Coordination behaviors of the bis-thiamacrocycle isomers incorporating a biphenyl subunit exhibiting different rotating barriers are reported. A mixture of region-isomers L1 and L2 was synthesized via the corresponding one-pot coupling reactions of 3,3',5,5'-tetrakis(bromomethyl)biphenyl with 3,6-dioxa-1,8-octanedithiol and separated using a column chromatography. L1 reacts with copper(I) halides to afford an isostructural 2D polymeric products, [(Cu2X2)(L1)]n (1a: X=Cl, 1b: X=Br, 1c: X=I), in which the macrocycles are linked by square-type Cu2I2 clusters via an exocyclic coordination mode. Meanwhile, reaction of L2 with CuI afforded a 2D polymeric network, {[(Cu2I2)(L2)].CH2Cl2}n (2), doubly linked by the Cu2I2 clusters with different connectivity pattern. The topological analysis of 1 and 2 shows sql and 4,4L1 topologies, respectively. |
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