Abstract

Despite extensive research and several stunning breakthroughs in the synthesis of interlocked molecular species, [3]catenanes, Borromean rings and ring-in-ring complexes are exceedingly rare and their targeted synthesis remains a formidable challenge. Herein, a series of Cp^*Rh-based homogeneous and heterogeneous interlocked structures have been prepared by coordination-driven self-assembly, not only including metalla[2]catenanes and molecular Borromean rings, but also linear metalla[3]catenanes and ring-in-ring complexes. The interlocked structures are all based on bithiophenyl groups. The bithiophenyl groups effectively enhance the strength of the inter-ring interactions and play a crucial role in the formation of these interlocked structures. By taking advantage of the strong interaction between π-donor (D) and π-acceptor (A) groups, the electron-deficient methylviologen cation was introduced into a cationic metallarectangle based on bithiophenyl groups. Taking inspiration from these results, a cationic metallarectangle based on A units was threaded into a metallarectangle based on D units, leading to a heterogeneous D–A ring-in-ring structure.

中文翻译：

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使用简单的 π 供体单元自组装金属 [3] 链、Borromean 环和环中配合物

摘要

尽管在互锁分子种类的合成方面进行了广泛的研究和多项惊人的突破，但 [3] 链烷、Borromean 环和环中环复合物极为罕见，它们的靶向合成仍然是一项艰巨的挑战。在此，通过配位驱动的自组装制备了一系列基于Cp ^* Rh的同质和异质互锁结构，不仅包括金属[2]链烷和分子Borromean环，还包括线性金属[3]链和环-环内复合物。互锁结构均基于联苯硫基。联噻吩基团有效地增强了环间相互作用的强度，并在这些互锁结构的形成中起关键作用。通过利用π-供体之间的强相互作用（D ) 和 π 受体 ( A ) 基团，将缺电子的甲基紫精阳离子引入基于联噻吩基团的阳离子金属矩形中。受这些结果的启发，基于A单元的阳离子金属矩形被连接到基于D单元的金属矩形，导致异质D - A环中环结构。