CN115322181A - Organic electroluminescent compound and preparation method and application thereof - Google Patents
Organic electroluminescent compound and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 230000005525 hole transport Effects 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 68
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 239000012044 organic layer Substances 0.000 claims description 19
- 238000001704 evaporation Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 125000005842 heteroatom Chemical group 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000001301 oxygen Substances 0.000 claims description 16
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- 239000011593 sulfur Substances 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 125000001072 heteroaryl group Chemical group 0.000 claims description 11
- 230000000903 blocking effect Effects 0.000 claims description 7
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 4
- 229910052805 deuterium Inorganic materials 0.000 claims description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000004020 luminiscence type Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000005264 aryl amine group Chemical group 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 4
- FTMRMQALUDDFQO-UHFFFAOYSA-N naphtho[2,3-b][1]benzofuran Chemical compound C1=CC=C2C=C3C4=CC=CC=C4OC3=CC2=C1 FTMRMQALUDDFQO-UHFFFAOYSA-N 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 125000005259 triarylamine group Chemical group 0.000 abstract 1
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 26
- 239000000706 filtrate Substances 0.000 description 26
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- 239000007858 starting material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
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- 238000007039 two-step reaction Methods 0.000 description 2
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- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- -1 willIntermediate 1 Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/1018—Heterocyclic compounds
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Abstract
The invention discloses an organic electroluminescent compound, a preparation method and application thereof, wherein the molecular formula of the compound is shown as the general formula (I):
the compound is connected with arylamine groups by taking benzonaphthofuran as a framework, the benzonaphthofuran has a rigid planar structure, the symmetry of molecules is further reduced by connecting aryl, cycloalkyl and the like, the conformational isomer of the molecules is increased, the compound is not easy to crystallize and aggregate, and the compound has good film-forming property, thermal stability and higher glass transition temperature; the arylamine group makes it have strong hole transport capacityThe single triarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules, prevent the molecules from moving on a plane, reduce the driving voltage of a device at a high hole transmission rate, and improve the efficiency and the service life of an organic electroluminescent device.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and relates to an organic electroluminescent compound, and a preparation method and application thereof.
Background
The organic electroluminescent (OLED) device technology in the prior art can be used for manufacturing display products and illumination products, is expected to replace the existing liquid crystal display and fluorescent lamp illumination, and has wide application prospect. An organic electric element utilizing an organic light emitting phenomenon generally has an anode, a cathode, and a structure including an organic layer therebetween, and the organic layer is generally composed of a multilayer structure composed of various substances in order to improve efficiency and stability of the organic electric element.
In such an organic light emitting diode, when a voltage is applied between an anode and a cathode, holes from the anode and electrons from the cathode are injected into an organic material layer. The generated excitons generate light having a specific wavelength while migrating to a ground state. It has the following structure: an anode, a cathode, and an organic material layer therebetween. In order to improve efficiency and stability of the organic EL element, the organic material layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). Among them, a layer having a function of transporting holes, such as a hole injection layer, a hole transport layer, an electron blocking layer, and the like, can change hole transport efficiency from holes to a light emitting layer, light emitting efficiency, lifetime, and the like, and has a great influence on performance data of an electronic device.
In order to improve the problems of light-emitting efficiency, lifetime, etc., a light-emitting auxiliary layer is usually added between the hole transport layer and the light-emitting layer (i.e., multiple hole transport layers are provided) to improve the lifetime and efficiency of the device. The light-emitting auxiliary layer can play a role in reducing potential barrier between the hole transport layer and the light-emitting layer, reducing the driving voltage of the organic electroluminescent device and further increasing the utilization rate of holes, thereby improving the luminous efficiency and the service life of the device and reducing the driving voltage. However, the existing functional materials capable of forming the light-emitting auxiliary layer are few, and particularly, the problems that the service life and the light-emitting efficiency of the OLED are not obviously improved, the glass transition temperature is low, and the like, lead to the development of organic functional materials with higher performance, and meet the requirements of panel manufacturing enterprises, and are very important.
Disclosure of Invention
An object of the present invention is to provide a novel organic electroluminescent compound.
In order to achieve the purpose, the invention adopts the following technical scheme:
an organic electroluminescent compound having a formula of formula (I):
Ar 1 is a benzene ring and is fused with the benzene ring of the adjacent dibenzofuran;
Ar 2 is substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
R 1 selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, the heteroatoms of which are selected from oxygen, nitrogen, sulphur; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
R 2 -R 5 each independently selected from hydrogen, deuterium, a halogen group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted 3-to 30-membered heterocycloalkyl group, the heteroatom of which is selected from oxygen, nitrogen, sulfur; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur.
In the present specification, "substituted" means substituted with one, two or more substituents selected from: C1-C20 alkyl, C1-C20 alkoxy, C6-C30 aryl, and C6-C30 heteroaryl, wherein the heteroatom is selected from oxygen, nitrogen, and sulfur.
Further, the organic electroluminescent compounds have the molecular formulas shown as general formulas (II-1) to (II-3):
further, said R 1 Selected from the following structural formulas:
wherein in the above formula, is represented as a connecting point.
Further, the organic electroluminescent compounds have the molecular formulas shown in the general formulas (III-1) to (III-15):
further, said Ar 2 Selected from the following structural formulas:
wherein R is 6 Selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted 3-to 18-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulphur, substituted or unsubstituted C1-C18 alkyl; in the above formula, a is represented as a connecting point.
Further, R 2 -R 5 Each independently selected from hydrogen, deuterium, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted 3-to 20-membered heterocycloalkyl group, the heteroatoms of which are selected fromOxygen, nitrogen, sulfur; substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3-20 membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur.
Further, the general formula 1 is represented by any one of the following formulas (1) to (126):
the second purpose of the present invention is to provide a preparation method of the above organic electroluminescent compound, which adopts the following technical scheme:
a preparation method of an organic electroluminescent compound comprises the following steps:
(1) Dissolving raw material A and raw material B in organic solvent, and reacting at N 2 Adding Pd under atmosphere 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating to 110-120 ℃, stirring for reaction for 10-12h, and performing suction filtration, washing, drying, evaporation and purification after the reaction is finished to obtain a compound shown as an intermediate 1;
(2) In N 2 Under protection, the intermediate 1, raw materials C and Pd 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating to 110-120 ℃, stirring for reaction for 12-14h, and performing suction filtration, washing, drying, evaporation and purification after the reaction is finished to obtain a compound shown in a general formula 1;
the specific synthetic route is shown as a reaction formula I:
in the formula R 1 ～R 5 、Ar 1 、Ar 2 Having the definitions given above.
Further, a method for preparing an organic electroluminescent compound, comprising the steps of:
dissolving the raw materials A and B in toluene, and reacting the solution in N 2 Adding Pd under atmosphere 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating to 110-120 ℃, stirring and reacting for 10-12h, performing suction filtration while hot by using diatomite after the reaction is finished, removing salt and a catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, separating liquid, retaining an organic phase, extracting an aqueous phase by using ethyl acetate, drying a combined organic layer by using magnesium sulfate, removing the solvent by using a rotary evaporator, and finally purifying the rest substance by using column chromatography by using a mixture of dichloromethane and petroleum ether as an eluent to obtain a compound shown as an intermediate 1;
at N 2 Under the protection of the water, willIntermediate 1, raw materials C and Pd 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating to 110-120 ℃, stirring for reaction for 12-14h, performing suction filtration by using diatomite while the diatomite is hot after the reaction is finished, removing salts and a catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, retaining an organic phase after liquid separation, extracting an aqueous phase by using ethyl acetate, drying a combined organic layer by using magnesium sulfate, removing the solvent by using a rotary evaporator, and finally purifying the rest substance by using a column chromatography by using a mixture of dichloromethane and petroleum ether as an eluent to obtain the compound shown in the general formula 1.
The third purpose of the invention is to provide an application of the organic electroluminescent compound in preparing an organic light-emitting device or a fluorescent lamp.
A fourth object of the present invention is to provide an organic electroluminescent device comprising a first electrode, a second electrode, one or more organic layers interposed between the first electrode and the second electrode; and the number of the first and second groups is,
the organic layer comprises a light-emitting auxiliary layer and also comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a light extraction layer and a cap layer; and the number of the first and second electrodes,
the light-emission assisting layer comprises one or more organic electroluminescent compounds as described above.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the invention provides an organic electroluminescent compound which takes benzonaphthofuran as a framework and is connected with arylamine groups to obtain the organic electroluminescent compound with excellent performance and used for a blue light luminescent auxiliary layer.
The arylamine group in the compound has strong hole transmission capability, the monotriarylamine structure can reduce the crystallinity of molecules, reduce the planarity of the molecules, prevent the molecules from moving on the plane, reduce the driving voltage of the device at high hole transmission rate, improve the efficiency of the organic electroluminescent device and prolong the service life of the organic electroluminescent device.
The benzonaphthofuran has a rigid planar structure, further reduces the symmetry of molecules by connecting aryl, cycloalkyl and the like, increases the conformational isomer of the molecules, ensures that the compound is not easy to crystallize and aggregate, and has good film-forming property, thermal stability and higher glass transition temperature.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a NMR spectrum of Compound 11 prepared in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In examples 1-4, the starting material A was obtained by the following two-step reaction:
dissolving raw material 1 (1 eq) in a dichloromethane solution, slowly adding liquid bromine (1.1 eq) and stirring at room temperature for 4 hours by TLC to monitor that the reaction of the raw materials is stopped after the reaction is finished, adding a saturated sodium thiosulfate solution for quenching, separating the solution, retaining an organic phase, removing the solvent by using a rotary evaporator, and finally purifying the remaining substance by column chromatography using a mixture of dichloromethane and petroleum ether (V: V = 1;
dissolving the intermediate 1-1 (1 eq) and the raw material 2 (1 eq) in a mixed solution of toluene, ethanol and water, then ventilating for 3 times, adding potassium carbonate and a tetratriphenylphosphine palladium catalyst under the protection of nitrogen, stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 6 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (2) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, carrying out suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain a raw material A.
Example 1
Starting materials A (40.00 mmol) and B (40.00 mmol) were dissolved in toluene and the solution was purified by filtration over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.40mmol)、P(t-Bu) 3 (2.00 mmol) and t-BuONa (80.00 mmol), heating to 120 ℃ and stirring for reaction for 12h, after the reaction is finished, carrying out suction filtration by using diatomite while hot, removing salts and a catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, retaining an organic phase after liquid separation, extracting an aqueous phase by using ethyl acetate, then drying a combined organic layer by using magnesium sulfate, removing the solvent by using a rotary evaporator, and finally purifying the remaining substance by using a column chromatography by using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent to obtain a compound represented by an intermediate 1 (10.70 g, yield: 69.47%);
intermediate 1 (27.75 mmol) and starting material C (27.75 mmol) were dissolved in toluene and then purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.27mmol)、P(t-Bu) 3 (1.38 mmol) and t-BuONa (55.50 mmol), heating to 120 ℃ and stirring for reactionAfter the reaction was completed, the reaction mixture was filtered with celite while hot to remove salts and a catalyst, the filtrate was cooled to room temperature, then distilled water was added to the filtrate to wash, the organic phase was retained after liquid separation, the aqueous phase was extracted with ethyl acetate, then the combined organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and finally the remaining substance was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent, to obtain compound 1 (13.91 g, yield: 71.35%, mw: 702.86).
Mass spectrum testing: theoretical value is 702.86; the test value was 702.59.
Elemental analysis:
the calculated values are: c,88.86; h,4.88; n,3.99; o,2.28.
The test values are: c,88.54; h,4.97; n,4.12; o,2.31.
Example 2
Starting material A (40.00 mmol) and starting material B (40.00 mmol) were dissolved in toluene and the solution was purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.40mmol)、P(t-Bu) 3 (2.00 mmol) and t-BuONa (80.00 mmol), heating to 120 ℃ and stirring for reaction for 12h, after the reaction is finished, suction-filtering with diatomaceous earth while hot to remove salts and catalyst, cooling the filtrate to room temperature, adding distilled water to the filtrate for washing, retaining the organic phase after liquid separation, extracting the aqueous phase with ethyl acetate, then drying the combined organic layer with magnesium sulfate, removing the solvent with a rotary evaporator, and finally purifying the remaining substance by column chromatography with a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent to give the compound represented by intermediate 1 (16.71 g, yield: 81.68%);
intermediate 1 (32.66 mmol) and starting material C (32.66 mmol) were dissolved in toluene and then purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.32mmol)、P(t-Bu) 3 (1.63 mmol) and t-BuONa (65.32 mmol), heating to 120 ℃ and stirring for 14h, after the reaction is finished, using kieselguhrAfter the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing, the organic phase was retained after liquid separation, the aqueous phase was extracted with ethyl acetate, and then the combined organic layer was dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and finally the remaining substance was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent, to obtain compound 11 (22.67 g, yield: 83.78%, mw: 829.02).
Mass spectrometry test: a theoretical value of 829.02; the test value was 828.88.
Elemental analysis:
the calculated values are: c,89.83; h,4.86; n,3.38; o,1.93.
The test values are: c,89.67; h,4.59; n,2.33; o,2.18.
Example 3
Starting material A (40.00 mmol) and starting material B (40.00 mmol) were dissolved in toluene and the solution was purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.40mmol)、P(t-Bu) 3 (2.00 mmol) and t-BuONa (80.00 mmol), heating to 120 ℃ and stirring for reaction for 12h, after the reaction is finished, carrying out suction filtration by using diatomite while hot, removing salts and a catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, retaining an organic phase after liquid separation, extracting an aqueous phase by using ethyl acetate, then drying a combined organic layer by using magnesium sulfate, removing the solvent by using a rotary evaporator, and finally purifying the remaining substance by using a column chromatography by using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent to obtain a compound represented by an intermediate 1 (16.30 g, yield: 79.67%);
intermediate 1 (31.85 mmol) and starting material C (31.85 mmol) were dissolved in toluene and the solution was purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.31mmol)、P(t-Bu) 3 (1.59 mmol) and t-BuONa (63.16 mmol), heating to 120 deg.C, stirring, reacting for 14h, filtering with diatomaceous earth, removing salt and catalystAfter the filtrate was cooled to room temperature, distilled water was added to the filtrate to wash, the organic phase was retained after liquid separation, the aqueous phase was extracted with ethyl acetate, then the combined organic layer was dried over magnesium sulfate, and the solvent was removed using a rotary evaporator, and finally the remaining substance was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent, to obtain compound 53 (19.97 g, yield: 75.68%, mw: 829.02).
Mass spectrometry test: a theoretical value of 829.02; the test value was 828.92.
Elemental analysis:
the calculated values are: c,89.83; h,4.86; n,3.38; o,1.93.
The test values are: c,89.23; h,5.29; n,3.56; o,2.21.
Example 4
Starting material A (40.00 mmol) and starting material B (40.00 mmol) were dissolved in toluene and the solution was purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.40mmol)、P(t-Bu) 3 (2.00 mmol) and t-BuONa (80.00 mmol), heating to 120 ℃ and stirring for reaction for 12h, after the reaction is finished, carrying out suction filtration by using diatomite while hot, removing salts and a catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, retaining an organic phase after liquid separation, extracting an aqueous phase by using ethyl acetate, then drying a combined organic layer by using magnesium sulfate, removing the solvent by using a rotary evaporator, and finally purifying the remaining substance by using a column chromatography by using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent to obtain a compound represented by an intermediate 1 (15.98 g, yield: 79.67%);
intermediate 1 (31.85 mmol) and starting material C (31.85 mmol) were dissolved in toluene and the solution was purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.31mmol)、P(t-Bu) 3 (1.59 mmol) and t-BuONa (63.16 mmol), heating to 120 ℃, stirring for reaction for 14h, performing suction filtration by using kieselguhr while the reaction is hot, removing salt and catalyst, cooling filtrate to room temperature, and steamingDistilled water was added to the filtrate to wash, the organic phase was retained after separation, the aqueous phase was extracted with ethyl acetate, then the combined organic layers were dried with magnesium sulfate, and the solvent was removed using a rotary evaporator, and finally the remaining substance was purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent, to obtain compound 61 (21.45 g, yield: 82.26%, mw: 819.02).
Mass spectrometry test: theoretical value is 819.02; the test value was 819.23.
Elemental analysis:
the calculated values are: c,89.46; h,5.17; n,3.42; o,1.95.
The test values are: c,89.23; h,5.29; n,3.56; o,2.21.
In example 5, the raw material A needs to be obtained by the following two-step reaction:
dissolving the raw material 3 (1 eq) in a chloroform solution, slowly adding liquid bromine (1.1 eq) and stirring at room temperature for 4 hours by TLC to monitor that the reaction of the raw material is stopped after the reaction is finished, adding a saturated sodium thiosulfate solution for quenching, separating the solution, retaining an organic phase, removing the solvent by using a rotary evaporator, and finally purifying the remaining substance by column chromatography using a mixture of dichloromethane and petroleum ether (V: V = 1);
dissolving the intermediate 1-2 and the raw material 4 in a mixed solution of toluene ethanol and water, then ventilating for 3 times, adding potassium carbonate and a palladium tetra-triphenylphosphine catalyst under the protection of nitrogen, uniformly stirring, heating to 90 ℃, and performing reflux reaction for 6 hours; after the reaction is finished, slightly cooling, filtering by using kieselguhr, removing salts and a catalyst, cooling the filtrate to room temperature, washing for three times by using water, retaining an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. And (2) completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly dropwise adding the dissolved organic matter into a petroleum ether solution, uniformly stirring, precipitating, carrying out suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain a raw material A.
Example 5
Starting material A (40.00 mmol) and starting material B (40.00 mmol) were dissolved in toluene and the solution was purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.40mmol)、P(t-Bu) 3 (2.00 mmol) and t-BuONa (80.00 mmol), heating to 120 ℃ and stirring for reaction for 12h, after the reaction is finished, carrying out suction filtration by using diatomite while hot, removing salts and a catalyst, cooling the filtrate to room temperature, adding distilled water into the filtrate for washing, retaining an organic phase after liquid separation, extracting an aqueous phase by using ethyl acetate, then drying a combined organic layer by using magnesium sulfate, removing the solvent by using a rotary evaporator, and finally purifying the remaining substance by using a column chromatography by using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent to obtain a compound represented by an intermediate 1 (15.68 g, yield: 76.67%);
intermediate 1 (30.64 mmol) and starting material C (30.64 mmol) were dissolved in toluene and then purified over N 2 Adding Pd under atmosphere 2 (dba) 3 (0.30mmol)、P(t-Bu) 3 (1.53 mmol) and t-BuONa (61.28 mmol), heating to 120 ℃ and stirring for reaction for 14h, after the reaction is finished, suction filtration is carried out using diatomaceous earth while hot, the salt and the catalyst are removed, after the filtrate is cooled to room temperature, distilled water is added to the filtrate for washing, the organic phase is retained after liquid separation, the aqueous phase is extracted with ethyl acetate, the combined organic layers are then dried using magnesium sulfate, and the solvent is removed using a rotary evaporator, and finally the remaining material is purified by column chromatography using a mixture of dichloromethane and petroleum ether (V: V = 1) as an eluent to give compound 98 (17.39 g, yield: 68.49%, mw: 829.02).
Mass spectrometry test: the theoretical value is 829.02; the test value was 828.79.
Elemental analysis:
the calculated values are: c,89.83; h,4.86; n,3.38; o,1.93.
The test values are: c,89.43; h,5.19; n,3.48; o,2.11.
Examples 6 to 30
The synthetic routes and principles of the other compounds of formula 1 of the present invention are the same as those of the above-listed examples and are therefore not exhaustive. According to the preparation method, the luminescent auxiliary material shown in the following table 1 can be obtained:
TABLE 1 molecular formulas, mass spectra and yields of the compounds prepared in examples 6-30
When the organic layer includes a light-emitting auxiliary layer, the light-emitting auxiliary layer includes the light-emitting auxiliary material provided in any of the above embodiments.
Device example 1
The preparation method of the organic electroluminescent device containing the luminescent auxiliary material specifically comprises the following steps:
a. an ITO anode: washing an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, ultrasonically washing for 30min, repeatedly washing for 2 times by using distilled water, ultrasonically washing for 10min, transferring to a spin dryer for spin-drying after washing is finished, baking for 2 hours at 220 ℃ by using a vacuum oven, and cooling after baking is finished. Using the substrate as an anode, performing a device evaporation process by using an evaporation machine, and sequentially evaporating other functional layers on the substrate;
b. HIL (hole injection layer): to be provided with
The vacuum evaporation of hole injection layer materials HT and P-dopant, the chemical formula of which is as followsShown; wherein the evaporation rate ratio of HT to P-dot is 97:3, the thickness is 10nm;
c. HTL (hole transport layer): to be provided with
The evaporation rate of (3), and evaporating 120nm HT as a hole transport layer on the hole injection layer in vacuum;
d. a light-emitting auxiliary layer: to be provided with
Vacuum deposition of 10nm of compound 1 provided in example 1 as a light-emitting auxiliary layer on top of the hole transport layer;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer to
The evaporation rate of (1), vacuum evaporation of Host material (Host) and Dopant material (span) with thickness of 25nm as the luminescent layer, the chemical formulas of Host and span are shown as follows; wherein, the evaporation rate ratio of Host to Dopant is 98:2;
f. HB (hole blocking layer): to be provided with
The evaporation rate of (2), vacuum evaporation of a hole blocking layer with the thickness of 5.0 nm;
g. ETL (electron transport layer): to be provided with
The evaporation rate of (3) and vacuum evaporation of ET and Liq with the thickness of 30nm as electron transport layers, wherein the chemical formula of ET is shown as follows; wherein the evaporation rate ratio of ET to Liq is 50:50;
h. EIL (electron injection layer): to be provided with
The evaporation rate of Yb (ytterbium) film layer is 1.0nm, and an electron injection layer is formed;
i. cathode: to be provided with
The evaporation rate ratio of (1) is (1);
j. light extraction layer: to be provided with
The evaporation rate of (3), CPL with a thickness of 70nm was vacuum evaporated on the cathode as a light extraction layer;
k. packaging the evaporated substrate: firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
The structural formula referred to above is as follows:
device examples 2-30:
device examples 2-30 were prepared by replacing the light-emission auxiliary layers in device example 1 with compounds 11, 53, 61, 98, 4, 16, 23, 26, 32, 38, 41, 44, 50, 54, 58, 62, 67, 70, 75, 79, 83, 89, 94, 97, 101, 107, 111, 119, 124, respectively.
Devices comparative examples 1-8:
this comparative example provides an organic electroluminescent device, which was fabricated by a method different from that of device example 1 only in that the organic electroluminescent device was fabricated by vapor deposition using the existing comparative compounds a, b, c, d, e, f, g, h, respectively, instead of the light-emitting auxiliary material (compound 1) in device example 1 above, to fabricate device comparative examples 1 to 8. Wherein the chemical structural formulas of the comparative compounds a, b, c, d, e, f, g and h are as follows:
the organic electroluminescent devices containing a light-emitting auxiliary material obtained in the above-described device examples 1 to 30 and device comparative examples 1 to 8 were characterized for driving voltage, light-emitting efficiency, BI value, and lifetime at a luminance of 1000 (nits). The test results are shown in table 2.
TABLE 2 test results of luminescence characteristics (brightness value 1000 nits)
Note: in the blue top-emitting device, the current efficiency is greatly affected by chromaticity, and therefore the ratio of the luminous efficiency to CIEy is defined as a BI value, i.e., BI = (cd/a)/CIEy, taking into consideration the influence of chromaticity on the efficiency.
As can be seen from table 2, the organic electroluminescent devices of examples 1 to 30, which were prepared using the luminescence auxiliary material provided by the present invention, had improved luminous efficiency and lifespan while driving voltage was reduced, as compared to the conventional organic electroluminescent devices of comparative examples 1 to 8.
Compared with a comparative compound, the compound has different parent nucleus, prolongs molecular conjugation through the change of a side chain, can improve the hole mobility of the compound, and changes a space structure through connecting a group at the position of the parent nucleus naphthobenzofurannaphthalene, so that the compound is more adaptive on a device, the service life and the luminous efficiency of an OLED device can be effectively prolonged, the glass transition temperature of the OLED device can be effectively improved, and the driving voltage can be reduced.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed in the embodiment corresponds to the method disclosed in the embodiment, so that the description is simple, and the relevant points can be referred to the description of the method part.
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 (10)
1. An organic electroluminescent compound having a formula represented by general formula (I):
Ar 1 is a benzene ring and is fused with the adjacent benzene ring of dibenzofuran;
Ar 2 is substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
R 1 selected from substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, the heteroatoms of which are selected from oxygen, nitrogen, sulphur; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur;
R 2 -R 5 each independently selected from hydrogen, deuterium, a halogen group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted 3-to 30-membered heterocycloalkyl group, the heteroatom of which is selected from oxygen, nitrogen, sulfur; substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur.
2. The organic electroluminescent compound according to claim 1, wherein the formula is represented by general formulae (II-1) to (II-3):
3. an organic electroluminescent compound according to claim 1 or 2, wherein R is 1 Selected from the following structural formulas:
wherein in the above formula, is represented as a connecting point.
4. An organic electroluminescent compound according to claim 1 or 2, characterized in that it has the formula (III-1) to (III-15):
5. an organic electroluminescent compound according to claim 1 or 2, wherein Ar is Ar 2 Selected from the following structural formulas:
wherein R is 6 Selected from the group consisting of substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted 3-to 18-membered heteroaryl, the heteroatoms of which are selected from the group consisting of oxygen, nitrogen, sulfur, substituted or unsubstituted C1-C18 alkyl; in the above formula, a is represented as a connecting point.
6. An organic electroluminescent compound according to claim 1 or 2, wherein R is 2 -R 5 Each independently selected from hydrogen, deuterium, a halogen group, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted 3-to 20-membered heterocycloalkyl group, the heteroatom of which is selected from oxygen, nitrogen, sulfur; substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted 3-20 membered heteroaryl, the heteroatoms of which are selected from oxygen, nitrogen, sulfur.
7. The organic electroluminescent compound according to claim 1, wherein the general formula 1 is represented by any one of the following formulae (1) to (126):
8. a method for producing an organic electroluminescent compound according to any one of claims 1 to 7, comprising the steps of:
(1) Dissolving raw material A and raw material B in organic solvent, and reacting at N 2 Adding Pd under atmosphere 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating to 110-120 ℃, stirring for reaction for 10-12h, and performing suction filtration, washing, drying, evaporation and purification after the reaction is finished to obtain a compound shown as an intermediate 1;
(2) At N 2 Under protection, the intermediate 1, raw materials C and Pd 2 (dba) 3 、P(t-Bu) 3 And t-BuONa, heating to 110-120 ℃, stirring for reaction for 12-14h, and performing suction filtration, washing, drying, evaporation and purification after the reaction is finished to obtain a compound shown in a general formula 1;
the specific synthetic route is shown as a reaction formula I:
in the formula R 1 ～R 5 、Ar 1 、Ar 2 Having the definitions given in claim 1.
9. Use of an organic electroluminescent compound according to any one of claims 1 to 7 for the production of an organic light-emitting device or a fluorescent lamp.
10. An organic electroluminescent device comprising a first electrode, a second electrode, one or more organic layers disposed between the first electrode and the second electrode; and the number of the first and second groups is,
the organic layer comprises a light-emitting auxiliary layer and also comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a light extraction layer and a cap layer; and the number of the first and second electrodes,
the luminescence auxiliary layer comprises one or more organic electroluminescent compounds as claimed in any of claims 1 to 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079802A (en) * | 2020-09-10 | 2020-12-15 | 吉林奥来德光电材料股份有限公司 | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device |
| CN112513034A (en) * | 2018-07-31 | 2021-03-16 | 株式会社半导体能源研究所 | Organic compound, light-emitting element, light-emitting device, electronic device, and lighting device |
| CN114790184A (en) * | 2022-06-22 | 2022-07-26 | 吉林奥来德光电材料股份有限公司 | Luminous auxiliary material and preparation method thereof, light-emitting device and light-emitting device |
| CN114853701A (en) * | 2022-05-25 | 2022-08-05 | 吉林奥来德光电材料股份有限公司 | Luminescent auxiliary material and preparation method and application thereof |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112513034A (en) * | 2018-07-31 | 2021-03-16 | 株式会社半导体能源研究所 | Organic compound, light-emitting element, light-emitting device, electronic device, and lighting device |
| CN112079802A (en) * | 2020-09-10 | 2020-12-15 | 吉林奥来德光电材料股份有限公司 | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device |
| CN114853701A (en) * | 2022-05-25 | 2022-08-05 | 吉林奥来德光电材料股份有限公司 | Luminescent auxiliary material and preparation method and application thereof |
| CN114790184A (en) * | 2022-06-22 | 2022-07-26 | 吉林奥来德光电材料股份有限公司 | Luminous auxiliary material and preparation method thereof, light-emitting device and light-emitting device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115557921A (en) * | 2022-12-02 | 2023-01-03 | 吉林奥来德光电材料股份有限公司 | Cap layer material, preparation method, organic electroluminescent device and display device |
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