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Scorpionate‐Type Coordination in MFU‐4 l Metal–Organic Frameworks: Small‐Molecule Binding and Activation upon the Thermally Activated Formation of Open Metal Sites
Author(s) -
Denysenko Dmytro,
Grzywa Maciej,
Jelic Jelena,
Reuter Karsten,
Volkmer Dirk
Publication year - 2014
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201310004
Subject(s) - hydride , chemistry , metal , catalysis , metal organic framework , molecule , chemisorption , copper , electrophile , inorganic chemistry , ligand (biochemistry) , adsorption , polymer chemistry , organic chemistry , biochemistry , receptor
Abstract Postsynthetic metal and ligand exchange is a versatile approach towards functionalized MFU‐4 l frameworks. Upon thermal treatment of MFU‐4 l formates, coordinatively strongly unsaturated metal centers, such as zinc(II) hydride or copper(I) species, are generated selectively. Cu I ‐MFU‐4 l prepared in this way was stable under ambient conditions and showed fully reversible chemisorption of small molecules, such as O 2 , N 2 , and H 2 , with corresponding isosteric heats of adsorption of 53, 42, and 32 kJ mol −1 , respectively, as determined by gas‐sorption measurements and confirmed by DFT calculations. Moreover, Cu I ‐MFU‐4 l formed stable complexes with C 2 H 4 and CO. These complexes were characterized by FTIR spectroscopy. The demonstrated hydride transfer to electrophiles and strong binding of small gas molecules suggests these novel, yet robust, metal–organic frameworks with open metal sites as promising catalytic materials comprising earth‐abundant metal elements.