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
Key Laboratory of Macromolecular Science of Shaanxi Province, Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an, Shaanxi 710062, China.
Key Laboratory of Magnetic Molecules & Magnetic Information, Materials Ministry of Education, School of Chemistry & Material Science, Shanxi Normal University, Linfen, Shanxi 041004, China.
ACS Appl Mater Interfaces. 2021 May 19;13(19):22457-22465. doi: 10.1021/acsami.1c03410. Epub 2021 May 10.
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 NH, NHOH, and (Me)NNH. 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 NH. The new molecular recognition concept thus makes SNNU-153 a powerful NH sensor, which should be far-reaching to other sensing elements.
我们报道了一种基于铟-二羟基对苯二甲酸金属有机框架（MOF，SNNU-153）的新型传感机制，其中空间适配的分析物-MOF氢键（H键）形成提供选择性识别，而分析物-H键辅助的激发态分子内质子转移（ESIPT）以及由此产生的比率发射作为具有超快响应的优异信号转导器。ESIPT信号转导与受限MOF孔的协同作用使SNNU-153传感器即使在含氮氢化物类似物（如NH、NHOH和（Me）NNH）中也能选择性地检测肼。铟-2,5-二甲氧基对苯二甲酸MOF（SNNU-152）进一步反证了H键和相关ESIPT的关键作用，其中羟基质子通过甲基化被去除，对NH表现出近乎惰性。这种新的分子识别概念使SNNU-153成为一种强大的NH传感器，这对其他传感元件应该具有深远影响。
