Copper-Linked Rotaxanes for the Building of Photoresponsive Metal Organic Frameworks with Controlled Cargo Delivery

• DOI: 10.1021/jacs.0c04477
• Publication Date: 2020-07-10T06:19:17Z
• Authors: Adrian Saura-Sanm...; Alberto Martinez-...; Delia Bautista; Mara R. B. Marzari; Marcos A. P. Martins; Mateo Alajarin; Jose Berna
• Keywords: CDU::5 - Ciencias puras y naturales::54 - Química::547 - Química orgánica; Rotaxanes; Metals; Metal organic frameworks; Irradiation; 02 engineering and technology; 0210 nano-technology; Materials

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.