A Simple Organic Molecule Realizing Simultaneous TADF,RTP, AIE,and Mechanoluminescence: Understanding the Mechanism Behind the Multifunctional Emitter

Aggregation‐induced emission (AIE), thermally activated delayed fluorescence (TADF), room‐temperature phosphorescence (RTP), and mechanoluminescence (ML) have attracted widespread interest. However, a multifunctional organic emitter exhibiting simultaneous AIE, TADF, RTP, and ML has not been reported. Now, two multifunctional blue emitters with very simple structures, mono‐DMACDPS and Me‐DMACDPS, exhibit typical AIE, TADF, and RTP properties but different behavior in mechanoluminescence. Crystal structure analysis reveals that large dipole moment and multiple intermolecular interactions with tight packing mode endow mono‐DMACDPS with strong ML. Combined with the data of crystal analysis and theoretical calculation, the separated monomer and dimer in the crystal lead to the typical TADF and RTP properties, respectively. Simple‐structure mono‐DMACDPS is the first example realizing TADF, RTP, AIE, and ML simultaneously.     

Manipulation of Molecular Aggregation States to Realize Polymorphism,AIE, MCL,and TADF in a Single Molecule

Multifunctional emitting materials are scarce and need to be further explored. Now, a newly anthraquinone derivative, 2‐(phenothiazine‐10‐yl)‐anthraquinone (PTZ‐AQ) was designed and synthesized and found to demonstrate polymorphism, multi‐color emission, aggregation‐induced emission (AIE), mechanochromic luminescence (MCL), and thermally activated delayed fluorescence (TADF) in its different solid forms. It is shown for the first time that TADF properties of a compound can be systematically tuned via its aggregation state. The optimized PTZ‐AQ crystal shows a small singlet–triplet energy splitting of 0.01 eV and exhibits red TADF with a photoluminescence quantum yield as high as 0.848. This study shows that the unique multiple functions can be integrated into one single compound through controlling the aggregation states, which provides a new strategy for the investigation and application of multifunctional organic materials.     

基于卤素取代邻苯二甲酰亚胺新型有机发光材料的合成及其性能研究(英文)

方便地合成了三个含有卤素取代邻苯二甲酰亚胺与咔唑基团的新型有机发光材料Br-Al-Cz,Cl-Al-Cz和F-AI-Cz,发现它们不仅具有强的聚集诱导发光效应,而且显示膜态下热激活延迟荧光以及晶态诱导的室温磷光性质.尤其是化合物Br-Al-Cz表现出肉眼可见的长余辉室温磷光现象,因此在数据加密等中具有潜在用途.     

一种热活化延迟荧光黄光材料的合成、性能及高效率电致发光器件

利用吩噁嗪和嘧啶分别作为电子给体和电子受体，通过Buchwald-Hartwig和Suzuki偶联反应成功合成了一种热活化延迟荧光黄光材料pPBPXZ.密度泛函理论计算显示，pPBPXZ分子中吩噁嗪和嘧啶结构单元间的二面角接近90°，而两个嘧啶结构单元与连接二者的苯环间的二面角接近0°；pPBPXZ的最高电子占据轨道主要分布在吩噁嗪结构单元上，最低电子未占轨道主要分布在嘧啶环和苯环上，两种分子轨道只有很小部分重叠.循环伏安、热重和差热测试表明，pPBPXZ具有高的电化学稳定性和热稳定性.在甲苯溶液中，pPBPXZ在360~495 nm显示出了明显的分子内电荷转移跃迁吸收，室温发光峰出现在535 nm.根据低温（77 K）荧光和磷光光谱，计算得到pPBPXZ的最低激发单重态和最低激发三重态能级分别为2.57 eV和2.48 eV，能级差（△E_ST）仅为0.09 eV.利用pPBPXZ作为发光层客体掺杂材料，制备出了高效率的黄光电致发光器件.器件的发射峰出现在552~560 nm，最大电流效率、功率效率和外量子效率分别达到了49.9 cd/A、49.0 lm/W和15.7%，而且发光效率受pPBPXZ掺杂浓度影响较小.     

Polymorph‐Dependent Thermally Activated Delayed Fluorescence Emitters: Understanding TADF from a Perspective of Aggregation State

Current research on thermally activated fluorescence (TADF) emitters is mainly based on the molecular levels, while the aggregation states of TADF emitters are to be explored deeply. Now two multifunctional emitters are reported with simultaneous TADF, aggregation induced emission (AIE), and multicolor mechanochromic luminescence (MCL) features. Both emitters also show polymorph‐dependent TADF emission. Crystal structure analysis reveals that the polymorphism is ascribed to the mutable conformations in different aggregation states. This work brings new insight to TADF emitters from a perspective of aggregation states.     

Molecular and Device Design Strategies for Ideal Performance White Organic Light‐Emitting Diodes

The progress of white organic light‐emitting diodes (WOLEDs) via adopting fluorescent and phosphorescent organic materials have attracted commercial interest for their broad range of visible spectrum and potential of 100 % internal quantum efficiency. In this account, smart molecular designs for developing efficient phosphorescent host and good color purity blue fluorescent emitters are prepared to be discussed, especially donor‐acceptor modification to regulate their triplet states and bipolar transport properties. Rational device configuration design strategies were also introduced by cooperating with efficient conventional fluorescent and thermally activated delayed fluorescent emitting molecules to achieve full exciton utilization and simplified device structures, further suggesting perspectives of potentially low‐cost, ideal performance and promoted operational lifetime in WOLED devices.     

Dicyano-Imidazole: A Facile Generation of Pure Blue TADF Materials for OLEDs

A series of dicyano-imidazole-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain pure blue-emitting organic light-emitting diodes (OLEDs). The targeted molecules used dicyano-imidazole with a short-conjugated system as the electron acceptor to strong intermolecular π-π interactions, and provide a relatively shallow energy level of the lowest unoccupied molecular orbital (LUMO). The cyano group was selected to improve imidazole as an electron acceptor due to its prominent electron-transporting characteristics. Four different electron donors, that is, 9,9-dimethyl-9,10-dihydroacridine (DMAC), 10H-spiro(acridine-9,9’-fluoren) (SPAC), and 9,9-diphenyl-9,10-dihydroacridine (DPAC), were used to alternate the highest occupied molecular orbital (HOMO) energy level to tune the emission color further. The crowded molecular structure in space makes the electron donor and acceptor almost orthogonal, reducing the energy gap (ΔE_ST) between the first excited singlet (S₁) and the triplet (T₁) states and introducing significant TADF property. The efficiencies of the blue-emissive devices with imM-SPAC and imM-DMAC obtained in this work are the highest among the reported imidazole-based TADF-OLEDs, which are 13.8 % and 13.4 %, respectively. Both of Commission Internationale de l′Eclairage (CIE) coordinates are close to the saturated blue region at (0.17, 0.18) and (0.16, 0.19), respectively. Combining these tailor-made TADF compounds with specific device architectures, electroluminescent (EL) emission from sky-blue to deep-blue could be achieved, proving their great potential in EL applications.     

Nonbonding/Bonding Molecular Orbital Regulation of Nitrogen-Boron-Oxygen-embedded Blue/Green Multiresonant TADF Emitters with High Efficiency and Color Purity

In this study, we synthesized and characterized multiresonant thermally activated delayed fluorescent (TADF) materials embedded with nitrogen-boron-oxygen (N−B−O), exhibiting color-tunability between blue and green, namely NBO , m-DiNBO , and p-DiNBO . The three emitter materials showed a high photoluminescence quantum yield (PLQY) and a state-of-the-art narrow full width at half maximum (FWHM) of 96 %/25 nm, 87 %/17 nm, and 99 %/19 nm, respectively. For m-DiNBO and p-DiNBO , the emission color could be tuned from blue to green by regulating the nonbonding/bonding molecular orbital characters. Owing to the expanded planar molecular structure, m-DiNBO and p-DiNBO showed high horizontal dipole ratio (Θ) of 88 % and 92 %, respectively. OLEDs were prepared with NBO , m-DiNBO , and p-DiNBO , exhibiting high external quantum efficiencies of 16.8 %, 24.2 %, and 21.6 %, respectively. NBO and m-DiNBO exhibited pure-blue emission with CIE coordinates of (0.137, 0.142) and (0.126, 0.098), respectively. p-DiNBO showed pure-green emission with a CIE coordinate of (0.258, 0.665).     

Twisted penta‐Carbazole/Benzophenone Hybrid Compound as Multifunctional Organic Host,Dopant or Non‐doped Emitter for Highly Efficient Solution‐Processed Delayed Fluorescence OLEDs

A new multi‐functional penta‐carbazole/benzophenone hybrid compound 5CzBP was designed and synthesized through a simple one‐step catalyst‐free C—N coupling reaction by using 2,3,4,5,6‐pentafluorobenzophenone and carbazole as starting materials. 5CzBP is very soluble in tetrahydrofuran (THF), which brings an environmentally friendly device fabrication for solution‐processed OLEDs instead of most widely used chlorinated solvents when 5CzBP is employed as the bulk‐phase of organic host or non‐doped emitter in the emissive layer. 5CzBP exhibits thermally activated delayed fluorescence (TADF) characteristic with relatively high triplet energy of 2.60 eV and a low ΔE_ST of 0.01 eV. By using the new TADF material as organic host for another green TADF emitter, maximum external quantum efficiency (EQE) of 12.5% has been achieved in simple solution‐processed OLED device. Besides, a maximum EQE of 8.9% and 5.7% was further obtained in TADF devices based on 5CzBP as dopant and non‐doped emitter, respectively. The simultaneously acting as efficient TADF host and non‐doped TADF emitter provides the potential guidance of the future simple single‐layer two‐color white OLEDs based on low‐cost pure organic TADF materials.     

Manipulation of Organic Afterglow by Thermodynamic and Kinetic Control

The fabrication of room-temperature organic phosphorescence and afterglow materials, as well as the transformation of their photophysical properties, has emerged as an important topic in the research field of luminescent materials. Here, we report the establishment of energy landscapes in dopant-matrix organic afterglow systems where the aggregation states of luminescent dopants can be controlled by doping concentrations in the matrices and the methods of preparing the materials. Through manipulation by thermodynamic and kinetic control, dopant-matrix afterglow materials with different aggregation states and diverse afterglow properties can be obtained. The conversion from metastable aggregation state to thermodynamic stable aggregation state of the dopant-matrix afterglow materials to leads to the emergence of intriguing afterglow transformation behavior triggered by thermal and solvent annealing. The thermodynamically unfavorable reversible afterglow transformation process can also be achieved by coupling the dopant-matrix afterglow system to mechanical forces.     

Four Dibenzofuran-Terminated High-Triplet-Energy Hole Transporters for High-Efficiency and Long-Life Organic Light-Emitting Devices

The weak stability of a hole-transporter upon approaching the anion state is one of the major bottlenecks for developing long-life organic light-emitting devices (OLEDs). Therefore, in this study, we developed a series of thermally and electrically stable hole-transporters that are end-capped with four dibenzofuran units. These materials exhibit i) high bond dissociation energy (BDE) toward the anion state, ii) a high glass transition temperature (T_g>130 °C), and iii) high triplet energy (E_T>2.7 eV), thereby enabling approximately 20 % high external quantum efficiency (EQE) and significantly prolonging the stability of both thermally activated delayed fluorescent (TADF) and phosphorescent OLEDs with an operation lifetime at 50 % (LT₅₀) of 20 000–30 000 h at 1000 cd m⁻². In addition, investigating their structure-property relationship revealed that ionization potential (I_P), BDE, and T_g are critical prerequisites for the hole-transporter to prolong lifetime in OLEDs.     

Acceptor Derivatization of the 4CzIPN TADF System: Color Tuning and Introduction of Functional Groups

We demonstrate modular modifications of the widely employed emitter 2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile (4CzIPN) by replacing one or both nitrile acceptors with oxadiazole groups via a tetrazole intermediate. This allows the introduction of various functional groups including halides, alkynes, alkenes, nitriles, esters, ethers and a protected amino acid while preserving the thermally activated delayed fluorescence (TADF) properties. The substituents control the emission maximum of the corresponding emitters, ranging between 472–527 nm, and show high solid-state photoluminescence quantum yields up to 85 %. The TADF emission of two compounds, 4CzCNOXDtBu and 4CzdOXDtBu, a mono- and a bis-oxadiazole substituted 4CzIPN is characterized in detail by time- and temperature-dependent photoluminescence. Solution-processed OLEDs comprising 4CzCNOXDtBu and 4CzdOXDtBu show a significant blue-shift of the emission compared to the reference 4CzIPN, with external quantum efficiencies of 16 %, 5.9 % and 17 % at 100 cd m⁻², respectively.     

Dithia[3.3]paracyclophane Core: A Versatile Platform for Triplet State Fine‐Tuning and Through‐Space TADF Emission

Thermally activated delayed fluorescence (TADF) based on through‐space donor and acceptor interactions constitute a recent and promising approach to develop efficient TADF emitters. Novel TADF isomers using a dithia[3.3]‐paracyclophane building block as a versatile 3D platform to promote through‐space interactions are presented. Such a 3D platform allows to bring together the D and A units into close proximity and to probe the effect of their orientation, contact site and distance on their TADF emission properties. This study provides evidence that the dithia[3.3]paracyclophane core is a promising platform to control intramolecular through‐space interactions and obtain an efficient TADF emission with short reverse‐intersystem crossing (RISC) lifetimes. In addition, this study demonstrates that this design can tune the energy levels of the triplet states and leads to an upconversion from ³CT to ³LE that promotes faster and more efficient RISC to the ¹CT singlet state.     

Recent Advances in Conjugated TADF Polymer Featuring in Backbone‐Donor/Pendant‐Acceptor Structure: Material and Device Perspectives

Along with the persistent research interest in organic light‐emitting diode (OLED) display and lighting technology, a new studying topic is now focused on developing thermally activated delayed fluorescence (TADF) polymer emitters, with the purpose to achieve high‐performance cost‐effective, solution‐processed OLEDs (s‐OLEDs) purely from fluorescent‐type materials. However, research in this topic is in its infancy about the designing rules of polymer structures, photophysical mechanisms and the correlated devices. In this Personal Account, mainly from our personal experience we will shortly introduce the historical developments, status and perspectives about one representative kinds of TADF polymers, i. e. the conjugated TADF polymers featuring in backbone‐donor/pendant‐acceptor (BDPA) structure scaffold, which shows very promising electroluminescent (EL) performance even using simple s‐OLED structure. Special attention is focused on illustrate the molecular designing & synthesis motivation, chemistry & device tactics towards solving the limiting factors about the quantum yields and aggregation‐quenching tendency in solid states. Further challenges and strategies towards optimizing their overall EL performance, e. g. simultaneous achieving extremely high external quantum efficiency, power efficiency and low roll‐off rate, are also discussed.     

1D CuI coordination polymers based on triphenylarsine and N,N'-ditopic co-ligands: synthesis,crystal structure and TADF properties

1D coordination polymers [Cu₂I₂(AsPh₃)₂(L)]_n (L = 4,4'-bi-pyridine, pyrazine) were synthesized via the reaction of CuI with AsPh₃ and N,N'-ditopic co-ligand s L. At ambient temperature, these polymers exhibit short-lived (2.3–3.2 μs) thermally activated delayed fluorescence (TADF) with _max at 530 nm (L = 4,4'-bipyridine) and 605 nm (L = pyrazine) and quantum efficiency up to 45%.     

Efficient Direct Reverse Intersystem Crossing between Charge Transfer-Type Singlet and Triplet States in a Purely Organic Molecule

In the field of organic light-emitting diodes, thermally activated delayed fluorescence (TADF) materials have achieved great performance. The key factor for this performance is the small energy gap (ΔE_ST) between the lowest triplet (T₁) and singlet excited (S₁) states, which can be realized in a well-separated donor-acceptor system. Such systems are likely to possess similar charge transfer (CT)-type T₁ and S₁ states. Recent investigations have suggested that the intervention of other type-states, such as locally excited triplet state(s), is necessary for efficient reverse intersystem crossing (RISC). Here, we theoretically and experimentally demonstrate that our blue TADF material exhibits efficient RISC even between singlet CT and triplet CT states without any additional states. The key factor is dynamic flexibility of the torsion angle between the donor and acceptor, which enhances spin-orbit coupling even between the charge transfer-type T₁ and S₁ states, without sacrificing the small ΔE_ST. This results in excellent photoluminescence and electroluminescence performances in all the host materials we investigate, with sky-blue to deep-blue emissions. Among the hosts investigated, the deepest blue emission with CIE coordinates of (0.15, 0.16) and the highest EQE_MAX of 23.9 % are achieved simultaneously.     

A Luminescent Two-Coordinate AuI Bimetallic Complex with a Tandem-Carbene Structure: A Molecular Design for the Enhancement of TADF Radiative Decay Rate

A luminescent bimetallic Au^I complex comprised of N-heterocyclic carbene (NHC) and carbazole (Cz) ligands, that is, (NHC’)Au(NHC)AuCz has been synthesized and studied. Both carbene ligands in the bimetallic complex act as electron acceptors in tandem to increase the energy separation between the ground and excited state, which is higher than those found in either monometallic analogue, (NHC)AuCz and (NHC’)AuCz. A coplanar geometry designed into the tandem complex ensures sufficient electronic coupling between the π-orbitals of the ligands to impart a strong oscillator strength to the singlet intra-ligand charge-transfer (¹ICT) transition. Theoretical modelling indicates that the emissive ICT excited state involves both NHC ligands. The tandem complex gives blue luminescence (λ_max=480 nm) with a high photoluminescent quantum yield (Φ_PL=0.80) with a short decay lifetime (τ=0.52 μs). Temperature-dependent photophysical studies indicate that emission is via thermally assisted delayed fluorescence (TADF) and give a small singlet-triplet energy difference (ΔE_ST=50 meV, 400 cm⁻¹) consistent with the short TADF lifetime.     

Optimizing Optoelectronic Properties of Pyrimidine‐Based TADF Emitters by Changing the Substituent for Organic Light‐Emitting Diodes with External Quantum Efficiency Close to 25 % and Slow Efficiency Roll‐Off

A series of green butterfly‐shaped thermally activated delayed fluorescence (TADF) emitters, namely PXZPM , PXZMePM , and PXZPhPM , are developed by integrating an electron‐donor (D) phenoxazine unit and electron‐acceptor (A) 2‐substituted pyrimidine moiety into one molecule via a phenyl‐bridge π linkage to form a D –π–A–π–D configuration. Changing the substituent at pyrimidine unit in these emitters can finely tune their emissive characteristics, thermal properties, and energy gaps between the singlet and triplet states while maintaining frontier molecular orbital levels, and thereby optimizing their optoelectronic properties. Employing these TADF emitters results in a green fluorescent organic light‐emitting diode (OLED) that exhibits a peak forward‐viewing external quantum efficiency (EQE) close to 25 % and a slow efficiency roll‐off characteristic at high luminance.     

Dual‐Phase Thermally Activated Delayed Fluorescence Luminogens: A Material for Time‐Resolved Imaging Independent of Probe Pretreatment and Probe Concentration

Developing luminescent probes with long lifetime and high emission efficiency is essential for time‐resolved imaging. However, the practical applications usually suffer from emission quenching of traditional luminogens in aggregated states, or from weak emission of aggregation‐induced emission type luminogens in monomeric states. Herein, we overcome this dilemma by a rigid‐and‐flexible alternation design in donor–acceptor–donor skeletons, to achieve a thermally activated delayed fluorescence luminogen with high emission efficiency both in the monomeric state (quantum yield up to 35.3 %) and in the aggregated state (quantum yield up to 30.8 %). Such a dual‐phase strong and long‐lived emission allows a time‐resolved luminescence imaging, with an efficiency independent of probe pretreatment and probe concentration. The findings open opportunities for developing luminescent probes with a usage in larger temporal and spatial scales.