Active template strategy for the preparation of π-conjugated interlocked nanocarbons
Active template strategy for the preparation of π-conjugated interlocked nanocarbons
复制标题
DOI：
10.1038/s41557-022-01106-9
复制
发表时间：
2023-01-12
期刊：
影响因子：
21.8
通讯作者：
Jasti, Ramesh
中科院分区：
文献类型：
--
作者：
May, James H.;Van Raden, Jeff M.;Jasti, Ramesh
由于制备这些不寻常的拓扑材料的困难，机械互锁碳纳米结构代表了碳纳米科学中一个相对未开发的前沿。在这里，我们展示了一种活性模板方法，其中[n]环对苯炔前体大环被两个与金属离子配位的会聚吡啶给体修饰。金属离子在大环的中心腔内催化炔-炔交叉偶联反应，产生的联锁产物可在随后的合成步骤中转化为完全共轭结构。具体来说，我们报道了一个由两个或三个相互穿透的[n]环对苯乙烯衍生的各种尺寸的大环组成的链烷家族的合成。此外，用同样的方法合成了一个完全偶联的[3]轮烷。利用不同拓扑结构的机械互锁碳纳米结构的合成方法的发展，可以帮助阐明机械键合对这类新兴纳米材料的影响，并允许建立结构-性能关系。
Mechanically interlocked carbon nanostructures represent a relatively unexplored frontier in carbon nanoscience due to the difficulty in preparing these unusual topological materials. Here we illustrate an active-template method in which a [n]cycloparaphenylene precursor macrocycle is decorated with two convergent pyridine donors that coordinate to a metal ion. The metal ion catalyses alkyne-alkyne cross-coupling reactions within the central cavity of the macrocycle, and the resultant interlocked products can be converted into fully pi-conjugated structures in subsequent synthetic steps. Specifically, we report the synthesis of a family of catenanes that comprise two or three mutually interpenetrating [n]cycloparaphenylene-derived macrocycles of various sizes. Additionally, a fully pi-conjugated [3]rotaxane was synthesized by the same method. The development of synthetic methods to access mechanically interlocked carbon nanostructures of varying topology can help elucidate the implications of mechanical bonding for this emerging class of nanomaterials and allow structure-property relationships to be established.