Chirality-Selective Functionalization of Semiconducting Carbon Nanotubes with a Reactivity-Switchable Molecule.
Chirality-Selective Functionalization of Semiconducting Carbon Nanotubes with a Reactivity-Switchable Molecule.
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DOI：
10.1021/jacs.7b05906
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发表时间：
2017-09-13
影响因子：
15
通讯作者：
Wang Y
中科院分区：
文献类型：
--
作者：
Powell LR;Kim M;Wang Y
十多年来，半导体单壁碳纳米管（SWCNTs）的手性选择性功能化一直是一个困难的合成目标。在这里，我们描述了一种按需共价化学来解决这个有趣的挑战。我们的方法包括合成和分离一种化学惰性重氮醚异构体，该异构体可以通过调节异构化的热力学势垒，通过pH和可见光与纳米管的光学频率共振，在原位切换到其反应形式。我们发现在没有光的情况下完全抑制反应是可能的，这是由敏感缺陷光致发光的极限决定的（少于0.01%的碳原子与官能团结合）。这种光学驱动的重氮醚化学使得在混合物中选择性地功能化特定的swcnts手性成为可能。即使对于直径和电子结构几乎相同的(6,5)-和(7,3)- swcnts这两种手性，我们也能够激活重氮醚化合物，使活性较弱的(7,3)- swcnts功能化，从而驱动化学反应几乎排除(6,5)- swcnts。这项工作为在单手性水平上化学定制SWCNTs提供了机会，用于纳米管分选、片上钝化和纳米级光刻。
Chirality-selective functionalization of semiconducting single-walled carbon nanotubes (SWCNTs) has been a difficult synthetic goal for more than a decade. Here we describe an on-demand covalent chemistry to address this intriguing challenge. Our approach involves the synthesis and isolation of a chemically inert diazoether isomer that can be switched to its reactive form in situ by modulation of the thermodynamic barrier to isomerization with pH and visible light that resonates with the optical frequency of the nanotube. We found that it is possible to completely inhibit the reaction in the absence of light, as determined by the limit of sensitive defect photoluminescence (less than 0.01% of the carbon atoms are bonded to a functional group). This optically driven diazoether chemistry makes it possible to selectively functionalize a specific SWCNT chirality within a mixture. Even for two chiralities that are nearly identical in diameter and electronic structure, (6,5)- and (7,3)-SWCNTs, we are able to activate the diazoether compound to functionalize the less reactive (7,3)-SWCNTs, driving the chemical reaction to near exclusion of the (6,5)-SWCNTs. This work opens opportunities to chemically tailor SWCNTs at the single chirality level for nanotube sorting, on-chip passivation, and nanoscale lithography.
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