We investigated the effects of sterically nonrestricted electron-accepting substituents of three isomeric indolocarbazole derivatives on their aggregation-induced emission enhancement, mechanochromic luminescence and thermally activated delayed fluorescence. The compounds are potentially efficient emitters for host-free organic light-emitting diodes. The films of indolocarbazole derivatives exhibit emissions with wavelengths of fluorescence intensity maxima from 483 to 500 nm and photoluminescence quantum yields from 31 to 58%. The ionization potentials of the solid samples, measured by photoelectron emission spectrometry, are in the narrow range of 5.78–5.99 eV. The electron affinities of the solid samples are in the range of 2.99–3.19 eV. The layers of the derivatives show diverse charge-transporting properties with maximum hole mobility reaching 10−4 cm2/Vs at high electric fields. An organic light-emitting diode with a light-emitting layer of neat compound shows a turn-on voltage of 4.1 V, a maximum brightness of 24,800 cd/m2, a maximum current efficiency of 12.5 cd/A and an external quantum efficiency of ca. 4.8%. When the compounds are used as hosts, green electroluminescent devices with an external quantum efficiency of ca. 11% are obtained. The linking topology of the isomeric derivatives of indolo[2,3-a]carbazole and indolo[3,2-b]carbazole and the electron-accepting anchors influences their properties differently, such as aggregation-induced emission enhancement, mechanochromic luminescence, thermally activated delayed fluorescence, charge-transporting, and electroluminescent properties. The derivative indolo[3,2-b]carbazole displays good light-emitting properties, while the derivatives of indolo[2,3-a]carbazole show good hosting properties, which make them useful for application in electroluminescent devices.
