Abstract
Emission and absorption spectra of a polyester having pyrene and N,N-dimethylaniline groups (I) were studied in 2-methyltetrahydrofuran (MTHF) between room temperature (r.t.) and 77 K and the results were compared with a series of model compounds (II, III, and IV). The following important results were obtained: i) I emits fluorescence from excited EDA (electron donor acceptro) complex (λmax≍440 nm) in a glassy matrix below ∼90 K while II hardly does so. ii) Exciplex emission by I at r.t. decreases with lowering temperature and the locally excited state of pyrene alone is observed at an intermediate temperature region, iii) EDA emission relative to pyrene emission is intensified by increasing the degree of polymerization (DP) of I whereas the concentration effect is not observed indicating that intrapolymer EDA complexes are formed with possible non-neighboring group participation, iv) The absorption spectrum of I at 77 K is much broader than that of II in support of EDA complex formation by I. v) In accordance with the results of absorption spectroscopy, the excitation spectrum monitored at 440 nm at 77 K is broader than that monitored pyrene emission. This is a good indication that the origin of absorption spectrum broadening is relevant to the EDA emission. Since these findings are very different from emission characteristics of a polymer bound exciplex at r.t., comparative study on EDA and exciplex emission was conducted and the possible factors controlling these emissions are discussed.
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Tazuke, S., Yuan, H. Inter- and Intramolecular Interactions of Polymers as Studied by Fluorescence Spectroscopy. XIV. Emission by Pyrene-N,N-Dimethylaniline Pair in Glassy 2-Methyltetrahydrofuran Matrix. Polym J 14, 695–703 (1982). https://doi.org/10.1295/polymj.14.695
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DOI: https://doi.org/10.1295/polymj.14.695