A DFT study of pyrrole-isoxazole derivatives as chemosensors for fluoride anion.

吡咯异恶唑衍生物作为氟阴离子化学传感器的 DFT 研究。

• 影响指数: 6.208
• 发表时间: 2012
• 来源期刊: Int J Mol Sci
• DOI: 10.3390/ijms130910986
• PMID: 23109833
• 文章类型: Journal Article
• 中科院分区: Q2
• 方向: 生物
• 作者列表: Jin R,Sun W,Tang S

关键词: BSSE (counterpoise) correction; atoms in molecules; chemosensor; intramolecular charge transfer; pyrrole-isoxazole derivatives

Mesh: Fluorescent Dyes / chemistry; Fluorides / analysis; Isoxazoles / chemistry; Models, Molecular; Pyrroles / chemistry; Quantum Theory; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Thiophenes / chemistry

Abstract

The interactions between chemosensors, 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-yl)isoxazole-4-carboxamide (AIC) derivatives, and different anions (F(-) Cl(-), Br(-), AcO(-), and H(2)PO(4) (-)) have been theoretically investigated using DFT approaches. It turned out that the unique selectivity of AIC derivatives for F(-) is ascribed to their ability of deprotonating the host sensors. Frontier molecular orbital (FMO) analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT). The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.

摘要

化学传感器之间的相互作用，3-氨基-5-（4,5,6,7-四氢-1H-吲哚-2-基）异恶唑-4-甲酰胺（AIC）衍生物，和不同的阴离子（F（-）Cl（-），Br(-),AcO(-),和H(2)PO(4)(-))已经使用DFT方法进行了理论研究。事实证明，AIC衍生物对F（-）的独特选择性归因于它们对宿主传感器去质子化的能力。前沿分子轨道（FMO）分析表明，传感信号的吸收和发射的垂直电子跃迁被表征为分子内电荷转移（ICT）。取代基效应的研究表明，除具有苯并[d]噻吩并[3,2-b]噻吩片段的衍生物外，所有取代的衍生物都有望在UV-vis和荧光光谱中成为氟化物化学传感器的有希望的候选物。仅用作比例荧光氟化物化学传感器。