三维纳米碳材料中关节的合成

The existing three-dimensional nano carbon materials are composed of various low dimensional nano materials through self-assembly, as a result, the unique properties of low dimensional materials usually can’t be embodied in these cases. The key to demonstrate the unique (and complex) properties of the three-dimensional (3D) nano carbon materials is construct definite structure by covalent bond connecting some low-dimensional nano carbon materials, however, this subject is challenging. This application is intended to design some suitable base joint components (saddle shaped surface), to realize a controllable and precise connection of various low dimensional nano carbon materials or molecular fragments. Meanwhile, the obtained three-dimensional nano carbon materials are expected not only maintain (or even beyond) the special properties of various materials, but also play a unique advantage of the precise 3D structure. The applicant has the basis of sythesizing template molecules such as saddle shaped curved molecules, planar graphene (HBC) and the shortest carbon nanotubes, and it is feasible to realize the connection of each template molecule through coupling reaction. The preparation of structure well-defined three-dimensional nano carbon materials is the basis for the successful application of nano carbon materials in the future.

现有的三维纳米碳材料是由各种低维纳米材料通过自组装的形式得到的复合材料，往往不能充分发挥低维材料各自独特的性能。将零维、一维、二维碳材料通过共价键构筑成具有精确结构的三维纳米碳材料是展现其独特(及其复合)性能的关键，但显然该课题具有极大的挑战性。本申请书拟通过合适的基础关节部件（马鞍形曲面）的设计，实现各种低维纳米碳材料或分子片段的可控、精确连接，使得到的三维纳米碳材料既能保持（甚至超越）原先各种材料自身的特殊性能，又能发挥出精确三维结构带来的独特优势。申请人在马鞍形曲面关节分子，平面石墨烯（HBC）以及最短碳纳米管等模板分子的合成方面已有基础，而且通过偶联反应的策略来实现各个模板分子的连接具有可行性。精确结构的三维纳米碳材料的制备为纳米碳材料将来在力学、电学方面的成功应用奠定了基础。

本项目主要针对设计合成三维碳材料的关节。通过4年的项目执行，完成了平面纳米石墨烯HBC分子，最短碳纳米管C50H10以及马鞍形曲面的关节C80H30的合成，并对平面HBC和马鞍形C80H30分子实现了精准的硼酯化修饰。取得了十吡咯碗烯、三维碳锥分子精准合成、双七元环富勒烯衍生物、富勒烯和二维蔻烯等的共价连接等重要研究成果。其科学意义总结如下：十吡咯碗烯的合成以及与几乎所有类型的富勒烯客体自组装的实现，解决了富勒烯结构难以准确确定的难题；碳锥的以往合成是通过物理-化学手段的极端条件实现的，不仅产率低，无法分离提纯，而且结构缺陷较多，本工作首次实现的碳锥的分子精准合成为碳锥的可控合成奠定了基础；通过富勒烯氢化物的碳氢键活化的研究，实现了零维富勒烯和二维蔻烯等的共价连接，实现了跨纬度碳分子材料的突破，跨维度分子材料有望兼具不同维度材料的优异性能；双七元环富勒烯衍生物的发现继续打破人类的认知，为富勒烯家族增添了新的成员。本项目基本实现了三维材料关节的合成及修饰工作，但没能实现一维碳管分子和关节分子的共价连接，这将是我们在后续的研究当中努力的目标之一。