Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs
Framework-Topology-Dependent Catalytic Activity of Zirconium-Based (Porphinato)zinc(II) MOFs
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DOI：
10.1021/jacs.6b09113
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发表时间：
2016-11-02
影响因子：
15
通讯作者：
Farha, Omar K.
中科院分区：
文献类型：
--
作者：
Deria, Pravas;Gomez-Gualdron, Diego A.;Farha, Omar K.
一组拓扑结构不同的锆基（卟啉）锌金属有机框架（MOFs）的酰基转移从N-乙酰基咪唑（NAI）到不同的吡啶基甲醇（PC）区域异构体（2-PC，3-PC，和4-PC）的催化活性被证明。所研究的MOD是PCN-222、MOD-525和NU-902，它们分别基于csq、ftw和scu拓扑结构。实验获得的反应动力学进行了讨论，根据分子模拟结果。示出的催化活性在整个系列的MOFs由于不同的程度，每个拓扑结构有利于反应物的预浓缩和对齐PC和NAI通过协调框架卟啉网站（取向效应）而变化。与MOF拓扑结构和PC区域异构体的实验初始反应速率的趋势是一致的预浓缩效果，这取决于每体积的MOF，以及与取向效应，这取决于每体积的MOF，结合PC和NAI的卟啉对的数量，以这样的方式，他们被引发形成所需的过渡态的卟啉位点的数量。目前的工作显示了催化连接体的适当排列如何提高MOFs中的反应速率。
Catalytic activity for acyl transfer from N-acetylimidazole (NAI) to different pyridylcarbinol (PC) regioisomers (2-PC, 3-PC, and 4-PC) is demonstrated for a set of topologically diverse, zirconium-based (porphinato)zinc metal organic frameworks (MOFs). The MOFs studied are PCN-222, MOF-525, and NU-902, which are based on the csq, ftw, and scu topologies, respectively. The experimentally obtained reaction kinetics are discussed in light of molecular modeling results. The catalytic activity is shown to vary across the series of MOFs due to the different extent to which each topology facilitates reactant preconcentration and alignment of PC and NAI via coordination to framework porphyrin sites (orientation effects). Trends of experimental initial reaction rates with MOF topology and PC regioisomer are consistent with preconcentration effects, which depend on the number of porphyrin sites per volume of MOF, as well as with orientation effects, which depend on the number of porphyrin pairs per volume of MOF that bind PC and NAI in such a way that they are primed to form the required transition state. The present work shows how the proper alignment of catalytic linkers can enhance reaction rates in MOFs.