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Metal–organic frameworks (MOFs) provide a crystalline scaffold that can act as a host for guest species. In this chapter, recent advances using MOFs as hosts for catalytic metal complexes are discussed. Particular emphasis is given to MOFs that can tether metal complexes to the framework such that the guests adopt a crystalline arrangement. The structures of the tethered complexes and their reactivity can be studied by a variety of techniques, including X-ray diffraction. We discuss examples of reactive species which are kinetically trapped and structurally characterised within an MOF and reports where tethering catalysts to MOFs can lead to enhanced catalytic performance. Finally, we describe guidelines for developing such approaches and for the use of MOFs to study catalytic processes.

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