Yuchong Yang, Yuyin Du, Tanya K. Ronson, Jonathan R. Nitschke
{"title":"配体间二面性和展宽的立体控制导致了 FeII6L6 和 FeII8L8 反三棱镜的形成","authors":"Yuchong Yang, Yuyin Du, Tanya K. Ronson, Jonathan R. Nitschke","doi":"10.31635/ccschem.024.202404281","DOIUrl":null,"url":null,"abstract":"Macrocycles have found uses in guest capture, sensing and porous materials, motivating the development of new methods for their synthesis. Here we report the construction of two types of barrel-shaped macrocyclic assemblies, with trigonal antiprismatic Fe<sup>II</sup><sub>6</sub>L<sub>6</sub> and square antiprismatic Fe<sup>II</sup><sub>8</sub>L<sub>8</sub> architectures, from Fe<sup>II</sup> and boron-containing tritopic ligands. Two factors, the steric hindrance of ligands and the preferred coordination angles at different vertices, were observed to regulate the dihedral angles between adjacent ligands, leading to the formation of the structures observed. The effects of ligand steric hindrance led to the formation of a Fe<sup>II</sup><sub>6</sub>L<sub>6</sub> trigonal antiprism, which efficiently encapsulated persistent environmental pollutant perfluorosulfonate anions. In contrast with the iminopyridine chelating groups of the Fe<sup>II</sup><sub>6</sub>L<sub>6</sub> structure, the incorporation of azopyridine moieties coordinated to the Fe<sup>II</sup> centres not only increased the vertex opening angle, resulting in the construction of a Fe<sup>II</sup><sub>8</sub>L<sub>8</sub> square antiprism, but also enabled the redox-driven reversible disassembly of this structure. The design strategies that have enabled the construction of these antiprismatic macrocycles may provide insight into the design principles governing the formation of more complex functional assemblies.\n<figure><img alt=\"\" data-lg-src=\"/cms/asset/c14fdcda-d303-4e80-bd7f-cf2d2c1744b4/keyimage.jpg\" data-src=\"/cms/asset/a25238e4-e4eb-4f88-b7fe-13e15064152a/keyimage.jpg\" src=\"/specs/ux3/releasedAssets/images/loader-7e60691fbe777356dc81ff6d223a82a6.gif\"/><ul>\n<li>Download figure</li>\n<li>Download PowerPoint</li>\n</ul>\n</figure>","PeriodicalId":9810,"journal":{"name":"CCS Chemistry","volume":null,"pages":null},"PeriodicalIF":9.4000,"publicationDate":"2024-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Steric control over inter-ligand dihedrals and splay leads to the formation of FeII6L6 and FeII8L8 antiprisms\",\"authors\":\"Yuchong Yang, Yuyin Du, Tanya K. Ronson, Jonathan R. Nitschke\",\"doi\":\"10.31635/ccschem.024.202404281\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Macrocycles have found uses in guest capture, sensing and porous materials, motivating the development of new methods for their synthesis. Here we report the construction of two types of barrel-shaped macrocyclic assemblies, with trigonal antiprismatic Fe<sup>II</sup><sub>6</sub>L<sub>6</sub> and square antiprismatic Fe<sup>II</sup><sub>8</sub>L<sub>8</sub> architectures, from Fe<sup>II</sup> and boron-containing tritopic ligands. Two factors, the steric hindrance of ligands and the preferred coordination angles at different vertices, were observed to regulate the dihedral angles between adjacent ligands, leading to the formation of the structures observed. The effects of ligand steric hindrance led to the formation of a Fe<sup>II</sup><sub>6</sub>L<sub>6</sub> trigonal antiprism, which efficiently encapsulated persistent environmental pollutant perfluorosulfonate anions. In contrast with the iminopyridine chelating groups of the Fe<sup>II</sup><sub>6</sub>L<sub>6</sub> structure, the incorporation of azopyridine moieties coordinated to the Fe<sup>II</sup> centres not only increased the vertex opening angle, resulting in the construction of a Fe<sup>II</sup><sub>8</sub>L<sub>8</sub> square antiprism, but also enabled the redox-driven reversible disassembly of this structure. The design strategies that have enabled the construction of these antiprismatic macrocycles may provide insight into the design principles governing the formation of more complex functional assemblies.\\n<figure><img alt=\\\"\\\" data-lg-src=\\\"/cms/asset/c14fdcda-d303-4e80-bd7f-cf2d2c1744b4/keyimage.jpg\\\" data-src=\\\"/cms/asset/a25238e4-e4eb-4f88-b7fe-13e15064152a/keyimage.jpg\\\" src=\\\"/specs/ux3/releasedAssets/images/loader-7e60691fbe777356dc81ff6d223a82a6.gif\\\"/><ul>\\n<li>Download figure</li>\\n<li>Download PowerPoint</li>\\n</ul>\\n</figure>\",\"PeriodicalId\":9810,\"journal\":{\"name\":\"CCS Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":9.4000,\"publicationDate\":\"2024-05-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"CCS Chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.31635/ccschem.024.202404281\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"CCS Chemistry","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.31635/ccschem.024.202404281","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Steric control over inter-ligand dihedrals and splay leads to the formation of FeII6L6 and FeII8L8 antiprisms
Macrocycles have found uses in guest capture, sensing and porous materials, motivating the development of new methods for their synthesis. Here we report the construction of two types of barrel-shaped macrocyclic assemblies, with trigonal antiprismatic FeII6L6 and square antiprismatic FeII8L8 architectures, from FeII and boron-containing tritopic ligands. Two factors, the steric hindrance of ligands and the preferred coordination angles at different vertices, were observed to regulate the dihedral angles between adjacent ligands, leading to the formation of the structures observed. The effects of ligand steric hindrance led to the formation of a FeII6L6 trigonal antiprism, which efficiently encapsulated persistent environmental pollutant perfluorosulfonate anions. In contrast with the iminopyridine chelating groups of the FeII6L6 structure, the incorporation of azopyridine moieties coordinated to the FeII centres not only increased the vertex opening angle, resulting in the construction of a FeII8L8 square antiprism, but also enabled the redox-driven reversible disassembly of this structure. The design strategies that have enabled the construction of these antiprismatic macrocycles may provide insight into the design principles governing the formation of more complex functional assemblies.
期刊介绍:
CCS Chemistry, the flagship publication of the Chinese Chemical Society, stands as a leading international chemistry journal based in China. With a commitment to global outreach in both contributions and readership, the journal operates on a fully Open Access model, eliminating subscription fees for contributing authors. Issued monthly, all articles are published online promptly upon reaching final publishable form. Additionally, authors have the option to expedite the posting process through Immediate Online Accepted Article posting, making a PDF of their accepted article available online upon journal acceptance.