Voltage Stimulated Anion Binding of Metalloporphyrin‐induced Crystalline 2D Nanoflakes

Voltage‐stimulated redox‐active materials have received significant attention in the field of organic electronics and sensor technology. Such stimuli‐responsive materials trigger the formation of crystalline nanostructures and facilitate the design of efficient smart devices hitherto unknown. Herein, we report that free‐base and metallo‐tetratolylporphyrin‐linked ferrocene derivatives ( H₂TTP ‐ Fc and ZnTTP ‐ Fc ) undergo distinct proton/anion binding mechanism in CHCl₃ during bulk electrolysis at applied voltage of 1.4 V to give H₄TTP ‐ Fc]⁺Cl^? and H⁺ (Cl)ZnTTP ‐ Fc]^? followed by nanospheres and crystalline 2D nanoflakes formation, confirmed by SEM and TEM images, by methanol vapor diffusion (MVD) approach. Moreover, X‐ray diffraction analysis suggest that protonated H₂TTP ‐ Fc aggregates exhibit amorphous nature, whereas H⁺ (Cl)ZnTTP ‐ Fc]^? depict crystalline nature from layer‐by‐layer arrangement of nanoflakes assisted by π–π stacking and ion‐dipole interactions.