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Hypervalent organoiodine(v) metal-organic frameworks: Syntheses, thermal studies and stoichiometric oxidants

Journal Article


Abstract


  • Iodinated analogues of the highly porous IRMOF-9 and UiO-67 frameworks were prepared and post-synthetically oxidised with dimethyldioxirane (DMDO). Analysis by X-ray photoelectron spectroscopy (XPS) confirmed promotion to the iodine(v) state and detailed differential scanning calorimetry-thermal gravimetric analysis (DSC-TGA) showed the hypervalent metal-organic frameworks (MOFs) undergo exothermic elimination at ∼200 °C with XPS showing hypervalency is maintained. The hypervalent MOFs are active heterogeneous reagents in sulfoxidation and alcohol oxidation reactions. The crystallinity and porosity of the MOFs were maintained following post-synthetic oxidation, thermolysis and after the heterogeneous reactions, as shown by powder X-ray diffraction (PXRD) and gas adsorption analyses. This work showcases the unique ability MOFs hold for studying chemical reactions and the potential for hypervalent organoiodine MOFs as reuseable oxidants.

Publication Date


  • 2020

Citation


  • Bryant, M. R., & Richardson, C. (2020). Hypervalent organoiodine(v) metal-organic frameworks: Syntheses, thermal studies and stoichiometric oxidants. Dalton Transactions, 49(16), 5167-5174. doi:10.1039/d0dt00870b

Scopus Eid


  • 2-s2.0-85084167789

Start Page


  • 5167

End Page


  • 5174

Volume


  • 49

Issue


  • 16

Abstract


  • Iodinated analogues of the highly porous IRMOF-9 and UiO-67 frameworks were prepared and post-synthetically oxidised with dimethyldioxirane (DMDO). Analysis by X-ray photoelectron spectroscopy (XPS) confirmed promotion to the iodine(v) state and detailed differential scanning calorimetry-thermal gravimetric analysis (DSC-TGA) showed the hypervalent metal-organic frameworks (MOFs) undergo exothermic elimination at ∼200 °C with XPS showing hypervalency is maintained. The hypervalent MOFs are active heterogeneous reagents in sulfoxidation and alcohol oxidation reactions. The crystallinity and porosity of the MOFs were maintained following post-synthetic oxidation, thermolysis and after the heterogeneous reactions, as shown by powder X-ray diffraction (PXRD) and gas adsorption analyses. This work showcases the unique ability MOFs hold for studying chemical reactions and the potential for hypervalent organoiodine MOFs as reuseable oxidants.

Publication Date


  • 2020

Citation


  • Bryant, M. R., & Richardson, C. (2020). Hypervalent organoiodine(v) metal-organic frameworks: Syntheses, thermal studies and stoichiometric oxidants. Dalton Transactions, 49(16), 5167-5174. doi:10.1039/d0dt00870b

Scopus Eid


  • 2-s2.0-85084167789

Start Page


  • 5167

End Page


  • 5174

Volume


  • 49

Issue


  • 16