Solvent‐Free Thermal Defect Engineering in Molecular Frameworks With Volatile Linkers
Year: 2025
Type: article
Abstract: The controlled generation of defects in crystalline materials is widely used to tune properties for improved performance. This strategy is increasingly applied to metal–organic frameworks (MOFs), where coordination vacancies are commonly introduced in solution by exploiting the reversibility of metal–ligand bonds. Here, an innovative solvent‐free approach for defect engineering in MOFs is reported based on the selective thermal removal of neutral volatile linkers. This method enables the generation of metal vacancies across a broad compositional space (0–100%) without requiring counterions, redox adjustments, or oxide formation to balance charge. Using a standard thermogravimetric analyser, the extent of linker sublimation is controlled with high precision and reproducibility. Key design criteria for applying this strategy are identified and validated with the Hofmann‐type MOF [Fe(pz){Pt(CN) 4 }] (pz = pyrazine). Structural and spectroscopic analyses reveal a local transformation from FeN 6 to FeN 4 environments, leading to redox‐stable unsaturated Fe II sites that remain chemically accessible. These open centres suppress spin crossover, coordinate to polar molecules such as water and acetonitrile, and catalyse Lewis acid‐type reactions. The ability to generate functional open metal sites without solvents or charge‐balancing agents offers an alternative route for designing defect‐functional materials via thermal linker removal.
Source: Advanced Materials
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $6,070
Funders: Ministerio de Ciencia, Innovación y Universidades, Elettra-Sincrotrone Trieste, European Commission, Generalitat Valenciana, Universitat de València, Ministerio de Ciencia e Innovación, European Regional Development Fund, Agencia Estatal de Investigación, Spanish National Plan for Scientific and Technical Research and Innovation, H2020 European Research Council
Awards: G1047231290, G1175115578, G1197883907, G1204740081, G120905174, G1272927172, G1289698517, G1387571101, G1422035950, G1463962793, G1521942520, G1530851820, G1553300614, G1561925909, G1730479140, G1749278720, G1836899976, G1855990336, G1927686253, G1977833963, G2262748287, G2309174360, G2320466433, G2376013711, G252646220, G2585816812, G2601397997, G2660406951, G2892785307, G3001761408, G300979063, G3033740217, G3220251042, G3291038552, G3480869486, G348919436, G3518538256, G3556610094, G3561276666, G3565621276, G357246561, G363809202, G3681454997, G3751777145, G3857581125, G3955602048, G4042783231, G405629836, G410571670, G421152860, G4243289221, G425668148, G430777504, G438930244, G451917667, G4530813438, G464105488, G4642345579, G4784454572, G5080475149, G5103795585, G5195188938, G531036588, G5421974903, G5539308778, G5795497077, G5845768719, G5849267730, G5967599077, G6092186830, G6310597218, G6458236290, G6803082892, G700394663, G7084143925, G745419941, G8347645112, G845913798, G8546142835, G8822771542, G99296377
OpenAlex ID: W4414248276