Department of Chemistry and Fermentation Sciences, Appalachian State University, Boone, NC, 28608, USA.
Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, CA, 92093, USA.
J Fluoresc. 2022 May;32(3):961-967. doi: 10.1007/s10895-022-02904-7. Epub 2022 Feb 26.
Nerve gas mimic binding with Rhodamine B ethylenediamine (1) was studied in organic media. Binding of the nerve gas mimic, diethyl chlorophosphate (DCP), with the probe generated a non-fluorescent intermediate and a fluorescent product. Fluorescent and non-fluorescent products generated were identified using mass spectrometry and X-ray crystallography. Time-dependent density functional theory calculations were also used to investigate the electronic structure of the fluorescent probe in the ground and lowest lying π → π* singlet excited state. Though good agreement between theory and experiment can be obtained for the intense peak in the experimental spectrum using non-hybrid functionals, care must be taken when modelling these complexes due to the appearance of an n → π* transition that is too low in energy and appears to fall in the shoulders of the π → π* transitions.
在有机介质中研究了拟神经毒气与罗丹明 B 乙二胺（1）的结合。拟神经毒气二氯膦酸乙酯（DCP）与探针结合生成非荧光中间体和荧光产物。使用质谱和 X 射线晶体学鉴定了生成的荧光和非荧光产物。还使用时变密度泛函理论计算研究了荧光探针在基态和最低的π→π单重激发态中的电子结构。尽管使用非杂化泛函可以很好地解释实验光谱中强峰的理论和实验之间的良好一致性，但在建模这些配合物时必须小心，因为出现的 n→π跃迁能量太低，似乎落在π→π*跃迁的肩部。
