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Updated: Feb 8, 2026

Author Spotlight: Functionalizing Metal-Organic Frameworks: Advancements, Challenges, and the Power of Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Post-Synthetic Ligand Exchange in Zirconium-Based Metal-Organic Frameworks: Beware of The Defects!
Marco Taddei1, Russell J Wakeham1, Athanasios Koutsianos1
1Energy Safety Research Institute, Swansea University, Fabian Way, Swansea, SA1 8EN, UK.
Abstract:
Post-synthetic ligand exchange in the prototypical zirconium-based metal-organic framework (MOF) UiO-66 was investigated by in situ solution 1 H NMR spectroscopy. Samples of UiO-66 having different degrees of defectivity were exchanged using solutions of several terephthalic acid analogues in a range of conditions. Linker exchange only occurred in defect-free UiO-66, whereas monocarboxylates grafted at defect sites were found to be preferentially exchanged with respect to terephthalic acid over the whole range of conditions investigated. A 1:1 exchange ratio between the terephthalic acid analogue and modulator was observed, providing evidence that the defects had missing-cluster nature. Ex situ characterisation of the MOF powders after exchange corroborated these findings and showed that the physical-chemical properties of the MOF depend on whether the functionalisation occurs at defective sites or on the framework.
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