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default_学術雑誌論文 / Journal Article(1) |
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タイトル |
Substituted effects on bonding characteristics of cyclopentane‐1,3‐diyl diradicals monitored by time‐resolved infrared spectroscopy |
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言語 |
en |
| 言語 |
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言語 |
eng |
| キーワード |
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言語 |
en |
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主題Scheme |
Other |
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主題 |
bonding properties |
| キーワード |
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言語 |
en |
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主題Scheme |
Other |
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主題 |
cyclopentane‐1,3‐diyl diradicals |
| キーワード |
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言語 |
en |
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主題Scheme |
Other |
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主題 |
time‐resolved IR spectroscopy |
| 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 |
| アクセス権 |
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アクセス権 |
metadata only access |
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アクセス権URI |
http://purl.org/coar/access_right/c_14cb |
| 著者 |
近藤 正人
Kuboki Shunsuke
Kume Hidetaka
Oda Eriku
安倍 学
石橋 孝章
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| 抄録 |
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内容記述タイプ |
Abstract |
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内容記述 |
Cyclopentane‐1,3‐diyl diradicals (DRs) provide excellent opportunities to study the properties of diradicals because their lifetimes can be significantly lengthened to up to milliseconds with the introduction of proper substituents. This study investigated the bonding characteristics of singlet and triplet DRs having C=O and p‐cyanophenyl groups (S‐DR3 and T‐DR3) by monitoring the photo‐induced formation of the diradicals from their precursor azo compounds using time‐resolved IR (TR‐IR) spectroscopy. Upon the formation of S‐DR3, a C=O stretching wavenumber was upshifted by 22 cm−1, whereas a C≡N stretching one was downshifted by 12 cm−1. The observed shifts indicate that the unpaired electrons increase and decrease the C=O and C≡N bond orders, respectively. The effects of the unpaired electrons in S‐DR3 were similar to those observed in our previous TR‐IR studies on a singlet cyclopentane‐1,3‐diyl diradical having C=O but no C≡N groups (S‐DR2) and on that having C≡N but no C=O groups (S‐DR1), respectively. Contrastingly, upon the formation of T‐DR3, the C=O wavenumber was downshifted by 16 cm−1, indicating that the unpaired electrons decrease the C=O bond order. More notably, no detectable shifts were observed in the C≡N stretching wavenumber. These observations are not clearly explained by a model suggested in the previous studies on S‐DRs. Here, we discuss and propose a more elaborated resonance hybrid of DRs that can explain the directions and relative magnitudes of the observed wavenumber shifts irrespective of spin multiplicities. We expect that the findings and suggestions presented here will stimulate research in both organic and theoretical chemistry.
Bonding properties of singlet and triplet cyclopentane‐1,3‐diyl diradicals (DRs) having C=O and C≡N groups (S‐DR3 and T‐DR3) were investigated by time‐resolved IR spectroscopy. The C=O and C≡N wavenumber shifts observed upon the formation of S‐DR3 and T‐DR3 were both quite different from each other, indicating that the effects of the unpaired electrons to the C=O and C≡N bond properties in DR3 strongly depend on its spin multiplicity. The observed difference was discussed based on a resonance hybrid of DRs. |
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言語 |
en |
| bibliographic_information |
en : Journal of Physical Organic Chemistry
巻 37,
号 2,
発行日 2024
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| 出版者 |
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出版者 |
Wiley |
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言語 |
en |
| item_10001_source_id_9 |
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収録物識別子タイプ |
EISSN |
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収録物識別子 |
1099-1395 |
| item_10001_relation_14 |
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識別子タイプ |
DOI |
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関連識別子 |
10.1002/poc.4575 |
| 権利 |
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権利情報 |
© John Wiley & Sons Ltd. |
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言語 |
en |
https://doi.org/10.1002/poc.4575
