CN111362866A - Azabenzene modified organic compound and application thereof - Google Patents

Azabenzene modified organic compound and application thereof Download PDF

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CN111362866A
CN111362866A CN201811598707.1A CN201811598707A CN111362866A CN 111362866 A CN111362866 A CN 111362866A CN 201811598707 A CN201811598707 A CN 201811598707A CN 111362866 A CN111362866 A CN 111362866A
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李崇
谢丹丹
王芳
张兆超
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention discloses an organic compound modified by aza-benzene and application thereof, belonging to the technical field of semiconductors. The structure of the organic compound modified by the aza-benzene is shown as a general formula (I):
Figure DDA0001921907160000011
the invention also discloses application of the organic compound. The organic compound provided by the invention has good thermal stability, higher glass transition temperature and proper HOMO energy level, and the device adopting the organic compound provided by the invention can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through structure optimization.

Description

Azabenzene modified organic compound and application thereof
Technical Field
The invention relates to an organic compound modified by aza-benzene and application thereof, belonging to the technical field of semiconductors.
Background
The organic electroluminescent 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 of a sandwich structure and comprises electrode material film layers and organic functional materials clamped between different electrode film layers, and the various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to two end electrodes of the OLED light-emitting device as a current device, positive and negative charges in the organic layer functional material film layer are acted through an electric field, and the positive and negative charges are further compounded in the light-emitting layer, namely OLED electroluminescence is generated.
At present, the OLED display technology has been applied in the fields of smart phones, tablet computers, and the like, and will further expand to large-size application fields such as televisions, but compared with actual product application requirements, the light emitting efficiency, the service life, and other performances of the OLED device need to be further improved. The research on the improvement of the performance of the OLED light emitting device 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 OLED photoelectric functional material are needed to create the functional material of the OLED with higher performance.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the OLED device structure applied in industry comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and other various film layers, namely the photoelectric functional material applied to the OLED device at least comprises a hole injection material, a hole transport material, a light emitting material, an electron transport material and the like, and the material type and the matching form have the characteristics of richness and diversity. In addition, for the collocation of OLED devices with different structures, the used photoelectric functional materials have stronger selectivity, and the performance of the same materials in the devices with different structures can also be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device, different functional film layers of the OLED device and the photoelectric characteristic requirements of the device, a more suitable OLED functional material or material combination with high performance needs to be selected to realize the comprehensive characteristics of high efficiency, long service life and low voltage of the device. In terms of the actual demand of the current OLED display illumination industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and the development of organic functional materials with higher performance is very important as a material enterprise.
Disclosure of Invention
An object of the present invention is to provide an organic compound modified with an azabenzene. The organic compound provided by the invention has good thermal stability, higher glass transition temperature and proper HOMO energy level, and the device adopting the organic compound provided by the invention can effectively improve the photoelectric property of an OLED device and the service life of the OLED device through structure optimization.
The technical scheme for solving the technical problems is as follows: an organic compound modified by aza-benzene, the structure of the organic compound is shown as general formula (1):
Figure BDA0001921907140000021
in the general formula (1), - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
m and n are respectively and independently represented as a number 0 or 1, and m + n is more than or equal to 1;
z represents a nitrogen atom or C-H, and at least one Z represents a nitrogen atom;
x represents a nitrogen atom or C (R)0) (ii) a X at the attachment site represents a carbon atom;
Ar1、Ar2each independently represents a single bond, substituted or unsubstituted C6-C30One of an arylene, a substituted or unsubstituted 5-to 30-membered heteroarylene containing one or more heteroatoms;
R1、R2、R3、R4each independently represents substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
R0represented by hydrogen atom, protium, deuterium, tritium, halogen atom, cyano group, C1-C20Alkyl, substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the substituents which may be substituted are optionally selected from protium, deuterium, tritium, cyano, halogen, C1-C20Alkyl of (C)6-C30Aryl radicals containing one or more hetero atomsOne or more of the 5 to 30 membered heteroaryl groups of (a);
the hetero atom in the heteroaryl is one or more selected from nitrogen atom, oxygen atom or sulfur atom.
The pi conjugated effect in the compound provided by the invention enables the compound to have strong hole transmission capability, the high hole transmission rate can reduce the initial voltage of the device, and the efficiency of the organic electroluminescent device is improved; the introduction of the aza-benzene increases the asymmetry of molecules, can reduce the crystallinity of the molecules, reduce the planarity of the molecules and prevent the molecules from moving on the plane, thereby improving the thermal stability of the molecules; meanwhile, the structure of the compound provided by the invention enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons and improves the recombination efficiency of excitons in the light-emitting layer.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, when m and n are both 1, at least two Z in the general formula (1) represent nitrogen atoms, and Z which is nitrogen is not located on the same aza-benzene.
Further, m + n is 1, and in the general formula (1), X represents that the number of nitrogen atoms is 0, 1 or 2.
Further, m + n is 1, and in the general formula (1), Z represents a number of nitrogen atoms of 1, 2 or 3.
Further, the organic compound may be represented by one of the following structures represented by general formula (2) to general formula (5):
Figure BDA0001921907140000031
wherein the symbols and indices used have the meanings given above.
Further, Ar is1、Ar2Each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted biphenylene groupOne of substituted terphenylene, substituted or unsubstituted naphthyridine, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted anthracenylene, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted benzoxazole, substituted or unsubstituted benzimidazole, and substituted or unsubstituted benzothiazole;
the R is1、R2、R3、R4Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinolyl group;
the R is0Represented by hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted biphenylyl group, substituted or unsubstituted terphenylyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuranyl group;
the substituent of the substitutable group is selected from protium, deuterium, tritium, cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, naphthyl, naphthyridinyl, pyridyl, biphenyl, terphenyl, furyl, carbazolyl or thienyl.
Further, the specific structural formula of the organic compound is as follows:
Figure BDA0001921907140000041
Figure BDA0001921907140000051
Figure BDA0001921907140000061
Figure BDA0001921907140000071
Figure BDA0001921907140000081
Figure BDA0001921907140000091
Figure BDA0001921907140000101
Figure BDA0001921907140000111
Figure BDA0001921907140000121
Figure BDA0001921907140000131
any one of them.
The second objective of the present invention is to provide an organic electroluminescent device. The compound has good application effect in OLED luminescent devices and good industrialization prospect.
The technical scheme for solving the technical problems is as follows: an organic electroluminescent device, the functional layer of which contains the above organic compound modified with azabenzene.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the light-emitting layer and/or the electron-blocking layer and/or the hole-transporting layer containing the organic compound modified with an azabenzene as described above is included.
It is a further object of the present invention to provide an illumination or display device. The organic electroluminescent device can be applied to display elements, so that the current efficiency, the power efficiency and the external quantum efficiency of the device are greatly improved; meanwhile, the service life of the device is obviously prolonged, and the OLED luminescent device has a good application effect and a good industrialization prospect.
The technical scheme for solving the technical problems is as follows: a lighting or display element comprising an organic electroluminescent device as described above.
The invention has the beneficial effects that:
1. the pi conjugation effect in the compound provided by the invention enables the compound to have strong hole transmission capability, the high hole transmission rate can reduce the initial voltage of the device, and the efficiency of the organic electroluminescent device is improved; the introduction of the aza-benzene increases the asymmetry of molecules, can reduce the crystallinity of the molecules, reduce the planarity of the molecules and prevent the molecules from moving on the plane, thereby improving the thermal stability of the molecules; meanwhile, the structure of the compound provided by the invention enables the distribution of electrons and holes in the luminescent layer to be more balanced, and under the appropriate HOMO energy level, the hole injection and transmission performance is improved; under a proper LUMO energy level, the organic electroluminescent material plays a role in blocking electrons and improves the recombination efficiency of excitons in the light-emitting layer.
2. The substituent on the aza-benzene increases the distance between molecules, and the interaction force between molecules is weakened, so the aza-benzene has lower evaporation temperature, and the industrial processing window of the material is widened.
3. When the compound is applied to an OLED device, high film stability can be kept through device structure optimization, and the photoelectric performance of the OLED device and the service life of the OLED device can be effectively improved. The compound has good application effect and industrialization prospect in OLED luminescent devices.
Drawings
Fig. 1 is a schematic structural diagram of the application of the materials enumerated in the present invention to an OLED device, wherein the components represented by the respective reference numerals are as follows:
the organic electroluminescent device comprises a substrate layer 1, a substrate layer 2, an ITO anode layer 3, a hole injection layer 4, a hole transport layer 5, an electron blocking layer 6, a light emitting layer 7, an electron transport layer or a hole blocking layer 8, an electron injection layer 9 and a cathode reflection electrode layer.
FIG. 2 is a graph of efficiency measured at different temperatures for a device made according to the present invention and a comparative device.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Synthesis of reaction raw material J-9:
Figure BDA0001921907140000141
Figure BDA0001921907140000151
adding 15mmol of raw material M-9 into 300mL of glacial acetic acid, heating for refluxing, adding 55mmol of zinc powder, continuing heating for refluxing reaction for 20-30min, filtering the reaction solution on diatomite, adding distilled water with the same volume as the filtrate for precipitation, recrystallizing and purifying the obtained crude product by using n-hexane to obtain an intermediate S-9, wherein the yield is as follows: 72 percent.
Adding 80mmol of phosphorus tribromide into 8mmol of intermediate S-9, heating the mixture to 160 ℃, reacting for 50min, cooling to room temperature, pouring into water with the volume 50 times that of the reaction solution, adding solid sodium bicarbonate to adjust the pH value until the mixture is neutral, extracting with dichloromethane, performing rotary evaporation and concentration on extract liquor, recrystallizing and purifying the obtained crude product with methanol to obtain an intermediate K-9, wherein the yield is as follows: 58 percent.
Dissolving 1.2mmol of intermediate K-9 and 1.3mmol of raw material N-9 into 250mL of acetonitrile in a three-neck flask under the protection of nitrogen, heating to 60 ℃, adding 3mmol of diazabicyclo, reacting for 3h, filtering, flushing a filter cake with 60 ℃ of acetonitrile, combining filtrate and washing liquid, carrying out rotary evaporation concentration, and recrystallizing and purifying the obtained crude product with toluene to obtain intermediate J-9, wherein the yield is as follows: 56 percent.
Elemental analysis Structure (molecular formula C)25H16BrN): theoretical value C, 73.18; h, 3.93; br, 19.47; n, 3.41; test values are: c, 73.15; h, 3.95; br, 19.48; n, 3.43. ESI-MS (M/z) (M)+): theoretical value is 409.05, found 409.02.
Synthesis of reaction raw material J-10: the detailed reaction conditions refer to the synthesis of starting material J-9.
Figure BDA0001921907140000152
Structural characterization: elemental analysis Structure (molecular formula C)24H15BrN2): theoretical value C, 70.09; h, 3.68; br, 19.43; n, 6.81; test values are: c, 70.05; h, 3.64; br, 19.40; and N, 6.83. ESI-MS (M/z) (M)+): theoretical value is 410.04, found 410.06.
Synthesis of reaction raw material J-11: the detailed reaction conditions refer to the synthesis of starting material J-9.
Figure BDA0001921907140000161
Structural characterization: elemental analysis Structure (molecular formula C)25H14BrN): theoretical value C, 73.54; h, 3.46; br, 19.57; n, 3.43; test values are: c, 73.55; h, 3.45; br, 19.54; and N, 3.40. ESI-MS (M/z) (M)+): theoretical value is 407.03, found 407.05.
Preparation of intermediate I:
Figure BDA0001921907140000162
in a 250mL three-necked flask, nitrogen gas was introduced, 0.04mol of the starting material A-1, 150mL of THF and 0.05mol of the starting material B-1, 0.0004mol of tetrakis (triphenylphosphine) palladium were added, and the mixture was stirred well, followed by addition of 0.06mol of K2CO3Heating an aqueous solution (2M) to 80 ℃, carrying out reflux reaction for 10 hours, sampling a sample, completely reacting, naturally cooling, extracting with 200mL dichloromethane, layering, drying an extract with anhydrous sodium sulfate, filtering, carrying out rotary evaporation on a filtrate, and purifying by a silica gel column to obtain an intermediate C-1; HPLC purity 99.6%, yield 80.4%. Elemental analysis Structure (molecular formula C)9H5Cl2N3): theoretical value C, 47.82; h, 2.23; cl, 31.36; n, 18.59; test values are: c, 47.81; h, 2.23; cl, 31.36; and N, 18.60. ESI-MS (M/z) (M)+): theoretical value is 224.99, found 225.10.
Figure BDA0001921907140000163
In a 250mL three-necked flask, nitrogen gas was introduced, 0.02mol of intermediate C-1, 120mL of THF and 0.025mol of raw material D-1, 0.0002mol of tetrakis (triphenylphosphine) palladium were added, and the mixture was stirred well, followed by addition of 0.03mol of K2CO3Heating an aqueous solution (2M) to 80 ℃, carrying out reflux reaction for 10 hours, sampling a sample, completely reacting, naturally cooling, extracting with 200mL dichloromethane, layering, drying an extract with anhydrous sodium sulfate, filtering, carrying out rotary evaporation on a filtrate, and purifying by a silica gel column to obtain an intermediate E-1; HPLC purity 99.1%, yield 67.3%. Elemental analysis Structure (molecular formula C)15H10ClN3): theoretical value C, 67.30; h, 3.77; cl, 13.24; n, 15.70; test values are: c, 67.31; h, 3.75; cl, 13.25; n, 15.71. ESI-MS (M/z) (M)+): theoretical value is 267.06, found 267.05.
Figure BDA0001921907140000171
Weighing 0.01mol of raw material F-1 in a nitrogen atmosphere, dissolving the raw material F-1 in 45ml of tetrahydrofuran, cooling to-78 ℃, slowly dripping a cyclohexane solution containing 0.02mol of n-butyllithium, and keeping the temperature and stirring for 30 minutes after dripping is finished; slowly dripping tetrahydrofuran solution containing 0.035mol trimethyl borate, after dripping, slowly heating to room temperature, and reacting for 10 hours under the condition of heat preservation; after the reaction is finished, cooling to 0 ℃, slowly dripping distilled water, stirring for 1 hour after no gas is generated, and then heating to room temperature; the reaction solution was extracted with 150ml of ethyl acetate, the extract was washed with 150ml of saturated brine three times, finally dried over anhydrous magnesium sulfate, the solution was distilled under reduced pressure, and the obtained solid was purified by distillation with 400ml of toluene: recrystallizing the mixed solution of 3:1 ethanol to obtain an intermediate G-1; HPLC purity 94.7%, yield 76.8%. Elemental analysis structure (molecular formula C7H5 BClNO): theoretical value: c, 42.60; h, 2.55; b, 5.48; n, 7.10; o, 24.32; test values are: c, 42.59; h, 2.54; b, 5.46; n, 7.11; o, 24.30; ESI-MS (M/z) (M +): theoretical value is 197.01, found 197.03.
Figure BDA0001921907140000172
Introducing nitrogen into a 250mL three-necked flask, adding 0.02mol of intermediate E-1, 150mL of THF, 0.025mol of intermediate G-1, 0.0002mol of tetrakis (triphenylphosphine) palladium, uniformly stirring, adding 0.03mol of K2CO3 aqueous solution (2M), heating to 80 ℃, carrying out reflux reaction for 10 hours, sampling a sample point plate, completely reacting, naturally cooling, extracting with 200mL of dichloromethane, layering, drying an extract with anhydrous sodium sulfate, filtering, carrying out rotary evaporation on a filtrate, and purifying by a silica gel column to obtain an intermediate H-1; HPLC purity 99.2%, yield 67.1%. Elemental analysis structure (molecular formula C22H13ClN 4O): theoretical value C, 68.67; h, 3.41; cl, 9.21; n, 14.56; o, 4.16; test values are: c, 68.66; h, 3.40; cl, 9.23; n, 14.55; o, 4.14; ESI-MS (M/z) (M +): the theoretical value is 384.08, found 384.05.
Figure BDA0001921907140000181
Introducing nitrogen into a 250mL three-neck flask, adding 0.02mol of intermediate H-1, dissolving in 150mL tetrahydrofuran, uniformly stirring 0.024mol of bis (pinacolato) diboron, 0.0002mol of (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.05mol of potassium acetate, heating and refluxing the mixed solution of the reactants at the reaction temperature of 80 ℃ for 5 hours, cooling after the reaction is finished, filtering the mixture, drying the filtrate in a vacuum oven, and separating and purifying by a silica gel column to obtain an intermediate I-1; HPLC purity 99.6%, yield 91.2%. Elemental analysis structure (molecular formula C28H25BN4O 3): theoretical value C, 70.60; h, 5.29; b, 2.27; n, 11.76; o, 10.08; test values are: c, 70.61; h, 5.26; b, 2.25; n, 11.75; o, 10.06; . ESI-MS (M/z) (M +): theoretical value is 476.20, found 476.22.
The intermediate I is prepared by a synthesis method of the intermediate I-1, and specific structures of various related raw materials are shown in Table 1. For convenience, the same species appears in different reaction steps with different reference numerals.
TABLE 1
Figure BDA0001921907140000182
Figure BDA0001921907140000191
Figure BDA0001921907140000201
Example 1
Figure BDA0001921907140000211
In a 250mL three-necked flask, nitrogen gas was introduced, 0.01mol of starting material J-1, 150mL of THF, 0.015mol of intermediate I-1, 0.0001mol of tetrakis (triphenylphosphine) palladium were added, and the mixture was stirred well, followed by addition of 0.02mol of K2CO3Heating an aqueous solution (2M) to 80 ℃, carrying out reflux reaction for 15 hours, sampling a sample, completely reacting, naturally cooling, extracting with 200mL of dichloromethane, layering, drying an extract solution with anhydrous sodium sulfate, filtering, carrying out rotary evaporation on a filtrate, and purifying with a silica gel column by using petroleum ether as an eluting agent to obtain a target compound 1; HPLC purityThe degree is 99.1%, and the yield is 76.8%. Elemental analysis Structure (molecular formula C)48H30N4O): theoretical value C, 84.93; h, 4.45; n, 8.25; o, 2.36; test values are: c, 84.91; h, 4.46; n, 8.23; o, 2.35. ESI-MS (M/z) (M)+): theoretical value is 678.24, found 678.25.
Example 2
Figure BDA0001921907140000212
Compound 1 was prepared according to the synthetic procedure for compound 93, except that intermediate I-1 was replaced with intermediate I-2, resulting in the desired compound 1 being 99.3% pure and 78.1% yield. Elemental analysis Structure (molecular formula C)42H28N2): theoretical value C, 89.97; h, 5.03; n, 5.00; test values are: c, 89.96; h, 5.05; and N, 5.01. ESI-MS (M/z) (M)+): theoretical value is 560.23, found 560.21.
Example 3
Figure BDA0001921907140000221
Compound 4 was prepared according to the synthetic procedure for compound 93, except that intermediate I-1 was replaced with intermediate I-3, resulting in a purity of 99.2% for the target compound 4 and a yield of 78.5%. Elemental analysis Structure (molecular formula C)41H27N3): theoretical value C, 87.67; h, 4.85; n, 7.48; test values are: c, 87.65; h, 4.86; and N, 7.46. ESI-MS (M/z) (M)+): theoretical value is 561.22, found 561.23.
Example 4
Figure BDA0001921907140000222
Compound 33 was prepared according to the synthetic method for compound 93, except that starting material J-2 was used in place of starting material J-1 and intermediate I-4 was used in place of intermediate I-1, and that the target compound 33 was obtained in a purity of 99.1% and a yield of 80.3%. Elemental analysis Structure (molecular formula C)41H25N3): the theoretical value of C is the sum of the values of,87.99; h, 4.50; n, 7.51; test values are: c, 87.98; h, 4.51; and N, 7.52. ESI-MS (M/z) (M)+): theoretical value is 559.20, found 559.22.
Example 5
Figure BDA0001921907140000231
Compound 34 was prepared according to the synthetic procedure for compound 93, except that starting material J-8 was used instead of starting material J-1 and intermediate I-5 was used instead of intermediate I-1, to give the desired compound 34 in 99.4% purity and 78.4% yield. Elemental analysis Structure (molecular formula C)43H31N5): theoretical value C, 83.60; h, 5.06; n, 11.34; test values are: c, 83.57; h, 5.03; n, 11.36. ESI-MS (M/z) (M)+): theoretical value is 617.26, found 617.28.
Example 6
Figure BDA0001921907140000232
Compound 58 was prepared according to the synthetic procedure for compound 93, except that starting material J-2 was used instead of starting material J-1 and intermediate I-6 was used instead of intermediate I-1, to give the title compound 58 in 99.3% purity and 72.7% yield. Elemental analysis Structure (molecular formula C)49H31N): theoretical value C, 92.86; h, 4.93; n, 2.21; test values are: c, 92.85; h, 4.95; and N, 2.20. ESI-MS (M/z) (M)+): theoretical value is 633.25, found 633.23.
Example 7
Figure BDA0001921907140000241
Compound 59 was prepared according to the synthetic procedure for compound 93, except that starting material J-2 was used instead of starting material J-1 and intermediate I-7 was used instead of intermediate I-1, to give the target compound 59 with a purity of 98.9% and a yield of 76.8%. Elemental analysis Structure (molecular formula C)47H29N3): theoretical value C, 88.79; h, 4.60; n, 6.61; test values are: c, 88.77; h, 4.62; and N, 6.63. ESI-MS (M/z) (M)+): theoretical value is 635.24, found 635.22.
Example 8
Figure BDA0001921907140000242
Compound 75 was prepared according to the synthetic procedure for compound 93, except that starting material J-3 was used instead of starting material J-1 and intermediate I-3 was used instead of intermediate I-1, to give the title compound 75 in 98.7% purity and 79.3% yield. Elemental analysis Structure (molecular formula C)56H34N6): theoretical value C, 85.04; h, 4.33; n, 10.63; test values are: c, 85.05; h, 4.35; n, 10.65. ESI-MS (M/z) (M)+): theoretical value is 790.28, found 790.26.
Example 9
Figure BDA0001921907140000251
Compound 79 was prepared according to the synthetic method for compound 93 except that starting material J-2 was used instead of starting material J-1 and intermediate I-8 was used instead of intermediate I-1, giving the desired compound 79 a purity of 99.2% and a yield of 78.3%. Elemental analysis Structure (molecular formula C)50H30N4): theoretical value C, 87.44; h, 4.40; n, 8.19; test values are: c, 87.41; h, 4.42; and N, 8.15. ESI-MS (M/z) (M)+): theoretical value is 686.25, found 686.27.
Example 10
Figure BDA0001921907140000252
Compound 84 was prepared according to the synthetic procedure for compound 93, except that starting material J-4 was used instead of starting material J-1 and intermediate I-9 was used instead of intermediate I-1, giving the desired compound 84 with a purity of 99.3% and a yield of 83.3%. Elemental analysis Structure (molecular formula C)51H37N3): theoretical value C, 88.54; h, 5.39; n, 6.07; test values are: c, 88.55; h, 5.39; and N, 6.08. ESI-MS (M/z) (M)+): theoretical value is 691.30, found 691.32.
Example 11
Figure BDA0001921907140000261
Compound 89 was prepared according to the synthetic method for compound 93 except that starting material J-5 was used instead of starting material J-1 and intermediate I-2 was used instead of intermediate I-1, giving target compound 89 with a purity of 98.6% and a yield of 81.5%. Elemental analysis Structure (molecular formula C)58H36N4): theoretical value C, 88.30; h, 4.60; n, 7.10; test values are: c, 88.28; h, 4.63; and N, 7.12. ESI-MS (M/z) (M)+): theoretical value is 788.29, found 788.30.
Example 12
Figure BDA0001921907140000262
Compound 99 was prepared according to the synthetic procedure for compound 93 except that starting material J-9 was used in place of starting material J-1 and intermediate I-10 was used in place of intermediate I-1 to give the desired compound 99.4% purity in 81.3% yield. Elemental analysis Structure (molecular formula C)47H30N6): theoretical value C, 83.16; h, 4.45; n, 12.38; test values are: c, 83.18; h, 4.43; n, 12.39. ESI-MS (M/z) (M)+): theoretical value is 678.25, found 678.23.
Example 13
Figure BDA0001921907140000271
Compound 144 was prepared according to the synthetic procedure for compound 93, except that intermediate I-1 was replaced with intermediate I-11 to afford target compound 144 with a purity of 98.9% in a yield of 78.7%. Elemental analysis Structure (molecular formula C)50H32N4): theoretical value C, 87.18; h, 4.68; n, 8.13; test values are: c, 87.16; h, 4.66; and N, 8.15. ESI-MS (M/z) (M)+): theoretical value is 688.26, found 688.25.
Example 14
Figure BDA0001921907140000272
Compound 109 was prepared according to the synthetic procedure for compound 93, except that starting material J-2 was used instead of starting material J-1 and intermediate I-12 was used instead of intermediate I-1, giving the desired compound 109 a 98.9% purity and 80.4% yield. Elemental analysis Structure (molecular formula C)48H30N2): theoretical value C, 90.82; h, 4.76; n, 4.41; test values are: c, 90.83; h, 4.77; n, 4.43. ESI-MS (M/z) (M)+): theoretical value is 634.24, found 634.25.
Example 15
Figure BDA0001921907140000273
Compound 114 was prepared according to the synthetic method for compound 93, except that starting material J-4 was used instead of starting material J-1 and intermediate I-13 was used instead of intermediate I-1, and the obtained target compound 114 was 99.3% pure in yield 80.1%. Elemental analysis Structure (molecular formula C)61H36N6O): theoretical value C, 84.31; h, 4.18; n, 9.67; o, 1.84; test values are: c, 84.33; h, 4.16; n, 9.65; o, 1.85. ESI-MS (M/z) (M)+): theoretical value is 868.30, found 868.33.
Example 16
Figure BDA0001921907140000281
Compound 119 was prepared according to the synthetic procedure for compound 93, except that starting material J-2 was used instead of starting material J-1 and intermediate I-14 was used instead of intermediate I-1, and the target compound 119 was obtained with a purity of 98.5% and a yield of 74.8%. Elemental analysis Structure (molecular formula C)47H29N3): theoretical value C, 88.79; h, 4.60; n, 6.61; test values are: c, 88.81; h, 4.61; and N, 6.60. ESI-MS (M/z) (M)+): theoretical value is 635.24, found 635.25.
Example 17
Figure BDA0001921907140000282
Compound 124 was prepared according to the synthetic procedure for compound 93, except that starting material J-7 was used instead of starting material J-1 and intermediate I-11 was used instead of intermediate I-1, to give the title compound 124 with a purity of 98.4% and a yield of 75.9%. Elemental analysis Structure (molecular formula C)51H31N3): theoretical value C, 89.32; h, 4.56; n, 6.13; test values are: c, 89.30; h, 4.33; and N, 6.15. ESI-MS (M/z) (M)+): theoretical value is 685.25, found 685.27.
Example 18
Figure BDA0001921907140000291
Compound 154 was prepared according to the synthetic procedure for compound 93, except that starting material J-2 was used instead of starting material J-1 and intermediate I-12 was used instead of intermediate I-1, to give the title compound 154 with 98.6% purity and 78.1% yield. Elemental analysis Structure (molecular formula C)45H27N5): theoretical value C, 84.75; h, 4.27; n, 10.98; test values are: c, 84.76; h, 4.26; and N, 10.99. ESI-MS (M/z) (M)+): theoretical value is 637.23, found 637.25.
Example 19
Figure BDA0001921907140000292
Compound 169 was prepared by the synthetic method for compound 93, except that starting material J-10 was used instead of starting material J-1 and intermediate I-13 was used instead of intermediate I-1, and that the purity of the objective compound 169 was 98.6% and the yield was 76.7%. Elemental analysis Structure (molecular formula C)55H36N6O): theoretical value C, 82.89; h, 4.55; n, 10.55; o, 2.01; test values are: c, 82.87; h, 4.52; n, 10.53; and O, 2.03. ESI-MS (M/z) (M)+): theoretical value is 796.30, found 796.32.
Example 20
Figure BDA0001921907140000301
Compound 174 was prepared according to the synthesis method for compound 93, except that starting material J-2 was used instead of starting material J-1 and intermediate I-14 was used instead of intermediate I-1, and that target compound 174 was obtained with a purity of 98.1% and a yield of 78.3%. Elemental analysis Structure (molecular formula C)55H36N4O): theoretical value C, 85.91; h, 4.72; n, 7.29; o, 2.08; test values are: c, 85.90; h, 4.71; n, 7.28; and O, 2.08. ESI-MS (M/z) (M)+): theoretical value is 768.29, found 768.30.
Example 21
Figure BDA0001921907140000302
Compound 179 was prepared according to the synthetic procedure for Compound 93, except that starting material J-4 was used instead of starting material J-1 and intermediate I-15 was used instead of intermediate I-1, giving the desired compound 179 a purity of 99.2% with a yield of 77.5%. Elemental analysis Structure (molecular formula C)66H43N7): theoretical value C, 84.86; h, 4.64; n, 10.50; test values are: c, 84.85; h, 4.65; n, 10.52. ESI-MS (M/z) (M)+): theoretical value is 933.36, found 933.38.
Example 22
Figure BDA0001921907140000311
Compound 184 was prepared according to the synthetic procedure for compound 93, except that starting material J-11 was used instead of starting material J-1 and intermediate I-16 was used instead of intermediate I-1, giving the title compound 184 purity of 98.5% with a yield of 76.3%. Elemental analysis Structure (molecular formula C)51H28N10O): theoretical value C, 78.45; h, 3.61; n, 17.94; test values are: c, 78.44; h, 3.60; and N, 17.95. ESI-MS (M/z) (M)+): theoretical value is 780.25, found 780.27.
The compound of the invention can be used in a light-emitting device, can be used as a material of a light-emitting layer, and can also be used as a material of a hole blocking/electron transport layer. The compounds prepared in the above examples of the present invention were tested for thermal performance, T1 energy level, and HOMO energy level, respectively, and the test results are shown in table 2:
TABLE 2
Figure BDA0001921907140000312
Figure BDA0001921907140000321
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 thermogravimetric temperature Td is a temperature at which 1% of the weight loss is observed in a nitrogen atmosphere, and is measured on a TGA-50H thermogravimetric analyzer of Shimadzu corporation, Japan, and the nitrogen flow rate is 20 mL/min; the triplet energy level T1 was measured by Hitachi F4600 fluorescence spectrometer under the conditions of 2X 10-5A toluene solution of mol/L; the highest occupied molecular orbital HOMO energy level was tested by a photoelectron emission spectrometer (AC-2 type PESA) in an atmospheric environment.
The data in the table show that the organic compound has high glass transition temperature, can improve the phase stability of the material film, and further improves the service life of the device; the high T1 energy level can block the energy loss of the light-emitting layer, thereby improving the light-emitting efficiency of the device; the appropriate HOMO energy level can solve the problem of carrier injection and can reduce the voltage of the device. Therefore, after the organic compound is used for an OLED device, the luminous efficiency and the service life of the device can be effectively improved.
The effect of the synthesized OLED material of the present invention in the application of the device is detailed below by device examples 1-22 and comparative example 1. Compared with the device example 1, the device examples 2 to 22 and the comparative example 1 of the present invention have the same manufacturing process, and adopt the same substrate material and electrode material, and the film thickness of the electrode material is also kept consistent, except that the material of the light emitting layer, the material of the electron blocking layer or the material of the hole transport layer in the device is replaced. The results of the performance tests of the devices obtained in the examples are shown in table 3.
Device example 1: an electroluminescent device is shown in fig. 1, and the specific preparation steps include:
a) cleaning the ITO anode layer 2 on the transparent substrate layer 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 HAT-CN with the thickness of 10nm on the ITO anode layer 2 in a vacuum evaporation mode, wherein the HAT-CN is a hole injection layer 3;
c) evaporating and plating 50nm HT-1 on the hole injection layer 3 in a vacuum evaporation mode, wherein the layer is a hole transport layer 4;
d) evaporating EB-1 with the thickness of 20nm as an electron blocking layer 5 on the hole transmission layer 4 in a vacuum evaporation mode;
e) evaporating a 30nm light-emitting layer 6 on the electron blocking layer 5, wherein the light-emitting layer comprises a host material and an object material, the selection of the specific materials is shown in table 3, and the rate is controlled by a film thickness meter according to the mass percentage of the host material and the object material;
f) evaporating ET-1 and Liq with the mass ratio of ET-1 to Liq of 40nm on the light-emitting layer 6 in a vacuum evaporation mode, wherein the material is used as a hole blocking/electron transporting layer 7;
g) vacuum evaporating LiF with the thickness of 1nm on the hole blocking/electron transporting layer 7, wherein the layer is an electron injection layer 8;
h) vacuum evaporating cathode Al (100nm) on the electron injection layer 8, which is a cathode electrode layer 9;
and finally, packaging the device. The molecular structural formula of the related existing materials is shown as follows:
Figure BDA0001921907140000331
the electroluminescent device was fabricated as described above and the current efficiency and lifetime of the device were measured. Testing of the OLED device: the measurement was carried out using an IVL (Current-Voltage-Brightness) test system (Japanese システム Teken Co., Ltd.). Measurement of an electroluminescence spectrum in which the current efficiency is in cd/A, current/voltage/brightness according to the resulting Lambert emission characteristicsDegree (IVL) characteristic curve, calculating and determining the lifetime of the device, the lifetime data being at 10mA/cm2At constant current density.
TABLE 3
Figure BDA0001921907140000341
Figure BDA0001921907140000351
Figure BDA0001921907140000361
Figure BDA0001921907140000371
The inspection data of the obtained electroluminescent device are shown in Table 4.
TABLE 4
Figure BDA0001921907140000372
Figure BDA0001921907140000381
The results in table 4 show that the organic compound modified by aza-benzene of the present invention can be applied to the fabrication of OLED light emitting devices, and compared with the comparative examples of devices, the lifetime and efficiency of the devices are improved to different degrees compared with the prior art in the comparative examples, and especially the lifetime of the devices is significantly improved.
Further experimental study shows that the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, and the results of efficiency tests of device examples 5, 13 and 20 and device comparative example 1 at the temperature of-10-80 ℃ are shown in Table 5.
TABLE 5
Figure BDA0001921907140000382
As can be seen from the data in table 5, device examples 5, 13, and 20 are device structures in which the material of the present invention and the known material are combined, and compared with device comparative example 1, the device has high low-temperature efficiency, and the efficiency is steadily increased during the temperature increase process.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. An organic compound modified with an azepine, characterized in that the structure of the organic compound is represented by general formula (1):
Figure FDA0001921907130000011
in the general formula (1), - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -;
m and n are respectively and independently represented as a number 0 or 1, and m + n is more than or equal to 1;
z represents a nitrogen atom or C-H, and at least one Z represents a nitrogen atom;
x represents a nitrogen atom or C (R)0) (ii) a X at the attachment site represents a carbon atom;
Ar1、Ar2each independently represents a single bond, substituted or unsubstituted C6-C30One of an arylene, a substituted or unsubstituted 5-to 30-membered heteroarylene containing one or more heteroatoms;
R1、R2、R3、R4each independently represents substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
R0represented by hydrogen atom, protium, deuterium, tritium, halogen atom, cyano group, C1-C20Alkyl, substituted or unsubstituted C6-C30One of an aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group containing one or more heteroatoms;
the substituents which may be substituted are optionally selected from protium, deuterium, tritium, cyano, halogen, C1-C20Alkyl of (C)6-C30One or more of aryl, 5-to 30-membered heteroaryl containing one or more heteroatoms;
the hetero atom in the heteroaryl is one or more selected from nitrogen atom, oxygen atom or sulfur atom.
2. An organic compound modified with an aza-benzene as claimed in claim 1, wherein when m and n are both 1, at least two of Z in the general formula (1) represent nitrogen atoms, and Z's that are nitrogen are not all located on the same aza-benzene.
3. An organic compound modified with an azepine according to claim 1 wherein m + n is 1 and the number of nitrogen atoms represented by X in formula (1) is 0, 1 or 2.
4. An organic compound modified with an azepine according to claim 1 wherein m + n is 1, and in the general formula (1), Z represents 1, 2 or 3 as the number of nitrogen atoms.
5. An organic compound modified with an azepine as claimed in claim 1, wherein the organic compound is represented by one of the following structures represented by general formula (2) to general formula (5):
Figure FDA0001921907130000021
wherein the symbols and indices used have the meanings given in claim 1.
6. An organic substance modified with an azepine benzene as claimed in claim 1Compound characterized by the fact that Ar is1、Ar2Each independently represents one of substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted pyridylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthyridine, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted anthrylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted phenanthrylene, substituted or unsubstituted benzoxazole, substituted or unsubstituted benzimidazole and substituted or unsubstituted benzothiazole;
the R is1、R2、R3、R4Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinolyl group;
the R is0Represented by hydrogen atom, protium, deuterium, tritium, cyano group, fluorine atom, methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted biphenylyl group, substituted or unsubstituted terphenylyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted dibenzofuranyl group;
the substituent of the substitutable group is selected from protium, deuterium, tritium, cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, naphthyl, naphthyridinyl, pyridyl, biphenyl, terphenyl, furyl, carbazolyl or thienyl.
7. The organic compound modified by azabenzene as claimed in claim 1, wherein the specific structural formula of the organic compound is:
Figure FDA0001921907130000031
Figure FDA0001921907130000041
Figure FDA0001921907130000051
Figure FDA0001921907130000061
Figure FDA0001921907130000071
Figure FDA0001921907130000081
Figure FDA0001921907130000091
Figure FDA0001921907130000101
Figure FDA0001921907130000111
any one of them.
8. An organic electroluminescent element, characterized in that a functional layer of the organic electroluminescent element contains the organic compound modified with an azabenzene according to any one of claims 1 to 7.
9. An organic electroluminescent device according to claim 8, comprising a light-emitting layer and/or an electron-blocking layer and/or a hole-transporting layer, wherein the light-emitting layer and/or the electron-blocking layer and/or the hole-transporting layer contains the organic compound modified with an azepine according to any one of claims 1 to 7.
10. A lighting or display element comprising the organic electroluminescent device according to claim 8 or 9.
CN201811598707.1A 2018-12-26 2018-12-26 Azabenzene modified organic compound and application thereof Pending CN111362866A (en)

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Publication number Priority date Publication date Assignee Title
CN114685427A (en) * 2020-12-28 2022-07-01 常州强力昱镭光电材料有限公司 Quinoline bipyridyl compound and application thereof in organic electroluminescent element

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WO2012128509A2 (en) * 2011-03-21 2012-09-27 덕산하이메탈(주) Compound and organic electric element using same, and electronic device thereof

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
WO2012128509A2 (en) * 2011-03-21 2012-09-27 덕산하이메탈(주) Compound and organic electric element using same, and electronic device thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114685427A (en) * 2020-12-28 2022-07-01 常州强力昱镭光电材料有限公司 Quinoline bipyridyl compound and application thereof in organic electroluminescent element
CN114685427B (en) * 2020-12-28 2023-12-22 常州强力昱镭光电材料有限公司 Quinoline bipyridine compound and application thereof in organic electroluminescent element

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