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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Porous frameworks constructed by non-covalent linking of substitution-inert metal complexes
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Porous frameworks constructed by non-covalent linking of substitution-inert metal complexes

机译：通过取代惰性金属络合物的非共价连接构建的多孔骨架

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The incorporation of active sites into metal-organic frameworks (MOFs) or porous coordination polymers (PCPs) is an attractive way to functionalise these materials. However, the methodology to organise substitution- inert metal-based secondary building units (SBUs) with active sites into MOFs or PCPs via coordination driven self-assembly is severely limited. In this study, we successfully assembled substitution-inert paddle-wheel Rh(II) dimers to afford three novel porous frameworks, Rh-2(ppeb)(4)(THF)(2) (1-THF), Rh-2(ppeb)(4)(3-pentanone)(2)(1-PN) and Rh-2(ppeb)(4)(1-adamantylamine)(2)(1-AD) (ppeb = 4-[(perfluorophenyl) ethynyl] benzoate), by using non-covalent interactions. Multipoint arene-perfluoroarene (Ar-Ar-F) interactions, which allow the unidirectional face-to-face interaction mode of aromatic rings, were used to assemble the substitution-inert paddle-wheel Rh(II) dimers. The obtained frameworks were structurally characterisation by single crystal X-ray diffraction, and it is found that all structures exhibited a one-dimensional channel with active axial sites exposed to the pores. The porous properties of the obtained frameworks were also investigated by thermogravimetric analysis, gas adsorption and powder X-ray diffraction measurements. Moreover, the ligand substitution reaction at the active axial sites was examined at the crystalline state and the flexible structural transformation with the change of channel shapes and sizes was observed.
机译：将活性部位结合到金属有机骨架（MOF）或多孔配位聚合物（PCP）中是一种吸引人的功能化方法。然而，通过协调驱动的自组装将具有活性位点的惰性惰性金属二级建筑单元（SBU）组织到MOF或PCP中的方法受到严格限制。在这项研究中，我们成功组装了取代惰性桨叶Rh（II）二聚体，从而提供了三种新型的多孔骨架Rh-2（ppeb）（4）（THF）（2）（1-THF），Rh-2（ ppeb）（4）（3-戊酮）（2）（1-PN）和Rh-2（ppeb）（4）（1-金刚烷基胺）（2）（1-AD）（ppeb = 4-[[（全氟苯基）乙炔基]苯甲酸酯），通过使用非共价相互作用。多点芳烃-全氟芳烃（Ar-Ar-F）相互作用，允许芳香环的单向面对面相互作用模式，被用于组装取代惰性桨叶式Rh（II）二聚体。所获得的骨架通过单晶X射线衍射进行结构表征，并且发现所有结构均表现出一维通道，其中活性轴向位点暴露于孔中。还通过热重分析，气体吸附和粉末X射线衍射测量研究了所得骨架的多孔性质。此外，在结晶状态下检查了活性轴向位点的配体取代反应，并观察到随着通道形状和尺寸的变化而发生的柔性结构转变。

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