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    Control of structural flexibility of layered-pillared metal-organic frameworks anchored at surfaces

    Year: 2019

    Journal: Nat. Commun., Volume 10, JAN 21

    Authors: Wannapaiboon, Suttipong; Schneemann, Andreas; Hante, Inke; Tu, Min; Epp, Konstantin; Semrau, Anna Lisa; Sternemann, Christian; Paulus, Michael; Baxter, Samuel J.; Kieslich, Gregor; Fischer, Roland A.

    Flexible metal-organic frameworks (MOFs) are structurally flexible, porous, crystalline solids that show a structural transition in response to a stimulus. If MOF-based solid-state and microelectronic devices are to be capable of leveraging such structural flexibility, then the integration of MOF thin films into a device configuration is crucial. Here we report the targeted and precise anchoring of Cu-based alkylether-functionalised layered-pillared MOF crystallites onto substrates via stepwise liquid-phase epitaxy. The structural transformation during methanol sorption is monitored by in-situ grazing incidence X-ray diffraction. Interestingly, spatially-controlled anchoring of the flexible MOFs on the surface induces a distinct structural responsiveness which is different from the bulk powder and can be systematically controlled by varying the crystallite characteristics, for instance dimensions and orientation. This fundamental understanding of thin-film flexibility is of paramount importance for the rational design of MOF-based devices utilising the structural flexibility in specific applications such as selective sensors.
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