Catalytic chemoselective functionalization of methane in a metal−organic framework

Identifying promising metal–organic frameworks for heterogeneous catalysis via high‐throughput periodic density functional theory

“…As a proof‐of‐concept, we use this HT workflow to screen MOFs with coordinatively unsaturated metal sites, also known as open metal sites (OMSs), for oxidative C—H bond activation. Due to the large economic demand for a catalyst that can directly convert methane to methanol and motivated by prior work involving MOFs for methane conversion, we specifically consider the partial oxidation of methane as the reaction of interest. In the process, we demonstrate the feasibility of a HT‐DFT screening workflow for MOF catalysis and make several recommendations for future work involving HT‐DFT screening studies of MOFs.…”

Toward Engineering Chiral Rodlike Metal–Organic Frameworks with Rare Topologies

“…This exponential growth has been underpinned, to some extent, on the thorough quest of rational design strategies to build/functionalize -in a controlled manner -MOFs with predetermined dimensionalities and topologies, [11][12][13] and the possibility to use X-ray crystallography to follow and rationalize the proposed synthetic methodology. [14][15][16] These have enable MOFs to find applications in such diverse fields as gas adsorption and separation, [17][18][19][20] catalysis, 21,22 molecular recognition processes, 23,24 drug delivery, 25,26 magnetism 27,28 and water remediation. [29][30][31] However, this has not been the case for MOFs constructed from one-dimensional (1D) rod-like Secondary Building Units (SBUs).…”

Efficient and Selective Methane Borylation Through Pore Size Tuning of Hybrid Porous Organic‐Polymer‐Based Iridium Catalysts

“…Research conducted by Baik, Mindiola, and co‐workers indicated that the use of a phosphine ligand (dmpe) to form iridium complexes could significantly enhance homogeneous catalytic efficiencies . More recently, a microporous metal organic framework containing an iridium complex as the active site was designed as a heterogeneous catalyst by Farha and co‐workers, and it demonstrated high chemoselectivity for methane monoborylation due to the shape‐selective concept . Despite these innovations, the catalytic C−H borylation of methane still warrants further investigation, especially the utilization of heterogeneous catalysts and the study of the relationship between their porosities and catalytic efficiencies.…”

“…Our previous works show that functional porous polycarbazoles, via oxidative coupling polymerization, can either be heterogeneous catalysts or the matrix in heterogeneous catalysis. Inspired by diimine‐supported iridium complexes as homogeneous catalysts for methane borylation, in our strategy shown in Scheme , a building block DCP including carbazole groups and phenanthroline ligands was coordinated with a [Ir(COD)(μ‐Cl)] 2 complex under argon atmosphere to form Ir I complex, followed further oxidation by exposure to air to produce an intermediate DCP‐Ir III , in which the OH groups were derived from air oxidation (Scheme S1 in the Supporting Information) . Polymerization of the DCP‐Ir, via a carbazole‐based oxidative coupling reaction using a FeCl 3 catalyst at room temperature, formed a homopolymer (CAL‐1‐Ir) with a built‐in iridium complex.…”