CN112409314A - Organic electroluminescent compound and preparation method and application thereof - Google Patents

Organic electroluminescent compound and preparation method and application thereof Download PDF

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CN112409314A
CN112409314A CN202011156601.3A CN202011156601A CN112409314A CN 112409314 A CN112409314 A CN 112409314A CN 202011156601 A CN202011156601 A CN 202011156601A CN 112409314 A CN112409314 A CN 112409314A
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organic electroluminescent
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汪康
王进政
黄悦
崔建勇
赵贺
李贺
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses an organic electroluminescent compound, which has a structural general formula shown in chemical formula 1:

Description

Organic electroluminescent compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent compound and a preparation method and application thereof.
Background
Organic electroluminescence is one of the most promising flat panel display technologies in the future, which has been studied most in recent 20 years, and is recognized as a possible substitute for liquid crystal. Compared with liquid crystal, the organic electroluminescent device has the characteristics of ultrathin property, self-luminescence, wide viewing angle, fast response, high luminous efficiency, good temperature adaptability, simple production process, low driving voltage, low energy consumption, low cost and the like, a luminous layer of the organic electroluminescent device is composed of organic molecular films of dozens of nanometers, and the thickness of a display device is only a few millimeters.
The organic electroluminescent element is a self-luminous element utilizing the following principle: by applying an electric field, the phosphorescent substance emits light by recombination energy of holes injected from the anode and electrons injected from the cathode. It has the following structure: an anode, a cathode, and an organic material layer therebetween. In order to improve the efficiency and stability of the organic electroluminescent element, the organic material layer generally includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). In such an organic light emitting element, 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, and the generated excitons generate light having a specific wavelength while migrating to a ground state. Wherein the hole transport layer can change hole transport efficiency, light emitting efficiency, lifetime, etc. of holes to the light emitting layer. Therefore, copper phthalocyanine (CuPc), 4 ' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB), N ' -diphenyl-N, N ' -bis (3-methylphenyl) - (1,1 ' -biphenyl) -4,4 ' -diamine (TPD), and the like are currently used as hole transport materials.
At present, research on organic electroluminescent materials has been widely conducted in academia and industry, and a large number of organic electroluminescent materials with excellent performance have been developed. In general, the organic electroluminescent device is developed into a white light device and a full color display device with high efficiency, long lifetime and low cost in the future, but the industrialization of the technology still faces many key problems.
Therefore, how to develop a compound which can stabilize the light emitting performance of the device and has high light emitting efficiency is a problem which needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides an organic electroluminescent compound with high electron transport performance, which can improve electron mobility, promote carrier injection balance, and further stabilize the light emitting performance of the device and improve the light emitting efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme: an organic electroluminescent compound, the structural general formula of which is shown in chemical formula 1:
Figure BDA0002742977440000021
wherein m, n and p are all 0 or 1 and cannot be 0 at the same time;
x is a connecting bond; or X is selected from-O-, -S-, -SO2-、-C(R3)(R4)-、-N(R5)-、-Si(R6)(R7)-、 -Sn(R8)(R9) -and-Ge (R)10)(R11) One of (1);
L1-L3each independently represents a bond; or L1-L3Each independently represents a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted 3-10 membered heteroarylene;
R1and R2Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, silicon, boryl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-30 membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-20 membered heteroaryl, substituted or unsubstituted 3-25 membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryloxy;
or, said R1And R2Are connected with each other to form a ring;
R3-R11each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heteroaryl group, a substituted or unsubstituted 3-30 membered heteroarylamino group, a substituted or unsubstituted C6-C60 arylamino group;
Ar1-Ar6each independently represents a substituted or unsubstituted C3-C30 cycloalkyl, a substituted or unsubstituted 3-20 membered heterocycloalkyl, a substituted or unsubstituted C6-C30 aryl, or a substituted or unsubstituted 3-10 membered heteroaryl, a substituted or unsubstituted 3-15 membered heteroarylamino, a substituted or unsubstituted C6-C60 arylamino.
Preferably, said R is1And R2When they are linked to each other to form a ring, they are represented by ring A;
the chemical formula 1 may also be represented as:
Figure BDA0002742977440000031
wherein q is 0 or 1, and m, n, p and q cannot be 0 simultaneously;
L4is a connecting bond; or L4Selected from substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted 3-10 membered heteroarylene;
Ar7and Ar8Each independently represents a substituted or unsubstituted C3-C30 cycloalkyl, a substituted or unsubstituted 3-20 membered heterocycloalkyl, a substituted or unsubstituted C6-C30 aryl or a substituted or unsubstituted 3-10 membered heteroaryl, a substituted or unsubstituted 3-15 membered heteroarylamine, a substituted or unsubstituted C6-C60 arylamine.
Ring A represents a substituted or unsubstituted C3-C10 cycloalkyl, a substituted or unsubstituted 3-to 10-membered heterocycloalkyl, a substituted or unsubstituted C6-C15 aryl, a substituted or unsubstituted 3-to 15-membered heteroaryl.
Preferably, said R is3-R11Each independently represents a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C7 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocycloalkyl group, a substituted or unsubstituted C6-C15 aryl group, a substituted or unsubstituted 3-15 membered heteroaryl group, a substituted or unsubstituted 3-10 membered heteroarylamino group, a substituted or unsubstituted C6-C30 arylamino group.
Preferably, Ar is1-Ar8Each independently represents a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-15 membered heteroaryl group, a substituted or unsubstituted 3-15 membered heteroarylamine group, a substituted or unsubstituted C6-C60 arylamine group.
Preferably, the heteroatoms in the cycloalkyl, heterocycloalkyl, heteroaryl and heteroarylamino are all selected from one of oxygen, nitrogen and sulfur.
In the above terms, "substituted" means that a hydrogen atom bonded to a carbon atom of a compound becomes an additional substituent, and the position of substitution is not limited as long as the position is a position at which the hydrogen atom is substituted (i.e., a position at which the substituent may be substituted), and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other.
That is, the "substitution" in the above-mentioned "substituted or unsubstituted", and preferable substituents are one or more of deuterium, cyano, halogen, nitro, hydroxyl, phosphoric acid group, boryl, silyl, C1-C8 alkyl, C2-C15 alkenyl, C2-C10 alkynyl, C6-C20 aryl, C3-C10 heteroaryl, C1-C10 alkoxy, C6-C20 arylamino.
In the above technical solution, the organic electroluminescent compound is selected from the following compounds of formula 1 with preferred structures HT- (1-88):
Figure BDA0002742977440000051
Figure BDA0002742977440000061
Figure BDA0002742977440000071
the invention also provides a preparation method of the organic electroluminescent compound, which comprises the following steps:
(1) under the protection of nitrogen, adding tetrahydrofuran into the raw material B, cooling to (-70) - (-78) ℃, then dropwise adding n-butyl lithium, and stirring and mixing to obtain a mixed solution A; dropwise adding the raw material A into the mixed solution A, and stirring for reaction to prepare an intermediate 1;
(2) and adding glacial acetic acid into the intermediate 1, heating, dropwise adding concentrated sulfuric acid, uniformly stirring, cooling, and then adding a sodium bicarbonate solution to terminate the reaction to prepare a solid intermediate 2.
(3) Under the protection of nitrogen, dissolving the intermediate 2 and the raw material C in a mixed solution of toluene, ethanol and water, then adding palladium tetratriphenylphosphine and potassium carbonate, uniformly stirring, heating and refluxing to prepare an intermediate 3;
(4) under the protection of nitrogen, dissolving the intermediate 3 and the raw material D in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide, uniformly stirring, heating and refluxing to prepare a chemical formula 1 or a chemical formula 1-1;
the synthetic route of chemical formula 1 is:
Figure BDA0002742977440000081
the synthetic route of chemical formula 1-1 is:
Figure BDA0002742977440000091
wherein, said Hal1And Hal2Is a halogen other than chlorine.
When L1, L2, L3 and L4 represent a connecting bond, chemical formula 1 and chemical formula 1-1 can be synthesized from intermediate 2 and starting material D.
Preferably, the molar ratio of the raw material B to the n-butyllithium to the raw material A is set to
(30-50): (36-60): (30-50), wherein the molar volume ratio of the raw material A to the tetrahydrofuran is (30-50) mmol: (80-160) mL;
the temperature of stirring and mixing is (-70) DEG C to (-78) DEG C, and the time is 1.5-2.5 h.
Preferably, in the step (2), the molar volume ratio of the intermediate 1, the glacial acetic acid and the sodium bicarbonate solution is (24-44) mmol: (125-200) mL: (24-44) mL; the stirring temperature is 110-130 ℃, and the stirring time is 5 min.
Preferably, in the step (3), the molar ratio of the intermediate 2, the raw material C, the tetratriphenylphosphine palladium and the potassium carbonate is: (18-33): (0.18-0.34): (36-65); the molar volume ratio of the intermediate body 2 to the mixed solution is (18-34) mmol: (110- > 200) mL; the volume ratio of the toluene, the ethanol and the water is (2.5-3.5) to (0.5-1.5); the temperature is increased to 80-100 ℃, and the reflux time is 4.5-5.5 h;
in the step (4), the molar ratio of the intermediate 3, the raw material D, the tris (dibenzylideneacetone) dipalladium, the tri-tert-butylphosphine and the sodium tert-butoxide is (14-27): (14-27): (0.14-0.28): (0.7-1.4): (28-56); the molar volume ratio of the intermediate 3 to the toluene solution is (14-27) mmol: (110-270) mL; the temperature is raised to 80-100 ℃, and the reflux time is 4.5-5.5 h.
The invention also provides an application of the organic electroluminescent compound in an organic electroluminescent device.
The invention also provides an organic electroluminescent device, which comprises a first electrode, a second electrode and an organic layer; at least one organic layer is arranged between the first electrode and the second electrode;
the organic material layer of the organic light-emitting device is of a single-layer structure; or, formed as a multilayer structure of two or more organic material layers;
the organic light emitting device 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 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.
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).
According to the technical scheme, compared with the prior art, the organic electroluminescent compound and the preparation method and application thereof are disclosed and provided, and the position of a substituent or the activity of the substituent is adjusted by the coordination of a heterocyclic ligand of the organic electroluminescent compound; and the amine unit on the complex has lower ionization potential, better electron donating property and higher hole mobility. Meanwhile, the symmetry of the molecule is reduced, and the conformational isomer of the molecule is increased; meanwhile, the R1 and R2 positions in the structural formula are connected with substituent groups or are mutually connected to form a substituted or unsubstituted single-ring or multi-ring structure, so that the compound has a rigid planar structure, the molecular weight is increased, the molecules are not easy to crystallize and aggregate, and the material has high photo-thermal stability; after the obtained hole transport material is used for an organic electroluminescent device, the luminous efficiency of the device is improved, the service life is delayed, and the driving voltage is reduced.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the following 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: preparation of Compound HT-9
Figure BDA0002742977440000111
1. Under the protection of nitrogen, the raw material B-9(50.00mmol) is added into a three-neck flask, 160.00 mL of anhydrous tetrahydrofuran is added, then the reaction system is cooled to-78 ℃, n-BuLi (60.00mmol) is added dropwise, and the mixture is stirred for 2h at-78 ℃ to obtain a mixed solution. Dissolving the raw material A-9(50.00mmol) in 150.00mL of tetrahydrofuran solution, then dropwise adding the solution into the mixed solution, heating to room temperature after the dropwise adding is finished, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over 20g of anhydrous magnesium sulfate. Then adding the solid obtained by drying into an ethanol solution, heating to 80 ℃, stirring for 5 hours, then carrying out suction filtration on the solution while the solution is hot to obtain a solid, then leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 1(18.99g, yield: 87.31%);
Figure BDA0002742977440000121
2. the intermediate 1(43.67mmol) was added to a three-necked flask, 200.00mL of glacial acetic acid was added, the mixture was heated to 120 ℃ and 4.40mL of concentrated sulfuric acid was added dropwise, followed by stirring for 5 min. Cooling to room temperature, adding 44.00mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding 30g of anhydrous magnesium sulfate for drying, removing the solvent by a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, performing suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 2(14.69g, yield: 80.67%);
Figure BDA0002742977440000122
3. under the protection of nitrogen, dissolving intermediate 2(33.58mmol) and raw material C-9(33.58mmol) in 200.00mL of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), adding tetrakistriphenylphosphine palladium (0.34mmol) and potassium carbonate (67.16mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using 30g of anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using dichloromethane, slowly dripping 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 absolute ethyl alcohol and petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 3(15.58g, yield: 86.59%);
Figure BDA0002742977440000131
4. under the protection of nitrogen, dissolving the intermediate 3(27.91mmol) and the raw material D-9(27.91mmol) in 270.00mL of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.28mmol), tri-tert-butylphosphine (1.40mmol) and sodium tert-butoxide (55.82mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and a catalyst, cooling the filtrate to room temperature, washing by using water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, drying was performed using 40g of 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 HT-9. (21.66g, yield: 83.44%, Mw: 930.15).
The compound HT-9 obtained was analyzed and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 930.16; the test value was 930.15.
Elemental analysis:
the calculated values are: c, 91.68; h, 5.09; n, 1.51; o, 1.72.
The test values are: c, 91.67; h, 5.10; n, 1.52; o, 1.71.
Example 2: preparation of Compound HT-25
Figure BDA0002742977440000141
1. Under the protection of nitrogen, adding the raw material B-25(30.00mmol) into a three-necked bottle, adding 90.00 mL of anhydrous tetrahydrofuran, then cooling the reaction system to-78 ℃, dropwise adding n-BuLi (36.00mL), and stirring at-78 ℃ for 2h to obtain a mixed solution. The raw material A-25(30.00mL) was dissolved in 70.00mL of tetrahydrofuran solution, and then added dropwise to the above mixture, after completion of the addition, the temperature was raised to room temperature, and the mixture was stirred for 10 hours. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined, washed successively with water and saturated brine, and then dried over 20g of anhydrous magnesium sulfate. Then adding the dried solid into an ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 1; (11.40g, yield: 87.38%);
Figure BDA0002742977440000142
2. adding the intermediate 1(25.29mmol) into a three-neck flask, adding 125.00mL of glacial acetic acid, heating to 120 ℃, dropwise adding 2.50mL of concentrated sulfuric acid, and stirring for 5 min. Cooling to room temperature, adding 25.00mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding 30g of anhydrous magnesium sulfate for drying, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, performing suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 2(8.50g, yield: 80.62%);
Figure BDA0002742977440000151
3. under the protection of nitrogen, dissolving intermediate 2(19.19mmol) and raw material C-25(19.19mmol) in 140.00mL of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1), adding palladium tetratriphenylphosphine (0.19mmol) and potassium carbonate (38.38mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining an organic phase, and then extracting an aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using 30g of anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using dichloromethane, slowly dripping 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 absolute ethyl alcohol and petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 3(10.20g, yield: 86.54%);
Figure BDA0002742977440000152
4. under the protection of nitrogen, dissolving the intermediate 3(16.27mmol) and the raw material D-25(16.27mmol) in 170.00mL of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.16mmol), tri-tert-butylphosphine (0.81mmol) and sodium tert-butoxide (32.54mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and a catalyst, cooling the filtrate to room temperature, washing by using water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, drying was performed using 40g of 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 HT-25(13.39g, yield: 83.51%, Mw: 985.21)
The compound HT-25 obtained was analyzed and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 985.20; the test value was 985.21.
Elemental analysis:
the calculated values are: c, 89.00; h, 4.91; n, 2.84; and O, 3.25.
The test values are: c, 89.01; h, 4.92; n, 2.83; and O, 3.24.
Example 3: preparation of Compound HT-42
Figure BDA0002742977440000161
1. Under the protection of nitrogen, adding the raw material B-42(30.00mmol) into a three-necked bottle, adding 100.00 mL of anhydrous tetrahydrofuran, then cooling the reaction system to-78 ℃, dropwise adding n-BuLi (36.00mmol), and stirring at-78 ℃ for 2h to obtain a mixed solution. Dissolving the raw material A-42(30.00mmol) in 100.00mmol of tetrahydrofuran solution, then dropwise adding into the mixed solution, heating to room temperature after the dropwise adding is finished, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined and successively washed with water and saturated brine, followed by drying over 20g of anhydrous magnesium sulfate. Adding the dried solid into an ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 1; (14.12g, yield: 87.35%);
Figure BDA0002742977440000171
2. adding the intermediate 1(25.97mmol) into a three-neck flask, adding 130.00mL of glacial acetic acid, heating to 120 ℃, dropwise adding 2.60mL of concentrated sulfuric acid, and stirring for 5 min. Cooling to room temperature, adding 26.00mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the water phase with dichloromethane for three times, collecting the organic phase, adding 30g of anhydrous magnesium sulfate to dry, removing the solvent through a rotary evaporator, adding the solid organic matter into the ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, filtering the solution to obtain a solid, leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 2; (10.87g, yield: 80.65%);
Figure BDA0002742977440000172
3.
3. under the protection of nitrogen, dissolving the intermediate 2(19.27mmol) and the raw material D-42(19.27mmol) in 180.00mL of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.19mmol), tri-tert-butylphosphine (0.96mmol) and sodium tert-butoxide (38.54mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 5 h; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and a catalyst, cooling the filtrate to room temperature, washing by using water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, drying was performed using 30g of 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 HT-42(14.09g, yield: 83.48%, Mw: 876.12).
The compound HT-42 obtained was analyzed and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 876.11; the test value was 876.12.
Elemental analysis:
the calculated values are: c, 87.94; h, 4.96; n, 1.60; o, 1.83; and S, 3.67.
The test values are: c, 87.95; h, 4.95; n, 1.61; o, 1.84; and S, 3.65.
Example 4: preparation of Compound HT-49
Figure BDA0002742977440000181
1. Under the protection of nitrogen, adding the raw material B-49(30.00mmol) into a three-necked bottle, adding 80.00mL of anhydrous tetrahydrofuran, then cooling the reaction system to-78 ℃, dropwise adding n-BuLi (36.00mmol), and stirring at-78 ℃ for 2h to obtain a mixed solution. The raw material A-49(30.00mmol) was dissolved in 80.00mL of tetrahydrofuran solution, and then added dropwise to the mixture, after completion of the addition, the temperature was raised to room temperature, and the mixture was stirred for 10 hours. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined, washed successively with water and saturated brine, and then dried over 20g of anhydrous magnesium sulfate. Adding the dried solid into an ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 1; (11.83g, yield: 87.40%);
Figure BDA0002742977440000191
2. adding the intermediate 1(24.39mmol) into a three-neck flask, adding 125.00mL of glacial acetic acid, heating to 120 ℃, dropwise adding 2.40mL of concentrated sulfuric acid, and stirring for 5 min. Cooling to room temperature, adding 24.00mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding 30g of anhydrous magnesium sulfate for drying, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, performing suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 2(8.51g, yield: 80.61%);
Figure BDA0002742977440000192
3. dissolving intermediate 2(18.48mmol) and raw material C-49(18.48mmol) in 110.00mL of a mixed solution of toluene, ethanol and water (V toluene: V ethanol: V water ═ 3:1:1) under nitrogen protection, adding tetrakistriphenylphosphine palladium (0.18mmol) and potassium carbonate (36.96mmol), stirring uniformly, heating to 90 ℃, refluxing for 5 hours, after the solution is cooled to room temperature, retaining the organic phase, and then extracting the aqueous phase with ethyl acetate; after the organic phases were combined, drying was performed using 30g of anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain a solid organic matter. Completely dissolving the solid organic matter by using dichloromethane, slowly dripping 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 absolute ethyl alcohol and petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 3(8.92g, yield: 86.57%);
Figure BDA0002742977440000201
4. under the protection of nitrogen, dissolving the intermediate 3(14.35mmol) and the raw material D-49(14.35mmol) in 110.00mmol of toluene solution, adding tris (dibenzylideneacetone) dipalladium (0.14mmol), tri-tert-butylphosphine (0.72mmol) and sodium tert-butoxide (28.70mmol), uniformly stirring, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling to 75 ℃, filtering by using diatomite to remove salt and a catalyst, cooling the filtrate to room temperature, washing by using water for three times to keep an organic phase, and extracting an aqueous phase by using ethyl acetate; after the organic phases were combined, 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 HT-49(8.93g, yield: 83.47%, Mw: 745.97).
The compound HT-49 thus obtained was analyzed and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 745.98; the test value was 745.97.
Elemental analysis:
the calculated values are: c, 88.56; h, 5.27; n, 1.88; and S, 4.30.
The test values are: c, 88.57; h, 5.26; n, 1.87; s, 4.31.
Example 5: preparation of Compound HT-77
Figure BDA0002742977440000211
1. Under the protection of nitrogen, adding the raw material B-72(30.00mmol) into a three-necked bottle, adding 80.00mL of anhydrous tetrahydrofuran, then cooling the reaction system to-78 ℃, dropwise adding n-BuLi (36.00mmol), and stirring at-78 ℃ for 2h to obtain a mixed solution. Dissolving the raw material A-72(36.00mmol) in 110.00mL of tetrahydrofuran solution, then dropwise adding the solution into the mixed solution, heating to room temperature after the dropwise adding is finished, and stirring for 10 h. Then, a saturated ammonium chloride solution was added to quench the reaction, the reaction solution was extracted 3 times with ethyl acetate, and the organic phases were combined, washed successively with water and saturated brine, and then dried over 20g of anhydrous magnesium sulfate. Adding the dried solid into an ethanol solution, heating to 80 ℃, stirring for 5 hours, carrying out suction filtration on the solution while the solution is hot to obtain a solid, leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 1; (14.54g, yield: 87.33%);
Figure BDA0002742977440000212
2. intermediate 1(25.22mmol) was added to a three-necked flask, 140.00mL of glacial acetic acid was added, heating was carried out to 120 ℃, 2.50mL of concentrated sulfuric acid was added dropwise, and stirring was carried out for 5 min. Cooling to room temperature, adding 25.00mL of sodium bicarbonate solution to terminate the reaction, separating the solution, extracting the aqueous phase with dichloromethane three times, collecting the organic phase, adding 30g of anhydrous magnesium sulfate for drying, removing the solvent through a rotary evaporator, adding the solid organic matter into an ethanol solution, heating to 80 ℃, stirring for 5 hours, after the solution is cooled to room temperature, performing suction filtration on the solution to obtain a solid, then leaching with petroleum ether, and drying (80 ℃, 3.5 hours) to prepare an intermediate 2(10.89g, yield: 80.64%);
Figure BDA0002742977440000221
3. under the protection of nitrogen, dissolving the intermediate 4(18.69mmol) and the raw material D2-72(18.69mmol) in 170.00mL of toluene solution, replacing air by nitrogen for 3 times, adding tris (dibenzylideneacetone) dipalladium (0.18mmol), tri-tert-butylphosphine (0.93mmol) and sodium tert-butoxide (37.38mmol), stirring uniformly, heating to 90 ℃, and carrying out reflux reaction for 5 hours; after the reaction is finished, slightly cooling to 75 ℃, filtering by using kieselguhr, removing salt and 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 carried out using 30g of 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 HT-77(13.89g, yield: 83.50%, Mw: 890.17).
The compound HT-77 thus obtained was analyzed and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 890.18; the test value was 890.17.
Elemental analysis:
the calculated values are: c, 86.35; h, 4.87; n, 1.57; and S, 7.20.
The test values are: c, 86.36; h, 4.88; n, 1.56; and S, 7.19.
The synthesis methods of other compounds are the same as the above examples, which are not repeated herein, and the mass spectra and molecular formulas of other synthesis examples are shown in table 1 below:
TABLE 1
Figure BDA0002742977440000231
Figure BDA0002742977440000241
The compounds synthesized in the above examples were tested for their glass transition temperature (tg) using TMA4000, as shown in table 2:
table 2:
compound (I) Glass transition temperature (tg) Compound (I) Glass transition temperature (tg)
9 177.3 56 181.1
15 180.1 62 179.5
20 178.3 68 180.6
25 179.7 71 181.7
29 177.6 77 182.3
36 178.4 85 178.9
42 181.5 88 178.6
49 179.2
As can be seen from table 2, the hole transport material of the present disclosure has high thermal stability.
The organic electroluminescent device prepared from the hole transport material provided in the above embodiment includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode.
When the organic layer includes a hole transport layer, the hole transport layer includes the hole transport material provided in the above embodiments.
Device example 1:
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 BDA0002742977440000251
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 transferred 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): a hole injection layer was formed by evaporation of 2-TNATA (N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylbenzene-1, 4-diamine) at 10 nm.
c. HTL (hole transport layer): the compound HT-915nm prepared in example 1 was evaporated to form a hole transport layer.
d. EML (light-emitting layer): the host material EMH-1 and the doping material EMD-1 are mixed and evaporated by weight ratio of 97: 3 for 40nm to form a luminescent layer. The structural formulas of the host material EMH-1 and the doping material EMD-1 are as follows;
f. ETL (electron transport layer): and evaporating ET-1 and Liq 40nm to form an electron transport layer. Wherein the weight ratio of ET-1 to Liq is 60:40, wherein the structural formula of ET-1 is as follows
g. EIL (electron injection layer): and evaporating Yb to 1.0nm to form an electron injection layer.
h. Cathode: and (4) evaporating and plating magnesium and silver at 18nm in a weight ratio of 1:9 to obtain the OLED device.
i. Light extraction layer: IDX001 was vacuum-deposited on the cathode to a thickness of 70nm as a light extraction layer.
Figure BDA0002742977440000261
With reference to the method provided in device example 1 above, compounds HT-15, HT-20, HT-25, HT-29, HT-36, HT-42, HT-49, HT-56, HT-62, HT-68, HT-71, HT-77, HT-85, and HT-88 were selected, respectively, to replace compound HT-9, and evaporation of the hole transport layer was performed, and corresponding organic electroluminescent devices were prepared, which were denoted as device examples 2 to 15, respectively.
Device comparative example 1:
the comparative example provides an organic electroluminescent device, and the only difference between the preparation method of the organic electroluminescent device and the device example 1 is that the organic electroluminescent device is prepared by adopting the existing comparative compound A to replace the hole transport material (compound HT-9) in the device example 1 for evaporation, and the corresponding organic electroluminescent device is marked as the device comparative example 1. Wherein the chemical structural formula of comparative compound a is:
Figure BDA0002742977440000262
device comparative example 2:
referring to the method provided by the device comparative example 1, a compound TCTA is selected to replace the compound A, evaporation of a hole transport layer is carried out, and a corresponding organic electroluminescent device is prepared and recorded as a device comparative example 2. Wherein, the chemical structural formula of TCTA is:
Figure BDA0002742977440000271
the organic electroluminescent devices obtained in the device examples 1 to 15 and the device comparative examples 1 to 2 were characterized at a luminance of 6000(nits), and the test results were as follows:
Figure BDA0002742977440000272
from table 3 above, it can be seen that: compared with an organic electroluminescent device prepared by taking two comparative compounds as the hole transport layer, the organic electroluminescent device prepared by taking the organic electroluminescent compound provided by the invention as the hole transport layer has lower starting voltage, and the luminous efficiency and the service life are obviously improved.
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, wherein the structural general formula of the organic electroluminescent compound is shown in chemical formula 1:
Figure FDA0002742977430000011
wherein m, n and p are all 0 or 1 and cannot be 0 at the same time;
x is a connecting bond; or X is selected from-O-, -S-, -SO2-、-C(R3)(R4)-、-N(R5)-、-Si(R6)(R7)-、-Sn(R8)(R9) -and-Ge (R)10)(R11) One of (1);
L1-L3each independently represents a bond; or L1-L3Each independently represents a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted 3-10 membered heteroarylene;
R1and R2Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, amino, silicon, boryl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-30 membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-20 membered heteroaryl, substituted or unsubstituted 3-25 membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C60 aryloxy;
or, said R1And R2Are connected with each other to form a ring;
R3-R11each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-30 membered heteroaryl group, a substituted or unsubstituted 3-30 membered heteroarylamino group, a substituted or unsubstituted C6-C60 arylamino group;
Ar1-Ar6each independently represents a substituted or unsubstituted C3-C30 cycloalkyl, a substituted or unsubstituted 3-20 membered heterocycloalkyl, a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted 3-10 membered heteroaryl, a substituted or unsubstituted 3-15 membered heteroarylamino, a substituted or unsubstituted C6-C60 arylamino.
2. The organic electroluminescent compound according to claim 1, wherein R is1And R2When they are linked to each other to form a ring, they are represented by ring A;
the chemical formula 1 is:
Figure FDA0002742977430000021
wherein q is 0 or 1, and m, n, p and q cannot be 0 simultaneously;
L4is a connecting bond; or L4Selected from substituted or unsubstitutedSubstituted C6-C30 arylene, substituted or unsubstituted 3-10 membered heteroarylene;
Ar7and Ar8Each independently represents substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-20 membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl or、Substituted or unsubstituted 3-10 membered heteroaryl, substituted or unsubstituted 3-15 membered heteroarylamino, substituted or unsubstituted C6-C60 arylamino.
Ring A represents a substituted or unsubstituted C3-C10 cycloalkyl, a substituted or unsubstituted 3-to 10-membered heterocycloalkyl, a substituted or unsubstituted C6-C15 aryl, a substituted or unsubstituted 3-to 15-membered heteroaryl.
3. The organic electroluminescent compound according to claim 2, wherein R is3-R11Each independently represents a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C7 cycloalkyl group, a substituted or unsubstituted 3-10 membered heterocycloalkyl group, a substituted or unsubstituted C6-C15 aryl group, a substituted or unsubstituted 3-15 membered heteroaryl group, a substituted or unsubstituted 3-10 membered heteroarylamino group, a substituted or unsubstituted C6-C30 arylamino group.
4. The organic electroluminescent compound according to claim 3, wherein Ar is Ar1-Ar8Each independently represents a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-15 membered heteroaryl group, a substituted or unsubstituted 3-15 membered heteroarylamine group, a substituted or unsubstituted C6-C60 arylamine group.
5. The organic electroluminescent compound of claim 4, wherein the hetero atoms in the cycloalkyl, heterocycloalkyl, heteroaryl and heteroarylamino groups are selected from oxygen, nitrogen and sulfur.
6. A method for producing the organic electroluminescent compounds as claimed in claims 1 to 5, characterized by comprising the steps of:
(1) under the protection of nitrogen, adding tetrahydrofuran into the raw material B, cooling to (-70) - (-78) ℃, then dropwise adding n-butyl lithium, and stirring and mixing to obtain a mixed solution A; dropwise adding the raw material A into the mixed solution A, and stirring for reaction to prepare an intermediate 1;
(2) and adding glacial acetic acid into the intermediate 1, heating, dropwise adding concentrated sulfuric acid, uniformly stirring, cooling, and then adding a sodium bicarbonate solution to terminate the reaction to prepare a solid intermediate 2.
(3) Under the protection of nitrogen, dissolving the intermediate 2 and the raw material C in a mixed solution of toluene, ethanol and water, then adding palladium tetratriphenylphosphine and potassium carbonate, uniformly stirring, heating and refluxing to prepare an intermediate 3;
(4) under the protection of nitrogen, dissolving the intermediate 3 and the raw material D in a toluene solution, adding tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and sodium tert-butoxide, uniformly stirring, heating and refluxing to prepare a chemical formula 1 or a chemical formula 1-1;
the synthetic route of chemical formula 1 is:
Figure FDA0002742977430000041
the synthetic route of chemical formula 1-1 is:
Figure FDA0002742977430000042
wherein, said Hal1And Hal2Is a halogen other than chlorine.
7. The method of producing an organic electroluminescent compound according to claim 6, wherein the molar ratio of the raw material B to the n-butyllithium to the raw material A is (30-50): (36-60): (30-50), wherein the molar volume ratio of the raw material A to the tetrahydrofuran is (30-50) mmol: (80-160) mL;
the temperature of stirring and mixing is (-70) DEG C to (-78) DEG C, and the time is 1.5-2.5 h.
8. The method of preparing an organic electroluminescent compound according to claim 6, wherein in the step (2), the ratio of the moles of the intermediate 1, the volume of the glacial acetic acid and the volume of the sodium bicarbonate solution is (24-44) mmol: (125-200) mL: (24-44) mL; the stirring temperature is 110-130 ℃, and the stirring time is 5 min.
9. The method of producing an organic electroluminescent compound according to claim 6, wherein in the step (3), the molar ratio of the intermediate 2, the raw material C, the tetratriphenylphosphine palladium, and the potassium carbonate is: (18-33): (0.18-0.34): (36-65); the molar volume ratio of the intermediate 2 to the mixed solution is (18-34) mmol: (110- > 200) mL; the volume ratio of the toluene to the ethanol to the water is (2.5-3.5) to (0.5-1.5); the temperature is increased to 80-100 ℃, and the reflux time is 4.5-5.5 h;
in the step (4), the molar ratio of the intermediate 3, the raw material D, the tris (dibenzylideneacetone) dipalladium, the tri-tert-butylphosphine and the sodium tert-butoxide is (14-27): (14-27): (0.14-0.28): (0.7-1.4): (28-56); the molar volume ratio of the intermediate 3 to the toluene solution is (14-27) mmol: (110-270) mL; the temperature is raised to 80-100 ℃, and the reflux time is 4.5-5.5 h.
10. Use of an organic electroluminescent compound according to any one of claims 1 to 5 or an organic electroluminescent compound prepared by a process according to any one of claims 6 to 9 in an organic electroluminescent device.
CN202011156601.3A 2020-10-26 2020-10-26 Organic electroluminescent compound and preparation method and application thereof Withdrawn CN112409314A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114133369A (en) * 2021-04-14 2022-03-04 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device
WO2022060020A1 (en) * 2020-09-21 2022-03-24 솔루스첨단소재 주식회사 Organic luminescent compound and organic electroluminescent device using same
US20220199910A1 (en) * 2020-12-10 2022-06-23 Samsung Display Co., Ltd. Light-emitting diode and amine compound for the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022060020A1 (en) * 2020-09-21 2022-03-24 솔루스첨단소재 주식회사 Organic luminescent compound and organic electroluminescent device using same
US20220199910A1 (en) * 2020-12-10 2022-06-23 Samsung Display Co., Ltd. Light-emitting diode and amine compound for the same
CN114133369A (en) * 2021-04-14 2022-03-04 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device

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