Synthesis, characterization, morphological behaviour, and photo- and electroluminescence of highly blue-emitting fluorene-carbazolecopolymers with alkyl side-chains of different lengths

Abstract

Four novel phenyl-end-capped π-conjugated polymers comprising alkyl chains of different lengths were synthesized: the poly(9,9-dihexyl-2,7-fluorene-alt-9,9-dioctylfluorene) (P0), the alternating fluorene–carbazole copolymers P1 and P2 comprising 20% and 50% of carbazole, respectively, and the homopolymer poly(9-hexyl-9H-carbazole) (P3). The non-end-capped alternating fluorene–carbazole copolymer P4 comprising 20% of carbazole was also synthesized for the sake of comparison with P1. P0–P2 and P4 were synthesized by a Pd-catalyzed Suzuki–Miyaura coupling in good yields (80–89%), while P3 was obtained by a Ni-catalyzed Yamamoto coupling reaction from the 3,6-dibromocarbazole monomer in a moderate yield (52%). P0–P4 polymers were characterized by NMR, elemental analysis, and GPC. The molecular weights are 40.30, 23.42, 14.33, 3.92, and 37.49 kDa, with polydispersity indices of 2.5, 1.7, 1.8, 1.3, and 2.6, for P0, P1, P2, P3, and P4, respectively. These polymers were found to show a high thermal stability, with decomposition temperatures in the range of 395–420 °C, and the glass transition temperature was found to regularly increase with the amount of carbazole inserted in the conjugated backbone. AFM images obtained on thin films (thickness of about 90 nm) of P0–P2 revealed films with surfaces of good quality, being homogeneous with low roughness (0.2 nm for the smaller ones). These polymers were found to be blue-emitting both in diluted dichloromethane and chlorobenzene solutions as well as in thin films and exhibit relatively high values of the absolute quantum yields in the range of 100–5.5% in dichloromethane and 51.4–7.7% in thin films. Blue-emitting electroluminescent devices were obtained with P0 and P1 as emitting layers, respectively. The device built with P1 showed improved performances (EQE of 1.32%) with respect to the one built with the parent polyfluorene material (EQE of 0.75%).