Scalable, Divergent Synthesis of a High Aspect Ratio Carbon Nanobelt
Scalable, Divergent Synthesis of a High Aspect Ratio Carbon Nanobelt
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DOI：
10.1021/jacs.1c04037
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发表时间：
2021-06-04
影响因子：
15
通讯作者：
Tilley, T. Don
中科院分区：
文献类型：
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作者：
Bergman, Harrison M.;Kiel, Gavin R.;Tilley, T. Don
碳纳米带是具有高度基础和技术意义的分子，因为它们的结构与碳纳米管相似，它们是碳纳米管的分子切口。尽管受到如此关注，合成可访问性仍然是一个主要障碍，因此少数已知策略提供的结构多样性、功能性和可扩展性有限。为了解决这个瓶颈，我们开发了一种新策略，利用通过位点选择性[2 + 2 + 2]环加成和高产率二茂锆介导的大环化构建的高度融合的单体单元，以实现大规模合成新的碳纳米带，并在倒数第二步中引入功能手柄。该纳米带代表了扶手椅碳纳米管的对角线横截面，因此具有纵横比为 1.6 的纵向延伸结构，是所有报道的纳米带中最高的。这种细长的结构促进固态填充到模仿母体碳纳米管的排列柱中，并促进非极性溶剂中与低聚亚芳基客体发生前所未有的主客体化学反应。
Carbon nanobelts are molecules of high fundamental and technological interest due to their structural similarity to carbon nanotubes, of which they are molecular cutouts. Despite this attention, synthetic accessibility is a major obstacle, such that the few known strategies offer limited structural diversity, functionality, and scalability. To address this bottleneck, we have developed a new strategy that utilizes highly fused monomer units constructed via a site-selective [2 + 2 + 2] cycloaddition and a high-yielding zirconocene-mediated macrocyclization to achieve the synthesis of a new carbon nanobelt on large scale with the introduction of functional handles in the penultimate step. This nanobelt represents a diagonal cross section of an armchair carbon nanotube and consequently has a longitudinally extended structure with an aspect ratio of 1.6, the highest of any reported nanobelt. This elongated structure promotes solid-state packing into aligned columns that mimic the parent carbon nanotube and facilitates unprecedented host-guest chemistry with oligo-arylene guests in nonpolar solvents.