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Zinc(II) and Copper(II) Metal–Organic Frameworks Constructed from a Terphenyl‐4,4′′‐dicarboxylic Acid Derivative: Synthesis, Structure, and Catalytic Application in the Cyanosilylation of Aldehydes
Author(s) -
Karmakar Anirban,
Paul Anup,
Rúbio Guilherme M. D. M.,
Guedes da Silva M. Fátima C.,
Pombeiro Armando J. L.
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600902
Subject(s) - chemistry , metal organic framework , trimethylsilyl cyanide , catalysis , zinc , copper , terphenyl , solvothermal synthesis , trimethylsilyl , inorganic chemistry , polymer chemistry , medicinal chemistry , organic chemistry , adsorption
Solvothermal reaction of zinc(II) and copper(II) salts with 3,3′′‐dipropoxy‐[1,1′:4′,1′′‐terphenyl]‐4,4′′‐dicarboxylic acid (H 2 L) gave rise to the 1D and 2D metal–organic frameworks (MOFs) [Zn(L)(dmf) 2 ] n ( 1 ), [Zn 2 (L)(NO 3 ) 2 (4,4′‐bipyridine) 2 ] n · n (DMF) ( 2 ), [Cu(L)(H 2 O) 2 ] n · 2 n (H 2 O) ( 3 ), and [Cu 3 (OH) 2 (L) 2 ] n · n (H 2 O) ( 4 ), which were characterized by elemental analysis, FTIR spectroscopy, and X‐ray single‐crystal diffraction. MOFs 1 and 3 have zigzag‐ and linear‐type 1D structures, respectively, whereas 2 and 4 possess rectangular grid‐ and layer‐type 2D structures. In 2 and in 4 , a dinuclear Zn II cluster (C 2 O 4 Zn 2 ) and a trinuclear µ 3 ‐hydroxo‐bridged Cu II cluster [Cu 3 (OH) 2 ] n , respectively, act as building block units. These frameworks act as heterogeneous catalysts (the Zn‐MOFs are more active than Cu‐MOFs, and 1 is the most efficient) for the cyanosilylation of aldehydes with trimethylsilyl cyanide at room temperature. These MOF‐based heterogeneous catalysts can be easily recovered and reused, at least over a few consecutive cycles, without losing activity.