Gradient-corrected density functional theory calculations have resulted in geometry-optimized structures for a series of six large dirhodium complexes that are important synthetic intermediates in the weak-link synthetic approach. Analysis of these computed structures and their electronic makeup (including natural localized molecular orbital (NLMO) bond order analysis, natural population analysis (NPA) atomic charges, atoms-in-molecules (AIM) calculations, single-point energy analysis, and calculated vibrational frequency analysis) has provided insight into subtle secondary ligand-ligand effects, which lead to product selection in the first step of this synthetic strategy toward supramolecular coordination complexes.