Supramolecular Chemistry of Boron Clusters with Cyclodextrins: From Synthesis to Applications

硼簇与环糊精的超分子化学：从合成到应用

• 批准号: 436182634
• 负责人: Professor Dr. Detlef Gabel
• 金额: --
• 依托单位: Department of Life Sciences and Chemistry
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/436182634?language=en
• 关键词: Supramolecular; Chemistry; Boron; Clusters; Cyclodextrins

The host-guest chemistry of boron cluster compounds has remained unexplored until 2015, when our team not only published the first study on their host-guest complexation behavior, but also reported record affinities with cyclodextrins (CDs), which render this field of research not only original but also conceptually interesting and practically promising. Anionic icosahedral boron clusters of the dodecaborate type ((B12X12)2− with X = H, CI, Br, I) were found to form inclusion complexes with large CDs (e.g., β-,γ-, and ε-CD) in aqueous solution with exceedingly strong binding affinities (Ka =10^3 to 10^6 M^(−1)). We have interpreted the high affinities of the dodecaborate anions based on their high polarizability and the superchaotropic nature, revealing the chaotropic effect as a general driving force for the intrinsic binding of water-structure breaking anions (chaotropic anions) to hydrophobic cavities. Such high binding affinities offer new opportunities for future applications. Through this project, we would like to strengthen our contribution to this emerging research field by exploring new boron cluster derivatives with the formulae (B10X10)^2–, (B12X12)^2–, (B21H18)^–, and (B12X11R)^2–. Through changing the substituent X (H, F, Cl, Br, and I), not only the size of the cluster, but also its polarizability, can be systematically varied. Moreover, based on the chemical formula, the charge and the molecular geometries can also be varied. The proposed study will cover the parent and different functionalized CDs in order to mimic different types of intermolecular interactions, which are involved in the stability of the formed host-guest complexes, as well as other potential host molecules (e.g., cucurbiturils and calixarenes of different sizes). Moreover, we propose novel synthetic approaches for the monofunctionalization of boron clusters (halogenated and non-halogenated), which will be essential to further modify the clusters and open the perspective of future applications. Applications which serve to demonstrate the power of the dodecaborate binding motif, and which will be explored within the context of this proposal, include non-covalent labeling, surface modifications, constructing stimuli-responsive systems, chiral discrimination and resolution, and sensing. In order to tackle this task, a group working on synthetic chemistry (DG) and a group working on supramolecular chemistry (WN) have joined their complementary expertise.

硼簇合物的主客体化学直到2015年才被探索，当时我们的团队不仅发表了关于其主客体络合行为的第一项研究，而且还报告了与环糊精（CD）的创纪录亲和力，这使得这一研究领域不仅具有原创性，而且在概念上也很有趣，实际上很有前途。十二硼酸盐型的阴离子二十面体硼簇（（B12 X12）2-，X = H，Cl，Br，I）被发现与大CD形成包合物（例如，β-、γ-和ε-CD）在水溶液中具有极强的结合亲和力（Ka =10^3至10^6 M^（−1））。我们已经解释了高亲和力的dodecaborate阴离子的基础上，他们的高极化率和superchaotropic性质，揭示了作为一个一般的驱动力的水结构破坏阴离子（离液阴离子）的内在结合的疏水空腔的离液效应。这种高结合亲和力为未来的应用提供了新的机会。通过这个项目，我们希望通过探索具有式（B10 X10）^2-、（B12 X12）^2-、（B21 H18）^-和（B12 X11 R）^2-的新的硼簇衍生物来加强我们对这一新兴研究领域的贡献。通过改变取代基X（H、F、Cl、Br和I），不仅可以系统地改变团簇的大小，而且可以系统地改变其极化率。此外，基于化学式，电荷和分子几何形状也可以变化。所提出的研究将涵盖母体和不同的官能化CD，以模拟不同类型的分子间相互作用，其涉及所形成的主体-客体复合物以及其他潜在的主体分子（例如，不同大小的葫芦脲和杯芳烃）。此外，我们提出了新的合成方法的单官能化的硼簇（卤化和非卤化），这将是必不可少的，以进一步修改集群和打开未来的应用前景。用于证明十二硼酸结合基序的能力并且将在本提议的背景下进行探索的应用包括非共价标记、表面修饰、构建刺激响应系统、手性鉴别和分辨率以及传感。为了解决这一任务，一个从事合成化学（DG）的小组和一个从事超分子化学（WN）的小组已经加入了他们互补的专业知识。