新型有机功能分子巴基碗的合成及性能研究

Buckybowls, bowl-shaped polycyclic aromatic hydrocarbons, also known as fullerene fragements or the cap structures of carbon nanotubes (CNTs), represent a class of hydrocarbons with unique properties and potentials for application as novel materials. The synthesis of these"open" geodesic polyarenes poses a great challenge to organic chemists due to their highly strained structures. Most of buckybowls were synthesized through FVP (Flash Vacuum Pyrolysis) methods under harsh conditions (> 500 ℃) with very low yield and poor functional group tolerance. Although in the last decade, synthesis of buckybowls under mild conditions have emerged, development of more efficient synthesis of known buckybowls and novel buckybowls are still urgent tasks to make buckybowls applicable as materials. We plan to develop a mild and efficient synthesis of buckybowls of various structures involving recently developed synthetic methods such as cove-region closure of fluoroarenes and silyl cation catalyzed Friedel-Crafts coupling reaction of fluoroarenes. Theoretical calculation will be used to predict the geometry of novel buckybowls, transitional state and energy requirments of key reactions. The structural, photochemical and electronic properties of prepared buckybowls will be extensively studied. Their dynamic bowl-to-bowl inversion and formation of complex with metals (concave or convex) will also be studied. While planar aromatic hydrocarbons such as acenes have proven to be excellent organic conductive materials, there are only few reports that some buckybowls such as sumanenen and corannulene derivatives show high charge mobility. Thus, we will pay more attentions to this interesting and promising topic. This research will probably lay a solid foundation for the application of buckybowls as the materials for organic devices.

巴基碗（Buckybowl）是一种具有碗状结构的曲面多环芳烃，结构上类似于富勒烯的片段或碳纳米管的封端部分。巴基碗具有一些独特的光电性质，是一类潜在的新型有机功能材料。巴基碗由于其独特的结构，具有较大的张力，合成比较困难，大部分巴基碗采用剧烈的瞬间真空裂解法(Flash Vacuum Pyrolysis)以极低的收率合成。因此，发展温和、高效的合成方法合成各种巴基碗及衍生物是一项紧迫而具有挑战性的任务。本课题旨在通过合理的路线设计，采用近年开发的新的合成方法结合金属催化的偶联等反应，辅以理论计算，实现一系列新型巴基碗的高效合成。我们将研究它们的分子结构、固体堆积方式、碗的翻转和光电性能，探讨该类分子作为有机导电材料的可行性，为该类分子在有机分子器件中的应用奠定基础。

碗状多环芳烃(Buckybowl，巴基碗)属于一类开口的曲面芳香化合物，其结构上类似于富勒烯的片段或碳纳米管的封端部分，是一类具有潜力的新型有机功能材料。然而，碗状芳烃合成具有较大的挑战性。我们从简单易得的原料出发，通过温和的反应条件，以简洁的路线合成了几类重要的多环芳烃类化合物。从得到的关键中间体出发，我们成功地合成了几类具有代表性的巴基碗—含杂原子花烯，该方法不需要采用真空高温热解的方法，条件温和、产率良好。通过实验和密度函（DFT）理论计算，我们还对得到的多环芳烃类化合物的晶体结构、热稳定性及其光电性能进行了研究，为进一步开发该类分子在有机分子器件方面的应用奠定了一定的基础。