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是超分子化学中最重要的领域之一，它能够检测、结合和传输相关的阴离子。虽然基于氢键的阴离子检测已经很成熟，但卤素键用于选择性阴离子识别的潜力是最近才意识到的。与氢键相比，强相关的卤素键表现出更强的取向偏好，对结合的共价贡献更高，以及与Lewis-碱性伙伴更强的相互作用，这使得能够构建高选择性的阴离子结合部位。卤代-1，2，3-三唑和卤代-1，2，3-三唑具有高度Lewis-酸性卤素原子，能够建立强大的卤素键。由于这些杂环的简单和模块化的合成，卤键可以很容易地实现到各种不同的体系中。这项研究旨在利用卤代-1，2，3-三氮唑和卤代-1，2，3-三氮杂环的简便和模块化合成来挖掘卤键的巨大潜力。更详细地说，将研究以下子项目(1至5)：1)通过对阴离子结合部位的特定修饰，将研究不同参数，即与阴离子的咬合角，卤素给电子体之间的间隔，电子引出基团以及体系的预组织，将对不同的离子对具有高选择性和结合强度的影响。2)通过将Ru(II)络合物与阴离子结合侧结合，将构建具有低检测下限的选择性阴离子传感器。3)通过利用协同效应，将设计出对不同离子对具有高选择性和结合强度的离子对受体。4)与类似的氢键体系相比，卤素键具有更高的方向性和更高的阴离子亲和力，有望设计出高效的有机催化剂。卤代-1，2，3-三氮唑的模块化合成允许手性部分的简单整合，这反过来又允许构建用于不对称反应的非常有趣的催化剂。5)由于卤素键强而不稳定，因此在自修复材料中具有潜在的应用前景。卤素键在阴离子识别方面的应用是当前的一个热点，具有巨大的潜力。这项研究旨在开发新的卤键给体，以设计新的阴离子传感器、有机催化剂以及功能材料。