A series of photochromic hybrid films were prepared through entrapping Dawson type tungsten heteropolyoxometallates (P2W18O626-) and molybdenum heteropolyoxometallate (P2Mo18O626-) into polyacrylamide matrix. FTIR results showed that the Dawson geometry of heteropolyoxometallates is still preserved inside the composites and strong coulombic interaction is built between heteropolyoxometallates and polyacrylamide via hydrogen bonding. Irradiated with ultraviolet light, the transparent films change from colorless to blue and show reversible photochromism. The bleaching process occurs when the films are in contact with air or O2 in the dark. The molybdenum heteropolyoxometallate hybrid film has higher photochromic efficiency and slower bleaching reaction than tungsten heteropolyoxometallate hybrid film. ESR results indicated that polyacrylamide is a hydrogen donor and the photoreduced process is in accordance with the radical mechanism.
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