Precision Nanotube Mimics via Self-Assembly of Programmed Carbon Nanohoops
Precision Nanotube Mimics via Self-Assembly of Programmed Carbon Nanohoops
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通过编程碳纳米环的自组装来模拟精密纳米管
DOI：
10.1021/acs.joc.9b02340
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Jasti, Ramesh
中科院分区：
文献类型：
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作者：
Van Raden, Jeff M.;Leonhardt, Erik J.;Zakharov, Lev N.;Pérez-Guardiola, A.;Pérez-Jiménez, A. J.;Marshall, Checkers R.;Brozek, Carl K.;Sancho-García, J. C.;Jasti, Ramesh
均匀、均匀的碳纳米材料的可规模化生产是当代有机合成的关键合成挑战，因为几乎所有当前的制备方法都提供了各种碳化产品的非均相混合物。尤其是碳纳米管(CNT)，无法获得特定直径或手性的结构，严重限制了其潜在的应用。在这里，我们提出了一种通过氟化纳米环的自组装来获得固态碳纳米管模拟结构的一般方法，这种结构可以以可伸缩的、尺寸选择性的方式合成。X射线结晶学表明，这些碳纳米管模拟物显示出均匀的通道直径，这些直径精确地由其纳米环成分的直径定义，这些纳米环成分通过芳烃-聚氟芳烃和C-H-F相互作用以管状方式自组装。这些体系的纳米管状组装导致了线性客体排列和可访问通道等能力，这两种能力在碳纳米管中都能观察到，但在类似的全烃纳米环体系中没有观察到。计算表明，晶体结构中观察到的有机氟相互作用对碳纳米管模拟系统的自组装和稳定性确实至关重要。这项工作通过弱相互作用建立了碳纳米环的自组装，作为一种有吸引力的方法来生成模仿碳纳米管的固态材料，重要的是通过有机合成实现了无与伦比的可调性。
The scalable production of homogeneous, uniform carbon nanomaterials represents a key synthetic challenge for contemporary organic synthesis as nearly all current fabrication methods provide heterogeneous mixtures of various carbonized products. For carbon nanotubes (CNTs) in particular, the inability to access structures with specific diameters or chiralities severely limits their potential applications. Here, we present a general approach to access solid-state CNT mimic structures via the self-assembly of fluorinated nanohoops, which can be synthesized in a scalable, size-selective fashion. X-ray crystallography reveals that these CNT mimics exhibit uniform channel diameters that are precisely defined by the diameter of their nanohoop constituents, which self-assemble in a tubular fashion via a combination of arene-pefluoroarene and C–H—F interactions. The nanotube-like assembly of these systems results in capabilities such as linear guest alignment and accessible channels, both of which are observed in CNTs but not in the analogous all-hydrocarbon nanohoop systems. Calculations suggest that the organofluorine interactions observed in the crystal structure are indeed critical in the self-assembly and robustness of the CNT mimic systems. This work establishes the self-assembly of carbon nanohoops via weak interactions as an attractive means to generate solid-state materials that mimic carbon nanotubes, importantly with the unparalleled tunability enabled by organic synthesis.