Five new carbazole-containing polymers have been synthesized. With poly(N-vinylcarbazole) these form two series in which (a) the nitrogen atom of the chromophore is attached to the polymer backbone with an increasingly flexible linking moiety, PNVK, I, -II, -III, and (b) a series in which the backbone is attached to the 9-, 2-and 3-ring positions, I, IV, V. The molecular weights of the polymers have been characterized by membrane osmometry and gel permeation chromatography. These polymers are susceptible to photochemical degradation which causes both scission of the chain backbone and diminution of carbazole chromophore fluorescence. Sensitive viscosity measurements made on samples undergoing this main-chain scission have been used to obtain the intrinsic viscosity-molecular weight K, a values of the resulting fragments. Comparison of the absorption and emission spectra shows that appreciable excimer emission occurs only in the case of poly(lV-vinylcarbazole) (PNVK) and poly [2-(9-ethyl)carbazolylmethyl methacrylate] (IV). Excimer emission from the latter is weakest in polar fluid solvents and strongest in a rigid glassy matrix. Luminescence decay measurements in the presence and absence of anthracene quencher suggest that down-chain energy migration is virtually absent in the sterically unhindered polymers I, II, III, and V, and this is confirmed by steady state analysis of collisional quenching. Collisional quenching of monomer excitation from IV indicates that the excitation is effectively immobilized in the region of not more than three neighboring chromophores. These
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