Highly Selective and Sensitive Turn-Off-On Fluorescent Probes for Sensing Al 3+ Ions Designed by Regulating the Excited-State Intramolecular Proton Transfer Process in Metal-Organic Frameworks.

The concept of high-performance excited-state intramolecular proton transfer (ESIPT)-based fluorescent metal-organic framework (MOF) probes for Al ³⁺ is proposed in this work. By regulating the hydroxyl groups on the organic linker step by step, new fluorescent magnesium-organic framework (Mg-MOF) probes for Al ³⁺ ions were established based on the ESIPT fluorescence mechanism. It is observed for the first time that the number of intramolecular hydrogen bonds between adjacent hydroxyl and carboxyl groups can effectively adjust the ESIPT process and lead to tunable fluorescence sensing performance. Together with the well-designed porous and anionic framework, the Mg-TPP-DHBDC probe decorating with a pair of intramolecular hydrogen bonds exhibits extra-high quantitative fluorescence response to Al ³⁺ through an unusual turn-off (0-1.2 μM) and turn-on (4.2-15 μM) luminescence sensing mechanism. Notably, the 28 nM limit of detection value represents the lowest record among all reported MOF-based Al ³⁺ fluorescent sensors up to now. Benefited from the unique turn-off-on ESIPT fluorescence detection process, the Mg-TPP-DHBDC MOF sensor exhibits single Al ³⁺ detection compared with other 16 common metal ions including Ga ³⁺ , In ³⁺ , Fe ³⁺ , Cr ³⁺ , Ca ²⁺ , and Mg ²⁺ . Impressively, such an Al ³⁺ selective sensing process can even be fulfilled by the reusable MOF test paper detected by naked eyes. Overall, the quantitative Al ³⁺ detection, together with the extraordinary sensitivity, selectivity, fast response, and good reusability, strongly supports our concept of ESIPT-based fluorescent MOF Al ³⁺ probes and makes Mg-TPP-DHBDC one of the most powerful Al ³⁺ fluorescent sensors.