Highly Stable and Rapid Switching Electrochromic Thin Films Based on Metal-Organic Frameworks with Redox-Active Triphenylamine Ligands.

Metal-organic frameworks (MOFs), known for their tailorable porous structures and large specific surface areas, are appealing for electrochromic applications as their abundant pores may greatly benefit the charge transport required for electrochromic switching. Herein, for the first time, a simple, scalable, and cost-effective electrochemical deposition method for fabrication of high-performance and durable MOFs-based electrochromic films with redox-active ligands was developed. The fabricated film can achieve rapid switching speed (both coloration and bleaching time <5 s) because the inherent cavities of the MOFs greatly facilitate ion insertion and extraction. In addition, the film constructed with optimized parameters shows a high optical contrast of 65%@700 nm and can be stably switched for 1000 cycles with <5% contrast attenuation, which is by far the best cycling performance for MOFs-based electrochromic materials ever reported. Furthermore, our method enables the scalable preparation of large-area MOFs-based electrochromic thin films without using large high-pressure reaction vessels, and the as-prepared film in this work could be switched well between colored and bleached states. This new method, therefore, opens up a new avenue to broaden the use of MOFs-based thin films for electrochromic applications.