CN114249686B - Carbazole-containing near ultraviolet/ultraviolet organic semiconductor material, preparation method thereof and application thereof in OLED - Google Patents
Carbazole-containing near ultraviolet/ultraviolet organic semiconductor material, preparation method thereof and application thereof in OLED Download PDFInfo
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000004065 semiconductor Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 30
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9h-carbazole Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- 238000010898 silica gel chromatography Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 claims description 3
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000004020 luminiscence type Methods 0.000 abstract description 7
- 238000005401 electroluminescence Methods 0.000 abstract description 5
- 230000005284 excitation Effects 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000001716 carbazoles Chemical class 0.000 abstract description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 2
- 230000005281 excited state Effects 0.000 abstract 1
- 239000000370 acceptor Substances 0.000 description 8
- 238000001194 electroluminescence spectrum Methods 0.000 description 8
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 description 6
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 6
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 6
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- -1 zhao Inorganic materials 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 4
- 238000006862 quantum yield reaction Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- ZMEAHKIIWJDJFT-UHFFFAOYSA-N 4-fluoro-3-methylbenzonitrile Chemical compound CC1=CC(C#N)=CC=C1F ZMEAHKIIWJDJFT-UHFFFAOYSA-N 0.000 description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- JGAVTCVHDMOQTJ-UHFFFAOYSA-N (4-carbazol-9-ylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 JGAVTCVHDMOQTJ-UHFFFAOYSA-N 0.000 description 1
- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 1
- SPICZPCIWHHXED-UHFFFAOYSA-N 1-fluoro-2-methyl-4-(trifluoromethyl)benzene Chemical compound CC1=CC(C(F)(F)F)=CC=C1F SPICZPCIWHHXED-UHFFFAOYSA-N 0.000 description 1
- 229910016460 CzSi Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- WIHKEPSYODOQJR-UHFFFAOYSA-N [9-(4-tert-butylphenyl)-6-triphenylsilylcarbazol-3-yl]-triphenylsilane Chemical compound C1=CC(C(C)(C)C)=CC=C1N1C2=CC=C([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)C=C2C2=CC([Si](C=3C=CC=CC=3)(C=3C=CC=CC=3)C=3C=CC=CC=3)=CC=C21 WIHKEPSYODOQJR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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Abstract
The invention belongs to the technical field of organic photoelectric materials, and discloses a carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material, a preparation method thereof and application thereof in OLED. According to the invention, different modification groups are connected to carbazole moieties to regulate and control the excited state property of carbazole derivatives, so that the organic semiconductor material has near ultraviolet light or ultraviolet light emission in a solid state and has remarkable thermoexciton luminescence property. The organic semiconductor material prepared by the invention can be used as a luminescent layer, has the characteristics of high-efficiency solid-state luminescence and high utilization rate of electric excitation excitons, and thus, the near ultraviolet light/ultraviolet light organic electroluminescent device with excellent electroluminescent performance, simple structure and low cost is obtained. The preparation method provided by the invention is simple, raw materials are easy to obtain, the yield is higher, the product structure is stable, and the preparation method has a wide application prospect in the field of organic electroluminescence.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to a carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material, a preparation method thereof and application thereof in OLED.
Background
Organic light emitting diodes (Organic Light Emitting Diode, OLEDs) are a class of devices based on organic semiconductor materials that enable conversion of electrical energy into light energy. The OLED has many advantages of light weight, low energy consumption, high contrast, self-luminescence, flexible bending, etc., and is considered as a new generation of display and illumination technology with the market prospect. The comprehensive performance of the OLED is directly related to the organic electroluminescent material used in the core functional layer, so the design and development of novel and excellent organic electroluminescent materials have become a research hot spot in the field of the OLED.
Over the past three decades, substantial progress has been made in the development of RGB (three primary colors red, green, blue) organic electroluminescent materials. Currently, the light-emitting band of the organic material is further expanded to open up a brand new application scene of the future OLED, and a strong research interest is being induced. For example, blue shifting of the light emission band to the near ultraviolet (wavelength less than 410 nm) or even ultraviolet (wavelength less than 400 nm) region, OLEDs not only have broad development potential in conventional applications such as excitation light sources, high density information storage, and chemical/biological sensing, but also can be used in biomedical and forensic fields. However, achieving efficient near uv/uv emission requires that the organic material have a limited degree of conjugation, suitable molecular rigidity, and molecular planarity, which makes the design space of its material structure more limited. The inherent wide forbidden band of the near ultraviolet light/ultraviolet light material is not beneficial to carrier injection in the OLED operation, so that the combination of carriers is reduced, and the performance of the device is poor. In addition, the near ultraviolet/ultraviolet light materials developed at present are mainly conventional fluorescent materials, so that only 25% of singlet excitons can be utilized to emit light, while 75% of triplet excitons are dissipated in a non-radiative form, and thus the efficiency is very low. (Luo, Y, li, S, zhao, Y, li, C, pang, Z, huang, Y, yang, M, zhou, L, zheng, X, pu, X, lu, Z, an Ultraviolet Thermally Activated Delayed Fluorescence OLED with Total External Quantum Efficiency over%. Adv. Mater.2020,32,2001248.)
The problem of carrier injection of the OLED material can be effectively improved by introducing donor and/or acceptor units; meanwhile, the charge transfer state generated between the donors and acceptors can also promote the conversion of triplet excitons into singlet excitons, so that more excitons can be utilized. Therefore, designing a near ultraviolet/ultraviolet material with a donor-acceptor structure is an effective way to produce a highly efficient near ultraviolet/ultraviolet OLED device. However, the charge transfer state generated to the acceptor structure may lead to a spectral red shift, which is contrary to the original purpose of obtaining near ultraviolet/ultraviolet light. In 2012, the Ma light topic group reported a novel "thermo-exciton" electroluminescence mechanism: the charge transfer state is constructed at a high energy level to realize the conversion from triplet state excitons to singlet state excitons, and a local luminescent state is reserved at a low energy level to realize the high-efficiency and high-saturation luminescence. The mechanism of the separation and construction of the radiation channel and the exciton conversion channel can solve the contradiction between the short-wavelength luminescence of the acceptor type material and the high exciton utilization rate. Based on the materials, researchers have prepared efficient deep blue OLED devices. However, near ultraviolet/ultraviolet materials with "thermo-exciton" electroluminescence mechanisms have yet to be developed.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a carbazole-containing near ultraviolet/ultraviolet organic semiconductor material, a preparation method thereof and application thereof in OLED. The material has the characteristics of a donor-acceptor structure and a thermoexciton, so that the material can not only improve the problem of carrier injection in the near ultraviolet/ultraviolet OLED, but also realize the effective utilization of triplet excitons. The organic semiconductor material has the characteristics of high-efficiency near ultraviolet/ultraviolet light luminescence, high utilization rate of electric excitation excitons and bipolar property, and can be used for preparing a near ultraviolet/ultraviolet OLED device with high efficiency and low-degree efficiency roll-off.
The aim of the invention is achieved by the following technical scheme.
A carbazole-containing near ultraviolet/ultraviolet organic semiconductor material has a chemical structural formula shown as follows:
wherein R is 1 And R is R 2 Different, R 1 To give or draw electricity to electron-donating groupsA sub-group, R 2 Is a large sterically hindered group; ar (Ar) 1 、Ar 2 Is a donor group.
The R is 1 Is one of the following structures 1-6:
the R is 2 Is one of the following 7-16 structures:
the Ar is as follows 1 、Ar 2 Is one of the following a-z structures:
the invention provides a preparation method of a carbazole-containing near ultraviolet/ultraviolet organic semiconductor material, which comprises the following steps:
(1) To contain R 1 And R is 2 The fluorobenzene and the 2, 7-dibromocarbazole of the substituent are taken as raw materials, potassium carbonate is added, and the corresponding intermediate is obtained through carbon-nitrogen coupling;
(2) Intermediate and Ar 1 And Ar is a group 2 And (3) adding corresponding boric acid or boric acid ester into the mixture to perform Suzuki reaction, so as to obtain the corresponding carbazole-containing near ultraviolet/ultraviolet organic semiconductor material.
Further, the 2, 7-dibromocarbazole of step (1) and the R-containing compound 1 And R is 2 The molar ratio of the fluorobenzene of the substituent groups is 1:1.2-1:1.5.
Further, the molar ratio of the 2, 7-dibromocarbazole to the potassium carbonate in the step (1) is 1:2.5-1:3.
Further, the intermediate of step (2) is reacted with Ar 1 And Ar is a group 2 The molar ratio of the corresponding boric acid or boric acid ester is 1:2.5-1:3.
Further, the molar ratio of the intermediate to the potassium carbonate in the step (2) is 1:2-1:3.
Further, in the step (1), the reaction temperature of the corresponding intermediate obtained by carbon-nitrogen coupling is 140-150 ℃ and the reaction time is 8-10 h.
Further, in the step (2), the reaction temperature of the Suzuki reaction is 110-120 ℃ and the reaction time is 5-6 h.
The invention also provides application of the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material in preparation of an organic electroluminescent device, in particular application in an organic light-emitting diode (OLED).
The invention properly separates the donor and the acceptor in a weak donor-acceptor connection mode to form a local state conjugate plane with larger molecular 'long axis' direction and a CT state (charge transfer state) with weaker molecular 'short axis' direction, and simultaneously selects carbazole with better hole transmission capability and blue light color as a molecular core group to design the near ultraviolet/ultraviolet OLED luminescent material with thermal exciton characteristics.
Compared with the prior art, the invention has the following advantages:
(1) The carbazole-containing near ultraviolet/ultraviolet organic semiconductor material has the characteristics of high-efficiency near ultraviolet/ultraviolet luminescence, high-electricity excitation exciton utilization rate and bipolar property, and can be used for preparing a near ultraviolet/ultraviolet OLED device with high efficiency and low-degree efficiency roll-off;
(2) The carbazole-containing near ultraviolet/ultraviolet organic semiconductor material has the advantages of simple preparation method, easily available raw materials, higher yield, stable product structure and simple storage;
(3) The carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material has excellent electroluminescent performance and wide application prospect in the field of organic electroluminescence.
Drawings
FIG. 1 is a J-V-L graph of undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 1;
FIG. 2 is a graph showing the luminance profile and electroluminescence spectrum of the efficiency of undoped OLEDs prepared from the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 1;
FIG. 3 is a J-V-L graph of undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 2;
FIG. 4 is a graph showing the luminance profile and electroluminescence spectrum of the efficiency of undoped OLEDs prepared from the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 2;
FIG. 5 is a J-V-L graph of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 3;
FIG. 6 is a graph showing the luminance profile and electroluminescence spectrum of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 3;
FIG. 7 is a J-V-L graph of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 4;
FIG. 8 is a graph showing the luminance profile and electroluminescence spectrum of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 4.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The reagents used in the following examples are all available from commercial sources.
Example 1: preparation of carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material 4- (2, 7-bis (4- (9H-carbazol-9-yl) phenyl l) -9H-carbazol-9-yl) -3-methyl azonizole, which is correspondingly abbreviated as p-Cz-CNCz.
The synthetic route is as follows:
(1) 3-methyl-4-fluorobenzonitrile (5.06 g,37.5 mmol), 2, 7-dibromocarbazole (8.125 g,25 mmol) and potassium carbonate (8.64 g,62.5 mmol) were weighed into a 250mL double neck round bottom flask, evacuated and N was vented 2 And (5) protecting. Thereafter, 60mL of ultra-dry DMF was poured into the reaction flask, and the reaction was refluxed at 150℃for 8 hours. After the reaction was completed, the mixture cooled to room temperature was poured into 200mL of water, and the crude product was obtained by precipitation and filtration. Then PE/DCM is used as an eluent to carry out separation and purification by a silica gel column chromatography to obtain a white intermediate m-2Br-CNCz with the yield of 82%.
(2) M-2Br-CNCz (1.14 g,2.6 mmol), 4- (9-carbazolyl) phenylboronic acid (1.87 g,6.5 mmol), pd (PPh) 3 ) 4 (0.3 g,0.26 mmol) and anhydrous potassium carbonate (1.08 g,7.8 mmol) were added to a 250mL double neck round bottom flask, and N was introduced after evacuation 2 And (5) protecting. Then, 100mL of a toluene/ethanol/water (volume ratio: 8:1:1) mixed solvent was injected into the reaction flask, and the reaction was heated to reflux for 6 hours at a reaction temperature of 110 ℃. After the reaction was cooled to room temperature, the reaction mixture was poured into dilute hydrochloric acid solution and extracted with DCM. The extract is dried over anhydrous magnesium sulfate, filtered and the solvent is dried by spin to obtain a mixed crude product. Then petroleum ether/dichloromethane is used as an eluent to carry out separation and purification by a silica gel column chromatography to obtain a white pure product p-Cz-CNCz with the yield of 76 percent.
1 H NMR(400MHz,CD 2 Cl 2 ),δ(TMS,ppm):1H 8.34(d,J＝8.0Hz,2H),8.17(d,J＝7.8Hz,4H),7.90(d,J＝8.3Hz,5H),7.82(d,J＝8.2Hz,2H),7.76–7.63(m,7H),7.53–7.39(m,8H),7.37–7.26(m,6H),2.18(s,3H).
Example 2: preparation of carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material 4- (9, 9 '-diphenyl-9H, 9' H- [3,2':7',3 '-tercarbazol ] -9' -yl) -3-methyl lbenzoniamide, which is abbreviated as 3,6Cz-CNCz correspondingly.
The synthetic route is as follows:
(1) 3-methyl-4-fluorobenzonitrile (4.05 g,30 mmol), 2, 7-dibromocarbazole (8.125 g,25 mmol) and potassium carbonate (10.37 g,75 mmol) were weighed into a 250mL double neck round bottom flask, and N was introduced after vacuum pumping 2 And (5) protecting. Thereafter, 60mL of ultra-dry DMF was poured into the reaction flask, and the reaction was refluxed at 140℃for 10 hours. After the reaction was completed, the mixture cooled to room temperature was poured into 200mL of water, and the crude product was obtained by precipitation and filtration. Then PE/DCM is used as eluent to carry out separation and purification by silica gel column chromatography to obtain a white intermediate m-2Br-CNCz with the yield of 81%.
(2) M-2Br-CNCz (1.14 g,2.6 mmol), N-phenyl-3-carbazoleboronic acid (2.24 g,7.8 mmol), pd (PPh) 3 ) 4 (0.3 g,0.26 mmol) and anhydrous potassium carbonate (0.72 g,5.2 mmol) were added to a 250mL double neck round bottom flask, and N was introduced after evacuation 2 And (5) protecting. Then, 100mL of a toluene/ethanol/water (volume ratio: 8:1:1) mixed solvent was injected into the reaction flask, and the reaction was heated to reflux for 5 hours at a reaction temperature of 120 ℃. After the reaction was cooled to room temperature, the reaction mixture was poured into dilute hydrochloric acid solution and extracted with DCM. The extract is dried over anhydrous magnesium sulfate, filtered and the solvent is dried by spin to obtain a mixed crude product. Then petroleum ether/dichloromethane is used as eluent to separate and purify the petroleum ether/dichloromethane by silica gel column chromatography to obtain white pure product 3.6Cz-CNC Z The yield was 78%.
1 H NMR(400MHz,CD 2 Cl 2 ),δ(TMS,ppm):8.27(d,J＝8.1Hz,2H),8.16(d,J＝7.7Hz,4H),7.83(t,J＝1.9Hz,2H),7.75(d,J＝7.9Hz,3H),7.72–7.64(m,5H),7.55(d,J＝8.1Hz,3H),7.47–7.37(m,8H),7.32–7.27(m,4H),7.24(d,J＝1.5Hz,2H),2.06(s,3H).
Example 3: preparation of carbazole-containing near ultraviolet/ultraviolet organic semiconductor material 4- (2, 7-di (napthalen-2-yl) -9H-carbaz ol-9-yl) benzonitrile, which is abbreviated as 2Na-CNCz.
The synthetic route is as follows:
(1) P-fluorobenzonitrile (3.63 g,30 mmol), 2, 7-dibromocarbazole (8.125 g,25 mmol) and potassium carbonate (10.37 g,75 mmol) were weighed into a 250mL double neck round bottom flask, evacuated and then N was vented 2 And (5) protecting. Thereafter, 60mL of ultra-dry DMF was poured into the reaction flask, and the reaction was refluxed at 140℃for 10 hours. After the reaction was completed, the mixture cooled to room temperature was poured into 200mL of water, and the crude product was obtained by precipitation and filtration. Then PE/DCM is used as an eluent to carry out separation and purification by a silica gel column chromatography to obtain a white intermediate 2Br-CNCz with the yield of 88%.
(2) 2Br-CNCz (1.1 g,2.6 mmol), 2-naphthaleneboronic acid (1.34 g,7.8 mmol), pd (PPh) 3 ) 4 (0.3 g,0.26 mmol) and anhydrous potassium carbonate (0.72 g,5.2 mmol) were added to a 250mL double neck round bottom flask, and N was introduced after evacuation 2 And (5) protecting. Then, 100mL of a toluene/ethanol/water (volume ratio: 8:1:1) mixed solvent was injected into the reaction flask, and the reaction was heated to reflux for 5 hours at a reaction temperature of 120 ℃. After the reaction was cooled to room temperature, the reaction mixture was poured into dilute hydrochloric acid solution and extracted with DCM. The extract is dried over anhydrous magnesium sulfate, filtered and the solvent is dried by spin to obtain a mixed crude product. Then petroleum ether/dichloromethane is used as an eluent to carry out separation and purification by a silica gel column chromatography to obtain a white pure product 2Na-CNCz, wherein the yield is 71%.
1 H NMR(400MHz,CD 2 Cl 2 ),δ(TMS,ppm):8.29(d,J＝8.1Hz,2H),8.13(s,2H),7.99(d,J＝8.5Hz,2H),7.94(t,J＝9.2Hz,4H),7.91–7.86(m,4H),7.84(dd,J＝8.4,1.6Hz,2H),7.80(s,2H),7.77(d,J＝8.1Hz,2H),7.57–7.45(m,4H).
Example 4: preparation of carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material 4- (2, 7-bis (4- (3, 6-di-tert-butyl-9H-car-bazol-9-yl) phenyl) -9H-carbazol-9-yl) benzonitrile, which is abbreviated as 2BuCz-CNCz.
The synthetic route is as follows:
(1) P-fluorobenzonitrile (3.63 g,30 mmol), 2, 7-dibromocarbazole (8.125 g,25 mmol) and potassium carbonate (10.37 g,75 mmol) were weighed into a 250mL double neck round bottom flask, evacuated and then N was vented 2 And (5) protecting. Thereafter, 60mL of ultra-dry DMF was poured into the reaction flask, and the reaction was refluxed at 140℃for 10 hours. After the reaction was completed, the mixture cooled to room temperature was poured into 200mL of water, and the crude product was obtained by precipitation and filtration. Then PE/DCM is used as an eluent to carry out separation and purification by a silica gel column chromatography to obtain a white intermediate 2Br-CNCz, and the yield is 78%.
(2) 2Br-CNCz (1.1 g,2.6 mmol), (4- (3, 6-di-tert-butyl-9-carbazole) -phenylboronic acid (3.11 g,7.8 mmol), pd (PPh) 3 ) 4 (0.3 g,0.26 mmol) and anhydrous potassium carbonate (0.72 g,5.2 mmol) were added to a 250mL double neck round bottom flask, and N was introduced after evacuation 2 And (5) protecting. Then, 100mL of a toluene/ethanol/water (volume ratio: 8:1:1) mixed solvent was injected into the reaction flask, and the reaction was heated to reflux for 5 hours at a reaction temperature of 120 ℃. After the reaction was cooled to room temperature, the reaction mixture was poured into dilute hydrochloric acid solution and extracted with DCM. The extract is dried over anhydrous magnesium sulfate, filtered and the solvent is dried by spin to obtain a mixed crude product. Then petroleum ether/dichloromethane is used as an eluent to carry out separation and purification by a silica gel column chromatography to obtain a white pure product 2BuCz-CNCz with the yield of 76 percent.
1 H NMR(400MHz,CD 2 Cl 2 ),δ(TMS,ppm):8.31(d,J＝8.0Hz,2H),8.18–8.13(m,6H),7.92–7.85(m,6H),7.79(s,2H),7.73(d,J＝8.0Hz,2H),7.66(d,J＝8.0Hz,4H),7.51–7.42(m,8H),1.47(s,36H).
Example 5: preparation of carbazole-containing near-UV/UV organic semiconductor Material 9,9' - ((9- (2-methyl-4- (trifluoromethyl) phenyl) -9H-carbazol-2, 7-diyl) bis (3, 1-phenyl)) bis (9H-carbazol), corresponding to the abbreviation m-Cz-CF 3 Cz。
The synthetic route is as follows:
(1) 3-methyl-4-fluoro-benzotrifluoride (5.34 g,30 mmol), 2, 7-dibromocarbazole (8.125 g,25 mmol) and potassium carbonate (10.37 g,75 mmol) were weighed into a 250mL double neck round bottom flask, and N was introduced after vacuum was pulled 2 And (5) protecting. Thereafter, 60mL of ultra-dry DMF was poured into the reaction flask, and the reaction was refluxed at 140℃for 10 hours. After the reaction was completed, the mixture cooled to room temperature was poured into 200mL of water, and the crude product was obtained by precipitation and filtration. Then PE/DCM is used as eluent to separate and purify the mixture by silica gel column chromatography to obtain a white intermediate 2Br-CF 3 Cz, yield 78%.
(2) Will 2Br-CF 3 Cz (1.25 g,2.6 mmol), (4- (3, 6-di-tert-butyl-9-carbazole) -phenylboronic acid (3.11 g,7.8 mmol), pd (PPh) 3 ) 4 (0.3 g,0.26 mmol) and anhydrous potassium carbonate (0.72 g,5.2 mmol) were added to a 250mL double neck round bottom flask, and N was introduced after evacuation 2 And (5) protecting. Then, 100mL of a toluene/ethanol/water (volume ratio: 8:1:1) mixed solvent was injected into the reaction flask, and the reaction was heated to reflux for 5 hours at a reaction temperature of 120 ℃. After the reaction was cooled to room temperature, the reaction mixture was poured into dilute hydrochloric acid solution and extracted with DCM. Anhydrous sulfur in the extractive solutionAnd (3) after drying the magnesium acid, filtering and spin-drying the solvent to obtain a mixed crude product. Then petroleum ether/dichloromethane is used as eluent to separate and purify the mixture by silica gel column chromatography to obtain white pure product m-Cz-CF 3 Cz, yield 76%.
HRMS:m/z807.2861(M+,calcd807.2861)
Example 6: carbazole-containing near ultraviolet/ultraviolet organic semiconductor material (p-Cz-CNCz) OLEDs device performance
Undoped devices were prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material (solid state fluorescence quantum yield=26.3%) prepared in example 1 as a light-emitting material, and the device performance was characterized by testing, and the results are shown in fig. 1 and fig. 2.
The device structure is as follows: (undoped Structure) ITO/HATCN (5 nm)/TAPC (50 nm)/TCTA (5 nm)/p-Cz-CNCz (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 1 is a J-V-L graph of undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 1. As can be seen from the figure, the maximum brightness of the p-Cz-CNCz-based undoped device is high and the starting voltage is low, respectively 2445cd/m 2 ，4.0V。
FIG. 2 is a graph showing the luminance profile and electroluminescence spectrum of the efficiency of undoped OLEDs prepared from the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 1. As can be seen from the figure, the p-Cz-CNCz-based undoped device has good external quantum efficiency and reduced efficiency roll, and is excellent in electroluminescent performance. When the brightness is 27cd/m 2 When the quantum efficiency is 5.5%; when the brightness is 1000cd/m 2 When the external quantum efficiency is 5.05%; the peak of the electroluminescent spectrum is 402nm.
Example 7: oleds device performance of carbazole-containing near ultraviolet/ultraviolet organic semiconductor material (3, 6 cz-CNCz)
Undoped devices were prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material prepared in example 2 (solid state fluorescence quantum yield=38.9%) as a light-emitting material, and the device performance was characterized by testing, and the results are shown in fig. 3 and fig. 4.
The device structure is as follows: (undoped Structure) ITO/HATCN (5 nm)/TAPC (50 nm)/TCTA (5 nm)/3, 6Cz-CNCz (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 3 is a J-V-L graph of undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 2. As can be seen from the figure, the maximum brightness of the 3,6Cz-CNCz based undoped device is high and the turn-on voltage is low, 2481cd/m, respectively 2 ，3.0V。
FIG. 4 is a graph showing the luminance profile and electroluminescence spectrum of the efficiency of undoped OLEDs prepared from the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 2. As can be seen from the figure, the 3,6cz-CNCz based undoped device has good external quantum efficiency and reduced efficiency roll, and excellent electroluminescent performance. When the brightness is 38cd/m 2 When the quantum efficiency is 3.27%; when the brightness is 1000cd/m 2 When the external quantum efficiency is 2.99%; the peak of the electroluminescent spectrum is 404nm.
Example 8: carbazole-containing near ultraviolet/ultraviolet organic semiconductor material (2 Na-CNCz) OLEDs device performance
Doped and undoped devices were prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material (solid state fluorescence quantum yield=58%) prepared in example 3 as a light-emitting material, and the device performance was characterized by testing, and the results are shown in fig. 5 and 6.
The device structure is as follows: (doping Structure) ITO/HATCN (10 nm)/TAPC (60 nm)/TCTA (5 nm)/CBP 10wt%2Na-CNCz (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm); (undoped Structure) ITO/HATCN (10 nm)/TAPC (60 nm)/TCTA (5 nm)/2 Na-CNCz (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 5 is a J-V-L graph of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 3. As can be seen from the figure, the maximum brightness of the 2 Na-CNCz-based doped and undoped devices is high and the starting voltage is low, 2122cd/m, respectively 2 3.6V and 4759cd/m 2 ，3.8V。
FIG. 6 is a graph showing the luminance profile and electroluminescence spectrum of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 3. As can be seen from the figure, both doped and undoped devices based on 2Na-CNCz have good external quantum efficiency and reduced efficiency roll, and excellent electroluminescent properties. When the brightness is 8cd/m respectively 2 And 62cd/m 2 When the quantum efficiency is 6.04% and 3.77%; when the brightness is 1000cd/m 2 When the quantum efficiency is 6.03% and 2.65%; the peak of the electroluminescent spectrum was 392nm and 398nm, respectively.
Example 9: oleds device performance of carbazole-containing near ultraviolet/ultraviolet organic semiconductor material (2 BuCz-CNCz)
Doped and undoped devices were prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material (solid state fluorescence quantum yield=35.7%) prepared in example 4 as a light-emitting material, and the device performance was characterized by testing, and the results are shown in fig. 7 and 8.
The device structure is as follows: (doping Structure) ITO/HATCN (10 nm)/TAPC (60 nm)/TCTA (5 nm)/CzSi 10wt%2BuCz-CNCz (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm); (undoped Structure) ITO/HATCN (10 nm)/TAPC (60 nm)/TCTA (5 nm)/2 BuCz-CNCz (20 nm)/TPBi (40 nm)/LiF (1 nm)/Al (120 nm).
FIG. 7 is a J-V-L graph of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 4. As can be seen from the figure, the maximum luminance of the 2 BuCz-CNCz-based doped and undoped devices is high and the starting voltage is low, 1572cd/m, respectively 2 3.6V and 2625cd/m 2 ，3.6V。
FIG. 8 is a graph showing the luminance profile and electroluminescence spectrum of doped and undoped OLEDs prepared using the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of example 4. As can be seen from the figure, both doped and undoped devices based on 2BuCz-CNCz have good external quantum efficiency and reduced efficiency roll, and excellent electroluminescent performanceDifferent from each other. When the brightness is 10cd/m respectively 2 And 29cd/m 2 When the quantum efficiency is 10.79% and 5.24% respectively; when the brightness is 1000cd/m respectively 2 The external quantum efficiency is 6.19% and 4.8% respectively; the peak of the electroluminescent spectrum was 396nm and 408nm, respectively.
The data show that the invention regulates and controls the excitation state property of carbazole derivatives by connecting different modification groups on carbazole moieties, the OLEDs prepared by taking the materials as a luminescent layer emit light in the near ultraviolet/ultraviolet region, and the doped and undoped OLEDs prepared based on the materials have higher external quantum efficiency and small efficiency roll-off degree. In a word, the carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material has a very wide application prospect in the field of organic electroluminescence.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and those skilled in the art should not depart from the spirit of the present invention, and all changes, substitutions, modifications and the like are intended to be included in the scope of the present invention.
Claims (2)
1. The preparation method of the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material is characterized by comprising the following steps:
(1) 30mmol of p-fluorobenzonitrile, 25mmol of 2, 7-dibromocarbazole and 75mmoll of potassium carbonate are weighed into a 250mL double-neck round bottom flask, and N is introduced after vacuumizing 2 After protection, 60mL of ultra-dry DMF is injected into a reaction bottle, reflux reaction is carried out for 10 hours at 140 ℃, after the reaction is finished, the mixture cooled to room temperature is poured into 200mL of water, the crude product is obtained through precipitation and filtration, and then PE/DCM is used as an eluent to separate and purify the crude product through silica gel column chromatography, so as to obtain a white intermediate 2Br-CNCz, wherein the structural formula is as follows:
(2) 2.6mmol of 2Br-CNCz, 7.8mmol 2-naphthaleneboronic acid, 0.26mmol Pd (PPh) 3 ) 4 And 5.2mmol of anhydrous potassium carbonate are added into a 250mL double-neck round-bottom flask, and N is introduced after vacuumizing 2 After protection, 100mL of toluene/ethanol/water mixed solvent with the volume ratio of 8:1:1 is injected into a reaction bottle, the reaction is carried out for 5 hours under heating and reflux, the reaction temperature is 120 ℃, the reaction is cooled to room temperature after the completion, the reacted mixture is poured into dilute hydrochloric acid solution and extracted by DCM, the extract is dried by anhydrous magnesium sulfate, the solvent is filtered and dried by spin to obtain mixed crude product, and then petroleum ether/dichloromethane is used as eluent to carry out separation and purification by silica gel column chromatography, thus obtaining carbazole-containing near ultraviolet light/ultraviolet light organic semiconductor material 4- (2, 7-di (nanoshalen-2-yl) -9H-carbazol-9-yl) benzonitrile with the following structural formula:
2. use of the carbazole-containing near ultraviolet/ultraviolet organic semiconductor material of claim 1 for the preparation of an organic electroluminescent device.
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| Han Zhang et al..High-Performance Ultraviolet Organic Light-Emitting Diode Enabled by High-Lying Reverse Intersystem Crossing.《Angew. Chem. Int. Ed.》.2021,第60卷第22241-22247页及SI 第3-4页. * |
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