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Revisiting aqueous redox process of alkyl-linked bis-viologen: Evaluation of redox potential inversion
http://hdl.handle.net/10069/38722
http://hdl.handle.net/10069/38722505242dc-3e42-41e7-9ddf-af5caaf685fd
名前 / ファイル | ライセンス | アクション |
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EleAct295_215.pdf (1.1 MB)
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Item type | 学術雑誌論文 / Journal Article(1) | |||||
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公開日 | 2020-12-18 | |||||
タイトル | ||||||
タイトル | Revisiting aqueous redox process of alkyl-linked bis-viologen: Evaluation of redox potential inversion | |||||
言語 | ||||||
言語 | eng | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | bis-viologen | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | dimerization | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | two-consecutive one-electron transfer | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | electroreflectance | |||||
キーワード | ||||||
主題Scheme | Other | |||||
主題 | ultra-micro electrode | |||||
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 | |||||
著者 |
Sagara, Takamasa
× Sagara, Takamasa× Eguchi, Hitomi |
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抄録 | ||||||
内容記述タイプ | Abstract | |||||
内容記述 | Redox reactions of highly water-soluble bis-viologens were examined at Au electrodes using ultra-micro electrode steady state voltammetry and electroreflectance methods in addition to conventional voltammetry. A bulk UV-vis absorption spectral approach was also used. Alkane-1,n-diyl bis-viologens appeared as a class of prototypical electroactive molecule possessing two equivalent redox centers; they undergo two-consecutive one-electron transfer processes. When intramolecular dimerization takes place immediately after accepting the second electron to produce a form having two viologen radical cation (V•+) sites in one molecule, the second reduction potential may be more positive than the first one. This redox potential inversion is caused by strong tendency to form a stable intramolecular π−π stacking between the two V•+ sites. The redox potential inversion of a highly water-soluble bis-viologen with a butane-1,4-diyl linkage was quantitatively obtained to be 116 mV (E1 – E2 = -116 mV). In contrast, the bis-viologen with an ethane-1,2-diyl linkage exhibited no dimerization below 0.2 mM, and its second redox potential was found to at 63 mV more negative than the first (E1 – E2 = 63 mV), highlighting repulsive interaction. The value of E1 – E2 = -116 mV for the bis-viologen with a butane-1,4-diyl linkage corresponds to the attractive interaction energy in the redox process of 5.9 kBT of room temperature; this value is apparently the same as the dimerization Gibbs free energy of methyl viologen in water. | |||||
書誌情報 |
Electrochimica Acta 巻 295, p. 215-223, 発行日 2019-02-01 |
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出版者 | ||||||
出版者 | Elsevier Ltd. | |||||
ISSN | ||||||
収録物識別子タイプ | ISSN | |||||
収録物識別子 | 00134686 | |||||
DOI | ||||||
関連タイプ | isVersionOf | |||||
識別子タイプ | DOI | |||||
関連識別子 | 10.1016/j.electacta.2018.10.052 | |||||
権利 | ||||||
権利情報 | c2019 Elsevier Ltd. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ | |||||
著者版フラグ | ||||||
出版タイプ | AM | |||||
出版タイプResource | http://purl.org/coar/version/c_ab4af688f83e57aa | |||||
引用 | ||||||
内容記述タイプ | Other | |||||
内容記述 | Electrochimica Acta, 295, pp.215-223; 2019 |