A luminescent auxiliary material, a preparation method thereof, and an electroluminescent device containing the same

Abstract

The present invention discloses a luminescence-assisting material having the general structural formula shown in Formula I: #imgabs0#, as well as a method for preparing the luminescence-assisting material and an electroluminescent device containing the material. By modifying the side chains and extending the molecular conjugation, the present invention avoids electron localization, facilitates electron separation and transport, and modifies the compound's mobility, spatial structure, and energy levels. By optimizing the device structure, the material can effectively improve the lifespan and luminous efficiency of OLED devices while reducing the driving voltage.

Description

Technical Field

[0001] The present invention relates to the field of organic photoelectric materials, and more particularly to a luminescent auxiliary material, a preparation method thereof, and an electroluminescent device containing the same. Background Art

[0002] Organic electroluminescent (OLED) device technology can be used to create both new display and lighting products, promising to replace existing liquid crystal displays and fluorescent lighting, and boasts a broad range of applications. Organic electrical components that utilize organic light-emitting diodes typically have an anode, a cathode, and an organic layer between them. To improve the efficiency and stability of organic electrical components, the organic layer is typically composed of multiple layers of various materials.

[0003] OLED optoelectronic functional materials used in OLED devices can be divided into two categories based on their application: charge injection and transport materials and luminescent materials. Charge injection and transport materials can be further divided into electron injection and transport materials, electron blocking materials, hole injection and transport materials, and hole blocking materials. Luminescent materials can also be divided into host luminescent materials and dopant materials.

[0004] The hole transport layer (HTL) is responsible for regulating the injection speed and injection amount of holes. This is because when the OLED is driven at high current, thermal stress occurs between the anode and the hole injection layer, and the thermal stress will significantly reduce the service life of the device, causing problems in efficiency, voltage and service life. Therefore, in order to solve the above problems, a luminescent auxiliary layer is usually added between the hole transport layer and the light-emitting layer (i.e., a multi-layer hole transport layer is provided) to improve the life and efficiency of the device. The luminescent auxiliary layer can reduce the potential barrier between the hole transport layer and the light-emitting layer, reduce the driving voltage of the organic electroluminescent device, further increase the utilization rate of the holes, thereby improving the luminous efficiency and life of the device and reducing the driving voltage. However, there are few functional materials that can form a luminescent auxiliary layer.

[0005] Therefore, how to develop a luminescence auxiliary material and a preparation method thereof and an electroluminescent device containing the same is a problem that needs to be solved urgently in this field. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a luminescent auxiliary material, which can change the side chain, extend the molecular conjugation, avoid electron localization, facilitate electron separation and transmission, and change the mobility, spatial structure and energy level of the compound. By optimizing the device structure, it can effectively improve the lifespan and luminous efficiency of OLED devices while reducing the driving voltage.

[0007] In order to achieve the above object, the present invention adopts the following technical solutions:

[0008] A luminescent auxiliary material, the general structural formula of which is shown in Formula I:

[0009]

[0010] wherein X is selected from oxygen or sulfur;

[0011] R is selected from a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 3-30 membered heteroaryl group;

[0012] Ar1 and Ar2 are each independently selected from one or more of a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted 3-30 membered heterocycloalkyl group, wherein the heteroatom is N, O, S, Si, P, Se, etc.; a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 3-20 membered heteroaryl group, wherein the heteroatom is N, O, S, Si, P, Se, etc.; a substituted or unsubstituted C10-C30 fused ring group, a substituted or unsubstituted C5-C30 spirocyclic group.

[0013] Furthermore, the above R is selected from one of hydrogen, methyl, ethyl, tert-butyl, methylbenzene, methoxy, phenyl, naphthyl, biphenyl, phenanthryl, carbazolyl, fluorenyl, dimethylfluorene, terphenyl, benzofuran, benzothiophene, and pyridyl.

[0014] Furthermore, the above Ar1 is connected to N at any connectable position, and Ar1 is selected from the following groups:

[0015]

[0016] Furthermore, the above Ar2 is connected to N at any connectable position, and Ar2 is selected from the following groups:

[0017]

[0018] Furthermore, the above formula I is selected from the following general formula:

[0019]

[0020]

[0021] Furthermore, the above formula I is selected from the following general formula:

[0022]

[0023] Wherein, R, Ar1, and Ar2 are the same as defined above.

[0024] In the above terms of the present invention, "substituted" means that a hydrogen atom bonded to a carbon atom of the compound is replaced by another substituent, and the position of the substitution is not limited as long as the position is the position where the hydrogen atom is replaced (i.e., the position where the substituent can replace it), and when two or more substituents are substituted, the two or more substituents can be the same or different from each other. The heteroatom in the 3-10 membered heteroaryl group is selected from one or more of N, S, O, Si, P or Se, C1-C10 alkoxy, and C6-C20 arylamino.

[0025] In the above technical solution, it is further preferred that the above-mentioned light-emitting auxiliary material formula I is any one of the following structures, but is not limited thereto:

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035] Another object of the present invention is to provide a method for preparing the above-mentioned luminescence auxiliary material. The synthetic route of Formula I is:

[0036]

[0037] In the above formula, R, X, Ar1 and Ar2 are consistent with the same parts in the above formula I, and Hal1, Hal2 and Hal3 are each independently selected from fluorine, chlorine, bromine or iodine.

[0038] Furthermore, the synthetic route of the above formula I specifically includes the following steps:

[0039] (1) Preparation of the compound represented by intermediate CI

[0040] Under N2 protection, reactant AI, reactant BI, tetrakis(triphenylphosphine)palladium, and potassium carbonate were respectively added to a mixed solvent of toluene, ethanol, and water, and the temperature was raised to 100-120°C for reaction for 8 hours. After the reaction, the mixture was cooled to room temperature. After solid precipitation was complete, it was filtered and washed with water to remove salt. The solid was then rinsed with a small amount of ethanol, and the filter cake was dried and recrystallized from 1,4-dioxane to obtain the compound represented by intermediate CI.

[0041] (2) Preparation of the compound represented by intermediate EI

[0042] After the intermediate CI and the reactant DI are dissolved in toluene, Pd2(dba)3, P(t-Bu)3 and t-BuONa are added under a N2 atmosphere, the temperature is raised to 105-115°C and the reaction is stirred for 8-12 hours. After the reaction is completed, diatomaceous earth is used for hot filtration to remove salts and catalysts. After the filtrate is cooled to room temperature, distilled water is added to the filtrate for washing. After separation, the organic phase is retained, the aqueous phase is extracted with ethyl acetate, and the combined organic layers are dried over magnesium sulfate. The solvent is removed using a rotary evaporator. Finally, the remaining substance is purified by column chromatography using a mixture of dichloromethane and petroleum ether as an eluent to obtain the compound represented by intermediate EI;

[0043] (3) Preparation of the compound represented by formula I

[0044] After the intermediate EI and the reactant FI are dissolved in toluene, Pd2(dba)3, P(t-Bu)3 and t-BuONa are added under a N2 atmosphere, the temperature is raised to 105-115°C and the reaction is stirred for 8-12 hours. After the reaction is completed, diatomaceous earth is used for hot filtration to remove salt and catalyst. After the filtrate is cooled to room temperature, distilled water is added to the filtrate for washing. After separation, the organic phase is retained, the aqueous phase is extracted with ethyl acetate, and the combined organic layer is dried with magnesium sulfate, and the solvent is removed using a rotary evaporator. Finally, a mixture of dichloromethane and petroleum ether is used as an eluent, and the remaining substance is purified by column chromatography to obtain the compound represented by formula I.

[0045] Furthermore, in step (1), the molar ratio of reactant AI, reactant BI, tetrakis(triphenylphosphine)palladium and potassium carbonate is 1:(1-1.2):(0.01-0.02):(2.1-2.3), and the volume ratio of toluene, ethanol and water is (2-4):1:1;

[0046] In step (2), the molar ratio of intermediate CI, reactant DI, Pd2(dba)3, P(t-Bu)3 and t-BuONa is 1:(1.0-1.4):0.01:(0.02-0.04):(1.5-3.0), and the volume ratio of dichloromethane and petroleum ether is 1:(1-9);

[0047] In step (3), the molar ratio of intermediate EI, reactant FI, Pd2(dba)3 (0.01eq), P(t-Bu)3 and t-BuONa is 1:(1.0-1.4):0.01:(0.02-0.04):(1.5-2.5), and the volume ratio of dichloromethane and petroleum ether is 1:(1-9).

[0048] Another object of the present invention is to provide an organic electroluminescent device containing a light-emitting auxiliary material, comprising: a first electrode;

[0049] a second electrode disposed opposite to the first electrode;

[0050] and one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers contains the aforementioned light-emitting auxiliary material.

[0051] The organic electroluminescent device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a luminescence-assisting layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as organic layers. However, the structure of the organic light-emitting element is not limited thereto and may include fewer or more organic layers.

[0052] The organic layer comprises a light-emitting auxiliary layer, and the light-emitting auxiliary layer comprises the compound represented by formula I prepared in the present invention.

[0053] When the organic light-emitting element includes a plurality of organic layers, the organic layers may be formed of the same substance or different substances.

[0054] When manufacturing an organic light-emitting device, the compound represented by Chemical Formula I can be deposited using either vacuum evaporation or solution coating to form an organic layer. Solution coating methods include, but are not limited to, spin coating, dip coating, doctor blade coating, inkjet printing, screen printing, spraying, and roller coating.

[0055] The organic light-emitting element of the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the materials used.

[0056] The organic electroluminescent device provided by the present invention can be applied to an organic light emitting device (OLED), an organic solar cell (OSC), electronic paper (e-paper), an organic photoreceptor (OPC) or an organic thin film transistor (OTFT).

[0057] It can be seen from the above technical solutions that compared with the prior art, the present invention has the following beneficial effects:

[0058] 1. The present invention uses a benzonaphthofuran or benzonaphthothiophene skeleton to connect an aromatic amine group through a phenyl group to obtain an organic electroluminescent compound with excellent performance for a blue light emitting auxiliary layer. The prepared device has the characteristics of high luminous efficiency, low driving voltage and long service life.

[0059] 2. The aromatic amine group in the compound of the present invention changes the side chain, extends the molecular conjugation, avoids electron localization, facilitates electron separation and transmission, and changes the hole mobility, spatial structure and energy level of the compound, thereby making it more adaptable to the device. By optimizing the device structure, the lifespan and luminous efficiency of the OLED device can be effectively improved while reducing the driving voltage.

[0060] 2. The asymmetry of the monotriarylamine structure in the compound of the present invention can reduce the planarity of the molecule and prevent the molecule from moving on the plane. The triarylamine also has a high hole transport rate, which can reduce the driving voltage of the device and further improve the efficiency and life of the organic electroluminescent device. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0062] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the luminescence auxiliary material prepared in Example 1 of the present invention;

[0063] Figure 2 This is a hydrogen nuclear magnetic resonance spectrum of the luminescence auxiliary material prepared in Example 2 of the present invention;

[0064] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the luminescence auxiliary material prepared in Example 3 of the present invention;

[0065] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of the luminescence auxiliary material prepared in Example 4 of the present invention. DETAILED DESCRIPTION

[0066] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0067] Example 1

[0068] The preparation method of the luminescence auxiliary material (Compound 1) and the synthetic route are as follows:

[0069]

[0070] The specific steps include the following:

[0071] (1) Preparation of the compound represented by intermediate C-1

[0072] Under N2 protection, 80 mmol of intermediate A-1, 88 mmol of reactant B-1, 1.6 mmol of tetrakis(triphenylphosphine)palladium, and 176 mmol of potassium carbonate were added to a mixed solvent of 800 mL of toluene, 200 mL of ethanol, and 200 mL of water, respectively. The temperature was raised to 100°C and the reaction was carried out for 8 h. After the reaction was completed, the mixture was cooled to room temperature. After the solid was precipitated, it was filtered and washed with water to remove salt. The solid was then rinsed with a small amount of ethanol, and the filter cake was dried and recrystallized from 1,4-dioxane to obtain the compound represented by intermediate C-1 (26.3 g, yield: 88%, Ms: 373.36).

[0073] (2) Preparation of the compound represented by intermediate E-1

[0074] After adding 68 mmol of intermediate C-1 and 81.6 mmol of reactant D-1 to a reaction vessel and dissolving them in toluene, 0.68 mmol of Pd2(dba)3, 1.36 mmol of P(t-Bu)3 and 136 mmol of t-BuONa were added under a N2 atmosphere. After the addition, the reaction temperature was slowly raised to 110°C, and the mixture was stirred and reacted for 12 hours. After the reaction, diatomaceous earth was used for hot filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing. After separation, the organic phase was retained, the aqueous phase was extracted with ethyl acetate, and the combined organic layers were dried over magnesium sulfate. The solvent was removed using a rotary evaporator. Finally, a mixture of dichloromethane and petroleum ether in a volume ratio of 1:5 was used as an eluent, and the remaining substance was purified by column chromatography to obtain compound intermediate E-1 (26.7 g, yield: 85%, Ms: 461.32);

[0075] (3) Preparation of the compound represented by compound 1

[0076] After adding 55 mmol of intermediate E-1 and 77 mmol of reactant F-1 and dissolving them in toluene in the reaction vessel, 0.55 mmol of Pd2(dba)3, 2.2 mmol of P(t-Bu)3 and 165 mmol of t-BuONa were added under N2 atmosphere. After the addition, the reaction temperature was slowly raised to 110°C and the mixture was stirred for 10 hours. After the reaction was completed, diatomaceous earth was used for hot filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator. Finally, a mixture of dichloromethane and petroleum ether in a volume ratio of 1:5 was used as an eluent, and the remaining substance was purified by column chromatography to obtain compound 1 (33.0 g, yield: 87%).

[0077] Characterization:

[0078] HPLC purity: >99.6%;

[0079] Mass spectrometry test: theoretical value is 663.82; tested value is 663.54.

[0080] Elemental analysis:

[0081] Theoretical values: C, 90.47; H, 5.01; N, 2.11; O, 2.41;

[0082] Test values: C, 90.20; H, 5.23; N, 2.20; O, 2.52.

[0083] H NMR spectrum Figure 1 shown.

[0084] Example 2

[0085] The preparation method of the luminescent auxiliary material (Compound 56) is as follows:

[0086]

[0087] The specific steps include the following:

[0088] (1) The preparation steps of the compound represented by intermediate C-56 are the same as those of intermediate C-1 in Example 1;

[0089] (2) The preparation steps of the compound represented by intermediate E-56 are the same as those of intermediate E-1 in Example 1;

[0090] (3) Preparation of the compound represented by intermediate E-56

[0091] After adding 55 mmol of intermediate E-56 and 66 mmol of reactant F-56 to the reaction vessel and dissolving them in toluene, 0.55 mmol of Pd2(dba)3, 1.65 mmol of P(t-Bu)3 and 137.5 mmol of t-BuONa were added under N2 atmosphere. After the addition, the reaction temperature was slowly raised to 110°C and the mixture was stirred for 8 hours. After the reaction was completed, diatomaceous earth was used for hot filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator. Finally, a mixture of dichloromethane and petroleum ether in a volume ratio of 1:5 was used as the eluent, and the remaining substance was purified by column chromatography to obtain compound 56 (32.5 g, yield: 84%).

[0092] Characterization:

[0093] HPLC purity: >99.7%;

[0094] Mass spectrometry test: theoretical value is 703.84; tested value is 703.59.

[0095] Elemental analysis:

[0096] Theoretical values: C, 88.74; H, 4.73; N, 1.99; O, 4.55;

[0097] Test values: C, 88.59; H, 4.98; N, 1.89; O, 4.74.

[0098] H NMR spectrum Figure 2 shown.

[0099] Example 3

[0100] The preparation method of the luminescence auxiliary material (Compound 89) is as follows:

[0101]

[0102] The specific steps include the following:

[0103] (1) The preparation steps of the compound represented by intermediate C-89 are the same as those of intermediate C-1 in Example 1;

[0104] (2) The preparation steps of the compound represented by intermediate E-89 are the same as those of intermediate E-1 in Example 1;

[0105] (3) Preparation of the compound represented by intermediate E-89

[0106] After adding 55 mmol of intermediate E-89 and 71.5 mmol of reactant F-89 and dissolving them in toluene into the reaction vessel, 0.55 mmol of Pd2(dba)3, 1.1 mmol of P(t-Bu)3 and 121 mmol of t-BuONa were added under N2 atmosphere. After the addition, the reaction temperature was slowly raised to 110°C and the mixture was stirred for 12 hours. After the reaction was completed, diatomaceous earth was used for hot filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator. Finally, a mixture of dichloromethane and petroleum ether in a volume ratio of 1:5 was used as the eluent and the remaining substance was purified by column chromatography to obtain compound 89 (33.2 g, yield: 86%).

[0107] Characterization:

[0108] HPLC purity: >99.8%;

[0109] Mass spectrometry test: theoretical value is 702.86; tested value is 702.55.

[0110] Elemental analysis:

[0111] Theoretical values: C, 88.86; H, 4.88; N, 3.99; O, 2.28;

[0112] Measured values: C, 88.96; H, 4.95; N, 3.87; O, 2.40.

[0113] H NMR spectrum Figure 3 shown.

[0114] Example 4

[0115] The preparation method of the luminescence auxiliary material (Compound 167) is as follows:

[0116]

[0117] The specific steps include the following:

[0118] (1) Preparation of the compound represented by intermediate C-167

[0119] Under N2 protection, 80 mmol of intermediate A-167, 88 mmol of reactant B-167, 1.6 mmol of tetrakis(triphenylphosphine)palladium, and 176 mmol of potassium carbonate were added to a mixed solvent of 800 mL of toluene, 200 mL of ethanol, and 200 mL of water, respectively. The temperature was raised to 100°C and the reaction was carried out for 8 h. After the reaction was completed, the mixture was cooled to room temperature. After the solid precipitated, it was filtered and washed with water to remove salt. The solid was then rinsed with a small amount of ethanol, and the filter cake was dried and recrystallized from 1,4-dioxane to obtain the compound represented by intermediate C-167 (29.5 g, yield: 82%, Ms: 449.55).

[0120] (2) Preparation of the compound represented by intermediate E-167

[0121] After adding 65 mmol of intermediate C-167 and 78 mmol of reactant D-167 and dissolving them in toluene in a reaction vessel, 0.65 mmol of Pd2(dba)3, 1.3 mmol of P(t-Bu)3 and 195 mmol of t-BuONa were added under a N2 atmosphere. After the addition, the reaction temperature was slowly raised to 110°C and the mixture was stirred for 12 hours. After the reaction was completed, the mixture was filtered while hot using diatomaceous earth to remove salts and catalyst. After the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate and the solvent was removed using a rotary evaporator. Finally, the remaining substance was purified by column chromatography using a mixture of dichloromethane and petroleum ether in a volume ratio of 1:5 as an eluent to obtain compound intermediate E-167 (27.9 g, yield: 80%, Ms: 537.58);

[0122] (3) Preparation of the compound represented by compound 167

[0123] After adding 50 mmol of intermediate E-167 and 65 mmol of reactant F-167 and dissolving them in toluene into the reaction vessel, 0.50 mmol of Pd2(dba)3, 1.5 mmol of P(t-Bu)3 and 110 mmol of t-BuONa were added under N2 atmosphere. After the addition, the reaction temperature was slowly raised to 110°C and the mixture was stirred for 10 hours. After the reaction, diatomaceous earth was used for hot filtration to remove salt and catalyst. After the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing. After separation, the organic phase was retained and the aqueous phase was extracted with ethyl acetate. The combined organic layers were then dried over magnesium sulfate and the solvent was removed using a rotary evaporator. Finally, a mixture of dichloromethane and petroleum ether in a volume ratio of 1:5 was used as the eluent and the remaining substance was purified by column chromatography to obtain compound 167 (31.2 g, yield: 79%).

[0124] Characterization:

[0125] HPLC purity: >99.6%;

[0126] Mass spectrometry test: theoretical value is 789.98; tested value is 789.67.

[0127] Elemental analysis:

[0128] Theoretical values: C, 91.23; H, 4.98; N, 1.77; O, 2.03;

[0129] Test values: C, 90.90; H, 5.21; N, 1.81; O, 2.22.

[0130] H NMR spectrum Figure 4 shown.

[0131] Example 5-31

[0132] Compound 2, compound 4, compound 8, compound 12, compound 19, compound 24, compound 30, compound 36, compound 41, compound 47, compound 53, compound 59, compound 63, compound 69, compound 75, compound 82, compound 90, compound 95, compound 101, compound 107, compound 113, compound 130, compound 146, compound 175, compound 196, compound 204 and compound 230 were prepared by referring to the synthesis method of Examples 1-4.

[0133] The molecular formula, mass spectrum and yield are shown in Table 1.

[0134] Table 1 Molecular formula, mass spectrum and yield of compounds of Examples 5-31

[0135] Example Compound Molecular formula Mass spectrometry theoretical value Mass spectrometry test value Yield (%) Example 5 2 <![CDATA[C 48 H 31 NO]]> 637.78 637.55 84 Example 6 4 <![CDATA[C 54 H 35 NO]]> 713.88 713.58 89 Example 7 8 <![CDATA[C 49 H 35 NO]]> 653.83 653.96 88 Example 8 12 <![CDATA[C 52 H 35 NO]]> 689.86 689.55 91 Example 9 19 <![CDATA[C 52 H 33 NO]]> 687.84 687.64 86 Example 10 24 <![CDATA[C 56 H 37 NO]]> 739.92 739.60 85 Example 11 30 <![CDATA[C 60 H 39 NO]]> 789.98 789.72 80 Example 12 36 <![CDATA[C 56 H 37 NO]]> 739.92 739.80 82 Example 13 41 <![CDATA[C 52 H 35 NO]]> 689.86 689.62 85 Example 14 47 <![CDATA[C 58 H 37 NO2]]> 779.94 779.65 78 Example 15 53 <![CDATA[C 46 H 29 NO2]]> 627.74 627.61 85 Example 16 59 <![CDATA[C 50 H 31 NO2]]> 677.80 677.64 76 Example 17 63 <![CDATA[C 50 H 31 NO2]]> 677.80 677.73 78 Example 18 69 <![CDATA[C 50 H 31 NO2]]> 677.80 677.51 81 Example 19 75 <![CDATA[C 52 H 33 WE]]> 719.90 719.70 84 Example 20 82 <![CDATA[C 56 H 36 N2O]]> 752.92 752.77 88 Example 21 90 <![CDATA[C 56 H 36 N2O]]> 752.92 752.60 76 Example 22 95 <![CDATA[C 52 H 34 N2O]]> 702.86 702.69 80 Example 23 101 <![CDATA[C 58 H 38 N2O]]> 778.96 778.68 78 Example 24 107 <![CDATA[C 58 H 38 N2O]]> 778.96 778.85 74 Example 25 113 <![CDATA[C 52 H 34 N2O]]> 702.86 702.93 89 Example 26 130 <![CDATA[C 68 H 44 N2O]]> 905.11 905.32 77 Example 27 146 <![CDATA[C 74 H 48 N2O]]> 981.21 905.54 81 Example 28 175 <![CDATA[C 66 H 43 NO]]> 866.08 866.41 76 Example 29 196 <![CDATA[C 62 H 39 NO2]]> 830.00 830.29 82 Example 30 204 <![CDATA[C 44 H 29 NS]]> 603.78 603.55 88 Example 31 230 <![CDATA[C 64 H 42 N2S]]> 871.11 871.35 81

[0136] In addition, it should be noted that other compounds of the present invention can be obtained by referring to the synthesis methods of the above-mentioned embodiments, so they are not listed here one by one.

[0137] Application Example 1

[0138] The preparation of an organic electroluminescent device containing a luminescent auxiliary material specifically comprises the following steps:

[0139] a. ITO anode: An ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150 nm was cleaned twice in distilled water, ultrasonically washed for 30 minutes, and then repeatedly washed twice with distilled water, ultrasonically washed for 10 minutes. After washing, it was ultrasonically washed with methanol, acetone, and isopropanol in sequence, each washing for 5 minutes. After drying, it was transferred to a plasma cleaner and washed for 5 minutes. It was then sent to an evaporation machine. With this substrate as the anode, other functional layers were sequentially evaporated on it;

[0140] b. HIL (hole injection layer): The hole injection layer materials HT and P-dopant were vacuum evaporated at a deposition rate of 97:3, and the thickness was 10 nm.

[0141] c. HTL (hole transport layer): At a deposition rate of 100 nm, 120 nm of HT was vacuum-deposited on the hole injection layer as a hole transport layer.

[0142] d. Luminous auxiliary layer: At a deposition rate of , 10 nm of the compound 1 provided in Example 1 was vacuum-deposited on the hole transport layer as a light-emitting auxiliary layer;

[0143] e. EML (light-emitting layer): Then on the above-mentioned light-emitting auxiliary layer, The host material (Host) and dopant material (Dopant) were vacuum-deposited to a thickness of 25 nm as the light-emitting layer. The chemical formulas of the Host and Dopant are shown below. The evaporation rate ratio of the Host and Dopant was 98:2.

[0144] f. HB (hole blocking layer): The hole blocking layer with a thickness of 5.0 nm was vacuum-deposited at a deposition rate of 100 nm.

[0145] g. ETL (Electron Transport Layer): At a deposition rate of , ET and Liq were vacuum-deposited with a thickness of 30 nm as an electron transport layer. The chemical formula of ET is shown below; wherein the deposition rate ratio of ET to Liq is 50:50;

[0146] h. EIL (electron injection layer): The evaporation rate is 1.0 nm, and a Yb film layer is evaporated to form an electron injection layer;

[0147] i. Cathode: 18 nm of magnesium and silver were evaporated at a deposition rate ratio of 1:9 to obtain an OLED device;

[0148] j. Light extraction layer: At a deposition rate of , a CPL with a thickness of 70 nm was vacuum-deposited on the cathode as a light extraction layer;

[0149] k. Package the vapor-deposited substrate: First, use the glue coating equipment to coat the cleaned cover with UV glue, then move the coated cover to the pressing section, place the vapor-deposited substrate on the upper end of the cover, and finally bond the substrate and cover with the bonding equipment, and complete the light curing of the UV glue at the same time.

[0150] Device structure:

[0151] ITO / Ag / ITO / HT:P-dopant (10 nm, 3%) / HT (120 nm) / Compound 1 (10 nm) / Host:Dopant (25 nm, 2%) / HB (5 nm) / ET:Liq (30 nm, 50%) / Yb (1 nm) / Mg:Ag (18 nm, 1:9) / CPL (70 nm).

[0152] The chemical formulas involved above are as follows:

[0153]

[0154] Application Example 2-151

[0155] The organic electroluminescent devices of Application Examples 2-151 were prepared according to the above-mentioned method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that Compound 1 in Application Example 1 was replaced by corresponding compounds to form a luminescent auxiliary layer.

[0156] Comparative Example 1

[0157] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that Compound 1 in Application Example 1 was replaced by Comparative Compound 1.

[0158] Among them, the structural formula of comparative compound 1 is as follows:

[0159]

[0160] Comparative Example 2

[0161] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that Compound 1 in Application Example 1 was replaced by Comparative Compound 2.

[0162] Among them, the structural formula of comparative compound 2 is as follows:

[0163]

[0164] Comparative Example 3

[0165] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that Compound 1 in Application Example 1 was replaced by Comparative Compound 3.

[0166] Among them, the structural formula of comparative compound 3 is as follows:

[0167]

[0168] Comparative Example 4

[0169] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that Compound 1 in Application Example 1 was replaced by Comparative Compound 4.

[0170] Among them, the structural formula of comparative compound 4 is as follows:

[0171]

[0172] Comparative Example 5

[0173] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that Compound 1 in Application Example 1 was replaced by Comparative Compound 5.

[0174] Among them, the structural formula of comparative compound 5 is as follows:

[0175]

[0176] Comparative Example 6

[0177] An organic electroluminescent device was prepared according to the above method for preparing an organic electroluminescent device containing a luminescent auxiliary material, except that Compound 1 in Application Example 1 was replaced by Comparative Compound 6.

[0178] Among them, the structural formula of comparative compound 6 is as follows:

[0179]

[0180] Comparative Example 7

[0181] An organic electroluminescent device was prepared according to the preparation method of the comparative compound organic electroluminescent device, except that Compound 1 in Application Example 1 was replaced by Comparative Compound 7.

[0182] Among them, the structural formula of comparative compound 7 is as follows:

[0183]

[0184] The driving voltage, luminous efficiency, BI value, and lifespan of the organic electroluminescent devices containing the luminescent auxiliary material obtained in the above-mentioned device application examples 1-151 and device comparative examples 1-7 were characterized at a brightness of 1000 (nits). The test results are shown in Table 2.

[0185] Table 2 Luminous characteristics test results (brightness value is 1000 nits)

[0186]

[0187]

[0188]

[0189]

[0190] As shown in Table 2, the organic electroluminescent devices prepared using the luminescent auxiliary materials provided by the present invention in Application Examples 1-151 are improved in driving voltage, luminous efficiency, BI and lifespan compared with the existing organic electroluminescent devices provided by Comparative Examples 1-7.

[0191] Compared with the comparative compounds, even with the same parent core, by changing the side chain and extending the molecular conjugation, the hole mobility of the compound can be improved and the spatial structure can be changed, making it more adaptable to the device, which can effectively improve the lifespan and luminous efficiency of the OLED device while reducing the driving voltage.

Claims

1. A luminescence auxiliary material, characterized in that: Any of the following structures:

2. A method for preparing the luminescence auxiliary material according to claim 1, characterized in that: The synthetic route is as follows: In the above formula, R, X, Ar1 and Ar2 are consistent with the same parts of the structural formula of the luminescence auxiliary material according to claim 1, and Hal1, Hal2 and Hal3 are each independently selected from fluorine, chlorine, bromine or iodine; The specific steps include the following: (1) Preparation of the compound represented by intermediate CI Under N2 protection, reactant AI, reactant BI, tetrakis(triphenylphosphine)palladium, and potassium carbonate were respectively added to a mixed solvent of toluene, ethanol, and water, and the temperature was raised to 100-120°C for reaction for 8 hours. After the reaction, the mixture was cooled to room temperature. After solid precipitation was complete, it was filtered and washed with water to remove salt. The solid was then rinsed with a small amount of ethanol, and the filter cake was dried and recrystallized from 1,4-dioxane to obtain the compound represented by intermediate CI. In step (1), the molar ratio of reactant AI, reactant BI, tetrakis(triphenylphosphine)palladium and potassium carbonate is 1:(1-1.2):(0.01-0.02):(2.1-2.3), and the volume ratio of toluene, ethanol and water is (2-4):1:1; (2) Preparation of the compound represented by intermediate EI After the intermediate CI and the reactant DI are dissolved in toluene, Pd2(dba)3, P(t-Bu)3 and t-BuONa are added under a N2 atmosphere, the temperature is raised to 105-115°C and the reaction is stirred for 8-12 hours. After the reaction is completed, diatomaceous earth is used for hot filtration to remove salts and catalysts. After the filtrate is cooled to room temperature, distilled water is added to the filtrate for washing. After separation, the organic phase is retained, the aqueous phase is extracted with ethyl acetate, and the combined organic layers are dried over magnesium sulfate. The solvent is removed using a rotary evaporator. Finally, the remaining substance is purified by column chromatography using a mixture of dichloromethane and petroleum ether as an eluent to obtain the compound represented by intermediate EI; In step (2), the molar ratio of the intermediate CI, the reactant DI, Pd2(dba)3, P(t-Bu)3 and t-BuONa is 1:(1.0-1.4):0.01:(0.02-0.04):(1.5-3.0), and the volume ratio of the dichloromethane and petroleum ether is 1:(1-9); (3) Preparation of the compound represented by formula I After the intermediate EI and the reactant FI are dissolved in toluene, Pd2(dba)3, P(t-Bu)3 and t-BuONa are added under a N2 atmosphere, the temperature is raised to 105-115°C and the reaction is stirred for 8-12 hours. After the reaction is completed, diatomaceous earth is used for hot filtration to remove salt and catalyst. After the filtrate is cooled to room temperature, distilled water is added to the filtrate for washing. After separation, the organic phase is retained, the aqueous phase is extracted with ethyl acetate, and then the combined organic layer is dried with magnesium sulfate, and the solvent is removed using a rotary evaporator. Finally, a mixture of dichloromethane and petroleum ether is used as an eluent, and the remaining substance is purified by column chromatography to obtain the luminescence auxiliary material; In step (3), the molar ratio of the intermediate EI, the reactant FI, Pd2(dba)3, P(t-Bu)3 and t-BuONa is 1:(1.0-1.4):0.01:(0.02-0.04):(1.5-2.5), and the volume ratio of dichloromethane and petroleum ether is 1:(1-9).

3. An organic electroluminescent device containing a luminescence auxiliary material, characterized in that: include: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers comprises the luminescence auxiliary material according to claim 1 .

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