CN114634485B - 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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CN114634485B
CN114634485B CN202210287009.XA CN202210287009A CN114634485B CN 114634485 B CN114634485 B CN 114634485B CN 202210287009 A CN202210287009 A CN 202210287009A CN 114634485 B CN114634485 B CN 114634485B
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dichloromethane
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王辉
段伟伟
牟杨
刘志远
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Jilin Optical and Electronic Materials Co Ltd
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    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
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Abstract

The invention discloses an organic electroluminescent compound, which has a structure shown in a 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, a preparation method thereof and an electroluminescent device.
Background
The organic electroluminescent technology is used as the latest generation of display technology, and the photoelectric device prepared by the organic electroluminescent technology is gradually accepted by the public due to the characteristics of low power consumption, high response speed, wide viewing angle, high resolution, wide temperature characteristic, light weight, curlability and the like, and the organic electroluminescent display technology is different from the traditional LCD display mode, does not need a backlight lamp, adopts a very thin organic material coating and a glass substrate, and emits light when current passes through. And the organic electroluminescent display screen can be made lighter and thinner, the visual angle is larger, and the electric energy can be obviously saved. Because Organic Light Emitting Diodes (OLEDs) have numerous advantages, OLED technology has a wider application range than LCD technology, and can be extended to the fields of electronics, business, traffic, industrial control, and medical, and in recent years, various international enterprises are continuously strengthening the research on OLED technology, and OLED technology has been further perfected.
At present, the materials of the organic light-emitting device mainly have the technical problem of short service life, low light-emitting efficiency, low power efficiency and high driving voltage, so that the use cost of the materials is increased, and the later use has great obstacle to the development of the market.
Currently, the hole mobility of the hole transport material in the existing OLED device is generally far greater than the electron mobility of the electron transport material, which is 100 times that of the electron transport material. Such an imbalance in carrier transport rate can lead to significant degradation in device performance. Therefore, it has better electron mobility to effectively transport electrons to the recombination zone away from the cathode. In addition, the electron transport material has better film forming property, otherwise, a uniform film cannot be formed during vapor deposition, crystallization is easy to generate, and the efficiency and the service life of a device are seriously influenced
However, the presently disclosed luminescent materials have relatively high requirements for synthesis processes, and the driving voltage or luminous efficiency of the fabricated device is not ideal. Therefore, development of a material having high light-emitting luminance and a long life is a technical problem to be solved at present.
Disclosure of Invention
In view of the above, the present invention provides an organic electroluminescent compound, a preparation method and application thereof. According to the organic electronic transmission material with the novel structure, the organic compound obtained by selecting the ligand combination of the specific heterocycle is used for the organic electroluminescent device, so that the luminous brightness of the device is improved, and the service life is long.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
an organic electroluminescent compound having a structure represented by chemical formula 1:
wherein:
R 1 to R 5 Each of which is the same or different from the others and is independently selected from the group consisting of hydrogen, deuterium, a halogen group, cyano, nitro, amino, C1-C40 alkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, heterocycloalkyl having 3 to 40 atomic cores, aryl having 6 to C60 atomic cores, heteroaryl having 5 to 60 atomic cores, alkoxy having 1 to C40 atomic cores,C6-C60 aryloxy, C1-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C1-C40 phosphino oxide or C6-C60 arylamino groups, or form a condensed ring with adjacent groups,
L 1 selected from single bond, arylene of C6-C18 or heteroarylene of 5-18 atomic nucleus.
Preferably, R 1 ～R 5 Each independently represents hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C 1 ～C 10 Alkyl, substituted or unsubstituted C 3 ～C 15 Cycloalkyl, substituted or unsubstituted 3-15 membered heterocycloalkyl, substituted or unsubstituted C 1 ～C 10 Alkoxy, substituted or unsubstituted C 1 ～C 15 Alkylamino, substituted or unsubstituted C 6 ～C 25 Arylamino, substituted or unsubstituted C 6 ～C 20 Aryl, substituted or unsubstituted 4-20 membered heteroaryl.
Preferably, the alkyl group is a straight chain alkyl group or a branched chain alkyl group.
More preferably, the alkyl is one or more of methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl;
preferably, the cycloalkyl and heterocycloalkyl are any one of monocyclic, polycyclic and spiro groups, and the carbon atom on the heterocycloalkyl may be substituted with at least one heteroatom; the heteroatom is at least one of N, O, S, si, se, ge;
more preferably, the cycloalkyl is one or more of cyclopropyl, cyclopentyl, cyclohexyl and adamantyl;
preferably, the aryl or heteroaryl is a monocyclic group or a polycyclic group; the polycyclic group has two carbons that are a plurality of rings common to two adjoining rings, wherein at least one ring is an aromatic ring and the other rings are at least one of cycloalkyl, cycloalkenyl, aryl, heteroaryl; wherein the heteroatom is at least one of N, O, S, si, se, ge;
more preferably, the aryl is any one or more of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene and pyrene.
More preferably, the heteroaryl is any one or more of furan, thiophene, pyridine and triazine.
Incidentally, the above-mentioned "substitution" means that a hydrogen atom bonded to a carbon atom of a compound becomes another substituent, and the position of substitution is not limited as long as the position is a position where a hydrogen atom is substituted, that is, a position where a substituent may be substituted, and when two or more substituents are substituted, two or more substituents may be the same as or different from each other.
Preferably, said R 1 ～R 5 Any one of the groups represented by the following structural formula (but not limited thereto):
the saidIs the position of radical connection.
Preferably, the chemical formula 1 is preferably selected from any one of the following structures D001 to D110:
the above only list some specific structural forms, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained by simply changing some simple groups and substituted positions thereof, and are not described in detail herein.
The beneficial effects of the above preferable technical scheme are as follows: the invention provides a novel electron transport material containing a heterocyclic structure, which has the advantages of excellent electron transport property, excellent hole mobility, good thermal stability, difficult crystallization and the like, and can be applied to an electroluminescent device.
The invention also provides a preparation method of the organic electroluminescent compound, which comprises the following steps:
(1) Under the protection of nitrogen, mixing the raw material D-1, the raw material D-2 and the sodium tert-butoxide, adding toluene, adding a catalyst, heating and uniformly stirring for reaction; after the reaction is finished, cooling, suction filtering, purifying and drying are carried out to obtain an intermediate D-3.
(2) Under the protection of nitrogen, mixing the raw material D-3, the bisboronic acid pinacol ester and the potassium acetate, adding dioxane, adding a catalyst, heating and stirring to uniformly react; after the reaction is finished, cooling, adding water liquid, extracting, filtering, purifying and drying to obtain an intermediate D-4.
(3) Under the protection of nitrogen, the raw material D-4, the raw material D-5 and anhydrous potassium carbonate are mixed and then added with THF/H 2 O, adding a catalyst, heating and uniformly stirring for reaction; and after the reaction is finished, cooling, suction filtering, purifying and drying to obtain a final product D.
The synthetic route is as follows:
step (1):
step (2):
step (3):
preferably, in the step (1), the molar ratio of the raw material D-1 to the raw material D-2 is 1 (1.05-1.3); the mol ratio of the raw material D-1 to the sodium tert-butoxide is 1 (1.5-2); the catalyst is tris (dibenzylideneacetone) dipalladium, 50% of tri-tert-butylphosphine, and the molar ratio of the raw material D-1 to the tris (dibenzylideneacetone) dipalladium is 1 (0.01-0.1); the mol ratio of the raw material D-1 to 50 percent of tri-tert-butylphosphine is 1 (0.02-0.2); the ratio of the raw material D-1 to the toluene is 4.3 mmol:20-30 mL; the heating temperature is 90-130 ℃, and the reaction time is 20-30 h; wherein the temperature of the drying is 70-80 ℃; the column chromatography adopts silica gel column chromatography, and dichloromethane and petroleum ether are used according to the following ratio of 1: (1-15) volume ratio as solvent.
Preferably, the molar ratio of the raw material D-1 to the raw material D-2 is 1:1.1.
Further preferably, the molar ratio of the raw material D-1 to the sodium tert-butoxide is 1:2.
Further preferably, the molar ratio of the raw material D-1 to tris (dibenzylideneacetone) dipalladium is 1:0.01.
Further preferably, the molar ratio of the raw material D-1 to 50% of tri-tert-butylphosphine is 1:0.022.
Preferably, in the step (2), the molar ratio of the raw material D-3 to the pinacol diboronate is 1 (1.5-3); the mole ratio of the raw material D-3 to the potassium acetate is 1 (2-3); the catalyst is tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, and the molar ratio of the raw material D-3 to the tris (dibenzylideneacetone) dipalladium is 1 (0.01-0.1); the mol ratio of the raw material D-3 to the 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl is 1 (0.05-0.2); the ratio of the raw material D-3 to the dioxane is 1 mmol:3-20 mL; the heating temperature is 90-130 ℃, and the reaction time is 20-30 h; the temperature of the drying is 90-120 ℃; the column chromatography adopts silica gel column chromatography, and dichloromethane and petroleum ether are used according to the following ratio of 1: (1-15) volume ratio as solvent.
Preferably, the molar ratio of the raw material D-3 to the pinacol ester of diboronic acid is 1:2.
Further preferably, the molar ratio of the raw material D-3 to potassium acetate is 1:2.5.
Further preferably, the molar ratio of the raw material D-3 to tris (dibenzylideneacetone) dipalladium is 1:0.01.
Further preferably, the molar ratio of the raw material D-3 to the 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl is 1:0.08.
Preferably, the molar ratio of the compound D-4 to the raw material D-5 in the step (3) is 1 (0.8-1); the molar ratio of the compound D-4 to the anhydrous potassium carbonate is 1 (2-3); the catalyst is tetra (triphenylphosphine) palladium, and the molar ratio of the compound D-4 to the tetra (triphenylphosphine) palladium is 1 (0.03-0.1); the ratio of the compound D-4 to the toluene is 20 mmol:100-150 mL, and the ratio of the compound D-4 to the absolute ethyl alcohol is 20 mmol:100-150 mL; the ratio of the compound D-4 to the purified water is 20 mmol:50-75 mL; the heating temperature is 70-90 ℃, and the reaction time is 20-30 h; the temperature of the drying is 70-80 ℃; the column chromatography adopts silica gel column chromatography, and dichloromethane and petroleum ether are used according to the following ratio of 1: (1-25) by volume ratio as a solvent.
Preferably, the molar ratio of the raw material D-4 to the raw material D-5 is 1:0.99.
Further preferably, the molar ratio of the raw material D-4 to anhydrous potassium carbonate is 1:2.
Further preferably, the molar ratio of the raw material D-4 to the tetrakis (triphenylphosphine) palladium is 1:0.03.
The invention also provides application of the organic electroluminescent compound in preparing an organic electroluminescent device.
The organic electroluminescent device described above includes:
an anode, a cathode, and a number of organic layers deposited between the anode and the cathode, wherein at least one of the organic layers comprises a compound of formula 1.
The organic layer includes a hole injection layer, an electron transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, wherein the electron transport layer includes the compound of formula 1.
The device of the invention can be used for organic light emitting devices, organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel electron transport material containing triazine and carbazole heterocyclic structures, which has the advantages of excellent electron transport property, excellent hole mobility, good thermal stability, difficult crystallization and the like, and can be applied to an electroluminescent device.
The preparation method of the organic electroluminescent compound provided by the invention has the advantages of simple process and high yield and purity of the prepared product.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Compound D005 was prepared as follows:
the preparation method specifically comprises the following steps:
(1) Under a nitrogen protection system, compound D-6 (28.04 mmol,10 g), D-7 (29.44 mmol,4.98 g) and sodium tert-butoxide (56.08 mmol,5.39 g) are weighed into a reaction system, 300ml of toluene solution is added into the reaction system, tris (dibenzylideneacetone) dipalladium (0.56 mmol,0.51 g) and 50% tri-tert-butylphosphine (1.23 mmol,0.50 g) are added into the reaction system, the mixture is heated to 120 ℃ and stirred uniformly for 24 hours, after the reaction is stopped, the system is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, washed and dried by absolute ethyl alcohol to obtain solid powder, and a mixed solution of dichloromethane and petroleum ether (V) Dichloromethane (dichloromethane) :V Petroleum ether =1:10) as solvent, and the filtrate was concentrated to precipitate a solid, to give D-8 (10.23 g, yield: 82%).
(2) Compound D-8 (10 g,22.47 mmol), pinacol biborate (11.41 g,44.94 mmol), potassium acetate (5.51 g,56.17 mmol) and 1, 4-dioxane (150 mL) were weighed out under a nitrogen protection system, tris (dibenzylideneacetone) dipalladium (0.23 mmol,0.21 g) were then added, X-phos (2.24 mmol,1.07 g) was heated to 120℃for 18 hours, the reaction was stopped, the system was cooled to room temperature, DCM was added to extract the reaction solution, and concentrated to give solid powder D-9 (7.59 g, yield: 63%).
(3) Under a nitrogen protection system, weighing compound D-9 (18.64 mmol,10 g), D-10 (20.5 mmol,5.49 g), anhydrous potassium carbonate (37.28 mmol,5.14 g) into a reaction system, adding 150ml toluene solution, 150ml ethanol and 75ml purified water into the reaction system, adding tetra (triphenylphosphine) palladium (0.56 mmol,0.65 g), heating to 90 ℃, stirring uniformly and reacting for 24 hours, cooling the reaction system to room temperature after stopping the reaction, precipitating, filtering the precipitate, washing and drying the precipitate with absolute ethanol to obtain solid powder, and adding a mixed solution of dichloromethane and petroleum ether (V Dichloromethane (dichloromethane) :V Petroleum ether =1:15) as solvent, and the filtrate was concentrated to precipitate a solid, to give D005 (10.17 g, yield: 85%).
HPLC purity: greater than 99.9%;
mass spectrometry: calculated 641.78 and tested 642.66;
elemental analysis:
calculated value C:84.22%; h:4.87%; n:10.91%;
test value C:84.67%; h:5.00%; n:10.11%.
Example 2
Compound D019 was prepared as follows:
(1) Under a nitrogen protection system, compound D-11 (28.04 mmol,10 g), D-7 (29.44 mmol,4.98 g) and sodium tert-butoxide (56.08 mmol,5.39 g) are weighed into a reaction system, 300ml of toluene solution is added into the reaction system, tris (dibenzylideneacetone) dipalladium (0.56 mmol,0.51 g) and 50% tri-tert-butylphosphine (1.23 mmol,0.50 g) are added into the reaction system, the mixture is heated to 120 ℃ and stirred uniformly for 24 hours, after the reaction is stopped, the system is cooled to room temperature, precipitates are separated out, the precipitates are filtered by suction, washed and dried by absolute ethyl alcohol to obtain solid powder, and a mixed solution of dichloromethane and petroleum ether (V) Dichloromethane (dichloromethane) :V Petroleum ether =1:10) as solvent, and the filtrate was concentrated to precipitate a solid, to give D-12 (10.72 g, yield: 86%).
(2) Compound D-12 (10 g,22.47 mmol), pinacol biborate (11.41 g,44.94 mmol), potassium acetate (5.51 g,56.17 mmol) and 1, 4-dioxane (150 mL) were weighed out under a nitrogen protection system, tris (dibenzylideneacetone) dipalladium (0.23 mmol,0.21 g) were then added, X-phos (2.24 mmol,1.07 g) was heated to 120℃for 18 hours, the reaction was stopped, the system was cooled to room temperature, DCM was added to extract the reaction solution, and concentrated to give solid powder D-13 (7.23 g, yield: 60%).
(3) Under a nitrogen protection system, compound D-13 (18.64 mmol,10 g), D-20 (20.5 mmol,7.05 g) and anhydrous potassium carbonate (37.28 mmol,5.14 g) were weighed into a reaction system,then 150ml of toluene solution, 150ml of ethanol and 75ml of purified water are added into the reaction system, then tetrakis (triphenylphosphine) palladium (0.56 mmol,0.65 g) is added, the mixture is heated to 90 ℃ and stirred uniformly and reacted for 24 hours, the system is cooled to room temperature after the reaction is stopped, precipitates are separated out, the precipitates are filtered by suction, the precipitates are washed and dried by absolute ethanol, solid powder is obtained, and a mixed solution of dichloromethane and petroleum ether (V Dichloromethane (dichloromethane) :V Petroleum ether =1:15) as solvent, and the filtrate was concentrated to precipitate a solid, to give D019 (10.97 g, yield: 82%). HPLC purity: greater than 99.9%;
mass spectrometry: calculated 717.81 and tested 718.61;
elemental analysis:
calculated value C:85.33%; h:4.91%; n:9.76%;
test value C:86.27%; h:4.90%; n:9.56%.
Example 3
Compound D051 was prepared as follows:
(1) Under a nitrogen protection system, compound D-14 (28.04 mmol,12.13 g), D-7 (29.44 mmol,4.98 g), sodium tert-butoxide (56.08 mmol,5.39 g) were weighed into a reaction system, 300ml of toluene solution was then added to the reaction system, followed by adding tris (dibenzylideneacetone) dipalladium (0.56 mmol,0.51 g), 50% tri-tert-butylphosphine (1.23 mmol,0.50 g) was heated to 120℃and stirred uniformly and reacted for 24 hours, after the reaction was stopped, the system was cooled to room temperature, precipitation was observed, the precipitate was suction filtered, washed with absolute ethanol and dried to obtain a solid powder, and a mixed solution of methylene chloride and petroleum ether (V) Dichloromethane (dichloromethane) :V Petroleum ether =1:10) as solvent, and the filtrate was concentrated to precipitate a solid, to give D-15 (12.42 g, yield: 85%).
(2) Compound D-15 (22.47 mmol,11.71 g), pinacol biboronate (44.94 mmol,11.41 g), potassium acetate (56.17 mmol,5.51 g) were weighed out under a nitrogen blanket, 1, 4-dioxane (150 mL) was added to the reaction, followed by tris (dibenzylideneacetone) dipalladium (0.23 mmol,0.21 g), X-phos (2.24 mmol,1.07 g) was heated to 120℃for 18 hours, the reaction was stopped, the system was cooled to room temperature, DCM was added to extract the reaction solution, and concentrated to give solid powder D-16 (9.64 g, yield: 76%).
(3) Under a nitrogen protection system, weighing compound D-16 (18.64 mmol,11.42 g), D-10 (20.5 mmol,5.49 g), anhydrous potassium carbonate (37.28 mmol,5.14 g) into a reaction system, adding 150ml toluene solution, 150ml ethanol and 75ml purified water into the reaction system, adding tetra (triphenylphosphine) palladium (0.56 mmol,0.65 g), heating to 90 ℃, stirring uniformly and reacting for 24 hours, cooling the reaction system to room temperature after stopping the reaction, precipitating, filtering the precipitate, washing and drying the precipitate with absolute ethanol to obtain solid powder, and adding a mixed solution of dichloromethane and petroleum ether (V Dichloromethane (dichloromethane) :V Petroleum ether =1:18) as solvent, and the filtrate was concentrated to precipitate a solid, to give D051 (11.37 g, yield: 85%). HPLC purity: greater than 99.9%;
mass spectrometry: calculated 717.88 and tested 718.81;
elemental analysis:
calculated value C:85.33%; h:4.91%; n:9.76%;
test value C:85.27%; h:4.82%; n:9.80%.
Example 4
Compound D074 was prepared as follows:
(1) Under a nitrogen protection system, compound D-17 (28.04 mmol,12.13 g), D-7 (29.44 mmol,4.98 g), sodium tert-butoxide (56.08 mmol,5.39 g) were weighed into a reaction system, 300ml of toluene solution was then added to the reaction system, followed by addition of tris (dibenzylideneacetone) dipalladium (0.56 mmol,0.51 g), 50% tri-tert-butylphosphine (1.23 mmol,0.50 g) was heated to 120℃and stirred uniformly and reacted for 24 hours, and after the reaction was stopped, the system was cooledCooling to room temperature, precipitating, vacuum filtering, washing with absolute ethanol, oven drying to obtain solid powder, and mixing with dichloromethane and petroleum ether (V Dichloromethane (dichloromethane) :V Petroleum ether =1:12) as solvent, and the filtrate was concentrated to precipitate a solid, to give D-18 (12.13 g, yield: 83%).
(2) Compound D-18 (22.47 mmol,11.71 g), pinacol biborate (44.94 mmol,11.41 g), potassium acetate (56.17 mmol,5.51 g) were weighed out under a nitrogen blanket, 1, 4-dioxane (150 mL) was added to the reaction, followed by tris (dibenzylideneacetone) dipalladium (0.23 mmol,0.21 g), X-phos (2.24 mmol,1.07 g) was heated to 120℃for 18 hours, the reaction was cooled to room temperature after stopping the reaction, DCM was added to extract the reaction solution, and concentrated to give solid powder D-19 (9.13 g, yield: 72%).
(3) Under a nitrogen protection system, weighing compound D-19 (18.64 mmol,11.42 g), D-10 (20.5 mmol,7.05 g), anhydrous potassium carbonate (37.28 mmol,5.14 g) into a reaction system, adding 150ml toluene solution, 150ml ethanol and 75ml purified water into the reaction system, adding tetra (triphenylphosphine) palladium (0.56 mmol,0.65 g), heating to 90 ℃, stirring uniformly and reacting for 24 hours, cooling the reaction system to room temperature after stopping the reaction, precipitating, filtering the precipitate, washing and drying the precipitate with absolute ethanol to obtain solid powder, and adding a mixed solution of dichloromethane and petroleum ether (V Dichloromethane (dichloromethane) :V Petroleum ether =1:15) as solvent, and the filtrate was concentrated to precipitate a solid, to give D074 (11.77 g, yield: 88%). HPLC purity: greater than 99.9%;
mass spectrometry: calculated 717.88 and tested 718.72;
elemental analysis:
calculated value C:85.33%; h:4.91%; n:9.76%;
test value C:84.67%; h:4.98%; n:9.66%.
Example 5
Compound D078 was prepared as follows:
(1) Under a nitrogen protection system, compound D-17 (28.04 mmol,12.13 g), D-7 (29.44 mmol,4.98 g), sodium tert-butoxide (56.08 mmol,5.39 g) were weighed into a reaction system, 300ml of toluene solution was then added to the reaction system, followed by adding tris (dibenzylideneacetone) dipalladium (0.56 mmol,0.51 g), 50% tri-tert-butylphosphine (1.23 mmol,0.50 g) was heated to 120℃and stirred uniformly and reacted for 24 hours, after the reaction was stopped, the system was cooled to room temperature, precipitation was observed, the precipitate was suction filtered, washed with absolute ethanol and dried to obtain a solid powder, and a mixed solution of methylene chloride and petroleum ether (V) Dichloromethane (dichloromethane) :V Petroleum ether =1:12) as solvent, and the filtrate was concentrated to precipitate a solid, to give D-18 (12.13 g, yield: 83%).
(2) Compound D-18 (22.47 mmol,11.71 g), pinacol biborate (44.94 mmol,11.41 g), potassium acetate (56.17 mmol,5.51 g) were weighed out under a nitrogen blanket, 1, 4-dioxane (150 mL) was added to the reaction, followed by tris (dibenzylideneacetone) dipalladium (0.23 mmol,0.21 g), X-phos (2.24 mmol,1.07 g) was heated to 120℃for 18 hours, the reaction was cooled to room temperature after stopping the reaction, DCM was added to extract the reaction solution, and concentrated to give solid powder D-19 (9.13 g, yield: 72%).
(3) Under a nitrogen protection system, weighing compound D-19 (18.64 mmol,11.42 g), D-20 (20.5 mmol,7.05 g), anhydrous potassium carbonate (37.28 mmol,5.14 g) into a reaction system, adding 150ml toluene solution, 150ml ethanol and 75ml purified water into the reaction system, adding tetra (triphenylphosphine) palladium (0.56 mmol,0.65 g), heating to 90 ℃, stirring uniformly and reacting for 24 hours, cooling the reaction system to room temperature after stopping the reaction, precipitating, filtering the precipitate, washing and drying the precipitate with absolute ethanol to obtain solid powder, and adding a mixed solution of dichloromethane and petroleum ether (V Dichloromethane (dichloromethane) :V Petroleum ether =1:16) as solvent, and the filtrate was concentrated to precipitate a solid, yielding D074 (12.73 g, yield: 86%). HPLC purity: greater than 99.9%;
mass spectrometry: calculated 793.97 and tested 794.89;
elemental analysis:
calculated value C:86.23%; h:4.95%; n:8.82%;
test value C:86.72%; h:4.98%; n:8.66%.
Example 6
Compound D108 was prepared as follows:
(1) Under a nitrogen protection system, compound D-21 (28.04 mmol,12.13 g), D-22 (29.44 mmol,7.22 g) and sodium tert-butoxide (56.08 mmol,5.39 g) are weighed into a reaction system, 300ml of toluene solution is added into the reaction system, tris (dibenzylideneacetone) dipalladium (0.56 mmol,0.51 g) and 50% tri-tert-butylphosphine (1.23 mmol,0.50 g) are added into the reaction system, the mixture is heated to 120 ℃ and stirred evenly and reacted for 24 hours, the system is cooled to room temperature after the reaction is stopped, precipitation is carried out, the precipitate is filtered by suction, washed and dried by absolute ethyl alcohol, and solid powder is obtained, and a mixed solution of dichloromethane and petroleum ether (V) Dichloromethane (dichloromethane) :V Petroleum ether =1:15) as solvent, and the filtrate was concentrated to precipitate a solid, to give D-23 (14.74 g, yield: 88%).
(2) Compound D-23 (22.47 mmol,13.42 g), pinacol biborate (44.94 mmol,11.41 g), potassium acetate (56.17 mmol,5.51 g) were weighed out under a nitrogen blanket, 1, 4-dioxane (150 mL) was added to the reaction, followed by tris (dibenzylideneacetone) dipalladium (0.23 mmol,0.21 g), X-phos (2.24 mmol,1.07 g) was heated to 120℃for 18 hours, the reaction was cooled to room temperature after stopping the reaction, DCM was added to extract the reaction solution, and concentrated to give solid powder D-24 (10.83 g, yield: 70%).
(3) Under a nitrogen protection system, compound D-24 (18.64 mmol,12.84 g), D-20 (20.5 mmol,7.05 g), anhydrous potassium carbonate (37.28 mmol,5.14 g) were weighed into a reaction system, then 150ml of toluene solution, 150ml of ethanol, 75ml of purified water were added to the reaction system, and then tetrakis (triphenylphosphine) palladium (0.56 mmo)l,0.65 g), heating to 90deg.C, stirring, reacting for 24 hr, cooling to room temperature after stopping the reaction, precipitating, filtering, washing with absolute ethanol, oven drying to obtain solid powder, and mixing with dichloromethane and petroleum ether (V) Dichloromethane (dichloromethane) :V Petroleum ether =1:14) as solvent, and the filtrate was concentrated to precipitate a solid, to give D108 (12.758 g, yield: 85%). HPLC purity: greater than 99.9%;
mass spectrometry: calculated 793.97 and tested 794.79;
elemental analysis:
calculated value C:86.23%; h:4.95%; n:8.82%;
test value C:86.22%; h:4.90%; n:8.76%.
Examples 7 to 16
The target compounds of examples 7-16 were synthesized according to the synthesis method in example 1, with only the corresponding reactants replaced, and the FD-MS (i.e., mass spectrum) results are shown in table 1.
TABLE 1 results of FD-MS of target Compounds of examples 7-16
The present invention also provides an organic electroluminescent device comprising the compound represented by the chemical formula 1 of the present invention.
Device example 1
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/HBL/ETL/EIL/cathode
a. ITO anode: the thickness of the coating is equal toThe ITO (indium tin oxide) glass substrate is washed 2 times in distilled water, ultrasonic washed for 30min, repeatedly washed 2 times with distilled water, and super-washedAfter the sonic washing is finished for 10min, the ultrasonic washing is sequentially performed by methanol, acetone and isopropanol (each time for 5 min), the ultrasonic washing is dried, then the ultrasonic washing is transferred into a plasma cleaning machine for 5min, and the ultrasonic washing is sent into a vapor deposition machine, and other functional layers are sequentially vapor deposited on the substrate serving as an anode.
b. HIL (hole injection layer): vacuum evaporation of 2-TNATA (i.e., N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylbenzene-1, 4-diamine)And forming a hole injection layer.
c. HTL (hole transport layer): vacuum deposition of NPB (i.e., N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine) on a hole injection layerA hole transport layer is formed.
d. EML (light emitting layer): the host luminescent material BPO and Balq3 dopant were co-deposited onto the hole transport layer region at a mass ratio of 96:4 to form a luminescent layer EML of about 30nm thickness.
e. HBL (hole blocking layer): vacuum vapor plating DPVBi on the light-emitting layerA hole blocking layer is formed.
f. ETL (electron transport layer): vacuum deposition of Compound D005 in Synthesis example 1 above on hole blocking layerAn electron transport layer is formed.
g. EIL (electron injection layer): vacuum evaporation of LiF on electron transport layerAn electron injection layer is formed.
h. And (3) cathode: vapor deposition of AlAnd forming a cathode to obtain the organic electroluminescent device.
Referring to the method provided in the device example 1, the organic electroluminescent devices of the corresponding compounds were prepared by evaporating the electron transport materials by replacing the compound D005 with the chemical structural formulas D004, D008, D024, D028, D029, D034, D035, D044, D049, D052, D069, D079, D080, D093, and D103, respectively, and recording as device examples 2 to 16.
Device comparative example 1
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/HBL/ETL/EIL/cathode
a. ITO anode: the thickness of the coating is equal toThe ITO (indium tin oxide) glass substrate is washed 2 times in distilled water, ultrasonic washing is carried out for 30min, then the distilled water is used for repeatedly washing for 2 times, ultrasonic washing is carried out for 10min, after washing is finished, methanol, acetone and isopropanol are used for ultrasonic washing (5 min for each time), drying is carried out, then the glass substrate is transferred into a plasma washer for washing for 5min, and then the glass substrate is sent into an evaporation machine, and other functional layers are sequentially evaporated on the glass substrate by taking the substrate as an anode.
b. HIL (hole injection layer): vacuum evaporation of 2-TNATA (i.e., N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylbenzene-1, 4-diamine)And forming a hole injection layer.
c. HTL (hole transport layer): vacuum deposition of NPB (i.e., N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine) on a hole injection layerA hole transport layer is formed. d. EML (light emitting layer): on the hole transport layer, a mixed material of a host material BPO and a doping material Balq3 is used as a light-emitting layer by vacuum evaporation, wherein the weight ratio of the host material to the doping material is 96:4, and the host material is thickDegree is->
e. HBL (hole blocking layer): vacuum vapor deposition of BAlq on light-emitting layerA hole blocking layer is formed.
f. ETL (electron transport layer): vacuum evaporation of Alq3 on hole blocking layerAn electron transport layer is formed, the structure of which is as follows: />
g. EIL (electron injection layer): vacuum evaporation of LiF on electron transport layerAn electron injection layer is formed.
h. And (3) cathode: vapor deposition of AlAnd forming a cathode to obtain the organic electroluminescent device.
The organic electroluminescent devices obtained in the above device examples 1 to 16 and device comparative example 1 were characterized in terms of driving voltage, luminous efficiency and lifetime at 6000 (nits) luminance, and the test results are shown in table 2 below:
table 2:
/>
as can be seen from table 2, the driving voltage of the device provided by the present invention is 3.1V to 3.9V, which is significantly smaller than that of comparative example 1, while the light-emitting efficiency is much higher than that of comparative example 1, and the lifetime (620 to 780) is 7 to 9 times that of comparative example 1, compared with comparative example 1, it can be seen that the organic electroluminescent device prepared using the compound provided by the present invention as an electron transport material has significantly reduced driving power, and significantly improved light-emitting efficiency and lifetime, compared with the organic electroluminescent device prepared using the comparative compound Alq3 as a light-emitting layer material.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
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 (2)

1. An organic electroluminescent compound, characterized in that the organic electroluminescent compound is selected from any one of the following structures: 。
2. use of an organic electroluminescent compound as claimed in claim 1 for the preparation of an organic electroluminescent device, wherein the organic electroluminescent device comprises an anode, a cathode and a number of organic layers deposited between the anode and the cathode; wherein at least one organic layer comprises the organic electroluminescent compound of claim 1.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110102055A (en) * 2010-03-10 2011-09-16 제일모직주식회사 Compound for organic photoelectric device and organic photoelectric device including the same
CN105408449A (en) * 2013-07-30 2016-03-16 默克专利有限公司 Materials for electronic devices
CN110678449A (en) * 2017-06-16 2020-01-10 材料科学有限公司 Organic compound and organic electroluminescent element comprising same
CN113666918A (en) * 2020-05-15 2021-11-19 南京高光半导体材料有限公司 Organic electroluminescent compound with high thermal stability and organic electroluminescent device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20110102055A (en) * 2010-03-10 2011-09-16 제일모직주식회사 Compound for organic photoelectric device and organic photoelectric device including the same
CN105408449A (en) * 2013-07-30 2016-03-16 默克专利有限公司 Materials for electronic devices
CN110678449A (en) * 2017-06-16 2020-01-10 材料科学有限公司 Organic compound and organic electroluminescent element comprising same
CN113666918A (en) * 2020-05-15 2021-11-19 南京高光半导体材料有限公司 Organic electroluminescent compound with high thermal stability and organic electroluminescent device

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