Multidirectionally Controlled Arrangement via Ion‐Pairing Assembly of Amphiphilic Charged π‐Electronic Systems

Charged π-electronic systems with hydrophilic substituents form lyotropic chromonic liquid crystals (LCLCs) through charge-by-charge assembly driven by ⁱπ-ⁱπ interactions and hydrophobic effects. In this study, the positions and numbers of triethylene glycol (TEG) chains in amphiphilic porphyrin Au^III complexes are tuned to control their assembly modes. In combination with the π-electronic anion pentacyanocyclopentadienide (PCCp^-), 5,15-TEG-aryl-substituted porphyrin Au^III complex generates lamello-columnar (Lam_col) phases via amphiphilic ⁱπ-ⁱπ interactions and proximal interactions at the unsubstituted sites. In the presence of water, the Lam_col phases, with lateral hydrophobic effects, exhibit transitions to nematic sheet (N_sheet) and isotropic sheet (Iso_sheet) phases depending on water content and temperature. The Lam_col phases align macroscopically under a magnetic field, and scanning transmission electron microscopy (STEM) reveals monolayer sheet structures as key components of the LCLCs. These findings demonstrate a controllable charge-by-charge strategy for designing π-electronic LCLCs with tunable structural and phase behaviors.