Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, Tehran 14117-13116, Islamic Republic of Iran.
Inorg Chem. 2022 May 23;61(20):7820-7834. doi: 10.1021/acs.inorgchem.2c00308. Epub 2022 May 11.
Pore decoration of metal-organic frameworks (MOFs) with functional groups is a useful strategy to attain high selectivity toward specific analytes, especially in the presence of interfering molecules with similar structures and energy levels, through selective host-guest interactions. In this work, we applied a dihydrotetrazine-decorated MOF, TMU-34, with the formula [Zn(OBA)(HDPT)]·DMF, where HOBA is 4,4'-oxybis(benzoic acid) and HDPT is 3,6-bis(pyridin-4-yl)-1,4-dihydro-1,2,4,5-tetrazine, for the highly selective detection of phenolic NACs, especially TNP (94% quenching efficiency, detection limit 8.1 × 10 M, = 182663 mol L), in the presence of other substituted NACs especially -NH-substituted NACs. Investigations reveal that the quenching mechanism is dominated by photoinduced MOF-to-TNP electron transfer through possible hydrogen-bonding interactions between the phenolic hydroxyl group of TNP and dihydrotetrazine functions of TMU-34. Despite extensive publications on the detection of TNP in the presence of other NACs, the significance of this work will be elucidated if attention is paid to the fact that TMU-34 is among the rare and highly selective MOF-based TNP sensors in the presence of -NH-substituted NACs as the serious interferers.
金属-有机骨架（MOFs）的孔道官能团修饰是一种获得对特定分析物高选择性的有效策略，特别是在存在具有相似结构和能级的干扰分子时，通过选择性的主客体相互作用。在这项工作中，我们应用了一种二氢三嗪修饰的 MOF，TMU-34，其化学式为[Zn(OBA)(HDPT)]·DMF，其中 HOBA 是 4,4'-氧双（苯甲酸），HDPT 是 3,6-双（吡啶-4-基）-1,4-二氢-1,2,4,5-四嗪，用于高选择性检测酚类 NACs，特别是 TNP（猝灭效率为 94%，检测限为 8.1×10 M， = 182663 mol L），在存在其他取代的 NACs 尤其是-NH 取代的 NACs 的情况下。研究表明，猝灭机制主要是通过 TNP 的酚羟基和 TMU-34 的二氢三嗪官能团之间可能的氢键相互作用，通过光诱导的 MOF 到 TNP 的电子转移来实现的。尽管已经有大量关于在存在其他 NACs 的情况下检测 TNP 的出版物，但如果注意到 TMU-34 是在存在-NH 取代的 NACs 作为严重干扰物的情况下，基于 MOF 的 TNP 传感器中少数几个高度选择性的传感器之一，那么这项工作的意义将得到阐明。
