Emission properties of vinylcarbazole polymers

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Abstract
The emission properties of poly(N‐vinylcarbazole) (PVK), poly(N‐ethyl‐2‐vinylcarbazole), and poly(N‐ethyl‐3‐vinylcarbazole) have been investigated. Dilute fluid solutions of all three vinylcarbazole polymers are observed to exhibit a structureless emission band at energies approximately 5400 cm−1 to the red of the (0,0) band of the normal molecular fluorescence of isolated monomer compounds. On the basis of earlier work appropriate model compounds, this emission is assigned as that from an intrachain excimer state in which two interacting pendant groups, one of which is electronically excited, achieve an overlapping, eclipsed, sandwichlike configuration. The emission spectrum of PVK is characterized by the appearance of a second structureless emission band which appears at higher energy than the intrachain excimer fluorescence common to all three vinylcarbazole polymers. This emission band is unique to PVK and under certain conditions to its model compound, 1,3‐bis(N‐carbazolyl)propane. This emission is assigned as that from a second intrachain excimer. Contrary to the lower energy intrachain excimer, the polymer conformation appropriate for formation of this state exists prior to the initial excitation step.
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