Two novel macromolecular constitutional isomers have been self-assembled from previously unreported terpyridine ligands in a three-component system. The terpyridine ligands were synthesized in high yields via a key Suzuki coupling. Restrictions of the possible outcomes for self-assembly ultimately provided optimum conditions for isolation of either a molecular bowtie or its isomeric butterfly motif. These isomers have been characterized by ESI-MS, TWIM-MS, H-1 NMR, and C-13 NMR. Notably, these structural isomers have remarkably different drift times in ion mobility separation, corresponding to different sizes and shapes at high charge states.