Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstrasse 10, 07743, Jena, Germany.
Jena Center of Soft Matter (JCSM), Friedrich Schiller University Jena, Philosophenweg 7, 07743, Jena, Germany.
Chemistry. 2020 Nov 17;26(64):14679-14687. doi: 10.1002/chem.202002738. Epub 2020 Oct 7.
An anion sensor is presented that combines a bidentate hydrogen- (HB) or halogen-bonding (XB) site with a luminescent monocationic Ir fragment for strong binding of common anions (K up to 6×10 m ) with diagnostic emission changes. A new emission-based protocol for fast and reliable detection was derived on the basis of correction for systematic but unspecific background effects. Such a simple correction routine circumvents the hitherto practical limitations of systematic emission-based analysis of anion binding with validated open-source software (BindFit). The anticipated order of K values was obeyed according to size and basicity of the anions (Cl>Br=OAc) as well as the donor atom of the receptor (XB: 6×10 m > HB: 5×10 m ), and led to submicromolar limits of detection within minutes. The results were further validated by advanced NMR techniques, and corroborated by X-ray crystallographic data and DFT analysis, which reproduced the structural and electronic features in excellent agreement. The results suggest that corrected emission-based sensing may become a complementary, reliable, and fast tool to promote the use of XB in various application fields, due to the simple and fast optical determination at high dilution.
本文提出了一种阴离子传感器，它将双齿氢键 (HB) 或卤素键 (XB) 位点与发光的一价铱片段结合在一起，用于与常见阴离子（K 高达 6×10 -5 m ）进行强结合，并伴有诊断性的发射变化。基于对系统但非特异性背景效应的校正，衍生出了一种新的基于发射的快速可靠检测协议。这种简单的校正程序规避了迄今为止基于系统发射的阴离子结合分析在经过验证的开源软件（BindFit）中的实际限制。根据阴离子的大小和碱性（Cl>Br=OAc）以及受体的供体原子（XB：6×10 -5 m > HB：5×10 -5 m ），预期的 K 值顺序得到了遵守，并在数分钟内达到了亚微摩尔的检测限。这些结果还通过先进的 NMR 技术进行了验证，并通过 X 射线晶体学数据和 DFT 分析得到了证实，这些数据非常吻合地再现了结构和电子特征。结果表明，由于在高稀释度下进行简单快速的光学测定，校正后的基于发射的传感可能成为一种互补、可靠和快速的工具，以促进 XB 在各个应用领域的应用。
