Supramolecular xerogel films as multicolor photoluminescent materials are ideal for applications in optical devices, such as photochromic smart windows and LEDs. Therefore, a blue-fluorescence supramolecular hydrogel has been successfully constructed from α-CD and benzimidazole derivatives (WCB) through host–guest interactions with supramolecular assembly-induced emission (SAIE) properties. The hydrogel WCB-α-CD enables the coordination with different lanthanide metal ions (Ms) to form supramolecular nanoparticles with spherical-like morphology, thus rendering the xerogel films for lanthanide luminescence. The xerogel films WCB-α-CD@Ms, with high luminous transmittance (T > 90%) and multicolor photoluminescence, exhibit a promising potential for smart optical film materials utilizing supramolecular assembly.

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