A Base-Resistant Metalloporphyrin Metal-Organic Framework for C-H Bond Halogenation
A Base-Resistant Metalloporphyrin Metal-Organic Framework for C-H Bond Halogenation
复制标题
一种用于C-H键卤化的耐碱金属卟啉金属有机骨架
DOI：
10.1021/jacs.6b09463
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发表时间：
2017-01-11
影响因子：
15
通讯作者：
Zhou, Hong-Cai
中科院分区：
文献类型：
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作者：
Lv, Xiu-Liang;Wang, Kecheng;Zhou, Hong-Cai
在网状合成策略的指导下，以12连接的[Ni-8(OH)(4)(H2O)(2)Pz(12)] （Pz =吡唑酸酯）簇和新设计的吡唑酸酯基卟啉配体5,10,15,20-四配体（4-（吡唑酸酯-4-基）苯基）卟啉为原料，构建了耐碱卟啉金属有机骨架（MOF） PCN-602。PCN-602除了在氢氧化物溶液中的稳定性外，在F-、CO32-和PO43-离子水溶液中也表现出优异的稳定性。有趣的是，作为一种可回收的MOF催化剂，Mn3+- php -yrinic PCN-602在碱性体系中对C-H键卤化反应表现出很高的催化活性，显著优于均相MOF催化剂。据我们所知，这是卟啉MOF首次在具有配位阴离子的碱性溶液中用作高效催化剂。
A base-resistant porphyrin metal organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni-8(OH)(4)(H2O)(2)Pz(12)] (Pz = pyrazolate) cluster and a newly designed pyrazolate-based porphyrin ligand, 5,10,15,20-tetralds (4- (pyrazolate-4-yl)phenyl)porphyrin under the guidance of the reticular synthesis strategy. Besides its robustness in hydroxide solution, PCN-602 also shows excellent stability in aqueous solutions of F-, CO32-, and PO43- ions. Interestingly, the Mn3+-porph-yrinic PCN-602, as a recyclable MOF catalyst, presents high catalytic activity for the C-H bond halogenation reaction in a basic system, significantly outperforming its homogeneous counterpart. For the first time, a porphyrinic MOF was thus used as an efficient catalyst in a basic solution with coordinating anions, to the best of our knowledge.