113Cd Nuclear Magnetic Resonance as a Probe of Structural Dynamics in a Flexible Porous Framework Showing Selective O2/N2 and CO2/N2 Adsorption

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• 作者：Ritesh Haldar ; Munehiro Inukai ; Satoshi Horike ; Kazuhiro Uemura ; Susumu Kitagawa ; Tapas Kumar Maji
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：May 2, 2016
• 年：2016
• 卷：55
• 期：9
• 页码：4166-4172
• 全文大小：517K
• 年卷期：0
• ISSN：1520-510X

文摘

Two new isomorphous three-dimensional porous coordination polymers, {[Cd(bpe)_0.5(bdc)(H₂O)]·EtOH}_n (1) and {[Cd(bpe)_0.5(bdc)(H₂O)]·2H₂O}_n (2) [bpe = 1,2-bis(4-pyridyl)ethane, and H₂bdc = 1,4-benzenedicarboxylic acid], have been synthesized by altering the solvent media. Both structures contain one-dimensional channels filled with metal-bound water and guest solvent molecules, and desolvated frameworks show significant changes in structure. However, exposure to the solvent vapors (water and methanol) reverts the structure back to the as-synthesized structure, and thus, the reversible flexible nature of the structure was elucidated. The flexibility and permanent porosity were further reinforced from the CO₂ adsorption profiles (195 and 273 K) that show stepwise uptake. Moreover, a high selectivity for O₂ over N₂ at 77 K was realized. The framework exhibits interesting solvent vapor adsorption behavior with dynamic structural transformation depending upon the size, polarity, and coordination ability of the solvent molecules. Further investigation was conducted by solid state ¹¹³Cd nuclear magnetic resonance (NMR) spectroscopy that unambiguously advocates the reversible transformation “pentagonal-bipyramidal CdO₆N → octahedral CdO₅N” geometry in the desolvated state. For the first time, ¹¹³Cd NMR has been used as a probe of structural flexibility in a porous coordination polymer system.