The photophysical, electrochemical, and optoelectronic properties of conjugated systems incorporating dibenzophosphole or phosphole moieties are described. Dibenzophosphole derivatives are not suitable materials for OLEDs due to their weak photoluminescence (PL) in the solid state and the instability of the devices. Variation of the substitution pattern of phospholes and chemical modification of their P atoms afford thermally stable derivatives, which are photo- and electroluminescent. Comparison of the optical properties of solution and thin film of thioxophospholes shows that these compounds do not form aggregates in the solid state. This property, which is also supported by an X-ray diffraction study of three novel derivatives, results in an enhancement of the fluorescence quantum yields in the solid state. In contrast, (phosphole)gold(I) complexes exhibit a broad emission in thin film, which is due to the formation of aggregates. Single- and multilayer OLEDs using these P derivatives as the emissive layer have been fabricated. The emission color of these devices and their performances vary with the nature of the P material. Interestingly, di(2-thienyl)thiooxophosphole is an efficient host for the red dopant DCJTB, and devices using the gold complexes have broad emission spectra.

White electroluminescent (EL) emission from single-layered solid-state light-emitting electrochemical cells (LECs) based on host-guest cationic iridium complexes has been successfully demonstrated. The devices show white EL spectra (Commission Internationale de l'Eclairage coordinates ranging from (x, y) = (0.45, 0.40) to (0.35, 0.39) at 2.9-3.3 V with high color rendering indices up to 80. Peak external quantum efficiency and peak power efficiency of the white LEC reach 4% and 7.8 lm/W, respectively. These results suggest that white LECs based on host-guest cationic transition metal complexes may be a promising alternative for solid-state lighting technologies.

Highly efficient orange and green emission from single‐layered solid‐state light‐emitting electrochemical cells based on cationic transition‐metal complexes [Ir(ppy)2sb]PF6 and [Ir(dFppy)2sb]PF6 (where ppy is 2‐phenylpyridine, dFppy is 2‐(2,4‐difluorophenyl)pyridine, and sb is 4,5‐diaza‐9,9′‐spirobifluorene) is reported. Photoluminescence measurements show highly retained quantum yields for [Ir(ppy)2sb]PF6 and [Ir(dFppy)2 sb]PF6 in neat films (compared with quantum yields of these complexes dispersed in m‐bis(N‐carbazolyl)benzene films). The spiroconfigured sb ligands effectively enhance the steric hindrance of the complexes and reduce the self‐quenching effect. The devices that use single‐layered neat films of [Ir(ppy)2sb]PF6 and [Ir(dFppy)2sb]PF6 achieve high peak external quantum efficiencies and power efficiencies of 7.1 % and 22.6 lm W–1) at 2.5 V, and 7.1 % and 26.2 lm W–1 at 2.8 V, respectively. These efficiencies are among the highest reported for solid‐state light‐emitting electrochemical cells, and indicate that cationic transition‐metal complexes containing ligands with good steric hindrance are excellent candidates for highly efficient solid‐state electrochemical cells.