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 (H2 TTP-Fc and ZnTTP-Fc) undergo distinct proton/anion binding mechanism in CHCl3 during bulk electrolysis at applied voltage of 1.4 V to give [H4 TTP-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 H2 TTP-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.