The reaction of neutral single-walled carbon nanotubes (SWCNTs) with diazonium salts proceeds with a high selectivity towards metallic carbon nanotube species; this reaction is well-understood and the mechanism has been elucidated. In the present joint theoretical and experimental study, we investigate the reaction of negatively charged SWCNTs – carbon nanotubides – with diazonium salts. Our density functional theory calculations predict a stronger binding of the aryl diazonium cations to charged metallic SWCNTs species and therefore lead to a preferential addend binding in the course of the reaction. The Raman resonance profile analysis on the reductive arylation of carbon nanotubides obtained by the solid state intercalation approach with potassium in varying concentrations confirms the predicted preferred functionalization of metallic carbon nanotubes. Furthermore, we were also able to show that the selectivity for metallic SWCNT species could be further increased when low potassium concentrations (K : C < 1 : 200) are used for an initial selective charging of the metallic species. Further insights into the nature of the bound addends were obtained by coupled thermogravimetric analysis of the functionalized samples.

中文翻译：

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碳纳米管的还原重氮化：实验和理论选择性研究†

中性单壁碳纳米管（SWCNT）与重氮盐的反应对金属碳纳米管物质具有很高的选择性。该反应是很好理解的，并且机理已经阐明。在目前的联合理论和实验研究中，我们研究带负电荷的SWCNT（碳纳米管）与重氮盐的反应。我们的密度泛函理论计算预测，芳基重氮阳离子与带电金属SWCNT的结合力更强，因此在反应过程中会导致优先的加成键结合。通过固态插层方法用变化浓度的钾获得的碳纳米管的还原芳基化的拉曼共振谱分析证实了金属碳纳米管的预期优选官能化。此外，我们还能够表明，当将低钾浓度（K：C <1：200）用于金属物种的初始选择性充电时，可以进一步提高金属SWCNT物种的选择性。通过结合热重量分析功能化的样品，可以进一步了解结合的加成物的性质。200）用于金属物质的初始选择性装料。通过结合热重量分析功能化的样品，可以进一步了解结合的加成物的性质。200）用于金属物质的初始选择性装料。通过结合热重量分析功能化的样品，可以进一步了解结合的加成物的性质。