A Partially Fluorinated, Water-Stable Cu(II)–MOF Derived via Transmetalation: Significant Gas Adsorption with High CO2 Selectivity and Catalysis of Biginelli Reactions

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• 作者：Tapan K. Pal ; Dinesh De ; S. Senthilkumar ; Subhadip Neogi ; Parimal K. Bharadwaj
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：August 15, 2016
• 年：2016
• 卷：55
• 期：16
• 页码：7835-7842
• 全文大小：480K
• 年卷期：0
• ISSN：1520-510X

文摘

A partially fluorinated, angular tetracarboxylic acid linker (H₄L) incorporating a pendant amine moiety forms a three-dimensional Zn(II) framework, 1. The structure consists of paddle-wheel Zn₂(CO₂)₄ secondary building units (SBUs) and Zn₁₂(CO₂)₂₄ supramolecular building blocks (SBBs). Thermal stability of 1 is found to be low. However, it undergoes transmetalation reaction with Cu(II) at room temperature without losing crystallinity affording an isostructural framework, 1_Cu. Framework 1_Cu is thermally robust and allows generation of the solvent-free porous framework 1_Cu′ upon activation with coordinatively unsaturated metal centers. Framework 1_Cu′ exhibits water stability and at 77 K, adsorbs 2.56 wt % of H₂ up to 1 bar that significantly increases to 4.01 wt % at 13 bar. Also, this framework gives a high adsorption of 164.70 cc/g of CH₄ (11.7 wt %) at 303 K and 60 bar. The channel surfaces decorated with −NH₂ group and unsaturated metal centers in 1_Cu′ allow a promising 36.4 wt % of CO₂ adsorption at 1 bar and 273 K. Moreover, it exhibits pronounced selectivity of CO₂ adsorption over N₂ and H₂ at 273 K. Finally, the versatility of 1_Cu′ is shown by its excellent heterogeneous catalytic activity in the Biginelli coupling reactions involving an aldehyde, urea, and ethylacetoacetate to afford dihydroprimidinones.