Tuning the Photoinduced Electron Transfer in a Zr‐MOF: Toward Solid‐State Fluorescent Molecular Switch and Turn‐On Sensor |
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Authors: | Bo Gui Yi Meng Yang Xie Jianwu Tian Ge Yu Weixuan Zeng Guanxin Zhang Shaolong Gong Chuluo Yang Deqing Zhang Cheng Wang |
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Affiliation: | 1. Key Laboratory of Biomedical Polymers of Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, China;2. Beijing National Laboratory for Molecular Sciences, Organic Solids Laboratory, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China |
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Abstract: | 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 µmol 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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Keywords: | fluorescent photoinduced electron transfer molecular switches solid state stimuli‐responsive metal‐organic framework turn‐on sensors |
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