A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation

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• 作者：Xiu-Liang Lv ; Kecheng Wang ; Bin Wang ; Jie Su ; Xiaodong Zou ; Yabo Xie ; Jian-Rong LiHong-Cai Zhou
• 刊名：Journal of the American Chemical Society
• 出版年：2017
• 出版时间：January 11, 2017
• 年：2017
• 卷：139
• 期：1
• 页码：211-217
• 全文大小：461K
• ISSN：1520-5126

文摘

A base-resistant porphyrin metal–organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni<sub>8sub>(OH)<sub>4sub>(H<sub>2sub>O)<sub>2sub>Pz<sub>12sub>] (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<sup>–sup>, CO<sub>3sub><sup>2–sup>, and PO<sub>4sub><sup>3–sup> ions. Interestingly, the Mn<sup>3+sup>-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.