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

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-BF 4 , is constructed using an imidazolinium ligand, H 2 Sp5-BF 4 , 1,3-bis(4-carboxyphenyl)-4,5-dihydro-1 H -imidazole-3-ium tetrafluoroborate. The resulting framework, which offers large pore apertures, enables the post-synthetic modification of the C 2 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.