An exciplex probe for end-to-end cyclization of polystyrene. Cyclization dynamics of polymers. 15

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Abstract
An asymmetrically end-labeled polystyrene of low polydispersity was synthesized. The labels are pyrene and dimethylaniline, which can form an emissive exciplex from excited pyrene. End-to-end cyliclization rate constants .ltbbrac.k1.rtbbrac. were calculated from fluorescence decay data in a variety of solvents. Steady-state measurements are also presented. Correction of the .ltbbrac.1.rtbbrac. for differences in solvent viscosity yields cylization rate constants of 0.7 .times. 106/s in good solvents and about twice this in poor (sub-.theta.) solvents. Cyclization rate constants .ltbbrac.k1.rtbbrac. in toluene and cyclohexane at 22.degree. C obtained using this pyrene/dimethylaniline exciplex probe are compared with those obtained previously using a pyrene/pyrene excimer probe.

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