Synchronous Electrochromism and Electrofluorochromism in a Zirconium Pyrenetetrabenzoate Metal-Organic Framework

0585656 - ÚFCH JH 2025 RIV DE eng J - Journal Article
Guerraf, Abdelqader El - Zeng, W. - Mantel, Arthur - Benhsina, Elhassan - Chin, J. M. - Shiozawa, Hidetsugu
Synchronous Electrochromism and Electrofluorochromism in a Zirconium Pyrenetetrabenzoate Metal-Organic Framework.
Advanced Electronic Materials. (2024). ISSN 2199-160X. E-ISSN 2199-160X
R&D Projects: GA ČR(CZ) GA19-15217S; GA ČR GA22-23407S; GA MŠMT 8F21010
Institutional support: RVO:61388955
Keywords : systems * density-functional theory * electrochromism * electrofluorochromism * fluorescence spectroscopy * metal-organic frameworks * nu-1000 * spectroelectrochemistry
OECD category: Physical chemistry
Impact factor: 6.2, year: 2022
Method of publishing: Open access
https://onlinelibrary.wiley.com/doi/10.1002/aelm.202300854

Redox-active materials that exhibit both electrochromism and electrofluorochromism have great potential as multifunctional elements in optoelectronics. Here, in situ spectroelectrochemistry is presented on NU-1000, a zirconium pyrenetetrabenzoate metal-organic framework. A thin film of NU-1000 exhibits reversible color changes between light yellow and dark blue when subjected to an alternating electrochemical potential. In situ fluorescence excitation-emission spectral mapping elucidates a dominant blue emission of highly fluorescent electrochromic NU-1000 that is being quenched via an oxidation reaction. Density-functional theory calculations reveal the forbidden optical transition between the singly occupied molecular orbital (SOMO) and the lowest unoccupied molecular orbital (LUMO) in the oxidized linker as the cause of the quenching. Double potential step chronoamperometry measures response times as fast as a dozen seconds and excellent switching stability over 500 cycles without noticeable attenuation of the color contrast. These findings provide valuable insight into the electrochromism and electrofluorochromism in metal-organic frameworks, offering exciting opportunities for developing advanced multifunctional porous materials with potential applications in optoelectronics and sensing.
Permanent Link: https://hdl.handle.net/11104/0353333