Copper(I) bromide complexes of two 15-memberd O2S2-macrocycles with different sulfur-to-sulfur separations: dimer and one-dimensional coordination polymer

Abstract

A comparative study on the exo-coordination-based networking of 15-membered O2S2-macrocycle isomers (L1 and L2) induced by interdonor distances is reported. In copper(I) bromide complexation, the isomer L1 incorporating a shorter sulfur-to-sulfur separation yielded a discrete dimer complex [(μ-Cu2Br2)(L1)2] (1) in which two macrocycles are bridged by a Cu2Br2 square cluster. While, the reaction of copper(I) bromide with the isomer L2 incorporating a longer sulfur-to-sulfur separation afforded a double-stranded one-dimensional (1D) coordination polymer {[(μ4-Cu2Br2)(L2)2]·CH2Cl2}n (2) as a kinetic product which converted to [(μ4-Cu2Br2)(L2)2]n (3) with different 1D connectivity pattern as a thermodynamic product. The results indicate as examples of programmed self-assembly that the proposed interdonor distances and the ligand isomerism play decisive roles cooperatively in the topologies of the supramolecular products via different coordination modes.