Supramolecular polymers from coronene multicarboxylates and multipyridiniums in water stabilized by ion-pair attraction and aromatic stacking

Coronene tatracarboxylate CTC and octacarboxylate COC have been utilized to interact with dipyridinium DP and tetrapyridinium TP to assemble new supramolecular polymers in water. It was revealed that CTC interacted with DP and TP in 1:2 and 1:1 stoichiometry, whereas the binding between COC and DP and TP occurred in 1:4 and 1:2 stoichiometry. For all complexations, DP and TP behaved as a uni- or siamesed tweezers to clamp CTC or COC driven by ion-pair attraction and hydrophobically driven stacking of the pyridinium and coronene units. Apparent association constants were determined to be 33400 (CTC/DP), 9400 (COC/DP), 151000 (CTC/TP), and 89000 (COC/TP) M^?1, respectively, for the single clamping binding motif of the four complexes. Dynamic light scattering and isothermal titration calorimetric experiments supported that the mixtures of CTC and COC with TP formed linear and cross-linked supramolecular polymers.