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Solvent induced structural transformation of a cerium(III) 2,5-furandicarboxylate metal-organic framework.

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Název: Solvent induced structural transformation of a cerium(III) 2,5-furandicarboxylate metal-organic framework.
Autoři: Das, Satarupa1, Tidey, Jeremiah P.2, Jie Liu2, Pickering, Katie S.1, Coe, James C.1, Walker, Marc2, Walton, Richard I.1 r.i.walton@warwick.ac.uk
Zdroj: CrystEngComm. 11/7/2025, Vol. 27 Issue 41, p6797-6804. 8p.
Témata: *METAL-organic frameworks, *COORDINATION polymers, *CERIUM, *HYDROTHERMAL synthesis, *SPECTROMETRY, *CRYSTALLOGRAPHY
Abstrakt: The synthesis and structural characterisation of a cerium(III) MOF, UOW-11, is reported. The material is constructed using the sustainably sourced 2,5-furandicarboxylate (FDC) linker under solvothermal conditions in N, N-dimethylformamide (DMF) solvent and scalable to gram-scale production. Single-crystal analysis using 3D electron diffraction reveals a unique framework architecture, P21/n space group, with composition [Ce4(FDC)7(DMF)2.36](DMA)2 that has a structure containing four cerium(III) sites that are connected via bridging FDC ligands to give a 3D extended anionic framework counterbalanced by occluded dimethylammonium (DMA) cations, formed via partial decomposition of DMF. Upon exposure to water, UOW-11 undergoes a structural transformation, forming a second, structurally distinct Ce(III) coordination polymer, [Ce2(FDC)2(H2O)10]FDC·6H2O, UOW-2(Ce), which crystallises in the triclinic space group P1. The asymmetric unit comprises two Ce3+ ions, coordinated by two FDC2- ligands, ten water molecules, with one additional uncoordinated FDC2- ligand, and six occluded water molecules. The transformation leads to significant changes in coordination geometry and composition, including the loss of DMA and a different Ce: FDC ratio, consistent with a dissolution-recrystallisation mechanism. Monitoring the conversion using in situ infra-red spectroscopy shows the transformation is complete after ~3 hours at room temperature. [ABSTRACT FROM AUTHOR]
Databáze: Academic Search Index
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Abstrakt:The synthesis and structural characterisation of a cerium(III) MOF, UOW-11, is reported. The material is constructed using the sustainably sourced 2,5-furandicarboxylate (FDC) linker under solvothermal conditions in N, N-dimethylformamide (DMF) solvent and scalable to gram-scale production. Single-crystal analysis using 3D electron diffraction reveals a unique framework architecture, P21/n space group, with composition [Ce4(FDC)7(DMF)2.36](DMA)2 that has a structure containing four cerium(III) sites that are connected via bridging FDC ligands to give a 3D extended anionic framework counterbalanced by occluded dimethylammonium (DMA) cations, formed via partial decomposition of DMF. Upon exposure to water, UOW-11 undergoes a structural transformation, forming a second, structurally distinct Ce(III) coordination polymer, [Ce2(FDC)2(H2O)10]FDC·6H2O, UOW-2(Ce), which crystallises in the triclinic space group P1. The asymmetric unit comprises two Ce3+ ions, coordinated by two FDC2- ligands, ten water molecules, with one additional uncoordinated FDC2- ligand, and six occluded water molecules. The transformation leads to significant changes in coordination geometry and composition, including the loss of DMA and a different Ce: FDC ratio, consistent with a dissolution-recrystallisation mechanism. Monitoring the conversion using in situ infra-red spectroscopy shows the transformation is complete after ~3 hours at room temperature. [ABSTRACT FROM AUTHOR]
ISSN:14668033
DOI:10.1039/d5ce00689a