A New Molecular Recognition Concept: Multiple Hydrogen Bonds and Their Optically Triggered Proton Transfer in Confined Metal-Organic Frameworks for Superior Sensing Element.

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.