Summary: Porphyrin–AuIII complexes were found to act as π-electronic cations, which can combine with various counteranions, including π-electronic anions. Single-crystal X-ray analyses revealed the formation of assemblies with contributions of charge-by-charge and charge-segregated assemblies, depending on the geometry and electronic state of the counteranions. Porphyrin–AuIII complexes possessing aliphatic alkyl chains formed dimension-controlled ion-pairing assemblies as thermotropic liquid crystals, whose ionic components were highly organized by π–π stacking and electrostatic interactions. : Chemistry; Supramolecular Chemistry; Electronic Materials Subject Areas: Chemistry, Supramolecular Chemistry, Electronic Materials
