Browsing by Subject "Metal organic frameworks"

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    Copper-Linked Rotaxanes for the Building of Photoresponsive Metal Organic Frameworks with Controlled Cargo Delivery
    (American Chemical Society, 2020-07-09) Saura Sanmartín, Adrián; Martinez-Cuezva, Alberto; Bautista, Delia; Marzari, Mara R. B.; Martins, Marcos A. P.; Alajarín, Mateo; Berná, José; Berná, José; Química Orgánica
    We have prepared a photoresponsive metal–organic framework by using an amide-based [2]rotaxane as linker and copper(II) ions as metal nodes. The interlocked linker was obtained by the hydrogen bond-directed approach employing a fumaramide thread as template of the macrocyclic component, this latter incorporating two carboxyl groups. Single crystal X-ray diffraction analysis of the metal–organic framework, prepared under solvothermal conditions, showed the formation of stacked 2D rhombohedral grids forming channels decorated with the interlocked alkenyl threads. A series of metal–organic frameworks differing in the E/Z olefin ratio were prepared either by the previous isomerization of the linker or by postirradiation of the reticulated materials. By dynamic solid state 2H NMR measurements, using deuterium-labeled materials, we proved that the geometry of the olefinic axis of the interlocked struts determined the obtention of materials with different independent local dynamics as a result of the strength of the intercomponent noncovalent interactions. Moreover, the usefulness of these novel copper-rotaxane materials as molecular dosing containers has also been assayed by the diffusion and photorelease of p-benzoquinone, evaluated in different solvents and temperatures.
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    Mechanically interlocked molecules in metal–organic frameworks
    (Royal Society of Chemistry, 2022-05-25) Saura-Sanmartin, Adrian; Pastor Vivero, Aurelia; Martinez-Cuezva, Alberto; Cutillas-Font, Guillermo; Alajarín, Mateo; Berná Cánovas, José; Química Orgánica
    Mechanically interlocked molecules (MIMs) have great potential in the development of molecular machinery due to their intercomponent dynamics. The incorporation of these molecules in a condensed phase makes it possible to take advantage of the control of the motion of the components at the macroscopic level. Metal–organic frameworks (MOFs) are postulated as ideal supports for intertwined molecules. This review covers the chemistry of the mechanical bond incorporated into metal–organic frameworks from the seminal studies to the latest published advances. We first describe some fundamental concepts of MIMs and MOFs. Next, we summarize the advances in the incorporation of rotaxanes and catenanes inside MOF matrices. Finally, we conclude by showing the study of the rotaxane dynamics in MOFs and the operation of some stimuli-responsive MIMs within MOFs. In addition to emphasising some selected examples, we offer a critical opinion on the state of the art of this research field, remarking the key points on which the future of these systems should be focused.