CN115260157A - Three-dimensional cycloquinoxaline compound, organic electroluminescent device, display device and application - Google Patents
Three-dimensional cycloquinoxaline compound, organic electroluminescent device, display device and application Download PDFInfo
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- CN115260157A CN115260157A CN202110477651.XA CN202110477651A CN115260157A CN 115260157 A CN115260157 A CN 115260157A CN 202110477651 A CN202110477651 A CN 202110477651A CN 115260157 A CN115260157 A CN 115260157A
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- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000463 material Substances 0.000 claims abstract description 35
- -1 cyclic quinoxaline compound Chemical class 0.000 claims abstract description 32
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- 239000004305 biphenyl Chemical class 0.000 claims description 4
- 238000005401 electroluminescence Methods 0.000 claims description 4
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- LZCZIHQBSCVGRD-UHFFFAOYSA-N benzenecarboximidamide;hydron;chloride Chemical compound [Cl-].NC(=[NH2+])C1=CC=CC=C1 LZCZIHQBSCVGRD-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- UNXISIRQWPTTSN-UHFFFAOYSA-N boron;2,3-dimethylbutane-2,3-diol Chemical compound [B].[B].CC(C)(O)C(C)(C)O UNXISIRQWPTTSN-UHFFFAOYSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The invention provides a stereo cyclic quinoxaline compound, an organic electroluminescent device, a display device and application. The stereo cyclic quinoxaline compound comprises: two compounds represented by the formula (A) and/or the formula (B). The steric hindrance of the compound can be increased by introducing a stereo ring on the nitrogen-containing ring of the quinoxaline, so that the evaporation temperature of the quinoxaline electron transport material in the application process can be reduced, and the crystallization tendency of the material can be inhibited. In the presence of quinoxalineThe non-nitrogen-containing ring of (2) is introduced with a benzene ring, which is also beneficial to improving the thermal stability of the stereo cyclic quinoxaline compound. When the organic electroluminescent material is used as an electron transmission material in an organic electroluminescent device, the working voltage of the device can be effectively reduced, the luminous efficiency is improved, and the service life is prolonged.
Description
Technical Field
The invention relates to the field of organic electroluminescence, in particular to a stereoscopic ring quinoxaline compound, an organic electroluminescent device, a display device and application.
Background
Organic Light Emitting Diodes (OLEDs) have the advantages of being light, thin, self-luminous, low power consumption, without backlight, wide viewing angle, fast response, and flexible, and have been gradually replacing liquid crystal display panels to become a new generation of flat panel displays, and have great potential in flexible display. Carrier mobility (carrier mobility) of a conventional electron transport material is one thousandth of that of a hole transport material, and thermal stability is poor, often resulting in the problems of fast light-emitting efficiency roll-off or poor device lifetime. The related document shows that the charge consumption ratio of the electron transport material is 35.9%, which is next to the consumption of the light emitting layer (39.8%). Therefore, the development of an electron transport material with high carrier mobility and good thermal stability is one of the key points of the current OLED material development.
Good electron transport materials generally need to meet the following characteristics: (1) The LUMO energy level matched to the light emitting layer facilitates electron transfer. (2) Lower than the HOMO level of the light emitting layer to facilitate confinement of excitons in the light emitting layer. (3) The triplet energy level T1 of the phosphorescent material is high enough to avoid exciton quenching. And (4) an amorphous phase, so that light scattering is avoided. (5) good thermal stability and high glass transition temperature.
The currently commonly used electron transport materials mainly include metal complexes, nitrogen-containing heterocyclic compounds, perfluorinated compounds, organosilicon compounds, organic boron compounds and the like. Among them, nitrogen-containing heterocyclic compounds are the most studied structures, and quinoxaline has been widely noted and applied due to its electron-deficient property and good planar structure. The prior document provides a condensed ring derivative containing quinoxaline groups, wherein a condensed ring is introduced at one side of a benzene ring of quinoxaline and is used as an electron transport material to be applied to an organic electroluminescent device, so that the working voltage can be effectively reduced and the device efficiency can be improved.
On the basis, the performances of the quinoxaline electron transport materials are still to be further optimized to realize low voltage and high efficiency of the device.
Disclosure of Invention
The invention mainly aims to provide a stereoscopic ring quinoxaline compound, an organic electroluminescent device, a display device and application, and aims to solve the problems that the existing quinoxaline electron transport material has high evaporation temperature and crystallization tendency when the organic electroluminescent device is prepared due to the coplanar structure and high molecular weight of fused rings.
In order to achieve the above object, an aspect of the present invention provides a stereo cyclic quinoxaline compound comprising: two compounds represented by formula (A) and/or formula (B):
wherein each R is1，R2，R3，R4，R5，R6，R7，R8Each independently selected from H, C1～20Straight or branched alkyl of (2), C6～20Aryl or heteroaryl of (a).
Further, each R1，R2，R3，R4，R5，R6And R7Each independently selected from H or C1～5Straight or branched alkyl of, each R8Is a substituent having the structure:
wherein Ar is1And Ar2Are each independently selected from C6～C30Substituted or unsubstituted aryl or C6～C30Substituted or unsubstituted heteroaryl of (a); x1And X2Is N, or X1And X2One is N and the other is CH.
Further, ar1And Ar2Each independently selected from phenyl, C1～5Alkyl-substituted phenyl, biphenyl, naphthyl, 9-dimethylfluorenyl, dibenzofuranyl, or dibenzothienyl.
Further, the stereo cyclic quinoxaline compound includes: two compounds represented by formula (A) and formula (B) in a molar ratio of 3.
Further, the two compounds represented by the formula (a) and the formula (B) are selected from the following compounds:
in another aspect, an organic electroluminescent device is provided, which comprises a light-emitting layer, a hole blocking layer and an electron transport layer, wherein at least one of the light-emitting layer, the hole blocking layer and the electron transport layer comprises a material layer formed by the stereo-quinoxaline compound provided by the application.
Still another aspect of the present application also provides a display apparatus including the organic electroluminescent device provided in the present application.
In still another aspect of the present application, there is provided an application of the stereo cyclic quinoxaline compound in the field of organic electroluminescence.
By applying the technical scheme of the invention, the steric hindrance of the compound can be increased by introducing the stereo ring on the nitrogen-containing ring of the quinoxaline, so that the evaporation temperature of the quinoxaline electron transport material in the application process can be reduced, and the crystallization trend of the material can be inhibited. Meanwhile, the benzene ring is introduced to the non-nitrogen-containing ring of the quinoxaline, so that the thermal stability of the stereo cyclic quinoxaline compound is improved. When the organic electroluminescent material is used as an electron transmission material in an organic electroluminescent device, the organic electroluminescent material can effectively reduce the working voltage of the device, improve the luminous efficiency and prolong the service life.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a schematic structural diagram of an optoelectronic device provided according to an embodiment of the present invention, which sequentially includes, from bottom to top, an anode layer 1, a hole injection layer 2, a hole transport layer 3, an electron blocking layer 4, a light emitting layer 5, a hole blocking layer 6, an electron transport layer 7, and a cathode layer 8, where the hole blocking layer 6 includes a stereo cyclo-quinoxaline compound according to the present invention.
FIG. 2 shows the preparation of the compounds (A1 + B1) according to the invention1H NMR spectrum.
FIG. 3 shows the preparation of the compounds (A7 + B7) according to the invention1H NMR spectrum.
FIG. 4 shows the preparation of the compounds (A13 + B13) according to the invention1H NMR spectrum.
FIG. 5 shows the preparation of the compounds (A3 + B3) of the present invention1H NMR test spectrum.
FIG. 6 shows a voltage-current density test chart of a device prepared according to the present invention.
FIG. 7 shows a current density-external quantum efficiency test chart of a device prepared by the present invention.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the quinoxaline electron transport material has the problems of high evaporation temperature and crystallization tendency when being used for preparing an organic electroluminescent device due to the coplanar structure and large molecular weight of the condensed ring. In order to solve the above technical problems, the present application provides a stereoscopic cyclic quinoxaline compound, including: two compounds represented by formula (A) and/or formula (B):
wherein each R is1，R2，R3，R4，R5，R6，R7，R8Each independently selected from H and C1～20Straight or branched alkyl of (2), C6～20Aryl or heteroaryl of (a).
The steric hindrance of the compound can be increased by introducing a stereo ring on the nitrogen-containing ring of the quinoxaline, so that the evaporation temperature of the quinoxaline electron transport material in the application process can be reduced, and the crystallization tendency of the material can be inhibited. Meanwhile, the benzene ring is introduced to the non-nitrogen-containing ring of the quinoxaline, so that the thermal stability of the stereo cyclic quinoxaline compound is improved. When the organic electroluminescent material is used as an electron transmission material in an organic electroluminescent device, the organic electroluminescent material can effectively reduce the working voltage of the device, improve the luminous efficiency and prolong the service life.
In a preferred embodiment, each R is1，R2，R3，R4，R5，R6And R7Each independently selected from H or C1～5Straight or branched alkyl of, each R8Is a substituent having the structure:
wherein Ar is1And Ar2Are each independently selected from C6～C30Substituted or unsubstituted aryl or C6～C30Substituted or notSubstituted heteroaryl; x1And X2Is N, or X1And X2One is N and the other is CH. R is to be1，R2，R3，R4，R5，R6And R7The restriction within the above range is advantageous for reducing the difficulty of synthesis, and the substituent of the above structure is selected as R8The method is favorable for further improving the electron transmission rate of the quinoxaline electron transmission material, so that the working efficiency of the prepared light-emitting device can be further improved.
Of course, R is not considered in the case of synthesis difficulty1，R2，R3，R4，R5，R6And R7And R8One or more of them may have a structure represented by the formula (C), and the more substitution, the more favorable the electron transport rate of the stereo cyclic quinoxaline.
By adjusting the radicals R8The kind of the triazine group or the pyrimidine group can adjust the energy level of the quinoxaline compound, increase the conjugation degree of the quinoxaline compound, and further match different light-emitting layers, preferably Ar1And Ar2Each independently selected from phenyl and C1～5Alkyl-substituted phenyl, biphenyl, naphthyl, 9-dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl. The substituent is introduced to the benzene ring of the quinoxaline, so that the polymerization difficulty is reduced, the conjugation degree of the quinoxaline compound can be further improved, different light-emitting layers can be matched, the light-emitting efficiency is further improved, and the application field of the quinoxaline compound is widened.
In a preferred embodiment, the above-mentioned stereo cyclic quinoxaline compound comprises: two compounds represented by formula (a) and formula (B) in a molar ratio of 3.
In order to further improve the overall performance of the above-mentioned stereo-quinoxaline compound in the field of electroluminescence, preferably, the two compounds represented by the formula (a) and the formula (B) are selected from the following compounds:
the second aspect of the present application also provides an organic electroluminescent device comprising a light-emitting layer, a hole-blocking layer and an electron-transporting layer, at least one of the electron-transporting layer, the hole-blocking layer and the light-emitting layer comprising a material layer formed of the stereoscopic cyclic quinoxaline compound provided herein.
The steric hindrance of the compound can be increased by introducing a stereo ring on the nitrogen-containing ring of the quinoxaline, so that the evaporation temperature of the quinoxaline electron transport material in the application process can be reduced, and the crystallization tendency of the material can be inhibited. Meanwhile, when the organic electroluminescent material is used as an electron transmission material in an organic electroluminescent device, the working voltage of the device can be effectively reduced, and the luminous efficiency is improved. Thus, the organic electroluminescent device containing the same has a lower operating voltage and higher luminous efficiency.
Furthermore, the organic electroluminescent device can be used for preparing a display device, and is also favorable for improving the display performance and reducing the energy consumption.
In another aspect, the application also provides an application of the stereo cyclo-quinoxaline compound provided by the application in the field of organic electroluminescent devices.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Synthetic examples
Example 1: synthesis of Compound (A1 + B1)
In a three-necked reaction flask, camphorquinone (60.0 g, 0.36mol), 4-bromoo-phenylenediamine (64.2g, 0.34mol) and 600mL of toluene were sequentially added, and the mixture was placed in a water separator, and stirred under reflux for 10 hours. After the reaction was completed, the product system was cooled to room temperature, filtered through silica gel pad, and the obtained filtrate was subjected to removal of toluene under vacuum to obtain a crude product, which was recrystallized from n-hexane to obtain 75g of intermediate I-1 as a white solid in powder with a yield of 70% and a purity of 99.59%.
In a three-necked flask, intermediate I-1 (10.0g, 31.5 mmol), 2, 4-diphenyl-6- [4- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine (13.7g, 31.5 mmol), potassium carbonate (8.7g, 63.0mmol), tetrakis- (triphenylphosphine) palladium (0.4 g), toluene (100 ml), ethanol (20 ml) and water (30 ml) were charged, and heated under reflux for 4 hours under nitrogen protection. After the reaction is finished, cooling the product system to room temperature, extracting with toluene and water, filtering the organic layer pad with silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, recrystallizing the crude product with a dichloromethane/ethanol mixed solvent to obtain 9g of a compound (A1 + B1) (wherein the molar ratio of the A1 to the B1 is 7) as a white solid powder, the yield is 90%, the purity is 98.94%, and the purity of the crude product is 99.52% after 1-time vacuum sublimation.
The structural characterization results of compound (A1 + B1) are as follows:
1H NMR(400MHz,CDCl3)δ8.88(dd,J＝8.5,2.2Hz,2H),8.83–8.74(m,4H),8.35(dd,J＝29.0,1.9Hz,(0.7+0.3)H),8.11(dd,J＝21.4,8.6Hz,1H),8.00(dd,J＝8.6,2.0Hz,1H),7.94(dd,J＝8.4,4.4Hz,2H),7.68–7.51(m,6H),3.08(d,J＝4.3Hz,1H),2.43–2.24(m,1H),2.18–1.98(m,1H),1.60(s,1H),1.47(t,J＝4.9Hz,4H),1.13(s,3H),0.66(s,3H)。
example 2: synthesis of Compound (A7 + B7)
In a three-necked flask, intermediate I-1 (40.0 g, 126mmol), 4-chloro-1-phenylboronic acid (26.0 g, 126mmol), potassium carbonate (44.2g, 252mmol), tetrakis- (triphenylphosphine) palladium (1.46 g), toluene (600 ml), ethanol (125 ml) and water (125 ml) were charged, and heated under reflux for 3 hours under nitrogen protection. After the reaction is finished, cooling the product system to room temperature, extracting with toluene and water, filtering the organic layer pad silica gel, evaporating the obtained filtrate under vacuum to remove the solvent to obtain a crude product, pulping the crude product with a normal hexane/ethanol mixed solvent to obtain 26.8g of an intermediate I-2 which is off-white solid powder, wherein the yield is 80 percent and the purity is 99.50 percent.
A three-necked flask was charged with intermediate I-2 (26.8g, 76.8mmol), pinacol diboron ester (23.4g, 92.1mmol) and toluene (500 mL), and the mixture was stirred under nitrogen for 15 minutes, followed by addition of potassium acetate (11.3g, 115.2mmol), tris (dibenzylideneacetone) dipalladium (0.7 g) and X-Phos (0.7 g), and heated under reflux for 4 hours. After the reaction was completed, the product system was cooled to room temperature, filtered through silica gel pad, and the solvent was evaporated in vacuo from the filtrate to give a crude product, which was slurried with n-hexane/dichloromethane (V: V = 10.
In a three-necked flask, intermediate I-3 (27.7g, 62.8mmol), 2-chloro-4, 6-di (naphthalen-2-yl) -1,3, 5-triazine (23.1g, 62.8mmol), potassium carbonate (26.0g, 188.4 mmol), tetrakis- (triphenylphosphine) palladium (1.45 g), toluene (500 ml), ethanol (150 ml) and water (90 ml) were charged, and heated under reflux under nitrogen for 6 hours. After the reaction is finished, cooling a product system to room temperature, evaporating the solvent in vacuum, carrying out suction filtration on the precipitated solid, washing with water and ethanol in sequence, carrying out hot dissolution on a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum on the filtrate to obtain a crude product, and recrystallizing the crude product with the toluene solvent to obtain 26.4g of a compound (A7 + B7) (wherein the molar ratio of the A7 to the B7 is 3.
The structural characterization results of compound (A7 + B7) are as follows:
1H NMR(400MHz,CDCl3)δ8.91(dd,J＝8.5,1.9Hz,2H),8.87(d,J＝8.4Hz,4H),8.45–8.31(m,(0.43+0.57)H),8.13(dd,J＝21.1,8.6Hz,1H),8.02(dt,J＝8.6,4.3Hz,1H),7.96(dd,J＝8.4,4.5Hz,2H),7.82(d,J＝8.4Hz,4H),7.77–7.66(m,4H),7.51(t,J＝7.5Hz,4H),7.42(t,J＝7.3Hz,2H),3.11(d,J＝4.3Hz,1H),2.34(tt,J＝14.8,7.4Hz,1H),2.19–2.01(m,1H),1.62(d,J＝9.9Hz,1H),1.52–1.46(m,4H),1.15(s,3H),0.68(s,3H)。
example 3: synthesis of Compound (A13 + B13)
In a three-necked flask, intermediate I-3 (22.0g, 50mmol), 2, 4-bis ([ 1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine (18.4g, 50mmol), potassium carbonate (20.7g, 150mmol), tetrakis- (triphenylphosphine) palladium (1.15 g), toluene (350 ml), ethanol (120 ml) and water (75 ml) were charged, and heated under reflux for 7 hours under nitrogen protection. After the reaction is finished, cooling the product system to room temperature, evaporating the solvent in vacuum, filtering the precipitated solid by suction, washing with water and ethanol in sequence, hot-dissolving the filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum on the filtrate to obtain a crude product, and recrystallizing the crude product with a toluene solvent to obtain 20.23g of a compound (A13 + B13) (wherein the molar ratio of A13 to B13 is 1) as yellow solid powder with the purity of 99.53%, and purifying the crude product by vacuum sublimation for 1 time, wherein the purity of 99.91%.
The structural characterization results of compound (a 13+ B13) are as follows:
1H NMR(400MHz,CDCl3)δ8.91(dd,J＝8.5,1.9Hz,2H),8.87(d,J＝8.4Hz,4H),8.45–8.31(m,(0.25+0.75)H),8.13(dd,J＝21.1,8.6Hz,1H),8.02(dt,J＝8.6,4.3Hz,1H),7.96(dd,J＝8.4,4.5Hz,2H),7.82(d,J＝8.4Hz,4H),7.77–7.66(m,4H),7.51(t,J＝7.5Hz,4H),7.42(t,J＝7.3Hz,2H),3.11(d,J＝4.3Hz,1H),2.34(tt,J＝14.8,7.4Hz,1H),2.19–2.01(m,1H),1.62(d,J＝9.9Hz,1H),1.52–1.46(m,4H),1.15(s,3H),0.68(s,3H)。
example 4: synthesis of Compound (A3 + B3)
In a three-necked flask, intermediate I-3 (13.2g, 30mmol), 2-chloro-4, 6-diphenylpyrimidine (8.0 g, 30mmol), potassium carbonate (12.4 g, 90mmol), tetrakis- (triphenylphosphine) palladium (0.69 g), toluene (200 ml), ethanol (70 ml) and water (45 ml) were charged, and heated under reflux under nitrogen for 5 hours. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, carrying out suction filtration on the precipitated solid, sequentially washing with water and ethanol, carrying out hot dissolution on a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum on the filtrate to obtain a crude product, and recrystallizing the crude product with a toluene solvent to obtain 10.6g of a compound (A3 + B3) (wherein the molar ratio of A3 to B3 is 53: 47) as a white-like solid powder, the purity is 99.38%, and the crude product is purified by vacuum sublimation for 1 time, and the purity is 99.85%.
The structural characterization results of compound (A3 + B3) are as follows:
1H NMR(400MHz,CDCl3)δ8.85(dd,J＝8.5,2.4Hz,2H),8.54–8.25(m,5H),8.11(dd,J＝21.4,8.6(m,(0.53+0.47)H),8.06–7.99(m,2H),7.98–7.87(m,2H),7.70–7.48(m,6H),3.09(d,J＝4.3Hz,1H),2.43–2.26(m,1H),2.19–1.99(m,1H),1.70(t,J＝12.6Hz,1H),1.57–1.45(m,4H),1.14(s,3H),0.67(s,3H)。
example 5: synthesis of Compound (A31 + B31)
In a three-necked flask, intermediate I-3 (21.0g, 47.6 mmol), 2-chloro-4- (3- (naphthalen-2-yl) phenyl) -6-phenyl-1, 3, 5-triazine (18.74g, 47.6 mmol), potassium carbonate (19.74g, 142.8 mmol), tetrakis- (triphenylphosphine) palladium (1.10 g), toluene (200 ml), ethanol (100 ml) and water (70 ml) were charged, and the mixture was refluxed under nitrogen for 5 hours. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, carrying out suction filtration on the precipitated solid, sequentially washing with water and ethanol, carrying out hot dissolution on a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum on the filtrate to obtain a crude product, and recrystallizing the crude product with a toluene solvent to obtain 20.9g of a compound (A31 + B31) (wherein the molar ratio of the A31 to the B31 is 51) as yellow solid powder, wherein the purity is 99.73%, and the crude product is purified by vacuum sublimation for 1 time, and the purity is 99.90%.
The structural characterization results of compound (a 31+ B31) are as follows:
1H NMR(400MHz,CDCl3)δ9.11(s,1H),8.91(d,J＝8.4Hz,2H),8.85–8.76(m,3H),8.33(d,J＝2.0Hz,(0.51+0.59)H),8.19(s,1H),8.15(d,J＝8.6Hz,1H),8.05–7.85(m,8H),7.70(t,J＝7.7Hz,1H),7.66–7.57(m,3H),7.57–7.48(m,2H),3.10(d,J＝4.3Hz,1H),2.45–2.24(m,1H),2.17–1.95(m,1H),1.62(s,1H),1.55–1.46(m,4H),1.15(s,3H),0.67(s,3H)。
example 6: synthesis of Compound (A32 + B32)
In a three-necked flask, intermediate I-3 (22.02g, 50.0 mmol), 2-chloro-4- (biphenyl-4-yl) -6-phenyl-1, 3, 5-triazine (17.19g, 50.0 mmol), potassium carbonate (20.73g, 150mmol), tetrakis- (triphenylphosphine) palladium (1.16 g), toluene (200 ml), ethanol (100 ml) and water (75 ml) were charged, and the mixture was refluxed under nitrogen for 5 hours. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, carrying out suction filtration on the precipitated solid, sequentially washing with water and ethanol, carrying out hot dissolution on a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum on the filtrate to obtain a crude product, and recrystallizing the crude product with a toluene solvent to obtain 19.27g of a compound (A32 + B32) (the molar ratio of the A32 to the B32 is 14) as yellow solid powder with the purity of 99.65%, wherein the crude product is purified by vacuum sublimation for 1 time, and the purity of 99.83%.
The structural characterization results of compound (a 32+ B32) are as follows:
1H NMR(400MHz,CDCl3)8.62(d,J＝8.4Hz,2H),8.56–8.45(m,3H),8.04(d,J＝1.8Hz,(0.42+0.51)H),7.90(s,1H),7.86(d,J＝8.4Hz,1H),7.76–7.56(m,7H),7.41(t,J＝7.5Hz,1H),7.37–7.28(m,3H),7.28–7.19(m,2H),3.18(d,J＝4.1Hz,1H),2.43–2.22(m,1H),2.16–1.95(m,1H),1.61(s,1H),1.56–1.47(m,4H),1.16(s,3H),0.68(s,3H)。
example 7: synthesis of Compound (A33 + B33)
A three-necked flask was charged with intermediate I-1 (31.72g, 100mmol), pinacol diboron (30.47g, 120mmol) and toluene (500 mL), and stirred under nitrogen for 15 minutes, followed by addition of potassium acetate (14.71g, 150mmol), tris (dibenzylideneacetone) dipalladium (0.91 g), X-Phos (0.91 g), and heating under reflux for 6 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered through silica gel pad, and the solvent was evaporated in the filtrate in vacuo to obtain a crude product, which was slurried with n-hexane/dichloromethane (V: V = 10.
Adding benzil ketone (19.6 g, 100mmol) and p-bromobenzaldehyde (19.4 g, 105mmol) into a three-neck flask, adding 150ml of ethanol, and stirring for 10min under the protection of nitrogen; adding 1.5g of sodium hydroxide, heating to 25 ℃ for reaction for 4 hours, obtaining an intermediate I-5 after the central control confirms that the diphenoxy ketone does not exist, continuously adding 3-pyridine amidoxime hydrochloride (15.76g, 100mmol) toluene (30 ml) and ethanol (70 ml) into a flask, stirring for 5 minutes, adding 6.5 g of sodium hydroxide, heating to 70 ℃, stirring for 3 hours, cooling to room temperature after the reaction is finished, filtering, leaching with methanol, washing with water, and drying to obtain 36.22g of intermediate I-6 of white solid powder, wherein the purity is 97.3%.
Intermediate I-4 (28.4 g, 78mmol), intermediate I-6 (36.22g, 78mmol), potassium carbonate (21.56g, 156mmol), tetrakis- (triphenylphosphine) palladium (1.79 g), toluene (400 ml), ethanol (75 ml) and water (75 ml) were charged in a three-necked flask and heated under reflux for 3 hours under nitrogen. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, carrying out suction filtration on the precipitated solid, sequentially washing with water and ethanol, carrying out hot dissolution on a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum on the filtrate to obtain a crude product, and recrystallizing the crude product with a toluene solvent to obtain 33.9g of a compound (A33 + B33) (wherein the molar ratio of A33 to B33 is 7.
The structural characterization results of compound (a 33+ B33) are as follows:
1H NMR(400MHz,CDCl3)δ9.93(d,J＝1.6Hz,1H),8.96(dt,J＝8.0,1.9Hz,1H),8.76(dd,J＝4.8,1.7Hz,1H),8.39(dd,J＝16.3,8.4Hz,4H),8.29(d,J＝1.8Hz,1H),8.12(s,1H),8.08(d,J＝8.6Hz,(0.35+0.65)H),8.01(dd,J＝8.7,2.0Hz,1H),7.93(d,J＝8.4Hz,2H),7.79(d,J＝8.4Hz,2H),7.73–7.65(m,2H),7.55–7.36(m,4H),3.08(d,J＝4.3Hz,1H),2.44–2.25(m,1H),2.20–2.00(m,1H),1.61(s,1H),1.49(t,J＝4.9Hz,4H),1.14(s,3H),0.68(s,3H)。
example 8: synthesis of Compound (A34 + B34)
Adding 2-acetonaphthone (17.21g, 100mmol) and p-bromobenzaldehyde (19.4g, 105mmol) into a 2L four-neck flask, adding 150ml of ethanol, and stirring for 10min under the protection of nitrogen; adding 1.5g of sodium hydroxide, heating to 25 ℃ for reaction for 4 hours, obtaining an intermediate I-7 after the 2-acetonaphthone is confirmed to be absent in the medium control, continuously adding benzamidine hydrochloride (15.66g, 100mmol) toluene (30 ml) and ethanol (70 ml) into a flask, stirring for 5min, adding 6.5 g of sodium hydroxide, heating to 70 ℃, stirring for 3 hours, cooling to room temperature after the reaction is finished, filtering, leaching with methanol, washing with water, and drying to obtain 27.11g of an intermediate I-8 of white solid powder with the purity of 98.1%.
Intermediate I-4 (22.57g, 62mmol), intermediate I-7 (27.11g, 62mmol), potassium carbonate (17.13g, 124mmol), tetrakis- (triphenylphosphine) palladium (1.42 g), toluene (320 ml), ethanol (60 ml) and water (60 ml) were charged in a three-necked flask, and heated under reflux for 3 hours under nitrogen. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, carrying out suction filtration on the precipitated solid, sequentially washing with water and ethanol, carrying out hot dissolution on a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum on the filtrate to obtain a crude product, and recrystallizing the crude product with a toluene solvent to obtain 25.8g of a compound (the molar ratio of A34 to B34 is 3.
The structural characterization results of compound (a 34+ B34) are as follows:
1H NMR(400MHz,CDCl3)8.49-8.35(m,4H),8.29-8.15(m,3H),8.09(s,1H),8.01(d,J＝8.4Hz,(0.3+0.7)H),7.96(dd,J＝8.5,1.6Hz,1H),7.83(d,J＝8.6Hz,2H),7.72(d,J＝8.6Hz,2H),7.63–7.55(m,2H),7.45–7.26(m,4H),3.11(d,J＝4.1Hz,1H),2.43–2.24(m,1H),2.21–1.99(m,1H),1.61(s,1H),1.46(t,J＝4.8Hz,4H),1.14(s,3H),0.66(s,3H)。
2. preparation of organic electroluminescent device
The organic compound of the present invention is particularly suitable for an electron transport layer in an OLED device, and the application effect of the organic compound of the present invention as a hole blocking layer in an OLED device is described in detail by specific embodiments in conjunction with the device structure of fig. 1.
Fig. 1 shows a schematic structural diagram of a preferred photoelectric device according to the present invention, which sequentially comprises an anode layer 1 (glass and transparent conductive layer (ITO) substrate layer), a hole injection layer 2, a hole transport layer 3, an electron blocking layer 4, a light emitting layer 5, a hole blocking layer 6, an electron transport layer 7, and a cathode layer 8 from bottom to top, wherein the hole blocking layer 6 comprises the stereo cyclic quinoxaline compound according to the present invention.
The structural formula of the organic material used is as follows:
FIG. 2 shows the preparation of the compounds (A1 + B1) of the present invention1H NMR test spectrum; FIG. 3 shows the preparation of the compounds (A7 + B7) according to the invention1H NMR test spectrum; FIG. 4 shows the preparation of the compounds (A13 + B13) of the present invention1H NMR test spectrum; FIG. 5 shows the preparation of the compounds (A3 + B3) according to the invention1H NMR spectrum.
Device example 1
Referring to the structure shown in fig. 1, the method for manufacturing the OLED device by using the Sunic sp1710 evaporator includes the following specific steps: ultrasonically washing a glass substrate (Corning glass 40mm x 0.7 mm) coated with ITO (indium tin oxide) with a thickness of 135nm for 5 minutes by using isopropanol and pure water respectively, cleaning by using ultraviolet ozone, and then conveying the glass substrate into a vacuum deposition chamber; vacuum (about 10 nm) of the hole transport material HT1 doped with 4% HD to a thickness of 20nm-7Torr) thermal deposition is carried out on the transparent ITO electrode to form a hole injection layer; depositing HT1 with the thickness of 90nm on the hole injection layer in a vacuum mode to form a hole transport layer; performing vacuum deposition on the hole injection layer to obtain HT1 with the thickness of 90nm as an electron blocking layer; vacuum depositing 30nm of RH doped 4% RD as a light emitting layer on the hole transport layer; then, a compound (A1 + B1) with the thickness of 5nm is deposited in vacuum to be used as a hole blocking layer; depositing an ET doped with liq (lithium 8-hydroxyquinoline) 50% at a thickness of 25nm on the hole blocking layer to form an electron transporting layer having a thickness of 30nm; finally, depositing metal ytterbium (Yb, an electron injection layer) with the thickness of 2nm and magnesium-silver alloy with the doping ratio of 10; finally the device was transferred from the deposition chamber to a glove box and then encapsulated with a UV curable epoxy and a glass cover plate containing a moisture absorber.
In the above manufacturing steps, the deposition rates of the organic material, ytterbium metal and Mg metal were maintained at 0.1nm/s, 0.05nm/s and 0.2nm/s, respectively.
The device structure is represented as: ITO/HT1:4% HD (200A)/HT 1 (900A)/HT 2 (700A)/96% RH 4% RD (300A)/compound (A1 + B1) (50A)/50% ET 50% Liq (250A)/Yb (20A)/Ag: mg (19) (1500A).
Device example 2
An experiment was performed in the same manner as in device example 1 except that: as the hole blocking layer, a compound (A7 + B7) was used instead of the compound (A1 + B1) in device example 1.
Device example 3
An experiment was performed in the same manner as in device example 1 except that: as the hole blocking layer, a compound (a 13+ B13) was used instead of the compound (A1 + B1) in device example 1.
Device example 4
An experiment was performed in the same manner as in device example 1 except that: as the hole blocking layer, a compound (A3 + B3) was used instead of the compound (A1 + B1) in device example 1.
Device example 5
An experiment was performed in the same manner as in device example 1 except that: as the hole blocking layer, a compound (a 31+ B31) was used instead of the compound (A1 + B1) in device example 1.
Device example 6
An experiment was performed in the same manner as in device example 1 except that: as the hole blocking layer, a compound (a 32+ B32) was used instead of the compound (A1 + B1) in device example 1.
Device example 7
An experiment was performed in the same manner as in device example 1 except that: as the hole blocking layer, a compound (a 33+ B33) was used instead of the compound (A1 + B1) in device example 1.
Device example 8
An experiment was performed in the same manner as in device example 1 except that: as the hole blocking layer, a compound (a 34+ B34) was used instead of the compound (A1 + B1) in device example 1.
Comparative device example 1
An experiment was performed in the same manner as in device example 1 except that: the hole blocking layer is omitted.
The device structure is represented as: ITO/HT1:4% HD (200A)/HT 1 (900A)/HT 2 (700A)/96% RH (4%) RD (300A)/50% ET 50% Liq (300A)/Yb (20A)/Ag: mg (19.
Comparative device example 2
The differences from example 1 are: under the same circumstances, a quinoxaline compound having a stereo ring structure adopted in the present application was replaced with a quinoxaline compound having no stereo ring structure (HB, available from chemical technology ltd, also available in shanghai province).
The luminance, luminous efficiency, EQE (external quantum efficiency) of the device were measured by the sfs-100 GA4 test, french, all in ambient temperature atmosphere, and the results are shown in fig. 6 and fig. 7. The device is at 10mA/cm2The performance data at current density are shown in table 2.
TABLE 2
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
compared with comparative devices 1 and 2, after the stereo-quinoxaline compound provided by the invention is used as a hole blocking layer, the driving voltage is reduced, and the efficiency of the device is obviously improved. The three-dimensional cyclic quinoxaline compound has large space obstruction, difficult crystallization and good film forming property, and is beneficial to reducing the interface potential barrier between an electron transmission layer and a luminescent layer. In addition, the appropriate HOMO energy level also helps to confine the holes transmitted from the anode in the light-emitting layer, and improves the efficiency of combining electrons and holes, thereby improving the efficiency of the device.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A stereo cyclic quinoxaline compound, comprising: two compounds represented by formula (A) and/or formula (B):
wherein each R is1，R2，R3，R4，R5，R6，R7，R8Each independently selected from H and C1～20Straight or branched alkyl of (2), C6～20Aryl or heteroaryl of (a).
2. A stereoscopic cycloquinoxaline compound according to claim 1, wherein each R is1Said R is2Said R is3Said R is4Said R is5Said R is6And said R7Each independently selected from H or C1～5Each of said R is a linear or branched alkyl group8Is a substituent having the structure:
wherein Ar is1And Ar2Are each independently selected from C6～C30Substituted or unsubstituted aryl or C6～C30Substituted or unsubstituted heteroaryl of (a); x1And X2Is N, or said X1And said X2One is N and the other is CH.
3. A stereoscopic cycloquinoxaline compound according to claim 2, wherein Ar1And Ar2Each independently selected from phenyl, C1～5Alkyl-substituted phenyl, biphenyl, naphthyl, 9-dimethylfluorenyl, dibenzofuranyl or diphenyl radicalAnd a thienyl group.
4. A stereoscopic cyclo-quinoxaline compound according to any one of claims 1 to 3, comprising: two compounds represented by formula (a) and formula (B) in a molar ratio of 3.
5. A stereo cyclo-quinoxaline compound according to claim 3, wherein the two compounds of formula (A) and (B) are selected from the following compounds:
6. an organic electroluminescent device comprising a light-emitting layer, a hole-blocking layer and an electron-transporting layer, characterized in that at least one of the light-emitting layer, the hole-blocking layer and the electron-transporting layer comprises a material layer formed of the stereoquinoxaline compound according to any one of claims 1 to 5.
7. A display device characterized by comprising the organic electroluminescent device according to claim 6.
8. Use of the stereoscopic cycloquinoxaline compound according to any one of claims 1 to 5 in the field of organic electroluminescence.
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| CN110577471A (en) * | 2018-06-11 | 2019-12-17 | 乐金显示有限公司 | electroluminescent compounds and electroluminescent devices comprising the same |
| CN111087387A (en) * | 2019-12-26 | 2020-05-01 | 厦门天马微电子有限公司 | Organic compound, display panel and display device |
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| KR20140094408A (en) * | 2013-01-22 | 2014-07-30 | 덕산하이메탈(주) | Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof |
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