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Electrochemical Deposition of Azobenzene-Containing Network Films with High-Contrast and Stable Photoresponse.

To fabricate stable photoresponsive films and devices, a cross-linked network that firmly fixes the position of the chromophores is an ideal structure, because aggregation and/or phase separation effects of chromophores in matrix can be effectively restrained in such robust films. Herein, the in situ electrochemical deposition (ED) of azo-based precursors containing multielectroactive carbazole units is utilized to construct highly cross-linked photoresponsive films. 2-(4-(9,9-bis(6-(9H-carbazol-9-yl)hexyl)-9H-fluoren-2-yl)phenyl)-1-(4-(9,9-bis(6-(9H-carbazol-9-yl)hexyl)-9H-fluoren-7-yl)phenyl)diazene (BFCzAzo) with high solvability in electrolyte solution, high electroactivity, and highly efficient photoresponsive ability is synthesized by Suzuki coupling reaction as a kind of ED precursor. A highly cross-linked photoresponsive film is fabricated by ED method using BFCzAzo as ED precursor. The film can be patterned in large area by irradiation with interfering laser beam (355 nm), and the pattern possesses excellent thermal stability and insoluble ability in both organic and inorganic solvents. Excellent reversibility of the nanostructures is demonstrated by irradiation with 550 nm laser beam.