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1.
An organic crystal of 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (pCBP) exhibits time-dependent afterglow color from blue to orange over 1 s. Both experimental and computational data confirm that the color evolution results from well-separated, long-persistent thermally activated delayed fluorescence (TADF) and room-temperature phosphorescence (RTP) with different but comparable decay rates. TADF is enabled by a small S1–T1 energy gap of 0.7 kcal mol−1. The good separation of TADF and RTP is due to a 11.8 kcal mol−1 difference in the S0 energies of the S1 and T1 structures, indicating that apart from the excited-state properties, tuning the ground state is also important for luminescence properties. This afterglow color evolution of pCBP allows its applications in anticounterfeiting and data encryption with high security levels.  相似文献   

2.
An organic crystal of 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl (pCBP) exhibits time‐dependent afterglow color from blue to orange over 1 s. Both experimental and computational data confirm that the color evolution results from well‐separated, long‐persistent thermally activated delayed fluorescence (TADF) and room‐temperature phosphorescence (RTP) with different but comparable decay rates. TADF is enabled by a small S1–T1 energy gap of 0.7 kcal mol?1. The good separation of TADF and RTP is due to a 11.8 kcal mol?1 difference in the S0 energies of the S1 and T1 structures, indicating that apart from the excited‐state properties, tuning the ground state is also important for luminescence properties. This afterglow color evolution of pCBP allows its applications in anticounterfeiting and data encryption with high security levels.  相似文献   

3.
The development of flexible, room-temperature phosphorescence (RTP) materials remains challenging owing to the quenching of their unstable triplet excitons via molecular motion. Therefore, a polymer matrix with Tg higher than room temperature is required to prevent polymer segment movement. In this study, a RTP material was developed by incorporating a 4-biphenylboronic acid (BPBA) phosphor into a poly(vinylidene fluoride) (PVDF) matrix (Tg=−27.1 °C), which exhibits a remarkable UV-light-dependent oxygen consumption phosphorescence with a lifetime of 1275.7 ms. The adjustable RTP performance is influenced by the crystallinity and polymorph (α, β, and γ phases) fraction of PVDF, therefore, the low Tg of the PVDF matrix enables the polymeric segmental motion upon microwave irradiation. Consequently, a reduction in the crystallinity and an increase in the α phase fraction in PVDF film induces RTP after 2.45 GHz microwave irradiation. These findings open up new avenues for constructing crystalline and phase-dependent RTP materials while demonstrating a promising approach toward microwave detection.  相似文献   

4.
Organic ultralong room temperature phosphorescence (RTP), or organic afterglow, is a unique phenomenon, gaining widespread attention due to its far-reaching application potential and fundamental interest. Here, two laterally expanded 9,10-dimesityl-dihydro-9,10-diboraanthracene (DBA) derivatives are demonstrated as excellent afterglow materials for red and blue-green light emission, which is traced back to persistent thermally activated delayed fluorescence and RTP. The lateral substitution of polycyclic DBA scaffold, together with weak transversal electron-donating mesityl groups, ensures the optimal molecular properties for (reverse) intersystem crossing and long-lived triplet states in a rigid poly(methyl methacrylate) matrix. The achieved afterglow emission quantum yields of up to 3 % and 15 %, afterglow lifetimes up to 0.8 s and 3.2 s and afterglow durations up to 5 s and 25 s (for red and blue-green emitters, respectively) are attributed to the properties of single molecules.  相似文献   

5.
A series of dicyano-imidazole-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain pure blue-emitting organic light-emitting diodes (OLEDs). The targeted molecules used dicyano-imidazole with a short-conjugated system as the electron acceptor to strong intermolecular π-π interactions, and provide a relatively shallow energy level of the lowest unoccupied molecular orbital (LUMO). The cyano group was selected to improve imidazole as an electron acceptor due to its prominent electron-transporting characteristics. Four different electron donors, that is, 9,9-dimethyl-9,10-dihydroacridine (DMAC), 10H-spiro(acridine-9,9’-fluoren) (SPAC), and 9,9-diphenyl-9,10-dihydroacridine (DPAC), were used to alternate the highest occupied molecular orbital (HOMO) energy level to tune the emission color further. The crowded molecular structure in space makes the electron donor and acceptor almost orthogonal, reducing the energy gap (ΔEST) between the first excited singlet (S1) and the triplet (T1) states and introducing significant TADF property. The efficiencies of the blue-emissive devices with imM-SPAC and imM-DMAC obtained in this work are the highest among the reported imidazole-based TADF-OLEDs, which are 13.8 % and 13.4 %, respectively. Both of Commission Internationale de l′Eclairage (CIE) coordinates are close to the saturated blue region at (0.17, 0.18) and (0.16, 0.19), respectively. Combining these tailor-made TADF compounds with specific device architectures, electroluminescent (EL) emission from sky-blue to deep-blue could be achieved, proving their great potential in EL applications.  相似文献   

6.
Three new emitters,namely 10,10'-(quinoline-2,8-diyl)bis(10 H-phenoxazine)(Fene),10,10'-(quinoline-2,8-diyl)bis(10 H-phenothiazine)(Fens) and 10,10'-(quinoline-2,8-diyl)bis(9,9-dimethyl-9,10-dihydroacridine)(Yad),featuring quinoline as a new electron acceptor have been designed and conveniently synthesized.These emitters possessed small singlet-triplet splitting energy(ΔEst) and twisted structures,which not only endowed them show thermally activated delayed fluorescence(TADF)properties but also afforded a remarkable aggregation-induced emission(AIE) feature.Moreover,they also showed aggregation-induced delayed fluorescence(AIDF) property and good photoluminescence(PL) property,which are the ideal emitters for non-doped organic light-emitting diodes(OLEDs).Furthermore,high-performance non-doped OLEDs based on Fene,Fens and Yad were achieved,and excelle nt maximum external quantum efficiencies(EQE_(max)) of 14,9%,13.1% and 17,4%,respectively,were obtained.It was also found that all devices exhibited relatively low turn-on voltages ranging from 3.0 V to3.2 V probably due to their twisted conformation and the AIDF properties.These results demonstrated the quinoline-based emitters could have a promising application in non-doped OLEDs.  相似文献   

7.
《中国化学快报》2023,34(8):108070
Carbon dots (CDs) with room-temperature phosphorescence (RTP) have attracted dramatically growing interest in optical functional materials. However, the photoluminescence mechanism of CDs is still a vital and challenging topic. In this work, we prepared CD-based RTP materials via melting boric acid with various lengths of alkyl amine compounds as precursors. The spatial effect on the structure and the RTP properties of CDs were systematically investigated. With the increase in carbon chain length, the interplanar spacing of the carbon core expands and crosslink-enhanced emission weakens, resulting in a decrease in the phosphorescence intensity and lifetimes. Meanwhile, based on triplet-to-singlet resonance energy transfer, we employed intense and long-lived phosphorescence CDs as the donor and short-lived fluorescent dyes as the acceptor to achieve long-lived multicolor afterglow. By the triplet-to-singlet resonance energy transfer, the afterglow color can change from green to orange. The afterglow lifetimes are more than 0.9 s. Thanks to the outstanding afterglow properties, the composites were used for time-resolved and multiple-color advanced anticounterfeiting. This work will promote the design of multicolor and long-lived afterglow materials and expand their applications.  相似文献   

8.
The configuration of the lowest excited state of acenaphthenone, S1(π, π*) or T1(π, π*), depending on the solvent, dominates photoluminescence. The T1(n, π*) state in aprotic organic solvents is responsible for the phosphorescence of acenaphthenone. The wavelengths of the phosphorescence measured in benzene are 576 nm and 635 nm (vibronic) with 3.3 × 10?4 quantum efficiency. However, the S1(π, π*) state in protic solution which dominates the fluorescence emission depending upon acidity is the most distinctive feature of acenaphthenone. The wavelengths of the emissions are 446 nm under water solvation with 0.185 quantum efficiency and 538 nm with 0.097 quantum efficiency under high acidity. The emission at 446 nm is assigned from a H-bonded keto-form excited state, whereas the emission at 538 nm is probably due to the excited state of protonated keto-form. The pKa value in aqueous solution measured by diminution of fluorescence in basic solutions is 12.5 ± 0.4.  相似文献   

9.
Four cyclometalated Pt(II) complexes, i.e., [(L2)PtCl] (1b), [(L3)PtCl] (1c), [(L2)PtCCC6H5] (2b) and [(L3)PtCCC6H5] (2c) (HL2 = 4-[p-(N-butyl-N-phenyl)anilino]-6-phenyl-2,2′-bipyridine and HL3 = 4-[p-(N,N′-dibutyl-N′-phenyl)phenylene-diamino]-phenyl-6-phenyl-2,2′-bipyridine), have been synthesized and verified by 1H NMR, 13C NMR and X-ray crystallography. Unlike previously reported complexes [(L1)PtCl] (1a) and [(L1)PtCCC6H5] (2a) (HL1 = 4,6-diphenyl-2,2′-bipyridine), intense and continuous absorption bands in the region of 300-500 nm with strong metal-to-ligand charge transfer (1MLCT) (dπ(Pt) → π(L)) transitions (ε ∼ 2 × 104 dm3 mol−1 cm−1) at 449-467 nm were observed in the UV-Vis absorption spectra of complexes 1b, 1c, 2b and 2c. Meanwhile, with the introduction of electron-donating arylamino groups in the ligands of 1a and 2a, complexes 1b and 2b display stronger phosphorescence in CH2Cl2 solutions at room temperature with bathochromically shifted emission maxima at 595 and 600 nm, relatively higher quantum yields of 0.11 and 0.26, and much longer lifetimes of 8.4 and 4.5 μs, respectively. An electrochromic film of 1b-based polymer was obtained on Pt or ITO electrode surface, which suggests an efficient oxidative polymerization behavior. An orange multilayer organic light-emitting diode with 1b as phosphorescent dopant was fabricated, achieving a maximum current efficiency of 11.3 cd A−1 and a maximum external efficiency of 5.7%. The luminescent properties of complexes 1c and 2c are dependent on pH value and solvent polarity, which is attributed to the protonation of arylamino units in the C^N^N cyclometalating ligands.  相似文献   

10.
Heavy atom-induced phosphorescence of organic chromophores that originates from spin?Corbit coupling (SOC) is always accompanied by fluorescence quenching concomitant with a reduction of the triplet excited state lifetime. However, such changes are typically manifest by fluorescence quenching at room temperature and phosphorescence sensitization at cryogenic temperatures. Herein we overview our efforts over the past decade in which both internal and external heavy-atom effects (HAEs) can trigger room temperature phosphorescence (RTP) with dramatic shortening of the phosphorescence radiative lifetime by several orders of magnitude. Such spectral properties render new classes of phosphorescent materials for potential use in organic light-emitting diodes (OLEDs). The molecular systems described in this paper are organic fluorophores that are ??-complexed or ??-bonded to a multinuclear d10 transition metal center, the presence of which leads to phosphorescence sensitization because of the significant SOC in such materials.  相似文献   

11.
We report on a luminescent phenomenon in Dy3+-doped SrSiO3 long-lasting phosphor. After irradiation by a 254-nm UV lamp for 5 min, the Dy3+-doped SrSiO3 phosphor emits white light-emitting long-lasting phosphorescence for more than 1 h even after the irradiation source has been removed. Photoluminescence, long-lasting phosphorescence and thermoluminescence (TL) spectra are used to explain this phenomenon. Photoluminescence spectra reveal that the white light-emitting long-lasting phosphorescence originated from the two mixtures of Dy3+ characteristic luminescence, the 480-nm blue emission (4F9/26H15/2) and the 572-nm yellow emission (4F9/26H13/2). TL spectra shows that the introduction of Dy3+ ions into the SrSiO3 host produces a highly dense trapping level at 377 K (0.59 eV), which is responsible for the long-lasting phosphorescence at room temperature. A possible mechanism of the long-lasting phosphorescence based on the experimental results is proposed. It is considered that the long-lasting phosphorescence is due to persistent energy transfer from the electron traps to the Dy3+ ions, which creates the persistent luminescence of Dy3+ to produce the white light-emitting long-lasting phosphorescence.  相似文献   

12.
Time-dependent density functional theory with quadratic response methodology is used in order to calculate and compare spin–orbit coupling effects and the main mechanism of phosphorescence of the neutral Ir(ppy)3 and cationic [Ir(bpy)3]3+ tris-iridium compounds, [Ir(ppy)2(bpy)]+ and [Ir(2-phenylpyridine)2(4,4′-tert-butyl-2,2′-bipyridine]+ complexes, including also the recently synthesised [Ir(2-phenylpyridine)2(4,4′-dimethylamino-2,2′-bipyridine]+ and [Ir(2,4-difluorophenylpyridine)2(4,4′-dimethylamino-2,2′-bipyridine]+ dyes, where ppy = 2-phenylpyridine and bpy = 2,2′-bipyridine ligands. Comparison with the symmetric, lighter and more studied [Ru(bpy)3]2+ and [Rh(bpy)3]3+ complexes is also presented. Variations in phosphorescence lifetimes for Ir(ppy)3 and [Ir(bpy)3]3+ dyes as well as for the mixed cationic complexes are well reproduced by the quadratic response method. All the ortho-metalated iridium compounds exhibit strong phosphorescence, which is used in organic light-emitting diodes (OLEDs) to overcome the efficiency limit imposed by the formation of triplet excitons. The results from the first principle theoretical analysis of phosphorescence have helped to clarify the connections between the main features of electronic structure and the photo-physical properties of the studied heavy organometallic OLED materials.  相似文献   

13.
Efficient multifunctional materials acting as violet-blue emitters, as well as host materials for phosphorescent OLEDs, are crucial but rare due to demand that they should have high first singlet state (S1) energy and first triplet state (T1) energy simultaneously. In this study, two new violet-blue bipolar fluorophores, TPA-PI-SBF and SBF-PI-SBF , were designed and synthesized by introducing the hole transporting moiety triphenylamine (TPA) and spirobifluorene (SBF) unit that has high T1 into high deep blue emission quantum yield group phenanthroimidazole (PI). As the results, the non-doped OLEDs based on TPA-PI-SBF exhibited excellent EL performance with a maximum external quantum efficiency (EQEmax) of 6.76 % and a violet-blue emission with Commission Internationale de L′Eclairage (CIE) of (0.152, 0.059). The device based on SBF-PI-SBF displayed EQEmax of 6.19 % with CIE of (0.159, 0.049), which nearly matches the CIE coordinates of the violet-blue emitters standard of (0.131, 0.046). These EL performances are comparable to the best reported non-doped deep or violet-blue emissive OLEDs with CIEy<0.06 in recent years. Additionally, the green, yellow and red phosphorescent OLEDs with TPA-PI-SBF and SBF-PI-SBF as host materials achieved a high EQEmax of about 20 % and low efficiency roll-off at the ultra-high luminance of 10 000 cd m−2. These results provided a new construction strategy for designing high-performance violet-blue emitters, as well as efficient host materials for phosphorescent OLEDs.  相似文献   

14.
溶液中N-乙酸基取代氮氧杂大环及其配合物稳定性研究   总被引:1,自引:0,他引:1  
用pH电位滴定法在25℃,0.5mol·L-1KNO3水溶液中测定了三种大环化合物:H2L1(1,12-二氮杂-3,4:9,10-二苯并-5,8-二氧杂环十五烷-N,N'-二乙酸);H3L2(1,12,15-三氮杂-3,4:9,10-二苯并-5,8-二氧杂环十七烷-N,N',N″-三乙酸)和H2L3(1,15-二氮杂-3,4:12,13-二苯并-5,8,11-三氧杂环十八烷-N,N′-二乙酸)的逐级质子化常数.又测定了它们与Cu2+、Ni2+、Pb2+配合物的稳定常数,以及H2L3与镧系金属La3+、Pr3+、Nd3+、Eu3+、Sm3+、Gd3+、Dy3+、Yb3+配合物的稳定常数.讨论了三种大环化合物质子化的一般顺序及其与各种离子配位时稳定性选择规律.说明了影响配位稳定性的有关因素.  相似文献   

15.
Organic room temperature phosphorescence (RTP) attracts extensive attentions, but still faces the challenge of achieving both high RTP efficiencies (ηRTP) and long lifetimes (τRTP), due to the intrinsic contradiction between triplet radiation and stabilization. In this work, we developed three carbazole-triphenylphosphine hybrids named xCzTPP, in which phosphine groups provide nonbonding electrons and steric hindrance to modulate intermolecular p-π and π-π interactions. With the rational orientations and spatial positions of functional groups, para-substituted pCzTPP achieves high ηRTP over 10 % and more than twofold increased τRTP (>600 ms), compared to ortho- and meta- isomers. Theoretical simulation and photophysical investigation indicate that the strongest intermolecular p-π and π-π electronic interplays of pCzTPP harmonize high transition probability of 3pπ state and triplet stability of 3ππ state, reflecting the p-π and π-π synergy in RTP process.  相似文献   

16.
《中国化学快报》2023,34(7):107882
The influence of 1H-benzo[f]indole (Bd) and its derivatives on room temperature phosphorescence (RTP) has raised great concern since they were found to significantly affect RTP of the extensively studied carbazole (Cz) derivatives. However, the role of Bd itself existing in Cz-based or other doping systems was still unclear. In order to clarify its intrinsic phosphorescent property, Bd was introduced as a guest into different organic matrixes including substituted Cz derivatives and polymers. The phosphorescence located in 560–620 nm was confirmed to be derived from Bd itself, which can be detected whatever Bd was doped in the crystal or amorphous state of Cz derivatives. The suitable energy gap between Cz derivatives and Bd is the key to achieve ultralong RTP of Bd. Additionally, when doped in polymers with plenty of hydrogen bonds, RTP of Bd with lifetime over 280 ms was easily obtained. Among them, Bd@PHEMA (poly(hydroxyethyl methacrylate) exhibited superior phosphorescence, with yellow afterglow lasting for over 2.5 s. Therefore, this work demonstrated that a new organic RTP phosphor, Bd, is discovered, and ultralong RTP of Bd can be achieved not only doped in Cz derivatives but also in polymers as the hosts.  相似文献   

17.
Developing efficient deep-blue non-doped organic light-emitting diodes (OLEDs) is of great significance in practical applications. Here, two highly efficient asymmetric anthracene-based fluorescent emitters, 1-phenyl-2-(4-(10-(4-(2-phenyl-1H-phenanthro[9,10-d]imidazole-1-yl)phenyl)anthracen-9-yl)phenyl)-1H-phenanthro [9,10-d]imidazole (PPI-An-NPPI) and 1-phenyl-2-(4-(10-(4-(2,4,5-triphenyl-1H-imidazole-1-yl)phenyl) anthracen-9-yl)phenyl)-1H-phenanthro[9,10-d]imidazole (PPI-An-NPIM), have been designed and synthesized by introducing large steric hindrance imidazole moieties to regulate molecular excited states and photophysical properties. Experimental data show that they have high photoluminescence efficiencies, good thermal stabilities, and suitable energy levels for carrier injection. Theoretical calculations present that their high-lying excited states exhibit dominant locally excited-state characteristics with enhancing oscillator strength compared with anthracene core. The calculated transition dipole moments data show that two molecules are preferentially oriented along the horizontal direction. In addition, some hot exciton mechanism-like channels are also observed and confirmed, which are beneficial for the productive triplet-singlet exciton conversion. The non-doped OLED using PPI-An-NPPI as the emitting layer achieves a maximum external quantum efficiency (EQEmax) of 7.75% and Commission Internationale de L’Eclairage (CIE) coordinates of (0.15, 0.11), whereas PPI-An-NPIM gives a better color purity of CIE (0.14, 10) with an EQEmax of 7.48%. Moreover, all devices exhibit an insignificant efficiency roll-off at high luminescence and still yield an EQE of 7.61% and 7.14% at 1,000 cd/m2. This work provides an interesting insight into developing efficient deep-blue fluorescent emitters for high-performance non-doped OLEDs.  相似文献   

18.
《中国化学快报》2023,34(2):107445
Due to the high decay rate of the non-radiative transition of long wavelengths, the molecular design of efficient and stable near-infrared (NIR) electroluminescent materials remains a big challenge. Herein, a new tetradentate cyclometalated platinum(II) complex with an NCCN coordinated framework has been developed and used as a dopant for NIR organic light-emitting diodes (OLEDs). The complex exhibited a short-lived (0.5–1.5 µs) metal-to-ligand charge transfer (MLCT) excited state in doped and neat films. The resulting NIR OLEDs (λEL = 730 nm) achieved maximum external quantum efficiency (EQEmax) of 5.2% and radiance of 74626 mW sr?1 m–2. Of note, the device exhibited excellent stability with operational lifetime of 119 h for LT90. This work demonstrated the great potential of tetradentate platinum(II) complexes in the field of NIR OLEDs.  相似文献   

19.
Acquiring desirable device performance with deep-blue color purity that fulfills practical application requirements is still a challenge. Bipolar fluorescent emitters with hybrid local and charge transfer (HLCT) state may serve to address this issue. Herein, by inserting anthracene core in the deep-blue building blocks, the authors successfully developed two highly twisted D-π-A fluorescent emitters, ICz-An-PPI and IP-An-PPI , featuring different acceptor groups. Both exhibited superb thermal stabilities, high photo luminescent quantum yields and excellent bipolar transport capabilities. The non-doped OLEDs using ICz-An-PPI and IP-An-PPI as the emitting layers showed efficient blue emission with an external quantum efficiency (EQEmax) of 4.32 % and 5.41 %, and the CIE coordinates of (0.147, 0.180) and (0.149, 0.150), respectively. In addition, the deep blue doped device based on ICz-An-PPI was achieved with an excellent CEmax of 5.83 cd A−1, EQEmax of 4.6 % and the CIE coordinate of (0.148, 0.078), which is extremely close to the National Television Standards Committee (NTSC) standard. Particularly, IP-An-PPI -based doped device had better performance, with an EQEmax of 7.51 % and the CIE coordinate of (0.150, 0.118), which was very impressive among the recently reported deep-blue OLEDs with the CIEy <0.12. Such high performance may be attributed to the hot exciton HLCT mechanism via T7 to S2. Our work may provide a new approach for designing high-efficiency deep-blue materials.  相似文献   

20.
Green-light-emitting long-lasting phosphorescence phosphor, Eu2+ activated calcium magnesium chlorosilicate Ca8Mg(SiO4)4Cl2, has been prepared by a modified solid-state reaction method using Ca2SiO4:Eu2+ as a precursor. Its properties have been discussed and analyzed utilizing XRD, photoluminescence, excited-state decay curve and long-lasting phosphorescence decay curve. Upon UV light excitation, the emission spectrum of Ca8Mg(SiO4)4Cl2:Eu2+ phosphor is composed of two separate bands centered at 425 nm and 505 nm, respectively. Furthermore, after irradiation by a 320-nm UV light for 3 min, the 2% Eu2+-doped Ca8Mg(SiO4)4Cl2 phosphor emits intense green-light-emitting afterglow from the 4f65d1→4f7 transition of Eu2+, and its afterglow can be seen with the naked eye in the dark clearly for more than 3 h after removal of the excitation source. The disappearance of the high-energy 425 nm band in the afterglow emission spectrum is explained by its different crystallographic sites. The afterglow decay curve of the Eu2+-doped Ca8Mg(SiO4)4Cl2 phosphor contains a fast decay component and another slow decay one. The possible mechanism of this long-lasting phosphorescence phosphor is also discussed based on the experimental results.  相似文献   

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