Beijing Key Laboratory for Green Catalysis and Separation and Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology , Beijing 100124, PR China.
Department of Chemistry, Texas A&M University , College Station, Texas 77842-3012, United States.
J Am Chem Soc. 2017 Jan 11;139(1):211-217. doi: 10.1021/jacs.6b09463. Epub 2016 Dec 23.
A base-resistant porphyrin metal-organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni(OH)(HO)Pz] (Pz = pyrazolate) cluster and a newly designed pyrazolate-based porphyrin ligand, 5,10,15,20-tetrakis(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, CO, and PO ions. Interestingly, the Mn-porphyrinic 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.
已构建出一种耐碱的卟啉金属-有机骨架（MOF），即 PCN-602，它由 12 连接的 [Ni(OH)(HO)Pz]（Pz = 吡唑）簇和新设计的基于吡唑的卟啉配体 5,10,15,20-四(4-(吡唑-4-基)苯基)卟啉，在网状合成策略的指导下。除了在氢氧化物溶液中的坚固性外，PCN-602 在 F、CO 和 PO 离子的水溶液中也表现出优异的稳定性。有趣的是，作为可回收 MOF 催化剂的 Mn-卟啉 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，明显优于其均相对应物。据我们所知，这是首次在含有配位阴离子的碱性溶液中使用卟啉 MOF 作为高效催化剂。
