Spirobifluorene amine-based compound and organic electroluminescent device

Abstract

The application discloses a spirobiperylene amine compound and an organic electroluminescent device thereof, and a structural formula of the compound is shown as formula 1: wherein Ar1 and Ar2 are independently selected from substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C5-C6 cycloalkyl, substituted or unsubstituted C6-C9 aromatic hydrocarbon group, substituted or unsubstituted C6-C9 heteroaromatic hydrocarbon group, substituted or unsubstituted naphthyl, substituted or unsubstituted C11-C18 aromatic hydrocarbon group, and substituted or unsubstituted C11-C18 heteroaromatic hydrocarbon group; Ar3 and Ar4 are independently selected from substituted or unsubstituted C1-C4 linear or branched alkyl, substituted or unsubstituted C6-C24 aromatic hydrocarbon group, and substituted or unsubstituted C5-C24 heteroaromatic hydrocarbon group; a substituent of Ar3 is designed at a 3-position of spirobifluorene, a substituent is designed at positions 5-8 of the spirobifluorene, and the other two substituents of the triarylamine are limited, so that more organic electroluminescent materials are expanded, better luminous efficiency is achieved, and the service life and luminous efficiency of the device are further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescence, in particular to a spirobifluorene amino compound and an organic electroluminescent device. BACKGROUND

[0002] Organic light-emitting devices (OLED) are self-luminous devices that use the following principle: when an electric field is applied, a fluorescent substance emits light through the recombination of holes injected by the positive electrode and electrons injected by the negative electrode. Such self-luminous devices have low voltage, high brightness, wide viewing angle, fast response, good temperature adaptability, and other characteristics, and are ultra-thin, can be made on flexible panels, and have other advantages, and are widely used in mobile phones, tablets, televisions, lighting, and other fields.

[0003] Organic light-emitting devices are like a sandwich structure, including electrode material film layers, and organic functional materials sandwiched between different electrode film layers, various different functional materials are stacked together according to the purpose to jointly constitute an organic light-emitting device. As a current device, when a voltage is applied to the two electrodes of the organic light-emitting device, positive and negative charges are generated in the organic layer functional material film layer by the action of the electric field, and the positive and negative charges are further recombined in the light-emitting layer to produce light, which is electroluminescence.

[0004] Research on improving the performance of organic light-emitting devices includes: reducing the driving voltage of the device, improving the luminous efficiency of the device, improving the service life of the device, etc. In order to continuously improve the performance of organic light-emitting devices, not only the innovation of the structure and manufacturing process of organic light-emitting devices is needed, but also the continuous research and innovation of organic electroluminescent functional materials are needed, and higher performance organic electroluminescent functional materials are created.

[0005] The compound of the triarylamine class is a common organic electroluminescent material, and the spirobipentyl is selected for substitution on the substituent group of the triarylamine to improve the hole transport capacity, and there are further improvement schemes on this basis in the existing patents, for example, the compound of the spirobipentyl triarylamine is disclosed in the invention patent with the publication number WO2022096172A1, the compound No. 92 in the patent further adopts tert-butyl substitution on the No. 4 and No. 7 positions of the spirobipentyl, so as to further improve the hole transport capacity thereof, but the material performance needs to be improved, and the specific compounds 1-58 disclosed in the patent with the publication number CN113372313A adopt tert-butyl substitution on the No. 3 position of the spirobipentyl, but the specific embodiments and specific effects thereof are not disclosed in the specific embodiments, at the same time, the specific compound limits another substituent group of the triphenylamine to be benzo cyclohexane, and the device effect of 1-57 is provided in the embodiments, and 1-58 is modified on the No. 3 and No. 6 positions of the spirobifluorene on the basis of 1-57, but better effects are not achieved due to the existence of the benzo cyclohexane. SUMMARY

[0006] The purpose of the present application is to solve the above technical problems, and provide a spirobifluorene amine-based compound and an organic electroluminescent device.

[0007] A spirobipentyl amine-based compound, characterized in that the structural formula is shown as formula 1:

[0008]

[0009] wherein Ar1, Ar2 are each independently selected from substituted or unsubstituted C1-C4 straight chain or branched alkyl, substituted or unsubstituted C5-C6 cycloalkyl, substituted or unsubstituted C6-C9 aromatic hydrocarbon group, substituted or unsubstituted C6-C9 heteroaromatic hydrocarbon group, substituted or unsubstituted naphthyl group, substituted or unsubstituted C11-C18 aromatic hydrocarbon group, substituted or unsubstituted C11-C18 heteroaromatic hydrocarbon group;

[0010] Ar3, Ar4 are each independently selected from substituted or unsubstituted C1-C4 straight chain or branched alkyl, substituted or unsubstituted C6-C24 aromatic hydrocarbon group, substituted or unsubstituted C5-C24 heteroaromatic hydrocarbon group.

[0011] As a preferred scheme of the present application, the compound is selected from the compounds of formula 2, formula 3, formula 4 and formula 5,

[0012]

[0013]

[0014] As a preferred embodiment of the present application, the compound is selected from the group consisting of compounds of formula 6, formula 7, formula 8, formula 9,

[0015]

[0016]

[0017] As a preferred embodiment of the present application, Ar1, Ar2are each independently selected from the group consisting of substituted or unsubstituted phenyl (excluding benzo cyclohexane), benzyl, phenethyl, naphthyl (excluding 1,2,3,4-tetrahydro(naphthalene), anthracene, phenanthrene, fluorene, oxofluorene, 9,9-spiro fluorene group, 9,9-dimethyl fluorene group, 9,9-diphenyl fluorene group, carbazole group, N-ethyl carbazole group, 4-hydroxy carbazole group, benzocarbazoie group, furan group, thiophene group, phenyl pyrimidine group, pyrimidine group, pyridine group, triazine group;

[0018] Ar3, Ar4are each independently selected from the group consisting of substituted or unsubstituted methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, cyclopentane, phenyl, biphenyl, 9,9-dimethyl fluorene group.

[0019] As a preferred embodiment of the present application, the substituent is selected from at least one of the following atoms or groups: deuterium, hydroxyl, cyano, monodeuterated methyl, di-deuterated methyl, tri-deuterated methyl, C1-C4 straight chain or branched alkyl, C6-C18 aromatic hydrocarbon group, C5-C24 heteroaromatic hydrocarbon group.

[0020] As a preferred embodiment of the present application, Ar1, Ar2are each independently selected from the group consisting of:

[0021]

[0022]

[0023] The Ar3, Ar4are each independently selected from the group consisting of:

[0024]

[0025] As a preferred embodiment of the present application, the spiro fluorene amine compound is one of the following compounds of structural formula:

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] An organic electroluminescent device includes a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, said organic layer containing an amine compound as claimed in any one of claims 1-5.

[0047] As a preferred embodiment of the present invention, the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; at least one of the hole injection layer, hole transport layer, electron blocking layer, light-emitting layer, hole blocking layer, electron transport layer, and electron injection layer contains the above-mentioned organic electroluminescent compound.

[0048] As a preferred embodiment of the present invention, the hole transport layer and the second hole transport layer contain the above-mentioned organic electroluminescent compound.

[0049] The synthetic route for the compound of the present invention having the structure shown in Formula 1 is as follows:

[0050] The beneficial effects of this invention are:

[0051] This invention designs an Ar3 substituent at position 3 of spirodifluorene and a substituent at positions 5-8 of spirodifluorene. It also restricts the other two substituents of the triarylamine. By restricting these two substituents, the compound exhibits good electrical conductivity and electron affinity, improving electron and hole transport properties. The substituents in Ar1 and Ar2 introduce additional electronic property changes, affecting the charge transfer characteristics of the molecule. Furthermore, the larger spatial substituents in the restricted substituents influence the electron distribution of the molecule and introduce steric effects, expanding the range of organic electroluminescent materials while achieving better luminous efficiency and lower start-up voltage. Attached Figure Description

[0052] Figure 1 This is a schematic diagram of the structure of the organic electroluminescent device provided by the present invention;

[0053] The numbers in the diagram represent: 1-anode, 2-hole injection layer, 3-hole transport layer, 4-electron blocking layer, 5-light emitting layer, 6-hole blocking layer, 7-electron transport layer, 8-electron injection layer, and 9-cathode.

[0054] Figure 2 This is the HPLC chromatogram of compound 65 of the present invention.

[0055] Figure 3 The DSC spectrum of compound 65 of this invention is shown below. Figure 3 It can be seen that the Tm value of compound 65 is 296.87℃.

[0056] Figure 4 The TGA spectrum of compound 65 of this invention is shown below. Figure 4 It can be seen that the thermal weight loss temperature Td of compound 65 is 390.32℃. Detailed Implementation

[0057] Embodiments of various aspects are further illustrated and described below. It should be understood that the description herein is not intended to limit the claims to the specific aspects described. Rather, it is intended to cover substitutions, modifications, and equivalents that may be included within the spirit and scope of this disclosure as defined by the appended claims.

[0058] As used herein, in the terms “deuterated” and “undeuterated,” the term “deuterated” means that at least one hydrogen in the group is recoordinated with deuterium. The term “undeuterated” means that none of the hydrogens in the group are recoordinated with deuterium.

[0059] In this document, "aromatic group," "aryl," or "aromatic group" refers to a group containing one or more aromatic rings, including but not limited to benzene, naphthalene, phenanthrene, fluorene, acenaphthene, pyridine, pyrrole, furan, thiophene, etc. In C6-C30 aromatic groups, C6-C30 means that the group contains 6-30 carbon atoms. In C1-C10 alkyl-substituted C6-C20 aromatic groups, C1-C10 refers to the number of carbon atoms in the substituent, and C6-C20 refers to the number of carbon atoms in the unsubstituent aromatic group. Aromatic groups can be divided into monocyclic aryl and polycyclic aryl groups. Specific aromatic groups in this invention include, but are not limited to, phenyl, biphenyl, terphenyl, anthracene, naphthyl, phenanthrene, fluorenyl, dibenzofuranyl, dibenzothiophene, 9,9-spirodifluorenyl, 9,9-dimethylfluorenyl, or 9,9-diphenylfluorenyl, etc. Aromatic groups can be substituted or unsubstituted.

[0060] As used herein, "cycloalkyl" refers to a monocyclic or fused ring group consisting entirely of carbon atoms (a "fused" ring means that each ring in the system shares an adjacent pair of carbon atoms with other rings in the system), wherein one or more rings are saturated alicyclic rings, generally having 3-20 carbon atoms, preferably 3-12 carbon atoms, and more preferably 3-10 carbon atoms. Cycloalkyl groups can be classified into monocyclic alkyl groups having only one ring and fused alkyl groups having multiple rings. Examples of monocyclic alkyl groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, and cycloheptane. Cycloalkyl groups can be substituted or unsubstituted.

[0061] As used herein, "cycloalkenyl" refers to a monocyclic or fused ring group consisting entirely of carbon (a "fused" ring means that each ring in the system shares a pair of adjacent carbon atoms with other rings in the system), wherein one or more rings do not have a fully connected π-electron system and contain at least one alkenyl group, which generally has 3-20 carbon atoms, preferably 3-12 carbon atoms, more preferably 3-10 carbon atoms. Examples of cycloalkenyl groups include, but are not limited to, cyclopentene, cyclohexene, cyclohexadiene, and cycloheptanetriene. The cycloalkenyl group can be substituted or unsubstituted.

[0062] In this article, "deuterated aromatic group" refers to an aromatic group in which one or more hydrogen atoms are replaced by deuterium.

[0063] In this article, "deuterated phenyl" refers to a group in which one or more hydrogen atoms in a phenyl group are replaced by deuterium.

[0064] In this article, "heteroaryl" refers to a heteroaryl group obtained by replacing one or more C atoms in the structure of "aryl" with one or more heteroatoms (such as N, O or S).

[0065] Unless otherwise specified in the examples, the procedures should be performed under standard conditions or conditions recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0066] Example 1:

[0067] Compound 65:

[0068]

[0069] Compound 4 was prepared according to the following method:

[0070] Scheme 65-ZJ1

[0071]

[0072] Procedure: Under nitrogen protection, 65-SM1 (100g, 0.438mol, 1eq), 65-SM2 (82g, 0.46mol, 1.05eq), potassium carbonate (121g, 0.876mol, 2eq), and toluene / ethanol / water (1600ml + 800ml + 480ml) were added to a 3L three-necked flask. Under N2 protection, tetraphenylphosphine palladium (10g, 8.76mmol, 0.02eq) was added. The mixture was heated to reflux and stirred. HPLC monitoring showed that 65-SM1 ≤ 1%.

[0073] Post-processing: Stop the reaction, add water, stir and separate the liquid phase. Extract the aqueous phase with DCM, combine the organic phases, dry with anhydrous sodium sulfate, filter, concentrate the filtrate to dryness, and use it directly in the next reaction without purification (overyield).

[0074] Scheme 65-ZJ2

[0075]

[0076] Procedure: Add 65-ZJ1 (theoretical 123.4g, 0.438mol, 1eq), sodium nitrite (151g, 2.19mol, 5eq), diiodomethane (235g, 0.876mol, 2eq), and DCM / water (1L+1L) to a 3L three-necked flask, stir and cool to below 0℃, then rapidly add acetic acid (526g, 8.76mol, 20eq). After the addition is complete, move to room temperature and stir to react overnight.

[0077] Post-processing: Stop the reaction, stir and separate the liquids, wash the organic phase with 1L of water, dry the organic phase with anhydrous sodium sulfate, concentrate to dryness under reduced pressure, load the sample by wet method, pack 1kg of 200-300 mesh silica gel into a column, wash with pure PE, collect the product spot, concentrate to dryness under reduced pressure, and obtain 244.4g of brown oily substance, which is above the yield.

[0078] Solution 65-ZJ3

[0079]

[0080] Procedure: Add 65-ZJ2 (theoretical 172g, 0.438mol, 1eq) and dry THF (860ml) to a 2L three-necked flask, cool to -78℃, and add 2.5M n-butyllithium (184ml, 0.46mol, 1.05eq) dropwise. After the addition is complete, maintain the temperature at -78℃ and stir for 1h. Then add 65-SM3 (85g, 0.394mol, 0.9eq) in THF (600ml) solution dropwise. After the addition is complete, raise the temperature to room temperature and stir for overnight.

[0081] Post-processing: Stop the reaction, add ammonium chloride aqueous solution, stir and separate the liquids. Extract the aqueous phase with DCM, combine the organic phases, concentrate under reduced pressure to dryness, and use directly for the next reaction without purification.

[0082] Solution 65-ZJ4

[0083]

[0084] Procedure: 65-ZJ3 (223.66 g, 0.438 mol, 1 eq) and DCM (1000 mL) were added to a 2 L single-necked flask. The mixture was cooled to below 0 °C, and methanesulfonic acid (253 g, 2.628 mol, 6 eq) was added dropwise. After the addition was complete, the mixture was stirred for 1 h. The concentration of 65-ZJ3 was monitored by HPLC to be ≤0.5%.

[0085] Post-processing: Stop the reaction, add water, stir and separate the liquid. Extract the aqueous phase with DCM, combine the organic phases, add 300g of 100-200 mesh silica gel to make sand, pack 1.5kg of 100-200 mesh silica gel into a column, perform column chromatography, PE / DCM = 50 / 1~25 / 1~15 / 1, collect the product spot, concentrate under reduced pressure to dryness, and obtain 40.8g of yellow oil (65-ZJ4). The four-step yield is 18.4%.

[0086] Option 65

[0087]

[0088] Procedure: 65-ZJ4 (40.8 g, 80.4 mmol, 1 eq), 65-SM4 (30.18 g, 80.4 mmol, 1 eq), sodium tert-butoxide (9.27 g, 96.48 mmol, 1.2 eq), tritert-tert-butylphosphine (6.5 mL, 3.216 mmol, 0.04 eq), and toluene (500 mL) were added to a 1 L three-necked flask. Under nitrogen protection, tris(dibenzylacetone)palladium (1.47 g, 1.608 mmol, 0.02 eq) was added. The mixture was heated to 110 °C and stirred. The reaction was monitored by HPLC, and the concentration of 65-ZJ4 was ≤0.5%.

[0089] Post-processing: After the reaction was complete, the reaction was stopped, the mixture was stirred and separated, the aqueous phase was extracted with DCM, the organic phases were combined and filtered through silica gel, the filtrate was concentrated to dryness under reduced pressure, 150 ml of toluene was added and heated to dissolve, then 300 ml of ethanol was added, the mixture was cooled and stirred to induce crystallization, and the mixture was filtered. The filter cake was recrystallized four times with toluene / ethanol (1 / 2), filtered, and the filter cake was dried at 85°C to obtain 36.4 g of off-white solid (65), with a purity of 99.9903% and a yield of 56.4%.

[0090] Compounds 1, 17, 33, 49, 81, 97, 113, 129, 145, 161, and 177 were obtained using similar methods (see Table 1 below). Table 1

[0091]

[0092]

[0093]

[0094] Example 13: Compound 67:

[0095]

[0096] Compound 67 was prepared according to the following method.

[0097] Scheme 67-ZJ1

[0098]

[0099] Procedure: Under nitrogen protection, 67-SM1 (100g, 0.295mol, 1eq), 67-SM2 (52.52g, 0.295mol, 1eq), potassium carbonate (89.7g, 0.649mol, 2.2eq), and toluene / ethanol / water (1600ml + 800ml + 480ml) were added to a 3L three-necked flask. Under N2 protection, tetraphenylphosphine palladium (6.8g, 5.9mmol, 0.02eq) was added. The mixture was heated to reflux and stirred. HPLC monitoring showed that 67-SM1 ≤ 1%.

[0100] Post-processing: Stop the reaction, add water, stir and separate the liquid phase. Extract the aqueous phase with DCM, combine the organic phases, dry with anhydrous sodium sulfate, filter, concentrate the filtrate to dryness, and use it directly in the next reaction without purification (overyield).

[0101] Scheme 67-ZJ2

[0102]

[0103] Procedure: Add 67-ZJ2 (theoretical 102g, 0.295mol, 1eq) and dry THF (800ml) to a 2L three-necked flask, cool to -78℃, and add 2.5M n-butyllithium (124ml, 0.31mol, 1.05eq) dropwise. After the addition is complete, maintain the temperature at -78℃ and stir for 1h. Then add 67-SM3 (72.7g, 0.28mol, 0.95eq) in THF (600ml) dropwise. After the addition is complete, raise the temperature to room temperature and stir for overnight.

[0104] Post-processing: Stop the reaction, add ammonium chloride aqueous solution, stir and separate the liquids. Extract the aqueous phase with DCM, combine the organic phases, concentrate under reduced pressure to dryness, and use directly for the next reaction without purification.

[0105] Solution 67-ZJ3

[0106]

[0107] Procedure: 67-ZJ2 (theoretical 150.8 g, 0.295 mol, 1 eq) and DCM (1000 mL) were added to a 2 L single-necked flask. The temperature was lowered to below 0 °C, and methanesulfonic acid (170 g, 1.77 mol, 6 eq) was added dropwise. After the addition was complete, the mixture was stirred for 1 h. The 67-ZJ2 content was monitored by HPLC to be ≤0.5%.

[0108] Post-processing: Stop the reaction, add water, stir and separate the liquid. Extract the aqueous phase with DCM, combine the organic phases, add 300g of 100-200 mesh silica gel to make sand, pack 1.5kg of 100-200 mesh silica gel into a column, perform column chromatography, PE / DCM = 50 / 1~25 / 1~15 / 1, collect the product spot, concentrate under reduced pressure to dryness, and obtain 54.1g of yellow oil (67-ZJ3), with a three-step yield of 36.1%.

[0109] Option 67

[0110]

[0111] Procedure: 67-ZJ3 (54.1 g, 0.107 mol, 1 eq), 67-SM4 (40 g, 0.107 mol, 1 eq), sodium tert-butoxide (12.3 g, 0.128 mol, 1.2 eq), tritert-tert-butylphosphine (8.6 mL, 4.28 mmol, 0.04 eq), and toluene (400 mL) were added to a 1 L three-necked flask. Under nitrogen protection, tris(dibenzylacetone)palladium (1.96 g, 2.14 mmol, 0.02 eq) was added. The mixture was heated to 110 °C and stirred. The concentration of 67-ZJ3 was monitored by HPLC to be ≤0.5%.

[0112] Post-processing: After the reaction was complete, the reaction was stopped, the mixture was stirred and separated, the aqueous phase was extracted with DCM, the organic phases were combined and filtered through silica gel, the filtrate was concentrated to dryness under reduced pressure, 150 ml of toluene was added and heated to dissolve, then 300 ml of ethanol was added, the mixture was cooled and stirred to induce crystallization, and the crystals were filtered. The filter cake was recrystallized four times with toluene / ethanol (1 / 2), filtered, and the filter cake was dried at 85°C to obtain 36.8 g of off-white solid (67), with a purity of 99.9501% and a yield of 42.9%.

[0113] Compounds 3, 19, 35, 51, 83, 99, 115, 131, 147, 163, and 179 were obtained using a similar method. See Table 2 below for details.

[0114] Table 2

[0115]

[0116]

[0117]

[0118]

[0119] Example 25:

[0120] Compound 77:

[0121]

[0122] Compound 77 was prepared according to the following method: Scheme 77-ZJ1

[0123]

[0124] For details on post-processing, please refer to 65-ZJ1.

[0125] Scheme 77-ZJ2

[0126]

[0127] For details on post-processing, please refer to 65-ZJ2.

[0128] Solution 77-ZJ3

[0129]

[0130] For specific post-processing details, please refer to 65-ZJ3.

[0131] Solution 77-ZJ4

[0132]

[0133] For specific post-processing details, please refer to 65-ZJ4.

[0134] Option 77

[0135]

[0136] For details on post-processing, please refer to page 65.

[0137] Compounds 13, 29, 45, 61, 93, 109, 125, 141, 157, 173, and 189 were obtained using a similar method. See Table 3 below for details.

[0138] Table 3

[0139]

[0140]

[0141]

[0142]

[0143] Example 37:

[0144] Compound 289:

[0145]

[0146] Compound 289 was prepared according to the following method: Scheme 289-ZJ1

[0147]

[0148] For details on post-processing, please refer to 65-ZJ1.

[0149] Solution 289-ZJ2

[0150]

[0151] For details on post-processing, please refer to 65-ZJ2.

[0152] Solution 289-ZJ3

[0153]

[0154] For specific post-processing details, please refer to 65-ZJ3.

[0155] Solution 289-ZJ4

[0156]

[0157] For specific post-processing details, please refer to 65-ZJ4.

[0158] Option 289

[0159]

[0160] For details on post-processing, please refer to page 65.

[0161] Compounds 305, 317, 333, 349, 365, 381, and 397 were obtained using similar methods (see Table 4 below).

[0162] Table 4

[0163]

[0164]

[0165]

[0166] Example 45:

[0167] Compound 291:

[0168]

[0169] Compound 291 was prepared according to the following method: Scheme 291-ZJ1

[0170]

[0171] For details on post-processing, please refer to 67-ZJ1.

[0172] Scheme 291-ZJ2

[0173]

[0174] For details on post-processing, please refer to 67-ZJ2.

[0175] Scheme 291-ZJ3

[0176]

[0177] For details on post-processing, please refer to 67-ZJ3.

[0178] Option 291

[0179]

[0180] For details on post-processing, please refer to section 67.

[0181] Compounds 307, 319, 335, 351, 367, 383, and 399 were obtained using similar methods. See Table 5 below for details.

[0182]

[0183]

[0184] The results of the synthesis and identification of the compounds prepared in Tables 1-5 above are shown in Table 6 below:

[0185] Table 6

[0186]

[0187]

[0188] Material property testing:

[0189] The thermogravimetric temperature Td and melting point Tm of compounds 65, 1, 17, 33, 49, 81, 97, 113, 129, 145, 161, 177, 67, 3, 19, 35, 51, 83, 99, 115, 131, 147, 163, 179, 77, 13, 29, 45, 61, 93, 109, 125, 141, 157, 173, and 189 of this invention were tested, and the test results are shown in Table 7 below.

[0190] Note: The thermogravimetric temperature Td is the temperature at which the mass loss is 5% in a nitrogen atmosphere, measured on a TGAN-1000 thermogravimetric analyzer at a nitrogen flow rate of 10 mL / min. The melting point Tm is determined by differential scanning calorimetry (DSC, Shinco DSC N-650) at a heating rate of 10 °C / min.

[0191] Table 7:

[0192]

[0193]

[0194] The data above show that the compounds synthesized in this invention have excellent thermal stability, indicating that compounds conforming to the general structural formula of this invention all have excellent thermal stability and can meet the requirements for use in organic electroluminescent materials.

[0195] Device performance testing:

[0196] Application Example 1:

[0197] ITO was used as the anode substrate material for the reflective layer, and its surface was treated sequentially with water, acetone, and N2 ions.

[0198] Above the ITO anode substrate, a hole injection layer (HIL) is formed by depositing an organic electroluminescent compound 28 doped with 3% wt HAT-CN in Example 1 of the present invention with a thickness of 10 nm.

[0199] An organic electroluminescent compound 65 prepared in Example 1 of the present invention is vapor-deposited over the hole injection layer (HIL) to form a hole transport layer (HTL) with a thickness of 85 nm.

[0200] EB-1 was vacuum-deposited above the hole transport layer (HTL) to form an electron blocking layer (EBL) with a thickness of 10 nm;

[0201] BH-1 was used as the main blue light material and BD-1 was used as the blue light dopant (the amount of BD-1 was 3% of the weight of ADN). They were evaporated at different rates on the hole transport layer (HTL) to form a light-emitting layer with a thickness of 20 nm.

[0202] HB-1 was deposited onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm;

[0203] ET-1 was deposited as an electron transport layer material (ET) onto a hole blocking layer (HBL) to obtain an electron transport layer (ETL) with a thickness of 30 nm. An electron injection layer (EIL) with a thickness of 2 nm was deposited on top of the electron transport layer (ETL).

[0204] Subsequently, magnesium (Mg) and silver (Ag) were mixed in a mass ratio of 9:1 and vapor-deposited to obtain a cathode with a thickness of 15 nm. A DNTPD with a thickness of 50 nm was deposited on the cathode sealing layer. In addition, the cathode surface was sealed with a UV-curable adhesive and a sealing film containing a desiccant to protect the organic electroluminescent device from the influence of oxygen or moisture in the atmosphere. Thus, an organic electroluminescent device was prepared.

[0205]

[0206] Application Example 2-48

[0207] Organic electroluminescent devices of Application Examples 2-48 were fabricated using compounds 1, 17, 33, 49, 81, 97, 113, 129, 145, 161, 177, 67, 3, 19, 35, 51, 83, 99, 115, 131, 147, 163, 179, 77, 13, 29, 45, 61, 93, 109, 125, 141, 157, 173, and 189 of the present invention as hole transport materials, with other parts being the same as in Application Example 1.

[0208] Compare with Examples 1-4:

[0209] The difference from Application Example 1 is that compound 92 in WO2022096172A1; compounds 1-58 in CN 113372313 A; and compounds 67-10 and 67-13 in WO2023063402A1 are used instead of compound 65 in this application as hole transport layer materials. Otherwise, they are the same as Application Example 1.

[0210] The organic electroluminescent device manufactured in the above application example and the organic electroluminescent device manufactured in the comparative example have the characteristic of operating at a current density of 10 mA / cm². 2 The results were measured under the specified conditions and are shown in Table 8.

[0211] Table 8:

[0212]

[0213]

[0214]

[0215] As shown in Table 8 above, when the compounds of Formula 2 and Formula 3 of this invention are used as hole transport layers (HTLs) in organic electroluminescent devices, the luminous efficiency is significantly improved under the same current density, the device startup voltage is reduced, the power consumption of the device is relatively reduced, and the device lifespan is correspondingly improved.

[0216] The organic electroluminescent devices prepared in Comparative Examples 1-4, Application Examples 1-5, 13-17, and 27-31 were subjected to luminescence lifetime tests to obtain the luminescence lifetime T97% data (the time for the luminous brightness to decrease to 97% of the initial brightness). The testing equipment was a TEO luminescent device lifetime testing system. The results are shown in Table 9.

[0217] Table 9:

[0218]

[0219]

[0220] As shown in Table 9 above, when the compounds of Formula 2 and Formula 3 of this invention are used as hole transport layers (HTLs) in organic electroluminescent devices, the lifespan of the prepared organic electroluminescent devices is greatly improved, so they have a very broad application prospect.

[0221] Application Example 37:

[0222] ITO was used as the anode substrate material for the reflective layer, and its surface was treated sequentially with water, acetone, and N2 ions.

[0223] A hole injection layer (HIL) is formed by depositing 10 nm of HT-1 doped with 2% NDP-9 by mass on top of the ITO anode substrate.

[0224] A first hole transport layer (HTL) is formed by depositing 100 nm of HT-1 above the hole injection layer (HIL);

[0225] Compound 289 of the present invention was vacuum-deposited over the first hole transport layer (HTL) to form a second hole transport layer (GPL) with a thickness of 30 nm.

[0226] Compounds G1 and G2 were co-deposited as green light host materials in a 5:5 mass ratio, and GD-1 was deposited as a dopant material (GD-1 amount was 8% of the total mass of G1 and G2) on the second hole transport layer (GPL) to form a light-emitting layer with a thickness of 30 nm.

[0227] HB-1 was deposited onto the light-emitting layer to obtain a hole blocking layer (HBL) with a thickness of 20 nm;

[0228] ET-1 and LiQ were co-deposited onto the hole blocking layer (HBL) at a mass ratio of 5:5 to obtain an electron transport layer (ETL) with a thickness of 30 nm.

[0229] Magnesium (Mg) and silver (Ag) are mixed in a mass ratio of 9:1 and vapor-deposited onto the electron transport layer (ETL) to form an electron injection layer (EIL) with a thickness of 50 nm.

[0230] Subsequently, silver (Ag) is vapor-deposited onto the electron injection layer to form a cathode with a thickness of 100 nm. A 50 nm thick DNTPD is then deposited on the cathode sealing layer. Furthermore, the cathode surface is sealed with a UV-curable adhesive and a sealing cap containing a desiccant to protect the organic electroluminescent device from the influence of atmospheric oxygen or moisture. Thus, an organic electroluminescent device is prepared.

[0231]

[0232] Application Examples 38-52

[0233] Using compounds 305, 317, 333, 349, 365, 381, 397, 291, 307, 319, 335, 351, 367, 383, and 399 from the embodiments of the present invention as the second hole transport materials, and with the other parts being the same as in Application Example 37, organic electroluminescent devices of Application Examples 38-52 were fabricated accordingly.

[0234] The difference from Application Example 37 is that compounds a20 and a23 from CN113380954A are used instead of compound 289 in this application as the second hole transport material, while the rest is the same as Application Example 37.

[0235] The organic electroluminescent device manufactured in the above application example and the organic electroluminescent device manufactured in the comparative example have the characteristic of operating at a current density of 10 mA / cm². 2 The results were measured under the specified conditions and are shown in Table 10.

[0236] Table 10:

[0237]

[0238] As shown in Table 10 above, when the compounds of Formulas 4 and 5 of this invention are used as the second hole transport layer (GPL) in organic electroluminescent devices, the luminous efficiency is significantly improved under the same current density, the device start-up voltage is reduced, the power consumption of the device is relatively reduced, and the device lifespan is correspondingly improved.

[0239] The organic electroluminescent devices prepared in Comparative Examples 1-2 and Application Examples 27-52 were subjected to luminescence lifetime tests to obtain the luminescence lifetime T97% data (the time for the luminous brightness to decrease to 97% of the initial brightness). The testing equipment was a TEO luminescent device lifetime testing system. The results are shown in Table 11:

[0240] Table 11:

[0241]

[0242]

[0243] As shown in Table 11 above, when the compounds of Formulas 4 and 5 of this invention are used as the second hole transport layer (GPL) in organic electroluminescent devices, the service life is greatly improved under the same current density, and they have broad application prospects.

Claims

1. A spirodiamylamine-based compound, characterized by, The spirobifluorene amine-based compound is one of the following compounds:

2. A spirodiamylamine-based compound, characterized by, The compound is selected from the compounds of Formula 4, Formula 5, Ar1, Ar2 are each independently selected from the following groups: each of said Ar3, Ar4is individually selected from the following atoms or groups:

3. A spirobifluorenamine compound according to claim 2, wherein The compound is selected from the compounds of Formula 10, Formula 11, Formula 12, Formula 13, Formula 14, 4. The spirobifluorenamine compound according to claim 2, wherein The spirobifluorene amine-based compound is one of the following compounds:

5. An organic electroluminescent device, characterized by An organic electroluminescence device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode, wherein the organic layer contains the amine-based compound according to any one of claims 1 to 4.

6. The organic electroluminescent device according to claim 5, characterized in that The organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer; at least one of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer contains the organic electroluminescence compound.

7. The organic electroluminescent device according to claim 5, wherein The hole transport layer and the second hole transport layer contain the organic electroluminescence compound.

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