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具有吡啶修饰通道的氢键开放框架:简便制备及其对溶液中酸性分子亲和力的深入研究

Hydrogen-Bonded Open-Framework with Pyridyl-Decorated Channels: Straightforward Preparation and Insight into Its Affinity for Acidic Molecules in Solution.

作者信息

Mouchaham Georges, Roques Nans, Khodja Walid, Duhayon Carine, Coppel Yannick, Brandès Stéphane, Fodor Tamás, Meyer Michel, Sutter Jean-Pascal

机构信息

CNRS, LCC (Laboratoire de Chimie de Coordination), 205 route de Narbonne, 31077, Toulouse, France.

Université de Toulouse, UPS, INPT, 31077, Toulouse, France.

出版信息

Chemistry. 2017 Sep 4;23(49):11818-11826. doi: 10.1002/chem.201701732. Epub 2017 Jul 24.

Abstract

A hydrogen-bonded open framework with pores decorated by pyridyl groups was constructed by off-charge-stoichiometry assembly of protonated tetrakis(4-pyridyloxymethyl)methane and [Al(oxalate) ] , which are the H-bond donor and acceptor of ionic H-bond interactions, respectively. This supramolecular porous architecture (SPA-2) has 1 nm-large pores interconnected in 3D with large solvent-accessible void (53 %). It demonstrated remarkable affinity for acidic organic molecules in solution, which was investigated by means of various carboxylic acids including larger drug molecules. Competing sorption between acetic acid and its halogenated homologues evidenced good selectivity of the porous material for the halogenated acids. The gathered results, including a series of guest@SPA-2 crystal structures and HRMAS-NMR spectra, suggest that the efficient sorption exhibited by the material relies not only on an acid-base interaction. The facile release of these guest molecules under neutral conditions makes this SPA a carrier of acidic molecules.

摘要

通过质子化的四(4-吡啶氧基甲基)甲烷与[Al(草酸盐)]的非化学计量电荷组装构建了一种氢键开放框架,其孔由吡啶基修饰,它们分别是离子氢键相互作用的氢键供体和受体。这种超分子多孔结构(SPA-2)具有1纳米大的孔,在三维空间中相互连接,具有较大的溶剂可及空隙(53%)。通过包括较大药物分子在内的各种羧酸研究表明,它对溶液中的酸性有机分子具有显著的亲和力。乙酸及其卤代同系物之间的竞争吸附证明了多孔材料对卤代酸具有良好的选择性。包括一系列客体@SPA-2晶体结构和高分辨魔角旋转核磁共振光谱在内的综合结果表明,该材料表现出的高效吸附不仅依赖于酸碱相互作用。这些客体分子在中性条件下的 facile 释放使得这种SPA成为酸性分子载体。 (注:“facile”此处可能有误,未找到准确对应中文,可根据上下文进一步确认其准确含义后调整翻译)

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