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.