Quantum Defects: What Pairs with the Aryl Group When Bonding to the sp 2 Carbon Lattice of Single-Wall Carbon Nanotubes?
Quantum Defects: What Pairs with the Aryl Group When Bonding to the sp 2 Carbon Lattice of Single-Wall Carbon Nanotubes?
复制标题
量子缺陷：当键合到单壁碳纳米管的 sp 2 碳晶格时，什么与芳基配对？
DOI：
10.1021/jacs.2c03846
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发表时间：
2022
影响因子：
15
通讯作者：
Wang, YuHuang
中科院分区：
文献类型：
--
作者：
Wang, Peng;Fortner, Jacob;Luo, Hongbin;Kłos, Jacek;Wu, Xiaojian;Qu, Haoran;Chen, Fu;Li, Yue;Wang, YuHuang
芳基重氮反应被广泛用于共价修饰石墨电极和低维碳材料，包括最近在单壁碳纳米管半导体上产生有机色心（OCC）。然而，由于实验上的困难，在解决小功能团广泛的碳晶格，一个基本的问题，直到现在仍然没有答案：什么基团，如果有的话，是配对的芳基sp3缺陷时，打破一个C C键的sp2碳晶格？在这里，我们发现水在完成与氯磺酸的碳纳米管的重氮反应中发挥了意想不到的作用，作为亲核试剂，贡献−OH作为配对基团。通过简单地用其他亲核溶剂取代水，我们发现有可能产生具有全新配对基团系列的OCC，包括− OCH 3，− OC 2 H5，− OC 3 H7，-i-OC 3 H7和− NH 2，这使我们能够系统地定制缺陷对和所得色心的光学性质。通过这些配对基团，我们进一步实现了具有空间体积庞大的对的OCC的合成，所述空间体积庞大的对表现出有效地覆盖第二近红外窗口和电信波长的高纯度缺陷光致发光。我们的研究进一步表明，这些重氮反应通过在氯磺酸中形成碳阳离子进行，而不是通常发生在水溶液中的自由基机制。这些发现揭示了未知的sp3缺陷对的一半，并提供了一种合成的方法来控制这些缺陷的量子信息，成像和传感色心。
Aryl diazonium reactions are widely used to covalently modify graphitic electrodes and low-dimensional carbon materials, including the recent creation of organic color centers (OCCs) on single-wall carbon nanotube semiconductors. However, due to the experimental difficulties in resolving small functional groups over extensive carbon lattices, a basic question until now remains unanswered: what group, if any, is pairing with the aryl sp3defect when breaking a C═C bond on the sp2carbon lattice? Here, we show that water plays an unexpected role in completing the diazonium reaction with carbon nanotubes involving chlorosulfonic acid, acting as a nucleophilic agent that contributes −OH as the pairing group. By simply replacing water with other nucleophilic solvents, we find it is possible to create OCCs that feature an entirely new series of pairing groups, including −OCH3, −OC2H5, −OC3H7, -i-OC3H7, and −NH2, which allows us to systematically tailor the defect pairs and the optical properties of the resulting color centers. Enabled by these pairing groups, we further achieved the synthesis of OCCs with sterically bulky pairs that exhibit high purity defect photoluminescence effectively covering both the second near-infrared window and the telecom wavelengths. Our studies further suggest that these diazonium reactions proceed through the formation of carbocations in chlorosulfonic acid, rather than a radical mechanism that typically occurs in aqueous solutions. These findings uncover the unknown half of the sp3defect pairs and provide a synthetic approach to control these defect color centers for quantum information, imaging, and sensing.