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

DOI: 10.1039/D1SC03108B DOI Help

Authors: Gemma F. Turner (University of Western Australia) , Scott C. Mckellar (University of Edinburgh) , David Robert Allan (Diamond Light Source) , Anthony K. Cheetham (University of California, Santa Barbara) , Sebastian Henke (Technische Universität Dortmund) , Stephen A. Moggach (University of Western Australia)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science

State: Published (Approved)
Published: September 2021

Open Access Open Access

Abstract: The guest-dependent flexibility of the pillared-layered metal-organic framework (MOF), Zn2bdc2dabco·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-medaited phase transition from I4/mcm to P4/mmm at 0.32 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 as well as negative linear compressibility parallel to the long diagonal of the channels under hydrostatic pressure. These results demonstrate the large influence of guest molecules on the phase behavior of flexible MOFs. Thus, guest-mediated framework flexibility is useful to engineering MOFs with bespoke pore shapes and compressibility.

Subject Areas: Chemistry, Materials

Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 29/09/2021 10:21


Discipline Tags:

Chemistry Materials Science Metal-Organic Frameworks Metallurgy Organometallic Chemistry

Technical Tags:

Diffraction High Pressure Single Crystal Diffraction