Organic light-emitting diodes(OLEDs)based on multiple resonance-thermallyactivated delayedfluorescence(MR-TADF)have the advantages of high excitonutilization and excellent color purity.However,the large conjugated plan...Organic light-emitting diodes(OLEDs)based on multiple resonance-thermallyactivated delayedfluorescence(MR-TADF)have the advantages of high excitonutilization and excellent color purity.However,the large conjugated planarity of gen-eral MR-TADF emitters makes them easily aggregate in the form ofπ–πstacking,resulting in aggregation-caused quenching(ACQ)and the formation of excimers,which reduce exciton utilization efficiency and color purity.To address these issues,large shielding units can be incorporated to prevent interchromophore interactions,whereas the majority of reported molecules are limited to blue-green light emis-sions.This work proposes a strategy of incorporating steric hindrance groups atdifferent sites of the B/N core to suppress interactions between chromophore,con-tributing to blue MR-TADF emitters with high photo-luminance quantum yields(PLQYs≥95%)and narrow full width at half maximum(FWHM),and importantly,great suppression of the ACQ effect.Therefore,blue OLEDs achieve high externalquantum efficiencies up to 34.3%and high color purity with FWHM of about 27 nmand CIE around(0.12,0.15),even at a high doping concentration of 20 wt%.展开更多
μ-calpain activities and shear force values of bovine M. longissimus from Chinese Yellow crossbred bulls were analyzed,and the effect of delay chilling on μ-calpain activities and the tenderness of beef during postm...μ-calpain activities and shear force values of bovine M. longissimus from Chinese Yellow crossbred bulls were analyzed,and the effect of delay chilling on μ-calpain activities and the tenderness of beef during postmortem aging were studied. The results showed that delay chilling significantly improved μ-calpain activities (P<0.05) and enhanced the tenderness of bovine M. longissimus during earlier aging periods compared with conventional chilling. But in later aging periods,delay chilling weakened the effect on the tenderness of beef because of premature consumption of μ-calpain. The experiment results confirmed that delay chilling improved the rate of postmortem aging of beef and remarkably enhanced the tenderness of beef through the effect of delay chilling on μ-calpain activities.展开更多
Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the exp...Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the explanation of the luminescent properties of(R)-5-(9H-carbazol-9-yl)-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione((R)-ImNCz),which was recently reported[Chemical Engineering Journal 418129167(2021)].The polarizable continuum model(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method are adopted in simulation of the property of the molecule in the gas phase,solvated in acetonitrile and in aggregation states.It is found that large spin–orbit coupling(SOC)constants and a smaller energy gap between the first singlet excited state and the first triplet excited state(△E_(st))in prism-like single crystals(SC_(p)-form)are responsible for the TADF of(R)-lmNCz,while no TADF is found in block-like single crystals(SC_(b)-form)with a larger △E_(st).The multiple ultralong phosphorescence(UOP)peaks in the spectrum are of complex origins,and they are related not only to ImNCz but also to a minor amount of impurities(ImNBd)in the crystal prepared in the laboratory.The dimer has similar phosphorescence emission wavelengths to the(R)-lmNCz-SC_(p) monomers.The complex composed of(R)-lmNCz and(R)-lmNBd contributes to the phosphorescent emission peak at about 600 nm,and the phosphorescent emission peak at about 650 nm is generated by(R)-lmNBd.This indicates that the impurity could also contribute to emission in molecular crystals.The present calculations clarify the relationship between the molecular aggregation and the light-emitting properties of the TADF emitters and will therefore be helpful for the design of potentially more useful TADF emitters.展开更多
Thermally activated delayedfluorescence(TADF)molecules are regarded as promis-ing materials for realizing high-performance organic light-emitting diodes(OLEDs).The connecting groups between donor(D)and acceptor(A)units...Thermally activated delayedfluorescence(TADF)molecules are regarded as promis-ing materials for realizing high-performance organic light-emitting diodes(OLEDs).The connecting groups between donor(D)and acceptor(A)units in D–A type TADF molecules could affect the charge transfer and luminescence performance of TADF materials in aggregated states.In this work,we design and synthesize four TADF molecules using planar and twisted linkers to connect the aza-azulene donor(D)and triazine acceptor(A).Compared with planar linkers,the twisted ones(Az-NP-T and Az-NN-T)can enhance A–A aggregation interaction between adjacent molecules to balance hole and electron density.As a result,highly efficient and stable deep-red top-emission OLEDs with a high electroluminescence efficiency of 57.3%and an impressive long operational lifetime(LT_(95)∼30,000 h,initial luminance of 1000 cd m^(-2))are obtained.This study provides a new strategy for designing more effi-cient and stable electroluminescent devices through linker aggregation engineering in donor–acceptor molecules.展开更多
Three kinds of triazine based organic molecules designed for thermally activated delayed fluorescence (TADF) emitters are investigated by first-principles calculations. An optimal Hartree-Fork (HF) method is adopt...Three kinds of triazine based organic molecules designed for thermally activated delayed fluorescence (TADF) emitters are investigated by first-principles calculations. An optimal Hartree-Fork (HF) method is adopted for the calculation of energy gap between the first singlet state (S1) and the first triplet state (T1). The natural transition orbital, the electron- hole (e-h) distribution and the e-h overlap diagram indicate that the S1 states for the three systems include both charge-transfer and some localized excitation component. Further quantitative analysis of the excitation property is performed by introducing the index Ar and the integral of e-h overlap S. It is found that symmetric geometry is a necessary condition for TADF emitters, which can provide more delocalized transition orbitals and consequently a small S1-T1 energy gap. Artful inserting aromatic groups between donors and acceptors can significantly enhance the oscillator strength. Finally, the energy state structures calculated with the optimal HF method is presented, which can provide basis for the study of the dynamics of excited states.展开更多
Fluorescence/phosphorescence hybrid white organic light-emitting devices(WOLEDs) based on double emitting layers(EMLs) with high color stability are fabricated.The simplified EMLs consist of a non-doped blue therm...Fluorescence/phosphorescence hybrid white organic light-emitting devices(WOLEDs) based on double emitting layers(EMLs) with high color stability are fabricated.The simplified EMLs consist of a non-doped blue thermally activated delayed fluorescence(TADF) layer using 9,9-dimethyl-9,10-dihydroacridine-diphenylsulfone(DMAC-DPS) and an ultrathin non-doped yellow phosphorescence layer employing bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2']iridium(acetylacetonate)((tbt)_2Ir(acac)).Two kinds of materials of 4,7-diphenyl-1,10-phenanthroline(Bphen) and 1,3,5-tris(2-Nphenylbenzimidazolyl) benzene(TPBi) are selected as the electron transporting layer(ETL),and the thickness of yellow EML is adjusted to optimize device performance.The device based on a 0.3-nm-thick yellow EML and Bphen exhibits high color stability with a slight Commission International de l'Eclairage(CIE) coordinates variation of(0.017,0.009) at a luminance ranging from 52 cd/m^2 to 6998 cd/m^2.The TPBi-based device yields a high efficiency with a maximum external quantum efficiency(EQE),current efficiency,and power efficiency of 10%,21.1 cd/A,and 21.3 lm/W,respectively.The ultrathin yellow EML suppresses hole trapping and short-radius Dexter energy transfer,so that Forster energy transfer(FRET)from DMAC-DPS to(tbt)_2Ir(acac) is dominant,which is beneficial to keep the color stable.The employment of TPBi with higher triplet excited state effectively alleviates the triplet exciton quenching by ETL to improve device efficiency.展开更多
High efficiency, stable organic light-emitting diodes (OLEDs) based on 2-pheyl-4'-carbazole-9-H-Thioxanthen-9- one-10, 10-dioxide (TXO-PhCz) with different doping concentration are constructed. The stability of t...High efficiency, stable organic light-emitting diodes (OLEDs) based on 2-pheyl-4'-carbazole-9-H-Thioxanthen-9- one-10, 10-dioxide (TXO-PhCz) with different doping concentration are constructed. The stability of the encap- sulated devices are investigated in detail. The devices with the 10 wt% doped TXO-PhCz emitter layer (EML) show the best performance with a current efficiency of 52.1 cd/A, a power efficiency of 32.71re^W, and an external quantum efficiency (EQE) of 17.7%. The devices based on the lOwt%-doped TXO-PhCz EML show the best operational stability with a half-life time (LTSO) of 8Oh, which is 8 h longer than that of the reference devices based on fac-tris(2-phenylpyridinato)iridium( Ⅲ) (Ir(ppy)a). These indicate excellent stability of TXO-PhCz for redox and oxidation processes under electrical excitation and TXO-PhCz can be potentially used as the emitters for OLEDs with high efficiency and excellent stability. The high-performance device based on TXO-PhCz with high stability can be further improved by the optimization of the encapsulation technology and the development of a new host for TXO-PhCz.展开更多
Thermally activated delayed fluorescence(TADF)molecules have attracted great attention as high efficient luminescent materials.Most of TADF molecules possess small energy gap between the first singlet excited state(S_...Thermally activated delayed fluorescence(TADF)molecules have attracted great attention as high efficient luminescent materials.Most of TADF molecules possess small energy gap between the first singlet excited state(S_(1))and the first triplet excited state(T_(1))to favor the up-conversion from T_(1)to S_(1).In this paper,a new TADF generation mechanism is revealed based on theoretical simulation.By systematic study of the light-emitting properties of SOBF-OMe in both toluene and in aggregation state,we find that the single SOBF-OMe could not realize TADF emission due to large energy gap as well as small up-conversion rates between S_(1)and T_(1).Through analysis of dimers,we find that dimers with intermolecular hydrogen bond(H-bond)are responsible for the generation of TADF,since smaller energy gap between S_(1)and T_(1)is found and the emission wavelength is in good agreement with experimental counterpart.The emission properties of SOBF-H are also studied for comparison,which reflect the important role of H-bond.Our theoretical results agree ith experimental results well and confirm the mechanism of H-bond induced TADF.展开更多
Based on the boron-containing thermally activated delayed fuorescence(TADF)compound p-AC(AC:acridine)5,9-dioxa-13 b-boranaphtho[3,2,1-de]anthracene(a),a series of new TADF molecules b1-b4 were designed via adding two ...Based on the boron-containing thermally activated delayed fuorescence(TADF)compound p-AC(AC:acridine)5,9-dioxa-13 b-boranaphtho[3,2,1-de]anthracene(a),a series of new TADF molecules b1-b4 were designed via adding two nitrogen atoms at the AC donor part.Density functional theory and time-dependent density functional theory calculations were performed on the frontier orbital energy levels,emission spectra,singlet-triplet states energy gaps(?EST),reverse intersystem crossing(RISC)rate constant(kRISC)for compounds a and b1-b4.Our calculation results show that the maximum emission wavelengths of b1-b4 are significantly blue-shifted by47-125 nm compared with that of a.Molecules b1 and b3 exhibit dark-blue emission,while molecules b2 and b4 display light-blue emission,indicating that these four derivatives could be potential organic light-emitting diode(OLED)candidates with blue-light emitting.Moreover,we found the RISC processes in a,b2,and b4 can occur not only from T_(1) state to S_(1) state,but also from T_(2) state to S_(1) state significantly,while the RISC processes in b1 and b3 mainly take place via the T_(2)→S_(1) hot exciton way.Importantly,the T_(1)→S_(1) kRISC values of b2 and b4 are predicted to be two to three times of that of a,indicating enhanced TADF property.Our results not only provide two promising boron-based TADF candidates(b2 and b4),but also offer useful theoretical basis for the design of blue OLED materials.展开更多
To enhance the potential application of thermally activated delayed fluorescence(TADF)molecular materials,new functions are gradually cooperated to the TADF molecules.Aggregation induced emission can effectively solve...To enhance the potential application of thermally activated delayed fluorescence(TADF)molecular materials,new functions are gradually cooperated to the TADF molecules.Aggregation induced emission can effectively solve the fluorescence quenching problem for TADF molecules in solid phase,thus aggregation-induced delayed fluorescence(AIDF)molecules were recently focused.Nevertheless,their luminescent mechanisms are not clear enough.In this work,excited state properties of an AIDF molecule DMF-BP-DMAC[reported in Chemistry-An Asian Journal 14828(2019)]are theoretically studied in tetrahydrofuran(THF)and solid phase.For consideration of surrounding environment,the polarizable continuum method(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method were applied for solvent and solid phase,respectively.Due to the increase of the transition dipole moment and decrease of the energy difference between the first single excited state(S1)and the ground state(S0),the radiative rate is increased by about 2 orders of magnitude in solid phase.The energy dissipation of the non-radiative process from S1 to S0 is mainly contributed by low-frequency vibrational modes in solvent,and they can be effectively suppressed in aggregation,which may lead to a slow non-radiation process in solid phase.Both factors would induce enhanced luminescence efficiency of DMF-BP-DMAC in solid phase.Meanwhile,the small energy gap between S1 and triplet excited states results in high reverse intersystem crossing(RISC)rates in both solvent and solid phase.Therefore,TADF is confirmed in both phases.Aggregation significantly influences both the ISC and RISC processes and more RISC channels are involved in solid state.The enhanced delayed fluorescence should be induced by both the enhanced fluorescent efficiency and ISC efficiency.Our calculation provides a reasonable explanation for experimental measurements and helps one to better understand the luminescence mechanism of AIDF molecules.展开更多
Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence(TADF) molecule(3, 5-bis(3,6-di-tert-butyl-9 H-carbazol-9-yl)-phenyl)(pyridin-4-yl) methan...Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence(TADF) molecule(3, 5-bis(3,6-di-tert-butyl-9 H-carbazol-9-yl)-phenyl)(pyridin-4-yl) methanone(DTCBPY) is theoretically studied by using the density functional theory(DFT) and time-dependent density functional theory(TD-DFT).Four conformations(named as A, B, C, and D) of the DTCBPY can be found by relax scanning, and the configuration C corresponds to the luminescent molecule detected experimentally. Besides, we calculate the proportion of each conformation by Boltzmann distribution, high configuration ratios(44% and 52%) can be found for C and D. Moreover, C and D are found to exist with an intramolecular π-π interaction between one donor and the acceptor; the intramolecular interaction brings a smaller Huang-Rhys factor and reduced reorganization energy. Our work presents a rational explanation for the experimental results and demonstrates the importance of the intramolecular π-π interaction to the photophysical properties of TADF molecules.展开更多
Single-molecule luminophores with dual-thermally activated delayed fluorescence(TADF)properties are receiving increasing attention.However,how to achieve these goals requires more in-depth studies.Herein,we demonstrat...Single-molecule luminophores with dual-thermally activated delayed fluorescence(TADF)properties are receiving increasing attention.However,how to achieve these goals requires more in-depth studies.Herein,we demonstrate a novel example emitter,10-(5-(2-(pyridin-3-yl)-[4,5′-bipyrimidin]-6-yl)pyridin-2-yl)-10Hphenoxazine(PmPy-PXZ),enabling dual-TADF properties due to its key feature of conformational isomerization.Introducing a pyridine bridge can greatly reduce the steric hindrance and facilitate dual-stable conformations in the ground state,where the quasi-axial(QA)forms predominate.Moreover,unlike previously reported TADF molecules with dual confirmations,both theoretical and experimental measurements show that not only the quasi-equatorial(QE)forms but also the QA forms exhibit distinct TADF characteristics,which can be attributed to an additional higher reverse intersystem crossing pathway.This is the first time that dual-TADF properties of single molecules have been achieved based on conformational isomerism.Its applications in“self-doping”organic light-emitting diode and biomedical imaging have further been investigated.All these results show the good potential of such dual-band TADF emitters based on molecular conformational isomerization.展开更多
The development of highly efficient thermally activated delayed fluorescence(TADF)emitters is persistently pursued for the application of organic light-emitting diodes(OLED)in full-colour display and solid-state light...The development of highly efficient thermally activated delayed fluorescence(TADF)emitters is persistently pursued for the application of organic light-emitting diodes(OLED)in full-colour display and solid-state lighting.Herein,we present a heptagonal intramolecular-lock strategy to design high-performance TADF emitters.As a proof-of-concept,a new type of tribenzotropone(TBP)acceptor has been designed and synthesized by a cascade decarboxylative cyclization of aryl oxoacetic acid derivative with biphenyl boronic acid.Compared with the unlocked benzophenone(BP)acceptor,the TBP acceptor has a highly twisted heptagonal geometry with moderate rigidity and flexibility,which enables a high-performance TADF emitter with a small single-triplet energy gap(ΔE_(ST))of 0.04 e V,a high photoluminescence quantum yield(Φ_(PL))of 99% and a large horizontal orientation factor(Θ_(//))of 84.0%.Consequently,highly efficient OLEDs with an external quantum efficiency as high as 33.8% are assembled,which is significantly higher than those of DPAC-BP with a highly rotatable BP acceptor(23.8%)as well as DPACFO with a rigid fluorenone(FO)acceptor(6.9%).展开更多
The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom...The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom in a monodentate fashion can lead to thermally activated delayed fluorescence(TADF)emissions with wide color tunability only through varying the noncoordinating acceptor moiety.A panel of TADF gold(Ⅰ)complexes with emission maxima(λmax)of 545–645 nm from metal perturbed intraligand charge-transfer(MPICT)excited states have been developed.Synergetic effects of heavy atom-induced spin-orbit coupling(SOC),steric-induced donor-acceptor twisting and suppressed intramolecular motions lead to high emission efficiencies of 65%-85%in doped films with delayed fluorescence lifetime of as short as 2.0μs.Transient absorption spectroscopic studies on selected complexes determined the kISCto be 6.5×10^(9)s^(-1).Theoretical calculations confirmed the participation of minor d orbital into the lowest excited state,which led to an SOC value of 5.19 cm^(-1)between the lowest-lying singlet and triplet excited states.The yellow to deep red solution-processed OLEDs based on the new gold(Ⅰ)complexes incorporated with various D-A ligands demonstrated promising performances.This study validates a modular design for TADF metal complexes,which will broaden the choices of metal centers and allow for facile color tuning via simple ligand synthesis.展开更多
Efficient multi-resonance thermally activated delayed fluorescence(MR-TADF)materials hold significant potential for applications in organic light-emitting diodes(OLEDs)and ultra-high-definition displays.However,the st...Efficient multi-resonance thermally activated delayed fluorescence(MR-TADF)materials hold significant potential for applications in organic light-emitting diodes(OLEDs)and ultra-high-definition displays.However,the stringent synthesis conditions and low yields typically associated with these materials pose substantial challenges for their practical applications.In this study,we introduce an innovative strategy that involves peripheral modification with sulfur and selenium atoms for two materials,CFDBNS and CFDBNSe.This approach enables a directed one-shot borylation process,achieving synthesis yields of 66%and 25%,respectively,while also enhancing reverse intersystem crossing rates.Both emitters exhibit ultra-narrowband sky-blue emissions centered around 474 nm,with full width at half maximum(FWHM)values as narrow as 19 nm in dilute toluene solutions,along with high photoluminescence quantum yields of 98%and 99%in doped films,respectively.The OLEDs based on CFDBNS and CFDBNSe display sky-blue emissions with peaks at 476 and 477 nm and exceptionally slender FWHM values of 23 nm.Furthermore,the devices demonstrate remarkable performances,achieving maximum external quantum efficiencies of 24.1%and 27.2%.This work presents a novel and straightforward approach for the incorporation of heavy atoms,facilitating the rapid construction of efficient MR-TADF materials for OLEDs.展开更多
Chirality is an important natural characteristic of organic molecules,and chiral organic molecules have shown extensive application in areas such as pharmaceutical development and material science.Benefiting from the ...Chirality is an important natural characteristic of organic molecules,and chiral organic molecules have shown extensive application in areas such as pharmaceutical development and material science.Benefiting from the ability to achieve circularly polarized luminescence(CPL),chiral luminescent materials have shown potential applications in anti-glare display,optical communication and,3D display,etc.Due to the ability to harvest both singlet and triplet excitons by a fast reverse intersystem crossing process without involving noble metals,chiral thermally activated delayed fluorescence(TADF)materials with point chirality,axial chirality,planar chirality and helical chirality are regarded as the state-of-the-art materials for circularly polarized organic light-emitting diodes(CP-OLEDs).In recent years,the chiral TADF materials and CP-OLEDs have rapidly developed,but unfortunately,the dissymmetry factors(g)are far from the requirement of practical applications.The ideal emitters and devices should have both high efficiency and a g factor,or at least a balance between these two elements.This review gives an overview of recent progress in chiral TADF materials,with a particular focus on the chiral skeleton,CPL property and device performance.Furthermore,the molecular design concept,device structure and methods to improve the g factors of chiral materials and CP-OLEDs are also discussed.展开更多
Chiral luminescence materials have potential applications in the field of three-dimensional displays due to their circularly polarized luminescence(CPL)characteristics.However,the further development of circularly pol...Chiral luminescence materials have potential applications in the field of three-dimensional displays due to their circularly polarized luminescence(CPL)characteristics.However,the further development of circularly polarized organic light-emitting diodes(CP-OLEDs)needs to meet the requirements of high efficiency,high color purity,low cost,and high dissymmetry factor(gPLor gEL),chiral multiple resonance thermally activated delayed fluorescence(MR-TADF)materials are considered as candidates in these aspects.Herein,based on a pair of chiral spirofluorene precursors,two pairs of high-performance chiral MR-TADF emitters((R/S)-p-Spiro-DtBuCzB and(R/S)-m-Spiro-DtBuCzB)are developed,which exhibit strong emissions peaking at 491 and 502 nm in toluene with full-width at half-maximum values of 25 and 33 nm,respectively.In addition,small singlet–triplet energy gaps of 0.15 and 0.10 eV with high absolute photoluminescence efficiencies of 95.0%and 96.7%are observed for p-Spiro-DtBuCzB and m-Spiro-DtBuCzB molecules,respectively.OLEDs based on p-Spiro-DtBuCzB and m-Spiro-DtBuCzB display high maximum external quantum efficiencies of 29.6%and 33.8%,respectively.Most importantly,CP-OLEDs present symmetric circularly polarized electroluminescence spectra with|gEL|factors of 3.36×10^(-4)and 7.66×10^(-4)for devices based on(R/S)-p-Spiro-DtBuCzB and(R/S)-m-Spiro-DtBuCzB enantiomers,respectively.展开更多
Thermally activated delayed fluorescence(TADF)polymeric materials based on through-space charge transfer(TSCT)have emerged as a highly studied topic in recent years.However,the construction of TSCT TADF materials via ...Thermally activated delayed fluorescence(TADF)polymeric materials based on through-space charge transfer(TSCT)have emerged as a highly studied topic in recent years.However,the construction of TSCT TADF materials via a supramolecular approach is still a big challenge.In this work,we report the noncovalent synthesis of TSCT TADF materials using a cyclic peptide-based bottle-brushed supramolecular polymer as a scaffold.By bringing the TSCT donor and acceptor in close proximity in space using the supramolecular scaffold,distinctive TADF emission in both solution and solid states could be achieved.Furthermore,the TADF system could be utilized as a sensitizer to coassemble with fluorescence acceptors to build thermally assisted fluorescence systems,resulting in color-tunable delayed fluorescence with high efficiency and color purity.Our findings provide a facile yet effective approach to designing and fabricating TSCT TADF materials,which might hold great potential for applications in the fields of organic light-emitting diode,bioimaging,and sensing.展开更多
Carbazole-triazine dendrimers with a bulky terminal substituent were synthesized,and the thermally activated delayed fluorescence(TADF)property was investigated.Compared to unsubstituted carbazole dendrimers,dendrimer...Carbazole-triazine dendrimers with a bulky terminal substituent were synthesized,and the thermally activated delayed fluorescence(TADF)property was investigated.Compared to unsubstituted carbazole dendrimers,dendrimers with bulky terminal substituents showed comparable to better photoluminescence quantum yields(PLQY)in neat films.Phenylfluorene(PF)-substituted dendrimers showed the highest PLQY of 81%,a smallΔEst of 0.06 eV,and the fastest reverse intersystem crossing(RISC)rate of∼1×10^(5 )s^(−1) compared to other dendrimers.Phosphorescence measurements of dendrimers and dendrons(fragments)indicate that the close proximity of the triplet energy of phenylfluorene-substituted carbazole dendrons(^(3)LE)to that of phenylfluorene-substituted dendrimers(^(1)CT,^(3)CT)contributes to RISC promotion and improves TADF efficiency.Terminal modification fine-tunes the energy level and suppresses intermolecular interactions,and this study provides a guideline for designing efficient solution-processable and non-doped TADF materials.展开更多
High-efficiency electroluminescent devices featuring simplified architecture have received considerable attention due to significant advantages in construction procedures and commercialized applications.However,there ...High-efficiency electroluminescent devices featuring simplified architecture have received considerable attention due to significant advantages in construction procedures and commercialized applications.However,there still remains a critical challenge with regard to the lack of organic semiconductors that simultaneously possess high luminescent efficiency and balanced carrier-transporting abilities.Herein,we design a thermally activated delayed fluorescence(TADF)emitter 4-(9,9-dimethyl-9,10-dihydroacridine)-4′-triphenylphosphineoxide-benzophenone(DMAC-BPTPO)by incorporating triphenylphosphine oxide into the donor–acceptor skeleton.The accessional electrontransporting moiety,rod-like dimer,and horizontally packing model synergistically enable DMAC-BP-TPO which possesses an excellent photoluminescence quantum yield of nearly 90%with a reverse intersystem crossing rate constant of 2.0×106 s−1,horizontal dipole ratio of 89%,and a balanced electron and hole mobilities with a small constrast ratio of 1.08.Eventually,simplified electroluminescent devices including organic lightemitting diodes(OLEDs)and organic light-emitting transistors(OLETs)incorporating DMAC-BP-TPO-based nondoped film are demonstrated due to their superior integrated optoelectronic properties along with preferable horizontal dipole orientation.A record-high external quantum efficiency value of 21.7%and 4.4%are finally achieved in the simplified nondoped OLED and OLET devices,which are among the highest values in the related research fields.This work provides a new avenue to develop a high-efficiency bipolar TADF emitter to advance the simplified electroluminescent devices.展开更多
基金National Natural Science Foundation of China,Grant/Award Numbers:51733010,52073316Basic and Applied Basic Research Foundation of Guangdong Province,Grant/Award Numbers:2022B1515020052,2021A1515110119。
文摘Organic light-emitting diodes(OLEDs)based on multiple resonance-thermallyactivated delayedfluorescence(MR-TADF)have the advantages of high excitonutilization and excellent color purity.However,the large conjugated planarity of gen-eral MR-TADF emitters makes them easily aggregate in the form ofπ–πstacking,resulting in aggregation-caused quenching(ACQ)and the formation of excimers,which reduce exciton utilization efficiency and color purity.To address these issues,large shielding units can be incorporated to prevent interchromophore interactions,whereas the majority of reported molecules are limited to blue-green light emis-sions.This work proposes a strategy of incorporating steric hindrance groups atdifferent sites of the B/N core to suppress interactions between chromophore,con-tributing to blue MR-TADF emitters with high photo-luminance quantum yields(PLQYs≥95%)and narrow full width at half maximum(FWHM),and importantly,great suppression of the ACQ effect.Therefore,blue OLEDs achieve high externalquantum efficiencies up to 34.3%and high color purity with FWHM of about 27 nmand CIE around(0.12,0.15),even at a high doping concentration of 20 wt%.
基金Supported by the National High Technology Research and Development Program of China(2006BAD05A03)~~
文摘μ-calpain activities and shear force values of bovine M. longissimus from Chinese Yellow crossbred bulls were analyzed,and the effect of delay chilling on μ-calpain activities and the tenderness of beef during postmortem aging were studied. The results showed that delay chilling significantly improved μ-calpain activities (P<0.05) and enhanced the tenderness of bovine M. longissimus during earlier aging periods compared with conventional chilling. But in later aging periods,delay chilling weakened the effect on the tenderness of beef because of premature consumption of μ-calpain. The experiment results confirmed that delay chilling improved the rate of postmortem aging of beef and remarkably enhanced the tenderness of beef through the effect of delay chilling on μ-calpain activities.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11974216,11874242,21933002 and 11904210)Shandong Provincial Natural Science Foundation,China(Grant No.ZR2019MA056)+1 种基金the support of the Taishan Scholar Project of Shandong Provincethe project funded by China Postdoctoral Science Foundation(Grant No.2018M642689)。
文摘Aggregation-induced thermally activated delayed fluorescence(TADF)phenomena have attracted extensive attention recently.In this paper,several theoretical models including monomer,dimer,and complex are used for the explanation of the luminescent properties of(R)-5-(9H-carbazol-9-yl)-2-(1,2,3,4-tetrahydronaphthalen-1-yl)isoindoline-1,3-dione((R)-ImNCz),which was recently reported[Chemical Engineering Journal 418129167(2021)].The polarizable continuum model(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method are adopted in simulation of the property of the molecule in the gas phase,solvated in acetonitrile and in aggregation states.It is found that large spin–orbit coupling(SOC)constants and a smaller energy gap between the first singlet excited state and the first triplet excited state(△E_(st))in prism-like single crystals(SC_(p)-form)are responsible for the TADF of(R)-lmNCz,while no TADF is found in block-like single crystals(SC_(b)-form)with a larger △E_(st).The multiple ultralong phosphorescence(UOP)peaks in the spectrum are of complex origins,and they are related not only to ImNCz but also to a minor amount of impurities(ImNBd)in the crystal prepared in the laboratory.The dimer has similar phosphorescence emission wavelengths to the(R)-lmNCz-SC_(p) monomers.The complex composed of(R)-lmNCz and(R)-lmNBd contributes to the phosphorescent emission peak at about 600 nm,and the phosphorescent emission peak at about 650 nm is generated by(R)-lmNBd.This indicates that the impurity could also contribute to emission in molecular crystals.The present calculations clarify the relationship between the molecular aggregation and the light-emitting properties of the TADF emitters and will therefore be helpful for the design of potentially more useful TADF emitters.
基金National Key R&D Program of China,Grant/Award Number:2022YFE0109000National Natural Science Foundation of China,Grant/Award Number:21975152+1 种基金China Postdoctoral Science Foundation,Grant/Award Number:2022M722028Deutsche Forschungsgemeinschaft,Grant/Award Number:3DMM2O−EXC−2082/1−390761711。
文摘Thermally activated delayedfluorescence(TADF)molecules are regarded as promis-ing materials for realizing high-performance organic light-emitting diodes(OLEDs).The connecting groups between donor(D)and acceptor(A)units in D–A type TADF molecules could affect the charge transfer and luminescence performance of TADF materials in aggregated states.In this work,we design and synthesize four TADF molecules using planar and twisted linkers to connect the aza-azulene donor(D)and triazine acceptor(A).Compared with planar linkers,the twisted ones(Az-NP-T and Az-NN-T)can enhance A–A aggregation interaction between adjacent molecules to balance hole and electron density.As a result,highly efficient and stable deep-red top-emission OLEDs with a high electroluminescence efficiency of 57.3%and an impressive long operational lifetime(LT_(95)∼30,000 h,initial luminance of 1000 cd m^(-2))are obtained.This study provides a new strategy for designing more effi-cient and stable electroluminescent devices through linker aggregation engineering in donor–acceptor molecules.
文摘Three kinds of triazine based organic molecules designed for thermally activated delayed fluorescence (TADF) emitters are investigated by first-principles calculations. An optimal Hartree-Fork (HF) method is adopted for the calculation of energy gap between the first singlet state (S1) and the first triplet state (T1). The natural transition orbital, the electron- hole (e-h) distribution and the e-h overlap diagram indicate that the S1 states for the three systems include both charge-transfer and some localized excitation component. Further quantitative analysis of the excitation property is performed by introducing the index Ar and the integral of e-h overlap S. It is found that symmetric geometry is a necessary condition for TADF emitters, which can provide more delocalized transition orbitals and consequently a small S1-T1 energy gap. Artful inserting aromatic groups between donors and acceptors can significantly enhance the oscillator strength. Finally, the energy state structures calculated with the optimal HF method is presented, which can provide basis for the study of the dynamics of excited states.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61675041 and 61605253)the Foundation for Innovation Research Groups of the National Natural Science Foundation of China(Grant No.61421002)the Science&Technology Department Program of Sichuan Province,China(Grant No.2016HH0027)
文摘Fluorescence/phosphorescence hybrid white organic light-emitting devices(WOLEDs) based on double emitting layers(EMLs) with high color stability are fabricated.The simplified EMLs consist of a non-doped blue thermally activated delayed fluorescence(TADF) layer using 9,9-dimethyl-9,10-dihydroacridine-diphenylsulfone(DMAC-DPS) and an ultrathin non-doped yellow phosphorescence layer employing bis[2-(4-tertbutylphenyl)benzothiazolato-N,C2']iridium(acetylacetonate)((tbt)_2Ir(acac)).Two kinds of materials of 4,7-diphenyl-1,10-phenanthroline(Bphen) and 1,3,5-tris(2-Nphenylbenzimidazolyl) benzene(TPBi) are selected as the electron transporting layer(ETL),and the thickness of yellow EML is adjusted to optimize device performance.The device based on a 0.3-nm-thick yellow EML and Bphen exhibits high color stability with a slight Commission International de l'Eclairage(CIE) coordinates variation of(0.017,0.009) at a luminance ranging from 52 cd/m^2 to 6998 cd/m^2.The TPBi-based device yields a high efficiency with a maximum external quantum efficiency(EQE),current efficiency,and power efficiency of 10%,21.1 cd/A,and 21.3 lm/W,respectively.The ultrathin yellow EML suppresses hole trapping and short-radius Dexter energy transfer,so that Forster energy transfer(FRET)from DMAC-DPS to(tbt)_2Ir(acac) is dominant,which is beneficial to keep the color stable.The employment of TPBi with higher triplet excited state effectively alleviates the triplet exciton quenching by ETL to improve device efficiency.
基金Supported by the National Natural Science Foundation of China under Grant Nos 61420106002,51373189,61178061,and 61227008the Hundred Talents Program of the Chinese Academy of Sciences,the National Basic Research Program of China under Grant No 2014CB932600the Start-Up Fund of the Technical Institute of Physics and Chemistry of the Chinese Academy of Sciences
文摘High efficiency, stable organic light-emitting diodes (OLEDs) based on 2-pheyl-4'-carbazole-9-H-Thioxanthen-9- one-10, 10-dioxide (TXO-PhCz) with different doping concentration are constructed. The stability of the encap- sulated devices are investigated in detail. The devices with the 10 wt% doped TXO-PhCz emitter layer (EML) show the best performance with a current efficiency of 52.1 cd/A, a power efficiency of 32.71re^W, and an external quantum efficiency (EQE) of 17.7%. The devices based on the lOwt%-doped TXO-PhCz EML show the best operational stability with a half-life time (LTSO) of 8Oh, which is 8 h longer than that of the reference devices based on fac-tris(2-phenylpyridinato)iridium( Ⅲ) (Ir(ppy)a). These indicate excellent stability of TXO-PhCz for redox and oxidation processes under electrical excitation and TXO-PhCz can be potentially used as the emitters for OLEDs with high efficiency and excellent stability. The high-performance device based on TXO-PhCz with high stability can be further improved by the optimization of the encapsulation technology and the development of a new host for TXO-PhCz.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11974216,11874242,21933002,and 11904210)the Natural Science Foundation of Shandong Province,China(Grant No.ZR2019MA056)+1 种基金the Taishan Scholar Project of Shandong Province,Chinathe Project funded by China Postdoctoral Science Foundation(Grant No.2018M642689)。
文摘Thermally activated delayed fluorescence(TADF)molecules have attracted great attention as high efficient luminescent materials.Most of TADF molecules possess small energy gap between the first singlet excited state(S_(1))and the first triplet excited state(T_(1))to favor the up-conversion from T_(1)to S_(1).In this paper,a new TADF generation mechanism is revealed based on theoretical simulation.By systematic study of the light-emitting properties of SOBF-OMe in both toluene and in aggregation state,we find that the single SOBF-OMe could not realize TADF emission due to large energy gap as well as small up-conversion rates between S_(1)and T_(1).Through analysis of dimers,we find that dimers with intermolecular hydrogen bond(H-bond)are responsible for the generation of TADF,since smaller energy gap between S_(1)and T_(1)is found and the emission wavelength is in good agreement with experimental counterpart.The emission properties of SOBF-H are also studied for comparison,which reflect the important role of H-bond.Our theoretical results agree ith experimental results well and confirm the mechanism of H-bond induced TADF.
基金supported by the National Natural Science Foundation of China(No.22173008)。
文摘Based on the boron-containing thermally activated delayed fuorescence(TADF)compound p-AC(AC:acridine)5,9-dioxa-13 b-boranaphtho[3,2,1-de]anthracene(a),a series of new TADF molecules b1-b4 were designed via adding two nitrogen atoms at the AC donor part.Density functional theory and time-dependent density functional theory calculations were performed on the frontier orbital energy levels,emission spectra,singlet-triplet states energy gaps(?EST),reverse intersystem crossing(RISC)rate constant(kRISC)for compounds a and b1-b4.Our calculation results show that the maximum emission wavelengths of b1-b4 are significantly blue-shifted by47-125 nm compared with that of a.Molecules b1 and b3 exhibit dark-blue emission,while molecules b2 and b4 display light-blue emission,indicating that these four derivatives could be potential organic light-emitting diode(OLED)candidates with blue-light emitting.Moreover,we found the RISC processes in a,b2,and b4 can occur not only from T_(1) state to S_(1) state,but also from T_(2) state to S_(1) state significantly,while the RISC processes in b1 and b3 mainly take place via the T_(2)→S_(1) hot exciton way.Importantly,the T_(1)→S_(1) kRISC values of b2 and b4 are predicted to be two to three times of that of a,indicating enhanced TADF property.Our results not only provide two promising boron-based TADF candidates(b2 and b4),but also offer useful theoretical basis for the design of blue OLED materials.
基金the National Natural Science Foundation of China(Grant Nos.11874242,11974216,and 11904210)Shandong Provincial Natural Science Foundation,China(Grant No.ZR2019MA056)Taishan Scholar Project of Shandong Province,China,and the China Postdoctoral Science Foundation(Grant No.2018M642689).
文摘To enhance the potential application of thermally activated delayed fluorescence(TADF)molecular materials,new functions are gradually cooperated to the TADF molecules.Aggregation induced emission can effectively solve the fluorescence quenching problem for TADF molecules in solid phase,thus aggregation-induced delayed fluorescence(AIDF)molecules were recently focused.Nevertheless,their luminescent mechanisms are not clear enough.In this work,excited state properties of an AIDF molecule DMF-BP-DMAC[reported in Chemistry-An Asian Journal 14828(2019)]are theoretically studied in tetrahydrofuran(THF)and solid phase.For consideration of surrounding environment,the polarizable continuum method(PCM)and the combined quantum mechanics and molecular mechanics(QM/MM)method were applied for solvent and solid phase,respectively.Due to the increase of the transition dipole moment and decrease of the energy difference between the first single excited state(S1)and the ground state(S0),the radiative rate is increased by about 2 orders of magnitude in solid phase.The energy dissipation of the non-radiative process from S1 to S0 is mainly contributed by low-frequency vibrational modes in solvent,and they can be effectively suppressed in aggregation,which may lead to a slow non-radiation process in solid phase.Both factors would induce enhanced luminescence efficiency of DMF-BP-DMAC in solid phase.Meanwhile,the small energy gap between S1 and triplet excited states results in high reverse intersystem crossing(RISC)rates in both solvent and solid phase.Therefore,TADF is confirmed in both phases.Aggregation significantly influences both the ISC and RISC processes and more RISC channels are involved in solid state.The enhanced delayed fluorescence should be induced by both the enhanced fluorescent efficiency and ISC efficiency.Our calculation provides a reasonable explanation for experimental measurements and helps one to better understand the luminescence mechanism of AIDF molecules.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11374195 and 21403133)Taishan Scholar Project of Shandong Normal University,China+1 种基金the Promotive Research Fund for Excellent Young and Middle-aged Scientists of Shandong Province,China(Grant No.BS2014cl001)the China Postdoctoral Science Foundation(Grant No.2014M560571)
文摘Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence(TADF) molecule(3, 5-bis(3,6-di-tert-butyl-9 H-carbazol-9-yl)-phenyl)(pyridin-4-yl) methanone(DTCBPY) is theoretically studied by using the density functional theory(DFT) and time-dependent density functional theory(TD-DFT).Four conformations(named as A, B, C, and D) of the DTCBPY can be found by relax scanning, and the configuration C corresponds to the luminescent molecule detected experimentally. Besides, we calculate the proportion of each conformation by Boltzmann distribution, high configuration ratios(44% and 52%) can be found for C and D. Moreover, C and D are found to exist with an intramolecular π-π interaction between one donor and the acceptor; the intramolecular interaction brings a smaller Huang-Rhys factor and reduced reorganization energy. Our work presents a rational explanation for the experimental results and demonstrates the importance of the intramolecular π-π interaction to the photophysical properties of TADF molecules.
基金supported by the National Natural Science Foundation of China(grant nos.52003186,52130304,51821002,and 52003185)the National Key Research and Development Program of China(grant nos.2020YFA0714601 and 2020YFA0714604)+1 种基金the Science and Technology Project of Suzhou(grant no.ZXL2022490)the Suzhou Key Laboratory of Functional Nano&Soft Materials,the Collaborative Innovation Center of Suzhou Nano Science and Technology,and the 111 Project.
文摘Single-molecule luminophores with dual-thermally activated delayed fluorescence(TADF)properties are receiving increasing attention.However,how to achieve these goals requires more in-depth studies.Herein,we demonstrate a novel example emitter,10-(5-(2-(pyridin-3-yl)-[4,5′-bipyrimidin]-6-yl)pyridin-2-yl)-10Hphenoxazine(PmPy-PXZ),enabling dual-TADF properties due to its key feature of conformational isomerization.Introducing a pyridine bridge can greatly reduce the steric hindrance and facilitate dual-stable conformations in the ground state,where the quasi-axial(QA)forms predominate.Moreover,unlike previously reported TADF molecules with dual confirmations,both theoretical and experimental measurements show that not only the quasi-equatorial(QE)forms but also the QA forms exhibit distinct TADF characteristics,which can be attributed to an additional higher reverse intersystem crossing pathway.This is the first time that dual-TADF properties of single molecules have been achieved based on conformational isomerism.Its applications in“self-doping”organic light-emitting diode and biomedical imaging have further been investigated.All these results show the good potential of such dual-band TADF emitters based on molecular conformational isomerization.
基金supported by the National Natural Science Foundation of China(22275127,22031007,22005204)。
文摘The development of highly efficient thermally activated delayed fluorescence(TADF)emitters is persistently pursued for the application of organic light-emitting diodes(OLED)in full-colour display and solid-state lighting.Herein,we present a heptagonal intramolecular-lock strategy to design high-performance TADF emitters.As a proof-of-concept,a new type of tribenzotropone(TBP)acceptor has been designed and synthesized by a cascade decarboxylative cyclization of aryl oxoacetic acid derivative with biphenyl boronic acid.Compared with the unlocked benzophenone(BP)acceptor,the TBP acceptor has a highly twisted heptagonal geometry with moderate rigidity and flexibility,which enables a high-performance TADF emitter with a small single-triplet energy gap(ΔE_(ST))of 0.04 e V,a high photoluminescence quantum yield(Φ_(PL))of 99% and a large horizontal orientation factor(Θ_(//))of 84.0%.Consequently,highly efficient OLEDs with an external quantum efficiency as high as 33.8% are assembled,which is significantly higher than those of DPAC-BP with a highly rotatable BP acceptor(23.8%)as well as DPACFO with a rigid fluorenone(FO)acceptor(6.9%).
基金supported by the National Natural Science Foundation of China(22322505,22271196,22301226)the Shenzhen Science and Technology Program(ZDSYS20210623091813040)support from the Department of Science and Technology of Guangdong Province(2019QN01C617)。
文摘The efficient harvesting of triplet excitons is crucial to the realization of high-performance organic light-emitting diodes(OLEDs).Herein,we show that coordination of donor-acceptor(D-A)type molecules to a metal atom in a monodentate fashion can lead to thermally activated delayed fluorescence(TADF)emissions with wide color tunability only through varying the noncoordinating acceptor moiety.A panel of TADF gold(Ⅰ)complexes with emission maxima(λmax)of 545–645 nm from metal perturbed intraligand charge-transfer(MPICT)excited states have been developed.Synergetic effects of heavy atom-induced spin-orbit coupling(SOC),steric-induced donor-acceptor twisting and suppressed intramolecular motions lead to high emission efficiencies of 65%-85%in doped films with delayed fluorescence lifetime of as short as 2.0μs.Transient absorption spectroscopic studies on selected complexes determined the kISCto be 6.5×10^(9)s^(-1).Theoretical calculations confirmed the participation of minor d orbital into the lowest excited state,which led to an SOC value of 5.19 cm^(-1)between the lowest-lying singlet and triplet excited states.The yellow to deep red solution-processed OLEDs based on the new gold(Ⅰ)complexes incorporated with various D-A ligands demonstrated promising performances.This study validates a modular design for TADF metal complexes,which will broaden the choices of metal centers and allow for facile color tuning via simple ligand synthesis.
基金supported by the National Natural Science Foundation of China(92256304,U23A20593)the Fundamental Research Funds for the Central Universities(020514380294)。
文摘Efficient multi-resonance thermally activated delayed fluorescence(MR-TADF)materials hold significant potential for applications in organic light-emitting diodes(OLEDs)and ultra-high-definition displays.However,the stringent synthesis conditions and low yields typically associated with these materials pose substantial challenges for their practical applications.In this study,we introduce an innovative strategy that involves peripheral modification with sulfur and selenium atoms for two materials,CFDBNS and CFDBNSe.This approach enables a directed one-shot borylation process,achieving synthesis yields of 66%and 25%,respectively,while also enhancing reverse intersystem crossing rates.Both emitters exhibit ultra-narrowband sky-blue emissions centered around 474 nm,with full width at half maximum(FWHM)values as narrow as 19 nm in dilute toluene solutions,along with high photoluminescence quantum yields of 98%and 99%in doped films,respectively.The OLEDs based on CFDBNS and CFDBNSe display sky-blue emissions with peaks at 476 and 477 nm and exceptionally slender FWHM values of 23 nm.Furthermore,the devices demonstrate remarkable performances,achieving maximum external quantum efficiencies of 24.1%and 27.2%.This work presents a novel and straightforward approach for the incorporation of heavy atoms,facilitating the rapid construction of efficient MR-TADF materials for OLEDs.
基金supported by the National Natural Science Foundation of China(92256304,U23A20593)the Fundamental Research Funds for the Central Universities(020514380294)。
文摘Chirality is an important natural characteristic of organic molecules,and chiral organic molecules have shown extensive application in areas such as pharmaceutical development and material science.Benefiting from the ability to achieve circularly polarized luminescence(CPL),chiral luminescent materials have shown potential applications in anti-glare display,optical communication and,3D display,etc.Due to the ability to harvest both singlet and triplet excitons by a fast reverse intersystem crossing process without involving noble metals,chiral thermally activated delayed fluorescence(TADF)materials with point chirality,axial chirality,planar chirality and helical chirality are regarded as the state-of-the-art materials for circularly polarized organic light-emitting diodes(CP-OLEDs).In recent years,the chiral TADF materials and CP-OLEDs have rapidly developed,but unfortunately,the dissymmetry factors(g)are far from the requirement of practical applications.The ideal emitters and devices should have both high efficiency and a g factor,or at least a balance between these two elements.This review gives an overview of recent progress in chiral TADF materials,with a particular focus on the chiral skeleton,CPL property and device performance.Furthermore,the molecular design concept,device structure and methods to improve the g factors of chiral materials and CP-OLEDs are also discussed.
基金supported by the National Natural Science Foundation of China(92256304,U23A20593)。
文摘Chiral luminescence materials have potential applications in the field of three-dimensional displays due to their circularly polarized luminescence(CPL)characteristics.However,the further development of circularly polarized organic light-emitting diodes(CP-OLEDs)needs to meet the requirements of high efficiency,high color purity,low cost,and high dissymmetry factor(gPLor gEL),chiral multiple resonance thermally activated delayed fluorescence(MR-TADF)materials are considered as candidates in these aspects.Herein,based on a pair of chiral spirofluorene precursors,two pairs of high-performance chiral MR-TADF emitters((R/S)-p-Spiro-DtBuCzB and(R/S)-m-Spiro-DtBuCzB)are developed,which exhibit strong emissions peaking at 491 and 502 nm in toluene with full-width at half-maximum values of 25 and 33 nm,respectively.In addition,small singlet–triplet energy gaps of 0.15 and 0.10 eV with high absolute photoluminescence efficiencies of 95.0%and 96.7%are observed for p-Spiro-DtBuCzB and m-Spiro-DtBuCzB molecules,respectively.OLEDs based on p-Spiro-DtBuCzB and m-Spiro-DtBuCzB display high maximum external quantum efficiencies of 29.6%and 33.8%,respectively.Most importantly,CP-OLEDs present symmetric circularly polarized electroluminescence spectra with|gEL|factors of 3.36×10^(-4)and 7.66×10^(-4)for devices based on(R/S)-p-Spiro-DtBuCzB and(R/S)-m-Spiro-DtBuCzB enantiomers,respectively.
基金The National Natural Science Foundation of China(grant no.22101124)Shenzhen Science and Technology Program(grant nos.20220815163454004 and JCYJ20210324105009025)+1 种基金Natural Science Foundation of Guangdong Province of China(grant no.2022A1515011394)Shenzhen Nobel Prize Scientists Laboratory Project(grant no.C17783101)are acknowledged for the financial support.
文摘Thermally activated delayed fluorescence(TADF)polymeric materials based on through-space charge transfer(TSCT)have emerged as a highly studied topic in recent years.However,the construction of TSCT TADF materials via a supramolecular approach is still a big challenge.In this work,we report the noncovalent synthesis of TSCT TADF materials using a cyclic peptide-based bottle-brushed supramolecular polymer as a scaffold.By bringing the TSCT donor and acceptor in close proximity in space using the supramolecular scaffold,distinctive TADF emission in both solution and solid states could be achieved.Furthermore,the TADF system could be utilized as a sensitizer to coassemble with fluorescence acceptors to build thermally assisted fluorescence systems,resulting in color-tunable delayed fluorescence with high efficiency and color purity.Our findings provide a facile yet effective approach to designing and fabricating TSCT TADF materials,which might hold great potential for applications in the fields of organic light-emitting diode,bioimaging,and sensing.
基金Ministry of Education,Culture,Sports,Science and Technology,Grant/Award Number:ARIM/JPMXP1222JI0040Japan Society for the Promotion of Science,Grant/Award Numbers:KAKENHI/JP20KK0316,KAKENHI/JP21H05405,KAKENHI/JP22H02055,KAKENHI/JP23H02026,KAKENHI/JP23H03966,KAKENHI/JP20H02801。
文摘Carbazole-triazine dendrimers with a bulky terminal substituent were synthesized,and the thermally activated delayed fluorescence(TADF)property was investigated.Compared to unsubstituted carbazole dendrimers,dendrimers with bulky terminal substituents showed comparable to better photoluminescence quantum yields(PLQY)in neat films.Phenylfluorene(PF)-substituted dendrimers showed the highest PLQY of 81%,a smallΔEst of 0.06 eV,and the fastest reverse intersystem crossing(RISC)rate of∼1×10^(5 )s^(−1) compared to other dendrimers.Phosphorescence measurements of dendrimers and dendrons(fragments)indicate that the close proximity of the triplet energy of phenylfluorene-substituted carbazole dendrons(^(3)LE)to that of phenylfluorene-substituted dendrimers(^(1)CT,^(3)CT)contributes to RISC promotion and improves TADF efficiency.Terminal modification fine-tunes the energy level and suppresses intermolecular interactions,and this study provides a guideline for designing efficient solution-processable and non-doped TADF materials.
基金financial support from the National Natural Science Foundation of China(grant nos.52103220,52273164,and 52233010)the Shandong Provincial Natural Science Foundation(grant nos.ZR2022ZD37 and ZR2023QE078)+4 种基金the Ministry of Science and Technology of China(grant nos.2022YFB3603800 and 2018YFA0703200)the Fundamental Research Funds for the Central Universities(grant no.QNTD20)the Beijing National Laboratory for Molecular Sciences(grant no.BNLMS-CXXM-202012)the Natural Science Foundation of Qingdao(grant no.23-2-1-75-zyyd-jch)the Shandong Provincial Regular Undergraduate University Teacher Visiting and Training Fund.
文摘High-efficiency electroluminescent devices featuring simplified architecture have received considerable attention due to significant advantages in construction procedures and commercialized applications.However,there still remains a critical challenge with regard to the lack of organic semiconductors that simultaneously possess high luminescent efficiency and balanced carrier-transporting abilities.Herein,we design a thermally activated delayed fluorescence(TADF)emitter 4-(9,9-dimethyl-9,10-dihydroacridine)-4′-triphenylphosphineoxide-benzophenone(DMAC-BPTPO)by incorporating triphenylphosphine oxide into the donor–acceptor skeleton.The accessional electrontransporting moiety,rod-like dimer,and horizontally packing model synergistically enable DMAC-BP-TPO which possesses an excellent photoluminescence quantum yield of nearly 90%with a reverse intersystem crossing rate constant of 2.0×106 s−1,horizontal dipole ratio of 89%,and a balanced electron and hole mobilities with a small constrast ratio of 1.08.Eventually,simplified electroluminescent devices including organic lightemitting diodes(OLEDs)and organic light-emitting transistors(OLETs)incorporating DMAC-BP-TPO-based nondoped film are demonstrated due to their superior integrated optoelectronic properties along with preferable horizontal dipole orientation.A record-high external quantum efficiency value of 21.7%and 4.4%are finally achieved in the simplified nondoped OLED and OLET devices,which are among the highest values in the related research fields.This work provides a new avenue to develop a high-efficiency bipolar TADF emitter to advance the simplified electroluminescent devices.