Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework
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DOI:
10.1038/nchem.1003
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发表时间:
2011-04-01
期刊:
影响因子:
21.8
通讯作者:
Morris, Russell E.
Morris, Russell E.
中科院分区:
化学1区
文献类型:
--
作者:
Mohideen, M. Infas H.;Xiao, Bo;Morris, Russell E.

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金属有机框架通过有机连接剂连接金属或金属簇形成,是一类具有结构和化学性质的固体,这些性质使它们成为许多新兴气体储存,分离,催化和生物医学应用的候选者。这些材料的重要特征包括它们的高孔隙率和它们响应于化学或物理刺激的柔性。在这里,已经制备了铜基金属-有机框架,其中起始连接体(苯-1,3,5-三羧酸)在合成期间经历选择性单酯化以产生具有两种不同通道系统的固体,所述通道系统分别由亲水性和疏水性表面内衬。该材料对不同化学性质的气体或蒸汽的反应不同,一些刺激微妙的框架灵活性或显示动力学吸附效应。吸附可以通过明智地选择条件在两个通道之间切换。单酯化的连接基可以定量收率回收,证明了金属有机框架在分子合成化学中作为“保护基团”的可能用途,以实现使用标准化学技术难以实现的选择性转化。
Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.