Blue emissions in organic light-emitting devices (OLEDs) are of great significance for their application in full color flat-panel displays and white lightings. [1] However, high-performance blue emitters are still relatively rare. In OLEDs, the injected electrons and holes recombine to form singlet and triplet excitons in the ratio of 1:3, according to the spin statistics, whereas only singlet exciton can decay radiatively in fluorescent materials. [2] Approximately 75% of the triplet excitons are wasted in nonradiative processes, leading to an upper limit of the internal quantum efficiency (IQE) of only 25% in conventional fluorescent devices. One of the methods to enhance the efficiency of OLEDs is to make use of the nonemissive triplet excitons. [3] Phosphorescent OLEDs (PhOLEDs) based on Ir, Pt, and Os organic-metal complexes can approach 100% IQE, which is attributed to the heavy-atom effect. [4] Yet, pure-blue and deep-blue phosphors with Commission Internationale de l'Eclairage (CIE) y values smaller than 0.15 are particularly scarce due to the inherently great challenge in their molecular design; similarly, proper host materials with a large band gap that allows for the refinement of the triplet excitons in devices are also rare. Therefore, it is important to find a way to develop efficient, stable, pure-and deep-blue fluorescent materials. In principle, new-generation, purely organic fluorescent materials can also utilize the nonemissive triplet excitons and achieve high efficiency by converting triplet excitons into singlet excitons. The main mechanisms involve triplet-triplet annihilation (TTA), thermally activated delayed fluorescence (TADF) and the "hot exciton" channel. [5] Essentially, both the TTA and TADF processes can promote the external quantum efficiency (EQE) of the devices by converting excitons from the lowest triplet excited state (T 1 ) to the lowest singlet excited state (S 1 ). Experimental results have confirmed that devices based on TTA and TADF materials can realize a high EQE with a breakthrough of the spin statistical limitation. [6] Although a high EQE has been obtained in TTA and TADF materials, pure-and deep-blue emitters with high efficiency and stability are still exiguous. Unlike TTA and TADF materials, the "hot exciton" materials reported by our group highlight the reverse intersystem crossing from Purely organic electroluminescent materials, such as thermally activated delayed fluorescent (TADF) and triplet-triplet annihilation (TTA) materials, basically harness triplet excitons from the lowest triplet excited state (T 1 ) to realize high efficiency. Here, a fluorescent material that can convert triplet excitons into singlet excitons from the high-lying excited state (T 2 ), referred to here as a "hot exciton" path, is reported. The energy levels of this compound are determined from the sensitization and nanosecond transient absorption spectroscopy measurements, i.e., small splitting energy between S 1 and T 2 and rather large T 2 -T 1 energy gap, which are expected to...

Hot exciton luminogens capable of harvesting nonemissive triplet excitons via reverse intersystem crossing from high-order triplet (hRISC) to singlet have great potential in high-efficiency fluorescent organic light-emitting diodes (OLEDs). Although spin–orbit coupling (SOC) is regarded as a key factor affecting the RISC process, its effects on hot exciton materials are poorly understood. Herein, we design and synthesize two blue-emitting hot exciton luminogens, PABP and PAIDO, to study this issue by modulating the excited-state properties. Theoretical and experimental research contributions demonstrate that a stronger SOC between energetically close S1 (π–π*) and T n (T3, n−π*) of PAIDO gives rise to faster and more efficient hRISC in comparison to that of PABP, leading to a higher external quantum efficiency and a higher exciton utilization efficiency. Crucially, the experimentally measured hRISC rate (k hRISC) of hot exciton materials is on the order of 107 s–1, which is much faster than that of the thermally activated delayed fluorescence materials.

A single crystal of N,N'-bis(4-methoxybenzyl)perylene-3,4,9,10-bis(dicarboximide) (mb-PBI) that possesses novel magic-angle stacking (M-type stacking) and strong intermolecular π-π interaction is achieved by physical vapor transport (PVT), which shows attractive optoelectronic functions such as efficient NIR emission and high electron mobility. In this special M-type staking, the strong Frenkel/CT mixing state promotes fluorescence and, importantly, the elimination of long-distance Förster resonance energy transfer enables the minimization of the possible fluorescence quenching, which ensure the highly efficient emission. Moreover, the strong π-π interaction elongates the "supramolecular conjugation" to reduce the energy gap and also benefits the electron mobility of the crystal. The experimental results clearly indicate that M-type staking is a novel approach to optimize the optoelectronic functions of organic semiconducting materials.

A novel, efficient, deep-blue fluorescent emitter mPAC, with a meta-connected donor–acceptor structure containing phenanthroimidazole (PPI) as the donor and phenylcarbazole-substituted anthracene (An-CzP) as the acceptor, was designed and synthesized. The meta-linkage provided a highly twisted molecular conformation, which efficiently interrupts the intramolecular π-conjugation, resulting in a deep-blue emission. The optimized nondoped device based on mPAC displayed a deep-blue emission with a narrow full width at half-maximum of 56 nm and Commission Internationale de L’Eclairage coordinates of (0.16, 0.09). The maximum external quantum efficiency (EQEmax) is 6.76%, corresponding to a high exciton utilization efficiency (EUE) of 59.3–88.9%. Experimental results and theoretical analysis indicated that the high EUE is mainly ascribed to the reverse intersystem crossing (RISC) from T2 to S1, a “hot exciton” path in which the large T2–T1 energy gap (1.45 eV) and small T2–S1 energy difference (0.18 eV, T2 > S1) hamper the internal crossing from T2 to T1 and facilitate the RISC process. For the hot exciton path, the T2 state can be feasibly arranged to a high energy level, forming a thermal equilibrium with S1, even slightly higher than the deep-blue S1 to realize an exergonic RISC process, which is usually difficult for the thermally activated delayed fluorescence emitters.

Photoinduced charge separation (CS) kinetics are observed to be strongly related to the molecular conformation of the monomeric units in perylene diimide (PDI) dyads, which contain identical or different PDI units linked through N−N covalent bonding. Ultrafast photoinduced intramolecular CS was observed in dichloromethane at room temperature for the dyads containing twisted tetra(phenoxy)-substituted PDI units (1−1 and 1−2), while the dyad containing two identical planar bay-area unsubstituted PDI units (2−2) maintains high fluorescence at the same conditions, although the freeenergy difference (ΔG CS ) for CS is all negative for these dyads. The interchromophore rotation at excited states between the adjacent chromophores in the dyads is a key factor for CS.