Bergman Harrison M, Fan Angela T, Jones Christopher G, Rothenberger August J, Jha Kunal K, Handford Rex C, Nelson Hosea M, Liu Yi, Tilley T Don
Department of Chemistry, University of California, Berkeley, California 94720, United States.
Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
J Am Chem Soc. 2025 Jun 4;147(22):19132-19138. doi: 10.1021/jacs.5c04268. Epub 2025 May 23.
Topologically complex carbon nanostructures are an exciting but largely unexplored class of materials due to their challenging synthesis. Previous methods are low yielding because they rely on irreversible C-C bond formation, which necessitates complex templating strategies to enforce entanglement. Here, reversible zirconocene coupling of alkynes is developed as a new method to access complex molecular topologies, where dynamic C-C bond formation facilitates entanglement under thermodynamic control, allowing the use of simple precursors without the need for preassembly. This strategy enables the scalable, high-yield synthesis of three topologically distinct nanocarbons, including the serendipitous discovery of a structure containing a new topological motif that was not previously identified or realized synthetically. This motif, consisting of an unusual combination of interlocking and interweaving, was recognized to be generalizable to a new topological class of molecules, introduced here as perplexanes.
拓扑复杂的碳纳米结构是一类令人兴奋但在很大程度上尚未被探索的材料，因为它们的合成具有挑战性。以前的方法产率较低，因为它们依赖于不可逆的C-C键形成，这需要复杂的模板策略来实现缠结。在这里，炔烃的可逆锆茂偶联被开发为一种获得复杂分子拓扑结构的新方法，其中动态C-C键的形成在热力学控制下促进缠结，允许使用简单的前体而无需预组装。该策略能够可扩展、高产率地合成三种拓扑不同的纳米碳，包括偶然发现的一种含有新拓扑基序的结构，该基序以前未被鉴定或通过合成实现。这种由互锁和交织的不寻常组合组成的基序被认为可推广到一类新的拓扑分子，在此引入为“困惑烷”。
