Geometric analysis of ligand libraries was successful in rapidly identifying pairs of complementary ligands for integrative self-assembly, demonstrating the viability of this simple approach. For ligands 1, with limited conformational freedom, relatively inexpensive xTB calculations were also able to mirror experimental results in identifying products of self-assembly. Extending this approach to more flexible ligands, however, presented significant challenges in predicting the topology of the thermodynamically most stable assemblies. The use of 'static' approximations of dynamic structures and single-molecule models (i.e. without explicit anions/solvent) likely contributed to the lack of success in using computed energy balances to predict self-assembly outcomes.