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Guest-mediated phase transitions in a flexible pillared-layered metal–organic framework under high-pressure

The guest-dependent flexibility of the pillared-layered metal–organic framework (MOF), Zn(2)bdc(2)dabco·X(guest), where guest = EtOH, DMF or benzene, has been examined by high-pressure single crystal X-ray diffraction. A pressure-induced structural phase transition is found for the EtOH- and DMF-inc...

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Detalles Bibliográficos
Autores principales: Turner, Gemma F., McKellar, Scott C., Allan, David R., Cheetham, Anthony K., Henke, Sebastian, Moggach, Stephen A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8549792/
https://www.ncbi.nlm.nih.gov/pubmed/34760164
http://dx.doi.org/10.1039/d1sc03108b
Descripción
Sumario:The guest-dependent flexibility of the pillared-layered metal–organic framework (MOF), Zn(2)bdc(2)dabco·X(guest), where guest = EtOH, DMF or benzene, has been examined by high-pressure single crystal X-ray diffraction. A pressure-induced structural phase transition is found for the EtOH- and DMF-included frameworks during compression in a hydrostatic medium of the guest species, which is dependent upon the nature and quantity of the guest in the channels. The EtOH-included material undergoes a phase transition from P4/mmm to C2/m at 0.69 GPa, which is accompanied by a change in the pore shape from square to rhombus via super-filling of the pores. The DMF-included material undergoes a guest-mediated phase transition from I4/mcm to P4/mmm at 0.33 GPa via disordering of the DMF guest. In contrast, the benzene-included framework features a structure with rhombus-shaped channels at ambient pressure and shows direct compression under hydrostatic pressure. These results demonstrate the large influence of guest molecules on the high-pressure phase behavior of flexible MOFs. Guest-mediated framework flexibility is useful for engineering MOFs with bespoke pore shapes and compressibility.