Four color electrochromism (yellow, magenta, blue, and navy) has been achieved in Cr(iii)-based metallo-supramolecular polymers (polyCr), which were synthesized by 1 : 1 complexation of Cr ions and 1,4-di[[2,2':6',2''-terpyridin]-4'-yl]benzene (L). The polymer structure was determined by X-ray absorption fine structure (XAFS) measurement and X-ray photoelectron spectroscopy (XPS). The molecular weight of polyCr was calculated as 3.2 × 10 Da using right angle light scattering (RALS). The EXAFS fitting indicated that the bond distances of Cr-N are 2.020 Å and 2.208 Å. A film of polyCr shows multi-color electrochromism (EC) or absorption: a sharp peak at 380 nm at 0 V Ag/Ag (yellow), a sharp peak at 510 nm and a broad peak at 800 nm at -0.6 V Ag/Ag (magenta), a broad peak at 610 nm and between 700-900 nm at -1.2 V Ag/Ag (blue), a broad peak between 450-900 nm at -1.8 V Ag/Ag (navy). The transmittances change (Δ), the switching times for coloring and bleaching ( , ) and the coloration efficiency ( , ): [Δ, ( , ), ( , )] were [39.2%, (5.56 s, 1.39 s), (169 cm C, 230 cm C)] at 510 nm between -0.6 and 0.2 V Ag/Ag, [67.0%, (6.93 s, 2.52 s), (138 cm C, 172 cm C)] at 610 nm between -1.2 and 0.2 V Ag/Ag, [86.1%, (6.80 s, 3.03 s), (167 cm C, 134 cm C)] at 780 nm between -1.8 and 0.2 V Ag/Ag, respectively, during the cycles. The durability experiment indicates that polyCr shows an EC property for at least 100 cycles.

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