Covalent Functionalization of Single-Walled Carbon Nanotubes by the Bingel Reaction for Building Charge-Transfer Complexes.,The Journal of Organic Chemistry

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Covalent Functionalization of Single-Walled Carbon Nanotubes by the Bingel Reaction for Building Charge-Transfer Complexes.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-08-21 , DOI: 10.1021/acs.joc.0c01384
Olga A Stasyuk ₁ , Anton J Stasyuk ₁ , Alexander A Voityuk _{1,

2} , Miquel Solà ₁

Affiliation

Functionalization of nanotubes with donor and acceptor partners by the Bingel reaction leads to the formation of charge-transfer dyads, which can operate in organic photovoltaic devices. In this work, we theoretically examine the mechanism of the Bingel reaction for the (6,5)-chiral, (5,5)-armchair, and (9,0)-zigzag single-walled carbon nanotubes (SWCNTs), and demonstrate that the reaction is regioselective and takes place at the perpendicular position of (6,5)- and (5,5)-SWCNTs, and the oblique position of (9,0)-SWCNT. Further, we design computationally the donor–acceptor complexes based on (6,5)-SWCNT coupled with partners of different electronic nature. Analysis of their excited states reveals that efficient photoinduced charge transfer can be achieved in the complexes with π-extended analogue of tetrathiafulvalene (exTTF), zinc tetraphenylporphyrin (ZnTPP), and tetracyanoanthraquinodimethane (TCAQ). The solvent can significantly affect the population of the charge-separated states. Our calculations show that electron transfer (ET) occurs in the normal Marcus regime on a sub-nanosecond time scale in the complexes with exTTF and ZnTPP, and in the inverted Marcus regime on a picosecond time scale in the case of the TCAQ derivative. The ET rate is found to be not very sensitive to the degree of functionalization of the nanotube.

中文翻译：

单壁碳纳米管通过Bingel反应共价官能化以建立电荷转移络合物。

通过Bingel反应，具有供体和受体配体的纳米管功能化导致形成电荷转移二元体，该二元体可以在有机光伏器件中运行。在这项工作中，我们从理论上检查了（6,5）-手性，（5,5）-扶手椅和（9,0）-之字形单壁碳纳米管（SWCNT）的Bingel反应机理，并论证了该反应是区域选择性的，发生在（6,5）-和（5,5）-SWCNT的垂直位置，以及在（9,0）-SWCNT的倾斜位置。此外，我们基于（6,5）-SWCNT结合不同电子性质的伙伴，通过计算设计了供体-受体复合物。对它们的激发态的分析表明，在具有四硫富瓦烯的π扩展类似物（exTTF）的配合物中，可以实现有效的光诱导电荷转移，四苯基卟啉锌（ZnTPP）和四氰基蒽醌二甲烷（TCAQ）。溶剂会显着影响电荷分离态的数量。我们的计算表明，与exTTF和ZnTPP形成的络合物，电子转移（ET）在亚纳秒级的正常马库斯体系中发生，而在TCAQ衍生物的情况下，在皮秒的时间级在反向马库斯体系中发生。发现ET速率对纳米管的官能化程度不是很敏感。如果是TCAQ导数，则在反向马库斯体制下，皮秒级的时间尺度。发现ET速率对纳米管的官能化程度不是很敏感。如果是TCAQ导数，则在反向马库斯体制下，皮秒级的时间尺度。发现ET速率对纳米管的官能化程度不是很敏感。

更新日期：2020-09-20

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