In this study, we have developed a new synthetic strategy to construct Ln heterobimetallic complexes, which takes a hybrid approach using both thermodynamic and kinetic control over speciation. Individual reagents were designed using the ancillary ligands to fulfil two purposes: 1) to be kinetically inert to redistribution under reaction and spectroscopic conditions, and 2) to tune the coordination properties of the Ln to thermodynamically predispose binding to one of the two different sites of an asymmetric bridging ligand. By tailoring the reagents in this way to a bridging ligand with desirable redox activity (pd), we successfully incorporated such a ligand in Ln heteromultimetallic complexes for the first time.