Across both triamines, the same energetic trend is observed for the M4L4 structure (A2 > A3 > A4 and B2 > B3 > B4). The differences between 3 and 4 are relatively small, but clearly suggest these are more energetically favorable than structures incorporating aldehyde 2. This trend broadly agrees with the experimental outcomes from the automated screen discussed above, in relation to their reactivity and successful formation of a self-assembled species. We infer that increased steric hinderance around the metal center leads to less favorable assembly outcomes due to their higher relative energies. However, while aldehyde 4 in the tetrahedral topology was the most energetically favored across the family, it typically led to the formation of a mixture of species including a M4L4 species (Table ), and therefore formation is not solely dependent on the energetics of the M4L4 topology. Due to the complexities of the M2X3 species (where X = L or I) and the fact that helicate structures may form based on different chirality at each metal center resulting in three configurations (homochiral helicates (ΔΔ and ΛΛ), or achiral mesocates (ΔΛ)), further modelling of these systems was not carried out.