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      Rotational Dynamics of Linkers in Metal–Organic Frameworks

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          Abstract

          Among the numerous fascinating properties of metal–organic frameworks (MOFs), their rotational dynamics is perhaps one of the most intriguing, with clear consequences for adsorption and separation of molecules, as well as for optical and mechanical properties. A closer look at the rotational mobility in MOF linkers reveals that it is not only a considerably widespread phenomenon, but also a fairly diverse one. Still, the impact of these dynamics is often understated. In this review, we address the various mechanisms of linker rotation reported in the growing collection of literature, followed by a highlight of the methods currently used in their study, and we conclude with the impacts that such dynamics have on existing and future applications.

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          Flexible metal-organic frameworks.

          Advances in flexible and functional metal-organic frameworks (MOFs), also called soft porous crystals, are reviewed by covering the literature of the five years period 2009-2013 with reference to the early pertinent work since the late 1990s. Flexible MOFs combine the crystalline order of the underlying coordination network with cooperative structural transformability. These materials can respond to physical and chemical stimuli of various kinds in a tunable fashion by molecular design, which does not exist for other known solid-state materials. Among the fascinating properties are so-called breathing and swelling phenomena as a function of host-guest interactions. Phase transitions are triggered by guest adsorption/desorption, photochemical, thermal, and mechanical stimuli. Other important flexible properties of MOFs, such as linker rotation and sub-net sliding, which are not necessarily accompanied by crystallographic phase transitions, are briefly mentioned as well. Emphasis is given on reviewing the recent progress in application of in situ characterization techniques and the results of theoretical approaches to characterize and understand the breathing mechanisms and phase transitions. The flexible MOF systems, which are discussed, are categorized by the type of metal-nodes involved and how their coordination chemistry with the linker molecules controls the framework dynamics. Aspects of tailoring the flexible and responsive properties by the mixed component solid-solution concept are included, and as well examples of possible applications of flexible metal-organic frameworks for separation, catalysis, sensing, and biomedicine.
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            Zeolitic imidazolate framework membrane with molecular sieving properties by microwave-assisted solvothermal synthesis.

            A zeolitic imidazolate framework (ZIF-8) as member of the metal-organic framework family has been crystallized as a thin porous layer on an asymmetric ceramic support. Hydrogen can be selected from other gases by molecular sieving.
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              Opening the gate: framework flexibility in ZIF-8 explored by experiments and simulations.

              ZIF-8 is a zeolitic imidazole-based metal-organic framework with large cavities interconnected by narrow windows. Because the small size of the windows, it allows in principle for molecular sieving of gases such as H(2) and CH(4). However, the unexpected adsorption of large molecules on ZIF-8 suggests the existence of structural flexibility. ZIF-8 flexibility is explored in this work combining different experimental techniques with molecular simulation. We show that the ZIF-8 structure is modified by gas adsorption uptake in the same way as it is at a very high pressure (i.e., 14,700 bar) due to a swing effect in the imidazolate linkers, giving access to the porosity. Tuning the flexibility, and so the opening of the small windows, has a further impact on the design of advanced molecular sieving membrane materials for gas separation, adjusting the access of fluids to the porous network. © 2011 American Chemical Society
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                Author and article information

                Journal
                Nanomaterials (Basel)
                Nanomaterials (Basel)
                nanomaterials
                Nanomaterials
                MDPI
                2079-4991
                02 March 2019
                March 2019
                : 9
                : 3
                : 330
                Affiliations
                [1 ]Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, 2629 Delft, The Netherlands
                [2 ]DPI, P.O. Box 902, 5600 AX Eindhoven, The Netherlands
                [3 ]Chimie ParisTech, PSL University, CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France; fx.coudert@ 123456chimieparistech.psl.eu
                Author notes
                [* ]Correspondence: a.m.gonzaleznelson@ 123456tudelft.nl (A.G.-N.); m.a.vanderveen@ 123456tudelft.nl (M.A.v.d.V.); Tel.: +31-15-2786-458 (M.A.v.d.V.)
                Author information
                https://orcid.org/0000-0003-2104-3870
                https://orcid.org/0000-0001-5318-3910
                https://orcid.org/0000-0002-0316-4639
                Article
                nanomaterials-09-00330
                10.3390/nano9030330
                6474009
                30832298
                34ac225e-bb0b-4e89-90f6-43f006ff3726
                © 2019 by the authors.

                Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license ( http://creativecommons.org/licenses/by/4.0/).

                History
                : 24 January 2019
                : 18 February 2019
                Categories
                Review

                metal–organic frameworks,linker dynamics,rotation,gate-opening effect,2h nmr,computational chemistry

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