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

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          Abstract

          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.

          Abstract

          Understanding the structural dynamics of flexible metal-organic frameworks at a thin-film level is key if they are to be implemented in devices. Here, Fischer and colleagues anchor flexible MOF crystallites onto substrates and identify a structural responsiveness that is distinct to that of the bulk.

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          Most cited references 48

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          Functional Porous Coordination Polymers

          The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.
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            Design and synthesis of an exceptionally stable and highly porous metal-organic framework

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              A rationale for the large breathing of the porous aluminum terephthalate (MIL-53) upon hydration.

              Aluminum 1,4-benzenedicarboxylate Al(OH)[O(2)C-C(6)H(4)-CO(2)]. [HO(2)C-C(6)H(4)-CO(2)H](0.70) or MIL-53 as (Al) has been hydrothermally synthesized by heating a mixture of aluminum nitrate, 1,4-benzenedicarboxylic acid, and water, for three days at 220 degrees C. Its 3 D framework is built up of infinite trans chains of corner-sharing AlO(4)(OH)(2) octahedra. The chains are interconnected by the 1,4-benzenedicarboxylate groups, creating 1 D rhombic-shaped tunnels. Disordered 1,4-benzenedicarboxylic acid molecules are trapped inside these tunnels. Their evacuation upon heating, between 275 and 420 degrees C, leads to a nanoporous open-framework (MIL-53 ht (Al) or Al(OH)[O(2)C-C(6)H(4)-CO(2)]) with empty pores of diameter 8.5 A. This solid exhibits a Langmuir surface area of 1590(1) m(2)g(-1) together with a remarkable thermal stability, since it starts to decompose only at 500 degrees C. At room temperature, the solid reversibly absorbs water in its tunnels, causing a very large breathing effect and shrinkage of the pores. Analysis of the hydration process by solid-state NMR ((1)H, (13)C, (27)Al) has clearly indicated that the trapped water molecules interact with the carboxylate groups through hydrogen bonds, but do not affect the hydroxyl species bridging the aluminum atoms. The hydrogen bonds between water and the oxygen atoms of the framework are responsible for the contraction of the rhombic channels. The structures of the three forms have been determined by means of powder X-ray diffraction analysis. Crystal data for MIL-53 as (Al) are as follows: orthorhombic system, Pnma (no. 62), a = 17.129(2), b = 6.628(1), c = 12.182(1) A; for MIL-53 ht (Al), orthorhombic system, Imma (no. 74), a = 6.608(1), b = 16.675(3), c = 12.813(2) A; for MIL-53 lt (Al), monoclinic system, Cc (no. 9), a = 19.513(2), b = 7.612(1), c = 6.576(1) A, beta = 104.24(1) degrees.
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                Author and article information

                Contributors
                roland.fischer@tum.de
                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group UK (London )
                2041-1723
                21 January 2019
                21 January 2019
                2019
                : 10
                Affiliations
                [1 ]ISNI 0000000123222966, GRID grid.6936.a, Chair of Inorganic and Metal-Organic Chemistry, Department of Chemistry, , Technical University of Munich, ; Lichtenbergstraße 4, 85787 Garching, Germany
                [2 ]GRID grid.472685.a, Synchrotron Light Research Institute (Public Organization), ; 111 University Avenue, Muang District, Nakhon Ratchasima 30000 Thailand
                [3 ]ISNI 0000 0004 0490 981X, GRID grid.5570.7, Chair of Inorganic Chemistry II, Faculty of Chemistry and Biochemistry, , Ruhr-University Bochum, ; Universitätstraße 150, 44801 Bochum, Germany
                [4 ]ISNI 0000 0001 0668 7884, GRID grid.5596.f, Centre for Surface Chemistry and Catalysis, , Katholieke Universiteit Leuven, ; Celestijnenlaan 200f, Box 2461, 3001 Leuven, Belgium
                [5 ]ISNI 0000 0001 0416 9637, GRID grid.5675.1, Fakultät Physik/DELTA, , Technische Universität Dortmund, ; Maria-Goeppert-Mayer Straße. 2, 44227 Dortmund, Germany
                [6 ]ISNI 0000 0001 2097 4943, GRID grid.213917.f, School of Chemistry and Biochemistry, , Georgia Institute of Technology, ; Atlanta, GA 30332 USA
                Article
                8285
                10.1038/s41467-018-08285-5
                6341086
                30664645
                © The Author(s) 2019

                Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

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