CN110878054A - Imidazole compound and application thereof - Google Patents

Imidazole compound and application thereof Download PDF

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CN110878054A
CN110878054A CN201811035286.1A CN201811035286A CN110878054A CN 110878054 A CN110878054 A CN 110878054A CN 201811035286 A CN201811035286 A CN 201811035286A CN 110878054 A CN110878054 A CN 110878054A
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魏金贝
李国孟
高文正
孙磊
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Beijing Eternal Material Technology Co Ltd
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Abstract

The present invention discloses compounds of the general formula (1):
Figure DDA0001790704550000011
wherein: z is S or O; x1～X10Each independently selected from CR3Or N, and X9And X10Can be connected by single bond or not; r1And R2Each independently selected from hydrogen and C1～C12Alkyl radical, C6～C30Aryl radical, C3～C30One of heteroaryl; r3Selected from hydrogen, C1～C12Alkyl radical, C6～C30Aryl radical, C3～C30One of heteroaryl; l is1And L2Each independently selected from the group consisting of a single bond, C6‑C30Aryl of (C)3‑C30One of the heteroaryl groups of (a); ar (Ar)1Selected from substituted or unsubstituted imidazole groups; ar (Ar)2Is selected from C6‑C30Aryl of (C)3‑C30One of the heteroaryl groups of (a). The compound of the present invention shows excellent device performance and stability when used as a light emitting material in an OLED device or as an electron transport material. The invention also protects the organic electroluminescent device adopting the compound with the general formula.

Description

Imidazole compound and application thereof
Technical Field
The invention relates to an imidazole organic compound which can be used as a main body material or an electron transport material of an organic electroluminescent device; the invention also relates to the application of the compound in an organic electroluminescent device.
Background
Organic electroluminescent diodes (OLEDs) have many advantages such as self-luminescence, wide viewing angle, low power consumption, and high contrast, and thus are widely used in the fields of white light illumination, flexible display, ultra-thin display, and transparent display.
Organic electroluminescent materials have been developed for thirty years since the discovery of OLEDs by professor of chinese scientist dunqing cloud in 1987. The first generation of luminescent materials are fluorescent materials, which can only utilize 25% singlet excitons to emit light, and have low luminous efficiency, directly resulting in high power consumption of OLEDs. Phosphorescent materials can emit light using both singlet and triplet excitons, thus theoretically maximizing 100% internal quantum utilization. Compared with a fluorescent device, the power consumption of the phosphorescent device is obviously reduced, and the efficiency is obviously improved. Phosphorescent materials are therefore also known as second generation luminescent materials. However, the phosphorescent materials generally contain heavy metals (such as iridium and platinum), which are expensive and pollute the environment to some extent, and further development of the phosphorescent materials is limited.
The concept of Thermally Activated Delayed Fluorescence (TADF) was proposed at kyushu university in 2012, and when the difference between the triplet and singlet energy levels of some metal-free organic molecules is small (e.g., less than 0.3eV), triplet excitons can emit light by undergoing an inverse intersystem hopping process back to the singlet state through absorption of ambient heat. Because the singlet excitons and the triplet excitons can be used for emitting light at the same time, the efficiency of the thermal activation delayed fluorescence device is greatly improved, and the efficiency value of part of light colors even exceeds that of the traditional phosphorescence device. TADF materials are also called third generation luminescent materials because they do not contain metals and are therefore relatively low cost. Highly efficient thermally activated delayed fluorescence devices often require TADF dyes to be doped into the host for use in order to reduce quenching of triplet excitons and improve luminous efficiency. The performance of the TADF device is not only related to the performance of the dye itself but also to the performance of the body.
A series of efficient phosphine-oxygen host materials (such as DPEPO, PPF and the like) are reported in documents (Adv.Mater.2017,29,1604856; chem.Sci.2016, 2016,7, 2870-2882; Sci.Adv.2017; 3: e1700904), the materials have good electron transport performance and high triplet state energy level, TADF devices based on the phosphine-oxygen host materials can achieve high luminous efficiency, and the TADF devices are widely applied to blue and green TADF devices.
Figure RE-GDA0001813685520000011
However, devices made of phosphine oxide materials tend to have higher driving voltages. In addition, the phosphine oxide host material has high polarity, which often causes red shift of the spectrum of the TADF device and poor color purity of the device. The poor stability of phosphine oxide materials also leads to extremely low device lifetime, which severely limits further development.
A series of compounds based on alkyl-substituted benzimidazoles, which exhibit excellent device performance as electron transport and injection materials, are reported in patent CN 104364250. Since benzimidazoles are substituted with alkyl groups, their stability is to be improved. Furthermore, in this patent, benzimidazoles are mostly attached to fused rings, the triplet level is low and the application of this series of compounds as TADF hosts is not reported.
Figure RE-GDA0001813685520000021
The TADF material has outstanding advantages in reducing device power consumption and cost as a third generation light-emitting material, and therefore, the development of a highly efficient and stable electronic TADF host material is in urgent need in the industry.
Disclosure of Invention
In order to solve the above-mentioned problems (i.e., poor stability of the electronic host, high driving voltage, short lifetime, etc.), the inventors have studied and designed a series of novel imidazole-based host materials.
The invention provides a compound based on an imidazole group, which has a structure shown as a general formula (1):
Figure RE-GDA0001813685520000022
further preferably, the compounds of the present invention are represented by the general formulae (1-1) to (1-3):
Figure RE-GDA0001813685520000023
in the general formula, Z is S or O;
X1～X10each independently selected from CR3Or N, and X9And X10Can be connected by single bond or not;
R1and R2Each independently represents a single substituent to the maximum permissible substituent or no substituent, and each is independently selected from hydrogen, C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
R3selected from hydrogen, C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
L1and L2Each independently selected from the group consisting of a single bond, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (a); preferably phenyl or pyridyl;
Ar1selected from substituted or unsubstituted imidazole groups;
Ar2selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (a);
when the above groups have substituents, the substituents are respectively and independently selected from halogen, cyano, C1-C10Alkyl or cycloalkyl of, C2-C6Alkenyl or cycloalkenyl of1-C6Alkoxy or thioalkoxy of C6-C30Aryl of (C)3-C30One of the heteroaryl groups of (a).
Further, Ar1More preferably a group of the following formulas (2-1) to (2-19);
Figure RE-GDA0001813685520000031
Figure RE-GDA0001813685520000041
in the above formulas 2-1 to 2-19: y is1-Y4Is CR5Or an N atom, and wherein is CR5The number of the active ingredients is not less than 2.
A1 and A2 are substituents in the above formula which are linked together, A1 and A2 are each independently selected from C11～C30With condensed ring aryl or C3～C30The fused ring heteroaryl of (a); r4To R6Are respectively and independently selected from hydrogen and C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl; wherein "-" indicates the attachment site at any position on the delineated loop structure that is capable of bonding.
Further, Ar1More preferred are the following groups:
Figure RE-GDA0001813685520000051
in the above formulae, R7And R8Are respectively and independently selected from hydrogen and C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl; denotes the attachment site, "-" denotes the attachment site located at any position on the delineated loop structure that is capable of bonding.
Further, Ar2Preferred are acceptor groups as follows: a substituted or unsubstituted imidazole group, a substituted or unsubstituted pyrimidine group, a substituted or unsubstituted pyridine group, a substituted or unsubstituted quinazoline group, a substituted or unsubstituted isoquinazoline group, a substituted or unsubstituted benzopyrazine group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted carboline group, a substituted or unsubstituted benzonitrile group.
Further, Ar2More preferred are the following groups:
Figure RE-GDA0001813685520000061
in the above formulae, R9And R10Are respectively and independently selected from hydrogen and C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl; denotes the attachment site, "-" denotes the attachment site located at any position on the delineated loop structure that is capable of bonding.
Further, the compounds of the general formula (1) of the present invention can be represented by specific compounds M1-M108.
Figure RE-GDA0001813685520000062
Figure RE-GDA0001813685520000071
Figure RE-GDA0001813685520000081
Figure RE-GDA0001813685520000091
The invention also provides, as another aspect thereof, the use of a compound as described above in an organic electroluminescent device. In particular, the material can be used as a luminescent host material or an electron transport layer material in an organic electroluminescent device
As still another aspect of the present invention, the present invention also provides an organic electroluminescent device comprising a first electrode, a second electrode and a plurality of organic layers interposed between the first electrode and the second electrode, characterized in that the organic layers contain the organic compound of the above general formula (1) or general formula (1-1).
The research shows that the compound with the general formula has good film-forming property and is suitable for being used as a luminescent main material and an electron transmission material. The principle is not clear, and it is assumed that the following reasons may be: the compound shown in the general formula (1) has imidazole groups, so that the material has good electron transmission performance, moderate polarity and stable structure.
When the material is used as a main material or an electron transport layer material of an organic electroluminescent device, compared with the prior art, the material can further reduce the starting voltage, improve the light color, and improve the efficiency and the service life of the device.
The technical scheme of the invention has the following advantages:
(1) the imidazole groups have good electron transmission capability, and can effectively reduce injection energy barrier, balance carrier transmission and reduce starting voltage when used as a main material.
(2) When O, S and the like are taken as bridging centers, the conjugation degree of molecules can be effectively reduced, the high triplet state energy level of related materials can be maintained, and the material can be further taken as a host material of common luminescent dyes.
(3) The imidazole connecting site is preferably easy to modify at the 1-position and the 2-position, so that the material system is convenient to expand. The combination of Ar1 and Ar2 can improve the film forming property of the polymer and improve the film forming quality.
Detailed Description
The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.
Compounds of synthetic methods not mentioned in the present invention are all starting products obtained commercially. Solvents and reagents used in the present invention, such as methylene chloride, petroleum ether, ethanol, tetrahydrofuran, N-dimethylacetamide, anhydrous magnesium sulfate, carbazole, benzimidazole and the like, can be purchased from domestic chemical product markets, such as reagents from national drug group, TCI, shanghai Bidi medicine, carbofuran, and the like. In addition, they can be synthesized by a known method by those skilled in the art.
The analytical testing of intermediates and compounds in the present invention uses an abciex mass spectrometer (4000QTRAP) and a siemens analyzer.
The synthesis of the compounds of the present invention is briefly described below.
Synthesis example 1: synthesis of M1
Figure RE-GDA0001813685520000101
Synthesis of intermediate M1-1:
12.2g (100mmol) of o-hydroxybenzaldehyde and 18.4g (100mmol) of o-bromobenzaldehyde are added into a new oven-dried 1000mL double-neck flask, 20.7g (150mmol) of anhydrous potassium carbonate and 600mL of dry N, N-Dimethylformamide (DMF) are added under the protection of nitrogen, stirred for 5 hours at room temperature and heated to 130 ℃ for further reaction for 10 hours. After the reaction, the temperature is reduced to room temperature, the solvent in the reaction system is distilled off under reduced pressure, and the crude product is dissolved in 500mL of dichloromethane and washed with a large amount of water. The organic phase was dried over anhydrous sodium sulfate and concentrated, dichloromethane: column chromatography with petroleum ether 1:1 as eluent gave 20g of an off-white solid in 88% yield. The mass of the molecules determined by mass spectrometry was: 226.02 (calculated value: 226.06); theoretical element content (%) C14H10O3: c, 74.33; h, 4.46; and O, 21.22. Measured elemental content (%): c, 74.26; h, 4.48. The above analysis results show that the obtained product is the expected product.
Synthesis of M1:
a dry 500mL single neck flask was charged with 2.3g (10mmol) of the M1-1 intermediate from the first step, 31g (300mmol) of sodium bisulfite, and 65mL deionized water. After stirring at room temperature for 5 hours, 3.68g (20mmol) of o-aminodiphenylamine and 135mL of anhydrous ethanol were added thereto, and after three times of nitrogen substitution, the mixture was refluxed for 24 hours. After the completion of the reaction, the solvent in the reaction system was removed by distillation under reduced pressure. Extraction with dichloromethane, washing with a large amount of water, combining organic phases and performing column chromatography. Column chromatography with dichloromethane as eluent gave a large amount of white solid, 5.1g, 93% yield. The molecular masses determined by mass spectrometry were: 554.20 (calculated value: 554.21); theoretical element content (%) C38H26N4O: c, 82.29; h, 4.73; n, 4.73; o, 2.88. Measured elemental content (%): c, 82.30; h, 4.76; and N, 4.72. The above analysis results show that the obtained product is the expected product.
Synthesis example 2: synthesis of M2
Figure RE-GDA0001813685520000111
Synthesis of intermediate M2-1:
12.2g (100mmol) of o-hydroxybenzaldehyde and 32.1g (100mmol) of 9- (2-bromophenyl) -9H-carbazole are added into a new dried 1000mL double-neck bottle, 20.7g (150mmol) of anhydrous potassium carbonate and 600mL of dried N, N-Dimethylformamide (DMF) are added under the protection of nitrogen, stirred for 5 hours at room temperature and heated to 130 ℃ for continuous reaction for 10 hours. After the reaction, the temperature is reduced to room temperature, the solvent in the reaction system is distilled off under reduced pressure, and the crude product is dissolved in 500mL of dichloromethane and washed with a large amount of water. The organic phase was dried over anhydrous sodium sulfate and concentrated, dichloromethane: column chromatography with petroleum ether 1:3 as eluent gave 35g of an off-white solid in 96% yield. The mass of the molecules determined by mass spectrometry was: 363.05 (calculated value: 363.13); theoretical element content (%) C25H17NO2: c, 82.63; h, 4.72; n, 3.85; and O, 8.80. Measured elemental content (%): c, 82.62; h, 4.74; n, 3.84. The above analysis results show that the obtained product is the expected product.
Synthesis of M2:
a dry 500mL single neck flask was charged with 3.6g (10mmol) of the M2-1 intermediate from the first step, 15.5g (150mmol) of sodium bisulfite, and 35mL of deionized water. After stirring at room temperature for 5 hours, 1.84g (10mmol) of o-aminodiphenylamine and 70mL of anhydrous ethanol were added thereto, and after three times of nitrogen substitution, the mixture was refluxed for 24 hours. After the completion of the reaction, the solvent in the reaction system was removed by distillation under reduced pressure. Extraction with dichloromethane, washing with a large amount of water, combining organic phases and performing column chromatography. Column chromatography with dichloromethane as eluent gave a large amount of white solid, 5.0g, 95% yield. The molecular masses determined by mass spectrometry were: 527.22 (calculated value: 527.20); theoretical element content (%) C37H25N3O: c, 84.23; h, 4.78; n, 7.96; and O, 3.03. Measured elemental content (%): c, 84.25; h, 4.76; and N, 7.80. The above analysis results show that the obtained product is the expected product.
Synthesis example 3: synthesis of M46
Figure RE-GDA0001813685520000121
Synthesis of intermediate M46-1:
32.4g (100mmol) of 4, 6-dibromodibenzothiophene and 112.8g (300mmol) of 2-formylphenylboronic acid are introduced into a fresh, oven-dried 3000mL two-necked flask, under nitrogen, 62.1g (450mmol) of anhydrous potassium carbonate, 6.9g (6mmol) of tetratriphenylphosphine palladium and also 225mL of water and 1500mL of 1, 4-dioxane. After the reaction, the temperature is reduced to room temperature, the solvent in the reaction system is distilled off under reduced pressure, and the crude product is dissolved in 500mL of dichloromethane and washed with a large amount of water. The organic phase was dried over anhydrous sodium sulfate and concentrated, dichloromethane: column chromatography with petroleum ether 1:1 as eluent gave 30g of off-white solid in 80% yield. The mass of the molecules determined by mass spectrometry was: 376.05 (calculated: 376.11); theoretical element content (%) C26H16O3: c, 82.96; h, 4.28; o, 12.75. Measured elemental content (%): c, 82.95; h, 4.30. The above analysis results show that the obtained product is the expected product.
Synthesis of M46:
a dry 500mL single neck flask was charged with 3.8g (10mmol) of the M46-1 intermediate from the first step, 31g (300mmol) of sodium bisulfite, and 65mL deionized water. After stirring at room temperature for 5 hours, 3.68g (20mmol) of o-aminodiphenylamine and 135mL of anhydrous ethanol were added thereto, and after three times of nitrogen substitution, the mixture was refluxed for 24 hours. After the completion of the reaction, the solvent in the reaction system was removed by distillation under reduced pressure. Extraction with dichloromethane, washing with a large amount of water, combining organic phases and performing column chromatography. Column chromatography with dichloromethane as eluent gave a large amount of white solid, 5.5g, 78% yield. The molecular masses determined by mass spectrometry were: 704.20 (calculated value: 704.26); theoretical element content (%) C50H32N4O: c, 85.20; h, 4.58; n, 7.95; o, 2.27. Measured elemental content (%): c, 85.20; h, 4.56; and N, 7.97. The above analysis results show that the obtained product is the expected product.
Synthesis example 4: synthesis of M70
Figure RE-GDA0001813685520000122
Synthesis of intermediate M70-1:
39.6g (100mmol) of 9- (3-bromophenyl) -9-phenyl-9H-fluorene and 12.2g (100mmol) of o-hydroxybenzaldehyde are introduced into a freshly dried 1000mL two-necked flask, 20.7g (150mmol) of anhydrous potassium carbonate and 600mL of dried N, N-Dimethylformamide (DMF) are added under nitrogen, stirred for 5 hours at room temperature and then heated to 130 ℃ for further reaction for 10 hours. After the reaction, the temperature is reduced to room temperature, the solvent in the reaction system is distilled off under reduced pressure, and the crude product is dissolved in 500mL of dichloromethane and washed with a large amount of water. The organic phase was dried over anhydrous sodium sulfate and concentrated, dichloromethane: column chromatography with petroleum ether 1:3 as eluent gave 40g of an off-white solid in 91% yield. The mass of the molecules determined by mass spectrometry was: 438.20 (calculated value: 438.16); theoretical element content (%) C32H22O2: c, 87.65; h, 5.06; and O, 7.30. Measured elemental content (%): c, 87.62; h, 5.04. The above analysis results show that the obtained product is the expected product.
Synthesis of M70:
a dry 500mL single neck flask was charged with 4.4g (10mmol) of the M70-1 intermediate from the first step, 15.5g (150mmol) of sodium bisulfite, and 35mL of deionized water. After stirring at room temperature for 5 hours, 1.84g (10mmol) of o-aminodiphenylamine and 70mL of anhydrous ethanol were added thereto, and after three times of nitrogen substitution, the mixture was refluxed for 24 hours. After the completion of the reaction, the solvent in the reaction system was removed by distillation under reduced pressure. Extraction with dichloromethane, washing with a large amount of water, combining organic phases and performing column chromatography. Column chromatography with dichloromethane as eluent gave a large amount of white solid, 5.5g, 91% yield. The mass of the molecular ions determined by mass spectrometry was: 602.26 (calculated value: 602.24); theoretical element content (%) C44H30N2O: c, 87.68; h, 5.02; n, 4.65; o, 2.65. Measured elemental content (%): c, 87.65; h, 5.06; and N, 4.64. The above analysis results show that the obtained product is the expected product.
Synthesis example 5: synthesis of M37
Synthesis method according to M1In the same procedure, 2-mercaptobenzaldehyde was used in place of o-hydroxybenzaldehyde to give a white solid, 4.5g, yield 79%. The molecular masses determined by mass spectrometry were: 570.20 (calculated value: 570.19); theoretical element content (%) C38H26N4S: c, 79.97; h, 4.59; n, 9.82; and S, 5.62. Measured elemental content (%): c, 79.95; h, 4.60; n, 9.81; and S, 5.63. The above analysis results show that the obtained product is the expected product.
Synthesis example 6: synthesis of M38
According to the synthesis method of M2, the same procedure was followed, using 2-mercaptobenzaldehyde instead of o-hydroxybenzaldehyde, to obtain a white solid, 4.6g, yield 85%. The molecular masses determined by mass spectrometry were: 543.19 (calculated value: 543.18); theoretical element content (%) C37H25N3S: c, 81.74; h, 4.64; n, 7.73; and S, 5.90. Measured elemental content (%): c, 81.74; h, 4.62; n, 7.71; and S, 5.89. The above analysis results show that the obtained product is the expected product.
Synthesis example 7: synthesis of M48
According to the procedure for the synthesis of M2, in the same manner as above, 4, 6-dibromodibenzothiophene was used in place of 4, 6-dibromodibenzofuran to carry out the reaction, whereby a white solid (5.7 g) was obtained in a yield of 79%. The molecular masses determined by mass spectrometry were: 720.21 (calculated value: 720.23); theoretical element content (%) C50H32N4S: c, 83.31; h, 4.47; n, 7.77; and S, 4.45. Measured elemental content (%): c, 83.34; h, 4.45; n, 7.72; and S, 4.48. The above analysis results show that the obtained product is the expected product.
Device embodiments
Detailed description of the preferred embodiments
The OLED includes first and second electrodes, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), or any combination thereof may be used. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-34; or any combination thereof.
Figure RE-GDA0001813685520000141
Figure RE-GDA0001813685520000151
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI1-HI3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI1-HI3 described below.
Figure RE-GDA0001813685520000161
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
According to different technologies, the luminescent layer material can be different materials such as fluorescent electroluminescent material, phosphorescent electroluminescent material, thermal activation delayed fluorescent luminescent material, and the like. In an OLED device, a single light emitting technology may be used, or a combination of a plurality of different light emitting technologies may be used. These technically classified different luminescent materials may emit light of the same color or of different colors.
In one aspect of the invention, the light-emitting layer employs a thermally activated delayed fluorescence emission technique. The fluorescent dopant of the light-emitting layer can be selected from, but is not limited to, one or more of TDE1-TDE39 listed below.
Figure RE-GDA0001813685520000162
Figure RE-GDA0001813685520000171
Figure RE-GDA0001813685520000181
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
In one aspect of the invention, the electron transport layer material may be selected from, but is not limited to, the combination of one or more of ET-1 through ET-57 listed below.
Figure RE-GDA0001813685520000182
Figure RE-GDA0001813685520000191
Figure RE-GDA0001813685520000201
Figure RE-GDA0001813685520000211
An electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer materials including, but not limited to, combinations of one or more of the following.
LiQ,LiF,NaCl,CsF,Li2O,Cs2CO3,BaO,Na,Li,Ca。
The light-emitting layer functional layer of the present invention should further contain the following compounds.
Figure RE-GDA0001813685520000212
Device example 1
The glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to obtain HI-3 serving as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
evaporating HT-29 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
a luminescent layer of the device is evaporated in vacuum on the hole transport layer, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material M1 is adjusted to be 0.1nm/s by using a multi-source co-evaporation method, the evaporation rate of the dye TDE-28 is set in a proportion of 10%, and the total film thickness of the evaporation is 30 nm;
vacuum evaporating an electron transport layer material ET-53 of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
Device example 2
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M7, and the dye material remained TDE-28, and the rest remained the same.
Device example 3
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M8, and the dye material remained TDE-28, and the rest remained the same.
Device example 4
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M32, and the dye material remained TDE-28, and the rest remained the same.
Device example 5
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M33, and the dye material remained TDE-28, and the rest remained the same.
Device example 6
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M40, and the dye material remained TDE-28, and the rest remained the same.
Device example 7
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M67, and the dye material remained TDE-28, and the rest remained the same.
Device example 8
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M71, and the dye material remained TDE-28, and the rest remained the same.
Device example 9
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M78, and the dye material remained TDE-28, and the rest remained the same.
Device example 10
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M79, and the dye material remained TDE-28, and the rest remained the same.
Device example 11
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to M80, and the dye material remained TDE-28, and the rest remained the same.
Comparative example 1
The fabrication process was substantially the same as that of device example 1, except that the Host material of the light-emitting layer was changed to Host-1, the dye material was still TDE-28, and the rest remained the same.
Comparative example 2
The fabrication process was substantially the same as that of device example 1, except that the Host material of the light emitting layer was changed to Host-2, the dye material was still TDE-28, and the rest remained the same.
Comparative example 3
The fabrication process was substantially the same as that of device example 1, except that the host material of the light emitting layer was changed to DPEPO, and the dye material was still TDE-28, and the rest remained the same.
Comparative example 4
The fabrication process was substantially the same as that of device example 1, except that the host material of the light-emitting layer was changed to PPF, and the dye material was still TDE-28, the rest remained the same.
Device example 12
The fabrication process is substantially the same as that of device example 1, except that the electron transport layer material is changed to M7, the host material is changed to 4, 4-bis (9-carbazole) biphenyl CBP, the dye material is still TDE-28, and the others remain unchanged.
Device example 13
The fabrication process is substantially the same as that of device example 1, except that the electron transport layer material is changed to M12, the host material is changed to 4, 4-bis (9-carbazole) biphenyl CBP, the dye material is still TDE-28, and the others remain unchanged.
Comparative device example 5
The fabrication process is substantially the same as that of device example 1, except that the electron transport layer material is changed to Host-1, the Host material is changed to 4, 4-bis (9-carbazole) biphenyl CBP, the dye material is still TDE-28, and the others remain unchanged.
Comparative device example 6
The fabrication process is substantially the same as that of device example 1, except that the electron transport layer material is changed to DPEPO, the host material is changed to 4, 4-bis (9-carbazole) biphenyl CBP, the dye material is still TDE-28, and the rest remains unchanged.
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
using digital source table and brightness under the same brightnessThe turn-on voltage and the lifetime of the organic electroluminescent devices prepared in examples 1 to 8 and comparative examples 1 to 4 were measured. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1cd/m2The voltage is the starting voltage, and the current density at the moment is measured; the ratio of the brightness to the current density is the current efficiency, and the external quantum efficiency is calculated according to the spectral data; the life test of LT95 is as follows: using a luminance meter at 10000cd/m2The luminance drop of the organic electroluminescent device was measured to be 9500cd/m by maintaining a constant current at luminance2Time in hours.
The properties of the organic electroluminescent device prepared according to the present invention are shown in tables 1 and 2 below.
Table 1:
Figure RE-GDA0001813685520000241
Figure RE-GDA0001813685520000251
TABLE 2
Figure RE-GDA0001813685520000252
From the data in tables 1 and 2 above, it can be seen that:
as can be seen from a comparison of the individual examples with the individual comparative examples, the compounds synthesized according to the invention, when used as host materials or as electron transport layer materials in OLED devices, have superior performance, both in terms of maximum brightness and maximum external quantum efficiency, compared to the performance of known OLED devices prepared using materials from the prior art, and at the same time have very good performance in terms of lifetime, and the ignition voltage is relatively lower.
The results show that when the novel organic material is used for the main body of the organic electroluminescent device, the novel organic material can effectively reduce the take-off and landing voltage, improve the current efficiency and have good stability.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.

Claims (10)

1. A compound of the formula (1):
Figure FDA0001790704530000011
in formula (1): z is S or O;
X1～X10each independently selected from CR3Or N, and X9And X10The dotted line between them represents X9And X10Can be connected by single bond or not;
R1and R2Each independently represents a single substituent to the maximum permissible substituent or no substituent, and each is independently selected from hydrogen, C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
R3selected from hydrogen, C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
L1and L2Each independently selected from the group consisting of a single bond, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (a);
Ar1selected from substituted or unsubstituted imidazole groups;
Ar2independently selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30One of the heteroaryl groups of (a);
when the above groups have substituents, the substituents are each independentlySelected from halogen, cyano, C1-C10Alkyl or cycloalkyl of, C2-C6Alkenyl or cycloalkenyl of1-C6Alkoxy or thioalkoxy of C6-C30Aryl of (C)3-C30One of the heteroaryl groups of (a).
2. The general formula compound according to claim 1, wherein formula (1) is represented by the following formulae (1-1) to (1-3):
Figure FDA0001790704530000012
Figure FDA0001790704530000021
z, X in formulae (1-1) to (1-3)1～X10、R1And R2、L1And L2、Ar1And Ar2Are the same as defined in formula (1).
3. A compound of general formula (la) according to claim 1 or 2, wherein in formula (1), formula (1-1) to formula (1-3), L1And L2Each independently selected from phenyl or pyridyl.
4. The compound of general formula (la) according to claim 1 or 2, wherein in formula (1), formula (1-1) to formula (1-3), Ar1A group selected from the following formulas (2-1) to (2-19);
Figure FDA0001790704530000022
Figure FDA0001790704530000031
in the above formulas 2-1 to 2-19: y is1-Y4Is CR6Or an N atom, and wherein is CR6The number of the active ingredients is not less than 2;
a1 and A2 are substituents in the above formula which are linked together, A1 and A2 are each independently selected from C11～C30With condensed ring aryl or C3～C30The fused ring heteroaryl of (a);
R4to R6Are respectively and independently selected from hydrogen and C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
wherein "-" indicates the attachment site at any position on the delineated loop structure that is capable of bonding.
5. A compound of general formula (la) according to claim 1 or 2, wherein formula (1), formula (1-1) to formula (1-3), Ar1A group selected from:
Figure FDA0001790704530000041
in the above formulae, R7And R8Are respectively and independently selected from hydrogen and C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
denotes the attachment site, "-" denotes the attachment site located at any position on the delineated loop structure that is capable of bonding.
6. The compound of general formula (la) according to claim 1 or 2, wherein in formula (1), formula (1-1) to formula (1-3), Ar2Preferred are the following groups: substituted or unsubstituted imidazole group, substituted or unsubstituted pyrimidine group, substituted or unsubstituted pyridine group, substituted or unsubstituted quinazoline group, substituted or unsubstituted isoquinazoline group, substituted or unsubstituted benzopyrazine group, substituted or unsubstituted carbazole group, substituted or unsubstituted fluorene group, substituted or unsubstituted carboline group, substituted or unsubstituted fluorene groupA substituted benzonitrile group.
7. The compound of general formula (la) according to claim 1 or 2, wherein in formula (1), formula (1-1) to formula (1-3), Ar2Preferred are the following groups:
Figure FDA0001790704530000051
in the above formulae, R9And R10Are respectively and independently selected from hydrogen and C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
denotes the attachment site, "-" denotes the attachment site located at any position on the delineated loop structure that is capable of bonding.
8. A compound of formula (la) according to claim 1 or 2, selected from the compounds of the following specific structures:
Figure FDA0001790704530000052
Figure FDA0001790704530000061
Figure FDA0001790704530000071
Figure FDA0001790704530000081
Figure FDA0001790704530000091
9. use of a compound of general formula (la) according to claim 1 or 2 as a light-emitting host material or as an electron transport material in an organic electroluminescent device.
10. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound of formula (la) according to any one of claims 1 or 2.
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KR20200038876A (en) * 2018-10-04 2020-04-14 주식회사 엘지화학 Compound and organic light emitting device comprising the same
WO2021235820A1 (en) * 2020-05-20 2021-11-25 엘티소재주식회사 Organic light-emitting device
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