Electrochromism in Isoreticular Metal-Organic Framework Thin Films with Record High Coloration Efficiency

The power of isoreticular chemistry has been widely exploited to engineer metal-organic frameworks (MOFs) with fascinating molecular sieving and storage properties but is underexplored for designing MOFs with tunable optoelectronic properties. Herein, three dipyrazole-terminated XDIs (X = PM (pyromellitic), N (naphthalene), or P (perylene); DI = diimide) with different lengths and electronic properties are prepared and employed as linkers for the construction of an isoreticular series of Zn-XDI MOFs with distinct electrochromism. The MOFs are grown on fluorine-doped tin oxide (FTO) as high-quality crystalline thin films and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Due to the constituting electronically isolated XDI linkers, each member of the isoreticular thin film series exhibits two reversible one-electron redox events, each at a distinct electrochemical potential. The orientation of the MOFs as thin films as well as their isoreticular nature results in identical cation-coupled electron hopping transport rates in all three materials, as demonstrated by comparable apparent electron diffusion coefficients, D-e(app). Upon electrochemical reduction to either the [XDI](center dot-) or [XDI](2-) state, each MOF undergoes characteristic changes in its optical properties as a function of linker length and redox state of the linker. Operando spectroelectrochemistry measurements reveal that Zn-PDI@FTO (PDI = perylene diimide) thin films exhibit a record high coloration efficiency of 941 cm(2) C-1 at 746 nm, which is attributed to the maximized Faradaic transformations at each electronically isolated PDI unit. The electrochromic response of the thin film is retained to more than 99% over 100 reduction-oxidation cycles, demonstrating the applicability of the presented materials.

Automated summary

The power of isoreticular chemistry was leveraged to design metal-organic frameworks (MOFs) with tunable optoelectronic properties. XDI linkers with different lengths and properties were used to construct a series of Zn-XDI MOFs, which exhibited distinct electrochromic properties. The thin films of these MOFs were grown on FTO substrates and characterized by XRD and SEM. The MOFs showed reversible redox events and changes in optical properties, depending on the linker length and redox state. Among them, Zn-PDI@FTO exhibited a record high coloration efficiency and excellent stability, suggesting its potential for practical applications.