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A Stimuli‐Responsive Zirconium Metal–Organic Framework Based on Supermolecular Design
Author(s) -
Krause Simon,
Bon Volodymyr,
Stoeck Ulrich,
Senkovska Irena,
Többens Daniel M.,
Wallacher Dirk,
Kaskel Stefan
Publication year - 2017
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.201702357
Subject(s) - physisorption , adsorption , metal organic framework , zirconium , microporous material , butane , desorption , supercritical fluid , materials science , diffraction , solvent , chemical engineering , chemistry , inorganic chemistry , organic chemistry , catalysis , optics , engineering , physics
A flexible, yet very stable metal–organic framework (DUT‐98, Zr 6 O 4 (OH) 4 (CPCDC) 4 (H 2 O) 4 , CPCDC=9‐(4‐carboxyphenyl)‐9 H ‐carbazole‐3,6‐dicarboxylate) was synthesized using a rational supermolecular building block approach based on molecular modelling of metal–organic chains and subsequent virtual interlinking into a 3D MOF. Structural characterization via synchrotron single‐crystal X‐ray diffraction (SCXRD) revealed the one‐dimensional pore architecture of DUT‐98, envisioned in silico. After supercritical solvent extraction, distinctive responses towards various gases stimulated reversible structural transformations, as detected using coupled synchrotron diffraction and physisorption techniques. DUT‐98 shows a surprisingly low water uptake but a high selectivity for pore opening towards specific gases and vapors (N 2 , CO 2 , n ‐butane, alcohols) at characteristic pressure resulting in multiple steps in the adsorption isotherm and hysteretic behavior upon desorption.