CN107417668B - Organic compound based on azabenzene and benzimidazole and application of organic compound to OLED - Google Patents

Organic compound based on azabenzene and benzimidazole and application of organic compound to OLED Download PDF

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CN107417668B
CN107417668B CN201710330212.XA CN201710330212A CN107417668B CN 107417668 B CN107417668 B CN 107417668B CN 201710330212 A CN201710330212 A CN 201710330212A CN 107417668 B CN107417668 B CN 107417668B
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张兆超
李崇
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention relates to an organic compound taking aza-benzene and benzimidazole as cores and application thereof in OLED devices, wherein the compound has higher glass transition temperature and molecular thermal stability; the absorption in the visible light field is low, the refractive index is high, and the light extraction efficiency of the OLED device can be effectively improved after the light extraction film is applied to a CPL layer of the OLED device; the compound also has a deep HOMO energy level and high electron mobility, can be used as a hole blocking/electron transport layer material of an OLED device, and can effectively block holes or energy from being transferred from a light emitting layer to one side of an electron layer, so that the recombination efficiency of the holes and electrons in the light emitting layer is improved, and the light emitting efficiency and the service life of the OLED device are improved.

Description

Organic compound based on azabenzene and benzimidazole and application of organic compound to OLED
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound taking aza-benzene and benzimidazole as cores and application thereof in an OLED (organic light emitting diode).
Background
The Organic Light Emission Diodes (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device is like a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and various different functional materials are mutually overlapped together according to purposes to form the OLED light-emitting device. When voltage is applied to electrodes at two ends of the OLED light-emitting device and positive and negative charges in the organic layer functional material film layer are acted through an electric field, the positive and negative charges are further compounded in the light-emitting layer, and OLED electroluminescence is generated.
Currently, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and further will be expanded to the large-size application fields of televisions and the like. However, since there is a great gap between the external quantum efficiency and the internal quantum efficiency of the OLED, the development of the OLED is greatly restricted. Therefore, how to improve the light extraction efficiency of the OLED becomes a hot point of research. Total reflection occurs at the interface between the ITO thin film and the glass substrate and at the interface between the glass substrate and the air, the light emitted to the front external space of the OLED device accounts for about 20% of the total amount of the organic material thin film EL, and the remaining about 80% of the light is mainly confined in the organic material thin film, the ITO thin film and the glass substrate in the form of guided waves. It can be seen that the light extraction efficiency of the conventional OLED device is low (about 20%), which severely restricts the development and application of the OLED. How to reduce the total reflection effect in the OLED device and improve the ratio of light coupled to the forward external space of the device (light extraction efficiency) has attracted much attention.
Currently, an important method for improving the external quantum efficiency of the OLED is to form structures such as folds, photonic crystals, microlens arrays (MLA), and the addition of surface coatings on the light-emitting surface of the substrate. The first two structures can influence the radiation spectrum angle distribution of the OLED, the third structure is complex in manufacturing process, the surface covering layer is simple in process, the luminous efficiency is improved by more than 30%, and people pay particular attention to the structure. According to the optical principle, when light is transmitted through the material with the refractive index n1To a refractive index of n2When (n) is1＞n2) Only in arcsin (n)2/n1) Can be incident within an angle of n2The absorbance B can be calculated by the following formula:
Figure BDA0001292279300000011
let n1＝nOrganic materials for OLEDs in general＝1.70，n2＝nGlassWhen 1.46, 2B is 0.49. Assuming that the light propagating outward is totally reflected by the metal electrode, only 51% of the light can be guided by the high refractive index organic film and the ITO layer, and the transmittance of the light when it is emitted from the glass substrate to the air can be calculated as well. So that only about 17% of the light emitted from the organic layer is visible to humans when it exits the exterior of the device. Therefore, in view of the current situation that the light extraction efficiency of the OLED device is low, a CPL layer, that is, a light extraction material needs to be added in the device structure, and according to the principles of optical absorption and refraction, the refractive index of the surface covering layer material should be as high as possible.
Current research into improving the performance of OLED light emitting devices includes: the driving voltage of the device is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the like. In order to realize the continuous improvement of the performance of the OLED device, not only the innovation of the structure and the manufacturing process of the OLED device but also the continuous research and innovation of the photoelectric functional material of the OLED are required to create the functional material of the OLED with higher performance.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides an organic compound with an aza-benzene and a benzimidazole as the core and its application in an organic electroluminescent device. The compound contains an aza-benzene and benzimidazole structure, has higher glass transition temperature and molecular thermal stability, low absorption and high refractive index in the field of visible light, and can effectively improve the light extraction efficiency of an OLED device after being applied to a CPL layer of the OLED device; and because the azabenzene and the benzimidazole have deep HOMO energy levels and wide forbidden band (Eg) energy levels, the azabenzene and the benzimidazole can be used as a hole blocking/electron transport layer material of an OLED device, and can block holes from being transferred from a light emitting layer to one side of an electron layer, so that the recombination degree of the holes and electrons in the light emitting layer is improved, and the light emitting efficiency and the service life of the OLED device are improved.
The technical scheme of the invention is as follows:
the applicant provides an organic compound taking azabenzene and benzimidazole as cores, and the structure is shown as a general formula (1):
Figure BDA0001292279300000021
in the general formula (1), X1～X6Independently represent N atom or C atom, and the number of N atoms is 1 or 2;
z is the number 1 or 2; m and n are respectively independent and represent a number 0 or 1; and m + n + z is 3;
in the general formula (1), Ar1、Ar2、Ar3Are each independently represented by C1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, a tritium atom substituted or unsubstituted phenyl; c1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, a tritium atom substituted or unsubstituted naphthyl group; c1-10Straight or branched chain alkyl, halogen atom, protium, deuterium, tritium atom substituted or unsubstituted biphenylyl; a terphenyl group; anthracenyl or C1-10One of linear chain or branched alkyl, halogen atom, protium, deuterium, tritium atom substituted or unsubstituted pyridyl; wherein Ar is2、Ar3Can also independently represent a single bond;
Ar1、Ar2、Ar3may be the same or different;
in the general formula (1), Ar1Can also be represented by a structure shown in a general formula (2), a general formula (3), a general formula (4) or a general formula (5);
Figure BDA0001292279300000031
in the general formula (2), each Y independently represents N or C, and at least one Y represents N;
in the general formula (3), each Z independently represents N or C, and at least one Z represents N;
in the general formulae (4) and (5), R3、R4、R5Are each independently represented by C1-10Straight or branched chain alkyl, halogen atom, protium, deuterium, tritium atom substituted or unsubstituted phenyl；C1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, a tritium atom substituted or unsubstituted naphthyl group; c1-10Straight or branched chain alkyl, halogen atom, protium, deuterium, tritium atom substituted or unsubstituted biphenylyl; a terphenyl group; an anthracene group; c1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, tritium atom-substituted or unsubstituted pyridyl group; dibenzofuran; dibenzothiophene; one of 9, 9-dimethylfluorene or N-phenylcarbazole;
R3、R4、R5may be the same or different;
in the general formula (1), R1、R2Each independently represents a structure represented by general formula (6), general formula (7) or general formula (8):
Figure BDA0001292279300000032
wherein Ar is4、Ar5、Ar6、Ar7Are each independently represented by C1-10Straight or branched alkyl, phenyl substituted or unsubstituted by halogen atoms, C1-10Straight or branched alkyl, naphthyl substituted or unsubstituted by halogen atoms, C1-10A straight or branched alkyl group, a halogen atom-substituted or unsubstituted biphenylyl group, a terphenylyl group, or C1-10One of a straight-chain or branched alkyl group, a halogen atom substituted or unsubstituted pyridyl group;
R1、R2may be the same or different.
Preferably, the specific structural formula of the organic compound is as follows:
Figure BDA0001292279300000033
Figure BDA0001292279300000041
Figure BDA0001292279300000051
Figure BDA0001292279300000061
Figure BDA0001292279300000071
Figure BDA0001292279300000081
Figure BDA0001292279300000091
Figure BDA0001292279300000101
Figure BDA0001292279300000111
Figure BDA0001292279300000121
Figure BDA0001292279300000122
any one of them.
The applicant also provides a preparation method of the organic compound, and a reaction equation generated in the preparation process is as follows:
the first step of reaction process:
(1) when Ar is1And the azabenzene is bonded by a C-C bond,
Figure BDA0001292279300000131
the specific reaction process is as follows:
weighing raw material A and dissolving in N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and mixing
Figure BDA0001292279300000132
And palladium acetate, stirring the mixture, adding a potassium phosphate aqueous solution, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120 ℃ and 150 ℃ for 5-15 hours; after the reaction is finished, cooling, adding water, filtering the mixture, drying the mixture in a vacuum drying oven, and purifying the obtained residue by a silica gel column to obtain a compound intermediate I;
the raw materials A and
Figure BDA0001292279300000133
the molar ratio of (A) to (B) is 1: 1.0-3, Pd (OAc)2The molar ratio of the raw material A to the raw material A is 0.001-0.04: 1, and K3PO4The molar ratio of the DMF to the raw material A is 1.0-4.0: 1, and the ratio of the amount of the DMF to the amount of the raw material A is 1g: 10-30 ml;
(2) when Ar is1When connected to the azabenzene by a C-N bond,
Figure BDA0001292279300000134
the specific reaction process is as follows:
weighing raw materials A and Ar1-H, dissolved with toluene; then adding Pd2(dba)3Tri-tert-butylphosphine, sodium tert-butoxide; reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃ in an inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate I;
the raw materials A and Ar1The molar ratio of-H to Pd is 1: 1.0-32(dba)3The molar ratio of the tert-butyl phosphine to the raw material A is 0.006-0.04: 1, the molar ratio of the tri-tert-butyl phosphine to the raw material A is 0.006-0.04: 1, and the molar ratio of the sodium tert-butoxide to the raw material A is 2.0-3.0: 1;
the second step of reaction process:
Figure BDA0001292279300000141
weighing intermediate I, dissolving in N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and mixing
Figure BDA0001292279300000142
And palladium acetate, stirring the mixture, adding a potassium phosphate aqueous solution, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120 ℃ and 150 ℃ for 10-24 hours; after the reaction is finished, cooling, adding water, filtering the mixture, drying the mixture in a vacuum drying oven, and purifying the obtained residue by a silica gel column to obtain a compound intermediate II;
the intermediates I and
Figure BDA0001292279300000143
the molar ratio of (A) is 1: 1.0-3, Pd (OAc)2The molar ratio of the intermediate I to the intermediate I is 0.001-0.04: 1, K3PO4The molar ratio of the intermediate I to the DMF is 1.0-4.0: 1, and the ratio of the amount of DMF to the amount of intermediate I is 1g: 10-40 ml;
the third step is a reaction process:
Figure BDA0001292279300000144
weighing intermediate II, dissolving in N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and mixing
Figure BDA0001292279300000145
And palladium acetate, stirring the mixture, adding a potassium phosphate aqueous solution, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120 ℃ and 150 ℃ for 10-24 hours; after the reaction is finished, cooling, adding water, filtering the mixture, drying the mixture in a vacuum drying oven, and purifying the obtained residue through a silica gel column to obtain a target compound;
said intermediate II with
Figure BDA0001292279300000146
The molar ratio of (A) is 1: 1.0-3, Pd (OAc)2The molar ratio of the intermediate II to the intermediate II is 0.001-0.04: 1, and K3PO4The molar ratio of the intermediate II to the intermediate II is 1.0-4.0: 1, and the ratio of the amount of DMF to the amount of intermediate II is 1g: 15-50 ml.
The organic compound taking the azabenzene and the benzimidazole as the cores is used for preparing the organic electroluminescent device. The applicant also provides a lighting or display element comprising said organic electroluminescent device.
The applicant also provides an organic electroluminescent device comprising at least one functional layer containing said organic compounds with an azabenzene and benzimidazole as core.
The organic electroluminescent device comprises a hole blocking layer/an electron transport layer, wherein the hole blocking layer/the electron transport layer contains the organic compound taking the azabenzene and the benzimidazole as the cores.
The applicant also provides an organic electroluminescent device comprising a CPL layer containing said organic compounds with an azabenzene and benzimidazole as core.
The beneficial technical effects of the invention are as follows:
the structure of the organic compound contains two rigid groups of aza-benzene and benzimidazole, so that the structural stability of the material is improved; the material contains benzimidazole groups with strong electron property in a spatial structure, and 3 groups are mutually crossed and separated, so that free rotation of the groups is avoided, the material has higher density, and higher refractive index is obtained; meanwhile, the material of the invention has high Tg temperature; the evaporation temperature of the material in a vacuum state is generally less than 350 ℃, so that the material is not decomposed for a long time in mass production, and the influence of heat radiation of the evaporation temperature on the deformation of evaporation MASK is reduced.
The material disclosed by the invention is applied to a CPL layer in an OLED device, does not participate in electron and hole transmission of the device, and has very high requirements on the thermal stability, film crystallinity and light transmission (high refractive index) of the material. As analyzed above, the azabenzene and the benzimidazole are rigid groups, so that the stability of the material is improved; the high Tg ensures that the material does not crystallize in a film state; the low evaporation temperature is the premise that the material can be applied to mass production; the high refractive index is the most important factor for the material of the present invention to be applied to the CPL layer.
The material has deep HOMO energy level and high electron mobility, and can effectively prevent holes or energy from being transferred from the light-emitting layer to one side of the electron layer, so that the recombination efficiency of the holes and electrons in the light-emitting layer is improved, the light-emitting efficiency of an OLED device is improved, and the service life of the OLED device is prolonged. After the invention is applied to the CPL layer of the OLED device, the light extraction efficiency of the OLED device can be effectively improved. In conclusion, the compound disclosed by the invention has good application effect and industrialization prospect in OLED light-emitting devices.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention; the OLED device comprises an OLED device substrate 1, an OLED device substrate 2, an anode layer 3, a hole injection layer 4, a hole transport layer 5, a light emitting layer 6, a hole blocking layer/electron transport layer 7, an electron injection layer 8, a cathode layer 9 and a CPL layer.
FIG. 2 is a graph of refractive index measurements for compound 76; FIG. 3 is a comparative graph of film acceleration experiments for compound 70 and known material CBP.
Detailed Description
Example 1: synthesis of intermediate I
When the aza-benzene and Ar1When they are linked by a C-C bond,
Figure BDA0001292279300000151
weighing Ar under nitrogen atmosphere1Dissolving bromide in Tetrahydrofuran (THF), adding bis (pinacolato) diboron, (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 70-90 ℃ for 5-10 hours; after the reaction was complete, water was added to cool, and the mixture was filtered and dried in a vacuum oven. Separating and purifying the obtained residue by a silica gel column to obtain Ar1Boronic acid pinacol ester of (a);
Figure BDA0001292279300000161
weighing raw material A and dissolving in N, N-Dimethylformamide (DMF) under nitrogen atmosphere, and mixing
Figure BDA0001292279300000162
And palladium acetate, stirring the mixture, adding a potassium phosphate aqueous solution, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120 ℃ and 150 ℃ for 5-15 hours; after the reaction is finished, cooling, adding water, filtering the mixture, drying the mixture in a vacuum drying oven, and purifying the obtained residue by a silica gel column to obtain a compound intermediate I;
the raw materials A and
Figure BDA0001292279300000163
the molar ratio of (A) is 1: 1.0-3, Pd (OAc)2The molar ratio of the raw material A to the raw material A is 0.001-0.04: 1, and K3PO4The molar ratio of the DMF to the raw material A is 1.0-4.0: 1, and the ratio of the amount of DMF to the amount of the raw material A is 1g: 10-30 ml;
when the aza-benzene and Ar1When they are linked by a C-N bond,
Figure BDA0001292279300000164
weighing raw materials A and Ar1-H, dissolved with toluene; then adding Pd2(dba)3Tri-tert-butylphosphine, sodium tert-butoxide; reacting the mixed solution of the reactants for 10-24 hours at the reaction temperature of 95-110 ℃ in an inert atmosphere, cooling and filtering the reaction solution, carrying out rotary evaporation on the filtrate, and passing through a silica gel column to obtain an intermediate I;
the raw materials A and Ar1The molar ratio of-H to Pd is 1: 1.0-32(dba)3The molar ratio of the tert-butyl phosphine to the raw material A is 0.006-0.04: 1, the molar ratio of the tri-tert-butyl phosphine to the raw material A is 0.006-0.04: 1, and the molar ratio of the sodium tert-butoxide to the raw material A is 2.0-3.0: 1;
synthesis example of intermediate A1
Figure BDA0001292279300000165
(1) In a 250mL three-necked flask, nitrogen gas was introduced, 0.02mol of 4-bromo-1, 1' -biphenyl was dissolved in 100mL of Tetrahydrofuran (THF), and 0.024mol of bis (pinacolato) diboron and 0.0002mol of (1, 1) were added’-bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.05mol of potassium acetate were added, the mixture was stirred, and the mixed solution of the above reactants was heated under reflux at a reaction temperature of 80 ℃ for 5 hours; after the reaction was finished, it was cooled and 100ml of water was added, and the mixture was filtered and dried in a vacuum oven. Separating and purifying the obtained residue by a silica gel column to obtain 4-biphenyl boronic acid pinacol ester; HPLC purity 99.9%, yield 92.7%.
Elemental analysis Structure (molecular formula C)18H21BO2): theoretical value C, 77.17; h, 7.55; b, 3.86; o, 11.42; test values are: c, 77.16; h, 7.54; b, 3.87; o, 11.43. ESI-MS (M/z) (M)+): theoretical value is 280.16, found 280.52.
Figure BDA0001292279300000171
(2) Introducing nitrogen into a 250mL three-neck flask, adding 0.02mol of raw material 4-bromo-2, 6-dichloropyridine, 150mL of DMF, 0.024mol of 4-biphenylboronic acid pinacol ester and 0.0002mol of palladium acetate, stirring, and then adding 0.03mol of K3PO4Heating the aqueous solution to 130 ℃, refluxing and reacting for 10 hours, taking a sample, and completely reacting. Naturally cooling, adding water, filtering the mixture, drying in a vacuum drying oven, and purifying the obtained residue with silica gel column to obtain compound intermediate A1; HPLC purity 99.5%, yield 88.3%.
Elemental analysis Structure (molecular formula C)17H11Cl2N): theoretical value C, 68.02; h, 3.69; cl, 23.62; n, 4.67; test values are: c, 68.04; h, 3.68; cl, 23.63; and N, 4.65. ESI-MS (M/z) (M)+): theoretical value is 299.03, found 299.41.
Synthesis example of intermediate A14
Figure BDA0001292279300000172
In a 250ml three-neck flask, under the atmosphere of introducing nitrogen, 0.01mol of 2-bromo-4, 6-dichloropyrimidine, 0.015mol of N-phenyl- [ 1, 1' -biphenyl ] -4-amine, 0.03mol of sodium tert-butoxide, 1 × 10-4mol Pd2(dba)3，1×10- 4Heating and refluxing tri-tert-butylphosphine and 150ml toluene for 24 hr, sampling the sample, and reacting completely; naturally cooling, filtering, rotatably evaporating the filtrate, and passing through a silica gel column to obtain an intermediate A14 with HPLC purity of 99.5% and yield of 82.7%.
Elemental analysis Structure (molecular formula C)22H15Cl2N3): theoretical value C, 67.36; h, 3.85; cl, 18.08; n, 10.71; test values are: c, 67.35; h, 3.84; cl, 18.09; n, 10.72. ESI-MS (M/z) (M)+): theoretical value is 391.06, found 391.06.
Intermediate I was prepared by the synthetic method of intermediates A1, A14, the specific structure is shown in Table 1.
TABLE 1
Figure BDA0001292279300000173
Figure BDA0001292279300000181
Figure BDA0001292279300000191
Figure BDA0001292279300000201
Example 2: intermediates
Figure BDA0001292279300000202
Synthesis of (2)
When R is1Or R2When the structure is represented by the general formula (6),
Figure BDA0001292279300000203
(1) in a 250mL three-necked flask, nitrogen gas was introduced, and 0.02mol of the starting material 2-bromo-benzimidazole and 0.03mol of I-Ar were added4Dissolving 0.04mol of sodium hydride, 0.004mol of cuprous iodide and 0.01mol of phenanthroline in 100ml of 1, 3-dimethyl-2-imidazolidinone, stirring for reaction for 20-30h, adding water and extracting with dichloromethane after the reaction is finished, drying an organic layer with anhydrous sodium sulfate, leaching with a mixture of petroleum ether and ethyl acetate as a leaching agent, wherein the volume ratio of the petroleum ether to the ethyl acetate in the leaching agent is 1:100, and purifying by column chromatography to obtain an intermediate M;
Figure BDA0001292279300000204
(2) weighing intermediate M, dissolving in tetrahydrofuran under nitrogen atmosphere, and adding Br-Ar2-B(OH)2And tetrakis (triphenylphosphine) palladium are added, the mixture is stirred, saturated potassium carbonate aqueous solution is added, and the mixed solution of the reactants is heated and refluxed for 10 to 20 hours at the reaction temperature of between 70 and 90 ℃; after the reaction is finished, cooling, extracting the mixed solution by using dichloromethane, drying the extract by using anhydrous sodium sulfate, concentrating under reduced pressure, and purifying the concentrated solid by using a silica gel column to obtain a compound intermediate N;
Figure BDA0001292279300000205
(3) weighing an intermediate N and dissolving the intermediate N in N, N-Dimethylformamide (DMF) under the atmosphere of nitrogen, adding bis (pinacolato) diboron, (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120-150 ℃ for 5-10 hours; after the reaction was completed, it was cooled, and the mixture was filtered and dried in a vacuum oven. Separating and purifying the obtained residue by a silica gel column to obtain a compound intermediate IV;
when R is1Or R2When the structure is represented by the general formula (7),
Figure BDA0001292279300000206
(1) weighing 2-bromo-benzimidazole and dissolving in tetrahydrofuran under nitrogen atmosphere, and then dissolving Ar5-B(OH)2And tetrakis (triphenylphosphine) palladium are added, the mixture is stirred, saturated potassium carbonate aqueous solution is added, and the mixed solution of the reactants is heated and refluxed for 5 to 15 hours at the reaction temperature of 70 to 90 ℃; after the reaction is finished, cooling, extracting the mixed solution by using dichloromethane, drying the extract by using anhydrous sodium sulfate, concentrating under reduced pressure, and purifying the concentrated solid by using a silica gel column to obtain a compound intermediate P;
Figure BDA0001292279300000211
(2) under the nitrogen atmosphere, adding intermediate P, I-Ar2dissolving-Br, sodium hydride, cuprous iodide and phenanthroline in 1, 3-dimethyl-2-imidazolidinone, stirring for reacting for 20-30h, adding water and extracting with dichloromethane after the reaction is finished, drying an organic layer with anhydrous sodium sulfate, leaching with a mixture of petroleum ether and ethyl acetate as a leaching agent, and purifying by column chromatography to obtain an intermediate Q;
Figure BDA0001292279300000212
(3) weighing an intermediate Q and dissolving the intermediate Q in N, N-Dimethylformamide (DMF) under the atmosphere of nitrogen, adding bis (pinacolato) diboron, (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120-150 ℃ for 5-10 hours; after the reaction was completed, it was cooled, and the mixture was filtered and dried in a vacuum oven. Separating and purifying the obtained residue by a silica gel column to obtain a compound intermediate IV;
when R is1Or R2When the structure is represented by the general formula (8),
Figure BDA0001292279300000213
(1) under the nitrogen atmosphere, W, I-Ar raw material is added7Dissolving sodium hydride, cuprous iodide and phenanthroline in 1, 3-dimethyl-2-imidazolidinone, stirring to react for 20-30h, adding water and extracting with dichloromethane after the reaction is finished, drying an organic layer with anhydrous sodium sulfate, leaching with a mixture of petroleum ether and ethyl acetate as a leaching agent, and purifying by column chromatography to obtain an intermediate X;
Figure BDA0001292279300000214
(2) weighing intermediate X and dissolving in tetrahydrofuran under nitrogen atmosphere, and then Ar6-B(OH)2And tetrakis (triphenylphosphine) palladium are added, the mixture is stirred, saturated potassium carbonate aqueous solution is added, and the mixed solution of the reactants is heated and refluxed for 5 to 15 hours at the reaction temperature of 70 to 90 ℃; after the reaction is finished, cooling, extracting the mixed solution by using dichloromethane, drying the extract by using anhydrous sodium sulfate, concentrating under reduced pressure, and purifying the concentrated solid by using a silica gel column to obtain a compound intermediate Y;
Figure BDA0001292279300000221
(3) weighing intermediate Y and dissolving in N, N-dimethylformamide under nitrogen atmosphere, and adding Br-Ar2-B(OH)2And palladium acetate, stirring the mixture, adding a potassium phosphate aqueous solution, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120 ℃ and 150 ℃ for 10-24 hours; after the reaction is finished, cooling, adding water, filtering the mixture, drying the mixture in a vacuum drying oven, and purifying the obtained residue through a silica gel column to obtain a compound intermediate Z;
Figure BDA0001292279300000222
(4) weighing an intermediate Z and dissolving the intermediate Z in N, N-Dimethylformamide (DMF) under the atmosphere of nitrogen, adding bis (pinacolato) diboron, (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120-150 ℃ for 5-10 hours; after the reaction was completed, it was cooled, and the mixture was filtered and dried in a vacuum oven. Separating and purifying the obtained residue by a silica gel column to obtain a compound intermediate IV;
synthesis example of intermediate B1
Figure BDA0001292279300000223
(1) Introducing nitrogen into a 250mL three-necked bottle, adding 0.02mol of raw materials of 2-bromo-1H-benzimidazole, 0.03mol of iodobenzene, 0.04mol of sodium hydride, 0.004mol of cuprous iodide and 0.01mol of phenanthroline, dissolving in 100mL of 1, 3-dimethyl-2-imidazolidinone, stirring for reaction for 20-30H, adding water and extracting with dichloromethane after the reaction is finished, drying an organic layer with anhydrous sodium sulfate, leaching with a mixture of petroleum ether and ethyl acetate as a leaching agent, wherein the volume ratio of the petroleum ether to the ethyl acetate in the leaching agent is 1:100, and purifying by column chromatography to obtain an intermediate M1; HPLC purity 99.5%, yield 75.8%.
Elemental analysis Structure (molecular formula C)13H9BrN2): theoretical value C, 57.17; h, 3.32; br, 29.26; n, 10.26; test values are: c, 57.18; h, 3.33; br, 29.25; and N, 10.24. ESI-MS (M/z) (M)+): theoretical value is 271.99, found 272.32.
Figure BDA0001292279300000224
(2) In a 250mL three-necked flask, nitrogen was purged, and 0.04mol of intermediate M1, 100mL of THF, 0.05mol of phenylboronic acid, 0.0004mol of tetrakis (triphenylphosphine) palladium were added thereto, followed by stirring and 0.06mol of K was added2CO3The aqueous solution (2M) was heated to 80 ℃ and refluxed for 10 hours, and the reaction was completed by sampling the sample. Cooling naturally, extracting with 200ml dichloromethane, layering, drying the extractive solution with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and purifying with silica gel column to obtain intermediate N1 with HPLC purity of 99.6% and yield of 84.9%。
Elemental analysis Structure (molecular formula C)19H13BrN2): theoretical value C, 65.35; h, 3.75; br, 22.88; n, 8.02; test values are: c, 65.36; h, 3.74; br, 22.89; and N, 8.03. ESI-MS (M/z) (M)+): theoretical value is 348.03, found 348.45.
Figure BDA0001292279300000231
(3) Introducing nitrogen into a 500mL three-neck flask, adding 0.05 intermediate N1, dissolving in 300mL N, N-Dimethylformamide (DMF), adding 0.06mol of bis (pinacolato) diboron, 0.0005mol of (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.125mol of potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 120 ℃ and 150 ℃ for 10 hours; after the reaction was finished, it was cooled and 200ml of water was added, and the mixture was filtered and dried in a vacuum oven. Separating and purifying the obtained residue by a silica gel column to obtain a compound intermediate B1; HPLC purity 99.5%, yield 84.1%.
Elemental analysis Structure (molecular formula C)25H25BN2O2): theoretical value C, 75.77; h, 6.36; b, 2.73; n, 7.07; o, 8.07; test values are: c, 75.79; h, 6.35; b, 2.72; n, 7.08; and O, 8.06. ESI-MS (M/z) (M)+): theoretical value is 396.20, found 396.62. Intermediate IV was prepared by the synthetic method of intermediate B1, the specific structure is shown in Table 2.
TABLE 2
Figure BDA0001292279300000232
Figure BDA0001292279300000241
Example 3: synthesis of Compound 3:
Figure BDA0001292279300000242
a250 mL three-necked flask was purged with nitrogen, charged with 0.01mol of intermediate A1, 150mL of DMF, 0.03mol of intermediate B1 and 0.0002mol of palladium acetate, stirred, and then charged with 0.02mol of K3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 24 hours, sampling a sample, and completely reacting. Naturally cooling, extracting with 200ml dichloromethane, layering, drying the extract with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and purifying with silica gel column to obtain the target product with HPLC purity of 99.4% and yield of 64.7%.
Elemental analysis Structure (molecular formula C)55H37N5): theoretical value C, 86.02; h, 4.86; n, 9.12; test values are: c, 86.05; h, 4.85; and N, 9.10. ESI-MS (M/z) (M)+): theoretical value is 767.30, found 767.58.
Example 4: synthesis of compound 9:
Figure BDA0001292279300000251
a250 mL three-necked flask was purged with nitrogen, charged with 0.01mol of intermediate A2, 150mL of DMF, 0.03mol of intermediate B1 and 0.0002mol of palladium acetate, stirred, and then charged with 0.02mol of K3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 24 hours, sampling a sample, and completely reacting. Naturally cooling, extracting with 200ml dichloromethane, layering, drying the extract with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and purifying with silica gel column to obtain the target product with HPLC purity of 99.1% and yield of 67.2%.
Elemental analysis Structure (molecular formula C)53H35N5): theoretical value C, 85.80; h, 4.76; n, 9.44; test values are: c, 85.80; h, 4.75; and N, 9.45. ESI-MS (M/z) (M)+): theoretical value is 741.29, found 741.72.
Example 5: synthesis of compound 10:
Figure BDA0001292279300000252
compound 10 was prepared as in example 3, except thatIntermediate a1 was replaced with intermediate A3. Elemental analysis Structure (molecular formula C)53H35N5): theoretical value C, 85.80; h, 4.76; n, 9.44; test values are: c, 85.80; h, 4.77; n, 9.43. ESI-MS (M/z) (M)+): theoretical value is 741.29, found 741.73.
Example 6: synthesis of compound 22:
Figure BDA0001292279300000253
compound 22 was prepared as in example 3, except intermediate a4 was used in place of intermediate a 1. Elemental analysis Structure (molecular formula C)58H41N5): theoretical value C, 86.22; h, 5.11; n, 8.67; test values are: c, 86.24; h, 5.10; and N, 8.66. ESI-MS (M/z) (M)+): theoretical value is 807.34, found 807.75.
Example 7: synthesis of compound 25:
Figure BDA0001292279300000261
compound 25 was prepared as in example 3, except intermediate a5 was used in place of intermediate a 1. Elemental analysis Structure (molecular formula C)61H42N6): theoretical value C, 85.29; h, 4.93; n, 9.78; test values are: c, 85.31; h, 4.92; and N, 9.77. ESI-MS (M/z) (M)+): theoretical value is 858.35, found 858.69.
Example 8: synthesis of compound 29:
Figure BDA0001292279300000262
compound 29 was prepared as in example 3, except intermediate a6 was used in place of intermediate a1 and intermediate B2 was used in place of intermediate B1. Elemental analysis Structure (molecular formula C)61H40N6): theoretical value C, 85.49; h, 4.70; n, 9.81; test values are: c, 85.47; h, 4.71; and N, 9.82. ESI-MS (M/z) (M)+): theoretical value of 856.33, found valueIs 856.74.
Example 9: synthesis of compound 41:
Figure BDA0001292279300000263
introducing nitrogen into a 250mL three-necked flask, adding 0.01mol of intermediate A7, 150mL of DMF, 0.015mol of intermediate B1 and 0.0001mol of palladium acetate, stirring, and adding 0.01mol of K3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 24 hours, sampling a sample, and completely reacting. Naturally cooling, extracting with 200ml dichloromethane, layering, drying the extract with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and purifying with silica gel column to obtain the target product with HPLC purity of 99.6% and yield of 67.2%.
Elemental analysis Structure (molecular formula C)46H31N5): theoretical value C, 84.51; h, 4.78; n, 10.71; test values are: c, 84.51; h, 4.77; n, 10.72. ESI-MS (M/z) (M)+): theoretical value is 653.26, found 653.68.
Example 10: synthesis of compound 44:
Figure BDA0001292279300000271
compound 44 was prepared as in example 9, except intermediate A8 was used in place of intermediate a1 and intermediate B3 was used in place of intermediate B1. Elemental analysis Structure (molecular formula C)48H31N5): theoretical value C, 85.06; h, 4.61; n, 10.33; test values are: c, 85.06; h, 4.62; n, 10.32. ESI-MS (M/z) (M)+): theoretical value is 677.26, found 677.65.
Example 11: synthesis of compound 58:
Figure BDA0001292279300000272
compound 58 was prepared as in example 9, except intermediate a9 was used in place of intermediate a 7. Elemental analysis Structure (molecular formula C)56H39N9): theoretical value C, 80.27; h, 4.69; n, 15.04; test values are: c, 80.28; h, 4.70; and N, 15.02. ESI-MS (M/z) (M)+): theoretical value is 837.33, found 837.70.
Example 12: synthesis of compound 70:
Figure BDA0001292279300000273
compound 70 was prepared as in example 3, except intermediate a10 was used in place of intermediate a 1. Elemental analysis Structure (molecular formula C)54H36N6): theoretical value C, 84.35; h, 4.72; n, 10.93; test values are: c, 84.35; h, 4.73; n, 10.92. ESI-MS (M/z) (M)+): theoretical value is 768.30, found 768.67.
Example 13: synthesis of compound 76:
Figure BDA0001292279300000281
compound 76 was prepared as in example 3, except intermediate a11 was used in place of intermediate a 1. Elemental analysis structure (molecular formula C52H34N 6): theoretical value C, 84.07; h, 4.61; n, 11.31; test values are: c, 84.08; h, 4.60; n, 11.32. ESI-MS (M/z) (M)+): theoretical value is 742.28, found 742.59.
Example 14: synthesis of compound 81:
Figure BDA0001292279300000282
compound 81 was prepared as in example 3, except intermediate a12 was used in place of intermediate a 1. Elemental analysis Structure (molecular formula C)51H33N7): theoretical value C, 82.35; h, 4.47; n, 13.18; test values are: c, 82.33; h, 4.48; n, 13.19. ESI-MS (M/z) (M)+): theoretical value is 743.28, found 743.61.
Example 15: synthesis of compound 88:
Figure BDA0001292279300000283
compound 88 was prepared as in example 3, except intermediate a13 was used in place of intermediate a 1. Elemental analysis Structure (molecular formula C)60H39N7): theoretical value C, 83.99; h, 4.58; n, 11.43; test values are: c, 83.98; h, 4.57; n, 11.45. ESI-MS (M/z) (M)+): theoretical value is 857.33, found 857.69.
Example 16: synthesis of compound 90:
Figure BDA0001292279300000284
a250 mL three-necked flask was purged with nitrogen, charged with 0.01mol of intermediate A14, 150mL of DMF, 0.03mol of intermediate B1 and 0.0002mol of palladium acetate, stirred, and then charged with 0.02mol of K3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 24 hours, sampling a sample, and completely reacting. Naturally cooling, extracting with 200ml dichloromethane, layering, drying the extract with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and purifying with silica gel column to obtain the target product with HPLC purity of 99.3% and yield of 65.4%.
Elemental analysis Structure (molecular formula C)60H41N7): theoretical value C, 83.79; h, 4.81; n, 11.40; test values are: c, 83.77; h, 4.82; n, 11.41. ESI-MS (M/z) (M)+): theoretical value is 859.34, found 859.72.
Example 17: synthesis of compound 97:
Figure BDA0001292279300000291
compound 97 was prepared as in example 3, except intermediate a15 was used instead of intermediate a1 and intermediate B2 was used instead of intermediate B1. Elemental analysis Structure (molecular formula C)50H32N8): theoretical value C, 80.63; h, 4.33; n, 15.04; test values are: c, 80.60; h, 4.35; n, 15.05. ESI-MS (M/z) (M)+): theory of the inventionThe value was 744.27, found 744.68.
Example 18: synthesis of compound 104:
Figure BDA0001292279300000292
compound 104 was prepared as in example 9, except intermediate a16 was used in place of intermediate a7 and intermediate B4 was used in place of intermediate B1. Elemental analysis Structure (molecular formula C)53H36N4): theoretical value C, 87.33; h, 4.98; n, 7.69; test values are: c, 87.31; h, 4.99; and N, 7.70. ESI-MS (M/z) (M)+): theoretical value is 728.29, found 728.66.
Example 19: synthesis of compound 110:
Figure BDA0001292279300000293
compound 110 was prepared as in example 9, except intermediate a17 was used instead of intermediate a7 and intermediate B3 was used instead of intermediate B1. Elemental analysis Structure (molecular formula C)45H28N8): theoretical value C, 86.96; h, 4.77; n, 8.28; test values are: c, 86.98; h, 4.75; and N, 8.27. ESI-MS (M/z) (M)+): theoretical value is 680.24, found 680.65.
Example 20: synthesis of compound 112:
Figure BDA0001292279300000301
compound 112 was prepared as in example 19, except intermediate a18 was used in place of intermediate a 17. Elemental analysis Structure (molecular formula C)47H30N6): theoretical value C, 83.16; h, 4.45; n, 12.38; test values are: c, 83.19; h, 4.45; n, 12.36. ESI-MS (M/z) (M)+): theoretical value is 678.25, found 678.71.
Example 21: synthesis of compound 126:
Figure BDA0001292279300000302
compound 126 was prepared as in example 9, except intermediate a19 was used in place of intermediate a 7. Elemental analysis Structure (molecular formula C)55H38N10): theoretical value C, 78.74; h, 4.57; n, 16.70; test values are: c, 78.71; h, 4.58; n, 16.71. ESI-MS (M/z) (M)+): theoretical value is 838.33, found 838.72.
Example 22: synthesis of compound 144:
Figure BDA0001292279300000303
a250 mL three-necked flask was charged with nitrogen, and then 0.01mol of intermediate A20, 150mL of DMF, 0.012mol of intermediate B1, and 0.0001mol of palladium acetate were added thereto, followed by stirring and 0.01mol of K3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 24 hours, sampling a sample, and completely reacting. Naturally cooling, extracting with 200ml dichloromethane, layering, drying the extract with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and purifying with silica gel column to obtain intermediate C1 with HPLC purity of 99.2% 0 and yield of 85.1%.
Elemental analysis Structure (molecular formula C)29H19ClN4): theoretical value C, 75.89; h, 4.17; cl, 7.72; n, 12.21; test values are: c, 75.91; h, 4.16; cl, 7.73; and N, 12.20. ESI-MS (M/z) (M)+): theoretical value is 458.13, found 458.53.
Introducing nitrogen into a 250mL three-necked flask, adding 0.01mol of intermediate C1, 150mL of DMF, 0.015mol of intermediate B5 and 0.0001mol of palladium acetate, stirring, and adding 0.01mol of K3PO4Heating the aqueous solution to 150 ℃, refluxing and reacting for 24 hours, sampling a sample, and completely reacting. Naturally cooling, extracting with 200ml dichloromethane, layering, drying the extract with anhydrous sodium sulfate, filtering, rotary evaporating the filtrate, and purifying with silica gel column to obtain the target product with HPLC purity of 99.5% and yield of 71.7%.
Elemental analysis Structure (molecular formula C)48H32N6): theory of thingsTheoretical value C, 83.21; h, 4.66; n, 12.13; test values are: c, 83.21; h, 4.68; n, 12.11. ESI-MS (M/z) (M)+): theoretical value is 692.27, found 692.66.
The organic compound of the present invention is used in a light emitting device as a CPL layer material, and has a high Tg (glass transition temperature) and a high refractive index. The compounds prepared in the examples were tested for thermal properties and refractive indexes, respectively, and the results are shown in table 3, in which fig. 2 is a graph of refractive index test of compound 76.
TABLE 3
Figure BDA0001292279300000311
Figure BDA0001292279300000321
Note: the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the refractive index was measured by an ellipsometer (U.S. J.A. Woollam Co. model: ALPHA-SE) and measured as an atmospheric environment.
As can be seen from the data in the table above, compared with the currently applied CBP, Alq3, TPBi and other materials, the organic compound of the invention has high glass transition temperature and high refractive index, and simultaneously, because of containing the rigid groups of azabenzene and benzimidazole, the thermal stability of the material is ensured. Therefore, the organic material taking the azabenzene and the benzimidazole as the core can effectively improve the light extraction efficiency of the device and ensure the long service life of the OLED device after being applied to the CPL layer of the OLED device.
The application effect of the synthesized OLED material in the device is explained in detail through device examples 1-21 and device comparative example 1. Compared with the device embodiment 1, the device embodiments 2-21 and the device comparative example 1 have the same manufacturing process, adopt the same substrate material and electrode material, keep the film thickness of the electrode material consistent, and are different in that the device embodiments 2-18 convert CPL layer materials in the device; device examples 19-21 were prepared by changing the hole blocking/electron transporting layer materials of the devices, and the performance test results of the devices obtained in each example are shown in table 4.
Device example 1: as shown in fig. 1, an electroluminescent device is prepared by the steps of:
a) cleaning an ITO anode layer 2 on a transparent OLED device substrate 1, respectively ultrasonically cleaning the ITO anode layer 2 with deionized water, acetone and ethanol for 15 minutes, and then treating the ITO anode layer 2 in a plasma cleaner for 2 minutes; b) evaporating a hole injection layer material HAT-CN on the ITO anode layer 2 in a vacuum evaporation mode, wherein the thickness of the hole injection layer material HAT-CN is 10nm, and the hole injection layer material HAT-CN is used as a hole injection layer 3; c) evaporating a hole transport material NPB on the hole injection layer 3 in a vacuum evaporation mode, wherein the thickness of the hole transport material NPB is 80nm, and the hole transport layer is a hole transport layer 4; d) depositing a light-emitting layer 5 of CBP as a host material Ir (ppy) on the hole transport layer 43As doping material, Ir (ppy)3The mass ratio of CBP to CBP is 1: 9, and the thickness is 30 nm; e) an electron transport material TPBI is evaporated on the light-emitting layer 5 in a vacuum evaporation mode, the thickness of the TPBI is 40nm, and the organic material of the TPBI layer is used as a hole blocking/electron transport layer 6; f) vacuum evaporating an electron injection layer LiF with the thickness of 1nm on the hole blocking/electron transport layer 6, wherein the layer is an electron injection layer 7; g) on the electron injection layer 7, a cathode Mg: an Ag/Ag layer, wherein the doping ratio of Mg to Ag is 9:1, the thickness of the Ag layer is 15nm, the thickness of the Ag layer is 3nm, and the layer is a cathode layer 8; h) on the cathode layer 8, the CPL material compound 3 was deposited by vacuum deposition to a thickness of 50nm, and this layer of organic material was used as the CPL layer 9.
After the electroluminescent device was fabricated according to the above procedure, the current efficiency and lifetime of the device were measured, and the results are shown in table 4. The molecular mechanism formula of the related material is as follows:
Figure BDA0001292279300000331
device example 2: the CPL layer material of the electroluminescent device becomes compound 9 of the present invention. Device example 3: the CPL layer material of the electroluminescent device becomes the compound 10 of the present invention. Device example 4: the CPL layer material of the electroluminescent device becomes the compound 22 of the present invention. Device example 5: the CPL layer material of the electroluminescent device becomes the compound 25 of the present invention. Device example 6: the CPL layer material of the electroluminescent device becomes compound 29 of the present invention. Device example 7: the CPL layer material of the electroluminescent device was changed to compound 41 of the present invention. Device example 8: the CPL layer material of the electroluminescent device becomes the compound 44 of the present invention. Device example 9: the CPL layer material of the electroluminescent device becomes the compound 58 of the present invention. Device example 10: the CPL layer material of the electroluminescent device becomes the compound 70 of the present invention. Device example 11: the CPL layer material of the electroluminescent device becomes the compound 76 of the present invention. Device example 12: the CPL layer material of the electroluminescent device becomes the compound 81 of the present invention. Device example 13: the CPL layer material of the electroluminescent device becomes the compound 88 of the present invention. Device example 14: the CPL layer material of the electroluminescent device becomes the compound 90 of the present invention. Device example 15: the CPL layer material of the electroluminescent device becomes the compound 97 of the present invention. Device example 16: the CPL layer material of the electroluminescent device becomes the compound 104 of the present invention. Device example 17: the CPL layer material of the electroluminescent device becomes the compound 110 of the present invention. Device example 18: the CPL layer material of the electroluminescent device becomes the compound 112 of the present invention. Device example 19: the hole blocking/electron transporting layer material of the electroluminescent device was changed to the compound 41 of the present invention. Device example 20: the hole blocking/electron transport layer material of the electroluminescent device becomes the compound 58 of the present invention. Device example 21: the hole blocking/electron transport layer material of the electroluminescent device becomes the compound 126 of the present invention. Device comparative example 1: the CPL layer material of the electroluminescent device became the well-known material Alq 3. The inspection data of the obtained electroluminescent device are shown in Table 4.
TABLE 4
Figure BDA0001292279300000332
Figure BDA0001292279300000341
The results in table 4 show that, when the organic compound with the core of the azabenzene and the benzimidazole of the present invention is applied to the fabrication of the OLED light emitting device, compared with the comparative device example 1, the light extraction is significantly improved, the device brightness and the device efficiency are both improved under the same current density, and as the brightness and the efficiency are improved, the power consumption of the OLED device at the constant brightness is relatively reduced, and the service life is also improved.
In order to illustrate the phase crystallization stability of the material film of the present invention, the material compound 70 of the present invention and the known material CBP were subjected to a film accelerated crystallization experiment: compound 70 and CBP were deposited on alkali-free glass by vacuum deposition, and encapsulated in a glove box (water oxygen content < 0.1ppm), the encapsulated sample was placed under double 85 (temperature 85 ℃, humidity 85%), the crystalline state of the material film was observed periodically with a microscope (LEICA, DM8000M, 5 × 10 magnification), and the experimental results are shown in table 5, and the surface morphology of the material is shown in fig. 3.
TABLE 5
Name of Material Compound 70 CBP
After the material is formed into film The surface shape is smooth and even The surface shape is smooth and even
After 72 hours of the experiment The surface shape is smooth, even and no crystal The surface forms a plurality of scattered circular crystal planes
After 600 hours of the experiment The surface shape is smooth, even and no crystal Surface cracking
The experiments show that the film crystallization stability of the material is far higher than that of the known material, and the material has a beneficial effect on the service life after being applied to an OLED device.

Claims (4)

1. An organic compound for forming a CPL layer of an organic electroluminescent device is an organic compound taking azabenzene and benzimidazole as cores, and is characterized in that the structure of the organic compound is shown as a general formula (1):
Figure FDF0000008780430000011
in the general formula (1), X2、X4、X6Independently represent N atom or C atom, and the number of N atoms is 1 or 2;
in the general formula (1), Ar1、Ar2、Ar3Are each independently represented by C1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, a tritium atom substituted or unsubstituted phenyl; c1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, a tritium atom substituted or unsubstituted naphthyl group; c1-10Straight or branched chain alkyl, halogen atom, protium, deuterium, tritium atom substituted or unsubstituted biphenylyl; or C1-10One of linear chain or branched alkyl, halogen atom, protium, deuterium, tritium atom substituted or unsubstituted pyridyl;
Ar1、Ar2、Ar3may be the same or different;
in the general formula (1), Ar1Can also be represented by a structure shown in a general formula (2), a general formula (3), a general formula (4) or a general formula (5);
Figure FDF0000008780430000012
in the general formula (2), each Y independently represents N or C, and at least one Y represents N;
in the general formula (3), each Z independently represents N or C, and at least one Z represents N;
in the general formulae (4) and (5), R3、R4、R5Are each independently represented by C1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, a tritium atom substituted or unsubstituted phenyl; c1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, a tritium atom substituted or unsubstituted naphthyl group; c1-10Straight or branched chain alkyl, halogen atom, protium, deuterium, tritium atom substituted or unsubstituted biphenylyl; c1-10A linear or branched alkyl group, a halogen atom, protium, deuterium, tritium atom-substituted or unsubstituted pyridyl group; dibenzofuran; dibenzothiophene; 9, 9-dimethylfluorene or N-phenylcarbazole;
R3、R4、R5may be the same or different;
in the general formula (1), R1、R2Each independently represents a structure represented by the general formula (6):
Figure FDF0000008780430000021
wherein Ar is4Is represented as C1-10Straight or branched alkyl, phenyl substituted or unsubstituted by halogen atoms, C1-10Straight or branched alkyl, naphthyl substituted or unsubstituted by halogen atoms, C1-10A straight or branched alkyl group, a biphenylyl group substituted or unsubstituted with a halogen atom, or C1-10One of a straight-chain or branched alkyl group, a halogen atom substituted or unsubstituted pyridyl group;
R1、R2may be the same or different.
2. The organic compound of claim 1, wherein the specific structural formula of the organic compound is:
Figure FDF0000008780430000022
Figure FDF0000008780430000031
Figure FDF0000008780430000041
Figure FDF0000008780430000051
Figure FDF0000008780430000052
any one of them.
3. An organic electroluminescent device comprising a CPL layer, characterized in that the CPL layer contains the organic compound having an azabenzene and benzimidazole as core according to claim 1 or 2.
4. A lighting or display element comprising the organic electroluminescent device according to claim 3.
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