All combinations with 1 Ph and 1 Th only showed formation of homoleptic assemblies (ESI section S3). The mixture of 1 DBF and 2 Th gave three distinct species (Fig. Thus [Pd2(1 DBF )2(2 Th )2] 4+ appeared to form as a kinetic product, although it could not be ruled out that the difference in energy with the homoleptic systems were very small. The combination of 1 DBF with 2 Py /2 Ph gave NMR spectra indicating clean formation of single species distinct from the homoleptic assemblies (Fig. and, respectively), with a 1:1 ratio of the two ligands. DOSY showed all ligand signals diffused at the same rate, indicative of being part of a single assembly (Fig. and). Through-space interactions between the ortho-pyridyl/isoquinolyl protons of ligands 1 and 2 were observed by nuclear Overhauser effect spectroscopy (NOESY; Fig. ).