Mrinalini Madoori, Pathak Sushil Swaroop, Achary B Shivaprasad, Panchakarla Leela S, Prasanthkumar Seelam
Polymers & Functional Materials Division, CSIR-Indian Institute of Chemical Technology (IICT), Tarnaka, Hyderabad-, 500007, Telangana, India.
Academy of Scientific and Innovation Research (AcSIR), New Delhi, India.
Chem Asian J. 2019 Feb 15;14(4):537-541. doi: 10.1002/asia.201801794. Epub 2019 Jan 30.
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 (H TTP-Fc and ZnTTP-Fc) undergo distinct proton/anion binding mechanism in CHCl during bulk electrolysis at applied voltage of 1.4 V to give [H 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 H 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.
电压刺激的氧化还原活性材料在有机电子学和传感器技术领域受到了广泛关注。这类刺激响应材料能引发晶体纳米结构的形成，并有助于设计出迄今未知的高效智能设备。在此，我们报告，在1.4 V外加电压下进行本体电解时，游离碱和金属四甲苯基卟啉连接的二茂铁衍生物（H TTP-Fc和ZnTTP-Fc）在CHCl中经历不同的质子/阴离子结合机制，生成[H TTP-Fc] Cl和H [(Cl)ZnTTP-Fc]，随后通过甲醇蒸汽扩散（MVD）方法形成纳米球和结晶二维纳米片，这由扫描电子显微镜（SEM）和透射电子显微镜（TEM）图像证实。此外，X射线衍射分析表明，质子化的H TTP-Fc聚集体呈现非晶态性质，而H [(Cl)ZnTTP-Fc]通过纳米片的逐层排列呈现晶体性质，这种排列由π-π堆积和离子偶极相互作用辅助。
