Dendron-functionalized perylene diimides with carrier-transporting ability for red luminescent materials

This paper presents a series of dendrimers via a convergent synthetic approach with three generations, which contain perylene diimide cores, Fréchet-type poly(aryl ether) dendrons, and carbazole (CZ) or oxadiazole (OXZ) peripheral functional groups. The higher generation dendrimer has an obvious site-isolation or dilution effect of dendrons, which results in a relatively small red-shift of absorption and emission spectra when it forms a solid thin film for applications. The interactions between peripheral units and perylene diimide core in the dendrimers are also studied by steady-state and time-resolved fluorescence spectra under both direct and indirect excitation. The fluorescence data show that there exist two possible mechanisms, Fِrster energy transfer (FRET) and photo-induced electron transfer (PET), for dendrimers bearing carbazole units. No enhanced core fluorescence is observed because the energy transfer or light-harvesting potential of peripheral carbazole is counteracted by PET. While for dendrimers bearing oxadiazole units, no PET can take place between OXZ and perylene diimide since both of them are high electron affinity. The FRET and higher light-harvesting ability of oxadiazole without PET interfering result in the distinct enhancement of core emission in higher generation dendrimers. DSC results indicate that the incorporation of Fréchet-type poly(aryl ether) dendrons can improve the amorphous property and increase glass transition temperature (Tg). The preliminary EL results with single-layer architectures demonstrate that these dendrimers could be utilized as a promising kind of active red luminescent emitters with carrier-transporting ability. EL emission has the same recombination zone as PL, indicating that the recombination of excitons in fabricated EL devices is not close to cathode or anode vicinity. It is suggested that the site-isolation effect of dendron wedges is attributed to prevent the core luminorphores from approaching electrodes efficiently.