Issue 12, 2016

A stable and porous iridium(iii)-porphyrin metal–organic framework: synthesis, structure and catalysis

Abstract

Self-assembly of a new metalloporphyrin tetracarboxylic ligand Ir(TCPP)Cl (TCPP = tetrakis(4-carboxyphenyl)porphyrin) with ZrCl4 in the presence of benzoic acid leads to the formation of a three-dimensional (3D) iridium(III)-porphyrin metal–organic framework (Ir-PMOF) with the formula of [(Zr63-O)8(OH)2(H2O)10)2(Ir(TCPP)Cl)3]·solvents (Ir-PMOF-1(Zr)), which possesses square-shaped channels of 1.9 × 1.9 nm2 (atom-to-atom distances across opposite Ir metal atoms) in three orthogonal directions as disclosed by the single-crystal X-ray diffraction analysis. Ir-PMOF-1(Zr) represents the first MOF bearing a self-supporting iridium-porphyrin catalytic framework, featuring high porosity and stability. The catalytic tests disclose that the activated Ir-PMOF-1(Zr) can promote O–H insertion with a turnover frequency (TOF) up to 4260 h−1. Ir-PMOF-1(Zr) can be recycled and reused for 10 runs without significant loss of catalytic activity, and the total turnover number (TON) for O–H insertion after 10 successive runs reaches 875.

Graphical abstract: A stable and porous iridium(iii)-porphyrin metal–organic framework: synthesis, structure and catalysis

Supplementary files

Article information

Article type
Paper
Submitted
08 Dec. 2015
Accepted
11 Febr. 2016
First published
12 Febr. 2016

CrystEngComm, 2016,18, 2203-2209

A stable and porous iridium(III)-porphyrin metal–organic framework: synthesis, structure and catalysis

H. Cui, Y. Wang, Y. Wang, Y. Fan, L. Zhang and C. Su, CrystEngComm, 2016, 18, 2203 DOI: 10.1039/C6CE00358C

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