Modulating Guest Uptake in Core–Shell MOFs with Visible Light

A two‐component core–shell UiO‐68 type metal–organic framework (MOF) with a nonfunctionalized interior for efficient guest uptake and storage and a thin light‐responsive outer shell was prepared by initial solvothermal MOF synthesis followed by solvent‐assisted linker exchange. The bulky shell linke...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2019-09, Vol.58 (37), p.12862-12867
Main Authors: Mutruc, Dragos, Goulet‐Hanssens, Alexis, Fairman, Sam, Wahl, Sebastian, Zimathies, Annett, Knie, Christopher, Hecht, Stefan
Format: Article
Language:English
Subjects:
azobenzene
Crystals
Diffusion barriers
Fluorination
guest uptake/release
Irradiation
Light irradiation
Metal-organic frameworks
photochromism
Radiation
Shells
Single crystals
visible light
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Summary:A two‐component core–shell UiO‐68 type metal–organic framework (MOF) with a nonfunctionalized interior for efficient guest uptake and storage and a thin light‐responsive outer shell was prepared by initial solvothermal MOF synthesis followed by solvent‐assisted linker exchange. The bulky shell linker features two tetra‐ortho‐fluorinated azobenzene moieties to exploit their advantageous photoisomerization properties. The obtained perfect octahedral MOF single crystals can be switched repeatedly and with an unprecedented efficiency between E‐ and Z‐rich states using visible light only. Due to the high photoswitch density per pore of the shell layer, its steric demand and thus molecular uptake (and release) can be conveniently modulated upon green and blue light irradiation. Therefore, the “smart” shell acts as a light‐controlled kinetic barrier or “gate” for the diffusion of cargo molecules in and out of the MOF crystals. Light opens and closes the gates to an inner porous storage compartment in azobenzene‐containing core–shell MOFs. Their photoswitchable outer shell controls cargo molecule uptake and release.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201906606