke Sebastian,
Kieslich Gregor,
Schwedler Inke,
Yang Miaosen,
Fraser Duncan A. X.,
O'Hare Dermot
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201608463
Subject(s) - isostructural , metal organic framework , metal , diffraction , crystallization , materials science , powder diffraction , phase (matter) , in situ , chemical physics , nanotechnology , chemistry , crystallography , crystal structure , organic chemistry , physics , adsorption , optics , metallurgy
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 M 2 (bdc) 2 dabco (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.