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Voltage Stimulated Anion Binding of Metallo-Porphyrin Induced Crystalline 2D Nanoflakes
摘要： Voltage stimulated redox active materials received significant attention in the field of organic electronics and sensor technology. Consequently, such stimuli responsive materials triggered the formation of crystalline nanostructures facilitates the design of efficient smart devices hitherto unknown. Thus, we reported 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 followed by nanospheres and crystalline 2D nanoflakes formation via MVD approach. Cyclic voltammetry and UV-Vis absorption studies of H2TTP-Fc and ZnTTP-Fc revealed the cation (H+)/anion (Cl-) binding affinity towards free ‘N’ atoms and Zn leads [H4TTP-Fc]+Cl- and H+[(Cl)ZnTTP-Fc]- thereby improvement in current and charge generation compared to initial state. SEM and TEM images revealed the nanospheres and 2D nanoflakes with average diameter of 50 – 200 nm and 0.2 - 1 μm. x-ray diffraction analysis suggest that protonated H2TTP-Fc aggregates exhibit amorphous nature, while H+[(Cl)ZnTTP-Fc]- revealed crystalline nature from layer-by-layer arrangement of nanoflakes assisted by π-π stacking and ion-dipole interactions. Hence, voltage responsive anion binding of metallo-porphyrins unique observation offer remarkable design of smart organic materials for sensors and biological applications.
关键词： anion binding,crystalline nanoflakes,metallo-porphyrin,self-assembly,bulk electrolysis
更新于2025-09-23 15:23:52
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Bulk Electrolysis of Zn-Phthalocyanine Unveils Self assembled Nanospheres via Anion Binding
摘要： Stimuli repsonsive π-conjugated macrocyclic systems has shown significant attention in organic electronics, however, amongst them, porphyrins and phthalocyanines unveiled remarkable growth towards materials and biological applications. Herein, we report bulk electrolysis of Zn-phthalocyanine system (ZnPc-OMe) under potential difference of 1.5 V in chloroform results anion binding mechanism directs the formation of self-assembled nanospheres by diffusion controlled approach. Electrochemical and UV-Vis absorption studies of ZnPc-OMe suggest that anion (Cl-) binding ability towards ‘Zn‘ whilst applied potential leads to the formation of H+[(Cl)ZnPc-OMe]- promote the enhanced current and charge generation. Microscopic analysis revealed that ZnPc-OMe and H+[(Cl)ZnPc-OMe]- exhibit the nanosheets and spheres with an average diameter of 0.5 - 1 μm and 300 – 500 nm, respectively. Powder X- ray diffraction analysis and raman spectra revealed the changes in crystalline phase transitions via ion-dipole and p -p stacking interactions. Thus, these unique features are atypical for phthalocyanine derivative hitherto unknown.
关键词： bulk electrolysis,Zn-phthalocyanine,voltage stimulus,anion binding,self-assembled nanospheres
更新于2025-09-23 15:19:57