Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 37, Pages 12862-12867Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201906606
Keywords
azobenzene; guest uptake; release; metal-organic frameworks; photochromism; visible light
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Funding
- FQRNT
- Deutsche Forschungsgemeinschaft [182087777 -SFB 951, BL 1269]
- Daimler Benz-Foundation [32-02/14]
- European Research Council [ERC-2012-StG_308117]
- Alexandervon Humboldt-Foundation
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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.
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