In addition to our previous works on the synthesis of regioisomers (o-bis-L and m-bis-L, see below) of bis-O₂S₂-macrocycle and their supramolecular silver(I)¹ and copper(I) iodide² complexes, borderline (Pb²⁺) and soft (Hg²⁺ and Cu⁺) metal salts were employed to investigate the isomer effect on the coordination modes and topologies of the coordination products.³ In the present work, we were able to isolate the para-form (p-bis-L, see below) as a final puzzle and the three completed isomers were structurally characterized by single crystal X-ray analysis. In complexations with the isomers, lead(II) perchlorate afforded an infinite one-dimensional (1-D) coordination polymer {[Pb₂(o-bis-L)(µ-ClO₄)₂(ClO4)₂]}_n (1) and a discrete complex [Pb₂(m-bis-L)(CH₃CN)₂(H₂O)₂(ClO₄)₂](ClO₄)₂ (2), both of which are based on the endocyclic binuclear complexes mainly due to the oxophilicity of lead(II) ion. Meanwhile, mercury(II) halides showed an endocyclic dinuclear complex [Hg₂(o-bis-L)I₂][Hg₃I₈] (3) and an exocyclic 1-D coordination polymer [Hg₃(m-bis-L)Br₆]_n (4) because the differences of sulfur-to-sulfur separation in the free ligand isomers might induce the different coordination modes. When a mixture of mercury(II) iodide and copper(I) iodide was used in the reaction with m-bis-L, a heterometallic 1-D coordination polymer [Cu₂Hg₂(m-bis-L)(μ-Cu₂I₂)(CH₃CN)₂I₆]_n (5, see below) was obtained. In 5, exocyclic dicopper(I) complex units are linked by -Hg-Cu₂I₄-Hg- segments to form an infinite zigzag chain. References [1] Siewe, A. D.; Kim, J.-Y.; Kim, S.; Park, I.-H.; Lee, S. S. Inorg. Chem. 2014, 53, 393. [2] Kim, S.; Siewe, A. D.; Lee, E.; Ju, H.; Park, I.-H.; Park, K.-M.; Ikeda, M.; Habata, Y.; Lee, S. S. Inorg. Chem. 2016, 55, 2018. [3] Kim, S.; Lee, S. S. Submitted.