Cyclopentannulated Decacyclenes as Carbon-Based Multistage Electron Acceptors.

IF 3.5 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Silas C Eiden, Erik Misselwitz, Frank Rominger, Milan Kivala
{"title":"Cyclopentannulated Decacyclenes as Carbon-Based Multistage Electron Acceptors.","authors":"Silas C Eiden, Erik Misselwitz, Frank Rominger, Milan Kivala","doi":"10.1002/asia.202500551","DOIUrl":null,"url":null,"abstract":"<p><p>We report a series of cyclopentannulated decacyclenes that act as remarkable multistage electron acceptors. The compounds were synthesized in a modular approach via Yamamoto cyclotrimerization of brominated pyracylene precursors, allowing the introduction of electron-withdrawing, -donating, and solubilizing fluoro, methoxy, and tert-butyl moieties, respectively. The subsequent π-expansion of the polycyclic scaffold was achieved by oxidative cyclodehydrogenation. X-ray crystallographic analysis revealed the propeller-shaped geometry of the decacyclene core with a pronounced bond length alternation in the central six-membered ring and the columnar packing motif in the solid state. Depending on the substitution pattern, the compounds are capable of up to six reversible reductions within a particularly narrow potential range between -1.45 and -2.86 V under electrochemical conditions. This result is in stark contrast to only two reductions of parent decacyclene and clearly demonstrates the major impact of strategic cyclopentannulation on the redox properties of the sp<sup>2</sup>-carbon scaffold, which was further supported by density functional theory studies.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00551"},"PeriodicalIF":3.5000,"publicationDate":"2025-06-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemistry - An Asian Journal","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1002/asia.202500551","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

We report a series of cyclopentannulated decacyclenes that act as remarkable multistage electron acceptors. The compounds were synthesized in a modular approach via Yamamoto cyclotrimerization of brominated pyracylene precursors, allowing the introduction of electron-withdrawing, -donating, and solubilizing fluoro, methoxy, and tert-butyl moieties, respectively. The subsequent π-expansion of the polycyclic scaffold was achieved by oxidative cyclodehydrogenation. X-ray crystallographic analysis revealed the propeller-shaped geometry of the decacyclene core with a pronounced bond length alternation in the central six-membered ring and the columnar packing motif in the solid state. Depending on the substitution pattern, the compounds are capable of up to six reversible reductions within a particularly narrow potential range between -1.45 and -2.86 V under electrochemical conditions. This result is in stark contrast to only two reductions of parent decacyclene and clearly demonstrates the major impact of strategic cyclopentannulation on the redox properties of the sp2-carbon scaffold, which was further supported by density functional theory studies.

环戊环十环烯作为碳基多级电子受体。
我们报道了一系列环戊环十环烯作为显著的多级电子受体。这些化合物是通过溴化吡乙炔前体的山本环三聚化以模块化的方法合成的,分别允许引入吸电子、给电子和可溶解的氟、甲氧基和叔丁基基团。多环支架随后的π膨胀是通过氧化环脱氢实现的。x射线晶体学分析揭示了十环核的螺旋桨形状,在中心六元环上有明显的键长变化,在固体状态下有柱状堆积基序。根据取代模式的不同,在电化学条件下,化合物能够在-1.45到-2.86 V的特别窄的电位范围内进行多达6次可逆还原。这一结果与母体十环的两次还原形成鲜明对比,清楚地表明战略性环戊烷化对sp2-碳支架氧化还原性能的主要影响,密度泛函理论研究进一步支持了这一结果。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Chemistry - An Asian Journal
Chemistry - An Asian Journal 化学-化学综合
CiteScore
7.00
自引率
2.40%
发文量
535
审稿时长
1.3 months
期刊介绍: Chemistry—An Asian Journal is an international high-impact journal for chemistry in its broadest sense. The journal covers all aspects of chemistry from biochemistry through organic and inorganic chemistry to physical chemistry, including interdisciplinary topics. Chemistry—An Asian Journal publishes Full Papers, Communications, and Focus Reviews. A professional editorial team headed by Dr. Theresa Kueckmann and an Editorial Board (headed by Professor Susumu Kitagawa) ensure the highest quality of the peer-review process, the contents and the production of the journal. Chemistry—An Asian Journal is published on behalf of the Asian Chemical Editorial Society (ACES), an association of numerous Asian chemical societies, and supported by the Gesellschaft Deutscher Chemiker (GDCh, German Chemical Society), ChemPubSoc Europe, and the Federation of Asian Chemical Societies (FACS).
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信