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

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• 作者：Anirban Karmakar ; Anup Paul ; Guilherme M. D. M. Rú ; bio ; M. Fá ; tima C. Guedes da Silva and Armando J. L. Pombeiro
• 刊名：European Journal of Inorganic Chemistry
• 出版年：2016
• 出版时间：December 2016
• 年：2016
• 卷：2016
• 期：36
• 页码：5557-5567
• 全文大小：3799K
• ISSN：1099-0682c

文摘

Solvothermal reaction of zinc(II) and copper(II) salts with 3,3′′-dipropoxy-[1,1′:4′,1′′-terphenyl]-4,4′′-dicarboxylic acid (H₂L) gave rise to the 1D and 2D metal–organic frameworks (MOFs) [Zn(L)(dmf)₂]_n (1), [Zn₂(L)(NO₃)₂(4,4′-bipyridine)₂]_n·n(DMF) (2), [Cu(L)(H₂O)₂]_n·2n(H₂O) (3), and [Cu₃(OH)₂(L)₂]_n·n(H₂O) (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 (C₂O₄Zn₂) and a trinuclear µ³-hydroxo-bridged Cu^II cluster [Cu₃(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.