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1 December 1997Low-energy photophysics of phenylene-based strapped copolymers
We present the absorption and emission properties of the phenylene-based copolymers, poly(pyridyl vinylene-phenylene vinylene) (PPyVPV), poly(thienylene p-phenylene) (PTpP) and poly(dithienylene p-phenylene) (PDTpP), which incorporate `straps' to bridge the 2 and 5 positions of the phenyl rings. The absorption and luminescence properties of the PPyVPV polymers are morphology dependent. The absorption maxima are at approximately 3.0 eV, with films having absorption edges that tail into the IR. The photoluminescence (PL) spectra are red shifted for films compared to solutions and powders, with the presence of smaller red shifted photoluminescence for the PPyVPV polymers with straps. A low lying absorption maximum occurs at 2.7 eV for both solution and film forms of PTpP. The (PL) spectra also are similar with features at 2.1 eV and 2.3 eV assigned to the 0-1 and 0-0 vibronic transitions, respectively. Solution and film photoluminescence excitation (PLE) profiles qualitatively follow the absorption spectra. Two low energy absorption maxima are seen for PDTpP at 2.8 eV and 3.2 eV with a single feature observed at 2.3 eV for the PL. The PLE spectra in PDTpP also follow the corresponding absorption features in both solution and film samples. Time resolved PL studies (ps to ns) show that there is smaller spectral shift for the films of polymers with straps, showing the importance of reduced aggregation. Steady state photoinduced absorption studies (ms) indicate the roles of both polarons and triplet excitons in these systems.
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Arthur J. Epstein, N. V. Piskun, Ilia V. Lebedenko, Scott W. Jessen, Terry L. Gustafson, Dian-Kui Fu, Timothy M. Swager, "Low-energy photophysics of phenylene-based strapped copolymers," Proc. SPIE 3145, Optical Probes of Conjugated Polymers, (1 December 1997); https://doi.org/10.1117/12.279284