In addition to the silver(I) complexes of regioisomers (o-bis-L and (m-bis-L) of bis-O₂S₂-macrocycle,¹ borderline (Pb²⁺) and soft (Hg²⁺ and Cu⁺) metal ions are employed to investigate the isomer effect.^2,3 CuI reacts with o-bis-L (W-binding site) and m-bis-L (U-binding site) to afford 1-D CPs, [(Cu₄I₄)(o-bis-L)]_n (1) and [(Cu₂I₂)(m-bis-L)]_n (2) linked by a spacious [Cu₄I₄] cluster and a smaller [Cu₂I₂] cluster, respectively, due to the different exo-binding sites. This result illustrates the adaptive cluster formation through the binding site design. Lead(II) perchlorate afforded a 1-D CP {[Pb₂(o-bis-L)(ClO₄)₂(ClO₄)₂]}_n (3) and a discrete complex [Pb₂(m-bis-L)(CH₃CN)₂(H₂O)₂(ClO₄)₂](ClO₄)₂ (4), in which both are based on the endocyclic binuclear complexes due to the oxophilicity of lead(II). Meanwhile, mercury(II) halides showed an endocyclic dinuclear complex [Hg₂(o-bis-L)I₂][Hg₃I₈] (5) and an exocyclic 1-D CP [Hg₃(m-bis-L)Br₆]_n (6) because of the different S…S separation in the two isomers. A mixture of mercury(II) iodide and copper(I) iodide afforded a heterometallic 1-D CP [Cu₂Hg₂(m-bis-L)(Cu₂I₂)(CH₃CN)₂I₆]_n (7) in which the exocyclic dicopper(I) complex units are linked by -Hg-Cu₂I₄-Hg- segments to form a 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.; Siewe, A. D.; Lee, E.; Ju, H.; Park, I.-H.; Jung, J. H.; Habata, Y.; Lee, S. S. Cryst Growth Des. 2018, 18, 2424.