Peripheral Modifications of meso-Hydroxyporphyrins: Formation of π-Electronic Anions and Ion-Pairing Assemblies.

Phenyl groups were introduced at the ß-positions proximal to the meso-hydroxy moiety in hydroxyporphyrin NiII complexes by oxidized BINAP PdII complexes. Ion-pairing assemblies of deprotonated π-electronic anions, anionic site of which was stabilized by the introduced phenyl moieties with a bulky cation, were formed. They showed charge-by-charge assemblies, assembly modes of which were modulated by the anionic building units.