Electrochemical and Theoretical Investigation of Corannulene Reduction Processes
Electrochemical and Theoretical Investigation of Corannulene Reduction Processes
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DOI：
10.1021/jp8045092
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发表时间：
2009-02-19
影响因子：
3.3
通讯作者：
Scott, Lawrence T.
中科院分区：
文献类型：
--
作者：
Bruno, Carlo;Benassi, Rois;Scott, Lawrence T.
corannulene阴离子的伏安生成的研究在很大范围的实验条件，包括“传统”的电化学溶剂，如二甲基甲酰胺，乙腈，和四氢呋喃，或“非常规”的溶剂，如液氨，液体甲胺，或液体二甲胺，和几种不同的支持电解质。强烈的离子配对效应被发现占主导地位的corannulene更高的阴离子的电化学生成，并通过适当的选择的溶剂/电解质系统，我们观察到，第一次，可逆的电化学生成的三重还原corannulene。实验得到的标准势与从头算和密度泛函方法计算的理论值进行了比较，其中明确考虑了溶剂化和离子配对效应。特别地，计算考虑了电解质阳离子尺寸对离子配对的影响，以使实验电势窗口内第三次还原的发生合理化。
The voltammetric generation of corannulene anions was investigated over a large range of experimental conditions comprising either "traditional" electrochemical solvents, such as dimethylformamide, acetonitrile, and tetrahydrofuran, or "unconventional" solvents, such as liquid ammonia, liquid methylamine, or liquid dimethylamine, and several different supporting electrolytes. Strong ion pairing effects were found to dominate the electrochemical generation of corannulene higher anions, and through the suitable choice of the solvent/electrolyte system, we observed, for the first time, the reversible electrochemical generation of up to the triply reduced corannulene. The standard potentials obtained experimentally compared rather well with the theoretical values calculated by ab initio and density functional methods, in which solvation and ion pairing effect were explicitly taken into account. In particular, the calculations considered the effect of the electrolyte cation size on ion pairing in order to rationalize the occurrence of the third reduction within the experimental potential window.