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能够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。虽然基于氢键的阴离子检测已经很成熟，但卤素键选择性阴离子识别的潜力直到最近才被认识到。与氢键相比，强相关的卤素键表现出更强的取向偏好、对结合的更高共价贡献以及与路易斯碱性伙伴更强的相互作用，从而能够构建高选择性阴离子结合位点。Halo-1,2,3-三唑和halo-1,2,3-三唑具有高度路易斯酸性卤素原子，能够 建立强卤素键。由于这些杂环的容易和模块化合成，卤素键可以很容易地应用到各种不同的系统中。该提案中描述的研究旨在通过利用卤代1,2,3-三唑和卤代1,2,3-三唑的简便和模块化合成来开发卤素键的巨大潜力。更详细地说，将研究以下子项目（1至5）：1）通过对阴离子结合位点的特定修饰，将研究不同参数的影响，即阴离子的咬角、卤素键供体与吸电子基团之间的间隔以及系统的预组织。2）通过将钌（II）络合物与阴离子结合面结合， 将构建具有低检测限的选择性阴离子传感器。3）通过利用协同效应，将设计对不同离子对表现出高选择性和结合强度的离子对受体。 4）相对于类似的基于氢键的系统，卤素键具有更高的方向性和更高的阴离子亲和力，预计将有助于设计高效的有机催化剂。卤代 1,2,3-三唑的模块化合成允许手性部分的简单整合，这反过来又允许构建用于对映选择性反应的非常有趣的催化剂。 5）由于卤键很强但不稳定，因此有望在自修复材料中得到应用。卤键在阴离子识别中的应用是目前的热门话题，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、有机催化剂以及功能材料。