Issue 21, 2022

3D vs. turbostratic: controlling metal–organic framework dimensionality via N-heterocyclic carbene chemistry

Abstract

Using azolium-based ligands for the construction of metal–organic frameworks (MOFs) is a viable strategy to immobilize catalytically active N-heterocyclic carbenes (NHC) or NHC-derived species inside MOF pores. Thus, in the present work, a novel copper MOF referred to as Cu-Sp5-BF4, is constructed using an imidazolinium ligand, H2Sp5-BF4, 1,3-bis(4-carboxyphenyl)-4,5-dihydro-1H-imidazole-3-ium tetrafluoroborate. The resulting framework, which offers large pore apertures, enables the post-synthetic modification of the C2 carbon on the ligand backbone with methoxide units. A combination of X-ray diffraction (XRD), solid-state nuclear magnetic resonance (ssNMR) and electron microscopy (EM), are used to show that the post-synthetic methoxide modification alters the dimensionality of the material, forming a turbostratic phase, an event that further improves the accessibility of the NHC sites promoting a second modification step that is carried out via grafting iridium to the NHC. A combination of X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) methods are used to shed light on the iridium speciation, and the catalytic activity of the Ir–NHC containing MOF is demonstrated using a model reaction, stilbene hydrogenation.

Graphical abstract: 3D vs. turbostratic: controlling metal–organic framework dimensionality via N-heterocyclic carbene chemistry

Supplementary files

Article information

Article type
Edge Article
Submitted
17 feb 2022
Accepted
09 maj 2022
First published
11 maj 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2022,13, 6418-6428

3D vs. turbostratic: controlling metal–organic framework dimensionality via N-heterocyclic carbene chemistry

I. Kochetygov, A. Justin, M. Asgari, S. Yang, V. Karve, T. Schertenleib, D. Stoian, E. Oveisi, M. Mensi and W. L. Queen, Chem. Sci., 2022, 13, 6418 DOI: 10.1039/D2SC01041K

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