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Mixed-linker solid solutions of functionalized pillared-layer MOFs – adjusting structural flexibility, gas sorption, and thermal responsiveness

DOI: 10.1039/C5DT03825A DOI Help
PMID: 26526973 PMID Help

Authors: Inke Schwedler (Ruhr University Bochum) , Sebastian Henke (University of Cambridge) , Michael Wharmby (Diamond Light Source) , Sneha Bajpe (University of Cambridge) , Anthony K. Cheetham (University of Cambridge) , Roland A. Fischer (Ruhr University Bochum)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Dalton Transactions

State: Published (Approved)
Published: October 2015
Diamond Proposal Number(s): 9225

Open Access Open Access

Abstract: Flexible metal–organic frameworks (MOFs) can undergo fascinating structural transitions triggered by external stimuli, such as adsorption/desorption of specific guest molecules or temperature changes. In this detailed study we investigate the potentials and limitations of tuning framework flexibility systematically by exploiting the powerful concept of mixed-linker solid solutions. We chose the prototypical family of functionalized pillared-layer MOFs of the general type Zn2(fu1-bdc)2x(fu2-bdc)2−2xdabco (with x = 1.00, 0.75, 0.50, 0.25 and 0.00; fu-bdc = 2,5-dialkoxy-1,4-benzenedicarboxylate with varying alkoxy chain length, dabco = 1,4-diazabicyclo[2.2.2]octane) and examined their guest responsive, as well as intrinsic temperature dependent structural flexibility by X-ray diffraction, gas physisorption and calorimetric measurements. The ratio of the different fu-bdc linkers can be adjusted freely, offering opportunity for a targeted design of these functional materials by modulating their key features, such as magnitude of framework contraction upon guest removal, breathing behaviour upon CO2 adsorption/desorption, thermoresponsive phase behaviour, and their general thermal expansivity, by the careful choice of fu-bdc linkers and their combination.

Subject Areas: Chemistry


Instruments: I11-High Resolution Powder Diffraction

Added On: 08/11/2015 19:19

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