Thermally activated delayed fluorescence (TADF) organic lightemitting diodes arise from the development of high-performance host materials and carrier transporting materials fitting for TADF dyes with optimized respective properties and interplays, making simultaneous performance improvement and device structure simplification feasible. In this work, a highly efficient blue TADF diode with simplified four-layer structure was successfully achieved by utilizing bis[4-(9,9-dimethyl-9,10-dihydroacridine)phenyl]sulfone (DMAC-DPS) as blue emitter, 4,6-bis(diphenylphosphoryl)dibenzothiophene (DBTDPO) as host, and 4,6-bis(diphenylphosphoryl)dibenzothiophene sulfone (46DBSODPO) as electron-transporting layer. The compatibilities between DBTDPO and DMAC-DPS and DBTDPO and 46DBSODPO were optimized with respect to configuration, polarity, energy level, and interfacial interaction, resulting in the unchanged roughness of ∼0.25 nm before and after doping, high photoluminescence quantum yield over 85%, and reduced interfacial exciplex emissions. With the similar triplet excited energy (T 1 ) of ∼3.0 eV but inferior electrical properties compared to its analogues 28DBSODPO and 37DBSODPO, besides the homogeneity with DBTDPO, 46DBSODPO suppressed the formation of interfacial exciplex and dipole for efficient exciton confinement and electron injection and transportation, in virtue of the steric effects of its orthosubstituted phosphine oxide groups. Consequently, DBTDPO and 46DBSODPO endowed their DMAC-DPS based four-layer devices with the state-of-the-art performance, for example, the maximum external quantum efficiency over 16%, which was more than two-fold of those of conventional electron-transporting material 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (TmPyPB). This design strategy about material compatibility could pave a way for developing high-performance blue TADF diodes with simplified configurations.

Three asymmetrical electron transporters as dibenzothiophene sulfone (DBSO)-diphenylphosphine oxide (DPPO) hybrids, collectively named mnDBSODPO, were designed and prepared. All of these materials achieve the high triplet energy of ∼3.0 eV to restrain the exciton linkage from emissive layers. The dependence of inductive and steric effects for DPPO groups on the substitution position, the intermolecular interaction suppression, the encapsulations of high-polar DBSO cores, and the favorable electrical performance are successfully integrated on 36DBSODPO, which can simultaneously suppress the exciton quenching by formation of an interfacial dipole and enhancing the charge flux balance. As a result, 36DBSODPO endowed its tetralayer blue thermally activated delayed fluorescence (TADF) devices with impressive performance, including the maximum external quantum efficiency around 19%, and reduced efficiency roll-offs, which verifies the great potential of asymmetrical electron transporting materials for highly efficient TADF devices.

A series of phosphine oxide hosts, 4,6-bis(diphenylphosphoryl) dibenzothiophene (DBTDPO) and 4- diphenylphosphoryldibenzothiophene (DBTSPO), and electron transporting materials (ETM), 2-(diphenylphosphoryl)dibenzothiophene sulfone (2DBSOSPO), 3-(diphenylphosphoryl)dibenzothiophene sulfone (3DBSOSPO) and 4-(diphenylphosphoryl)dibenzothiophene sulfone (4DBSOSPO) were developed to support blue thermally activated delayed fluorescence (TADF) devices with high performance through optimizing intralayer and interlayer compatibility of emissive layers. On the basis of the triplet energy of ~3.0 eV for the hosts and ETMs, excitons can be effectively confined on DMAC-DPS. Compared to DBTSPO, DBTDPO can support the excellent distribution uniformity to blue TADF dye bis[4-(9,9-dimethyl–9,10-dihydroacridine) phenyl] sulfone (DMAC-DPS), owing to their configuration similarity; while 3DBSOSPO and 4DBSOSPO are superior in compatibility with the hosts due to the similar molecular polarity or configuration. Through adjusting the molecular configuration, the electrical performance of ETMs can be feasibly tuned, including the excellent electron mobility (μe) by the order of 10−3 cm2 V−1 s−1. As the result, DBTDPO and 4DBSOSPO endowed their four-layer blue TADF devices with the maximum current efficiency of 33.5 cd A−1 and the maximum external quantum efficiency more than 17%, which are impressive among the best blue TADF devices. It is showed that intralayer compatibility determines the maximum efficiencies, while interlayer compatibility influences efficiency stability.

Two bis–bis­(urea) ligands (L 1 and L 2 ) incorporating the photoactive 9,10-diphenylanthracene fragment were designed for the construction of anion-coordination-driven assemblies and subsequent oxygenation of anthracene moieties for singlet oxygen storage. The corresponding A2L2-type sulfate complexes [TEA]4[(SO4)2(L 1 )2] (1) and [TEA]4[(SO4)2(L 2 )2] (2), where TEA = tetraethylammonium, were achieved by coordinating the ligands L 1 or L 2 with sulfate anions. Both 1 and 2 were able to undergo [4 + 2] photooxygenation to form endoperoxide photoproducts 1-EPO and 2-EPO, which can be partially converted back to the original anthracene compounds after heating. The structures of 1-EPO and 2-EPO were unambiguously confirmed by X-ray crystallography, NMR and UV–vis spectroscopy, and high-resolution electrospray ionization mass spectrometry.

The understanding of the external enhancement effects from host matrixes on thermally activated delayed fluorescence (TADF) emitters is crucial but incomprehensive at present. Herein, a series of phosphine oxide (PO) acceptors mDBSOSPO (m = 2, 3, and 4, corresponding to PO substitution position) and 4,4'-bis(9-carbazolyl)-2,2'-dimethylbiphenyl (CDBP) as donor is used to construct CDBP:mDBSOSPO exciplex matrixes with typical TADF behaviors. After doped with a conventional yellow TADF emitter 4CzTPNBu, the exciplex matrixes dramatically elevate the reverse intersystem crossing (RISC) efficiencies up to 99%, effectively reduce triplet nonradiative rate constant, and tenfold increase singlet radiative/nonradiative ratio beyond 30 in the case of CDBP:2DBSOSPO:3% 4CzTPNBu. The time-resolved photoluminescence and electroluminescence (EL) spectra demonstrate that in contrast to single-molecular hosts, besides the additional RISC channel for TADF facilitation, the exciplexes support the charge preseparation for the step-by-step charge transfer-based energy transfer featuring effective quenching suppression. These external enhancement effects of the exciplex matrixes lead to the stateof-the-art EL performances of their yellow TADF diodes, including the recording power and quantum efficiencies of 114.9 lm W −1 and 30.3% to date.