Delayed Fluorescence Molecules Research Articles

Inside Front Cover: Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge

Inside Front Cover: Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge

Inside Front Cover: Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge

Inside Front Cover: Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge

Robust Sandwich-Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12-Dihydroindolo[2,3-a]carbazole as Bridge.

Constructing folded molecular structures is emerging as a promising strategy to develop efficient thermally activated delayed fluorescence (TADF) materials. Most folded TADF materials have V-shaped configurations formed by donors and acceptors linked on carbazole or fluorene bridges. In this work, a facile molecular design strategy is proposed for exploring sandwich-structured molecules, and a series of novel and robust TADF materials with regular U-shaped sandwich conformations are constructed by using 11,12-dihydroindolo[2,3-a]carbazole as bridge, xanthone as acceptor, and dibenzothiophene, dibenzofuran, 9-phenylcarbazole and indolo[3,2,1-JK]carbazole as donors. They hold outstanding thermal stability with ultrahigh decomposition temperatures (556-563 °C), and exhibit fast delayed fluorescence and excellent photoluminescence quantum efficiencies (86 %-97 %). The regular and close stacking of acceptor and donors results in rigidified molecular structures with efficient through-space interaction, which are conducive to suppressing intramolecular motion and reducing reorganized excited-state energy. The organic light-emitting diodes (OLEDs) using them as emitters exhibit excellent electroluminescence performances, with maximum external quantum efficiencies of up to 30.6 %, which is a leading value for the OLEDs based on folded TADF emitters. These results demonstrate the proposed strategy of employing 11,12-dihydroindolo[2,3-a]carbazole as bridge for planar donors and acceptors to construct efficient folded TADF materials is applicable.

Robust Sandwich‐Structured Thermally Activated Delayed Fluorescence Molecules Utilizing 11,12‐Dihydroindolo[2,3‐a]carbazole as Bridge

AbstractConstructing folded molecular structures is emerging as a promising strategy to develop efficient thermally activated delayed fluorescence (TADF) materials. Most folded TADF materials have V‐shaped configurations formed by donors and acceptors linked on carbazole or fluorene bridges. In this work, a facile molecular design strategy is proposed for exploring sandwich‐structured molecules, and a series of novel and robust TADF materials with regular U‐shaped sandwich conformations are constructed by using 11,12‐dihydroindolo[2,3‐a]carbazole as bridge, xanthone as acceptor, and dibenzothiophene, dibenzofuran, 9‐phenylcarbazole and indolo[3,2,1‐JK]carbazole as donors. They hold outstanding thermal stability with ultrahigh decomposition temperatures (556–563 °C), and exhibit fast delayed fluorescence and excellent photoluminescence quantum efficiencies (86 %–97 %). The regular and close stacking of acceptor and donors results in rigidified molecular structures with efficient through‐space interaction, which are conducive to suppressing intramolecular motion and reducing reorganized excited‐state energy. The organic light‐emitting diodes (OLEDs) using them as emitters exhibit excellent electroluminescence performances, with maximum external quantum efficiencies of up to 30.6 %, which is a leading value for the OLEDs based on folded TADF emitters. These results demonstrate the proposed strategy of employing 11,12‐dihydroindolo[2,3‐a]carbazole as bridge for planar donors and acceptors to construct efficient folded TADF materials is applicable.

Exploration of red and deep red Thermally activated delayed fluorescence molecules constructed via intramolecular locking strategy

Red and deep red (DR) organic light-emitting diodes (OLEDs) have garnered increasing attention due to their widespread applications in display technology and lighting devices. However, most red OLEDs exhibit low luminescence efficiency, severely limiting their practical applications. To address this challenge, we theoretically design four novel TADF molecules with red and DR luminescence using intramolecular locking strategies building upon the experimental findings of DCN-DLB and DCN-DSP, and their crystal structures are predicted with the lower energy and higher packing density. The photophysical properties and luminescence mechanism of six molecules in toluene and crystal are clarified using the first principles calculation and thermal vibration correlation function (TVCF) method. The proposed design strategy is anticipated to offer several advantages: enhanced electron-donating capabilities, more rigid structures, longer emission wavelengths and higher luminescence efficiency. Specifically, we introduce oxygen atoms and nitrogen atoms as intramolecular locks, and the newly developed DCN-DBF and DCN-PHC have redshifted emission, narrow singlet–triplet energy gap (ΔEST), fast reverse intersystem crossing rate and enhanced photoluminescence quantum yield (PLQY). Notably, DCN-DBF achieves both long wavelength emission and high efficiency, with emission peaks at 598 nm and 587 nm corresponding to PLQY of 52.13 % and 43.42 % in toluene and crystal, respectively. Our work not only elucidates the relationship between molecular structures and photophysical properties, but also proposes feasible intramolecular locking design strategies and four promising red and DR TADF molecules, which could provide a valuable reference for the design of more efficient red and DR TADF emitters.

Exciplex, Not Heavy-Atom Effect, Controls the Triplet Dynamics of a Series of Sulfur-Containing Thermally Activated Delayed Fluorescence Molecules.

The efficiency of thermally activated delayed fluorescence (TADF) in organic materials relies on rapid intersystem crossing rates and fast conversion of triplet (T) excitons into a singlet (S) state. Heavy atoms such as sulfur or selenium are now frequently incorporated into TADF molecular structures to enhance these properties by increased spin-orbit coupling [spin orbit coupling (SOC)] between the T and S states. Here a series of donor-acceptor (D-A) molecules based on 12H-benzo[4,5]thieno[2,3-a]carbazole and dicyanopyridine is compared with their nonsulfur control molecules designed to probe such SOC effects. We reveal that unexpected intermolecular interactions of the D-A molecules with carbazole-containing host materials instead serve as the dominant pathway for triplet decay kinetics in these materials. In-depth photophysical and computational studies combined with organic light emitting diode measurements demonstrate that the anticipated heavy-atom effect from sulfur is overshadowed by exciplex formation. Indeed, even the unsubstituted acceptor fragments exhibit pronounced TADF exciplex emission in appropriate carbazole hosts. The intermolecular charge transfer and TADF in these systems are further confirmed by detailed time-dependent density functional theory studies. This work demonstrates that anticipated heavy-atom effects in TADF emitters do not always control or even impact the photophysical and electroluminescence properties.

Sandwich-type thermally activated delayed fluorescence molecules with through-space charge transfer excited state for red OLEDs

Exploring through-space charge transfer (TSCT) excited state for the design of thermally activated delayed fluorescence (TADF) emitters has been receiving increasing interest for organic light-emitting diodes (OLEDs). In this work, we developed two TSCT-TADF molecules, namely 2DPXZ-QX and 2DPXZ-DFQX, which have sandwich-type donor-acceptor-donor (D-A-D) structures supported by two carbazole bridges. Dibenzo[a,c]phenazine (QX) and its fluorinated derivative (DFQX) were used as the acceptors and O-bridged triphenylamine (DPXZ) was used as the donor. The two donors and acceptor in each molecule are aligned in a face-to-face orientation and thus result in the presence of intramolecular π–π interactions, as revealed by their single crystal X-ray structures. The emission maxima (λPL) of 2DPXZ-QX and 2DPXZ-DFQX in doped 1,3-bis(N-carbazolyl)benzene films are 595 and 600 nm with photoluminescence quantum yields of 67 % and 54 %, respectively. The delayed fluorescence lifetimes are 8.8 and 6.7 μs. OLEDs based on the new sandwich-type emitters show maximum external quantum efficiencies of up to 19.1 %.

Multi‐Resonance Thermally Activated Delayed Fluorescence Molecules for Triplet‐Triplet Annihilation Upconversion

AbstractTriplet‐triplet annihilation upconversion (TTA‐UC) has made significant progress in recent years in several key applications, including solar energy harvesting, photocatalysis, stereoscopic 3D printing, and disease therapeutics. In TTA‐UC research, photosensitizers serve the vital function of harvesting low‐energy photons. The photophysical characteristics of photosensitizers, including absorbance, triplet state quantum yield, triplet state energy level, triplet state lifetime, etc., determine the performance of TTA‐UC. Thus, the study of photosensitizers has been a key aspect of TTA‐UC. In recent years, multi‐resonance thermally activated delayed fluorescence (MR‐TADF) molecules have received extensive attention due to their excellent photophysical properties and electroluminescent device performance. MR‐TADF molecules not only present a narrow energy gap between the singlet and triplet excited states, but also have stronger absorption and better wavelength regulation than conventional TADF molecules. Nowadays, the preliminary attempts in TTA‐UC using MR‐TADF molecules as photosensitizers have resulted in the development of green to ultraviolet, blue to ultraviolet, and even near‐infrared to blue emission. This concept will summarize the research progress of MR‐TADF molecules as photosensitizers in TTA‐UC, analyzing the challenges and giving possible solutions. Finally, we prospect the future development of MR‐TADF molecules as photosensitizers, including the molecular design as well as the possible application areas.

Visualization of Multiple-Resonance-Induced Frontier Molecular Orbitals in a Single Multiple-Resonance Thermally Activated Delayed Fluorescence Molecule.

The spatial distribution and electronic properties of the frontier molecular orbitals (FMOs) in a thermally activated delayed fluorescence (TADF) molecule contribute significantly to the TADF properties, and thus, a detailed understanding and sophisticated control of the FMOs are fundamental to the design of TADF molecules. However, for multiple-resonance (MR)-TADF molecules that achieve spatial separation of FMOs by the MR effect, the distinctive distribution of these molecular orbitals poses significant challenges for conventional computational analysis and ensemble averaging methods to elucidate the FMOs' separation and the precise mechanism of luminescence. Therefore, the visualization and analysis of electronic states with the specific energy level of a single MR-TADF molecule will provide a deeper understanding of the TADF mechanism. Here, scanning tunneling microscopy/spectroscopy (STM/STS) was used to investigate the electronic states of the DABNA-1 molecule at the atomic scale. FMOs' visualization and local density of states analysis of the DABNA-1 molecule clearly show that MR-TADF molecules also have well-separated FMOs according to the internal heteroatom arrangement, providing insights that complement existing theoretical prediction methods.

"Core-Shell" Wave Function Modulation in Organic Narrowband Emitters.

Efficient red-green-blue primary luminescence with an extraordinarily narrow band and durability is crucial for advanced display applications. Recently, the emergence of multiple-resonance (MR) from short-range atomic interactions has been shown to induce extremely narrow spectral widths in pure organic emitters. However, achieving wide-range color tuning without compromising color purity remains a persistent challenge for MR emitters. Herein, the concept of electronic donor/acceptor "core-shell" modulation is proposed within a boron/nitrogen (B/N) MR skeleton, enabling the rational utilization of intramolecular charge transfer to facilitate wavelength shift. The dense B atoms localized at the center of the molecule effectively compress the electron density and stabilize the lowest unoccupied molecular orbital wave function. This electron-withdrawing core is embedded with peripheral electron-donating atoms. Consequently, doping a single B atom into a deep-blue MR framework led to a profound bathochromic shift from 447 to 624 nm (∼0.8 eV) while maintaining a narrow spectral width of 0.10 eV in this pure-red emitter. Notably, organic light-emitting diodes assisted by thermally activated delayed fluorescence molecules achieved superb electroluminescent stability, with an LT99 (99% of the initial luminance) exceeding 400 h at an initial luminance of 1000 cd m-2, approaching commercial-level performance without the assistance of phosphors.

Effective donor and acceptor modifications of carbazole-benzonitrile thermally activated delayed fluorescence molecules enabling high-performance OLEDs

Carbazole-benzonitrile derivatives (CzBNs) have great potential to enable thermally activated delayed fluorescence (TADF) molecules with both high efficiency and good stability simultaneously. However, the device performances of most CzBN-based organic light-emitting diodes (OLEDs) still lag behind other types of TADF molecules. In this work, we proposed a design strategy to construct efficient CzBN-TADF molecules through acceptor and donor modifications. The cyano-modified acceptor enables the extension of the lowest unoccupied molecular orbital while mostly preserving the overlapped area with the highest occupied molecular orbital. The optimized distributions of frontier molecular orbitals contribute to tiny singlet-triplet energy gaps while maintaining a high radiative decay rate. The incorporation of tert-butyl units in the donor groups further enhances the TADF property of resulted tPCNBN molecule due to suppressed non-radiative decay and reduced exciton self-quenching. Accordingly, OLEDs based on tPCNBN present the best device performances, such as a maximum external quantum efficiency of 33.1 % at 400 cd m−2, which is still as high as 26.3 % at a high luminance of 4000 cd m−2, demonstrating relatively low efficiency roll-off. These results confirm the effectiveness of the proposed design strategy in developing efficient and stable CzBN-TADF materials and devices.

Role of Bridging Groups in Regulating the Luminescence and Charge Transfer Properties of Thermally Activated Delayed Fluorescence Molecules: A Theoretical Perspective.

Organic emitters with a simultaneous combination of aggregation-induced emission (AIE) and thermally activated delayed fluorescence (TADF) characteristics are in great demand due to their excellent comprehensive performances toward efficient organic light-emitting diodes (OLEDs), biomedical imaging, and the telecommunications field. However, the development of efficient AIE-TADF materials remains a substantial challenge. In this work, light-emitting properties of two AIE-TADF molecules with different bridging groups ICz-BP and ICz-DPS are theoretically investigated in the solid state with the combined quantum mechanics/molecular mechanics (QM/MM) method and the thermal vibration correlation function (TVCF) theory. The research indicates that the C═O bridging bond in ICz-BP is more favorable than the S═O bridging bond in ICz-DPS for enhancing the planarity of the acceptor, increasing conjugation, and thereby elevating the transition dipole moment density. Simultaneously, the stacking pattern of ICz-BP in the solid facilitates a reduction in energy gap between S1 and T1 (ΔEST), achieving rapid reverse intersystem crossing rate (kRISC). Furthermore, compared to toluene, the stacking patterns of ICz-BP and ICz-DPS in the solid effectively suppress the out-of-plane wagging vibration of the acceptor, thereby inhibiting the loss of nonradiative energy in the excited state and realizing aggregation-induced emission. Moreover, the charge transport properties of both electrons and holes in ICz-BP are found to be higher than the corresponding rates in ICz-DPS, attributed to the smaller internal reorganization energy of ICz-BP in the solid state. Additionally, the calculations reveal a more balanced charge transport characteristic in ICz-BP, contributing to efficient exciton recombination and emission and ultimately mitigating efficiency roll-off. Based on these computational results, we aim to unveil the relationship between molecular structure and light-emitting properties, aiding in the design and development of efficient AIE-TADF devices.

Regulation for photophysical properties of thermally activated delayed fluorescence molecules with through-space charge transfer by substitution effect

Thermally activated delayed fluorescence (TADF) molecules with through-space charge transfer (TSCT) have attracted much attention in recent years. The photophysical properties of four TADF molecules with TSCT properties were studied in toluene and in solid phase. Our calculation results indicate that ortho substitution and fluorine substitution not only favor the generation of TADF, but also promote room temperature phosphorescence in solid phase. The results provide deeper understanding of substitution effect on light-emitting properties of TSCT-TADF emitters and may favor the design of TADF emitters.

Self-doping mechanism for thermally activated delayed fluorescence molecules: a theoretical perspective

Interesting properties of dual conformations of thermally activated delayed fluorescence molecules show various novel applications in self-doping systems. However, the species and quantities of self-doping systems are not enough to satisfy the requirements and a theoretical investigation to reveal the self-doping mechanism is highly desired. By analysing the potential energy surface, two stable conformations of TP2P-PXZ-qa (QA) and TP2P-PXZ-qe (QE) are determined. The basic geometric and electronic structures are optimised, frontier orbital distributions and energies are obtained, transition properties are analysed and the energy consumption processes of excited states are analysed. Results indicate that two conformations (QA and QE) coexist in the solid phase, the QA conformation acts as host and the QE conformation acts as guest. Efficient intersystem crossing (ISC) and reverse ISC processes are determined for QE conformation. In addition, a substantial overlap exists between the emission spectrum of the QA conformation and the absorption spectrum of the QE conformation, indicating an effective energy transfer process from host to guest. Thus, relationships between molecular structures and photophysical properties are illustrated and a self-doping mechanism is theoretically revealed. Our work rationalises the experimental observations and offers a theoretical perspective for the self-doping mechanism, contributing to the development of efficient non-doped emitters.

Diradical-Based Strategy in Designing Narrowband Thermally Activated Delayed Fluorescence Molecules with Tunable Emission Wavelengths.

In the design of thermally activated delayed fluorescence (TADF) materials, narrow-band emission is of particular importance for the development of organic light-emitting diodes (OLEDs). In this work, we proposed a new strategy for designing TADF molecules utilizing degenerate nonbonding (NB) orbitals of diradical parent molecules, and these designed molecules are termed NB-TADF molecules. Based on this strategy, a series of NB-TADF molecules is finely designed and systematically studied by theoretical calculations. Taking advantage of the nonbonding properties, these NB-TADF molecules exhibit desirable narrowband emissions and high quantum yields. More importantly, the emission bands can be easily tuned from blue to near-infrared by changing the conjugate length of the parent group in the NB-TADF molecules. We hope that this new strategy can open a new door for the design of novel TADF materials.

Peripheral Selenium Modification of Multi‐Resonance Thermally Activated Delayed Fluorescence Molecules for High‐Performance Blue Organic Light‐Emitting Diodes

AbstractMulti‐resonance thermally activated delayed fluorescence (MR‐TADF) molecules have attracted much attention in the academia owing to their unique photoelectrical properties. However, MR‐TADF emitters usually show slow reverse intersystem crossing (RISC) rate, resulting in high efficiency roll‐off of organic light‐emitting diodes (OLEDs) and seriously limiting their further development. Here, a peripheral selenium (Se) modification is presented for MR‐TADF molecules to promote the RISC process while keeping the narrowband emission for high‐performance blue OLEDs. Compared to the parent molecules (NBN and tBuNBN), SeNBN and SetBuNBN exhibited narrower full‐width at half maximum (FWHM) value of 23 nm and more obvious delayed fluorescence properties with a high efficiency of delayed fluorescence up to 86%, shorter delayed lifetime of 2.4 µs as well as a faster RISC rate of 3.34×105 s−1. Therefore, high‐performance OLEDs based on these two Se modified MR‐TADF emitters are achieved with a high maximum external quantum efficiency (EQE) up to 25.5% and extremely suppressed efficiency roll‐offs of 3.9% at 100 cd m−2 and 24.4% at 1000 cd m−2. This work demonstrated that the introduction of peripheral Se atom can achieve high‐performance organic semiconductors with both narrowband emission and fast RISC rate constant for high‐performance organic optoelectronic devices.

Conformational Isomerization Effect on Singlet/Triplet Energy Consumption Process of Thermally Activated Delayed Fluorescence Molecules with Aggregation Induced Emission: A QM/MM Study.

Thermally activated delayed fluorescence (TADF) molecules with aggregation-induced emission (AIE) properties hold tremendous potential in biomedical sensing/imaging and telecommunications. In this study, a multiscale method combined with thermal vibration correlation function (TVCF) theory is used to investigate the photophysical properties of the novel TADF molecule CNPy-SPAC in toluene and crystal and amorphous states. In the crystal state, an increase in radiative rates and a decrease in nonradiative rates lead to AIE. Additionally, conformational isomerization effects result in significantly different luminescent efficiencies between the two crystal structures. Furthermore, the isomerization effect allows for the coexistence of three configurations in the amorphous state. Among them, the non-TADF quasi-axial (Qa) configuration may facilitate energy transfer to the TADF-characteristic quasi-equal/quasi-equal-H (Qe/Qe-H) configurations, enhancing AIE. Moreover, the Qa configuration enables rapid electron transport, offering the potential for self-doped devices. Our work elucidates a new mechanism for the isomerization effect in AIE-TADF molecules.

Exploring the Early Time Behavior of the Excited States of an Archetype Thermally Activated Delayed Fluorescence Molecule.

Optical pump-probe techniques allow for an in-depth study of dark excited states. Here, we utilize them to map and gain insights into the excited states involved in the thermally activated delayed fluorescence (TADF) mechanism of a benchmark TADF emitter DMAC-TRZ. The results identify different electronic excited states involved in the key TADF transitions and their nature by combining pump-probe and photoluminescence measurements. The photoinduced absorption signals are highly dependent on polarity, affecting the transition oscillator strength but not their relative energy positions. In methylcyclohexane, a strong and vibronically structured local triplet excited state absorption (3LE → 3LEn) is observed, which is quenched in higher polarity solvents as 3CT becomes the lowest triplet state. Furthermore, ultrafast transient absorption (fsTA) confirms the presence of two stable conformers of DMAC-TRZ: (1) quasi-axial (QA) interconverting within 20 ps into (2) quasi-equatorial (QE) in the excited state. Moreover, fsTA highlights how sensitive excited state couplings are to the environment and the molecular conformation.

Efficient Blue Thermally Activated Delayed Fluorescence Molecules with Sandwich‐Structured Through‐Space Charge Transfer for Fabricating High‐Performance OLEDs

AbstractExploring robust blue luminescent materials is of high significance but challenging for the commercialization application of organic light‐emitting diodes (OLEDs). In this work, it is wished to report two blue thermally activated delayed fluorescence (TADF) molecules with a through‐space charge transfer feature. They have sandwich‐structured molecular backbones comprised of one triphenyltriazine acceptor and two 9‐phenylcarbazole or 3,6‐di(tert‐butyl)‐9‐phenylcarbazole donors that are linked at the 1,8,9‐positions of a 3,6‐di(tert‐butyl)carbazole holder, and exhibit high thermal stability and strong blue delayed fluorescence with high photoluminescence quantum yields and fast reverse intersystem crossing. The blue OLEDs use 2TBCTC as an emitter and provide outstanding maximum external quantum efficiencies (EQEmaxs) of up to 32.76% with Commission Internationale de I'Eclairage coordinates of (0.160, 0.206). To the best of knowledge, 2TBCTC is the most efficient blue TADF emitter based on through‐space charge transfer in the literature. Moreover, the interlayer‐sensitizing OLED employs 2TBCTC as a sensitizer for blue multi‐resonance TADF (MR‐TADF) molecule (v‐DABNA) as guest emitter attains an excellent EQEmax of 32.69% with a narrow full width at half maximum of 18 nm, validating the excellent potential of 2TBCTC as sensitizer for MR‐TADF emitters and the feasibility and effectiveness of the interlayer sensitization strategy for blue hyperfluorescence OLEDs.

Creating Efficient Red Thermally Activated Delayed Fluorescence Materials with Cyano-Substituted 11,12-Diphenyldipyrido[3,2-a:2',3'-c]phenazine Acceptors.

Red luminescent materials are essential components for full color display and white lightening based on organic light-emitting diode (OLED) technology, but the extension of emission color towards red or deep red region generally leads to decreased photoluminescence and electroluminescence efficiencies. Herein, we wish to report two new luminescent molecules (2CNDPBPPr-TPA and 4CNDPBPPr-TPA) consisting of cyano-substituted 11,12-diphenyldipyrido[3,2-a:2',3'-c]phenazine acceptors and triphenylamine donors. As the increase of cyano substituents, the emission wavelength is greatly red-shifted and the reverse intersystem crossing process is promoted, resulting in strong red delayed fluorescence. Meanwhile, due to the formation of intramolecular hydrogen bonds, the molecular structures become rigidified and planarized, which brings about large horizontal dipole ratios. As a result, 2CNDPBPPr-TPA and 4CNDPBPPr-TPA can perform as emitters efficiently in OLEDs, furnishing excellent external quantum efficiencies of 28.8 % at 616 nm and 20.2 % at 648 nm, which are significantly improved in comparison with that of the control molecule without cyano substituents. The findings in this work demonstrate that the introduction of cyano substituents to the acceptors of delayed fluorescence molecules could be a facile and effective approach to explore high-efficiency red or deep red delayed fluorescence materials.