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Trifluoromethyl group containing C3 symmetric coumarin-triazole based fluorometric tripodal receptors for selective fluoride ion recognition: A theoretical and experimental approach
Journal of Fluorine Chemistry ( IF 1.9 ) Pub Date : 2018-06-18 , DOI: 10.1016/j.jfluchem.2018.06.005
Anshu Jain , Yachana Jain , Ragini Gupta , Madhu Agarwal

A series of unique C3 symmetric tripodal receptors, A–E containing hexasubstituted aryl core decorated with an alternate array of coumarin-triazole moieties and methyl groups have been synthesized, characterized and investigated for fluoride ion recognition (tetrabutylammonium salt) in dimethyl sulphoxide (DMSO). A pleothora of spectroscopic studies (fluorescence, UV–vis, 1H NMR and 19F NMR titrations) exhibits that out of the five derivatives synthesized, only one, receptor D displays selective five fold fluorescence enhancement with fluoride ion (TBA salt) at 480 nm wavelength over other anions at a detection limit of 2.6 × 10−5 M. Selectivity may be ascribed to strategical incorporation of trifluoromethyl group in the scaffold of receptor D which modulated the binding ability of the receptor, so that it is able to bind fluoride ion exclusively and selectively in preorganized C3 symmetric cavity formed by its three arms. 1H NMR and 19F NMR titration validate CH⋯F- hydrogen binding interactions via downfield shift of CH peak at δ 8.47 ppm by δ 0.5 ppm and upfield shift of peak at δ −102 ppm due to free fluoride ion 2.98 ppm, respectively. Further, HRMS study of receptor-fluoride complex gave evidence for the formation of 1:1 stoichiometric ratio between receptor and fluoride ion. Computations using density functional theory have shown that in 1:1 complex of receptor and fluoride ion, the three arms are directed in same orientation forming a cavity where it fits fluoride ion by CH⋯F- hydrogen binding interactions.



中文翻译:

基于三氟甲基C 3对称香豆素-三唑的荧光三脚架受体用于选择性氟离子识别:理论和实验方法

合成了一系列独特的C 3对称三脚架受体,含有六取代的芳基核心并饰有香豆素-三唑部分和甲基的交替排列的A–E,表征并研究了其在二甲基亚砜(DMSO)中的氟离子识别(四丁基铵盐)的特性。 )。大量的光谱研究(荧光,UV-vis,1 H NMR和19 F NMR滴定)显示,在合成的五种衍生物中,只有一种受体D在480处显示出氟化物离子(TBA盐)选择性的五倍荧光增强作用在2.6×10 -5的检出限下超过其他阴离子的nm波长M.选择性可能归因于三氟甲基在受体D支架中的战略性结合,从而调节了受体的结合能力,因此它能够在其三臂形成的预组织的C 3对称腔中排他并选择性地结合氟离子。。1 H NMR和19 F NMR滴定验证Ç ħ⋯F-氢结合相互作用通过的C低磁场移位处于H峰δ 8.47 ppm的δ 0.5ppm的和在峰的高磁场位移δ由于游离氟离子为2.98 ppm,因此分别为-102 ppm。此外,受体-氟化物络合物的HRMS研究为受体与氟离子之间化学计量比为1:1的形成提供了证据。使用密度泛函理论的计算表明,在受体与氟离子的1:1络合物中,三个臂以相同的方向定向,形成一个空腔,通过C H⋯F-氢键相互作用使其适合氟离子。

更新日期:2018-06-18
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