Since the seminal report by Adachi and co-workers in 2012, there has been a veritable explosion of interest in the design of thermally activated delayed fluorescence (TADF) compounds, particularly as emitters for organic light-emitting diodes (OLEDs). With rapid advancements and innovation in materials design, the efficiencies of TADF OLEDs for each of the primary color points as well as for white devices now rival those of state-of-the-art phosphorescent emitters. Beyond electroluminescent devices, TADF compounds have also found increasing utility and applications in numerous related fields, from photocatalysis, to sensing, to imaging and beyond. Following from our previous review in 2017 ( Adv. Mater. 2017, 1605444), we here comprehensively document subsequent advances made in TADF materials design and their uses from 2017-2022. Correlations highlighted between structure and properties as well as detailed comparisons and analyses should assist future TADF materials development. The necessarily broadened breadth and scope of this review attests to the bustling activity in this field. We note that the rapidly expanding and accelerating research activity in TADF material development is indicative of a field that has reached adolescence, with an exciting maturity still yet to come.

Unlike conventional thermally activated delayed fluorescence chromophores, boron-centered azatriangulene-like molecules combine a small excited-state singlet-triplet energy gap with high oscillator strengths and minor reorganization energies. Here, using highly correlated quantum-chemical calculations, we report this is driven by short-range reorganization of the electron density taking place upon electronic excitation of these multi-resonant structures. Based on this finding, we design a series of π-extended boron- and nitrogen-doped nanographenes as promising candidates for efficient thermally activated delayed fluorescence emitters with concomitantly decreased singlet-triplet energy gaps, improved oscillator strengths and core rigidity compared to previously reported structures, permitting both emission color purity and tunability across the visible spectrum.

A new design strategy is introduced to address a persistent weakness with resonance thermally activated delayed fluorescence (R‐TADF) emitters to reduce aggregation‐caused quenching effects, which are identified as one of the key limiting factors. The emitter Mes₃DiKTa shows an improved photoluminescence quantum yield of 80% compared to 75% for the reference DiKTa in 3.5 wt% 1,3‐bis(N‐carbazolyl)benzene. Importantly, emission from aggregates, even at high doping concentrations, is eliminated and aggregation‐caused quenching is strongly curtailed. For both molecules, triplets are almost quantitatively upconverted into singlets in electroluminescence, despite a significant (≈0.21 eV) singlet‐triplet energy gap (ΔE_ST), in line with correlated quantum‐chemical calculations, and a slow reverse intersystem crossing. It is speculated that the lattice stiffness responsible for the narrow fluorescence and phosphorescence emission spectra also protects the triplets against nonradiative decay. An improved maximum external quantum efficiencies (EQE_max) of 21.1% for Mes₃DIKTa compared to the parent DiKTa (14.7%) and, importantly, reduced efficiency roll‐off compared to literature resonance TADF organic light‐emitting diodes (OLEDs), shows the promise of this design strategy for future design of R‐TADF emitters for OLED applications.

Quantum-chemical calculations are combined to a model Frenkel-Holstein Hamiltonian to assess the nature of the lowest electronic excitations in the pentacene crystal. We show that an admixture of charge-transfer excitations into the lowest singlet excited states form the origin of the Davydov splitting and mediate instantaneous singlet exciton fission by direct optical excitation of coherently coupled single and double exciton states, in agreement with recent experiments.