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

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 flexibilit...

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Veröffentlicht in:Dalton transactions : an international journal of inorganic chemistry Jg. 45; H. 10; S. 4230 - 4241
Hauptverfasser: Schwedler, Inke, Henke, Sebastian, Wharmby, Michael T, Bajpe, Sneha R, Cheetham, Anthony K, Fischer, Roland A
Format: Journal Article
Sprache:Englisch
Veröffentlicht: England 01.01.2016
ISSN:1477-9234
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Zusammenfassung: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(fu(1)-bdc)2x(fu(2)-bdc)(2-2x)dabco (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.
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ISSN:1477-9234
DOI:10.1039/c5dt03825a