In recent years, coordination-driven self-assembly has been utilized in the synthesis of complex molecular topologies such as Solomon links, Hopf’s links and Borromean rings. Our group has also reported a number of self-assembled interlocked architectures using highly conjugated thiophene based electron rich donors and tetracene-based Ru(II) acceptor. Thiophene possesses the highest resonance energy among the five membered heterocycles. In addition, two or three annulated thiophene rings are also known for various applications such as functional materials and photosensitization. Herein, we report the synthesis of a new ligand and four metallamacrocycles self-assembled with thieno[2,3-b]thiophene donor and arene-Ru(II) acceptors. All the new compounds are fully characterized with various spectroscopic techniques.