CN115010608A - Luminescent auxiliary material, preparation method thereof and organic electroluminescent device - Google Patents

Luminescent auxiliary material, preparation method thereof and organic electroluminescent device Download PDF

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CN115010608A
CN115010608A CN202210588596.6A CN202210588596A CN115010608A CN 115010608 A CN115010608 A CN 115010608A CN 202210588596 A CN202210588596 A CN 202210588596A CN 115010608 A CN115010608 A CN 115010608A
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汪康
马晓宇
贾宇
王永光
黄悦
李东
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses a luminous auxiliary material and a preparation method thereof, wherein the luminous auxiliary material has the following structure:
Figure RE-DDA0003779995930000011
the organic electroluminescent auxiliary material with dibenzofluorene and triarylamine functional groups can greatly improve the hole transmission efficiency and the electron blocking capability, and the charge of holes and electrons in a light-emitting layer is increased in a balanced manner, so that the light is well emitted in the light-emitting layer instead of the surface of a hole transport layer, thereby judging the maximization efficiency and the service life; the invention also provides an organic electroluminescent device containing the luminescent auxiliary material.

Description

Luminescence auxiliary material, preparation method thereof and organic electroluminescent device
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a luminous auxiliary material, a preparation method thereof and an organic electroluminescent device.
Background
Generally, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic light emitting device using an organic light emitting phenomenon has a wide viewing angle, excellent contrast, a fast response time, and excellent luminance, driving voltage, and response speed characteristics, and thus a great deal of research is being conducted.
Many improvements have been made to make organic EL devices practical. For example, it is known that high efficiency and high durability can be achieved by further distributing various functions of a laminated structure and forming an anode, and a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are provided on a substrate.
With this organic EL device, charges injected from the two electrodes are recombined in the light emitting layer to obtain light emission. In this case, how to efficiently transfer charges of holes and electrons to the light emitting layer is important, and the device is required to have excellent carrier balance. Also, the light emitting efficiency is improved by enhancing a hole injecting property and an electron blocking property of blocking electrons injected from the cathode to increase a recombination probability of holes and electrons, and by confining excitons generated in the light emitting layer. Therefore, the role of the luminescence assisting material is so important.
The research on organic electroluminescent materials has been widely carried out in academia and industry, but the development of stable and efficient organic layer materials for organic electronic devices has not been fully developed so far, and the industrialization of the technology still faces many key problems, so that the development of new materials is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a light-emitting auxiliary material, a method of preparing the same, and an organic electroluminescent device that can produce an organic electroluminescent device having low driving voltage, high luminous efficiency, and/or long life characteristics.
In order to achieve the purpose, the invention adopts the following technical scheme:
a luminescent auxiliary material has a structure shown in chemical formula I:
Figure BDA0003664112030000021
wherein, in the formula:
x is selected from O, S or-C (CH) 3 ) 2 -；
R 1 Alkyl selected from C1-C8;
R 2 selected from hydrogen;
z is selected from the group consisting of a bond, oxygen, sulfur, CR 5 ,R 6 Or NR 7 ；
Ar 1 Selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C30 fused ring group;
R 5 、R 6 and R 7 Each independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxylA group, a sulfonic acid group, a phosphoric acid group, a boryl group, a substituted or unsubstituted C1-C25 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted 3-to 20-membered heterocycloalkyl group in which hetero atoms are N, O, S, Si, P, Se, or the like, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 3-to 30-membered heteroaryl group in which hetero atoms are N, O, S, Si, P, Se, or the like;
ring A is a substituent fused on the benzene ring, and is specifically selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-20 membered heteroaryl, wherein the heteroatom is N, O, S, Si, P, Se, etc.
Preferably, Z is a connecting bond;
ar is 1 Selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted 3-to 20-membered heteroaryl, or substituted or unsubstituted C10-C25 fused ring;
the ring A is substituted or unsubstituted C6-C10 aryl.
Preferably, the ring a is phenyl;
ar is 1 Any one of the following structures:
Figure BDA0003664112030000031
preferably, the formula I includes the following structure:
Figure BDA0003664112030000041
Figure BDA0003664112030000051
Figure BDA0003664112030000061
Figure BDA0003664112030000071
in the above technical solutions, the term "substituted or unsubstituted" means substituted by one, two or more substituents selected from: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; a substituted or unsubstituted alkylamino group; substituted or unsubstituted heterocyclylamino; substituted or unsubstituted arylamine; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent in which two or more substituents among the above-shown substituents are connected, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
More preferably, the formula I includes the following structure:
8、
Figure BDA0003664112030000081
Figure BDA0003664112030000091
Figure BDA0003664112030000101
Figure BDA0003664112030000111
Figure BDA0003664112030000121
Figure BDA0003664112030000131
another object of the present invention is to provide a method for preparing the above luminescent auxiliary material, wherein the synthesis scheme 1 is as follows:
Figure BDA0003664112030000141
or/and;
scheme 1:
Figure BDA0003664112030000142
the preparation method comprises the following steps:
step 1, preparation of intermediate 1
Dissolving the raw material B (1.0eq) in a THF solution, cooling to 0 ℃, dropwise adding the raw material A (2.0eq) into the solution under the protection of nitrogen, naturally heating to room temperature, uniformly stirring, and detecting by TLC. After the reaction is finished, quenching the mixture by using an ammonium chloride aqueous solution, extracting an organic phase by using ethyl acetate to obtain a solid substance, leaching the solid substance by using water and spin-drying the solid substance to obtain an intermediate 1;
step 2, preparation of intermediate 2
After intermediate 1(1.0eq) was dissolved in a mixed solvent of THF and toluene (V: V ═ 1:1) and added to the reaction vessel, MSA (10.0eq) was slowly added dropwise to the aforementioned mixture; after stirring the mixture at room temperature for 8 hours, water was added and the mixture was extracted with dichloromethane. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator to give a solid organic. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly and dropwisely adding the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, precipitating the precipitate, carrying out suction filtration to obtain a solid, sequentially leaching the solid by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2;
step 3, preparation of intermediate 3
Dissolving the intermediate 2(1.0eq) and the raw material C (1.0eq) in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.01eq), tri-tert-butylphosphine (0.05eq) and sodium tert-butoxide (2.0eq) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 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 combining the organic phases, drying was performed using 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 dichloromethane: V petroleum ether ═ 10:4) to obtain formula I.
Scheme 2:
Figure BDA0003664112030000161
the preparation method comprises the following steps:
step 1, preparation of intermediate 1
After charging the starting material B (1.1eq) and THF into the reaction vessel, the air was replaced sufficiently with nitrogen three times and the temperature was lowered to 0 ℃, the starting material a (1.0eq) was added, and after stirring the mixture for 5 hours, water was added and the mixture was extracted with dichloromethane. Then drying the extracted organic layer by using sodium sulfate, removing the solvent by using a rotary evaporator, and drying to obtain a solid organic matter intermediate 1;
step 2, preparation of intermediate 2
N 2 Under protection, adding the intermediate 1(1.0eq) and the raw material C (1.0eq) into a reaction vessel, dissolving in HOAC, heating to 100 ℃, and dropwise adding H 2 SO 4 (0.1mL), stirring for reaction for 1h, cooling to room temperature, adding saturated sodium bicarbonate solution to terminate the reaction, separating liquid, extracting the water phase with dichloromethane, collecting the organic phase, adding anhydrous magnesium sulfate for drying, removing the solvent by a rotary evaporator, drying the solid, completely dissolving the solid organic matter with a small amount of dichloromethane, slowly dripping into petroleum ether solution, stirring uniformly, precipitating, and filtering to obtain the solidA bulk organic intermediate 2;
step 3, preparation of intermediate 3
After intermediate 2(1.1eq) and THF were added to the reaction vessel, the air was replaced sufficiently with nitrogen three times to be cooled to 0 ℃, raw material D (1.0eq) was added, and after stirring the mixture for 5 hours, water was added and the mixture was extracted with dichloromethane. Then drying the extracted organic layer by using sodium sulfate, removing the solvent by using a rotary evaporator, and drying to obtain a solid organic matter intermediate 3;
step 4, preparation of intermediate 4
After intermediate 3(1.0eq) was dissolved in a mixed solvent of THF and toluene (V: V ═ 1:1) and added to the reaction vessel, MSA (10.0eq) was slowly added dropwise to the previous mixture; after stirring the mixture at room temperature for 8 hours, water was added and the mixture was extracted with dichloromethane. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator to give a solid organic. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly and dropwisely adding the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, precipitating the precipitate, carrying out suction filtration to obtain a solid, sequentially leaching by using absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 4;
step 5, preparation of chemical formula I
Under the protection of nitrogen, dissolving the intermediate 4(1.0eq) and the raw material E (1.0eq) in a toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.01eq), tri-tert-butylphosphine (0.05eq) and sodium tert-butoxide (2.0eq), uniformly stirring, heating to reflux, and reacting for 5 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 combining the organic phases, drying was performed using 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 dichloromethane: V petroleum ether ═ 10:4) to obtain formula I.
Z, X, Ar therein 1 、R 1 、R 2 Ring a is as defined above for formula I.
It is a further object of the present invention to provide an organic electroluminescent device comprising a first electrode, a second electrode and at least one organic layer disposed between said first electrode and said second electrode;
the organic layer comprises the light-emitting auxiliary material;
the organic material layer of the organic light emitting device in the present invention may be formed in a single layer structure, but may also be formed in a multilayer structure in which a layer and two or more organic material layers are present. For example, the organic light emitting device in the present invention may have a structure including a hole injection layer, a hole transport layer, a hole injection and transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron injection and transport layer, and the like as organic material layers. However, the structure of the organic light emitting device is not limited thereto, and a smaller number of organic material layers or a larger number of organic material layers may be included.
As the anode material, a material having a large work function is generally preferred so that holes are smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the invention include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, e.g. ZnO: Al or SnO 2 Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.
The hole injecting material is a material that advantageously receives holes from the anode at low voltages, and the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanenitrile-based hexaazatriphenylene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, and polyaniline-and polythiophene-based conductive polymer, and the like, but are not limited thereto, and may further include another compound capable of p-doping.
The hole transport material is a material capable of receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer, and a material having high hole mobility is suitable. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers having both conjugated portions and non-conjugated portions, and the like, but are not limited thereto.
The light emitting layer may emit red, green or blue light, and may be formed of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in a visible light region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons, and is preferably a material having favorable quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-Hydroxyquinoline aluminum complex (Alq) 3 ) (ii) a A carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzocarbazole-, benzothiazole-, and benzimidazole-based compounds; polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; a polyfluorene; rubrene, and the like, but is not limited thereto.
The host material of the light-emitting layer includes a condensed aromatic ring derivative, a heterocyclic ring-containing compound, and the like. Specifically, the fused aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the heterocycle-containing compound includes a carbazole derivative, a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative, and the like, however, the material is not limited thereto.
The electron transport layer may function to facilitate electron transport. The electron transport material is a material that favorably receives electrons from the cathode and transports the electrons to the light emitting layer, and a material having high electron mobility is suitable. Specific examples thereof include: an Al complex of 8-hydroxyquinoline; comprising Alq 3 The complex of (1); an organic radical compound; a hydroxyflavone-metal complex; and the like, but are not limited thereto. The thickness of the electron transport layer may be 1nm to 50 nm. The electron transport layer having a thickness of 1nm or more has a prevention propertyThe electron transport property is degraded, and the thickness of 50nm or less has an advantage of preventing an increase in driving voltage for enhancing electron transfer caused by too thick an electron transport layer.
The electron injection layer may function to promote electron injection. The electron-injecting material is preferably a compound of: it has an ability to transport electrons, has an electron injection effect from a cathode, has an excellent electron injection effect on a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from migrating to a hole injection layer, and, in addition, has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complexes, nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto.
As the cathode material, a material having a small work function is generally preferable so that electrons are smoothly injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; materials of multilayer construction, e.g. LiF/Al or LiO 2 Al; and the like, but are not limited thereto.
The organic electroluminescent device provided by the invention can be applied to Organic Light Emitting Devices (OLEDs), Organic Solar Cells (OSCs), electronic paper (e-paper), Organic Photoreceptors (OPC) or Organic Thin Film Transistors (OTFTs).
Through the technical scheme, compared with the prior art, the invention has the following beneficial effects:
the invention provides an organic electroluminescent auxiliary material of functional groups of naphthobenzofluorene or naphthobenzofuran or naphthobenzothiophene and triarylamine, which can greatly improve the hole transmission efficiency and the electron blocking capability, and the charge balance of holes and electrons in a luminescent layer is increased, so that the luminescence is well formed in the luminescent layer instead of the surface of a hole transport layer, thereby greatly improving the efficiency and the service life of a device.
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 description of the embodiments or the prior art 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 shows the hydrogen nuclear magnetic resonance spectrum of compound 9 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Figure BDA0003664112030000211
Dissolving the raw material B-9(30.00mmol) in 60.00ml of THF solution, cooling to 0 ℃, dropwise adding the raw material A-9(60.00mmol) into the solution under the protection of nitrogen, naturally heating to room temperature, uniformly stirring, and detecting by TLC. After the reaction is finished, quenching the mixture by using an ammonium chloride aqueous solution, extracting an organic phase by using ethyl acetate to obtain a solid substance, leaching the solid substance by using water and spin-drying the solid substance to obtain an intermediate 1; (5.77g, yield: 62.36%)
Intermediate 1(16.19mmol) was dissolved in 50.00ml of a mixed solvent of THF and toluene (V: V ═ 1:1), and after addition to the reaction vessel, MSA (161.90mmol) was slowly added dropwise to the aforementioned mixture; after stirring the mixture at room temperature for 8 hours, water was added and the mixture was extracted with dichloromethane. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator to give a solid organic. 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, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2; (3.58g, yield: 76.00%)
Dissolving the intermediate 2(7.29mmol) and the raw material C-9(7.29mmol) in 60.00ml of toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.07mmol), tri-tert-butylphosphine (0.36mmol) and sodium tert-butoxide (14.58mmol) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 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 combining the organic phases, drying was performed using 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 dichloromethane: V petroleum ether ═ 10:4) to obtain compound-9. (3.90g, yield: 80.49%, Mw:665.88)
The detection analysis of the obtained compound-9 was carried out, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 665.88; the test value was 665.44.
Elemental analysis:
the calculated values are: c, 91.99; h, 5.90; and N, 2.10.
The test values are: c, 91.47; h, 6.18; and N, 2.38.
Example 2
Figure BDA0003664112030000221
Dissolving the raw material B-66(30.00mmol) in 60.00ml THF solution, cooling to 0 deg.C, adding the raw material A-66(60.00mmol) dropwise into the above solution under nitrogen protection, naturally heating to room temperature, stirring well, and detecting by TLC. After the reaction is finished, quenching the mixture by using an ammonium chloride aqueous solution, extracting an organic phase by using ethyl acetate to obtain a solid substance, and leaching the solid substance by using water and spin-drying the solid substance to obtain an intermediate 1; (5.81g, yield: 62.74%)
After intermediate 1(16.19mmol) was dissolved in 50.00ml of a mixed solvent of THF and toluene (V: V ═ 1:1) and added to the reaction vessel, MSA (161.90mmol) was slowly added dropwise to the aforementioned mixture; after stirring the mixture at room temperature for 8 hours, water was added and the mixture was extracted with dichloromethane. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator to give a solid organic. 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, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2; (3.59g, yield: 76.17%)
Dissolving the intermediate 2(10.32mmol) and the raw material C-66(10.32mmol) in 80.00ml of toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.10mmol), tri-tert-butylphosphine (0.52mmol) and sodium tert-butoxide (20.64mmol) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 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; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain compound-66. (5.57g, yield: 76.42%, Mw:705.95) the compound-66 thus obtained was examined and found to have the following results:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 705.95; the test value was 705.61.
Elemental analysis:
the calculated values are: c, 91.88; h, 6.14; n, 1.98.
The test values are: c, 91.53; h, 6.29; and N, 2.27.
Example 3
Figure BDA0003664112030000241
Dissolving the raw material B-103(30.00mmol) in 60.00ml THF solution, cooling to 0 deg.C, adding the raw material A-103(60.00mmol) dropwise into the above solution under nitrogen protection, naturally heating to room temperature, stirring well, and detecting by TLC. After the reaction is finished, quenching the mixture by using an ammonium chloride aqueous solution, extracting an organic phase by using ethyl acetate to obtain a solid substance, leaching the solid substance by using water and spin-drying the solid substance to obtain an intermediate 1; (5.79g, yield: 62.50%)
Intermediate 1(16.19mmol) was dissolved in 50.00ml of a mixed solvent of THF and toluene (V: V ═ 1:1), and after addition to the reaction vessel, MSA (161.90mmol) was slowly added dropwise to the aforementioned mixture; after stirring the mixture at room temperature for 8 hours, water was added and the mixture was extracted with dichloromethane. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator to give a solid organic. Completely dissolving the solid organic matter by using a small amount of dichloromethane, slowly and dropwisely adding the dissolved solid organic matter into a petroleum ether solution, uniformly stirring, precipitating the precipitate, carrying out suction filtration to obtain a solid, sequentially leaching the solid by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2; (3.58g, yield: 76.25%)
Dissolving the intermediate 2(10.32mmol) and the raw material C-103(10.32mmol) in 100.00ml of toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.10mmol), tri-tert-butylphosphine (0.52mmol) and sodium tert-butoxide (20.64mmol) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 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; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain compound-103. (5.09g, yield: 77.19%, Mw:639.80) the compound-103 thus obtained was examined, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 639.80; the test value was 639.52.
Elemental analysis:
the calculated values are: c, 90.11; h, 5.20; n, 2.19; o, 2.50.
The test values are: c, 89.88; h, 5.43; n, 2.36; o, 2.74.
Example 4
Figure BDA0003664112030000251
Dissolving raw material B-169(30.00mmol) in 60.00ml THF solution, cooling to 0 deg.C, adding raw material A-169(60.00mmol) dropwise into the above solution under nitrogen protection, naturally heating to room temperature, stirring well, and detecting by TLC. After the reaction is finished, quenching the mixture by using an ammonium chloride aqueous solution, extracting an organic phase by using ethyl acetate to obtain a solid substance, and leaching the solid substance by using water and spin-drying the solid substance to obtain an intermediate 1; (5.77g, yield: 62.33%)
Intermediate 1(16.19mmol) was dissolved in 50.00ml of a mixed solvent of THF and toluene (V: V ═ 1:1), and after addition to the reaction vessel, MSA (161.90mmol) was slowly added dropwise to the aforementioned mixture; after stirring the mixture at room temperature for 8 hours, water was added and the mixture was extracted with dichloromethane. The extracted organic layer was then dried over sodium sulfate and the solvent was removed using a rotary evaporator to give a solid organic. 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, separating out a precipitate, performing suction filtration to obtain a solid, sequentially leaching by using 300mL of absolute ethyl alcohol and 200mL of petroleum ether, and drying to obtain an intermediate 2; (3.59g, yield: 76.31%)
Dissolving the intermediate 2(10.32mmol) and the raw material C-169(10.32mmol) in 70.00ml of toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.10mmol), tri-tert-butylphosphine (0.52mmol) and sodium tert-butoxide (20.64mmol) under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 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; the remaining material was purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V dichloromethane: V petroleum ether ═ 10:4) to obtain compound-169. (5.25g, yield: 74.81%, Mw:679.86) the compound-169 thus obtained was analyzed for detection, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 679.86; the test value was 679.52.
Elemental analysis:
the calculated values are: c, 90.10; h, 5.49; n, 2.06; o, 2.35.
The test values are: c, 89.86; h, 5.71; n, 2.31; o, 2.56.
The general structural formula is the chemical formula I in the summary of the invention, and the synthetic routes and principles of other compounds are the same as those of the above-listed examples. In embodiments 5 to 38 of the present invention, the luminescent auxiliary material shown in table 1 below can be obtained according to the above preparation method:
table 1:
Figure BDA0003664112030000271
Figure BDA0003664112030000281
when the organic layer includes the light-emitting auxiliary layer, the light-emitting auxiliary layer includes the light-emitting auxiliary material provided in the above embodiment.
Device example 1 preparation of Green organic electroluminescent device
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/ETL/EIL/cathode/light extraction layer
a. An ITO anode: coating with a thickness of
Figure BDA0003664112030000291
The ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate is cleaned in distilled water for 2 times, ultrasonically cleaned for 30min, repeatedly cleaned in distilled water for 2 times, ultrasonically cleaned for 10min, and then ultrasonically cleaned with methanol, acetone and isopropanol (each time for 5min) after the cleaning is finished, dried, then transferred into a plasma cleaning machine for cleaning for 5min, and then conveyed into an evaporation machine, and other functional layers are sequentially evaporated on the substrate by taking the substrate as an anode.
b. HIL (hole injection layer): to be provided with
Figure BDA0003664112030000292
The hole injection layer materials HT-1 and P-dopant were vacuum evaporated, and the chemical formulas are shown below. The evaporation rate ratio of HT-1 to P-dock is 97: 3, the thickness is 10 nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003664112030000293
The evaporation rate of (2), and evaporating 130nm HT-1 on the hole injection layer in vacuum to form a hole transport layer;
d. a light-emitting auxiliary layer: to be provided with
Figure BDA0003664112030000294
Vacuum evaporating 10nm of the compound 9 provided in the above example as a light-emitting auxiliary layer on the hole transport layer;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer to
Figure BDA0003664112030000295
The ratio of Host1 to Host2 was 50:50, and two Host materials (Host1 and Host2) and a Dopant material (Dopant-1) having a thickness of 200nm were vacuum-evaporated as light-emitting layers. The chemical formulas of Host1, Host2 and Dopan are shown below. Wherein the evaporation rate ratio of the double Host to the Dopan is 98: 2.
f. HBL (hole blocking layer): to be provided with
Figure BDA0003664112030000296
The hole-blocking layer HB was vacuum-deposited at a thickness of 5.0 nm.
g. ETL (electron transport layer): to be provided with
Figure BDA0003664112030000297
The chemical formula of ET-1 is shown below, and ET-1 and Liq with the thickness of 35nm are vacuum evaporated to be used as electron transport layers. Wherein the evaporation rate ratio of ET-1 to Liq is 50: 50.
h. EIL (electron injection layer): to be provided with
Figure BDA0003664112030000298
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003664112030000299
The evaporation rate ratio of the (1) to the (9) is 1:9, and the OLED device is obtained.
j. Light extraction layer: to be provided with
Figure BDA0003664112030000301
CPL-1 was vacuum-deposited on the cathode at a thickness of 70nm to form a light extraction layer.
K. And then 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.
Figure BDA0003664112030000302
By referring to the method provided in device example 1 above, compounds 6, 10, 11, 13, 18, 26, 34, 36, 37, 38, 57, 58, 59, 96, 99, 103, 186, 192, and 199 were selected instead of compound 9, respectively, and evaporation of a light-emitting auxiliary layer was performed to prepare corresponding organic electroluminescent devices, which are denoted as device examples 2 to 20, respectively.
Device comparative example 1:
this comparative example provides an organic electroluminescent device whose preparation method differs from that of device example 1 only in that the organic electroluminescent device was subjected to evaporation using existing comparative compound 1 instead of the light-emitting auxiliary material (compound 1) in device example 1 described above. Wherein, the chemical structural formula of comparative compound 1 is as follows:
device comparative example 2:
this comparative example provides an organic electroluminescent device whose preparation process differs from that of device example 1 only in that the organic electroluminescent device was vapor-deposited using the existing comparative compound 2 instead of the light-emitting auxiliary material (compound 2) in device example 1 described above. Wherein, the chemical structural formula of comparative compound 2 is as follows:
Figure BDA0003664112030000311
the organic electroluminescent devices obtained in the device examples 1 to 20 and the device comparative examples 1 to 2 were characterized at a luminance of 15000(nits), and the test results were as follows:
table 2:
Figure BDA0003664112030000312
Figure BDA0003664112030000321
Figure BDA0003664112030000331
device example 21 preparation of Red light organic electroluminescent device
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/ETL/EIL/cathode/light extraction layer
a. An ITO anode: coating with a thickness of
Figure BDA0003664112030000332
The ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate is cleaned in distilled water for 2 times, ultrasonically cleaned for 30min, then repeatedly cleaned for 2 times by distilled water, ultrasonically cleaned for 10min, and after the cleaning is finished, ultrasonically cleaned by methanol, acetone and isopropanol in sequence (each time for 5min), dried, then transferred into a plasma cleaning machine for cleaning for 5min, and then sent into an evaporation machine, and other functional layers are evaporated on the substrate by taking the substrate as an anode in sequence.
b. HIL (hole injection layer): to be provided with
Figure BDA0003664112030000333
The hole injection layer materials HT-1 and P-dopant were vacuum evaporated, and the chemical formulas are shown below. The evaporation rate ratio of HT-1 to P-dock is 97: 3, the thickness is 10 nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003664112030000334
The evaporation rate of (2), and evaporating 130nm HT-1 on the hole injection layer in vacuum to form a hole transport layer;
d. a light-emitting auxiliary layer: to be provided with
Figure BDA0003664112030000341
Vacuum evaporation of 10nm of the compound 6 provided in the above example 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 so as to
Figure BDA0003664112030000342
The Host material (Host3) and the Dopant material (Dopant-2) as the light-emitting layer are vacuum-evaporated to a thickness of 20nm, and the chemical formulas of the Host3 and the Dopant-2 are shown below. Wherein the evaporation rate ratio of the double Host3 to the Dopan-2 is 98: 2.
f. HBL (hole blocking layer): to be provided with
Figure BDA0003664112030000343
The hole blocking layer HB was vacuum-deposited at a thickness of 5.0 nm.
g. ETL (electron transport layer): to be provided with
Figure BDA0003664112030000344
The chemical formula of ET-1 is shown below, and ET-1 and Liq with the thickness of 35nm are vacuum evaporated to be used as electron transport layers. Wherein the evaporation rate ratio of ET-1 to Liq is 50: 50.
h. EIL (electron injection layer): to be provided with
Figure BDA0003664112030000345
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003664112030000346
The evaporation rate ratio of the (1) to the (9) is 1:9, and the OLED device is obtained.
j. Light extraction layer: to be provided with
Figure BDA0003664112030000347
CPL-1 was vacuum-deposited on the cathode at a thickness of 70nm to form a light extraction layer.
K. And then 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.
Figure BDA0003664112030000351
With reference to the method provided in device example 21 above, compounds 11, 45, 50, 66, 69, 81, 82, 83, 96, 99, 103, 108, 126, 129, 131, 132, 169, 170, 186, 192, and 199 were selected instead of compound 6, respectively, and evaporation of a light-emitting auxiliary layer was performed, and corresponding organic electroluminescent devices, which are described as device examples 21 to 42, respectively, were prepared.
Device comparative example 3:
this comparative example provides an organic electroluminescent device which was produced by a method different from that of device example 21 only in that the organic electroluminescent device was subjected to evaporation using existing comparative compound 1 instead of the light-emitting auxiliary material (compound 6) in device example 21 described above. Wherein, the chemical structural formula of comparative compound 1 is as follows:
device comparative example 4:
this comparative example provides an organic electroluminescent device which was produced by a process which differs from that of device example 21 only in that the organic electroluminescent device was subjected to evaporation using the existing comparative compound 2 instead of the light-emitting auxiliary material (compound 6) in device example 21 described above. Wherein, the chemical structural formula of comparative compound 2 is as follows:
device comparative example 5:
this comparative example provides an organic electroluminescent device which was produced by a method different from that of device example 21 only in that the organic electroluminescent device was subjected to evaporation using existing comparative compound 3 instead of the light-emitting auxiliary material (compound 6) in device example 21 described above. Wherein comparative compound 3 has the following chemical structure:
Figure BDA0003664112030000361
the organic electroluminescent devices obtained in the device examples 21 to 42 and the device comparative examples 3 to 5 were characterized for driving voltage, light emission efficiency and lifetime at a luminance of 6000(nits), and the test results are shown in the following table 3:
table 3:
Figure BDA0003664112030000362
Figure BDA0003664112030000371
Figure BDA0003664112030000381
as can be seen from tables 2 and 3, in both the green device and the red device, the device performance is changed by changing the substituents and the positions of the substituents. Compared with the existing organic electroluminescent device provided by the comparative compound, the organic electroluminescent device prepared by using the luminescent auxiliary material provided by the invention has the advantages that the driving voltage, the luminous efficiency and the service life are improved, and the organic electroluminescent device can be simultaneously applied to the organic electroluminescent devices of red light and green light.
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 by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
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 (9)

1. A luminescent auxiliary material is characterized in that the structure is shown as a chemical formula I:
Figure FDA0003664112020000011
wherein, in the formula:
x is selected from O, S or-C (CH) 3 ) 2 -；
R 1 Alkyl selected from C1-C8;
R 2 selected from hydrogen;
z is selected from the group consisting of a bond, oxygen, sulfur, CR 5 ,R 6 Or NR 7 ；
Ar 1 Selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heteroaryl, substituted or unsubstituted C10-C30 fused ring group;
R 5 、R 6 and R 7 Each independently selected from hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, sulfonic acid group, phosphoric acid group, boryl, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted 3-to 20-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted 3-to 30-membered heteroaryl;
ring A is a substituent fused to a benzene ring, and is specifically selected from a substituted or unsubstituted C6-C30 aryl group, and a substituted or unsubstituted 3-to 20-membered heteroaryl group.
2. A luminescent aid according to claim 1, wherein Z is a bond;
ar is 1 Selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted 3-to 20-membered heteroaryl, or substituted or unsubstituted C10-C25 fused ring;
the ring A is substituted or unsubstituted C6-C10 aryl.
3. A luminescent support material as claimed in claim 1, wherein ring a is phenyl;
ar is 1 Any one of the following structures:
Figure FDA0003664112020000021
4. a luminescent auxiliary material as claimed in claim 1, wherein the formula I comprises the following structure:
Figure FDA0003664112020000031
Figure FDA0003664112020000041
Figure FDA0003664112020000051
Figure FDA0003664112020000061
5. a luminescent auxiliary material as claimed in claim 1, wherein the formula I comprises the following structure:
Figure FDA0003664112020000071
Figure FDA0003664112020000081
Figure FDA0003664112020000091
Figure FDA0003664112020000101
Figure FDA0003664112020000111
Figure FDA0003664112020000121
6. a method for preparing a luminescent support material as claimed in any of claims 1 to 5, characterized in that the synthetic route is as follows:
Figure FDA0003664112020000131
or/and;
Figure FDA0003664112020000132
the preparation method comprises the following steps:
(1) dissolving a raw material B in a THF solution, cooling to 0 ℃, dropwise adding the raw material A into the solution under the protection of nitrogen, naturally heating to room temperature, uniformly stirring, quenching after detection reaction is finished, extracting an organic phase with ethyl acetate to obtain a solid substance, leaching and spin-drying to obtain an intermediate 1;
(2) dissolving the intermediate 1 in a mixed solvent of THF and toluene, adding the mixed solvent into a reaction vessel, dropwise adding MSA, stirring at room temperature for 8 hours, adding water and extracting, drying an extracted organic layer, removing the solvent to obtain a solid organic matter, completely dissolving the solid organic matter, dropwise adding the solid organic matter into a petroleum ether solution, uniformly stirring, precipitating, carrying out suction filtration to obtain a solid, leaching, and drying to obtain an intermediate 2;
(3) dissolving the intermediate 2 and the raw material C in a toluene solution, then ventilating for 3 times, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide under the protection of nitrogen, stirring uniformly, heating to reflux, and reacting for 5 hours; after the reaction is finished, cooling to 40-50 ℃, filtering to remove salt and catalyst, cooling the filtrate to room temperature, washing for 3 times, retaining an organic phase, extracting a water phase, combining the organic phase, drying, and removing the solvent; purifying the remaining material to obtain formula I.
7. A method for preparing a luminescent support material as claimed in any of claims 1 to 5, characterized in that the synthetic route is as follows:
Figure FDA0003664112020000141
the preparation method comprises the following steps:
1) adding the raw material B and THF into a reaction vessel, then fully replacing air with nitrogen, cooling to 0 ℃ for three times, adding the raw material A, stirring the mixture for 5 hours, adding water and extracting the mixture, then drying the extracted organic layer, removing the solvent, and drying to obtain a solid organic matter intermediate 1;
2)N 2 under protection, adding the intermediate 1 and the raw material C into a reaction vessel, dissolving in HOAC, heating to 100 ℃, and dropwise adding H 2 SO 4 Stirring for reaction for 1h, cooling to room temperature, adding a saturated sodium bicarbonate solution to terminate the reaction, separating liquid, extracting a water phase, collecting an organic phase, drying, removing the solvent, drying the solid, completely dissolving the solid organic matter, dripping the solid organic matter into a petroleum ether solution, stirring uniformly, precipitating, and filtering to obtain a solid organic matter intermediate 2;
3) adding the intermediate 2(1.1eq) and THF into a reaction vessel, then fully replacing air with nitrogen for three times, cooling to 0 ℃, adding the raw material D, stirring the mixture for 5 hours, adding water, extracting the mixture, drying the extracted organic layer, removing the solvent, and drying to obtain a solid organic matter intermediate 3;
4) dissolving the intermediate 3 in a mixed solvent of THF and toluene, adding the intermediate into a reaction container, and dropwise adding MSA; stirring the mixture at room temperature for 8 hours, adding water and extracting the mixture, then drying the extracted organic layer, removing the solvent to obtain a solid organic matter, completely dissolving the solid organic matter, then dropwise adding the solid organic matter into a petroleum ether solution, uniformly stirring, precipitating, carrying out suction filtration to obtain a solid, sequentially leaching with absolute ethyl alcohol and petroleum ether, and drying to obtain an intermediate 4;
5) under the protection of nitrogen, dissolving the intermediate 4 and the raw material E in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide, stirring uniformly, heating to reflux, and reacting for 5 hours; after the reaction is finished, cooling to 30-50 ℃, filtering to remove salt and catalyst, cooling the filtrate to room temperature, washing for 3 times, retaining an organic phase, extracting a water phase, combining the organic phase, drying, and removing the solvent; purifying the remaining material to obtain formula I.
8. An organic electroluminescent device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode;
the organic layer comprises the luminescent auxiliary material according to any one of claims 1 to 5.
9. Use of the organic electroluminescent device as claimed in claim 8 in organic light-emitting devices, organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors.
CN202210588596.6A 2022-05-26 2022-05-26 Luminescent auxiliary material, preparation method thereof and organic electroluminescent device Pending CN115010608A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
CN115947706A (en) * 2023-03-09 2023-04-11 吉林奥来德光电材料股份有限公司 Luminous auxiliary material and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN112079731A (en) * 2020-09-18 2020-12-15 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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112079731A (en) * 2020-09-18 2020-12-15 吉林奥来德光电材料股份有限公司 Luminescent auxiliary material and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115947706A (en) * 2023-03-09 2023-04-11 吉林奥来德光电材料股份有限公司 Luminous auxiliary material and preparation method and application thereof

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