CN114409659A - Organic electroluminescent compound, preparation method thereof and organic electroluminescent device - Google Patents

Organic electroluminescent compound, preparation method thereof and organic electroluminescent device Download PDF

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CN114409659A
CN114409659A CN202210037485.6A CN202210037485A CN114409659A CN 114409659 A CN114409659 A CN 114409659A CN 202210037485 A CN202210037485 A CN 202210037485A CN 114409659 A CN114409659 A CN 114409659A
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organic electroluminescent
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王辉
段伟伟
刘福全
张国旭
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device. The structural formula of the organic electroluminescent compound is shown as follows:

Description

Organic electroluminescent compound, preparation method thereof and organic electroluminescent device
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 organic electroluminescent device.
Background
The organic electroluminescence (abbreviated as OLED) refers to the phenomenon that a thin film device prepared from organic electroluminescence materials emits light under the excitation action of an electric field, and the photoelectric device prepared by utilizing the principle has the characteristics of low power consumption, high response speed, wide visual angle, high resolution, wide temperature characteristic, light weight, crimpability and the like. In addition, the display screen manufactured by utilizing the organic electroluminescence principle is different from the traditional LCD display screen, a backlight lamp is not needed, and only the organic photoelectric functional material coating and the glass substrate are adopted, so that the display screen can emit light when current passes through, and can be lighter and thinner, has a larger visual angle, and can obviously save electric energy.
However, the existing photoelectric device made of organic electroluminescent material has the problems of short service life, low luminous efficiency and high driving voltage, thereby increasing the use cost of the organic electroluminescent material and being not beneficial to the large-scale popularization of the later market.
Therefore, it is an urgent problem to provide a new organic electroluminescent material with long service life and low cost.
Disclosure of Invention
The invention provides an organic electroluminescent compound, a preparation method thereof and an organic electroluminescent device.
The invention is realized by the following steps:
in a first aspect, an embodiment of the present invention provides an organic electroluminescent compound, whose structural formula is as follows:
Figure BDA0003468595410000021
wherein R is1Is a mono substituent, R1Represents any one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; r2、R3、R4And R5Are each a monosubstituted or polysubstituted radical, and R2、R3、R4、R5And R6Each independently represents one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.
In a second aspect, embodiments of the present invention provide a method for preparing an organic electroluminescent compound, including: the organic electroluminescent compounds were synthesized with reference to the following synthesis steps:
Figure BDA0003468595410000022
wherein X is halogen.
In a third aspect, embodiments of the present invention provide an organic electroluminescent device, which is prepared from the above organic electroluminescent compound.
The invention has the beneficial effects that: the organic electroluminescent compound provided by the embodiment of the invention has high electronegativity, electron-rich groups and a carbazole ring structure with rigid characteristics, and can promote intermolecular charge transition; meanwhile, R of the structural formula of the compound1The position is connected with a substituent group, so that the molecular weight is increased, and the intermolecular is not easy to crystallize and aggregate, so that the material has higher photo-thermal stability; on the other hand, increasing the intermolecular stacking makes it easier to achieve horizontal molecular orientation, thereby enabling fast electron flow characteristics. Therefore, the compound provided by the invention can be applied to the preparation of an organic electroluminescent device, and the service life of the organic electroluminescent device is prolonged.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following provides a detailed description of an organic electroluminescent compound, a method for preparing the same, and an organic electroluminescent device.
The embodiment of the invention provides an organic electroluminescent compound, which has the following structural formula:
Figure BDA0003468595410000031
wherein R is1Is a mono substituent, R1Represents any one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; r2、R3、R4And R5Are each a monosubstituted or polysubstituted radical, and R2、R3、R4、R5And R6Each independently represents one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.
In addition, R is2、R3、R4And R5Each independently is a mono-or polysubstituent, meaning R2When mono-substituted, it is a substituent at any position on the benzene ring, R2When the substituent is polysubstituted, the substituent is disubstituted at any 2 positions or trisubstituted at any 3 positions on the benzene ring, and similarly, R3Is a mono-substituent, a di-substituent, a tri-substituent or a tetra-substituent; the R is4Is a mono-substituent, a di-substituent, a tri-substituent, a tetra-substituent or a penta-substituent; r6Can only be monosubstituted.
Further, R2、R3、R4、R5And R6Each independently represents one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylamino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted 4-to 30-membered heteroaryl; r2、R3、R4、R5And R6Each independently represents one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted 3-to 15-membered heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C15 alkylamino, substituted or unsubstituted C6-C25 arylamino, substituted or unsubstituted C6-C20 aryl, and substituted or unsubstituted 4-to 25-membered heteroaryl.
Further, R1Represents any one of a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted 3-to 30-membered heterocycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkylamino group, a substituted or unsubstituted C6 to C30 arylamino group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted 4-to 30-membered heteroaryl group; preferably, R1Represents any of a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted 3-to 15-membered heterocycloalkyl group, a substituted or unsubstituted C6-C20 arylamino group, a substituted or unsubstituted C6-C25 aryl group, and a substituted or unsubstituted 4-to 20-membered heteroaryl group.
Further, R1Selected from any one of the groups shown in the following structural formula (but not limited thereto),
Figure BDA0003468595410000051
need to explainIs (1) in the structural formula
Figure BDA0003468595410000052
Represents the position of attachment of the group.
(2) The above alkoxy group is generally represented by RO-, and is a substituent group in the molecule of an organic compound, and is composed of an alkyl group and an oxygen atom. The alkylamino group is composed of an alkyl group and an amino group. Arylamino groups are composed of aryl groups and amino groups. Alkyl includes straight chain or branched alkyl; for example, alkyl groups include, but are not limited to, any of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl. The cycloalkyl is any one of monocycloalkyl, polycycloalkyl and spirocycloalkyl; for example, cycloalkyl groups include, but are not limited to, any of cyclopropyl, cyclopentyl, cyclohexyl, and adamantyl. Heterocycloalkyl is any of a monoheterocycloalkyl group in which at least one carbon atom is replaced with a heteroatom, a polyheteroheterocycloalkyl group in which at least one carbon atom is replaced with a heteroatom, and a spiroheterocycloalkyl group in which at least one carbon atom is replaced with a heteroatom, the alkyl groups in the heteroalkyl group being as selected with reference to the cycloalkyl groups above, except that there are carbon atoms replaced with a heteroatom (including but not limited to at least one of N, O, S, Si, Se, Ge). Aryl is monocyclic aryl or polycyclic aryl; wherein the polycyclic aryl group includes a structure in which two carbon atoms are shared by two adjoining rings, at least one of which is aromatic; for example, including, but not limited to, any of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, and pyrene. Heteroaryl is a monocyclic aryl group in which at least one carbon atom is replaced by a heteroatom or a polycyclic aryl group in which at least one carbon atom is replaced by a heteroatom; the selection of aryl groups in heteroaryl groups may be made with reference to the selection of aryl groups described above, except that at least one carbon atom is replaced by a heteroatom (including but not limited to at least one of N, O, S, Si, Se, Ge), for example, heteroaryl groups include but are not limited to any of furan, thiophene, pyridine, and triazine.
(3) 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 at which the hydrogen atom is substituted, that is, 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.
Further, the organic electroluminescent compound is selected from any one of the compounds represented by the following structural formula:
Figure BDA0003468595410000061
Figure BDA0003468595410000071
Figure BDA0003468595410000081
Figure BDA0003468595410000091
Figure BDA0003468595410000101
Figure BDA0003468595410000111
Figure BDA0003468595410000121
Figure BDA0003468595410000131
Figure BDA0003468595410000141
Figure BDA0003468595410000151
Figure BDA0003468595410000161
the numerical values below the above-mentioned compounds are only the numbers thereof, and the numbers correspond to the compounds corresponding to the numbers in the following examples, and do not indicate the importance of the compounds.
Some specific structural forms are listed above, but the series of compounds are not limited to the above molecular structures, and other specific molecular structures can be obtained through simple transformation of some simple groups, substituted groups and substituted positions thereof, and are not described in detail herein.
The organic electroluminescent compound provided by the embodiment of the invention can promote intermolecular charge transition due to structural characteristics, has high photo-thermal stability, and can realize rapid electron flow, so that an organic electroluminescent device prepared by using the organic electroluminescent compound has long service life, relatively low driving voltage, excellent luminous efficiency and high-purity color.
In a second aspect, an embodiment of the present invention provides a method for synthesizing the organic electroluminescent compound, including:
step 1: synthesis was performed with reference to the following synthesis route:
Figure BDA0003468595410000171
specifically, the method comprises the following steps: under the protection of inert gas, mixing a raw material D-1, a raw material D-2, sodium tert-butoxide, tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and toluene for reaction, specifically, under the protection of nitrogen, mixing the raw material D-1, the raw material D-2 and sodium tert-butoxide, adding toluene, then adding a catalyst, heating and stirring uniformly for reaction.
And after the reaction is finished, cooling (for example, at 15-30 ℃), precipitating, washing, drying, and carrying out column chromatography (silica gel column chromatography is adopted for column chromatography, and dichloromethane and petroleum ether are mixed according to the volume ratio of 1 (1-15) to be used as a solvent) to obtain the compound with the structure of the formula D-3, namely the raw material D-3.
Wherein X is halogen, preferably bromine; the molar ratio of the raw material D-1 to the raw material D-2 is 1 (1.05-1.3); the molar ratio of the raw material D-1 to the sodium tert-butoxide is 1 (2-2.5); the molar ratio of the raw material D-1 to the tris (dibenzylideneacetone) dipalladium is 1 (0.01-0.1); the molar ratio of the raw material D-1 to the tri-tert-butylphosphine is 1 (0.02-0.2); the tri-tert-butylphosphine accounts for 50% of the total mass of the tri-tert-butylphosphine; the ratio of the raw material D-1 to the toluene is 1mmol: 5-10 mL; the reaction temperature is 90-140 ℃, and the reaction time is 20-30 h; the drying temperature is 70-80 ℃.
Step 2: synthesis was performed with reference to the following synthesis route:
Figure BDA0003468595410000172
specifically, the method comprises the following steps: under the protection of inert gas, the raw materials D-3, AlCl3 and xylene are mixed for a retaining ring reaction, and after the reaction is finished, the compound with the structure of the formula A, namely the raw material A, is obtained through cooling, column chromatography and concentration. More specifically, under the protection of nitrogen, raw materials D-3, NaCl and AlCl are mixed3Dissolving in benzene, hydrolyzing, washing with water and sodium bicarbonate water solution, drying with magnesium sulfate, concentrating, dissolving the concentrated solution in small amount of hot p-xylene, passing through a column, and recrystallizing the residual solution with methylcyclohexane to obtain raw material A.
Wherein the molar ratio of the raw material D-3 to NaCl is 1 (15-20); raw materials D-3 and AlCl3The molar ratio of (1) to (30-50); preferably 1: 30-40 parts of; the ratio of the raw material D-3 to the dimethylbenzene is 1 (2-2.5).
And step 3: synthesis was performed with reference to the following synthesis route:
Figure BDA0003468595410000181
specifically, under the protection of inert gas, raw material A, raw material B, cesium carbonate, a catalyst and DMSO are mixed for reaction, and after the reaction is finished, the reaction is carried outAnd (4) carrying out suction filtration, alcohol washing, drying, column chromatography and concentration to obtain the compound shown in the formula I. More specifically, under the protection of nitrogen, mixing the raw material A, the raw material B and cesium carbonate, adding dimethyl sulfoxide, then adding a catalyst, heating and stirring uniformly to react; cooling to 15-30 ℃ after the reaction is stopped, carrying out suction filtration after precipitation is separated out, washing with absolute ethyl alcohol, and drying at the temperature of 70-80 ℃ to obtain light yellow powder; carrying out column chromatography on the light yellow powder, concentrating the filtrate and precipitating a solid to obtain an organic electroluminescent compound; wherein, the column chromatography adopts silica gel column chromatography, and dichloromethane and petroleum ether are used according to the weight ratio of 1: (1-15) mixing the components in a volume ratio to serve as a solvent.
Wherein X is halogen, and the molar ratio of the raw material A to the raw material B is 1 (1.05-1.3); the molar ratio of the raw material A to the cesium carbonate is 1 (2.5-3); the molar ratio of the raw material A to the catalyst is 1 (0.01-0.1), and the catalyst is 4-dimethylaminopyridine; the ratio of the raw material A to the dimethyl sulfoxide is 4.3mmol: 20-30 mL; the heating temperature is 90-140 ℃, and the reaction time is 20-30 h; the drying temperature is 70-80 ℃; the column chromatography is carried out by silica gel column chromatography with dichloromethane and petroleum ether according to the ratio of 1: (1-15) mixing the components in a volume ratio to serve as a solvent.
Preferably, the molar ratio of the raw material A to the raw material B is 1: 1.1; the molar ratio of the raw material A to the cesium carbonate is 1: 3; the molar ratio of the raw material A to the 4-dimethylaminopyridine is 1: 0.05.
The preparation method provided by the embodiment of the invention is simple to operate, the preparation process is easy to control, and the prepared organic electroluminescent compound can be applied to the preparation of organic electroluminescent devices.
In a third aspect, embodiments of the present invention provide an organic electroluminescent device, which is prepared from the above organic electroluminescent compound.
Specifically, the organic electroluminescent device comprises a first electrode, a second electrode and at least one organic layer arranged between the first electrode and the second electrode, wherein the organic layer is prepared from the organic electroluminescent compound.
Specifically, the organic layer includes a light emitting layer; the luminescent layer is prepared from a doping material and the organic electroluminescent compound; the mass ratio of the organic electroluminescent compound to the doping material is (90-99.5) to (0.5-10); further, the organic layer further includes a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
The above organic electroluminescent device exhibits a relatively low driving voltage by improving interface characteristics, and exhibits excellent luminous efficiency, high purity color, and long service life.
The following description specifically describes an organic electroluminescent compound, a method for preparing the same, and an organic electroluminescent device, with reference to specific examples.
Example 1
This example provides a method for preparing an organic electroluminescent compound (marker: D029) by the following synthetic route:
step 1:
Figure BDA0003468595410000191
in particular, the amount of the solvent to be used,
raw material D-4(33mmol, 9.7g), raw material D-5(36.3mmol, 6.14g) and sodium tert-butoxide (66mmol, 634g) were weighed into the reaction system under nitrogen protection, then 250mL of toluene solution was added to the reaction system followed by tris (dibenzylideneacetone) dipalladium (0.33mmol, 0.30g) and 50% tri-tert-butylphosphine (0.66mmol, 0.27g), heated to 120 deg.C, stirred uniformly and reacted for 24 h.
Cooling to room temperature of 25 ℃ after the reaction is stopped, carrying out suction filtration after precipitation is separated out, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain solid powder. Adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum ether1:30) was used as a solvent, and the above product was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain a raw material D-6(8.88g, yield: 70.0%).
Step 2:
Figure BDA0003468595410000201
in particular, the amount of the solvent to be used,
under the protection of nitrogen, raw material D-6(26mmol, 10g), raw material NaCl (390mmol, 22.79g) and AlCl are weighed3(780mmol, 103.99g) was dissolved in benzene, hydrolyzed, washed with water and aqueous sodium bicarbonate, dried over magnesium sulfate, and concentrated. Then the concentrated solution is dissolved in a small amount of hot p-xylene and is subjected to column chromatography, and the residual solution is recrystallized by using methylcyclohexane to obtain a raw material A029.
And step 3:
Figure BDA0003468595410000202
in particular, the amount of the solvent to be used,
raw material A029(52.57mmol, 20.1g), raw material B029(57.85mmol, 11.72g) and cesium carbonate (157.71mmol, 51.38g) were weighed into a reaction system under a nitrogen protection system, followed by addition of 300mL of dimethyl sulfoxide solution, followed by addition of 4-dimethylaminopyridine (2.63mmol, 0.32g), heating to 90 ℃, stirring and reaction for 24 h. Cooling to room temperature of 25 ℃ after the reaction is stopped, leaching after precipitation, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain light yellow powder. With a mixed solution of dichloromethane and petroleum ether (V)Methylene dichloride:VPetroleum ether1:10) as a solvent, and a pale yellow powder was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain the final pale yellow carbazole derivative D029(23.64g, yield: 82%).
And (3) characterization: HPLC purity: greater than 99%. Mass spectrum: the calculated value was 548.65 and the test value was 549.51. Elemental analysis: calculated value C: 87.57 percent; h: 4.41 percent; n: 5.11 percent; 2.92 percent of O; test value C: 87.57 percent; h: 4.47%; n: 5.01 percent; 2.95 percent of O.
As can be seen by comparing the above calculated values with the test values, the measured values substantially agreed with the theoretical values, and it was confirmed that the product prepared by this example was the compound D029 represented by the following structural formula:
Figure BDA0003468595410000211
example 2
This example provides a method for preparing an organic electroluminescent compound (label: D045) by referring to the following synthesis scheme:
Figure BDA0003468595410000212
in particular, the amount of the solvent to be used,
raw material A029(52.57mmol, 20.1g), raw material B045(57.85mmol, 14.62g) and cesium carbonate (157.71mmol, 51.38g) were weighed into a reaction system under a nitrogen protection system, and then 300mL of dimethyl sulfoxide solution, 4-dimethylaminopyridine (2.63mmol, 0.32g) were added to the reaction system, heated to 90 ℃, stirred uniformly and reacted for 24 h.
Cooling to room temperature of 25 ℃ after the reaction is stopped, leaching after precipitation, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain light yellow powder. Adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum etherAs a solvent, the pale yellow gel was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain a final pale yellow carbazole derivative D045(24.55g, yield: 78.0%).
And (3) characterization: HPLC purity: greater than 99%. Mass spectrum: the calculated value was 598.20 and the test value was 599.11. Elemental analysis: calculated value C: 88.27 percent; h: 4.38 percent; n: 4.68 percent; o: 2.67 percent; test value C: 88.27 percent; h: 4.35 percent; n: 4.58 percent; o: 2.70 percent.
As can be seen from a comparison of the calculated values with the test values, the measured values substantially agree with the theoretical values, and it is thus confirmed that the product prepared by this example is a compound D045 represented by the following structural formula:
Figure BDA0003468595410000221
example 3
This example provides a process for the preparation of an organic electroluminescent compound (marker: D078) according to the following synthesis scheme:
Figure BDA0003468595410000222
in particular, the amount of the solvent to be used,
raw material A029(52.57mmol, 20.11g), raw material B078(57.85mmol, 13.92g) and cesium carbonate (157.71mmol, 51.38g) were weighed into a reaction system under a nitrogen protection system, and then 300mL of a dimethyl sulfoxide solution, 4-dimethylaminopyridine (2.63mmol, 0.32g) were added to the reaction system, heated to 90 ℃, stirred uniformly and reacted for 24 hours.
Cooling to room temperature of 25 ℃ after the reaction is stopped, carrying out suction filtration after precipitation is separated out, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain light yellow powder; adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum ether1:10) as a solvent, the light yellow gel was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain the final light yellow carbazole derivative D078(26.52g, yield: 86%).
And (3) characterization: purity of PLC: greater than 99%. Mass spectrum: the calculated value was 586.70 and the test value was 587.69. Elemental analysis: calculated value C: 85.98 percent; h: 4.47%; n: 9.55 percent; test value C: 85.69 percent; h: 4.35 percent; n: 9.66 percent.
As can be seen by comparing the above calculated values with the test values, the measured values substantially agreed with the theoretical values, and it was confirmed that the product prepared by this example was the compound D078 represented by the following structural formula:
Figure BDA0003468595410000231
example 4
This example provides a process for the preparation of an organic electroluminescent compound (reference: D083) according to the following synthesis scheme:
Figure BDA0003468595410000232
in particular, the amount of the solvent to be used,
raw material A029(52.57mmol, 20.11g), raw material B083(57.85mmol, 19.89g) and cesium carbonate (157.71mmol, 51.38g) were weighed into a reaction system under a nitrogen protection system, and then 300mL of a dimethyl sulfoxide solution, 4-dimethylaminopyridine (2.63mmol, 0.32g) were added to the reaction system, heated to 90 ℃, stirred uniformly and reacted for 24 h.
Cooling to room temperature of 25 ℃ after the reaction is stopped, leaching after precipitation, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain light yellow powder. Adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum ether1:10) as a solvent, subjecting the pale yellow gel to silica gel column chromatography, and concentrating the filtrate to precipitate a solid, to obtain the final pale yellow carbazole derivative D083(28.65g, yield: 79%).
And (3) characterization: HPLC purity: greater than 99%. Mass spectrum: the calculated value was 689.82 and the test value was 690.71. Elemental analysis: calculated value C: 85.32 percent; h: 4.53 percent; n: 10.15 percent; test value C: 85.49 percent; h: 4.45 percent; n: 10.36 percent.
As can be seen by comparing the above calculated values with the test values, the measured values substantially agree with the theoretical values, and it is thus confirmed that the product prepared by this example is the compound D083 represented by the following structural formula:
Figure BDA0003468595410000241
example 5
This example provides a process for the preparation of an organic electroluminescent compound (marker: D109) according to the following synthesis scheme:
Figure BDA0003468595410000242
in particular, the amount of the solvent to be used,
raw material A029(52.57mmol, 20.11g), raw material B109(57.85mmol, 16.07g) and cesium carbonate (157.71mmol, 51.38g) were weighed into a reaction system under a nitrogen protection system, and then 300mL of a dimethyl sulfoxide solution, 4-dimethylaminopyridine (2.63mmol, 0.32g) were added to the reaction system, heated to 90 ℃, stirred uniformly and reacted for 24 hours.
Cooling to room temperature of 25 ℃ after the reaction is stopped, leaching after precipitation, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain light yellow powder. Adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum ether1:10) was taken as a solvent, the pale yellow gel was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain a final pale yellow carbazole derivative D109(27.87g, yield: 85%).
And (3) characterization: HPLC purity: greater than 99%. Mass spectrum: the calculated value was 623.76 and the test value was 624.68. Elemental analysis: calculated value C: 88.58 percent; h: 4.69 percent; n: 6.74 percent; test value C: 88.49 percent; h: 4.55 percent; n: 6.66 percent.
As can be seen by comparing the above calculated values with the test values, the measured values substantially agree with the theoretical values, and it is thus confirmed that the product prepared by this example is compound D109 represented by the following structural formula:
Figure BDA0003468595410000251
example 6
This example provides a process for the preparation of an organic electroluminescent compound (marker: D143) according to the following synthesis scheme:
Figure BDA0003468595410000261
in particular, the amount of the solvent to be used,
raw material A029(52.57mmol, 20.11g), raw material B143(57.85mmol, 9.81g) and cesium carbonate (157.71mmol, 51.38g) were weighed into a reaction system under a nitrogen protection system, and then 300mL of a dimethyl sulfoxide solution, 4-dimethylaminopyridine (2.63mmol, 0.32g) were added to the reaction system, heated to 90 ℃, stirred uniformly and reacted for 24 hours.
Cooling to room temperature of 25 ℃ after the reaction is stopped, leaching after precipitation, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain light yellow powder. Adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum ether1:10) as a solventThe resulting pale yellow clear solution was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, whereby the final pale yellow carbazole derivative D143(19.51g, yield: 72%) was obtained.
And (3) characterization: HPLC purity: greater than 99%. Mass spectrum: the calculated value was 515.67 and the test value was 516.55. Elemental analysis: calculated value C: 88.51 percent; h: 6.06 percent; n: 5.43 percent; test value C: 88.49 percent; h: 6.05 percent; n: 5.61 percent.
As can be seen from a comparison of the above calculated values with the test values, the measured values substantially agree with the theoretical values, and it is thus confirmed that the product prepared by this example is compound D143 represented by the following structural formula:
Figure BDA0003468595410000262
example 7
This example provides a method for preparing an organic electroluminescent compound (marker: D206), the synthetic route is:
step 1:
Figure BDA0003468595410000271
in particular, the amount of the solvent to be used,
raw material D-4(33mmol, 9.7g), raw material D-7(36.3mmol, 7.96g) and sodium tert-butoxide (66mmol, 634g) were weighed into a reaction system under nitrogen protection, then 250mL of toluene solution was added to the reaction system followed by tris (dibenzylideneacetone) dipalladium (0.33mmol, 0.30g), 50% tri-tert-butylphosphine (0.66mmol, 0.27g), heated to 120 deg.C, stirred uniformly and reacted for 24 h.
Cooling to room temperature of 25 ℃ after the reaction is stopped, carrying out suction filtration after precipitation is separated out, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain solid powder. Adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum ether1:30) was used as a solvent, and the above product was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain raw material D-8(10.47g, yield: 73.0%).
Step 2:
Figure BDA0003468595410000272
in particular, the amount of the solvent to be used,
under the protection of nitrogen, raw materials D-8(26mmol, 11.3g), NaCl (390mmol, 22.79g) and AlCl are weighed3(780mmol, 103.99g) was dissolved in benzene, hydrolyzed, washed with water and aqueous sodium bicarbonate, dried over magnesium sulfate, and concentrated. The concentrated solution was then dissolved in a small amount of hot p-xylene and passed through a column, and the residue was recrystallized from methylcyclohexane to give the starting material A206.
And step 3:
Figure BDA0003468595410000281
in particular, the amount of the solvent to be used,
raw material A206(52.57mmol, 22.74g), raw material B206(57.85mmol, 10.91g) and cesium carbonate (157.71mmol, 51.38g) were weighed into a reaction system under a nitrogen protection system, and then 300mL of dimethyl sulfoxide solution, 4-dimethylaminopyridine (2.63mmol, 0.32g) were added to the reaction system, heated to 90 ℃, stirred uniformly and reacted for 24 h.
Cooling to room temperature of 25 ℃ after the reaction is stopped, leaching after precipitation, washing with absolute ethyl alcohol, and drying at the temperature of 80 ℃ to obtain light yellow powder. Adopts a mixed solution (V) of dichloromethane and petroleum etherMethylene dichloride:VPetroleum ether1:10) was used as a solvent, the pale yellow gel was subjected to silica gel column chromatography, and the filtrate was concentrated to precipitate a solid, to obtain a final pale yellow carbazole derivative D206(24.59g, yield: 80%).
And (3) characterization: HPLC purity: greater than 99%. Mass spectrum: the calculated value was 584.72 and the test value was 585.75. Elemental analysis: calculated value C: 90.38 percent; h: 4.83 percent; n: 4.79 percent; test value C: 90.49 percent; h: 4.05 percent; n: 4.61 percent.
As can be seen by comparing the above calculated values with the test values, the measured values substantially agree with the theoretical values, and it is thus confirmed that the product prepared by this example is compound 206 represented by the following structural formula:
Figure BDA0003468595410000282
examples 8 to 17
The synthesis method provided with reference to example 1 corresponds to the synthesis of the organic electroluminescent compounds of examples 8 to 17, with the difference that only the corresponding reactants are replaced, and the corresponding FD-MS results are shown in table 1.
TABLE 1
Figure BDA0003468595410000291
Application example 1
The application example provides an organic electroluminescent device which comprises a first electrode, and a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer and a second electrode which are sequentially arranged on the first electrode. Wherein the first electrode is an ITO anode; the second electrode is a cathode; the light-emitting layer was prepared from the organic electroluminescent compound D029 prepared in example 1 of the present invention and the dopant material E.
The embodiment also provides a preparation method of the organic electroluminescent device, which comprises the following steps:
a. an ITO anode: coating with a thickness of
Figure BDA0003468595410000292
Cleaning an ITO (indium tin oxide) glass substrate in distilled water for 2 times, ultrasonically cleaning for 30min, repeatedly cleaning with distilled water for 2 times, ultrasonically cleaning for 10min, ultrasonically cleaning with methanol, acetone and isopropanol in sequence (each time for 5min), drying, and then transferring to a plasma cleaning machine for cleaning for 5min to obtain an ITO anode;
b. HIL (hole injection layer): in the evaporator, 2-TNATA (N1- (2-naphthyl) -N4, N4-di (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenyl benzene-1, 4-diamine) is vacuum evaporated on the ITO anode
Figure BDA0003468595410000302
Forming a hole injection layer;
c. HTL (hole transport layer): then, NPB (i.e., N '-diphenyl-N, N' - (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine) was vacuum-evaporated on the hole injection layer
Figure BDA0003468595410000303
Forming a hole transport layer;
d. EML (light-emitting layer): on the hole transport layer, a mixed material of the host material and the dopant material E of the compound D029 obtained in the above example 1 was vacuum-evaporated as a light emitting layer, wherein the weight ratio of the host material to the dopant material was 90:10, and the thickness thereof was set to be
Figure BDA0003468595410000304
Wherein the structural formula of the doping material E is as follows;
Figure BDA0003468595410000301
e. HBL (hole blocking layer): on the luminescent layer, bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1,1' -biphenyl-4-hydroxy) aluminum (BALq) was vacuum evaporated
Figure BDA0003468595410000305
Forming a hole blocking layer;
f. ETL (electron transport layer): vacuum evaporation of 8-hydroxyquinoline aluminum (Alq3) onto the hole-blocking layer
Figure BDA0003468595410000306
Forming an electron transport layer;
g. EIL (electron injection layer): vacuum evaporation on the electron transport layer
Figure BDA0003468595410000307
Forming an electron injection layer;
h. cathode: vapor plating on the electron injection layer
Figure BDA0003468595410000308
And forming a cathode to obtain the organic electroluminescent device.
Application examples 2 to 16
An organic electroluminescent device was prepared with reference to the preparation method provided in application example 1, except that D002, D003, D028, D029, D044, D045, D046, D053, D055, D058, D068, D071, D080, D093, D103 were selected to replace the organic electroluminescent compound D004 in application example 1 for evaporation of the host material.
Comparative example 1 an organic electroluminescent device was manufactured with reference to the manufacturing method provided in application example 1, except that compound RH was selected to replace organic electroluminescent compound D004 in application example 1 for evaporation of the host material. Wherein the structural formula of the compound RH is
Figure BDA0003468595410000311
Detection of
The organic electroluminescent devices obtained in the above application examples 1 to 16 and comparative example 1 were characterized at a luminance of 6000(nits) for driving voltage, luminous efficiency and lifetime, and the test results are shown in the following table 2:
TABLE 2
Figure BDA0003468595410000312
Figure BDA0003468595410000321
As can be seen from table 2, compared with comparative example 1, the driving voltage of the organic electroluminescent device provided in application examples 1 to 16 of the present invention is 3.2V to 3.6V, which is significantly lower than the driving voltage of comparative example 1, and the luminous efficiency is much higher than that of comparative example 1, and the lifetime (490 to 580) is 8 to 10 times that of comparative example 1, so that it can be seen that the organic electroluminescent device prepared by using the organic electroluminescent compound provided in the present invention as a luminescent layer material has significantly reduced driving voltage, and significantly improved luminous efficiency and lifetime, as compared with the organic electroluminescent device prepared by using the comparative compound RH as a luminescent layer material.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. An organic electroluminescent compound, characterized in that it has the following structural formula:
Figure FDA0003468595400000011
wherein R is1Is a mono substituent, R1Represents any one of substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;
R2、R3、R4and R5Are each a monosubstituted or polysubstituted radical, and R2、R3、R4、R5And R6Each independently represents one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl.
2. The organic electroluminescent compound according to claim 1, wherein R is2And R5Respectively is a mono-substituent, a di-substituent or a tri-substituent; r3Is a mono-substituent, a di-substituent,A tri-or tetra-substituent; r4Is a mono-substituent, a di-substituent, a tri-substituent, a tetra-substituent or a penta-substituent;
preferably, R2、R3、R4、R5And R6Each independently represents one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 30-membered heterocycloalkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C1-C30 alkylamino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted 4-to 30-membered heteroaryl;
preferably, R2、R3、R4、R5And R6Each independently represents one or more of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted 3-to 15-membered heterocycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C15 alkylamino, substituted or unsubstituted C6-C25 arylamino, substituted or unsubstituted C6-C20 aryl, and substituted or unsubstituted 4-to 25-membered heteroaryl.
3. The organic electroluminescent compound according to claim 1, wherein R is1Represents any one of a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted 3-to 30-membered heterocycloalkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C1 to C30 alkylamino group, a substituted or unsubstituted C6 to C30 arylamino group, a substituted or unsubstituted C6 to C30 aryl group, and a substituted or unsubstituted 4-to 30-membered heteroaryl group;
preferably, R1Represents a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted 3-to 15-membered heterocycloalkyl group, a substituted or unsubstituted C6-C20 arylamino group, a substituted or unsubstituted C6-C25 aryl group, and a substituted or unsubstituted 4-to 20-membered heteroAny of aryl groups;
preferably, R1Selected from any one of the groups shown in the following structural formula,
Figure FDA0003468595400000021
Figure FDA0003468595400000031
4. an organic electroluminescent compound according to any one of claims 1 to 3, wherein the alkyl group comprises a straight-chain alkyl group or a branched-chain alkyl group;
preferably, the alkyl group is selected from any one of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and tert-butyl;
preferably, the cycloalkyl group is any one of a monocycloalkyl group, a polycycloalkyl group, and a spirocycloalkyl group;
preferably, the cycloalkyl group is any one of cyclopropyl, cyclopentyl, cyclohexyl, and adamantyl;
preferably, the heterocycloalkyl group is any one of a monoheterocycloalkyl group in which at least one carbon atom is substituted with a heteroatom, a polyheteroheterocycloalkyl group in which at least one carbon atom is substituted with a heteroatom, and a spiroheterocycloalkyl group in which at least one carbon atom is substituted with a heteroatom;
preferably, the aryl group is a monocyclic aryl group or a polycyclic aryl group; wherein the polycyclic aryl group includes a structure in which two carbon atoms are shared by two adjoining rings, at least one of which is aromatic;
preferably, the aryl group is any one of benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene and pyrene;
preferably, the heteroaryl group is a monocyclic aryl group in which at least one carbon atom is substituted by a heteroatom or a polycyclic aryl group in which at least one carbon atom is substituted by a heteroatom;
preferably, the heteroatom is at least one of N, O, S, Si, Se and Ge;
preferably, the heteroaryl group is any one of furan, thiophene, pyridine and triazine.
5. The organic electroluminescent compound according to claim 1, wherein the organic electroluminescent compound is selected from any one of the compounds represented by the following structural formulae:
Figure FDA0003468595400000041
Figure FDA0003468595400000051
Figure FDA0003468595400000061
Figure FDA0003468595400000071
Figure FDA0003468595400000081
Figure FDA0003468595400000091
Figure FDA0003468595400000101
Figure FDA0003468595400000111
Figure FDA0003468595400000121
Figure FDA0003468595400000131
Figure FDA0003468595400000141
6. a method for producing the organic electroluminescent compound according to claim 1, comprising: the organic electroluminescent compounds were synthesized with reference to the following synthesis steps:
Figure FDA0003468595400000142
wherein X is halogen.
7. The method of claim 6, comprising: mixing a raw material A, a raw material B, cesium carbonate, a catalyst and DMSO for reaction;
preferably, the molar ratio of the raw material A to the raw material B is 1 (1.05-1.3);
preferably, the molar ratio of the raw material A to the cesium carbonate is 1 (2.5-3);
preferably, the molar ratio of the raw material A to the catalyst is 1 (0.01-0.1); more preferably, the catalyst is 4-dimethylaminopyridine;
preferably, the ratio of the raw material A to the DMSO is 4.3mmol: 20-30 mL;
preferably, the reaction temperature is 90-140 ℃, and the reaction time is 20-30 h;
preferably, the method comprises the following steps: after the reaction is finished, carrying out post-treatment, wherein the post-treatment comprises the following steps: carrying out suction filtration, alcohol washing, drying, column chromatography and concentration;
preferably, the drying temperature is 70-80 ℃; the column chromatography is carried out by silica gel column chromatography with dichloromethane and petroleum ether according to the ratio of 1: (1-15) mixing the components in a volume ratio to serve as a solvent.
8. The method according to claim 6, wherein the starting material A is synthesized by referring to the following synthesis steps:
Figure FDA0003468595400000151
and
Figure FDA0003468595400000152
preferably, the step of forming the feedstock D-3 comprises: mixing a raw material D-1, a raw material D-2, sodium tert-butoxide, tris (dibenzylideneacetone) dipalladium, tri-tert-butylphosphine and toluene for reaction;
preferably, the molar ratio of the raw material D-1 to the raw material D-2 is 1 (1.05-1.3);
preferably, the molar ratio of the raw material D-1 to the sodium tert-butoxide is 1 (2-2.5);
preferably, the molar ratio of the raw material D-1 to the tris (dibenzylideneacetone) dipalladium is 1 (0.01-0.1);
preferably, the molar ratio of the raw material D-1 to the tri-tert-butylphosphine is 1 (0.02-0.2); the tri-tert-butylphosphine accounts for 50% of the total mass of the tri-tert-butylphosphine;
preferably, the ratio of the raw material D-1 to the toluene is 1mmol: 5-10 mL;
preferably, the conditions for forming the raw material D-3 include: the reaction temperature is 90-140 ℃, and the reaction time is 20-30 h;
preferably, the step of forming the feedstock a comprises: mixing raw materials D-3 and AlCl3Mixing with dimethylbenzene to carry out a buckle ring reaction;
preferably, the raw material D-3 and the AlCl are3The molar ratio of (1) to (30-50);
preferably, the molar ratio of the raw material D-3 to the xylene is 1 (2-2.5).
9. An organic electroluminescent element produced from the organic electroluminescent compound according to claim 1.
10. The organic electroluminescent device according to claim 9, 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 being prepared from the organic electroluminescent compound according to claim 1;
preferably, the organic layer includes a light emitting layer; the light-emitting layer is prepared by a doping material and the organic electroluminescent compound according to claim 1;
preferably, the mass ratio of the organic electroluminescent compound to the doping material is (90-99.5): (0.5-10);
preferably, the organic layer further includes a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
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