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

Abstract 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.