The results of an experimental investigation of luminescence and energy trapping in the polymeric systems atactic and isotactic polystyrene and atactic polyvinylnaphthalene are presented. It is shown that the anomalous emission bands observed at 3350 Å in the polystyrenes and at 4100 Å in atactic polyvinylnaphthalene are transitions from an excimer state formed by the interaction of nearby chromophores on the same polymer chain. In support of this interpretation, the spectra of a number of model compounds in the diphenylalkane and paracyclophane series are presented and analyzed. The role of charge-transfer-state contribution to the splitting in rigidly helical isotactic polystyrene is investigated and conclusions concerning the microscopic conformations of the polymer chromophores are drawn. In addition, the possibility of excitation energy trapping due to conformational changes of the chromophore groups is discussed.
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Vala et al. (1965) studied this question.
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