Defined halogen bond receptors for polymeric architectures: Adaption of behavior in solution as tool to create new functional materials

聚合物结构的定义卤素键受体：适应溶液中的行为作为创建新功能材料的工具

• 批准号: 280016777
• 负责人: Professor Dr. Ulrich S. Schubert
• 金额: --
• 依托单位: Institut für Organische Chemie und Makromolekulare Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/280016777?language=en
• 关键词: Defined; halogen; bond; receptors; polymeric

The design of selective anion binding sites, which enable a detection, binding and transport of relevant anions, is one of the most important fields in supramolecular chemistry. While anion detection based on hydrogen bonds is well established, the potential of halogen bonds for selective anion recognition was only realized very recently. In contrast to the hydrogen bond, the strongly related halogen bond exhibits a stronger orientational preference, a higher covalent contribution to the binding as well as a stronger interaction with a Lewis-basic partner, which enables the construction of highly selective anion binding sites.Halo-1,2,3-triazoles and halo-1,2,3-triazoliums feature highly Lewis-acidic halogen atoms that are capable of establishing strong halogen bonds. Owing to the facile and modular synthesis of these heterocycles, the halogen bond can be readily implemented into a variety of different systems. The research described in this proposal aims at exploiting the great potential of halogen bonds by making use of the facile and modular synthesis of halo-1,2,3-triazoles and halo-1,2,3-triazoliums. In more detail, the following sub-projects (1 to 5) will be investigated: 1) By the help of specific modifications on the anion binding site, the effect of different parameters, namely the bite angle to the anion, the spacer between the halogen-bond donors the electron-withdrawing group as well as the preorganization of the system, will be studied.2) By combining a ruthenium(II) complex with an anion binding side, selective anion sensors with low detection limits will be constructed.3) By exploiting cooperative effects, ion-pair receptors that exhibit high selectivity and binding strength for different ion pairs will be designed. 4) The higher directionality as well as the higher anion affinities of halogen bonds relative to analogous hydrogen-bond-based systems is expected to enable the design of highly efficient organo-catalysts. The modular synthesis of halo-1,2,3-triazoles allows a simple integration of chiral moieties, which, in turn, allows the construction of highly interesting catalysts for enantioselective reactions. 5) Since halogen bonds are strong but labile, the potential application in self-healing materials is planned.The application of the halogen bond for anion recognition is currently a hot topic and offers an immense potential. This research described herein aims at developing new halogen bond donors in order to design new anion sensors, organo-catalysts as well as functional materials.

选择性阴离子结合位点的设计，可以实现相关阴离子的检测，结合和运输，是超分子化学中最重要的领域之一。尽管基于氢键基于氢键的阴离子检测已很好地确定，但仅最近才实现了选择性阴离子识别的卤素键的潜力。与氢键相反，密切相关的卤素键表现出更强的定向偏好，更高的共价贡献对结合以及与刘易斯基底伴侣的相互作用以及更强的相互作用，可以构建高度选择性的阴离子结合位点。Halo-1,2,3-3- triazoles和Halo-1,2,2-2-2-2-2-2-3-二维二氮化酶的功能强度建立牢固的卤素键。由于这些杂环的简便和模块化合成，可以轻松地将卤素键实现为多种不同的系统。该提案中描述的研究旨在利用卤素键的巨大潜力，利用晕Halo-1,2,3-三唑和Halo-1,2,3-三唑群的简便和模块化合成。更详细地，将研究以下子项目（1至5）：1）借助于阴离子结合位点上的特定修改，不同参数的影响，即与阴离子的咬合角，卤素键入供体的间隔者的间隔者之间的间隔者之间的间隔者在电子启动组之间以及系统的bignion nirient and nir.2）将构建具有低检测极限的选择性阴离子传感器。3）通过利用合作效应，将设计具有高选择性的离子对受体和不同离子对的结合强度。 4）相对于基于类似的氢键的系统，卤素键的较高方向性以及较高的阴离子亲和力有望实现高效的有机催化剂的设计。晕晕1,2,3-三唑的模块化合成允许手性部分的简单整合，这反过来允许构建非常有趣的催化剂以进行对映选择性反应。 5）由于卤素键很强，但不稳定，因此计划在自我修复材料中的潜在应用。卤素键在阴离子识别中的应用是当前的热门话题，并具有巨大的潜力。 本文描述的这项研究旨在开发新的卤素键供体，以设计新的阴离子传感器，有机催化剂和功能材料。