Jain Akshita, Sivasakthi Pandiyan, Samanta Pralok K, Chakravarty Manab
Department of Chemistry, Birla Institute of Technology and Sciences-Pilani-Hyderabad Campus, Jawahar Nagar Hyderabad 500078, India.
J Org Chem. 2024 Apr 5;89(7):4384-4394. doi: 10.1021/acs.joc.3c02490. Epub 2024 Mar 15.
This work introduces metal/column-free facile quantitative access to conformationally twisted catechol-linked organophosphonate () as a blue-emitting solid that could reversibly detect only 1,3-diaminopropane (DAP) and 1,2-ethylenediamine (EDA) vapors, belonging to industrially and pharmaceutically abundant crucial diamines. In , two adjacent hydroxy groups in a benzene ring facilitate selective diamine-dihydroxy (amine-phenol type) interactions in the solid phase, leading to a quenched emission with selectively smaller aliphatic PAs, that is, DAP and EDA. The disparity was noticed with an isomeric resorcinol-linked emitter (), detecting various polyamine vapors with superior sensitivity. A one-carbon-away placed hydroxy group in can only generate a monoamine-hydroxy complex, not diamine-dihydroxy. The more acidic nature of resorcinol would prefer ionizing the amines and, consequently, creating amine/hydroxy interactions. More systematic investigations reveal an exciting role of amine-hydroxy realization for the catechol analog in the solid phase with a syn-anti conformation for . Unlike , 's available crystal void space creates considerable room in which to come closer and facilitates amine-phenol interactions. The role of phosphonates in the selective detection of PAs is also examined. Observed outcomes are substantiated by FT-IR, single-crystal X-ray diffraction, SEM, XPS, and mass spectroscopic studies. The proposed amine-hydroxy interactions are further supported by DFT-optimized molecular structures.
这项工作介绍了一种无需金属/柱的简便定量方法，可获得构象扭曲的儿茶酚连接的有机膦酸酯（），作为一种蓝色发光固体，它只能可逆地检测1,3 - 二氨基丙烷（DAP）和1,2 - 乙二胺（EDA）蒸气，这两种物质属于工业和制药领域中大量存在的关键二胺。在中，苯环上的两个相邻羟基促进了固相中选择性的二胺 - 二羟基（胺 - 酚类型）相互作用，导致发射淬灭，对于选择性较小的脂肪族多胺，即DAP和EDA。通过检测各种多胺蒸气具有更高灵敏度的间苯二酚连接的异构体发射体（）注意到了这种差异。中的羟基相隔一个碳原子只能生成单胺 - 羟基络合物，而不是二胺 - 二羟基络合物。间苯二酚的酸性更强，更倾向于使胺离子化，从而产生胺/羟基相互作用。更系统的研究揭示了儿茶酚类似物在固相中胺 - 羟基实现的一个令人兴奋的作用，其具有的顺 - 反构象。与不同，的可用晶体空隙空间创造了相当大的空间，使它们能够靠得更近并促进胺 - 酚相互作用。还研究了膦酸酯在多胺选择性检测中的作用。通过傅里叶变换红外光谱（FT - IR）、单晶X射线衍射、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）和质谱研究证实了观察到的结果。密度泛函理论（DFT）优化的分子结构进一步支持了所提出的胺 - 羟基相互作用。
