Preparation of Photoswitchable Polyacrylic Nanocomposite Fibers Containing Au Nanorods and Spiropyran: Optical and Plasmonic Properties

Photoswitchable nanofibers and nanocomposite fibers containing plasmonic nanoparticles have attracted a great deal of interest in optical and plasmonic devices. Herein, photoswitchable poly(methyl methacrylate-co-vinylimidazole-co-spiropyran ethyl acrylate) (MVSP) and its copolymer with butyl acrylate (MBVSP) were prepared via emulsion polymerization, and the corresponding nanofibers (MVSP@NF and MBVSP@NF) and nanocomposite fibers (MVSP/Au@NF and MBVSP/Au@NF) containing AuNRs were fabricated through electrospinning. FTIR and ¹H NMR analyses confirmed the progress of the copolymerization reaction. The morphology of the prepared nanofibers containing AuNRs with an aspect ratio of 2.5 was identified by SEM and TEM techniques. The inclusion of vinylimidazole into the copolymer chains resulted in well-dispersed AuNRs. Photoisomerization studies revealed a higher photochromic efficiency for MBVSP@F (reflective intensity of 37.4%) with respect to MVSP@NF (reflective intensity of 62.5%) because of the greater flexibility of the chains. In addition, the presence of AuNRs in the nanocomposite fibers with high absorptivity intensified the photochromic properties for both samples. The polarization-dependent plasmonic band of AuNRs was switched between 650 and 634 nm through the photoisomerization of nonpolar SP to polar MC reversibly for MVSP/Au@NF. This displacement was just 4 nm for MBVSP/Au@NF, owing to the limited coupling between AuNRs and MC isomers. Besides, the capability of both nanocomposite fibers for reversible optical patterning was investigated by fast write–erase cycles. Enhanced photofatigue resistance in those fibers and the photomodulation of the plasmonic band of AuNRs using SP to MC isomerization revealed their promising potential for optical patterning and on-demand real-time plasmonic devices.