Stable, π-conjugated radical anions of boron–nitrogen dihydroindeno[1,2-b]fluorenes

IF 1.1 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Tony Nguyen, Tyler Hannah, Warren E. Piers, Benjamin Gelfand
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引用次数: 2

Abstract

We have recently reported the synthesis and application of boron–nitrogen dihydroindeno[1,2-b]fluorene derivatives as acceptors in organic photovoltaic devices. Their modest observed efficiencies may be related to the properties of their reduced congeners. In this work, we report two new members of this family of compounds prepared via the electrophilic borylation of 2,5-di- p-tolylpyrazine followed by an arylation of the boron center with ZnAr 2 reagents. Two derivatives, 1 (Ar = 2,4,6-F 3 C 6 H 2 ) and 2 (Ar = C 6 F 5 ) were synthesized, and their radical anions, 1 •− and 2 •− , were formed via chemical reductions with CoCp* 2 and CoCp 2 , respectively. Through comparison of structural parameters, as well as spectroscopic and computational data, the unpaired electron in the radical anions is localized in the planar core of the molecule, and dimerization is disfavored as a result. However, unlike the neutral starting materials, 1 •− and 2 •− are reactive toward ambient atmosphere. These observations suggest that the reduced compounds are stable toward intrinsic degradation pathways but subject to extrinsic degradation in device operation.
硼氮二氢茚[1,2-b]芴的稳定π共轭自由基阴离子
我们最近报道了硼氮二氢茚[1,2-b]芴衍生物作为受体在有机光伏器件中的合成和应用。它们所观察到的适度效率可能与它们的还原同系物的性质有关。在这项工作中,我们报告了该家族化合物的两个新成员,它们是通过2,5-二对甲基吡嗪的亲电硼化,然后用ZnAr 2试剂将硼中心进行芳化而制备的。合成了两个衍生物1 (Ar = 2,4,6- f3c6h 2)和2 (Ar = c6f 5),它们的自由基阴离子1•−和2•−分别由CoCp* 2和CoCp 2化学还原形成。通过结构参数的比较,以及光谱和计算数据的比较,发现自由基阴离子中的未配对电子定位在分子的平面核心,不利于二聚化。然而,与中性起始材料不同的是,1•−和2•−对周围大气具有反应性。这些观察结果表明,减少的化合物是稳定的内在降解途径,但受制于外在的降解装置操作。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Canadian Journal of Chemistry
Canadian Journal of Chemistry 化学-化学综合
CiteScore
1.90
自引率
9.10%
发文量
99
审稿时长
1 months
期刊介绍: Published since 1929, the Canadian Journal of Chemistry reports current research findings in all branches of chemistry. It includes the traditional areas of analytical, inorganic, organic, and physical-theoretical chemistry and newer interdisciplinary areas such as materials science, spectroscopy, chemical physics, and biological, medicinal and environmental chemistry. Articles describing original research are welcomed.
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