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Self-assembly of metalla[3]catenanes, Borromean rings and ring-in-ring complexes using a simple π-donor unit

2020; Oxford University Press; Volume: 7; Issue: 10 Linguagem: Inglês

10.1093/nsr/nwaa164

2095-5138

Ye Lu, Dong Liu, Yue‐Jian Lin, Zhen Hua Li, Guo‐Xin Jin,

Crystallography and molecular interactions

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.