Journal
ADVANCED MATERIALS
Volume 30, Issue 34, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adma.201802329
Keywords
fluorescent photoinduced electron transfer; molecular switches; solid state; stimuli-responsive metal-organic framework; turn-on sensors
Categories
Funding
- National Natural Science Foundation of China [21572170, 21772149]
- Funds for Creative Research Groups of Hubei Province [2017CFA002]
- Fundamental Research Funds for the Central Universities
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The immobilization of fluorescent photoinduced electron transfer (PET) switches/sensors into solid state, which usually cannot maintain their identical properties in solution, has remained a big challenge. Herein, a water-stable anthracene and maleimide appended zirconium-based-metal-organic framework (Zr-MOF; UiO-68-An/Ma) is reported. Unlike the regular intramolecular fluorophore-spacer-receptor format, the separated immobilization of fluorescent (anthracene) and acceptor (maleimide) groups into the framework of a multivariate MOF can also favor a pseudo-intramolecular fluorescent PET process, resulting in UiO-68-An/Ma with very weak fluorescence. Interestingly, after Diels-Alder reaction or thiol-ene reaction of maleimide groups, the pseudo-intramolecular fluorescent PET process in UiO-68-An/Ma fails and the solid-state fluorescence of the crystals is recovered. In addition, UiO-68-An/Ma shows an interesting application as solid-state fluorescent turn-on sensor for biothiols, with the naked eye response at a low concentration of 50 mu mol L-1 within 5 min. This study represents a general strategy to enable the efficient tuning of fluorescent PET switches/sensors in solid state, and considering the fluorescence of the PET-based MOFs can be restored after addition of analyte/target species, this research will definitely inspire to construct stimuli-responsive fluorescent MOFs for interesting applications (e.g., logic gate) in future.
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