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 i π – i π 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 i π – i π 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.