CN115260157B - Stereo ring quinoxaline compound, organic electroluminescent device, display device and application - Google Patents
Stereo ring quinoxaline compound, organic electroluminescent device, display device and application Download PDFInfo
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Abstract
The application provides a stereo-ring quinoxaline compound, an organic electroluminescent device, a display device and application. The stereocyclic quinoxaline compound includes: two compounds represented by the formula (A) and/or the formula (B). By introducing a steric ring on the nitrogen-containing ring of the quinoxaline, the steric hindrance of the compound can be increased, which can reduce the evaporation temperature of the quinoxaline electron transport material in the application process, and can also inhibit the crystallization tendency of the material. Meanwhile, the introduction of benzene rings on the non-nitrogen-containing ring of the quinoxaline is also beneficial to improving the thermal stability of the three-dimensional ring quinoxaline compound. When the organic light-emitting diode is used as an electron transport material in an organic light-emitting diode, the working voltage of the device can be effectively reduced, the light-emitting efficiency is improved, and the service life of the device is prolonged.
Description
Technical Field
The application relates to the field of organic electroluminescence, in particular to a stereo-ring quinoxaline compound, an organic electroluminescent device, a display device and application.
Background
The organic electroluminescent element (organic light emitting diodes, OLED) has advantages of light weight, thin thickness, self-luminescence, low power consumption, no backlight source, wide viewing angle, fast response, flexibility, etc., has gradually replaced the liquid crystal display panel to become a new generation of flat panel display, and has great potential in flexible display. Carrier mobility (carrier mobility) of conventional electron transport materials is one thousandth of that of hole transport materials, and thermal stability is poor, often resulting in problems of rapid roll-off of light emission efficiency or poor device lifetime. The relevant literature indicates that the electron transport material occupies a charge consumption ratio of 35.9%, which is inferior to the consumption of the light emitting layer (39.8%). Therefore, development of an electron transport material with high carrier mobility and good thermal stability is one of the key points of current OLED material development.
Good electron transport materials are generally required to meet the following characteristics: (1) LUMO energy levels matched to the light emitting layer to facilitate electron transfer. (2) Lower than the HOMO energy level of the light emitting layer to facilitate confinement of excitons in the light emitting layer. (3) The triplet energy level T1 which is high enough to match with the phosphorescent material is matched, so that exciton quenching is avoided. (4) amorphous phase, avoiding light scattering. (5) good thermal stability and high glass transition temperature.
The electron transport materials commonly used at present mainly comprise metal complexes, nitrogen-containing heterocyclic compounds, perfluorinated compounds, organic silicon compounds, organic boron compounds and the like. Among them, nitrogen-containing heterocyclic compounds are studied for a large number of structures, and quinoxalines have been widely paid attention to and used due to their electron-deficient properties and good planar structures. The prior literature provides a condensed ring derivative containing a quinoxaline group, wherein a condensed ring is introduced to one side of a benzene ring of the quinoxaline, and the condensed ring is used as an electron transport material to be applied to an organic electroluminescent device, so that the working voltage can be effectively reduced, the device efficiency can be improved, but the condensed ring has a coplanar structure and high molecular weight, so that the evaporation temperature is increased and crystallization tends to occur when the condensed ring is actually prepared.
On the basis, the performance of the quinoxaline electron transport material needs to be further optimized to realize low voltage and high efficiency of the device.
Disclosure of Invention
The application mainly aims to provide a three-dimensional ring quinoxaline compound, an organic electroluminescent device, a display device and application, so as to solve the problems that the existing quinoxaline electron transport material has high evaporation temperature and crystallization tendency when preparing the organic electroluminescent device due to the coplanar structure and large molecular weight of a condensed ring.
In order to achieve the above object, an aspect of the present application provides a stereocyclic quinoxaline compound comprising: two compounds represented by the formula (A) and/or the formula (B):
wherein each R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 Are respectively and independently selected from H, C 1～20 Straight or branched alkyl, C 6～20 Aryl or heteroaryl groups of (a).
Further, each R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 And R is 7 Independently selected from H or C 1～5 Straight or branched alkyl of each R 8 Is a substituent having the structure:
wherein Ar is 1 And Ar is a group 2 Are independently selected from C 6 ～C 30 Substituted or unsubstituted aryl or C 6 ～C 30 Substituted or unsubstituted heteroaryl; x is X 1 And X 2 Is N, or X 1 And X 2 One of which is N and the other is CH.
Further, ar 1 And Ar is a group 2 Are independently selected from phenyl, C 1 ～ 5 Alkyl-substituted phenyl, biphenyl, naphthyl, 9-dimethylfluorenyl, dibenzofuranyl or dibenzothiophenyl groups.
Further, the stereocyclic quinoxaline compound includes: the molar ratio of the two compounds shown in the formula (A) and the formula (B) is 3:7-7:3.
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 includes a light emitting layer, a hole blocking layer, and an electron transport layer, at least one of the light emitting layer, the hole blocking layer, and the electron transport layer includes a material layer formed of the stereocycloquinoxaline compound provided by the present application.
The application further provides a display device, which comprises the organic electroluminescent device.
In still another aspect, the application provides an application of the stereocyclic quinoxaline compound in the field of organic electroluminescence.
By applying the technical scheme of the application, the steric hindrance of the compound can be increased by introducing the steric 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 introduction of benzene rings on the non-nitrogen-containing ring of the quinoxaline is also beneficial to improving the thermal stability of the three-dimensional ring quinoxaline compound. When the organic light-emitting diode is used as an electron transport material in an organic light-emitting diode, the working voltage of the device can be effectively reduced, the light-emitting efficiency is improved, and the service life of the device is prolonged.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
fig. 1 shows a schematic structural diagram of an optoelectronic device according to an embodiment of the present application, 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, wherein the hole blocking layer 6 includes a stereo-cyclic quinoxaline compound according to the present application.
FIG. 2 shows the compound (A1+B1) of the present application 1 H NMR test spectra.
FIG. 3 shows the compound (A7+B7) of the present application 1 H NMR test spectra.
FIG. 4 shows the compound (A13+B13) of the present application 1 H NMR test spectra.
FIG. 5 shows the compound (A3+B3) of the present application 1 H NMR test spectra.
Fig. 6 shows a voltage-current density test chart for a device prepared in accordance with the present application.
Fig. 7 shows a graph of current density versus external quantum efficiency for a device prepared in accordance with the present application.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As described in the background art, the existing quinoxaline electron transport material has the problems of high evaporation temperature and crystallization tendency in the preparation of an organic electroluminescent device due to the coplanar structure and the large molecular weight of a condensed ring. In order to solve the above technical problems, the present application provides a stereocyclic quinoxaline compound comprising: two compounds represented by the formula (A) and/or the formula (B):
wherein each R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 ，R 7 ，R 8 Are respectively and independently selected from H, C 1～20 Straight or branched alkyl, C 6～20 Aryl or heteroaryl groups of (a).
By introducing a steric ring on the nitrogen-containing ring of the quinoxaline, the steric hindrance of the compound can be increased, which can reduce the evaporation temperature of the quinoxaline electron transport material in the application process, and can also inhibit the crystallization tendency of the material. Meanwhile, the introduction of benzene rings on the non-nitrogen-containing ring of the quinoxaline is also beneficial to improving the thermal stability of the three-dimensional ring quinoxaline compound. When the organic light-emitting diode is used as an electron transport material in an organic light-emitting diode, the working voltage of the device can be effectively reduced, the light-emitting efficiency is improved, and the service life of the device is prolonged.
In a preferred embodiment, each R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 And R is 7 Independently selected from H or C 1～5 Straight or branched alkyl of each R 8 Is a substituent having the structure:
wherein Ar is 1 And Ar is a group 2 Are independently selected from C 6 ～C 30 Substituted or unsubstituted aryl or C 6 ～C 30 Substituted or unsubstituted heteroaryl; x is X 1 And X 2 Is N, or X 1 And X 2 One of which is N and the other is CH. R is R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 And R is 7 The limitation in the above range is beneficial to reducing the synthesis difficulty, and the substituent with the above structure is selected as R 8 The electron transfer rate of the quinoxaline electron transfer material is further improved, so that the working efficiency of the light-emitting device prepared by the quinoxaline electron transfer material can be further improved.
Of course, R is not considered in consideration of the difficulty of synthesis 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 And R is 7 R is R 8 One or more of (C) may have a structure represented by the formula (C), and the more substitution is, the more favorable it is to increase the electron transfer rate of the stereocycloquinoxaline.
By adjusting the radicals R 8 The kind of triazine group or pyrimidine group can adjust the energy level of the quinoxaline compound, increase the conjugation degree of the quinoxaline compound, and further match different luminescent layers, preferably Ar 1 And Ar is a group 2 Are independently selected from phenyl, C 1 ～ 5 Alkyl-substituted phenyl, biphenyl, naphthyl, 9-dimethylfluorenyl, dibenzofuranyl or dibenzothiophenyl groups. The substituent is introduced on the benzene ring of the quinoxaline, so that on one hand, the polymerization difficulty is reduced, on the other hand, the conjugation degree of the quinoxaline compound can be further improved, and further, different luminescent layers can be matched, the luminescent efficiency is further improved, and the application field is widened.
In a preferred embodiment, the above-mentioned stereocyclic quinoxaline compound comprises: the molar ratio of the two compounds shown in the formula (A) and the formula (B) is 3:7-7:3.
In order to further improve the overall properties of the above-mentioned stereocycloquinoxaline 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 application also provides an organic electroluminescent device comprising a light-emitting layer, a hole blocking layer and an electron transport layer, at least one of the electron transport layer, the hole blocking layer and the light-emitting layer comprising a material layer formed of the stereocycloquinoxaline compound provided by the application.
By introducing a steric ring on the nitrogen-containing ring of the quinoxaline, the steric hindrance of the compound can be increased, which can reduce the evaporation temperature of the quinoxaline electron transport material in the application process, and can also inhibit the crystallization tendency of the material. Meanwhile, when the organic light-emitting diode is used as an electron transport material in an organic light-emitting diode, the working voltage of the device can be effectively reduced, and the light-emitting efficiency is improved. Therefore, the organic electroluminescent device containing the organic electroluminescent device has lower working voltage and higher luminous efficiency.
Furthermore, the organic electroluminescent device can be used for preparing a display device, which is also beneficial to improving the display performance and reducing the energy consumption.
The application also provides an application of the stereo-ring quinoxaline compound in the field of organic electroluminescent devices.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Synthetic examples
Example 1: synthesis of Compound (A1+B1)
In a three-port reaction flask, camphorquinone (60.0 g,0.36 mol), 4-bromophthalenediamine (64.2 g,0.34 mol), toluene 600mL, an overhead water separator, and reflux-stirring for 10 hours were sequentially added. After the reaction was completed, the product system was cooled to room temperature, silica gel was used for filtration, toluene was removed from the obtained filtrate under vacuum to obtain a crude product, and the crude product was recrystallized with n-hexane to obtain 75g of intermediate I-1 as a pink solid, yield 70% and purity 99.59%.
In a three-necked flask, intermediate I-1 (10.0 g,31.5 mmol), 2, 4-diphenyl-6- [4- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl ] -1,3, 5-triazine (13.7 g,31.5 mmol), potassium carbonate (8.7 g,63.0 mmol), tetrakis- (triphenylphosphine) palladium (0.4 g), toluene (100 ml), ethanol (20 ml) and water (30 ml) were added and heated under reflux under nitrogen for 4 hours. After the reaction is finished, the product system is cooled to room temperature, toluene and water are used for extraction, an organic layer is taken to be filled with silica gel for filtration, the filtrate is distilled off in vacuum to remove the solvent, and a crude product is obtained, and the crude product is recrystallized by using a dichloromethane/ethanol mixed solvent to obtain 9g of compound (A1+B1) (wherein the mol ratio of A1 to B1 is 7:3) which is white solid powder, the yield is 90%, the purity is 98.94%, and the crude product is purified by vacuum sublimation for 1 time, and the purity is 99.52%.
The structural characterization of compound (a1+b1) results are as follows:
1H NMR(400MHz,CDCl 3 )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,126 mmol), 4-chloro-1-phenylboronic acid (26.0 g,126 mmol), potassium carbonate (44.2 g,252 mmol), tetrakis- (triphenylphosphine) palladium (1.46 g), toluene (600 ml), ethanol (125 ml) and water (125 ml) were charged, and heated under reflux under nitrogen for 3 hours. After the reaction is finished, the product system is cooled to room temperature, toluene and water are used for extraction, an organic layer is taken for being filled with silica gel for filtration, the obtained filtrate is distilled off the solvent under vacuum to obtain a crude product, and the crude product is pulped by using a mixed solvent of normal hexane and ethanol to obtain 26.8g of intermediate I-2 which is off-white solid powder with the yield of 80 percent and the purity of 99.50 percent.
In a three-necked flask, intermediate I-2 (26.8 g,76.8 mmol), pinacol diboronate (23.4 g,92.1 mmol) and toluene (500 mL) were added, followed by stirring with nitrogen for 15 minutes, and then potassium acetate (11.3 g,115.2 mmol), tris (dibenzylideneandene acetone) dipalladium (0.7 g), X-Phos (0.7 g) were added and heated under reflux for 4 hours. After the reaction was completed, the product system was cooled to room temperature, silica gel was used for filtration, the solvent was distilled off from the filtrate in vacuo to give a crude product, which was slurried with n-hexane/methylene chloride (V: v=10:1) for 1 hour, suction-filtered, and n-hexane was washed twice to give 27.7g of intermediate I-3 as a white solid powder in 82% yield and 98.9% purity.
In a three-necked flask, intermediate I-3 (27.7 g,62.8 mmol), 2-chloro-4, 6-bis (naphthalen-2-yl) -1,3, 5-triazine (23.1 g,62.8 mmol), potassium carbonate (26.0 g,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 the product system to room temperature, evaporating the solvent in vacuum, filtering the precipitated solid, washing the solid with water, washing the solid with ethanol, dissolving the filter cake with toluene, filtering the filter cake with silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, and recrystallizing the crude product with toluene solvent to obtain 26.4g of compound (A7+B7) (wherein the molar ratio of A7 to B7 is 3:4) which is yellow solid powder, wherein the purity is 99.65%, and the crude product is purified by vacuum sublimation for 1 time, and the purity is 99.88%.
The structural characterization of compound (a7+b7) results are as follows:
1H NMR(400MHz,CDCl 3 )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 (22.0 g,50 mmol), 2, 4-bis ([ 1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine (18.4 g,50 mmol), potassium carbonate (20.7 g,150 mmol), tetrakis- (triphenylphosphine) palladium (1.15 g), toluene (350 ml), ethanol (120 ml) and water 75 ml) were added, and the mixture was heated under reflux under nitrogen for 7 hours. After the reaction is finished, cooling the product system to room temperature, evaporating the solvent under vacuum, carrying out suction filtration on the precipitated solid, washing the solid with water, washing the solid with ethanol, carrying out hot melting on a filter cake with toluene, filtering the solid with silica gel, carrying out vacuum evaporation on the filtrate to remove the solvent to obtain a crude product, and recrystallizing the crude product with the toluene solvent to obtain 20.23g of compound (A13+B13) (wherein the mol ratio of A13 to B13 is 1:3) which is yellow solid powder, wherein the purity is 99.53%, and the crude product is purified by vacuum sublimation for 1 time, and the purity is 99.91%.
The structural characterization of compound (a13+b13) results 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 (13.2 g,30 mmol), 2-chloro-4, 6-diphenylpyrimidine (8.0 g,30 mmol), potassium carbonate (12.4 g,90 mmol), 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, filtering the precipitated solid, sequentially washing with water, ethanol, thermally dissolving a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum from the filtrate to obtain a crude product, and recrystallizing the crude product with toluene solvent to obtain 10.6g of compound (A3+B3) (wherein the molar ratio of A3 to B3 is 53:47) which is off-white solid powder with the purity of 99.38%, and purifying the crude product for 1 time by vacuum sublimation with the purity of 99.85%.
The structural characterization of compound (a3+b3) results are as follows:
1H NMR(400MHz,CDCl 3 )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 (21.0 g,47.6 mmol), 2-chloro-4- (3- (naphthalen-2-yl) phenyl) -6-phenyl-1, 3, 5-triazine (18.74 g,47.6 mmol), potassium carbonate (19.74 g,142.8 mmol), tetrakis- (triphenylphosphine) palladium (1.10 g), toluene (200 ml), ethanol (100 ml) and water (70 ml) were added, and heated under reflux under nitrogen for 5 hours. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, filtering the precipitated solid, sequentially washing with water, ethanol, thermally dissolving a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum from the filtrate to obtain a crude product, and recrystallizing the crude product with toluene solvent to obtain 20.9g of compound (A31+B31) (wherein the molar ratio of A31 to B31 is 51:59) 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 of compound (a31+b31) results are as follows:
1H NMR(400MHz,CDCl 3 )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 (22.02 g,50.0 mmol), 2-chloro-4- (biphenyl-4-yl) -6-phenyl-1, 3, 5-triazine (17.19 g,50.0 mmol), potassium carbonate (20.73 g,150 mmol), tetrakis- (triphenylphosphine) palladium (1.16 g), toluene (200 ml), ethanol (100 ml) and water (75 ml) were added, and the mixture was heated under reflux under nitrogen for 5 hours. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, filtering the precipitated solid, sequentially washing with water, ethanol, thermally dissolving a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum from the filtrate to obtain a crude product, and recrystallizing the crude product with toluene solvent to obtain 19.27g of compound (A32+B32) (the mol ratio of A32 to B32 is 14:17) as yellow solid powder, wherein the purity is 99.65%, and the crude product is purified by vacuum sublimation for 1 time, and the purity is 99.83%.
The structural characterization of compound (a32+b32) results are as follows:
1H NMR(400MHz,CDCl 3 )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)
In a three-necked flask, intermediate I-1 (31.72 g,100 mmol), pinacol diboronate (30.47 g,120 mmol) and toluene (500 mL) were added, followed by stirring with nitrogen for 15 minutes, and then potassium acetate (14.71 g,150 mmol), tris (dibenzylideneandene acetone) dipalladium (0.91 g), X-Phos (0.91 g) were added and heated under reflux for 6 hours. After the reaction was completed, cooling to room temperature, filtering with silica gel, and evaporating the solvent from the filtrate in vacuo to obtain a crude product, pulping the crude product with n-hexane/dichloromethane (V: v=10:1) for 1 hour, suction-filtering, and washing with n-hexane twice to obtain 28.4g of intermediate I-4 as a white solid powder, with a yield of 78% and a purity of 99.3%.
In a three-necked flask, adding and weighing diacetone (19.6 g,100 mmol), p-bromobenzaldehyde (19.4 g,105 mmol) into a 2L four-necked flask, adding 150ml of ethanol, and stirring for 10min under the protection of nitrogen; 1.5g of sodium hydroxide is added, the mixture is heated to 25 ℃ for reaction for 4 hours, intermediate I-5 is obtained after the absence of the biacetophenone is confirmed by central control, 3-pyridine amidoxime hydrochloride (15.76 g,100 mmol) toluene (30 ml) and ethanol (70 ml) are continuously added into a flask, 6.5 g of sodium hydroxide is added after stirring for 5 minutes, the temperature is raised to 70 ℃, the mixture is stirred for 3 hours, the mixture is cooled to room temperature after the reaction is finished, and the mixture is filtered, rinsed with methanol and washed with water, and dried to obtain 36.22g of intermediate I-6 of white solid powder, wherein the purity is 97.3%.
In a three-necked flask, intermediate I-4 (28.4 g,78 mmol), intermediate I-6 (36.22 g,78 mmol), potassium carbonate (21.56 g,156 mmol), tetrakis- (triphenylphosphine) palladium (1.79 g), toluene (400 ml), ethanol (75 ml) and water 75 ml) were charged, and heated under reflux under nitrogen for 3 hours. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, filtering the precipitated solid, sequentially washing with water, ethanol, thermally dissolving a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum from the filtrate to obtain a crude product, and recrystallizing the crude product with toluene solvent to obtain 33.9g of compound (A33+B33) (wherein the molar ratio of A33 to B33 is 7:13) which is off-white solid powder with the purity of 99.37 percent, and purifying the crude product for 1 time by vacuum sublimation with the purity of 99.81 percent.
The structural characterization of compound (a33+b33) results were as follows:
1H NMR(400MHz,CDCl 3 )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)
2-naphthacenedione (17.21 g,100 mmol) and p-bromobenzaldehyde (19.4 g,105 mmol) were put into a three-necked flask, and 150ml of ethanol was added thereto and stirred under nitrogen protection for 10min; adding 1.5g of sodium hydroxide, heating to 25 ℃ for reaction for 4 hours, obtaining an intermediate I-7 after a central control confirms no 2-naphthacene, continuously adding 30ml of toluene (15.66 g,100 mmol) of benzamidine hydrochloric acid and 70ml of ethanol 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, eluting with methanol, washing with water, and drying to obtain 27.11g of intermediate I-8 of white solid powder, wherein the purity is 98.1%.
In a three-necked flask, intermediate I-4 (22.57 g,62 mmol), intermediate I-7 (27.11 g,62 mmol), potassium carbonate (17.13 g,124 mmol), tetrakis- (triphenylphosphine) palladium (1.42 g), toluene (320 ml), ethanol (60 ml) and water 60 ml) were charged, and heated under reflux under nitrogen for 3 hours. After the reaction is finished, cooling to room temperature, evaporating the solvent in vacuum, filtering the precipitated solid, sequentially washing with water, ethanol, thermally dissolving a filter cake with toluene, filtering with silica gel, evaporating the solvent in vacuum from the filtrate to obtain a crude product, recrystallizing the crude product with toluene solvent to obtain 25.8g of compound (the molar ratio of A34 to B34 is 3:7) which is off-white solid powder with the purity of 99.42 percent, and purifying the crude product for 1 time by vacuum sublimation with the purity of 99.88 percent.
The structural characterization of compound (a34+b34) results were as follows:
1H NMR(400MHz,CDCl 3 )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 above-mentioned organic compound of the present application is particularly suitable for an electron transport layer in an OLED device, and the application effect of the organic compound of the present application as a hole blocking layer in an OLED device will be described in detail below by way of specific examples in conjunction with the device structure of fig. 1.
Fig. 1 shows a schematic structural diagram of a preferred optoelectronic device according to the present application, which is 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 in this order from bottom to top, wherein the hole blocking layer 6 comprises the stereocyclic quinoxaline compound of the present application.
The structural formula of the organic material used therein is as follows:
FIG. 2 shows the compound (A1+B1) of the present application 1 H NMR test spectra; FIG. 3 shows the compound (A7+B7) of the present application 1 H NMR test spectra; FIG. 4 shows the compound (A13+B13) of the present application 1 H NMR test spectra; FIG. 5 shows the compound (A3+B3) of the present application 1 H NMR test spectra.
Device example 1
Referring to the structure shown in fig. 1, an OLED device is manufactured by using a Sunic sp1710 evaporator, and the specific steps are as follows: ultrasonic washing a glass substrate (corning glass 40 mm. Times.40 mm. Times.0.7 mm) coated with ITO (indium tin oxide) having a thickness of 135nm with isopropyl alcohol and pure water, respectively, for 5 minutes, washing with ultraviolet ozone, and then transferring the glass substrate into a vacuum deposition chamber; the hole transport material HT1 doped with 4% HD was evacuated at a thickness of 20nm (about 10 -7 Torr) thermally depositing on the transparent ITO electrode to form a hole injection layer; vacuum depositing HT1 with the thickness of 90nm on the hole injection layer to serve as a hole transport layer; vacuum depositing HT1 with the thickness of 90nm on the hole injection layer to serve as an electron blocking layer; vacuum depositing RH doped with 4% RD of 30nm as a light emitting layer on the hole transport layer; then vacuum depositing 5nm compound (A1+B1) as hole blocking layer; depositing an ET doped with 50% LiQ (8-hydroxyquinoline lithium) with a thickness of 25nm on the hole blocking layer to form an electron transport layer with a thickness of 30nm; finally, sequentially depositing 2nm thick ytterbium (Yb, electron injection layer) and magnesium-silver alloy with doping ratio of 10:1 to form a cathode; finally, the device is 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 absorbent.
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 expressed 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 (19:1.6) (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, the compound (a13+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, the 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, the compound (a31+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, the compound (a32+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, the compound (a33+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, the compound (a34+b34) was used instead of the compound (a1+b1) in device example 1.
Device comparative 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 expressed 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 (19:1.6) (1500A).
Device comparative example 2
The differences from example 1 are: in the same case, the quinoxaline compound of the stereochemistry employed in the present application is replaced with a quinoxaline compound having no stereochemistry (HB, commercially available from Shanghai Seiki Co., ltd.).
The brightness, luminous efficiency, and EQE (external quantum efficiency) of the device were measured by FS-100GA4, fuda, su, all in room temperature atmosphere, and the measurement results are shown in fig. 6 and 7. The device was at 10mA/cm 2 The performance data at current density are shown in table 2.
TABLE 2
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects:
device examples 1 to 8 the efficiency of the device is significantly improved by using the stereocyclic quinoxaline compound of the present application as a hole blocking layer, the driving voltage is reduced, as compared with device comparative examples 1 and 2. The three-dimensional ring quinoxaline compound has large space obstruction, is not easy to crystallize, has good film forming property and is beneficial to reducing interface potential barrier between an electron transport layer and a light emitting layer. In addition, the proper HOMO energy level also helps to limit holes transmitted by the anode in the light-emitting layer, so that the combination efficiency of electrons and holes is improved, and the efficiency of the device is improved.
It should be noted that the terms "first," "second," and the like in the description and in the claims are used for distinguishing between similar objects 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 herein.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (6)
1. A stereocyclic quinoxaline compound, wherein said stereocyclic quinoxaline compound is selected from the group consisting of: two compounds represented by the formula (A) and the formula (B):
wherein each R 1 ，R 2 ，R 3 ，R 4 ，R 5 ，R 6 And R is 7 Independently selected from H or C 1～ C 5 Straight or branched alkyl of each R 8 Is a substituent having the structure:
Ar 1 and Ar is a group 2 Are independently selected from phenyl, C 1 ～C 5 Alkyl-substituted phenyl, biphenyl, naphthyl, 9-dimethylfluorenyl, dibenzofuranyl, or dibenzothienyl; x is X 1 And X 2 Is N, or X 1 And X 2 One of which is N and the other is CH.
2. The stereocyclic quinoxaline compound according to claim 1, wherein said stereocyclic quinoxaline compound is selected from the group consisting of: the molar ratio of the two compounds shown in the formula (A) and the formula (B) is 3:7-7:3.
3. A stereocyclic quinoxaline compound, wherein said stereocyclic quinoxaline compound is selected from the group consisting of: two compounds represented by formula (a) and formula (B), and the two compounds represented by formula (a) and formula (B) are selected from the following compounds:
4. an organic electroluminescent device comprising 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 of the stereocycloquinoxaline compound according to any one of claims 1 to 3.
5. A display device characterized in that it comprises the organic electroluminescent device according to claim 4.
6. Use of a stereocyclic quinoxaline compound according to any one of claims 1 to 3 in the field of organic electroluminescence.
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