Indolocarbazoles with Sterically Unrestricted Electron-Accepting Anchors Showcasing Aggregation-Induced Thermally Activated Delayed Mechanoluminescence for Host-Free Organic Light-Emitting Diodes.

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.

Synthesis and properties of quinazoline-based versatile exciplex-forming compounds.

Three compounds, bearing a quinazoline unit as the acceptor core and carbazole, dimethyldihydroacridine, or phenothiazine donor moieties, were designed and synthesized in two steps including a facile copper-catalyzed cyclization and a nucleophilic aromatic substitution reaction. The photophysical properties of the compounds, based on theoretical calculations and experimental measurements, as well as the electrochemical and thermal properties, are discussed. The synthesized compounds form glasses with glass-transition temperatures ranging from 116 °C to 123 °C. The ionization potentials estimated by cyclic voltammetry of the derivatives were in the range of 5.22-5.87 eV. The 3,6-di-tert-butylcarbazole-substituted quinazoline-based compound forms a sky-blue emitting exciplex in solid mixture with the acceptor 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine as well as an orange emitting exciplex with the donor 4,4',4″-tris[3-methylphenyl(phenyl)amino]triphenylamine. A white OLED based on these versatile exciplex systems with a relatively high maximum brightness of 3030 cd/m2 and an external quantum efficiency of 0.5% was fabricated.

Exciplex energy transfer through spacer: White electroluminescence with enhanced stability based on cyan intermolecular and orange intramolecular thermally activated delayed fluorescence.

Capability of exciplex energy transfer through a spacer was investigated using three exciplex-forming solid mixtures which contained the well-known electron accepting 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine and appropriately designed bipolar cyanocarbazolyl-based derivatives functionalized by attachment of carbazolyl, acridanyl or phenyl units. These novel cyanocarbazolyl-based derivatives were used as both the spacer and exciplex-forming donor. Efficient organic light-emitting diodes with electroluminescence in cyan-yellow region and maximum external quantum efficiency of up to 7.7% were fabricated owing to efficient thermally activated fluorescence (TADF) of the newly discovered exciplexes. An approach of exciton separation by the spacer between the studied exciplexes and selected orange TADF emitter was proposed for the fabrication of white electroluminescent devices with prolonged lifetime comparing to that of single-color exciplex-based devices. Exciplex-forming systems were tested for exciton separation between inter- and intramolecular TADF. Exciplex energy transfer through a spacer was observed on relatively long distance for one system due to the energy resonance between triplet levels of the exciplex and spacer. First time observed here exciplex energy transfer through a spacer can be useful for both improvement of device stability and obtaining of white electroluminescence.