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New Insights into Metal Ion-Crown Ether Complexes Revealed by SEIRA Spectroscopy

https://hiroshima.repo.nii.ac.jp/records/2007791
https://hiroshima.repo.nii.ac.jp/records/2007791
e8987e21-5c71-489f-92f1-2cafdd19ee84
名前 / ファイル ライセンス アクション
NewJChem_2015_39_8673.pdf NewJChem_2015_39_8673.pdf (1.4 MB)
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
タイトル New Insights into Metal Ion-Crown Ether Complexes Revealed by SEIRA Spectroscopy
言語 en
作成者 Inokuchi, Yoshiya

× Inokuchi, Yoshiya

en Inokuchi, Yoshiya

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Ebata, Takayuki

× Ebata, Takayuki

en Ebata, Takayuki

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Ikeda, Toshiaki

× Ikeda, Toshiaki

en Ikeda, Toshiaki

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Haino, Takeharu

× Haino, Takeharu

en Haino, Takeharu

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Kimura, Tetsunari

× Kimura, Tetsunari

en Kimura, Tetsunari

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Guo, Hao

× Guo, Hao

en Guo, Hao

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Furutani, Yuji

× Furutani, Yuji

en Furutani, Yuji

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アクセス権
アクセス権 open access
アクセス権URI http://purl.org/coar/access_right/c_abf2
権利情報
権利情報 Copyright (c) The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2015
権利情報
権利情報 This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.
主題
主題Scheme NDC
主題 430
内容記述
内容記述 We demonstrate a powerful spectroscopic technique, surface-enhanced infrared absorption (SEIRA) spectroscopy, not only for detecting host-guest complexes in solution but for examining the relationship between the guest selectivity, complex structure, and solvent effect. We synthesize thiol derivatives of 15-crown-5 and 18-crown-6 [2-(6-mercaptohexyloxy)methyl-15-crown-5 (15C5-C1OC6-SH) and 2-(6-mercaptohexyloxy)methyl-18-crown-6 (18C6-C1OC6-SH)] and adsorb them on gold surfaces through S–Au bonds. The IR difference spectra of the M+•15C5-C1OC6 (M = Li, Na, K, Rb, and Cs) complexes on gold are observed using aqueous solutions of MCl by SEIRA spectroscopy. The spectra show noticeable change in the C–O stretching vibration around 1100 cm–1. The spectral patterns of M+•15C5-C1OC6 are similar for Li+ and Na+, and for K+, Rb+, and Cs+; the interaction between the metal ions and 15C5-C1OC6 changes drastically between Na+ and K+ in the series of alkali metal ions. On the other hand, the equilibrium constant of the complex formation determined by the IR intensity shows clear preference for Na+ ion. We also observe the IR difference spectra of M+•18C6-C1OC6 in methanol and compare them with those in water. The spectral patterns in methanol are almost the same as those in water, but the equilibrium constant in methanol does not show preference for any ion, different from the K+ preference in water. From these findings we attribute the origin of the ion selectivity of 15C5 and 18C6 in solution to the interaction between the metal ions and the crown ethers in the complexes or the solvation energy of free ions. In the case of 15C5-C1OC6 in water, the preference of Na+ over K+, Rb+, and Cs+ can be attributed to the strength of the interaction or the size matching between the metal ions and 15C5-C1OC6; the Na+ selectivity over Li+ ion is dominated by the solvation energy of free ions. For 18C6-C1OC6 in methanol, the equilibrium constant for the complex formation becomes much bigger in methanol than that in water and loses the selectivity in methanol, because the solvation energy in methanol is fairly smaller than that in water, predominating the contribution from the strength of the interaction between the metal ions and 18C6-C1OC6. The IR spectra measured by SEIRA spectroscopy are quite sensitive to the property of host-guest complexes such as the intermolecular interaction, the structure, and the orientation against the gold surface. However, the evidence of the guest selectivity emerges primarily in the intensity of the spectra, rather than band positions or spectral patterns in the IR spectra.
言語 en
内容記述
内容記述タイプ Other
内容記述 This work was partly supported by grants from JSPS to YF (22247024 and 24650203).
出版者
出版者 Royal Society of Chemistry
言語
言語 eng
資源タイプ
資源タイプ識別子 http://purl.org/coar/resource_type/c_6501
資源タイプ journal article
出版タイプ
出版タイプ AO
出版タイプResource http://purl.org/coar/version/c_b1a7d7d4d402bcce
関連情報
識別子タイプ DOI
関連識別子 10.1039/c5nj01787d
関連情報
関連タイプ isVersionOf
識別子タイプ DOI
関連識別子 http://doi.org/10.1039/c5nj01787d
収録物識別子
収録物識別子タイプ ISSN
収録物識別子 1144-0546
開始ページ
開始ページ 8673
書誌情報 New Journal of Chemistry
New Journal of Chemistry

巻 39, 号 11, p. 8673-8680, 発行日 2015-11-01
旧ID 40790
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