| Item type |
デフォルトアイテムタイプ_（フル）(1) |
| 公開日 |
2023-03-18 |
| タイトル |
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タイトル |
Pseudorotaxanes in the Gas Phase: Structure and Energetics of Protonated Dibenzylamine–Crown Ether Complexes |
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言語 |
en |
| 作成者 |
Kida, Motoki
Shimoyama, Daisuke
Ikeda, Toshiaki
Sekiya, Ryo
Haino, Takeharu
Ebata, Takayuki
Jouvet, Christophe
Inokuchi, Yoshiya
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| アクセス権 |
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アクセス権 |
open access |
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アクセス権URI |
http://purl.org/coar/access_right/c_abf2 |
| 権利情報 |
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権利情報 |
Copyright (c) the Owner Societies 2018 |
| 権利情報 |
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|
権利情報 |
This is the accepted manuscript of the article is available at https://doi.org/10.1039/C8CP02707B |
| 権利情報 |
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権利情報 |
This is not the published version. Please cite only the published version. この論文は出版社版でありません。引用の際には出版社版をご確認ご利用ください。 |
| 主題 |
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主題Scheme |
NDC |
|
主題 |
430 |
| 内容記述 |
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内容記述 |
We observe UV spectra of protonated dibenzylamine (dBAMH+) and its complexes with 15-crown-5 (dBAMH+–15C5), 18-crown-6 (dBAMH+–18C6), and 24-crown-8 (dBAMH+–24C8) under cold (~10 K) gas-phase conditions by UV photodissociation (UVPD) and UV-UV hole-burning (HB) spectroscopy. The UVPD spectrum of the dBAMH+–15C5 complex shows an extensive low-frequency progression, which originates from a unique conformation of the dBAMH+ part with benzene rings facing closely to each other, while UVPD and calculation results suggest open conformations of the dBAMH+ part for dBAMH+–18C6 and dBAMH+–24C8. UV-UV HB spectra of the dBAMH+–24C8 complex indicate that there exist at least two conformers; multiple conformations can contribute to high stability of dBAMH+–24C8 pseudorotaxane due to “conformational" entropic effects. The UVPD experiment indicates that the dissociation probability of dBAMH+–24C8 into dBAMH+ and 24C8 is substantially smaller than that of dBAMH+–15C5 and dBAMH+–18C6, which can be related to the barrier height in the dissociation process. The energetics of the dBAMH+–24C8 complex is investigated experimentally with NMR spectroscopy and theoretically with the global reaction route mapping (GRRM) method. An energy barrier of ~60 kJ mol–1 is present in the pseudorotaxane formation in solution, whereas there is no barrier in the gas phase. In the course of the photodissociation, excited dBAMH+–24C8 complexes can be trapped at many local minima corresponding to multiple conformations. This can result in effective dissipation of internal energy into degrees of freedom not correlated to the dissociation and decrease the dissociation probability for the dBAMH+–24C8 complex in the gas phase. The energy barrier for the pseudorotaxane formation in solution originates not simply from the slippage process but rather from solvent effects on the dBAMH+–24C8 complex. |
|
言語 |
en |
| 内容記述 |
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|
内容記述タイプ |
Other |
|
内容記述 |
This work was partly supported by the JSPS KAKENHI Grant Number JP16H04098 and the MAEE/JSPS France-Japan Collaboration Program (SAKURA). |
| 出版者 |
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出版者 |
Royal Society of Chemistry |
| 言語 |
|
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言語 |
eng |
| 資源タイプ |
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資源タイプ識別子 |
http://purl.org/coar/resource_type/c_6501 |
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資源タイプ |
journal article |
| 出版タイプ |
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出版タイプ |
AO |
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出版タイプResource |
http://purl.org/coar/version/c_b1a7d7d4d402bcce |
| 関連情報 |
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識別子タイプ |
DOI |
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関連識別子 |
10.1039/C8CP02707B |
| 関連情報 |
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識別子タイプ |
PMID |
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関連識別子 |
29955748 |
| 収録物識別子 |
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収録物識別子タイプ |
ISSN |
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収録物識別子 |
1463-9076 |
| 収録物識別子 |
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収録物識別子タイプ |
ISSN |
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収録物識別子 |
1463-9084 |
| 開始ページ |
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開始ページ |
18678 |
| 書誌情報 |
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics
巻 20,
号 27,
p. 18678-18687,
発行日 2018-07-11
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| 旧ID |
45951 |
| 備考 |
Post-print version/PDF may be used in an institutional repository after an embargo period of 12 months. |
PhysChemChemPhys_2018_20_18678.pdf (6.2 MB)
