CN117510424B - Fluorene material and preparation method and application thereof - Google Patents
Fluorene material and preparation method and application thereof Download PDFInfo
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- CN117510424B CN117510424B CN202410010402.3A CN202410010402A CN117510424B CN 117510424 B CN117510424 B CN 117510424B CN 202410010402 A CN202410010402 A CN 202410010402A CN 117510424 B CN117510424 B CN 117510424B
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 81
- 238000006243 chemical reaction Methods 0.000 claims description 74
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 150000001875 compounds Chemical class 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 28
- 239000012074 organic phase Substances 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
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- 239000002994 raw material Substances 0.000 claims description 21
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- 230000000903 blocking effect Effects 0.000 claims description 17
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
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- 239000012046 mixed solvent Substances 0.000 claims description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
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- 238000000034 method Methods 0.000 claims description 7
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- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 7
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- 239000001257 hydrogen Substances 0.000 claims description 6
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
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- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 claims 1
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- QRXMUCSWCMTJGU-UHFFFAOYSA-N 5-bromo-4-chloro-3-indolyl phosphate Chemical compound C1=C(Br)C(Cl)=C2C(OP(O)(=O)O)=CNC2=C1 QRXMUCSWCMTJGU-UHFFFAOYSA-N 0.000 description 7
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- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 6
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- QBYJBZPUGVGKQQ-SJJAEHHWSA-N aldrin Chemical compound C1[C@H]2C=C[C@@H]1[C@H]1[C@@](C3(Cl)Cl)(Cl)C(Cl)=C(Cl)[C@@]3(Cl)[C@H]12 QBYJBZPUGVGKQQ-SJJAEHHWSA-N 0.000 description 6
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 101710110702 Probable chorismate pyruvate-lyase 1 Proteins 0.000 description 2
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- XNKVIGSNRYAOQZ-UHFFFAOYSA-N dibenzofluorene Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1CC1=CC=CC=C12 XNKVIGSNRYAOQZ-UHFFFAOYSA-N 0.000 description 2
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- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 1
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 1
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- KKHFRAFPESRGGD-UHFFFAOYSA-N 1,3-dimethyl-7-[3-(n-methylanilino)propyl]purine-2,6-dione Chemical compound C1=NC=2N(C)C(=O)N(C)C(=O)C=2N1CCCN(C)C1=CC=CC=C1 KKHFRAFPESRGGD-UHFFFAOYSA-N 0.000 description 1
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- VVCMGAUPZIKYTH-VGHSCWAPSA-N 2-acetyloxybenzoic acid;[(2s,3r)-4-(dimethylamino)-3-methyl-1,2-diphenylbutan-2-yl] propanoate;1,3,7-trimethylpurine-2,6-dione Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O.CN1C(=O)N(C)C(=O)C2=C1N=CN2C.C([C@](OC(=O)CC)([C@H](C)CN(C)C)C=1C=CC=CC=1)C1=CC=CC=C1 VVCMGAUPZIKYTH-VGHSCWAPSA-N 0.000 description 1
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- POFVJRKJJBFPII-UHFFFAOYSA-N N-cyclopentyl-5-[2-[[5-[(4-ethylpiperazin-1-yl)methyl]pyridin-2-yl]amino]-5-fluoropyrimidin-4-yl]-4-methyl-1,3-thiazol-2-amine Chemical compound C1(CCCC1)NC=1SC(=C(N=1)C)C1=NC(=NC=C1F)NC1=NC=C(C=C1)CN1CCN(CC1)CC POFVJRKJJBFPII-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Abstract
The invention belongs to the field of organic photoelectric materials, and discloses a fluorene material, a preparation method and application thereof. The structural general formula of the fluorene material isWhen the fluorene material is used for an organic electroluminescent device, the energy levels of HOMO and LUMO are easy to adjust due to the asymmetry of the structure of the fluorene material, and the fluorene material can be effectively matched with other layer materials, so that the driving voltage of the device is reduced, and the efficiency of the device is improved.
Description
Technical Field
The invention belongs to the field of organic photoelectric materials, relates to a fluorene material, and in particular relates to a fluorene electron transport/hole blocking material, a preparation method and application thereof.
Background
Along with the rapid development of information technology, new targets and requirements are also put forward on the performance of an information display system, and a display has high brightness, high resolution, wide viewing angle and low energy consumption, so that the display becomes a research hot spot. The organic electroluminescence (OLED) display technology can meet the above requirements of people, and has a wide operating temperature, and can realize other advantages such as flexible display, so that it is a new pet for new generation of flat panel display after CRT (cathode ray tube) display, LCD (liquid crystal display), PDP (plasma display) flat panel display, and the organic electroluminescence display technology is also known as a flat panel display technology with fantasy display characteristics.
The organic electroluminescent element is a self-luminous element utilizing the following principle: by applying an electric field, the fluorescent substance emits light by the recombination energy of holes injected from the anode and electrons injected from the cathode. It has the following structure: an anode, a cathode, and an organic material layer interposed therebetween. In order to improve efficiency and stability of the organic electroluminescent element, the organic material layer generally includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL).
The electron transport/hole blocking materials generally have proper HOMO/LUMO values, so that the driving voltage can be reduced due to the fact that smaller electron injection potential barriers are adopted, meanwhile, higher electron transport rate, higher glass transition temperature and higher thermal stability are required, common electron injection materials in the industry such as azole derivatives, quinoline derivatives and metal chelates are required, but the materials are easy to crystallize, the service life of the device is short, and the materials cannot be effectively matched with the HOMO/LUMO of the adjacent functional layer materials due to overlarge energy gaps, so that energy cannot be fully utilized, the injection potential barriers are too high, and the device has the problems of overhigh driving voltage and lower efficiency.
Therefore, developing an organic electroluminescent device with high mobility electron transport/hole blocking materials, which has the advantages of low driving voltage, high efficiency and long service life, is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a fluorene material, which aims to solve the problems of reduced efficiency, poor stability, short lifetime, etc. of the existing light emitting device.
In order to achieve the above object, a first object of the present invention is to provide a fluorene material, which adopts the following technical scheme:
a fluorene material has the following structural general formula:
；
wherein,
Z 1 -Z 3 is C or N, and Z 1 -Z 3 At least 2N;
l is selected from a bond, a substituted or unsubstituted C 6 -C 30 Arylene of (C) substituted or unsubstituted 6 -C 30 Is selected from the group consisting of oxygen, nitrogen, sulfur;
R 1 、R 2 are identical or different from one another and are each independently selected from hydrogen, substituted or unsubstituted C 6 -C 30 Aryl, substituted or unsubstituted C 6 -C 30 Heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
wherein the term "substituted or unsubstituted C 6 -C 30 The aryl group in the aryl group is selected from phenyl, naphthyl, phenanthryl, anthryl, biphenyl, terphenyl and fluorenyl.
The aryl groups mentioned above may be substituted by cyano groups.
Ar 1 -Ar 2 Are identical or different from one another and are each independently selected from the following groups:
。
further, the L is selected from a bond or the following group:
。
further, R 1 、R 2 Are identical or different from one another and are each independently selected from hydrogen or from the following groups:
。
wherein "×" denotes the point of connection.
In the above terms, "substituted" refers to substitution with one, two or more substituents selected from the group consisting of: hydrogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, 3-to 10-membered heterocycloalkyl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur; C6-C20 aryl, 3-to 10-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
further preferably Z 1 -Z 3 And is also N.
Further, formula I is selected from the structures of formula I-1:
。
in the above technical solution, the fluorene material is selected from any one of the following structures, but is not limited thereto:
/> />。
the second object of the present invention is to provide a preparation method of fluorene materials as described above, which specifically comprises the following steps:
under nitrogen, raw material b (1.0 eq) was dissolved in tetrahydrofuran (5.0 eq) and the solution was cooled to-70 ℃ using liquid nitrogen; n-butyllithium (1.1 eq) was slowly injected and the mixture was stirred for 40-60min; subsequently, a raw material a (1.1 eq) dissolved in (5.0 eq) tetrahydrofuran was slowly injected into the reaction vessel; the reactor was warmed to room temperature and then the mixture was stirred 10-12 h; after the reaction is completed, pouring reactants into an ammonium chloride aqueous solution and separating an organic layer, removing a solvent, and drying to obtain an intermediate 1;
intermediate 1 (1.0 eq) was dissolved in dry DCM and stirred at 0 ℃ for 30-40 min, then MSA (5.0 eq) was added dropwise, and after that, the mixture was slowly warmed to room temperature and reacted for 5-6h; adding sodium bicarbonate to quench the reaction after the reaction is completed; the resulting mixture was extracted with dichloromethane to give an organic phase, which was then treated with anhydrous magnesium sulfate to remove water, and the resulting residue was separated and purified by flash column chromatography to give intermediate 2;
intermediate 2 (1.0 eq) and t-BuOK (1.5 eq) were added to the reaction flask, DMF solvent was added and mixed thoroughly with stirring; CH is added dropwise at room temperature 3 I (1.0 eq), heating to 100-110 deg.C, reacting for 1-2 hoursDropwise adding CH 3 I (2.0 eq), after 2-3 hours of reaction, CH is added dropwise 3 I (2.0 eq) and reacted overnight; cooling to room temperature, pouring the reaction solution into cold water, extracting with ethyl acetate and washing with water twice, drying over anhydrous magnesium sulfate, and eluting with a mixture of dichloromethane and petroleum ether (V DCM ：V PE =1:16), the remaining material was purified by column chromatography to afford intermediate 3;
under the protection of nitrogen, uniformly stirring intermediate 3 (1.0 eq) and raw material c (1.1 eq) in 280mL of mixed solvent of toluene, ethanol and water (volume ratio is 2:1:1), adding X-Phos (0.05 eq), palladium acetate (0.05 eq) and cesium carbonate (2.0 eq), heating to 80-90 ℃ after stirring, stirring and reacting for 10-11h, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, reserving an organic phase, and extracting an aqueous phase with ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain the compound represented by formula I.
The specific synthetic route is shown in the reaction formula I:
；
reaction formula I
Wherein Z is 1 -Z 3 、L、R 1 、R 2 、Ar 1 、Ar 2 Having the definition given above.
A third object of the present invention is to provide an application of the fluorene material in the preparation of an organic electroluminescent device.
Further, the organic electroluminescent device includes a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode; and, in addition, the method comprises the steps of,
the organic layer at least comprises one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.
Still further, the electron transport layer or hole blocking layer comprises one or more fluorene-based materials as described above.
The method for producing the organic electroluminescent device is not particularly limited, but it is preferable to vapor-deposit a metal, an oxide having conductivity, and an alloy thereof on a substrate by a method such as thin film vapor deposition, electron beam evaporation, or physical vapor deposition to form an anode, and then form an organic layer and a vapor-deposited cathode thereon to obtain the organic electroluminescent device.
Compared with the prior art, the fluorene material, the preparation method and the application thereof provided by the invention have the following excellent effects:
the organic electroluminescent device prepared by using the fluorene material disclosed by the invention has the characteristics of low driving voltage, high efficiency and long service life.
Specifically, the fluorene material introduces nitrogen-containing heterocycle and cyano to break the symmetry of molecules, avoids the aggregation action among molecules, and has the characteristics of difficult crystallization, difficult aggregation, good film forming property and the like among molecules. And sp at 9-position of fluorene ring 3 The hybrid carbon can keep the spatial configuration of the compound, avoid poor film forming property and short service life of the device caused by molecular stacking, introduce functional groups/groups with strong electron withdrawing capability such as triazine and the like, and effectively improve the electron mobility of the material.
When the fluorene material is used for an organic electroluminescent device, the energy levels of HOMO and LUMO are easy to adjust due to the asymmetry of the structure of the fluorene material, and other layer materials (such as a main body material and an injection layer material) can be effectively matched, so that the driving voltage of the device is reduced, and the efficiency of the device is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of compound 16 of the present invention.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 118 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made in detail and with reference to the accompanying drawings, wherein it is apparent that the embodiments described are only some, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
；
Under nitrogen, raw material b-1 (1.0 eq) was dissolved in tetrahydrofuran (5.0 eq) and the solution was cooled to-70 ℃ using liquid nitrogen; n-butyllithium (1.1 eq) was slowly injected and the mixture was stirred for 40 min; subsequently, a raw material a-1 (1.1 eq) dissolved in (5.0 eq) tetrahydrofuran was slowly injected into the reaction vessel; the reactor was warmed to room temperature and then the mixture was stirred 12h; after the reaction was completed, the reactant was poured into an aqueous ammonium chloride solution and the organic layer was separated, the solvent was removed, and dried, thereby obtaining intermediate 1. (yield: 81.2%)
Intermediate 1 (1.0 eq) was dissolved in dry DCM and stirred at 0 ℃ for 30min, then MSA (5.0 eq) was added dropwise, and after that, the reaction was continued for 5h slowly warming to room temperature; adding sodium bicarbonate to quench the reaction after the reaction is completed; the resulting mixture was extracted with methylene chloride to obtain an organic phase, which was then treated with anhydrous magnesium sulfate to remove water, and the residue thus obtained was separated and purified by flash column chromatography to obtain intermediate 2. (yield: 89.5%)
Intermediate 2 (1.0 eq) and t-BuOK (1.5 eq) were added to the reaction flask, DMF solvent was added and mixed thoroughly with stirring; CH is added dropwise at room temperature 3 I (1.0 eq), heating to 100deg.CAfter 1 hour of reaction, CH was added dropwise 3 I (2.0 eq), after 2 hours of reaction, CH was added dropwise 3 I (2.0 eq) and reacted overnight; cooling to room temperature, pouring the reaction solution into cold water, extracting with ethyl acetate, washing with water twice, drying over anhydrous magnesium sulfate, and eluting with a mixture of dichloromethane and petroleum ether (V) DCM ：V PE =1:16), the remaining material was purified by column chromatography to afford intermediate 3. (yield: 68.6%)
Under the protection of nitrogen, uniformly stirring intermediate 3 (1.0 eq) and raw material c-1 (1.1 eq) in 280mL of mixed solvent of toluene, ethanol and water (volume ratio is 2:1:1), adding X-Phos (0.05 eq), palladium acetate (0.05 eq) and cesium carbonate (2.0 eq), heating to 90 ℃ after stirring fully, stirring and reacting for 10 hours, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain compound 1, the yield of compound 1 was calculated to be 66.1%.
MS(ESI，m/Z):[M+H]+：538.24
Elemental analysis:
the calculated values are: c,87.12, H, 5.06, N, 7.82.
The test values are: c, 86.88, H,5.33, N, 8.05.
Example 2
；
Under nitrogen, raw material b-4 (1.0 eq) was dissolved in tetrahydrofuran (5.0 eq) and the solution was cooled to-70 ℃ using liquid nitrogen; n-butyllithium (1.1 eq) was slowly injected and the mixture was stirred for 40 min; subsequently, a raw material a-4 (1.1 eq) dissolved in (5.0 eq) tetrahydrofuran was slowly injected into the reaction vessel; the reactor was warmed to room temperature and then the mixture was stirred 12h; after the reaction was completed, the reactant was poured into an aqueous ammonium chloride solution and the organic layer was separated, the solvent was removed, and dried, thereby obtaining intermediate 1. (yield: 75.9%)
Intermediate 1 (1.0 eq) was dissolved in dry DCM and stirred at 0 ℃ for 30min, then MSA (5.0 eq) was added dropwise, and after that, the reaction was continued for 5h slowly warming to room temperature; adding sodium bicarbonate to quench the reaction after the reaction is completed; the resulting mixture was extracted with methylene chloride to obtain an organic phase, which was then treated with anhydrous magnesium sulfate to remove water, and the residue thus obtained was separated and purified by flash column chromatography to obtain intermediate 2. (yield: 88.3%)
Intermediate 2 (1.0 eq) and t-BuOK (1.5 eq) were added to the reaction flask, DMF solvent was added and mixed thoroughly with stirring; CH is added dropwise at room temperature 3 I (1.0 eq), after heating to 100 ℃, the reaction is carried out for 1 hour and CH is added dropwise 3 I (2.0 eq), after 2 hours of reaction, CH was added dropwise 3 I (2.0 eq) and reacted overnight; cooling to room temperature, pouring the reaction solution into cold water, extracting with ethyl acetate, washing with water twice, drying over anhydrous magnesium sulfate, and eluting with a mixture of dichloromethane and petroleum ether (V) DCM ：V PE =1:16), the remaining material was purified by column chromatography to afford intermediate 3. (yield: 68.7%)
Under the protection of nitrogen, uniformly stirring intermediate 3 (1.0 eq) and raw material c-4 (1.1 eq) in 280mL of mixed solvent of toluene, ethanol and water (volume ratio is 2:1:1), adding X-Phos (0.05 eq), palladium acetate (0.05 eq) and cesium carbonate (2.0 eq), heating to 90 ℃ after stirring fully, stirring and reacting for 10 hours, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain compound 4, the yield of compound 4 was calculated to be 59.8%.
MS(ESI，m/Z):[M+H]+：614.26
Elemental analysis:
the calculated values are: c, 88.06H, 5.09N, 6.85.
The test values are: c,87.71, H,5.34, N, 7.26.
Example 3
；
Under nitrogen, raw material b-16 (1.0 eq) was dissolved in tetrahydrofuran (5.0 eq) and the solution was cooled to-70 ℃ using liquid nitrogen; n-butyllithium (1.1 eq) was slowly injected and the mixture was stirred for 40 min; subsequently, a raw material a-16 (1.1 eq) dissolved in (5.0 eq) tetrahydrofuran was slowly injected into the reaction vessel; the reactor was warmed to room temperature and then the mixture was stirred 12h; after the reaction was completed, the reactant was poured into an aqueous ammonium chloride solution and the organic layer was separated, the solvent was removed, and dried, thereby obtaining intermediate 1. (yield: 81.7%)
Intermediate 1 (1.0 eq) was dissolved in dry DCM and stirred at 0 ℃ for 30min, then MSA (5.0 eq) was added dropwise, and after that, the reaction was continued for 5h slowly warming to room temperature; adding sodium bicarbonate to quench the reaction after the reaction is completed; the resulting mixture was extracted with methylene chloride to obtain an organic phase, which was then treated with anhydrous magnesium sulfate to remove water, and the residue thus obtained was separated and purified by flash column chromatography to obtain intermediate 2. (yield: 91.3%)
Intermediate 2 (1.0 eq) and t-BuOK (1.5 eq) were added to the reaction flask, DMF solvent was added and mixed thoroughly with stirring; CH is added dropwise at room temperature 3 I (1.0 eq), after heating to 100 ℃, the reaction is carried out for 1 hour and CH is added dropwise 3 I (2.0 eq), after 2 hours of reaction, CH was added dropwise 3 I (2.0 eq) and reacted overnight; cooling to room temperature, pouring the reaction solution into cold water, extracting with ethyl acetate, washing with water twice, drying over anhydrous magnesium sulfate, and eluting with a mixture of dichloromethane and petroleum ether (V) DCM ：V PE =1:16), the remaining material was purified by column chromatography to afford intermediate 3. (yield: 71.8%)
Under the protection of nitrogen, uniformly stirring intermediate 3 (1.0 eq) and raw material c-16 (1.1 eq) in 280mL of mixed solvent of toluene, ethanol and water (volume ratio is 2:1:1), adding X-Phos (0.05 eq), palladium acetate (0.05 eq) and cesium carbonate (2.0 eq), heating to 90 ℃ after stirring fully, stirring and reacting for 10 hours, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain compound 16 (see fig. 1), the yield of compound 16 was calculated to be 64.1%.
MS(ESI，m/Z):[M+H]+：639.26
Elemental analysis:
the calculated values are: c,86.49, H, 4.73, N, 8.77.
The test values are: c,85.98, H,4.96, N, 9.05.
Example 4
；
Under nitrogen, raw material b-64 (1.0 eq) was dissolved in tetrahydrofuran (5.0 eq) and the solution was cooled to-70 ℃ using liquid nitrogen; n-butyllithium (1.1 eq) was slowly injected and the mixture was stirred for 40 min; subsequently, a raw material a-64 (1.1 eq) dissolved in (5.0 eq) tetrahydrofuran was slowly injected into the reaction vessel; the reactor was warmed to room temperature and then the mixture was stirred 12h; after the reaction was completed, the reactant was poured into an aqueous ammonium chloride solution and the organic layer was separated, the solvent was removed, and dried, thereby obtaining intermediate 1. (yield: 79.2%)
Intermediate 1 (1.0 eq) was dissolved in dry DCM and stirred at 0 ℃ for 30min, then MSA (5.0 eq) was added dropwise, and after that, the reaction was continued for 5h slowly warming to room temperature; adding sodium bicarbonate to quench the reaction after the reaction is completed; the resulting mixture was extracted with methylene chloride to obtain an organic phase, which was then treated with anhydrous magnesium sulfate to remove water, and the residue thus obtained was separated and purified by flash column chromatography to obtain intermediate 2. (yield: 88.6%)
Intermediate 2 (1.0 eq) and t-BuOK1.5 eq) was added to the reaction flask, DMF solvent was added and mixed thoroughly with stirring; CH is added dropwise at room temperature 3 I (1.0 eq), after heating to 100 ℃, the reaction is carried out for 1 hour and CH is added dropwise 3 I (2.0 eq), after 2 hours of reaction, CH was added dropwise 3 I (2.0 eq) and reacted overnight; cooling to room temperature, pouring the reaction solution into cold water, extracting with ethyl acetate, washing with water twice, drying over anhydrous magnesium sulfate, and eluting with a mixture of dichloromethane and petroleum ether (V) DCM ：V PE =1:16), the remaining material was purified by column chromatography to afford intermediate 3. (yield: 69.2%)
Under the protection of nitrogen, uniformly stirring intermediate 3 (1.0 eq) and raw material c-64 (1.1 eq) in 280mL of mixed solvent of toluene, ethanol and water (volume ratio is 2:1:1), adding X-Phos (0.05 eq), palladium acetate (0.05 eq) and cesium carbonate (2.0 eq), heating to 90 ℃ after stirring fully, stirring and reacting for 10 hours, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain compound 64, the yield of compound 64 was calculated to be 67.8%.
MS(ESI，m/Z):[M+H]+：690.29
Elemental analysis:
the calculated values are: c,88.79, H, 5.11, N, 6.09.
The test values are: c, 87.48, H,5.36, N, 6.26.
Example 5
；
Under nitrogen, raw material b-118 (1.0 eq) was dissolved in tetrahydrofuran (5.0 eq) and the solution was cooled to-70 ℃ using liquid nitrogen; n-butyllithium (1.1 eq) was slowly injected and the mixture was stirred for 40 min; subsequently, a raw material a-118 (1.1 eq) dissolved in (5.0 eq) tetrahydrofuran was slowly injected into the reaction vessel; the reactor was warmed to room temperature and then the mixture was stirred 12h; after the reaction was completed, the reactant was poured into an aqueous ammonium chloride solution and the organic layer was separated, the solvent was removed, and dried, thereby obtaining intermediate 1. (yield: 80.3%)
Intermediate 1 (1.0 eq) was dissolved in dry DCM and stirred at 0 ℃ for 30min, then MSA (5.0 eq) was added dropwise, and after that, the reaction was continued for 5h slowly warming to room temperature; adding sodium bicarbonate to quench the reaction after the reaction is completed; the resulting mixture was extracted with methylene chloride to obtain an organic phase, which was then treated with anhydrous magnesium sulfate to remove water, and the residue thus obtained was separated and purified by flash column chromatography to obtain intermediate 2. (yield: 85.7%)
Intermediate 2 (1.0 eq) and t-BuOK (1.5 eq) were added to the reaction flask, DMF solvent was added and mixed thoroughly with stirring; CH is added dropwise at room temperature 3 I (1.0 eq), after heating to 100 ℃, the reaction is carried out for 1 hour and CH is added dropwise 3 I (2.0 eq), after 2 hours of reaction, CH was added dropwise 3 I (2.0 eq) and reacted overnight; cooling to room temperature, pouring the reaction solution into cold water, extracting with ethyl acetate, washing with water twice, drying over anhydrous magnesium sulfate, and eluting with a mixture of dichloromethane and petroleum ether (V) DCM ：V PE =1:16), the remaining material was purified by column chromatography to afford intermediate 3. (yield: 70.4%)
Under the protection of nitrogen, dissolving the intermediate 3 (1.0 eq) and the raw material c-118 (1.0 eq) into 100.00ml of 1, 4-dioxane solution, adding potassium acetate (2.0 eq), [1,1' -bis (diphenylphosphine) (ferrocene) ] palladium dichloride (0.02 eq), stirring uniformly, heating to 110 ℃, and carrying out reflux reaction for 12h; after the reaction, slightly reducing the temperature, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator, the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=2:1) to obtain intermediate 4 (yield: 88.2%)
Under the protection of nitrogen, uniformly stirring intermediate 4 (1.0 eq) and raw material d-118 (1.1 eq) in 280mL of a mixed solvent of toluene, ethanol and water (volume ratio is 2:1:1), adding X-Phos (0.05 eq), palladium acetate (0.05 eq) and cesium carbonate (2.0 eq), heating to 90 ℃ after stirring fully, stirring and reacting for 10 hours, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain intermediate 5 (yield: 83.7%).
Under the protection of nitrogen, uniformly stirring intermediate 5 (1.0 eq) and raw material e-118 (1.1 eq) in 280mL of mixed solvent of toluene, ethanol and water (volume ratio is 2:1:1), adding X-Phos (0.05 eq), palladium acetate (0.05 eq) and cesium carbonate (2.0 eq), heating to 90 ℃ after full stirring, stirring and reacting for 10 hours, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase with ethyl acetate; after combining the organic phases, drying was performed using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain compound 118 (see fig. 2), the yield of compound 118 was calculated to be 66.2%.
MS(ESI，m/Z):[M+H]+：690.30
Elemental analysis:
the calculated values are: c,88.79, H, 5.11, N, 6.09.
The test values are: c, 87.51, H,5.42, N, 6.31.
The synthesis method of other compounds is the same as that of the above examples, and is not repeated here, the mass spectrum test is performed by using a mass spectrometer with model number of Waters XEVO TQD, the accuracy is low, the test is performed by using ESI source, and the mass spectrum test values, molecular formulas and yield of other synthesis examples are shown in table 1 below:
device example 1: organic electroluminescent device fabrication
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, repeatedly washing with distilled water for 2 times, washing with ultrasonic waves for 10min, transferring into a spin dryer for spin drying after washing, baking with a vacuum oven at 220 ℃ for 2 hours, and cooling after baking is finished to use; using the substrate as an anode, and using an evaporator to perform an evaporation device process, and evaporating other functional layers on the substrate in sequence;
b. HIL (hole injection layer): the hole injection layer materials HT-1 and P-dock were vacuum evaporated at an evaporation rate of 1 Å/s, and the structural formula is shown below. The evaporation rate ratio of HT-1 to P-dock is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): vacuum evaporating 130nm HT-1 on the hole injection layer as hole transport layer at evaporation rate of 1 Å/s, and the structure formula is shown below;
d. light-emitting auxiliary layer: vacuum evaporating 10nm EB-1 on the hole transport layer as light-emitting auxiliary layer at evaporation rate of 0.5 Å/s, and the structural formula is shown as follows;
e. EML (light emitting layer): on the above-mentioned light-emitting auxiliary layer, a Host material (Host) and a Dopant material (Dopant) having a thickness of 20nm were vacuum-deposited as light-emitting layers at a deposition rate of 1 Å/s, and the structural formulae of Host and Dopant are as follows, and the deposition rate ratio of Host to Dopant is 98:2;
f. HBL (hole blocking layer): vacuum evaporating HB-1 with a thickness of 5nm on the light-emitting layer as a hole blocking layer at an evaporation rate of 0.5 Å/s, wherein the structure formula is shown as follows;
g. ETL (electron transport layer): vacuum evaporating the compound 1 provided by the invention on the hole blocking layer at the evaporation rate of 1 Å/s to form an electron transport layer, wherein the electron transport layer is 30 nm;
h. EIL (electron injection layer): evaporating Yb film layer 1.0nm at an evaporation rate of 0.5 Å/s to form an electron injection layer;
i. and (3) cathode: evaporating magnesium and silver at an evaporation rate ratio of 1 Å/s of 18nm, wherein the evaporation rate ratio of magnesium to silver is 1:9, so as to obtain an OLED device;
j. light extraction layer: vacuum evaporating CPL-1 with the thickness of 70nm on a cathode at the evaporation rate of 1 Å/s to obtain a light extraction layer; and packaging the substrate subjected to evaporation, firstly coating the cleaned cover plate with UV glue by using glue coating equipment, then moving the coated cover plate to a pressing working section, placing the substrate subjected to evaporation at the upper end of the cover plate, finally bonding the substrate and the cover plate under the action of bonding equipment, and simultaneously completing the irradiation curing of the UV glue.
The structural formula of the used materials is shown as follows:
。
device example 2-device example 17 referring to the above method, the corresponding organic electroluminescent device was prepared by replacing the compound 1 used in the device example 1 with the compound 4, the compound 16, the compound 3, the compound 5, the compound 8, the compound 11, the compound 14, the compound 19, the compound 23, the compound 29, the compound 33, the compound 37, the compound 43, the compound 45, the compound 50, and the compound 56, respectively, as electron transport layers.
Device comparative examples 1-2:
the comparative example of the device provides an organic electroluminescent device, and the only difference between the preparation method and the device example 1 is that: the electron transport layer (compound 1) in device example 1 was evaporated using the existing comparative compounds a, b, respectively, to finally prepare device comparative examples 1-2.
Wherein, the chemical structural formulas of the comparison compounds a and b are as follows:
。
the organic electroluminescent devices obtained in the above device examples 1 to 17 and device comparative examples 1 to 2 were characterized in terms of driving voltage, luminous efficiency and lifetime at a luminance of 1000 (nits), and the test results are shown in table 2 below:
note that: in the blue top emission device, the current efficiency is greatly affected by chromaticity, and thus, the ratio of the luminous efficiency to CIEy is defined as a BI value, i.e., bi= (cd/a)/CIEy, taking into consideration the factor of chromaticity on efficiency.
Device example 18 preparation of organic electroluminescent device
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, repeatedly washing with distilled water for 2 times, washing with ultrasonic waves for 10min, transferring into a spin dryer for spin drying after washing, baking with a vacuum oven at 220 ℃ for 2 hours, and cooling after baking is finished to use; using the substrate as an anode, and using an evaporator to perform an evaporation device process, and evaporating other functional layers on the substrate in sequence;
b. HIL (hole injection layer): the hole injection layer materials HT-1 and P-dock were vacuum evaporated at an evaporation rate of 1 Å/s, and the structural formula is shown below. The evaporation rate ratio of HT-1 to P-dock is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): vacuum evaporating 130nm HT-1 on the hole injection layer as hole transport layer at evaporation rate of 1 Å/s, and the structure formula is shown below;
d. light-emitting auxiliary layer: vacuum evaporating 10nm EB-1 on the hole transport layer as light-emitting auxiliary layer at evaporation rate of 0.5 Å/s, and the structural formula is shown as follows;
e. EML (light emitting layer): on the above-mentioned light-emitting auxiliary layer, a Host material (Host) and a Dopant material (Dopant) having a thickness of 20nm were vacuum-deposited as light-emitting layers at a deposition rate of 1 Å/s, and the structural formulae of Host and Dopant are as follows, and the deposition rate ratio of Host to Dopant is 98:2;
f. HBL (hole blocking layer): vacuum evaporating 5nm of the compound 64 provided by the invention on the light-emitting layer at an evaporation rate of 0.5 Å/s to serve as a hole blocking layer;
g. ETL (electron transport layer): vacuum evaporating ET-1 with a thickness of 30nm on the hole blocking layer at an evaporation rate of 1 Å/s to serve as an electron transport layer, wherein the structural formula is shown as follows;
h. EIL (electron injection layer): evaporating Yb film layer 1.0nm at an evaporation rate of 0.5 Å/s to form an electron injection layer;
i. and (3) cathode: evaporating magnesium and silver at an evaporation rate ratio of 1 Å/s of 18nm, wherein the evaporation rate ratio of magnesium to silver is 1:9, so as to obtain an OLED device;
j. light extraction layer: vacuum evaporating CPL-1 with the thickness of 70nm on a cathode at the evaporation rate of 1 Å/s to obtain a light extraction layer; and packaging the substrate subjected to evaporation, firstly coating the cleaned cover plate with UV glue by using glue coating equipment, then moving the coated cover plate to a pressing working section, placing the substrate subjected to evaporation at the upper end of the cover plate, finally bonding the substrate and the cover plate under the action of bonding equipment, and simultaneously completing the irradiation curing of the UV glue.
The structural formula of the used materials is shown as follows:
。
device example 19-device example 40 referring to the above-described method, the corresponding organic electroluminescent device was prepared by replacing the compound 64 used in the device example 18 with the compound 62, the compound 65, the compound 71, the compound 78, the compound 82, the compound 85, the compound 89, the compound 92, the compound 95, the compound 102, the compound 104, the compound 107, the compound 110, the compound 111, the compound 114, the compound 116, the compound 117, the compound 118, the compound 120, the compound 127, the compound 132, and the compound 137, respectively, as hole blocking layers.
Device comparative examples 3-5:
the comparative example of the device provides an organic electroluminescent device, and the only difference between the preparation method and the device example 18 is that: the hole blocking layer (compound 64) in device example 18 above was replaced with the existing comparative compounds c, d, e, respectively, for evaporation to finally prepare device comparative examples 3-5.
Wherein, the chemical structural formulas of the comparative compounds c, d and e are as follows:
。
the organic electroluminescent devices obtained in the above device examples 18 to 40 and device comparative examples 3 to 5 were characterized in terms of driving voltage, luminous efficiency and lifetime at a luminance of 1000 (nits), and the test results are shown in table 3 below:
note that: in the blue top emission device, the current efficiency is greatly affected by chromaticity, and thus, the ratio of the luminous efficiency to CIEy is defined as a BI value, i.e., bi= (cd/a)/CIEy, taking into consideration the factor of chromaticity on efficiency.
As can be seen from table 2, the organic electroluminescent device prepared by using the fluorene material provided by the present invention as an electron transport layer has a lower starting voltage, and significantly improved luminous efficiency and lifetime, compared with the organic electroluminescent device prepared by using the compounds a and b as electron transport layers.
Specifically, compound 16 and comparative example compound a are parallel comparative examples, and the introduction of cyano group into compound 16 improves electron withdrawing ability and improves electron mobility; the compound 1 and the comparative compound b are parallel comparative examples, the compound 1 introduces naphthyl on the basis of dibenzofluorene to break the symmetry of molecules, avoid the aggregation action among molecules, have the characteristics of difficult crystallization among molecules, difficult aggregation, good film forming property and the like, and improve the luminous efficiency of the device and the service life of the device.
As can be seen from the data in Table 3, the organic electroluminescent device prepared by using the fluorene material provided by the present invention as a hole blocking layer has a lower starting voltage, and significantly improved luminous efficiency and lifetime, compared with the organic electroluminescent device prepared by using the comparative compounds c, d, e as hole blocking layers.
Compared with the comparative compounds c and d, the compound 118 has the advantages that the triazine group in the compound 118 is connected with four positions of the mother nucleus fluorene, the conjugation space of the connecting site is large, the torsion angle of the molecule is large, the conjugation is shortened, the triplet state energy level of the material is high, and the exciton diffusion is prevented, so that the device efficiency is improved. Compared with the compound a of the comparative example, the compound 137 has the advantages that the compound 137 is introduced into naphthalene based on dibenzofluorene to break the symmetry of molecules, avoid the aggregation action among the molecules, have the characteristics of difficult crystallization among the molecules, difficult aggregation, good film forming property and the like, and improve the luminous efficiency of the device and the service life of the device.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. The fluorene material is characterized by having the following structural general formula:；
wherein,
Z 1 -Z 3 is N;
l is selected from a bond or the following group:；
R 1 、R 2 are identical or different from one another and are each independently selected from hydrogen or from the following groups:；
Ar 1 -Ar 2 are identical or different from each other and are each independently selectedFrom the following groups:。
2. fluorene-based material according to claim 1, characterized in that said general formula I is selected from structures of formula I-1:。
3. fluorene-based material according to claim 2, characterized in that said general formula I is selected from the following structures: />。
4. a method for producing a fluorene-based material as claimed in claim 1, comprising the following reaction steps:
1.0eq of feed b was dissolved in 5.0eq of tetrahydrofuran under nitrogen and the solution was cooled to-70 ℃ using liquid nitrogen; slowly injecting 1.1eq of n-butyllithium, and stirring the mixture for 40-60min; subsequently, 1.1eq of starting material a dissolved in 5.0eq of tetrahydrofuran was slowly injected into the reaction vessel; the reactor was warmed to room temperature and the mixture was then stirred 10-12 h; after the reaction is completed, pouring reactants into an ammonium chloride aqueous solution, separating an organic layer, removing a solvent, and drying to obtain an intermediate 1;
1.0eq of intermediate 1 is dissolved by dry DCM, stirred for 30-40 minutes at 0 ℃, then 5.0eq of MSA is added dropwise, the mixture is slowly warmed to room temperature after the dripping, and the reaction is continued for 5-6 hours; adding sodium bicarbonate to quench the reaction after the reaction is completed; the resulting mixture was extracted with dichloromethane to give an organic phase, which was then treated with anhydrous magnesium sulfate to remove water, and the resulting residue was separated and purified by flash column chromatography to give intermediate 2;
1.0eq of intermediate 2 and 1.5eq of t-BuOK are added into a reaction bottle, DMF solvent is added and stirred fully; 1.0eq CH is added dropwise at room temperature 3 I, heating to 100-110 ℃, reacting for 1-2 hours, and then dripping 2.0eq CH 3 I, 2.0eq CH is added dropwise after 2-3 hours of reaction 3 I, reacting overnight; cooling to room temperature, pouring the reaction solution into cold water, extracting with ethyl acetate and washing twice, drying with anhydrous magnesium sulfate, and purifying the rest substances by column chromatography with a mixture of dichloromethane and petroleum ether in a volume ratio of 1:16 as an eluent to obtain an intermediate 3;
under the protection of nitrogen, 1.0eq of intermediate 3 and 1.1eq of raw material c are uniformly stirred in 280mL of mixed solvent of toluene, ethanol and water with the volume ratio of 2:1:1, then 0.05eq of X-Phos,0.05eq of palladium acetate and 2.0eq of cesium carbonate are added, after stirring is complete, the temperature is raised to 80-90 ℃ and stirring is carried out for 10-11h, after the reaction is finished, the temperature is slightly reduced, diatomite is used for filtering, salt and catalyst are removed, the filtrate is cooled to room temperature, then the filtrate is washed three times with water, the organic phase is reserved, and then the aqueous phase is extracted by ethyl acetate; after combining the organic phases, drying using anhydrous magnesium sulfate and removing the solvent using a rotary evaporator to give the compound of formula I;
the specific synthetic route is shown in the reaction formula I:；/>
wherein Z is 1 -Z 3 、L、R 1 、R 2 、Ar 1 、Ar 2 Having the definition as given in claim 1.
5. Use of a fluorene-based material according to claim 1, in the preparation of an organic electroluminescent device.
6. The use according to claim 5, wherein the organic electroluminescent device comprises a first electrode, a second electrode, one or more organic layers interposed between the first electrode and the second electrode; and, in addition, the method comprises the steps of,
the organic layer at least comprises one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.
7. The use according to claim 6, wherein the electron transport layer or hole blocking layer comprises one or more of said fluorene-based materials.
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| CN116640126A (en) * | 2023-05-29 | 2023-08-25 | 长春海谱润斯科技股份有限公司 | Organic electroluminescent compound and organic electroluminescent device thereof |
| CN116640127A (en) * | 2023-05-29 | 2023-08-25 | 长春海谱润斯科技股份有限公司 | Compound and organic electroluminescent device thereof |
| CN116655611A (en) * | 2023-08-01 | 2023-08-29 | 吉林奥来德光电材料股份有限公司 | Electron transport material, preparation method and organic electroluminescent device |
| CN117024287A (en) * | 2023-10-10 | 2023-11-10 | 吉林奥来德光电材料股份有限公司 | Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device |
| CN117143030A (en) * | 2022-05-20 | 2023-12-01 | 烟台显华科技集团股份有限公司 | Naphthyl substituted electricity-absorbing fragment compound, electron transport material and application |
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| CN117143030A (en) * | 2022-05-20 | 2023-12-01 | 烟台显华科技集团股份有限公司 | Naphthyl substituted electricity-absorbing fragment compound, electron transport material and application |
| CN116640126A (en) * | 2023-05-29 | 2023-08-25 | 长春海谱润斯科技股份有限公司 | Organic electroluminescent compound and organic electroluminescent device thereof |
| CN116640127A (en) * | 2023-05-29 | 2023-08-25 | 长春海谱润斯科技股份有限公司 | Compound and organic electroluminescent device thereof |
| CN116655611A (en) * | 2023-08-01 | 2023-08-29 | 吉林奥来德光电材料股份有限公司 | Electron transport material, preparation method and organic electroluminescent device |
| CN117024287A (en) * | 2023-10-10 | 2023-11-10 | 吉林奥来德光电材料股份有限公司 | Light-emitting auxiliary material, preparation method thereof, organic electroluminescent device and organic electroluminescent device |
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