Mi Ouyang,Pingjing Wang,Wubin Yu,Senbiao Huang,Jingwei Sun,Bin Hu,Xiaojing Lv,Zhiyan Fu,Cheng Zhang
A novel ferrocene-containing compound 6-(3,6-di(thiophen-2-yl)-9H-carbazol-9-yl)hexyl ferrocenecarboxylate (BTC-H-Fc) was synthesized by simple chemical route, and 3,6-di(thiophen-2-yl)-9H-carbazole (BTC) was prepared for comparison. Both of the homopolymers of BTC-H-Fc and BTC were successfully synthesized by electropolymerization and kept the redox activity upon repeated cycling between 0.0 V and 1.4 V. Compared to PBTC which could only showed two colors (yellow and purple), P(BTC-H-Fc) film could exhibit four colors (yellow, awny, purple and indigo-blue) as a consequence of mixing colors of main chain and Fc group. Meanwhile, P(BTC-H-Fc) film presented higher optical contrast of 52% and more excellent coloration efficiency (573.72 cm2 C−1). All the results demonstrate that Fc could be a good choice as a functional group to improve the electrochromic properties of the electrochromic polymers.
A novel triphenylamine (TPA) derivative (E) N-(4-(Diphenylamino)phenyl)- formimidoylferrocene) (TPAFc) containing ferrocene (Fc) unit was designed and synthesized successfully. Theoretical calculation and experimental data show TPAFc possesses higher HOMO energy level and the lower onset oxidative potential compared to TPA monomer . Cyclic voltammetry test demonstrates coupling reaction between TPA units and the formation of an electroactive polymer film during successive scans. This intriguing phenomenon may be ascribed to the multi-step oxidation process and Fc unit plays an important role as charge transport center for electrons moving from TPA units and the surface of the forming oligomer film to the electrode. SEM images indicate PTPAFc film shows the surface morphology of uniform tubular structures, which may largely increase the area of interface between the electrolyte solution and the polymer film. Interestingly, PTPAFc film exhibits reversible multicolor changes switched from neutral transparent color to light orange and blue in fully oxidized state, which are attributed to that the existence of Fc unit brings out multiple redox states. In addition, the polymer film presents excellent electrochromic performances in the aspect of high optical contrast (∼58%), good coloration efficiency (∼130 cm 2 C −1 ) and fast switching time (∼2 s). In view of these excellent features, the developed PTPA derivative is very satisfactory for applications on high-performance electrochromic devices .
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