Quinone 1 e(-) and 2 e(-)/2 H(+) Reduction Potentials: Identification and Analysis of Deviations from Systematic Scaling Relationships.
Quinone 1 e(-) and 2 e(-)/2 H(+) Reduction Potentials: Identification and Analysis of Deviations from Systematic Scaling Relationships.
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DOI：
10.1021/jacs.6b05797
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发表时间：
2016-12-14
影响因子：
15
通讯作者：
Hammes-Schiffer S
中科院分区：
文献类型：
--
作者：
Huynh MT;Anson CW;Cavell AC;Stahl SS;Hammes-Schiffer S
醌类化合物在化学和生物学中参与多种电子转移和质子耦合电子转移过程。为了了解这些氧化还原过程之间的关系，进行了实验研究，以探测一些常见的醌类化合物的1 e-和2 e-/2 H+还原电位。结果表明1 e-和2 e-/2 H+还原电位之间存在非线性相关性。这一意想不到的观察结果促使对134种不同的醌进行计算研究，探测它们的1 e-还原电位、pKa值和2 e-/2 H+还原电位。密度泛函理论计算揭示了这三个性质之间的近似线性相关性和一个有效的Hammett常数与醌取代基（S）。然而，偏离这种线性比例关系是显而易见的醌，其特征在于分子内氢键的氢醌，卤素取代基，带电的取代基，和/或空间体积庞大的取代基。这些结果，特别是不同的取代基效应的1 e-与2 e-/2 H+还原电位，具有重要的意义，设计醌定制的氧化还原性能。
Quinones participate in diverse electron transfer and proton-coupled electron transfer processes in chemistry and biology. To understand the relationship between these redox processes, an experimental study was carried out to probe the 1 e– and 2 e–/2 H+ reduction potentials of a number of common quinones. The results reveal a non-linear correlation between the 1 e– and 2 e–/2 H+ reduction potentials. This unexpected observation prompted a computational study of 134 different quinones, probing their 1 e– reduction potentials, pKa values, and 2 e–/2 H+ reduction potentials. The density functional theory calculations reveal an approximately linear correlation between these three properties and an effective Hammett constant associated with the quinone substituent(s). However, deviations from this linear scaling relationship are evident for quinones that feature intramolecular hydrogen bonding in the hydroquinone, halogen substituents, charged substituents, and/or sterically bulky substituents. These results, particularly the different substituent effects on the 1 e– versus 2 e–/2 H+ reduction potentials, have important implications for designing quinones with tailored redox properties.
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