ABSTRACT Benzocrown ethers incorporating phenyl and nitrophenyl urea and thiourea moieties were synthesised. Both the nitrophenyl urea and thiourea derivative gave a fluoride-specific colorimetric response but only the urea derivative bound the organophosphonate nerve agent simulants dimethyl methylphosphonate (DMMP) and diisopropyl methylphosphonate (DIMP). This suggested an application as sensors for the nerve agents sarin, soman and cyclosarin which release fluoride upon hydrolysis. Although no fluoride-induced response was observed in the UV-visible spectrum, binding to soman was determined by 1H NMR. DFT computational simulations suggested that the two crowns adopt different conformations in which both can bind fluoride but only the urea derivative can bind DMMP, DIMP and soman. The results show that, for this system, simulant- and soman-binding behaviours are in good agreement. Graphical Abstract

中文翻译：

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冠（硫）脲复合物中与阴离子、化学战剂和模拟物的氢键相互作用

摘要合成了包含苯基和硝基苯基脲和硫脲部分的苯并冠醚。硝基苯基脲和硫脲衍生物均产生氟化物特异​​性比色反应，但只有脲衍生物与有机膦酸神经毒剂模拟物甲基膦酸二甲酯 (DMMP) 和甲基膦酸二异丙酯 (DIMP) 结合。这表明其可用作神经毒剂沙林、梭曼和环沙林的传感器，它们在水解时会释放氟化物。虽然在紫外-可见光谱中没有观察到氟化物诱导的反应，但通过 1 H NMR 确定了与梭曼的结合。DFT 计算模拟表明，两个冠采用不同的构象，其中都可以结合氟化物，但只有尿素衍生物可以结合 DMMP、DIMP 和 soman。结果表明，对于该系统，simulant-和soman-binding 行为是非常一致的。图形概要