Objective The assay of DNA mismatch repair (MMR) activity can be used as a biomarker for environmental condition detection and human disease diagnosis. Radioactive 32p-endlabeled DNA containing mismatch is extensive...Objective The assay of DNA mismatch repair (MMR) activity can be used as a biomarker for environmental condition detection and human disease diagnosis. Radioactive 32p-endlabeled DNA containing mismatch is extensively used as the substrate for MMR activity analyses. The aim of the present study is to develop a simple non-radioactive, but equally specific and sensitive method for the MMR activity assay. Methods A fluorescent label was chosen to replace the radioactive isotope label. Sensitive evaluation of the fluorescent label was carried out for the first time, and then the fluorescent label was compared with the isotope label in the MMR activity and DNA binding assays. Result LOD (limit of detection) of the fluorescent label was about 0.1 fmol and the relative signal strength displayed a pretty good linear relationship. Moreover, the fluorescent label method has equivalent sensitivity and performance as compared with the classical radioactive method in experiments. Conclusion In light of the sensitivity, reproducibility, safety, rapidity and long lifespan of the fluorescent label, this improved method can be applied to evaluation of biologic and toxic effects of environmental pollutants on man and other forms of life.展开更多
Objective To construct Cox7a2 fluorescent vector and study its effect on cytochrome C oxidase ( COX) activity in mouse Sertoli cell line TM4. Methods The coding region of CoxTa2 was amplified from mouse Sertoli cell l...Objective To construct Cox7a2 fluorescent vector and study its effect on cytochrome C oxidase ( COX) activity in mouse Sertoli cell line TM4. Methods The coding region of CoxTa2 was amplified from mouse Sertoli cell line TM4 by RT-PCR. PCR product was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
Near-infrared(NIR),particularly NIR-containing dual-/multimode afterglow,is very attractive in many fields of application,but it is still a great challenge to achieve such property of materials. Herein,we report a fac...Near-infrared(NIR),particularly NIR-containing dual-/multimode afterglow,is very attractive in many fields of application,but it is still a great challenge to achieve such property of materials. Herein,we report a facile method to prepare green and NIR dual-mode afterglow of carbon dots(CDs) through in situ embedding o-CDs(being prepared from o-phenylenediamine) into cyanuric acid(CA) matrix(named o-CDs@CA). Further studies reveal that the green and NIR afterglows of o-CDs@CA originate from thermal activated delayed fluorescence(TADF) and room temperature phosphorescence(RTP) of o-CDs,respectively. In addition,the formation of covalent bonds between o-CDs and CA,and the presence of multiple fixation and rigid e ects to the triplet states of o-CDs are confirmed to be critical for activating the observed dual-mode afterglow. Due to the shorter lifetime and insensitiveness to human vision of the NIR RTP of o-CDs@CA,it is completely covered by the green TADF during directly observing. The NIR RTP signal,however,can be readily captured if an optical filter(cut-o wavelength of 600 nm) being used. By utilizing these unique features,the applications of o-CDs@CA in anti-counterfeiting and information encryption have been demonstrated with great confidentiality. Finally,the as-developed method was confirmed to be applicable to many other kinds of CDs for achieving or enhancing their afterglow performances.展开更多
AIM: To explore the effects of the nucleoside analogues β-L-D4A and β-LPA on hepatitis B virus (HBV) promoters. METHODS: Four HBV promoters were amplified by polymerase chain reaction (PCR) and subcloned into ...AIM: To explore the effects of the nucleoside analogues β-L-D4A and β-LPA on hepatitis B virus (HBV) promoters. METHODS: Four HBV promoters were amplified by polymerase chain reaction (PCR) and subcloned into the expression vector pEGFP-1. The four recombinants controlled by HBV promoters were confirmed by restriction analysis and sequencing. Human hepatoma HepG2 cells transfected with the recombinant plasmids were treated with various concentrations of β-L-D4A and β-LPA. Then, enhanced green fluorescent protein (EGFP)-positive cells were detected by fluorescence microscopy and using a fluorescence activated cell sorter RESULTS: Four HBV promoters were separately obtained and successfully cloned into pEGFP-1, Expression of EGFP under the control of the surface promoter (Sp) and the X promoter (Xp) was inhibited by β-L-D4A in a dosedependent manner, while expression of EGFP under the control of the core promoter (Cp) and Xp was inhibited by β-LPA in a dose-dependent manner. CONCLUSION: The two novel nucleoside analogues investigated here can inhibit the activities of HBV promoters in a dose-dependent manner. These findings may explain the mechanisms of action by which these two novel compounds inhibit HBV DNA replication.展开更多
Hydrothermal plumes released from the eruption of sea floor hydrothermal fluids contain large amounts of oreforming materials. They precipitate within certain distances from the hydrothermal vent. Six surficial sedime...Hydrothermal plumes released from the eruption of sea floor hydrothermal fluids contain large amounts of oreforming materials. They precipitate within certain distances from the hydrothermal vent. Six surficial sediment samples from the Southwest Indian Ridge(SWIR) were analyzed by a portable X-ray fluorescence(PXRF) analyzer on board to find a favorable method fast and efficient enough for sea floor sulfide sediment geochemical exploration. These sediments were sampled near, at a moderate distance from, or far away from hydrothermal vents. The results demonstrate that the PXRF is effective in determining the enrichment characteristics of the oreforming elements in the calcareous sediments from the mid-ocean ridge. Sediment samples(〉40 mesh) have high levels of elemental copper, zinc, iron, and manganese, and levels of these elements in sediments finer than 40 mesh are lower and relatively stable. This may be due to relatively high levels of basalt debris/glass in the coarse sediments, which are consistent with the results obtained by microscopic observation. The results also show clear zoning of elements copper, zinc, arsenic, iron, and manganese in the surficial sediments around the hydrothermal vent. Sediments near the vent show relatively high content of the ore-forming elements and either high ratios of copper to iron content and zinc to iron content or high ratios of copper to manganese content and zinc to manganese content. These findings show that the content of the ore-forming elements in the sediments around hydrothermal vents are mainly influenced by the distance of sediments to the vent, rather than grain size. In this way, the PXRF analysis of surface sediment geochemistry is found to satisfy the requirements of recognition geochemical anomaly in mid-ocean ridge sediments. Sediments with diameters finer than 40 mesh should be used as analytical samples in the geochemical exploration for hydrothermal vents on mid-oceanic ridges. The results concerning copper, zinc, arsenic, iron, and manganese and their ratio features can be used as indicators in sediment geochemical exploration of seafloor sulfides.展开更多
Organic optoelectronic integrated devices(OIDs) with ultraviolet(UV) photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence(TADF) material 4, 5-bis(ca...Organic optoelectronic integrated devices(OIDs) with ultraviolet(UV) photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence(TADF) material 4, 5-bis(carbazol-9-yl)-1, 2-dicyanobenzene(2 CzPN) as host. The OIDs doping with typical red phosphorescent dye [tris(1-phenylisoquinoline)iridium(Ⅲ), Ir(piq)3], orange phosphorescent dye {bis[2-(4-tertbutylphenyl)benzothiazolato-N,C-(2')]iridium(acetylacetonate),(tbt)2 Ir(acac)}, and blue phosphorescent dye [bis(2, 4-di-fluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(Ⅲ), FIr6] were investigated and compared. The(tbt)2 Ir(acac)-doped orange device showed better performance than those of red and blue devices, which was ascribed to more effective energy transfer. Meanwhile, at a low dopant concentration of 3 wt.%, the(tbt)2 Ir(acac)-doped OIDs showed the maximum luminance, current efficiency, power efficiency of 70786 cd/m^2, 39.55 cd/A, and 23.92 lm/W, respectively, and a decent detectivity of 1.07 × 10^11 Jones at a bias of -2 V under the UV-350 nm illumination. This work may arouse widespread interest in constructing high efficiency and luminance OIDs based on doping phosphorescent dye.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
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
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
High cost of phosphors and significant efficiency roll-off at high brightness are the two main factors that limit the wide application of phosphorescent organic light-emitting diodes (PHOLEDs). Efforts have been pai...High cost of phosphors and significant efficiency roll-off at high brightness are the two main factors that limit the wide application of phosphorescent organic light-emitting diodes (PHOLEDs). Efforts have been paid to find ways to reduce the phosphors' concentration and efficiency roll-off of PHOLEDs. In this work, we reported red emission PHOLEDs with low dopant concentration and low efficiency roll-off based on a novel host material 2,4-biscyanophenyl-6-(12-phenylindole[2,3-a]carbazole-ll-yl)-1,3,5-triazine (BCPICT), with thermally activated delayed fluorescent (TADF) properties. The device with 1.0% dopant concentration displayed a maximum external quantum efficiency of 10.7%. When the dopant concentration was increased to 2.0%, the device displayed a maximum external quantum efficiency of 10.5% and a low efficiency roll-off of 5.7% at 1000 cd/m^2.展开更多
Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling betwe...Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling between carbazoledendrons and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine core.It is found that,compa red with the commo nly-used tert-butyl groups,the use of n-butoxy encapsulation groups can lead to smallersinglet-triplet energy gap for the dendrimers,producing stronger TADF effect together with faster reverse intersystem crossing process.Solution-processed TADF organic light-emitting diodes(OLEDs) utilizingalkoxy-encapsulated dendrimers O-D1 and O-D2 as emitters exhibitstate-of-the-art device efficiency withthe maximum external quantum efficiency up to 16.8% and 20.6%,respectively,which are ~1.6 and~2.0 times that of the tert-butyl-encapsulated counterparts.These results suggest that alkoxy encapsulation of the carbazole-based TADF dendrimers can be a promising approach for developing highly efficient emitters for solution-processed OLEDs.展开更多
Three carbazole derivatives, Ac PTC, Px PTC and Pt PTC, consisting of two 9,9-dimethyl-9,10-dihydroacridine,phenoxazine or phenothiazine donor groups and one diphenyltriazine acceptor group fixed at 1,8,9-positions of...Three carbazole derivatives, Ac PTC, Px PTC and Pt PTC, consisting of two 9,9-dimethyl-9,10-dihydroacridine,phenoxazine or phenothiazine donor groups and one diphenyltriazine acceptor group fixed at 1,8,9-positions of a single carbazole ring via phenylene, are designed and synthesized. X-ray diffraction analysis of Ac PTC reveals that there exist multiple π-π interactions between the donor and acceptor groups to form a sandwich-like structural unit with edge-to-face interaction model. The compounds thus show obvious thermally activated delayed fluorescence with through-space charge transfer character and possess considerable photoluminescence quantum yields of up to 73% in doped films with sky-blue to yellow emissions. The solution-processed electroluminescent devices achieve the highest maximum external quantum efficiencies of 10.0%, 11% and 5.6% for Ac PTC, Px PTC and Pt PTC, respectively, with small efficiency roll-offs.展开更多
Thermally activated delayed fluorescence(TADF) sensitized fluorescent organic light-emitting diodes(TSF-OLEDs) have shown great potential for the realization of high efficiency with low efficiency rolloff and good col...Thermally activated delayed fluorescence(TADF) sensitized fluorescent organic light-emitting diodes(TSF-OLEDs) have shown great potential for the realization of high efficiency with low efficiency rolloff and good color purity. However, the superior examples of TSF-OLEDs are still limited up to now.Herein, a trade-off strategy is presented for designing efficient TADF materials and achieving highperformance TSF-OLEDs via the construction of a new type of triazolotriazine(TAZTRZ) acceptor. The enhanced electron-withdrawing ability of TAZTRZ acceptor, fused by triazine(TRZ) and triazole(TAZ)together, enables TADF luminogens with small singlet-triplet energy gap(ΔE_(ST)) values. Meanwhile, the increased planarity from the TRZ-phenyl linkage(6:6 system) to the TAZ-phenyl linkage(5:6 system)can compensate the decrease of oscillator strength(f) while lowing ΔE_(ST), thus achieving a trade-off between small ΔE_(ST) and high f. As a result, the related TSF-OLED achieved an extremely low turn-on voltage of 2.1 V, an outstanding maximum external quantum efficiency(EQEmax) of 23.7% with small efficiency roll-off(EQE1000 of 23.2%;EQE5000 of 20.6%) and an impressively high maximum power efficiency of 82.1 lm W^(-1), which represents the state-of-the-art performance for yellow TSF-OLEDs.展开更多
Multi-resonance thermally activated delayed fluorescence(MR-TADF)emitters can enable narrowband emission with high color purity and electroluminescence efficiency.Nitrogen/carbonyl(N/C=O)system is receiving increasing...Multi-resonance thermally activated delayed fluorescence(MR-TADF)emitters can enable narrowband emission with high color purity and electroluminescence efficiency.Nitrogen/carbonyl(N/C=O)system is receiving increasing attention while the nitrogen/boron(N/B)system has been widely studied.Donor decoration is an effective approach for N/B type MR-TADF system but always leads to broadening and red-shifting of the emission band in N/C=O MR-TADF system.We attribute these unfavorable phenomena to the formation of intramolecular charge transfer between the MR-core and peripheral donors.To address this issue,we have developed a new strategy by decorating DMQAO(a fused N/C=O MR-core)with a triazine acceptor and a neutral terphenyl group to construct MTDMQAO and MBDMQAO,respectively.The introduction of the triazine acceptor not only realizes efficient narrowband emission in MTDMQAO,but also accelerates the reverse intersystem crossing process through enhanced spin-orbital coupling.As a result,MTDMQAO exhibits a significantly higher external quantum efficiency of 29.4%compared to the referent emitters,validating the rationality of our derivation strategy.This study highlights the potential of the N/C=O system for MR-TADF emitters and provides important insights for understanding the difference between N/B and N/C=O systems.展开更多
This study optimized the TADF feature of axial chiral enantiomers through precise donor engineering,and multicolor CP-TADFwas achieved in the axial chiral framework.Three pairs of axial enantiomers with donor-regulate...This study optimized the TADF feature of axial chiral enantiomers through precise donor engineering,and multicolor CP-TADFwas achieved in the axial chiral framework.Three pairs of axial enantiomers with donor-regulated TADF feature,namely(R/S)-TPCBD,(R/S)-DPCBD,and(R/S)-DPACBD,were synthesized by introducing carbazole donors with different substituents onto biphenyl cyanide acceptors.As the electron-donating ability of donors increases,the emission of these axial enantiomers ranges from 455,476 to 552 nm,their singlet-triplet energy gaps(ΔE_(ST))gradually decrease from 0.30,0.22 to 0.02 e V,accompanied by an increasement in the transition rate(k_(RISC))of RISC process,and the k_(RISC)of DPACBD could reach up to 7.16×10^(5)s^(-1).These axial enantiomers also exhibit mirror-image CD and circularly polarized luminescence(CPL)properties.Moreover,OLEDs based on TPCBD,DPCBD,and DPACBD as emitter were then fabricated,which displayed blue,green,and orange electroluminescence with EQE_(max)of 13.0%,16.4%,and 25.0%,respectively.The results also exhibited a phenomenon of device efficiency increasing with the enhancement of donor abilities.Notably,the CP-OLEDs using(R/S)-TPCBD,(R/S)-DPCBD and(R/S)-DPACBD as emitters displayed intense CPEL signals with g_(EL)values of 3.4×10^(-3)/-4.1×10^(-3),3.2×10^(-3)/-3.1×10^(-3)and2.3×10^(-3)/-2.1×10^(-3),respectively.By convenient molecular engineering of donor regulation in the same molecular skeleton,CP-TADF materials with multicolor CPEL and improved device performance could be conveniently achieved.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
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
基金grants from the Chinese National Natural Sciences Foundation(30821006,50973046)the Doctoral Station Science Foundation from the Chinese Ministry of Education(200802840023)the Jiangsu Provincial Natural Science Foundation (BK2010046,BK2008138,BK2008072,BY2009147)
文摘Objective The assay of DNA mismatch repair (MMR) activity can be used as a biomarker for environmental condition detection and human disease diagnosis. Radioactive 32p-endlabeled DNA containing mismatch is extensively used as the substrate for MMR activity analyses. The aim of the present study is to develop a simple non-radioactive, but equally specific and sensitive method for the MMR activity assay. Methods A fluorescent label was chosen to replace the radioactive isotope label. Sensitive evaluation of the fluorescent label was carried out for the first time, and then the fluorescent label was compared with the isotope label in the MMR activity and DNA binding assays. Result LOD (limit of detection) of the fluorescent label was about 0.1 fmol and the relative signal strength displayed a pretty good linear relationship. Moreover, the fluorescent label method has equivalent sensitivity and performance as compared with the classical radioactive method in experiments. Conclusion In light of the sensitivity, reproducibility, safety, rapidity and long lifespan of the fluorescent label, this improved method can be applied to evaluation of biologic and toxic effects of environmental pollutants on man and other forms of life.
文摘Objective To construct Cox7a2 fluorescent vector and study its effect on cytochrome C oxidase ( COX) activity in mouse Sertoli cell line TM4. Methods The coding region of CoxTa2 was amplified from mouse Sertoli cell line TM4 by RT-PCR. PCR product was
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the National Natural Science Foundation of China (52003284,51872300 and U1832110)the China Postdoctoral Science Foundation (BX20190338)S&T Innovation 2025 Major Special Program of Ningbo (2018B10054) for financially supporting this work。
文摘Near-infrared(NIR),particularly NIR-containing dual-/multimode afterglow,is very attractive in many fields of application,but it is still a great challenge to achieve such property of materials. Herein,we report a facile method to prepare green and NIR dual-mode afterglow of carbon dots(CDs) through in situ embedding o-CDs(being prepared from o-phenylenediamine) into cyanuric acid(CA) matrix(named o-CDs@CA). Further studies reveal that the green and NIR afterglows of o-CDs@CA originate from thermal activated delayed fluorescence(TADF) and room temperature phosphorescence(RTP) of o-CDs,respectively. In addition,the formation of covalent bonds between o-CDs and CA,and the presence of multiple fixation and rigid e ects to the triplet states of o-CDs are confirmed to be critical for activating the observed dual-mode afterglow. Due to the shorter lifetime and insensitiveness to human vision of the NIR RTP of o-CDs@CA,it is completely covered by the green TADF during directly observing. The NIR RTP signal,however,can be readily captured if an optical filter(cut-o wavelength of 600 nm) being used. By utilizing these unique features,the applications of o-CDs@CA in anti-counterfeiting and information encryption have been demonstrated with great confidentiality. Finally,the as-developed method was confirmed to be applicable to many other kinds of CDs for achieving or enhancing their afterglow performances.
基金Supported by The National Natural Science Foundation of China, No. 30330680
文摘AIM: To explore the effects of the nucleoside analogues β-L-D4A and β-LPA on hepatitis B virus (HBV) promoters. METHODS: Four HBV promoters were amplified by polymerase chain reaction (PCR) and subcloned into the expression vector pEGFP-1. The four recombinants controlled by HBV promoters were confirmed by restriction analysis and sequencing. Human hepatoma HepG2 cells transfected with the recombinant plasmids were treated with various concentrations of β-L-D4A and β-LPA. Then, enhanced green fluorescent protein (EGFP)-positive cells were detected by fluorescence microscopy and using a fluorescence activated cell sorter RESULTS: Four HBV promoters were separately obtained and successfully cloned into pEGFP-1, Expression of EGFP under the control of the surface promoter (Sp) and the X promoter (Xp) was inhibited by β-L-D4A in a dosedependent manner, while expression of EGFP under the control of the core promoter (Cp) and Xp was inhibited by β-LPA in a dose-dependent manner. CONCLUSION: The two novel nucleoside analogues investigated here can inhibit the activities of HBV promoters in a dose-dependent manner. These findings may explain the mechanisms of action by which these two novel compounds inhibit HBV DNA replication.
基金The Open Fund of Key Laboratory of Marine Mineral Resources,Ministry of Land and Resources under contract No.KLMMR-2015-B-03the China Ocean Mineral Resources Research and Development Association Project under contract Nos DY125-11-R-01 and DY125-11-R-05the National Basic Research Program(973 program)of China under contract No.2012CB417305
文摘Hydrothermal plumes released from the eruption of sea floor hydrothermal fluids contain large amounts of oreforming materials. They precipitate within certain distances from the hydrothermal vent. Six surficial sediment samples from the Southwest Indian Ridge(SWIR) were analyzed by a portable X-ray fluorescence(PXRF) analyzer on board to find a favorable method fast and efficient enough for sea floor sulfide sediment geochemical exploration. These sediments were sampled near, at a moderate distance from, or far away from hydrothermal vents. The results demonstrate that the PXRF is effective in determining the enrichment characteristics of the oreforming elements in the calcareous sediments from the mid-ocean ridge. Sediment samples(〉40 mesh) have high levels of elemental copper, zinc, iron, and manganese, and levels of these elements in sediments finer than 40 mesh are lower and relatively stable. This may be due to relatively high levels of basalt debris/glass in the coarse sediments, which are consistent with the results obtained by microscopic observation. The results also show clear zoning of elements copper, zinc, arsenic, iron, and manganese in the surficial sediments around the hydrothermal vent. Sediments near the vent show relatively high content of the ore-forming elements and either high ratios of copper to iron content and zinc to iron content or high ratios of copper to manganese content and zinc to manganese content. These findings show that the content of the ore-forming elements in the sediments around hydrothermal vents are mainly influenced by the distance of sediments to the vent, rather than grain size. In this way, the PXRF analysis of surface sediment geochemistry is found to satisfy the requirements of recognition geochemical anomaly in mid-ocean ridge sediments. Sediments with diameters finer than 40 mesh should be used as analytical samples in the geochemical exploration for hydrothermal vents on mid-oceanic ridges. The results concerning copper, zinc, arsenic, iron, and manganese and their ratio features can be used as indicators in sediment geochemical exploration of seafloor sulfides.
基金Project supported by the National Natural Science Foundation of China(Grant No.61675041)the National Science Funds for Creative Research Groups of China(Grant No.61421002)
文摘Organic optoelectronic integrated devices(OIDs) with ultraviolet(UV) photodetectivity and different color emitting were constructed by using a thermally activated delayed fluorescence(TADF) material 4, 5-bis(carbazol-9-yl)-1, 2-dicyanobenzene(2 CzPN) as host. The OIDs doping with typical red phosphorescent dye [tris(1-phenylisoquinoline)iridium(Ⅲ), Ir(piq)3], orange phosphorescent dye {bis[2-(4-tertbutylphenyl)benzothiazolato-N,C-(2')]iridium(acetylacetonate),(tbt)2 Ir(acac)}, and blue phosphorescent dye [bis(2, 4-di-fluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(Ⅲ), FIr6] were investigated and compared. The(tbt)2 Ir(acac)-doped orange device showed better performance than those of red and blue devices, which was ascribed to more effective energy transfer. Meanwhile, at a low dopant concentration of 3 wt.%, the(tbt)2 Ir(acac)-doped OIDs showed the maximum luminance, current efficiency, power efficiency of 70786 cd/m^2, 39.55 cd/A, and 23.92 lm/W, respectively, and a decent detectivity of 1.07 × 10^11 Jones at a bias of -2 V under the UV-350 nm illumination. This work may arouse widespread interest in constructing high efficiency and luminance OIDs based on doping phosphorescent dye.
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 (51525304)the National Key Basic Research and Development Program of China (2015CB655002)
文摘High cost of phosphors and significant efficiency roll-off at high brightness are the two main factors that limit the wide application of phosphorescent organic light-emitting diodes (PHOLEDs). Efforts have been paid to find ways to reduce the phosphors' concentration and efficiency roll-off of PHOLEDs. In this work, we reported red emission PHOLEDs with low dopant concentration and low efficiency roll-off based on a novel host material 2,4-biscyanophenyl-6-(12-phenylindole[2,3-a]carbazole-ll-yl)-1,3,5-triazine (BCPICT), with thermally activated delayed fluorescent (TADF) properties. The device with 1.0% dopant concentration displayed a maximum external quantum efficiency of 10.7%. When the dopant concentration was increased to 2.0%, the device displayed a maximum external quantum efficiency of 10.5% and a low efficiency roll-off of 5.7% at 1000 cd/m^2.
基金the financial support from the Science and Technology Development Plan Project of Jilin Province (No.20180520003JH)the Natural Science Fund Project of Changchun University of Science and Technology (No.XQNJJ2017-14)the Youth Innovation Promotion Association of Chinese Academy of Sciences (No.2015180)。
文摘Two n-butoxy-encapsulated dendritic thermally activated delayed fluorescent(TADF) emitters(namely O-D1 and O-D2) with the first-/second-generation carbazoledendrons are designed and synthesized via C—N coupling between carbazoledendrons and 2,4,6-tris(4-bromophenyl)-1,3,5-triazine core.It is found that,compa red with the commo nly-used tert-butyl groups,the use of n-butoxy encapsulation groups can lead to smallersinglet-triplet energy gap for the dendrimers,producing stronger TADF effect together with faster reverse intersystem crossing process.Solution-processed TADF organic light-emitting diodes(OLEDs) utilizingalkoxy-encapsulated dendrimers O-D1 and O-D2 as emitters exhibitstate-of-the-art device efficiency withthe maximum external quantum efficiency up to 16.8% and 20.6%,respectively,which are ~1.6 and~2.0 times that of the tert-butyl-encapsulated counterparts.These results suggest that alkoxy encapsulation of the carbazole-based TADF dendrimers can be a promising approach for developing highly efficient emitters for solution-processed OLEDs.
基金supported by the National Natural Science Foundation of China (Nos. 51973210, 21805271 and 21674110)the Science and Technology Development Project of Jilin Province, China (No. 20190201071JC)。
文摘Three carbazole derivatives, Ac PTC, Px PTC and Pt PTC, consisting of two 9,9-dimethyl-9,10-dihydroacridine,phenoxazine or phenothiazine donor groups and one diphenyltriazine acceptor group fixed at 1,8,9-positions of a single carbazole ring via phenylene, are designed and synthesized. X-ray diffraction analysis of Ac PTC reveals that there exist multiple π-π interactions between the donor and acceptor groups to form a sandwich-like structural unit with edge-to-face interaction model. The compounds thus show obvious thermally activated delayed fluorescence with through-space charge transfer character and possess considerable photoluminescence quantum yields of up to 73% in doped films with sky-blue to yellow emissions. The solution-processed electroluminescent devices achieve the highest maximum external quantum efficiencies of 10.0%, 11% and 5.6% for Ac PTC, Px PTC and Pt PTC, respectively, with small efficiency roll-offs.
基金This work was supported by the National Natural Science Foundation of China(21432005)the Fundamental Research Funds for the Central Universities and the Comprehensive Training Platform Specialized Laboratory,College of Chemistry,Sichuan University。
文摘Thermally activated delayed fluorescence(TADF) sensitized fluorescent organic light-emitting diodes(TSF-OLEDs) have shown great potential for the realization of high efficiency with low efficiency rolloff and good color purity. However, the superior examples of TSF-OLEDs are still limited up to now.Herein, a trade-off strategy is presented for designing efficient TADF materials and achieving highperformance TSF-OLEDs via the construction of a new type of triazolotriazine(TAZTRZ) acceptor. The enhanced electron-withdrawing ability of TAZTRZ acceptor, fused by triazine(TRZ) and triazole(TAZ)together, enables TADF luminogens with small singlet-triplet energy gap(ΔE_(ST)) values. Meanwhile, the increased planarity from the TRZ-phenyl linkage(6:6 system) to the TAZ-phenyl linkage(5:6 system)can compensate the decrease of oscillator strength(f) while lowing ΔE_(ST), thus achieving a trade-off between small ΔE_(ST) and high f. As a result, the related TSF-OLED achieved an extremely low turn-on voltage of 2.1 V, an outstanding maximum external quantum efficiency(EQEmax) of 23.7% with small efficiency roll-off(EQE1000 of 23.2%;EQE5000 of 20.6%) and an impressively high maximum power efficiency of 82.1 lm W^(-1), which represents the state-of-the-art performance for yellow TSF-OLEDs.
基金supported by the National Natural Science Foundation of China(51873139,22175124,62175171,61961160731)the Natural Science Foundation of Jiangsu Province of China(BK20220057)+4 种基金the Suzhou Science and Technology Plan Project(SYG202010)supported by the Suzhou Key Laboratory of Functional Nano&Soft Materialsthe Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 Projectthe Joint International Research Laboratory of Carbon-Based Functional Materials and Devices。
文摘Multi-resonance thermally activated delayed fluorescence(MR-TADF)emitters can enable narrowband emission with high color purity and electroluminescence efficiency.Nitrogen/carbonyl(N/C=O)system is receiving increasing attention while the nitrogen/boron(N/B)system has been widely studied.Donor decoration is an effective approach for N/B type MR-TADF system but always leads to broadening and red-shifting of the emission band in N/C=O MR-TADF system.We attribute these unfavorable phenomena to the formation of intramolecular charge transfer between the MR-core and peripheral donors.To address this issue,we have developed a new strategy by decorating DMQAO(a fused N/C=O MR-core)with a triazine acceptor and a neutral terphenyl group to construct MTDMQAO and MBDMQAO,respectively.The introduction of the triazine acceptor not only realizes efficient narrowband emission in MTDMQAO,but also accelerates the reverse intersystem crossing process through enhanced spin-orbital coupling.As a result,MTDMQAO exhibits a significantly higher external quantum efficiency of 29.4%compared to the referent emitters,validating the rationality of our derivation strategy.This study highlights the potential of the N/C=O system for MR-TADF emitters and provides important insights for understanding the difference between N/B and N/C=O systems.
基金supported by the National Natural Science Foundation of China(22122111,92256304)the Ministry of Science and Technology of China(2022YFA1204401)。
文摘This study optimized the TADF feature of axial chiral enantiomers through precise donor engineering,and multicolor CP-TADFwas achieved in the axial chiral framework.Three pairs of axial enantiomers with donor-regulated TADF feature,namely(R/S)-TPCBD,(R/S)-DPCBD,and(R/S)-DPACBD,were synthesized by introducing carbazole donors with different substituents onto biphenyl cyanide acceptors.As the electron-donating ability of donors increases,the emission of these axial enantiomers ranges from 455,476 to 552 nm,their singlet-triplet energy gaps(ΔE_(ST))gradually decrease from 0.30,0.22 to 0.02 e V,accompanied by an increasement in the transition rate(k_(RISC))of RISC process,and the k_(RISC)of DPACBD could reach up to 7.16×10^(5)s^(-1).These axial enantiomers also exhibit mirror-image CD and circularly polarized luminescence(CPL)properties.Moreover,OLEDs based on TPCBD,DPCBD,and DPACBD as emitter were then fabricated,which displayed blue,green,and orange electroluminescence with EQE_(max)of 13.0%,16.4%,and 25.0%,respectively.The results also exhibited a phenomenon of device efficiency increasing with the enhancement of donor abilities.Notably,the CP-OLEDs using(R/S)-TPCBD,(R/S)-DPCBD and(R/S)-DPACBD as emitters displayed intense CPEL signals with g_(EL)values of 3.4×10^(-3)/-4.1×10^(-3),3.2×10^(-3)/-3.1×10^(-3)and2.3×10^(-3)/-2.1×10^(-3),respectively.By convenient molecular engineering of donor regulation in the same molecular skeleton,CP-TADF materials with multicolor CPEL and improved device performance could be conveniently achieved.
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(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.