Patterned Redox Arrays of Polyarylamines I. Synthesis and Electrochemistry of a p-Phenylenediamine and Arylamino-Appended p-Phenylenediamine Arrays
Patterned Redox Arrays of Polyarylamines I. Synthesis and Electrochemistry of a p-Phenylenediamine and Arylamino-Appended p-Phenylenediamine Arrays
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聚芳胺的图案化氧化还原阵列 I. 对苯二胺和芳基氨基附加的对苯二胺阵列的合成和电化学
DOI：
10.1021/cm0106769
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发表时间：
2002
影响因子：
8.6
通讯作者：
S. C. Blackstock
中科院分区：
文献类型：
--
作者：
T. D. Selby;and Do Young Kim;S. C. Blackstock
报道了四对茴香基对苯二胺（TAPD，1）及其二芳氨基氧化还原基团衍生物（2AA/PD，2和4AA/1 PD，3）的合成。这种混合氧化还原阵列在材料背景下由于其投射的定向电子传输性质和潜在的电荷捕获性质而引起兴趣。氧化还原阵列3具有壳/核结构，其中具有较高氧化电位的四个AA基团围绕具有较低氧化电位的中心对苯二胺（PD）基团。这些基板的电化学表征的报告，和阵列2和3中的氧化还原梯度估计为10.2 V.的间位连接的AA和PD基团的2和3观察到弱电子耦合。EPR和电化学数据显示2+·和3+·是PD局部化的自由基阳离子（即，2AA/PD+·和4AA/PD+·）。尽管AA屏蔽了3中的核心PD基团，但其溶液相循环伏安图似乎是正常的，这表明相对容易的异源性。
The synthesis of tetra-p-anisyl-p-phenylenediamine (TAPD, 1) and its derivatives containing appended diarylamino (AA) redox groups (2AA/PD, 2 and 4AA/1PD, 3) is presented. Such mixed redox arrays are of interest in a materials context for their projected directional electron transport properties and potential charge-trapping properties. Redox array 3 has a shell/core structure in which the four AA groups of higher oxidation potential surround a central p-phenylenediamine (PD) group of lower oxidation potential. Electrochemical characterization of these substrates is reported, and the redox gradients in arrays 2 and 3 are estimated to be ∼0.2 V. The meta-linked AA and PD groups of 2 and 3 are observed to be weakly electronically coupled. EPR and electrochemical data show 2+• and 3+• to be PD-localized radical cations (i.e., 2AA/PD+• and 4AA/PD+•, respectively). Despite AA shielding of the core PD group in 3, its solution-phase cyclic voltammogram appears to be normal, indicating relatively facile heterogen...