A Regulable Internal Cavity inside a Resorcinarene‐Based Hemicarcerand
Chemistry A European Journal 26 巻 26 号
5810-5817 頁
2020-05-07 発行
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| ファイル情報(添付) | |
| タイトル ( eng ) |
A Regulable Internal Cavity inside a Resorcinarene‐Based Hemicarcerand
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| 作成者 |
Harada Kentaro
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| 収録物名 |
Chemistry A European Journal
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| 巻 | 26 |
| 号 | 26 |
| 開始ページ | 5810 |
| 終了ページ | 5817 |
| 抄録 |
Covalent organic capsules, such as carcerands and hemicarcerands, are an interesting class of molecular hosts. These container molecules have confined spaces capable of hosting small molecules, although the fact that the size of the inner cavities cannot be changed substantially limits the scope of their applications. The title covalently linked container was produced by metal‐directed dimerization of a resorcinarene‐based cavitand having four 2,2′‐bipyridyl arms on the wide rim followed by olefin metathesis at the vertices of the resulting capsule with a second‐generation Grubbs catalyst. The covalently linked bipyridyl arms permit expansion of the inner cavity by demetalation. This structural change influences the molecular recognition properties; the metal‐coordinated capsule recognizes only 4,4′‐diacetoxybiphenyl, whereas the metal‐free counterpart can encapsulate not only 4,4′‐diacetoxybiphenyl, but also 2,5‐disubstituted‐1,4‐bis(4‐acetoxyphenylethynyl)benzene, which is 9.4 Å longer than the former guest. Molecular mechanics calculations predict that the capsule expands the internal cavity to encapsulate the long guest by unfolding the folded conformation of the alkyl chains, which demonstrates the flexible and regulable nature of the cavity. Guest competition experiments show that the preferred guest can be switched by metalation and demetalation. This external‐stimuli‐responsive guest exchange can be utilized for the development of functional supramolecular systems controlling the uptake, transport, and release of chemicals.
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| 著者キーワード |
hemicarcerands
host–guest systems
molecular recognition
resorcinarenes
supramolecular chemistry
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| 内容記述 |
This work was supported by JSPS KAKENHI Grant Numbers 18K05085, JP17H05375, JP19H04585, and JP17H05159. Funding from the Ogasawara Foundation for the Promotion of Science & Engineering, the Futaba Electronics Memorial Foundation, the Nippon Sheet Glass Foundation, the Iketani Science and Technology Foundation, the Takahashi Industrial and Economic Research Foundation, and the Fukuoka Naohiko Memorial Foundation is gratefully acknowledged.
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| 言語 |
英語
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| 資源タイプ | 学術雑誌論文 |
| 出版者 |
Wiley
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| 発行日 | 2020-05-07 |
| 権利情報 |
This is the peer reviewed version of the following article: K. Harada, R. Sekiya, T. Haino, Chem. Eur. J. 2020, 26, 5810, which has been published in final form at https://doi.org/10.1002/chem.201905805. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
This is not the published version. Please cite only the published version. この論文は出版社版ではありません。引用の際には出版社版をご確認、ご利用ください。
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| 出版タイプ | Author’s Original（十分な品質であるとして、著者から正式な査読に提出される版） |
| アクセス権 | オープンアクセス |
| 収録物識別子 |
[ISSN] 0947-6539
[ISSN] 1521-3765
[DOI] 10.1002/chem.201905805
[DOI] https://doi.org/10.1002/chem.201905805
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| 備考 | The full-text file will be made open to the public on 7 May 2021 in accordance with publisher's 'Terms and Conditions for Self-Archiving' |
