CN111233867A - Organic compound with carbazole derivative as core and application thereof in organic electroluminescent device - Google Patents

Organic compound with carbazole derivative as core and application thereof in organic electroluminescent device Download PDF

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CN111233867A
CN111233867A CN201811443878.7A CN201811443878A CN111233867A CN 111233867 A CN111233867 A CN 111233867A CN 201811443878 A CN201811443878 A CN 201811443878A CN 111233867 A CN111233867 A CN 111233867A
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李崇
梁丽
王芳
谢丹丹
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Jiangsu Sunera Technology Co Ltd
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Abstract

The invention relates to an organic compound taking carbazole derivatives as cores and application thereof in organic electroluminescent devices, the organic compound provided by the invention takes carbazole derivatives as cores, the structure is shown as a general formula (1),
Figure DDA0001885279130000011
the 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

Organic compound with carbazole derivative as core and application thereof in organic electroluminescent device
Technical Field
The invention relates to the technical field of semiconductors, in particular to an organic compound taking carbazole derivatives as cores and application thereof in an organic electroluminescent device.
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 is already applied in the fields of smart phones, tablet computers, and the like, and is further expanded to the large-size application field of televisions, and the like, but compared with the actual product application requirements, the performance of the OLED device, such as light emitting efficiency, service life, and the like, needs to be further improved.
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.
The photoelectric functional materials of the OLED applied to the OLED device can be divided into two categories from the aspect of application, namely charge injection transmission materials and luminescent materials. Further, the charge injection transport material may be classified into an electron injection transport material, an electron blocking material, a hole injection transport material, and a hole blocking material, and the light emitting material may be classified into a host light emitting material and a doping material.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, as a host material of a light-emitting layer, good bipolar, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, the OLED device structure applied in industry comprises a hole injection layer, a hole transmission layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transmission 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 transmission material, a light emitting material, an electron transmission 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 material has stronger selectivity, and the performance of the same material in the devices with different structures can be completely different.
Therefore, aiming at the industrial application requirements of the current OLED device and the requirements of different functional film layers and photoelectric characteristics of the OLED device, a more suitable OLED functional material or material combination with higher 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 lighting industry, the development of the current OLED material is far from enough, and lags behind the requirements of panel manufacturing enterprises, and it is very important to develop a higher-performance organic functional material as a material enterprise.
Disclosure of Invention
In view of the above problems in the prior art, the present applicant provides an organic compound with carbazole derivatives as the core and its application in organic electroluminescent devices. 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 of the invention is as follows: an organic compound with a carbazole derivative as a core, wherein the structure of the organic compound is shown as a general formula (1):
Figure BDA0001885279110000021
in the general formula (1), Ar1Represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzocarbazolyl group, a substituted or unsubstituted dibenzocarbazolyl group, a substituted or unsubstituted benzofuranyl group;
Ar2represented by a structure represented by the general formula (2);
Figure BDA0001885279110000022
L、Laeach independently represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted pyridylene group, a substituted or unsubstituted carbazolyl group, or a substituted or unsubstituted dibenzofuranylene group;
in the general formula (2), X1Represented by-O-, -S-or-C (R)3)(R4)；
R1、R2Is represented by a hydrogen atom or a structure represented by the general formula (3), except that R1And R2Not hydrogen at the same time;
Figure BDA0001885279110000031
in the general formula (3), X2、X3Respectively represented by-O-, -S-, -C (R)3)(R4) -or-N (R)5)-；X3May also represent a single bond;
R3～R5are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30One of aryl and substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms in the heteroaryl are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms; r3And R4Can be bonded to each other to form a ring;
general formula (3) by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL5-CL6Key, CL6-CL7Bond or CL7-CL8A bond is annulated to formula (1);
the substituent of the above-mentioned substitutable group is optionally selected from one or more of cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, dibenzofuranyl, carbazolyl or furanyl.
As a further improvement of the invention, the structural general formula of the organic compound is represented as;
Figure BDA0001885279110000032
Figure BDA0001885279110000041
any one of (a);
in the general formulae (2-1) to (2-9), X4～X7Independently represent-O-, -S-, -C (R)3)(R4) -or-N (R)5)-；X5、X7May also represent a single bond;
R3～R5are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30One of aryl and substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms in the heteroaryl are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms; r3And R4Can be bonded to each other to form a ring;
said substituted C6-30The substituents for the aryl group and the substituted 5-to 30-membered heteroaryl group are optionally one or more selected from cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenylyl, terphenylyl, naphthyridinyl, pyridyl, benzofuranyl, carbazolyl or furanyl.
As a further improvement of the invention, R3～R5Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, terphenyl, naphthyridinyl, biphenylyl or pyridyl.
As a further improvement of the invention, the specific structure of the organic compound taking the carbazole derivative as the core is
Figure BDA0001885279110000042
Figure BDA0001885279110000051
Figure BDA0001885279110000061
Figure BDA0001885279110000071
Figure BDA0001885279110000081
Figure BDA0001885279110000091
Figure BDA0001885279110000092
Any one of them.
The reaction equation occurring during the preparation of the organic compound is:
Ar2represented by a general structural formula shown in a general formula (2),
Figure BDA0001885279110000101
the preparation method comprises the following steps: weighing the intermediate I and the intermediate II, dissolving the intermediate I and the intermediate II in a toluene/water/ethanol mixed solution with the volume ratio of 3:1:1, and adding palladium acetate, cesium carbonate and 2-dicyclohexyl phosphorus-2 ',4',6' -triisopropyl biphenyl; microwave reacting at 120 deg.C under nitrogen protection for 3 hr, extracting with dichloromethane to obtain organic layer, and adding anhydrous MgSO4Drying, and further separating and purifying by a column chromatography method to obtain a target product;
the molar ratio of the intermediate I to the intermediate II is 1.0-3.0: 1, and Pd (OAc)2The molar ratio of the intermediate I to the intermediate I is 0.001-0.003: 1, and Cs2CO3The molar ratio of the Xphos to the intermediate I is 0.5-3: 1, and the molar ratio of the Xphos to the intermediate I is 1.0-4: 1.
The organic compound taking the carbazole derivative as the core is used for preparing an organic electroluminescent device.
An organic electroluminescent device comprising at least one functional layer containing the organic compound having the carbazole derivative as a core.
As a further improvement of the present invention, the functional layer includes an electron blocking layer or a hole transporting layer, and the electron blocking layer or the hole transporting layer contains the organic compound having the carbazole derivative as a core.
In a further improvement of the present invention, the functional layer includes a light-emitting layer containing the organic compound having the carbazole derivative as a core.
As a further improvement of the present invention, a lighting or display element comprises the organic light emitting device.
The beneficial technical effects of the invention are as follows:
the organic compound has a structure which enables the distribution of electrons and holes in the light-emitting layer to be more balanced, and under the proper 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 luminescent layer; when the carbazole derivative is used as an electron blocking layer material of an OLED light-emitting device, the carbazole derivative is matched with the branched chain in the range of the invention, so that the exciton utilization rate and the fluorescence radiation efficiency can be effectively improved, the efficiency roll-off under high current density is reduced, the voltage of the device is reduced, the current efficiency of the device is improved, and the service life of the device is prolonged.
The compound takes a carbazole derivative as a core, the carbazole parallel-ring structure has a deeper HOMO energy level, the HOMO energy level can be effectively adjusted by matching with the branched chain in the range of the invention, the compound with shallow HOMO energy level can be used as an electron blocking or hole transport layer material, and the compound with deep HOMO energy level can be used as a host material.
The structure disclosed in patent CN106233489A has a higher similarity to the compound of the present invention, and is different in that the branched chain of the compound of the present invention is in a star structure, so that the intermolecular distance is larger, the intermolecular interaction force is weaker, and the smaller the intermolecular interaction force is, the easier it is to overcome the intermolecular interaction force to evaporate onto the substrate, and therefore the evaporation temperature can be reduced.
When the organic compound is applied to an OLED device, the structure of the device is optimized, so that high film stability can be kept, and the photoelectric property 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 light-emitting devices.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device using the materials listed in the present invention; the organic electroluminescent device comprises a transparent substrate layer 1, a transparent 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, a hole blocking/electron transport layer 8, an electron injection layer 9, a cathode layer 10 and a light extraction 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 present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1: synthesis of intermediate IV
Synthesis of intermediate IV-1
Figure BDA0001885279110000111
(1) In a 250mL three-necked flask, 0.01mol of the starting material V-1 and 0.015mol of the starting material VI-1 were added under nitrogen protection, dissolved in a mixed solvent of toluene and ethanol (wherein the mixed solvent contains 90mL of toluene and 45mL of ethanol), and then added with a solution containing 0.03mol of Na2CO3Na of (2)2CO3Aqueous solution (2M), stirred for 1h under nitrogen and then 0.0001mol Pd (PPh) was added3)4And heating and refluxing for 15h, sampling a sample point plate, and completely reacting. Naturally cooling, filtering, rotatably evaporating filtrate, and passing residue through a silica gel column to obtain an intermediate VII-1; HPLC purity 97.7%, yield 85.9%;
elemental analysis Structure (molecular formula C)30H20N2O2): theoretical value C, 81.80; h, 4.58; n, 6.36; o, 7.26; test values are: c, 81.82; h, 4.56; n, 6.34; and O, 7.23. ESI-MS (M/z) (M +): theoretical value is 440.15, found 440.18.
(2) Adding 0.02mol of intermediate VII-1 into a 250mL three-neck flask under the protection of nitrogen, dissolving with 100mL o-dichlorobenzene, adding 0.03mol of triphenylphosphine, stirring at 170-190 ℃ for reaction for 12-16 h, cooling to room temperature after the reaction is finished, filtering, decompressing and rotary-steaming the filtrate, and passing through a neutral silica gel column to obtain an intermediate IV-1; HPLC purity 96.5%, yield 78.6%;
elemental analysis Structure (molecular formula C)30H20N2): theoretical value C, 88.21; h, 4.94; n, 6.86; test values are: c, 88.23; h, 4.92; and N, 6.83. ESI-MS (M/z) (M +): theoretical value is 408.16, found 408.13.
The synthesis of the intermediate IV-1 comprises two steps: synthesizing an intermediate VII-1 from the raw material VI-1 and the raw material V-1; and performing cyclization reaction on the intermediate VII-1 to form an intermediate IV-1. The preparation method of other intermediate IV is similar to that of intermediate IV-1, and the specific structure of the intermediate IV used in the invention is shown in Table 1.
TABLE 1
Figure BDA0001885279110000121
Figure BDA0001885279110000131
Figure BDA0001885279110000141
Figure BDA0001885279110000151
Figure BDA0001885279110000161
Figure BDA0001885279110000171
Figure BDA0001885279110000181
Example 2: synthesis of intermediate I
Synthesis of intermediate I-1
Figure BDA0001885279110000182
A250 ml three-necked flask was charged with 0.01mol of the starting III-1, 0.012mol of the intermediate IV-1, 0.03mol of potassium tert-butoxide, 1X 10 mol under a nitrogen gas atmosphere-4mol Pd2(dba)3，1×10-4Heating and refluxing triphenylphosphine and 150ml toluene for 12 hours, sampling a sample, and completely reacting; naturally cooling, filtering, rotatably steaming the filtrate, and passing through a silica gel column to obtain an intermediate I-1; HPLC purity 98.7%, yield 85.9%; elemental analysis Structure (molecular formula C)46H29ClN2): theoretical value C, 85.63; h, 4.53; cl, 5.49; n, 4.34; test values are: c, 85.65; h, 4.55; cl, 5.51; and N, 4.31. ESI-MS (M/z) (M +): theoretical value is 644.20, found 644.23.
The preparation method of other intermediates I is similar to that of the intermediate I-1, and the specific structure of the intermediate I used in the invention is shown in Table 2.
TABLE 2
Figure BDA0001885279110000191
Figure BDA0001885279110000201
Example 3: synthesis of intermediate II-1
Figure BDA0001885279110000202
In a 250mL three-necked flask, nitrogen gas was introduced and 10.0mol of the raw material VIII-1, 12.0mol of the raw material IX-1, 0.3g of Pd (dppf) Cl230.0mmol of potassium acetate was added to 100mL of 1, 4-dioxane and reacted at 130 ℃ for 5 hours. The target product is obtained by silica gel column chromatography separation and purification, the HPLC purity is 99.8 percent, and the yield is 60.5 percent. Elemental analysis Structure (molecular formula C)18H19BO3): theoretical value C, 73.50; h, 6.51; b, 3.67; o, 16.32; test values are: c, 73.52; h, 6.53; b, 3.65; o, 16.34. ESI-MS (M/z) (M)+): theoretical value is 294.14, found 294.19.
Synthesis of the remaining intermediates II reference was made to the synthesis of intermediate II-1.
EXAMPLE 4 Synthesis of Compound 1
Figure BDA0001885279110000211
The preparation method comprises the following steps: weighing 11.11mol of intermediate I-1 and 7.40mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; further, 0.012molPd (OAc)2、7.21mmol Cs2CO3And 14.42mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.8% and yield of 66%.
Elemental analysis Structure (molecular formula C)58H36N2O): theoretical value C, 89.66; h, 4.67; n, 3.61; o, 2.06; test values are: c, 89.65; h, 4.64; n, 3.63; and O, 2.04. ESI-MS (M/z) (M)+): theoretical value is 776.28, found 776.25.
EXAMPLE 5 Synthesis of Compound 2
Figure BDA0001885279110000212
The preparation method comprises the following steps: weighing 11.82mol of intermediate I-2 and 7.91mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.015mol Pd (OAc) is added2、7.82mmol Cs2CO3And 16.61mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.8% and yield of 66%.
Elemental analysis Structure (molecular formula C)58H36N2O): theoretical value C, 89.66; h, 4.67; n, 3.61; o, 2.06; test values are: c, 89.63; h, 4.66;N,3.64；O,2.05。ESI-MS(m/z)(M+): theoretical value is 776.28, found 776.26.
EXAMPLE 6 Synthesis of Compound 5
Figure BDA0001885279110000213
The preparation method comprises the following steps: weighing 12.1mol of intermediate I-4 and 8.1mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.016mol Pd (OAc)2、7.83mmol Cs2CO3And 15.74mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 64%.
Elemental analysis Structure (molecular formula C)54H34N2O): theoretical value C, 89.23; h, 4.71; n, 3.85; o, 2.20; test values are: c, 89.25; h, 4.72; n, 3.88; o, 2.25. ESI-MS (M/z) (M)+): theoretical value is 726.27, found 726.26.
EXAMPLE 7 Synthesis of Compound 62
Figure BDA0001885279110000221
The preparation method comprises the following steps: weighing 11.43mol of intermediate I-3 and 7.62mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.017mol Pd (OAc)2、7.43mmol Cs2CO3And 14.81mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 67%.
Elemental analysis Structure (molecular formula C)51H33NO3): theoretical value C, 86.54; h, 4.70; n, 1.98; o, 6.78; test values are: c,86.56；H,4.76；N,1.95；O,6.75。ESI-MS(m/z)(M+): theoretical value is 707.25, found 707.28.
EXAMPLE 8 Synthesis of Compound 98
Figure BDA0001885279110000222
The preparation method comprises the following steps: weighing 11.41mol of intermediate I-6 and 7.62mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.016molPd (OAc)2、7.91mmol Cs2CO3And 15.92mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 68%.
Elemental analysis Structure (molecular formula C)66H39N3O2): theoretical value C, 87.49; h, 4.34; n, 4.64; o, 3.53; test values are: c, 87.51; h, 4.35; n, 4.65; and O, 3.51. ESI-MS (M/z) (M)+): theoretical value is 905.30, found 905.33.
EXAMPLE 9 Synthesis of Compound 106
Figure BDA0001885279110000231
The preparation method comprises the following steps: weighing 11.84mol of intermediate I-5 and 7.45mol of intermediate II-2, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.021mol Pd (OAc) is added2、7.67mmol Cs2CO3And 14.83mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.8% and yield of 66%.
Elemental analysis Structure (molecular formula C)57H36N2S2): theoretical value C, 84.20; h4.46; n, 3.45; s, 7.89; test values are: c, 84.25; h, 4.48; n, 3.48; and S, 7.85. ESI-MS (M/z) (M)+): theoretical value is 812.23, found 812.26.
EXAMPLE 10 Synthesis of Compound 107
Figure BDA0001885279110000232
The preparation method comprises the following steps: weighing 11.72mol of intermediate I-12 and 7.31mol of intermediate II-2, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.016mol Pd (OAc)2、8.19mmol Cs2CO3And 14.42mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 65%.
Elemental analysis Structure (molecular formula C)63H43N3): theoretical value C, 89.86; h, 5.15; n, 4.99; test values are: c, 89.85; h, 5.16; and N, 4.94. ESI-MS (M/z) (M)+): theoretical value is 841.35, found 841.33.
EXAMPLE 11 Synthesis of Compound 115
Figure BDA0001885279110000241
The preparation method comprises the following steps: weighing 11.85mol of intermediate I-10 and 7.46mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.022mol Pd (OAc) is added2、7.67mmol Cs2CO3And 15.34mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.8% and yield of 66%.
Elemental analysis Structure (molecular formula C)60H41NO2): theoretical value C,89.19; h, 5.11; n, 1.73; o, 3.96; test values are: c, 89.21; h, 5.12; n, 1.75; and O, 3.94. ESI-MS (M/z) (M)+): theoretical value is 807.31, found 807.35.
EXAMPLE 12 Synthesis of Compound 122
Figure BDA0001885279110000242
The preparation method comprises the following steps: weighing 10.31mol of intermediate I-11 and 7.23mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.011mol Pd (OAc)2、6.56mmol Cs2CO3And 13.12mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 66%.
Elemental analysis Structure (molecular formula C)70H51N3O): theoretical value C, 88.48; h, 5.41; n, 4.42; o, 1.68; test values are: c, 88.43; h, 5.43; n, 4.44; o, 1.65. ESI-MS (M/z) (M)+): theoretical value is 949.40, found 949.42.
EXAMPLE 13 Synthesis of Compound 128
Figure BDA0001885279110000243
The preparation method comprises the following steps: weighing 11.35mol of intermediate I-8 and 7.11mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.016mol Pd (OAc)2、7.36mmol Cs2CO3And 14.72mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 64%.
Elemental analysis Structure (molecular formula C)54H39NO3): theoretical value C, 86.49; h, 5.24; n, 1.87; o, 6.40; test values are: c, 86.51; h, 5.26; n, 1.88; and O, 6.36. ESI-MS (M/z) (M)+): theoretical value is 749.29, found 749.35.
EXAMPLE 14 Synthesis of Compound 133
Figure BDA0001885279110000251
The preparation method comprises the following steps: weighing 12.11mol of intermediate I-8 and 7.62mol of intermediate II-3, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.025mol Pd (OAc)2、7.98mmol Cs2CO3And 15.12mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.8% and yield of 66%.
Elemental analysis Structure (molecular formula C)54H39NO3): theoretical value C, 86.49; h, 5.24; n, 1.87; o, 6.40; test values are: c, 86.51; h, 5.26; n, 1.85; o, 6.43. ESI-MS (M/z) (M)+): theoretical value is 749.29, found 749.25.
EXAMPLE 15 Synthesis of Compound 143
Figure BDA0001885279110000252
The preparation method comprises the following steps: weighing 11.84mol of intermediate I-7 and 7.42mol of intermediate II-4, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.017mol Pd (OAc)2、7.71mmol Cs2CO3And 15.38mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 67%.
Elemental analysis Structure (molecular formula C)58H41NO2S): theoretical value C, 85.37; h, 5.06; n, 1.72; o, 3.92; s, 3.93; test values are: c, 85.35; h, 5.04; n, 1.73; o, 3.94; and S, 3.91. ESI-MS (M/z) (M)+): theoretical value is 815.29, found 815.33.
EXAMPLE 16 Synthesis of Compound 146
Figure BDA0001885279110000261
The preparation method comprises the following steps: weighing 11.67mol of intermediate I-9 and 7.32mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.016mol Pd (OAc)2、7.60mmol Cs2CO3And 14.60mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 68%.
Elemental analysis Structure (molecular formula C)64H39N3O): theoretical value C, 88.76; h, 4.54; n, 4.85; o, 1.85; test values are: c, 88.77; h, 4.55; n, 4.87; o, 1.83. ESI-MS (M/z) (M)+): theoretical value is 865.31, found 865.35.
EXAMPLE 17 Synthesis of Compound 150
Figure BDA0001885279110000262
The preparation method comprises the following steps: weighing 11.82mol of intermediate I-13 and 7.91mol of intermediate II-5, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.018mol Pd (OAc)2、7.71mmol Cs2CO3And 14.89mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 65%.
Elemental analysis Structure (molecular formula C)55H37NO): theoretical value C, 90.75; h, 5.12; n, 1.92; o, 2.20; test values are: c, 90.72; h, 5.13; n, 1.94; o, 2.22. ESI-MS (M/z) (M)+): theoretical value is 727.29, found 727.24.
EXAMPLE 18 Synthesis of Compound 156
Figure BDA0001885279110000271
The preparation method comprises the following steps: weighing 11.43mol of intermediate I-14 and 7.91mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.018mol Pd (OAc)2、7.71mmol Cs2CO3And 14.89mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.7% and yield of 65%.
Elemental analysis Structure (molecular formula C)46H27NO2): theoretical value C, 88.30; h, 4.35; n, 2.24; o, 5.11; test values are: c, 88.31; h, 4.33; n, 2.25; and O, 5.12. ESI-MS (M/z) (M)+): theoretical value is 625.20, found 625.24.
EXAMPLE 19 Synthesis of Compound 162
Figure BDA0001885279110000272
The preparation method comprises the following steps: weighing 11.41mol of intermediate I-15 and 7.62mol of intermediate II-5, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.016mol Pd (OAc)2, 7.91mmol Cs2CO3 and 15.92mmol Xphos are added; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane, dried over anhydrous MgSO4, and further separated and purified by column chromatography to obtain the target product with HPLC purity 99.7% and yield 68%.
Elemental analysis Structure (molecular formula C)63H42N2O): theoretical value C, 89.76; h, 5.02; n, 3.32; o, 1.90; test values are: c, 89.77; h, 5.03; n, 3.33; o, 1.88. ESI-MS (M/z) (M +): theoretical value is 842.33, found 842.31.
EXAMPLE 20 Synthesis of Compound 168
Figure BDA0001885279110000281
The preparation method comprises the following steps: weighing 11.84mol of intermediate I-16 and 7.45mol of intermediate II-1, and dissolving by using a toluene/water/ethanol mixed solution with a volume ratio of 3:1: 1; then 0.021mol Pd (OAc) is added2、7.67mmol Cs2CO3And 14.83mmol Xphos; and carrying out microwave reaction for 3 hours at the temperature of 120 ℃ under the protection of nitrogen. After the reaction, the organic layer was extracted with dichloromethane and anhydrous MgSO4Drying, and further separating and purifying by column chromatography to obtain the target product with HPLC purity of 99.8% and yield of 66%.
Elemental analysis Structure (molecular formula C)52H29NO3): theoretical value C, 87.25; h, 4.08; n, 1.96; o, 6.71; test values are: c, 87.23; h, 4.05; n, 1.93; and O, 6.72. ESI-MS (M/z) (M +): theoretical value is 715.21, found 715.16.
The organic compound is used in a light-emitting device, has high glass transition temperature (Tg) and triplet state energy level (T1), and suitable HOMO and LUMO energy levels, and can be used as a light-emitting layer material. The thermal performance, T1 energy level and HOMO energy level of the compound of the present invention and the existing material were measured, respectively, and the results are shown in table 3.
TABLE 3
Figure BDA0001885279110000282
Figure BDA0001885279110000291
Note: the triplet state energy level T1 was measured by Hitachi F4600 fluorescence spectrometer, test strip of materialThe parts being 2 x 10- 5A toluene solution of mol/L; the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC204F1 DSC, Germany Chi corporation), the heating rate is 10 ℃/min; the highest occupied molecular orbital HOMO energy level was calculated from a photoelectron emission spectrometer (AC-2 type PESA) and an ultraviolet spectrophotometer (UV) test, which is an atmospheric environment.
As can be seen from the data in the table above, the compound of the present invention has a suitable HOMO energy level and is suitable for being used as an electron blocking layer material; meanwhile, the compound has higher thermal stability, so that the service life of an OLED device using the compound is prolonged.
The arrangement mode and the interaction energy between two molecules are calculated by using Gaussian 16 software and adopting a B3LYP/6-31G (d) method, and the smaller the value of the interaction energy between the molecules is, the larger the energy released by the molecules is, the larger the interaction force between the molecules is, the more stable the molecules are, and the less separation is easy to occur. The results of comparison of compound 34 of the present invention with compound C-325 disclosed in patent CN106233489A are shown in Table 4:
TABLE 4
Figure BDA0001885279110000292
The data in table 4 show that the comparative compound C-325 has a large intermolecular interaction force, and when the comparative compound is used in an electroluminescent device, the display effect of the device is adversely affected, because when the comparative compound is used as an OLED device, the film formation method used is an evaporation method, and when an organic compound having an excessively large intermolecular interaction force is heated and evaporated, the evaporation temperature is significantly increased to overcome the intermolecular interaction force, and the evaporation temperature is excessively increased to cause decomposition of organic molecules, thereby generating impurities and reducing the service life of the device; the compound of the invention has relatively small intermolecular interaction force, is easy to overcome the problem that intermolecular interaction force is evaporated onto a substrate, so that the evaporation temperature can be reduced, and the problem of organic molecule decomposition caused by overhigh evaporation temperature of the molecules of the contrast compound is solved.
The following device examples 1 to 17 and comparative example 1 illustrate in detail the application effects of the synthesized compound of the present invention as an electron blocking layer and a light emitting layer in a device. Compared with the device embodiment 1, the device embodiments 2-10 and the device comparative example 1 have the advantages that the manufacturing processes of the devices are completely the same, the same substrate material and the same electrode material are adopted, the film thicknesses of the electrode materials are also kept consistent, and the difference is that the material of the electron blocking layer in the device is changed; device examples 11 to 17 change the material of the light emitting layer of the device. The composition of the resulting device structure of each example is shown in table 4. The results of the performance tests of the devices obtained in the examples are shown in table 5.
Device example 1
As shown in fig. 1, a method for manufacturing an electroluminescent device includes the following steps:
as shown in fig. 1, the transparent substrate layer 1 is a transparent PI film, and the ITO anode layer 2 (film thickness of 150nm) is washed, i.e., washed with alkali, washed with pure water, dried, and then washed with ultraviolet rays and ozone to remove organic residues on the surface of the transparent ITO. On the ITO anode layer 2 after the above washing, HAT-CN having a film thickness of 10nm was deposited by a vacuum deposition apparatus to be used as the hole injection layer 3. Then, HT-1 was evaporated to a thickness of 60nm as a hole transport layer. Compound 1 was then evaporated to a thickness of 20nm as an electron blocking layer. After the evaporation of the hole transport material is finished, a light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the light emitting layer 6 comprises GH-1 and GH-2 used by the OLED light emitting layer 6 as main materials, GD-1 used as a doping material, the doping proportion of the doping material is 10% by weight, and the thickness of the light emitting layer is 40 nm. After the light-emitting layer 6, the electron transport layer materials ET-1 and Liq are continuously vacuum-evaporated. The vacuum evaporation film thickness of the material was 40nm, and this layer was a hole-blocking/electron-transporting layer 7. On the hole-blocking/electron-transporting layer 7, a lithium fluoride (LiF) layer having a film thickness of 1nm was formed by a vacuum evaporation apparatus, and this layer was an electron-injecting layer 8. On the electron injection layer 8, a vacuum deposition apparatus was used to produce a 15 nm-thick Mg: an Ag electrode layer, which is used as the cathode layer 9. On the cathode layer 9, 70nm of CP-1 was vacuum-deposited as a CPL layer 10.
Figure BDA0001885279110000301
Figure BDA0001885279110000311
TABLE 4
Figure BDA0001885279110000312
Figure BDA0001885279110000321
TABLE 5
Figure BDA0001885279110000322
Figure BDA0001885279110000331
The device test performance is referred to comparative example 1; the current efficiency is all 10mA/cm2Measured under the condition; the life test System is an OLED device life tester developed by LTD and having model number of EAS-62C.
The results in table 5 show that the compound of the present invention can be used as an electron blocking layer material and a light emitting layer material for fabricating an OLED light emitting device, and compared with comparative example 1, the efficiency and lifetime of the compound are greatly improved compared with those of the known OLED material, and especially the driving lifetime of the device is greatly prolonged.
Further, the efficiency of the OLED device prepared by the material is stable when the OLED device works at low temperature, the efficiency test is carried out on the device examples 1, 3 and 15 and the device comparative example 1 at the temperature of-10-80 ℃, and the obtained results are shown in the table 6 and the figure 2.
TABLE 6
Figure BDA0001885279110000341
As can be seen from the data in table 6, examples 1, 3 and 15 are device structures in which the material of the present invention and the known material are combined, and compared with comparative device 1, the efficiency is high at low temperature, and the efficiency is steadily increased during the temperature increase process.
From the data application, the compound has good application effect as an electron blocking layer material in an OLED light-emitting device and has good industrialization prospect.
Although the present invention has been disclosed by way of examples and preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and similar arrangements as would be apparent to those skilled in the art. The scope of the following claims is, therefore, to be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements.

Claims (10)

1. An organic compound having a carbazole derivative as a core, characterized in that the structure of the organic compound is represented by general formula (1):
Figure FDA0001885279100000011
in the general formula (1), Ar1Represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzocarbazolyl group, a substituted or unsubstituted dibenzocarbazolyl group, a substituted or unsubstituted benzofuranyl group;
Ar2represented by a structure represented by the general formula (2);
Figure FDA0001885279100000012
L、Laeach independently represents a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted pyridinylene group;
in the general formula (2), X1Represented by-O-, -S-or-C (R)3)(R4)；
R1、R2Is represented by a hydrogen atom or a structure represented by the general formula (3), except that R1And R2Not hydrogen at the same time;
Figure FDA0001885279100000013
in the general formula (3), X2、X3Respectively represented by-O-, -S-, -C (R)3)(R4) -or-N (R)5)-；X3May also represent a single bond;
the R is3～R5Are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30One of aryl and substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms in the heteroaryl are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms; r3And R4Can be bonded to each other to form a ring;
general formula (3) by CL1-CL2Key, CL2-CL3Key, CL3-CL4Key, CL5-CL6Key, CL6-CL7Bond or CL7-CL8A bond is annulated to formula (1);
the substituent of the above-mentioned substitutable group is optionally selected from one or more of cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenyl, pyridyl, dibenzofuranyl, carbazolyl or furanyl.
2. The organic compound according to claim 1, wherein the structural formula of the organic compound is represented by;
Figure FDA0001885279100000021
any one of (a);
in the general formulae (2-1) to (2-9), X4～X7Independently represent-O-, -S-, -C (R)3)(R4) -or-N (R)5)-；X5、X7May also represent a single bond;
R3～R5are each independently represented by C1-10Alkyl, substituted or unsubstituted C6-30One of aryl and substituted or unsubstituted 5-30-membered heteroaryl containing one or more heteroatoms, wherein the heteroatoms in the heteroaryl are selected from one or more of oxygen atoms, sulfur atoms or nitrogen atoms; r3And R4Can be bonded to each other to form a ring;
said substituted C6-30The substituents for the aryl group and the substituted 5-to 30-membered heteroaryl group are optionally one or more selected from cyano, fluorine atom, methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, biphenylyl, terphenylyl, naphthyridinyl, pyridyl, benzofuranyl, carbazolyl or furanyl.
3. The organic compound of claim 2, R3～R5Each independently represents methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, phenyl, naphthyl, terphenyl, naphthyridinyl, biphenylyl or pyridyl.
4. The organic compound according to claim 1, wherein the specific structure of the carbazole derivative-centered organic compound is:
Figure FDA0001885279100000031
Figure FDA0001885279100000041
Figure FDA0001885279100000051
Figure FDA0001885279100000061
Figure FDA0001885279100000071
Figure FDA0001885279100000081
Figure FDA0001885279100000082
any one of them.
5. A method for producing an organic compound according to any one of claims 1 to 4, wherein the reaction equation occurring during the production is:
Ar2represented by a general structural formula shown in a general formula (2),
Figure FDA0001885279100000083
the preparation method comprises the following steps: weighing the intermediate I and the intermediate II, dissolving the intermediate I and the intermediate II in a toluene/water/ethanol mixed solution with the volume ratio of 3:1:1, and adding palladium acetate, cesium carbonate and 2-dicyclohexyl phosphorus-2 ',4',6' -triisopropyl biphenyl; microwave reacting at 120 deg.C under nitrogen protection for 3 hr, extracting with dichloromethane to obtain organic layer, and adding anhydrous MgSO4Drying, and further separating and purifying by a column chromatography method to obtain a target product;
the intermediate I and the intermediateII in a molar ratio of 1.0-3.0: 1, Pd (OAc)2The molar ratio of the intermediate I to the intermediate I is 0.001-0.003: 1, and Cs2CO3The molar ratio of the Xphos to the intermediate I is 0.5-3: 1, and the molar ratio of the Xphos to the intermediate I is 1.0-4: 1.
6. Use of an organic compound having a carbazole derivative as defined in any one of claims 1 to 4 as a core for the preparation of an organic electroluminescent device.
7. An organic electroluminescent element comprising at least one functional layer containing the carbazole derivative-based organic compound according to any one of claims 1 to 4.
8. An organic electroluminescent device according to claim 7, wherein the functional layer comprises an electron blocking layer or a hole transporting layer, and the electron blocking layer or the hole transporting layer contains the carbazole derivative-based organic compound according to any one of claims 1 to 4.
9. An organic electroluminescent device according to claim 7, wherein the functional layer comprises a light-emitting layer, and the light-emitting layer contains the carbazole derivative-based organic compound according to any one of claims 1 to 4.
10. A lighting or display element, characterized in that it comprises an organic light-emitting device according to claims 7-9.
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CN112592308A (en) * 2020-12-17 2021-04-02 北京燕化集联光电技术有限公司 Novel organic compound and application thereof in OLED device
CN112624959A (en) * 2020-12-17 2021-04-09 北京燕化集联光电技术有限公司 Heterocyclic compound containing indolone and application thereof
CN113563871A (en) * 2021-09-27 2021-10-29 浙江华显光电科技有限公司 Host material, organic photoelectric device and display or lighting device
CN113943300A (en) * 2020-07-15 2022-01-18 沈阳药科大学 Preparation method and application of 2, 7-dimethoxycarbazole fused compound

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Publication number Priority date Publication date Assignee Title
CN113943300A (en) * 2020-07-15 2022-01-18 沈阳药科大学 Preparation method and application of 2, 7-dimethoxycarbazole fused compound
CN113943300B (en) * 2020-07-15 2023-02-10 沈阳药科大学 Preparation method and application of 2, 7-dimethoxycarbazole fused compound
CN112521327A (en) * 2020-12-17 2021-03-19 北京燕化集联光电技术有限公司 Organic compound and application thereof
CN112592308A (en) * 2020-12-17 2021-04-02 北京燕化集联光电技术有限公司 Novel organic compound and application thereof in OLED device
CN112624959A (en) * 2020-12-17 2021-04-09 北京燕化集联光电技术有限公司 Heterocyclic compound containing indolone and application thereof
CN113563871A (en) * 2021-09-27 2021-10-29 浙江华显光电科技有限公司 Host material, organic photoelectric device and display or lighting device

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