New insight into the ultra-long lifetime of excitons in organic-inorganic perovskite： Reverse intersystem crossing

Recently, an effective exciton diffusion length L exceeding 100μm has been reported for organic- inorganic halide perovskites owing to both the high mobility and ultra-long lifetime of the excitons; however, the origin of ultra-long L is still unclear in nature. In some photoelectric materials, reverse intersystem crossing （RISC） from the triplet to the singlet state can enhance the quantum yield of pho- toluminescence greatly. In this study, our theoretical investigation indicated that the energy difference △E_st between the singlet state and the triplet state of CH_3NH_3Pbl_3 was less than 0.1 eV, which represents one crucial prerequisite for the occurrence of RISC. Meanwhile, the experimental results showed that the photoluminescence lifetime increased with the increasing temperature, a typical feature of RISC. Based on this study, we put forward the hypothesis that the ultra-long lifetime of excitons in organic-inorganic halide perovskite might be caused by the RISC process. This may provide a new insight into the important photophysical properties of such novel photovoltaic materials.

Efficient and Fast X-Ray Luminescence in Organic Phosphors Through High-Level Triplet-Singlet Reverse Intersystem Crossing

Organic scintillators that efficiently generate bright triplet excitons are of critical importance for highperformance X-ray-excited luminescence in radiation detection.However,the nature of triplet-singlet spinforbidden transitions in these materials often result in long-lived phosphorescence,which is undesirable for ultrafast X-ray detection and imaging.Here we demonstrate that the effect of hybridized local and charge-transfer(HLCT)excited states enables organic scintillators to exhibit highly efficient and fast radioluminescence(RL)in response to X-ray irradiation.Our experimental and theoretical investigation shows that the oxidized 1,8-naphthalimide-phenothiazine dyad(OMNI-PTZ 2)with HLCT-excited states has an enhanced overlap integral of the highest occupied molecular orbital(HOMO)and lowest unoccupied molecular orbital(LUMO)on MNIπ-orbitals,and moderate donor–acceptor electron interactions.As a result,the RL of these crystals exhibits a 61-fold increase and its monoexponential decay lifetime is three orders of magnitude faster compared to its corresponding thermally activated delayed fluorescence(TADF)molecule MNI-PTZ 1.We further demonstrate the practical utility of the OMNI-PTZ 2(G)in high-performance X-ray detection and imaging,achieving an X-ray dose sensitivity of 97 nGy s−1 and an exceptional spatial resolution of 20 lp/mm.Our study provides a promising molecular design principle for utilizing triplet excitons to develop high-efficiency and fast X-ray scintillators for the development of next-generation flexible and stretchable X-ray imaging detectors.

Aggregation-induced delayed electrochemiluminescence of organic dots in aqueous media

Full utilization of the excited species at both singlet states(1R*)and triplet states(3R*)is crucial to improving electrochemiluminescence(ECL)efficiency but is challenging for organic luminescent materials.Here,an aggregation-induced delayed ECL(AIDECL)active organic dot(OD)containing a benzophenone acceptor and dimethylacridine donor is reported,which shows high ECL efficiency via reverse intersystem crossing(RISC)of non-emissive 3R*to emissive 1R*,overcoming the spin-forbidden radiative decay from 3R*.By introducing dual donor-acceptor pairs into luminophores,it is found that nonradiative pathway could be further suppressed via enhanced intermolecular weak interactions,and multiple spin-up conversion channels could be activated.As a consequence,the obtained OD enjoys a 6.8-fold higher ECL efficiency relative to the control AIDECL-active OD.Single-crystal studies and theoretical calculations reveal that the enhanced AIDECL behaviors come from the acceleration of both radiative transition and RISC.This work represents a major step towards purely organic,high-efficiency ECL dyes and a direction for the design of next-generation ECL dyes at the molecular level.

Sky-Blue Aggregation-Induced Delayed Fluorescence Luminogens with High Horizontal Dipole Orientation for Efficient Organic Light-Emitting Diodes

Efficient and stable blue luminescent organic materials are highly demanded in the field of organic light-emitting diodes(OLEDs)but still remain challenging.In this work,two new sky-blue luminescent molecules comprised of electron acceptor of benzophenone and electron donors of spiro[acridine-9,9'-fluorene]and carbazole are designed and synthesized,and their thermal stability,electrochemical behaviors,photophysical properties,carrier transport ability and electroluminescence performance are investigated.

Tailoring Excited State Properties and Energy Levels Arrangement via Subtle Structural Design on D-π-A Materials

The donor-n-conjugated-acceptor （D-n-A） structure is an important design for the luminescent materials be- cause of its diversity in the selections of donor, n-bridge and acceptor groups. Herein, we demonstrate two examples of D-^-A structures capable to finely modulate the excited state properties and arrangement of energy levels, TPA-AN-BP and CZP-AN-BP, which possess the same acceptor and n-bridge but different donor. The investigation of their photophysical properties and DFT calculation revealed that the D-n-A structure with proper donor, n-bridge and acceptor can result in separation of frontier molecular orbitals on the corresponding donor and acceptor with an obvious overlap on the n-bridge, resulting in a hybridized local and charge-transfer （HLCT） excited state with high photoluminescent （PL） efficiencies. Meanwhile, their singlet and triplet states are arranged on corresponding moie- ties with large energy gap between T2 and T1, and a small energy gap between S1 and T2, which favor the reverse intersystem crossing （RISC） from high-lying triplet levels to singlet levels. As a result, the sky-blue emission non-doped OLED based on the TPA-AN-BP reached maximum external quantum efficiency （EQE） of 4.39% and a high exciton utilization efficiency （EUE） of 77%. This study demonstrates a new strategy to construct highly effi- cient OLED materials.

Novel thioxanthone host material with thermally activated delayed fluorescence for reduced efficiency roll-off of phosphorescent OLEDs

2,7-Di（9,9-dimethyl-9H-fluoren-l-yl）-9H-thioxanthen-9-one （DMBFTX） with thermally activated delayed fluorescence （TADF） was well designed and synthesized. The phosphorescent organic lightemitting device （PHOLED） based on this novel TADF host material displays a stable red phosphorescence region, a peak external quantum efficiency （EQE） value of 12.9% and a low EQE roll-off of 38.8%at a luminance of 10000 cd/m2, which is benefited from the reverse intersystem crossing （RISC） of TADF host and less populated triplet exitons. Notably, the red device based on the TADF host DMBFrX exhibits superior electroluminescence performance and reduced efficiency roll-offcompared with the one hosted by commercially available host 1,3-bis（9-carbazolyl）benzene （mCP）, illustrating the high potential of employing the TADF host material with small energy gap to reduce efficiency roll-off in PHOLED.