Monomeric heteroleptic copper complexes (1–4) on reaction with diphenyl phosphate yielded dinuclear phosphate bridged copper(II) complexes (5–7) and a tetra-nuclear dihydroxo bridged complex (8). Interestingly, the resultant complexes contain only one type of ligand even though the starting complexes contain two different ligands. This supports the ligand expulsion when the phosphodiester interacts with the heteroleptic complexes. All the phosphate bridged complexes were well characterized including single crystal XRD. The complexes exhibit intra-antiferromagnetic interactions as supported by SQUID magnetic data.