Hierarchically Organized Cocrystal of Tetra‐Anionic Porphyrin and Di‐Cationic Viologen: Ion Conformations, Supramolecule Interactions, and Porphyrin Arrays

Abstract

Ionic co-assembly of tetra-anionic porphyrins has been extensively researched in the construction of hierarchically organized architectures with potential application value in organic semiconductors, sunlight catalysts and supramolecular chirality systems. However, such architectures are difficult to grow to a size suitable for single-crystal X-ray diffraction (SCXRD); the lack of single-crystal structures of these architectures leads to challenges in gaining deeper comprehension about that. This study reports a hierarchically organized cocrystal of meso-tetra(4-sulfonato-phenyl)-por-phyrin (TSPP 4À ) and N, N'-diethyl-viologen (DEV 2 + ), wherein wave-like and saddle-like TSPP 4À ions co-aggregate at a stoichiometric ratio of 1 : 2 to form unique porphyrin arrays; the spectrum characteristics and calculated coulombic exciton coupling energy show that these porphyrin arrays are Jaggregates. We prove that the distortion of porphyrin ring of TSPP 4À strongly correlates with the deflection of its phenyl groups. The crystal comprises six different ionic conformations, and the multiplicity of ionic conformation leads to intricate supramolecular interactions.