Publication: Copper-Linked Rotaxanes for the Building of Photoresponsive Metal Organic Frameworks with Controlled Cargo Delivery
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Date
2020-07-09
Authors
Saura Sanmartín, Adrián ; Martinez-Cuezva, Alberto ; Bautista, Delia ; Marzari, Mara R. B. ; Martins, Marcos A. P. ; Alajarín, Mateo ; Berná, José
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Berná, José
Publisher
American Chemical Society
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DOI
https://doi.org/10.1021/jacs.0c04477
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info:eu-repo/semantics/article
Description
©2020. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This document is the Accepted version of a Published Work that appeared in final form in Journal of the American Chemical Society. To access the final edited and published work see https://doi.org/10.1021/jacs.0c04477
Abstract
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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Citation
Journal of the American Chemical Society, 142, 31, 2020, 13442-13449
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