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

Abstract

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

Authors:
 [1];  [2];  [1];  [3];  [4];  [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Beijing Univ. of Technology (China). College of Environmental and Energy Engineering, Beijing Key Lab. for Green Catalysis and Separation, and Dept. of Chemistry and Chemical Engineering
  2. Texas A&M Univ., College Station, TX (United States). Dept. of Chemistry
  3. Stockholm Univ. (Sweden). Berzelii Centre EXSELENT on Porous Materials and Inorganic and Structural Chemistry, Dept. of Materials and Environmental Chemistry
  4. Stockholm Univ. (Sweden). Berzelii Centre EXSELENT on Porous Materials and Inorganic and Structural Chemistry, Dept. of Materials and Environmental Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1347012
DOE Contract Number:
SC00010150
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 139; Journal Issue: 1
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Lv, Xiu-Liang, Wang, Kecheng, Wang, Bin, Su, Jie, Zou, Xiaodong, Xie, Yabo, Li, Jian-Rong, and Zhou, Hong-Cai. A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation. United States: N. p., 2017. Web. doi:10.1021/jacs.6b09463.
Lv, Xiu-Liang, Wang, Kecheng, Wang, Bin, Su, Jie, Zou, Xiaodong, Xie, Yabo, Li, Jian-Rong, & Zhou, Hong-Cai. A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation. United States. doi:10.1021/jacs.6b09463.
Lv, Xiu-Liang, Wang, Kecheng, Wang, Bin, Su, Jie, Zou, Xiaodong, Xie, Yabo, Li, Jian-Rong, and Zhou, Hong-Cai. Wed . "A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation". United States. doi:10.1021/jacs.6b09463.
@article{osti_1347012,
title = {A Base-Resistant Metalloporphyrin Metal–Organic Framework for C–H Bond Halogenation},
author = {Lv, Xiu-Liang and Wang, Kecheng and Wang, Bin and Su, Jie and Zou, Xiaodong and Xie, Yabo and Li, Jian-Rong and Zhou, Hong-Cai},
abstractNote = {A base-resistant porphyrin metal–organic framework (MOF), namely PCN-602 has been constructed with 12-connected [Ni8(OH)4(H2O)2Pz12] (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–, CO32–, and PO43– ions. Interestingly, the Mn3+-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.},
doi = {10.1021/jacs.6b09463},
journal = {Journal of the American Chemical Society},
number = 1,
volume = 139,
place = {United States},
year = {Wed Jan 11 00:00:00 EST 2017},
month = {Wed Jan 11 00:00:00 EST 2017}
}