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• W1979852760 abstract "The rate of photoinduced intramolecular charge separation (CS) kCS in polymer solids was evaluated by the fluorescence lifetime measurement over a temperature range 100−400 K. Nine kinds of carbazole−spacer−acceptor dyads (Cz−S−A) were embedded in a series of poly(alkyl methacrylate) films with various glass transition temperatures (Tg's). The rate kCS of Cz−S−A increased above Tg or melting temperature Tm of each polymer solid. The temperature dependence of kCS in a poly(butyl methacrylate) glassy solid was in agreement with that of the dielectric constant at higher frequencies, indicating that orientational motions faster than the CS rate are effectively coupled to the CS event. The effective dielectric constant (ε‘) for CS was evaluated with a novel fluorescent probe of carbazole−terephthalate cyclophane (Cz−TP). The free energy gap and temperature dependence of kCS were well explained by a single quantum mode electron transfer (ET) formula with ε‘ rather than a static dielectric constant εS in a poly(butyl methacrylate) glassy solid. In conclusion, CS in poly(alkyl methacrylate)s is promoted above Tg or Tm by enhancement in orientational motions of ester groups with a relaxation time comparable to the CS event." @default.
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• W1979852760 date "2004-09-25" @default.
• W1979852760 modified "2023-10-16" @default.
• W1979852760 title "Photoinduced Intramolecular Charge Separation in Poly(alkyl methacrylate) Solids Studied by Using a Fluorescent Polarity Probe" @default.
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• W1979852760 doi "https://doi.org/10.1021/jp047354n" @default.
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