To expand the chemical space being explored, however, it was desirable to assume no a priori structural information, allowing analysis of ligands for which experimental self-assembly data are ambiguous or unknown. As a preliminary exploration, geometry-optimised structures and SPEs (GFN2-xTB) were calculated for [Pdn1 DBF 2n] 2n+ assemblies of common PdnL2n cage topologies (n = 2, 3, 4, 6, 12 and 24). Gratifyingly, the lowest energy structure from these was identified as the Pd6L12 architecture that has previously been shown to form experimentally (Fig. ). This approach also successfully predicted the experimentally observed Pd12L24 topology for 1 Ph , and Pd24L48 for 1 Th , although the purported thermodynamic Pd30L60 product for the latter appeared less stable (Fig. ). It is noted that implicit solvent was required within the model to obtain results congruent with experimental data, highlighting the importance of identifying essential factors for useful computational modelling whilst omitting those that increase expense without notable benefit. For the assemblies of ligands 2, initial computational exploration was limited to Pd2L4 structures as these species had been detected by various techniques (MS or SCXRD) for all four ligands, and the precise structure of possible Pd3L6 assemblies remained ambiguous. All four xTBoptimised structures and SPEs were calculated using the approach outlined above.