It was previously established that the flexible tetraimidazolium macrocycle cyclo[2](2,6-bis(1H-imidazol-1-yl)pyridine)[2](1,4-dimethylenebenzene) (1(4+)) is capable of stabilizing higher order supramolecular structures via both anion and cation recognition. Described herein is a set of structurally related imidazolium macrocycles (2(4+)-4(4+)) that contain modified central cores. The flexible nature of these new constructs is highlighted by the isolation of several independent crystalline forms for the same basic structure. Each of the individual receptors was found to bind the 2,6-naphthalenedicarboxylate dianion and to stabilize the formation of self-associated structures. The observed binding modes and resulting supramolecular organizational forms were found to differ dramatically depending on the nature of the bridging group present in the imidazolium macrocycle. This finding was established by solution studies involving, inter alia, one- and two-dimensional (H-1, H-1-H-1 COSY, DOSY, and NOESY) NMR spectroscopy as well as electrospray ionization mass spectrometry. The new systems in this report serve to expand the available "tool box" for the construction of complex self-assembled materials while providing insights into the determinants that regulate the formation of specific supramolecular structures from flexible receptors capable of adopting multiple stable conformations.