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首页> 外文期刊>Journal of the American Chemical Society >Tuning Delocalization in the Radical Cations of 1,4-Bis[4-(diarylamino)styryl]benzenes, 2,5-Bis[4-(diarylamino)styryl]thiophenes, and 2,5-Bis[4-(diarylamino)styryl]pyrroles through Substituent Effects
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Tuning Delocalization in the Radical Cations of 1,4-Bis[4-(diarylamino)styryl]benzenes, 2,5-Bis[4-(diarylamino)styryl]thiophenes, and 2,5-Bis[4-(diarylamino)styryl]pyrroles through Substituent Effects

机译：调整1，4-双[4-（二芳基氨基）苯乙烯基]苯，2,5-双[4-（二芳基氨基）苯乙烯基]噻吩和2,5-双[4-（二芳基氨基）苯乙烯基]的自由基阳离子中的离域取代基]吡咯

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摘要

Radical cations have been generated for 10 bis[4-(diarylamino)styryl]arenes and heteroarenes to investigate the effect of the electron-richness of the terminal groups and of the bridging (hetero)arene on delocalization. The intervalence charge-transfer bands of these radical cations vary from weak broad Gaussians, indicative of localized class-Ⅱ mixed-valence species, to strong relatively narrow asymmetric bands, characteristic of delocalized class-Ill bis(diarylamino) species, to narrow symmetric bands in cases where the bridge contribution to the singly occupied molecular orbital is largest. Hush analysis of these bands yields estimates of the electronic coupling varying from 480 cm~(-1) (electron-poor bridge, most electron-rich terminal aryl groups) to 1000 cm~(-1) (electron-rich bridge, least electron-rich termini) if the diabatic electron-transfer distance, R_(ab), is equated to the N-N separation. Computational and electron spin resonance (ESR) evidence for displacement of the diabatic states into the bridge (reduced R_(ab)) suggests that these values are underestimates and that even more variation is to be expected through the series. Several dications have also been studied. The vis-NIR absorption of the dication of (E,E)-1,4-bis{4-[bis(4-n-butoxyphenyl)amino]styryl}-2,5-dicyanobenzene is seen at an energy similar to that of the strongest band in the spectrum of the corresponding weakly coupled monocation, with approximately twice the absorptivity, and its ESR spectrum suggests essentially noninteracting radical centers. In contrast, the electronic spectra of class-Ⅲ monocations show no clear relationship to those of the corresponding dications, which ESR reveals to be singlet species.
机译：已经为10个双[4-（二芳基氨基）苯乙烯基]芳烃和杂芳基生成了自由基阳离子，以研究末端基团的电子富集和桥接（杂）芳烃对离域的影响。这些自由基阳离子的间隔电荷转移带从弱的宽高斯分布（指示局部化的Ⅱ类混合价态物种）到强的相对较窄的不对称带（具有离域化的Ⅲ类双（二芳基氨基）物种的特征）到较窄的对称带而变化如果桥对单独占据的分子轨道的贡献最大。对这些带进行静默分析可得出电子耦合的估计值，其范围从480 cm〜（-1）（电子贫乏的桥，大多数电子富集的末端芳基）到1000 cm〜（-1）（富电子的桥，最少的电子） -富末端），如果非绝热电子传输距离R_（ab）等于NN分离。计算和电子自旋共振（ESR）证明了非绝热态向桥的位移（R_（ab）降低）表明这些值被低估了，并且预计整个系列还会有更多的变化。还研究了几种适应症。 （E，E）-1,4-双{4- [双[4-（双（4-正丁氧基苯基）氨基]苯乙烯基} -2,5-二氰基苯]的二价离子的近红外吸收相应的弱耦合单阳离子光谱中最强谱带的峰吸收率约为吸收率的两倍，它的ESR谱表明基本上没有相互作用的自由基中心。相比之下，Ⅲ类单阳离子的电子光谱与相应的指示没有明显的关系，ESR显示为单重态。

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  • 来源
    《Journal of the American Chemical Society》 |2012年第24期|p.10146-10155|共10页
  • 作者

    Stephen Barlow; Chad Risko; Susan A. Odom; Shijun Zheng; Veaceslav Coropceanu; Luca Beverina; Jean-Luc Bredas; Seth R. Marder;

  • 作者单位

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

    Center for Organic Photonics and Electronics and School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta,Georgia 30332-0400, United States;

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