A New Molecular Recognition Concept: Multiple Hydrogen Bonds and Their Optically Triggered Proton Transfer in Confined Metal–Organic Frameworks for Superior Sensing Element
2021
Lei, Jiao | Wang, Bingqiang | Li, Yong-Peng | Ji, Wen-Juan | Wang, Ke | Qi, Honglan | Chou, Pi-Tai | Zhang, Miao-Miao | Bian, Hongtao | Zhai, Quan-Guo
We report a new sensing mechanism based on an indium-dihydroxyterephthalic acid metal–organic framework (MOF, SNNU-153), in which the spatially fitted analyte-MOF hydrogen-bond (H-bond) formation provides selective recognition while the analyte-H-bond assisted excited-state intramolecular proton transfer (ESIPT) and the resulting ratiometric emission act as a superior signal transducer with ultrafast response. The synergy of ESIPT signal transduction and confined MOF pore enables the SNNU-153 sensor selectively sensing hydrazine even among nitrogen-containing hydride analogs such as NH₃, NH₂OH, and (Me)₂NNH₂. The key of H-bond and associated ESIPT was further counter evidenced by an indium-2,5-dimethoxyterephthalic acid MOF (SNNU-152), where the hydroxyl protons were removed by methylation, showing near inertness to N₂H₄. The new molecular recognition concept thus makes SNNU-153 a powerful N₂H₄ sensor, which should be far-reaching to other sensing elements.
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