Excimer and aggregate formations in poly(fluorene)s

This paper investigates the absorption and emission changes in poly(di-n-hexylfluorene)s. We prepared the poly(di-n-hexylfluorene)s end capped with 2-bromofluorene, 2-bromo-9,9-di-n-hexylfluorene, and 9-bromoanthracene through Ni (0) mediated polymerization. In addition, we also synthesized a structurally distorted copolymer of 2,7-dibromo-9,9-di-n-hexylfluorene and 9,9-bis(4-bromophenyl) fluorene end capped with 2-bromofluorene through the same polymerization method. The absorption and emission changes of these polymers between before and after thermal annealing in a nitrogen atmosphere clarify the role of aggregate/excimer formation in poly(fluorene)s. The large absorption changes must be attributed to aggregate formation (ground state interaction), which causes only a slight red shift of the vibronically structured emission bands. We assign the additional long wavelength emission as an excimer band (excited state interaction), which is preferably formed at chain ends.