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Construction of Coordination Nanosheets Based on Tris(2,2′-bipyridine)–Iron (Fe2+) Complexes as Potential Electrochromic Materials

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journal contribution
posted on 28.02.2019, 00:00 by Manas Kumar Bera, Taizo Mori, Takefumi Yoshida, Katsuhiko Ariga, Masayoshi Higuchi
The coordination nanosheets (CONASHs) are emerging as a new class of functional two-dimensional materials, which are one of the most active research areas of chemistry and physics in this decade. Despite the success of various structural and functional CONASHs, the development of a new molecular structure to discover alluring functional CONASHs remains challenging. Herein, we report successful preparation of two novel CONASHs (NBP1 and NBP2) through coordination between one of the unexplored molecular frameworks of bis­(2,2′-bipyridine)-based ligands (BP1 and BP2) and Fe2+ ions. Using a liquid–liquid interface as a platform, large-scale thin films of multilayer CONASHs have been prepared without any support, which can be deposited onto any desired substrate. Detailed characterization of the CONASHs using various microscopic and spectroscopic techniques reveals homogeneous and flat morphology of nanometer thickness with the quantitative formation of tris­(2,2′-bipyridine)–Fe2+ complex motifs in the nanosheet frameworks. The color of the films has been tuned from blue to magenta by the suitable molecular design of the ligands. Owing to the insolubility of the CONASH films in any solvent and the presence of redox-active Fe2+, we explore the functionality of these nanostructured thin films deposited on indium tin oxide as electrochromic materials. The CONASHs exhibit color-to-colorless and color-to-color electrochromic transitions with attractive response times, switching stabilities, and coloration efficiencies. Finally, we demonstrate solid-state electrochromic devices of the CONASHs operated at a potential range of +2.5 to −2.5 V, which are electrochemically stable for several switching cycles, suggesting that these CONASHs are potential electrochromic materials for next-generation display applications.