A methacrylate-functionalized 9,9′-spirobifluorene trimer is copolymerized with methylmethacrylate (MMA). The photophysical characterization of this copolymer using pump-probe studies, in solution, as films and in plastic optical fibers (POFs) demonstrates that it shows interesting photonic properties for data communication such as high-stimulated emission cross section (σSE = 2.5 × 10−16 cm2), good thermal, and optical stability, the ability to perform all-optical ultrafast switching, and low attenuation when doped into POFs. In addition, the material shows interesting optically induced conformational control in solution and the studies demonstrate the surprising result that intrachain polaron pairs can be generated even in well-isolated 3-unit oligomers. Although the material is not yet soluble enough in MMA to create highly efficient photonic devices and the gain spectrum is not optimized to overlap with the region of low attenuation in polymethylmethacrylate POFs, these studies are a good starting point to further optimize copolymers for incorporation into POF networks. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010
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