Porphyrin Au^III Complexes Bearing Bulky <i>Meso</i>-Substituents as Building Blocks of Stacking-Frustrated Ion-Pairing Assemblies

Stacking-frustrated ion-pairing assemblies comprising bulky charged π-electronic systems hinder efficient stacking of π-planes, owing to spatial constraints. In this study, porphyrin Au^III complexes bearing bulky aryl groups induce a spatial barrier that significantly separates the charged π-planes. With weakly coordinating anions, stacking frustration arises between the positively charged porphyrin π-planes, whereas π-electronic anions cause cation-anion stacking frustration. These results highlight the importance of both steric and electronic factors in the π-plane organization.