Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, United States.
J Am Chem Soc. 2021 Mar 17;143(10):3874-3880. doi: 10.1021/jacs.0c12329. Epub 2021 Mar 3.
We herein describe the preparation, characterization, and recognition characteristics of novel hexapodal capsule composed of two benzenes joined by six hydrogen bonding (HB) groups to encircle space. This barrel-shaped host was obtained by reversible imine condensation of hexakis-aldehyde and hexakis-amine in the presence of oxyanions or halides acting as templates. Fascinatingly, capsule includes 18 HB donating (C-H and N-H) and 12 HB accepting groups (C═O and C═N) surrounding a binding pocket (78 Å). In this regard, the complexation of fluoride, chloride, carbonate, sulfate, and hydrogen phosphate was probed by NMR spectroscopy (DMSO) and X-ray diffraction analysis to disclose the adaptive nature of undergoing an adjustment of its conformation to complement each anionic guest. Furthermore, the rate by which encapsulated chloride was substituted by sulfate or hydrogen phosphate was slow (>7 days) while the stability of [SO⊂] was greatest in the series with > 10 M in highly competitive DMSO. With facile access to , the stage is set to probe this modular, polyvalent, and novel host to further improve the extraction of tetrahedral oxyanions from waste and the environment or control their chemistry in living systems.
我们在此描述了一种新型六足胶囊的制备、表征和识别特性，该胶囊由两个苯环通过六个氢键（HB）基团连接而成，以包围空间。这种桶形主体是通过六醛 和六胺 在阴离子或卤化物模板存在下的可逆亚胺缩合得到的。有趣的是，胶囊包含 18 个供体（C-H 和 N-H）和 12 个受体（C=O 和 C=N）的氢键，围绕一个结合口袋（78 Å）。在这方面，通过 NMR 光谱（DMSO）和 X 射线衍射分析研究了氟化物、氯化物、碳酸盐、硫酸盐和氢磷酸盐的络合，以揭示 的自适应性质，其构象会进行调整以补充每个阴离子客体。此外，氯被硫酸盐或氢磷酸盐取代的速度较慢（>7 天），而在高度竞争的 DMSO 中，[SO⊂]的稳定性在系列中最高，超过 10 M。由于 易于获得，现在可以研究这种模块化、多价和新型主体，以进一步提高从废物和环境中提取四面体含氧阴离子的效率，或控制它们在生物体系中的化学性质。
