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A 1-D chain-like hybrid coordination polymer [(CuBr)2(bpy)]n(bpy = 2,2′-bipyridine) was first synthesized viaa hydrothermal reaction of copper(I) bromide with 2,2′-bipyridine (bpy). The most fascinating feature of [(CuBr)2(bpy)]nis the unusual six-member-(Cu3Br3)-ring motif. The skeleton of copper bromide combined with bpy in [(CuBr)2(bpy)]nhas not been reported. In addition, research on pyrolysis of [(CuBr)2(bpy)]nwas reported in this paper. Oriented growth of single crystalline Cu(111) flake, which is usually prepared through depositing onto the surface of high-quality metal films (substrates), was synthesized by simply pyrolyzing [(CuBr)2(bpy)]nby adjusting the heating procedures. No capping reagent was induced to simplify the system. Since most of the research of pyrolysis of coordination polymers focuses on the relationship between the structure of precursor and sinter, the results of this paper show how the reaction conditions affect the morphology of the product and give a simple method for the synthesis of a Cu(111) flake, which has wide application in industry. [ABSTRACT FROM AUTHOR]