Versatile coordination groups in the designed DSDC4−ligand dictate rich potential coordination modes that mayfacilitate the formation of versatile Cu−O moieties and lead tovarious polymeric complexes. As for a systematic comparison,complexes 2 and 3 with additional different auxiliary ligandshave also been synthesized and their photocatalytic activitieshave been studied and compared with that of complex 1regarding the same reaction.