Dual-emissive 2-(2′-hydroxyphenyl)oxazoles for high performance organic electroluminescent devices: discovery of a new equilibrium of excited state intramolecular proton transfer with a reverse intersystem crossing process

摘要

The photoluminescence (PL) and electroluminescence (EL) properties of two highly efficient excited state intramolecular proton transfer (ESIPT) molecules, 2-(2′-hydroxyphenyl)oxazoles containing one triphenylamine (TPA) (>1) and two TPAs (>2) respectively, are studied systematically. The enol-forms of both >1 and >2 possess highly hybridized local and charge transfer (HLCT) excited state character, while their excited-state keto-forms are not of obvious HLCT character. A >1-based device exhibits green-white electroluminescence with Commission Internationale d’Eclairage (CIE) coordinates of (0.25, 0.41) and a high external quantum efficiency (EQE) up to 5.3%, which is the highest EQE value recorded for single molecular white light-emitting materials. A >2-based device shows sky-blue emission with CIE coordinates of (0.18, 0.16) and an EQE of 8.0%, which is the highest EQE in the reported HLCT materials. The fluorescence intensities of the enol-forms of >1 and >2 in EL spectra are increased remarkably relative to their PL spectra. Experimental data and theoretical calculations reveal a new ESIPT equilibrium with a reverse intersystem crossing (RISC) process arising from the HLCT character. In EL, the RISC of the enol-form excitons from the triplet state to the singlet state triggers an increase in the number of enol-form singlet excitons, which further leads to a shift of the ESIPT equilibrium towards an enhanced enol-form emission. Thus, the difference between the ESIPT equilibria in PL and EL may be ascribed to the HLCT character of the enol-form excited state.