With the level of molecular complexity of MOCs there is no single 'gold-standard' against which calculations for these systems can be compared. Consequently, it seemed prudent to investigate different DFT methods (with both geometry optimisation and SPEs). PBE0, B3LYP, B97D3, and HSE methods were all used to probe the equilibrium between homoleptic and heteroleptic species with the assemblies of 1 DBF and 2 Py . PBE0, B3LYP and B97D3 showed qualitatively the same storythe homoleptic systems were favoured in all cases (Table ). This remained true when using the SCXRD structure of [Pd2(2 Py )4] 4+ as the starting geometry for the DFT-optimised structure; indeed, this was universally ~20 kJ mol -1 more stable than the stk-generated structure.