Multivariate Modulation of Metal-Organic Frameworks

We have recently invented a new pore functionalisation protocol for metal-organic frameworks (MOFs), porous networks of inorganic clusters connected by organic linkers, called multivariate (MTV) modulation (Angew. Chem. Int. Ed. 2020, 59, 5211). Multiple functionalised modulators - monotopic analogues of the multitopic ligands that connect MOFs - are included in syntheses and become incorporated as charge-compensating defects throughout their internal porosity, this functionalising the porosity. The project will develop MTV modulation into a wide-ranging, general protocol for pore-functionalisation of MOFs by careful scrutiny of the fundamentals of modulated self-assembly, while scoping out the potential applications MTV- modulated MOFs in selective gas storage and as highly specific heterogeneous catalysts. Specifically, we will use chemically stable tri- and tetra-valent MOFs as benchmark materials for MTV modulation, pushing the limits of the technique to generate highly functionalised MOFs with a range of pore chemistries and topologies, while correlating defect-structure-property relationships through advanced spectroscopies. Optimal materials will be carried forward for applications, with assistance from a global network of expert collaborators.