Spiro sterically hindered triarylamine compound as well as preparation method and application thereof

Abstract

The invention belongs to the field of organic electroluminescent materials and devices, and particularly relates to a spiro steric hindrance triarylamine compound as well as a preparation method and application thereof. The general formula of the spiro steric hindrance triarylamine compound is shown as a formula (I). The rigid spiral ring structure of the compound provided by the invention is beneficial to formation of a stable amorphous film, and the high thermal stability of the compound is expected to allow deposition of a high-quality film at a lower temperature, so that the process energy consumption is reduced, the thermal damage is reduced, and the process window is widened. As a B Prime layer material, the compound is beneficial to balancing distribution of current carriers near a light-emitting layer and limiting an exciton recombination region, so that the aging process of a device is possibly slowed down, and the operation life is prolonged. While the potential process and stability advantages are achieved, the compound is well matched with an adjacent functional layer in energy level, and it can be guaranteed that the device has low driving voltage, high efficiency and other core photoelectric properties. Formula (I).

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescent materials and devices, specifically relating to a spirocyclic sterically hindered triarylamine compound, its preparation method, and its application. Background Technology

[0002] The efficiency, driving voltage, and lifetime of OLED devices largely depend on the intrinsic properties of the functional layer materials. Among numerous candidate materials, spirocyclic sterically hindered triarylamine compounds exhibit unique potential: their rigid three-dimensional framework (such as 9,9'-spirodifluorene) can effectively suppress molecular aggregation and ensure the morphological stability of the thin film; at the same time, their triarylamine structure provides efficient hole transport channels, making them ideal host materials for high-performance hole transport layers or light-emitting layers.

[0003] However, the controllable preparation of such sterically hindered molecules remains a core bottleneck for industrialization. Their synthesis often relies on multi-step CN coupling, making the design of the reaction sequence and precise matching of the catalytic system at each step crucial. Inappropriate selection can lead to increased side reactions, low overall yield, and difficulties in product purification. In particular, conventional catalysts often fail due to insufficient activity when constructing the final highly crowded triarylamine center, hindering reaction scale-up and resulting in mixed crystal forms of the obtained products. This leads to significant batch-to-batch variations in material performance, severely restricting the performance consistency and reliability of OLED devices.

[0004] Therefore, developing a dedicated method for the directional and high-yield synthesis of a single stable crystal form is crucial for promoting the practical application of this type of material. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to address the shortcomings of the prior art by providing a spirocyclic sterically hindered triarylamine compound with a defined Q crystal form, its proprietary three-step synthesis method, and the application of the compound as a hole transport layer material or host material in organic light-emitting devices, thereby obtaining organic electroluminescent devices with better performance, more defined structure, and easier large-scale preparation.

[0006] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0007] The first aspect of the present invention provides a spirocyclic sterically hindered triarylamine compound, the general formula of which is shown in formula (I):

[0008]

[0009] Formula (I)

[0010] X and Y are each independently selected from single bonds, O and N-Ar bonds. 8 Any one of the following, and X and Y are not both 0 at the same time;

[0011] Ar 1 ~Ar 6 Each is independently selected from any one of substituted or unsubstituted phenyl, naphthyl, dibenzofuranyl and carbazoleyl;

[0012] Ar 7 It is selected from any one of naphthyl, phenanthryl, carbazolyl, dibenzofuranyl, arylbenzofuranyl and arylbenzoindolyl, whether substituted or unsubstituted;

[0013] Ar 8 Selected from any one of substituted or unsubstituted phenyl, naphthyl, dibenzofuranyl and para-biphenyl;

[0014] Ar 1 ~Ar 8 Each substituent in the substituted group is independently selected from any one of deuterium, fluorine, cyano, phenyl, naphthyl, dibenzofuranyl, and carbazoleyl.

[0015] In some embodiments of the present invention, Ar 1 ~Ar 6 Each is independently selected from any of the following general formulas:

[0016] ;

[0017] Among them, Ar 9 Existence or non-existence; when Ar 9 When it exists, it is selected from any of the following general formulas:

[0018] .

[0019] In some embodiments of the present invention, the Ar 1 ~Ar 6 Each is independently selected from any of the following general formulas:

[0020] .

[0021] In some embodiments of the present invention, Ar 5 ~Ar 6 Each is independently selected from any of the following general formulas:

[0022] .

[0023] In some embodiments of the present invention, the general formula of the spirocyclic sterically hindered triarylamine compound is selected from any one of the following formulas I-1 to I-8:

[0024]

[0025] In some embodiments of the present invention, Ar 7 Selected from any of the following general formulas:

[0026]

[0027] Among them, Ar 10 Existence or non-existence; when Ar 10 When it exists, it is selected from any of the following general formulas: .

[0028] In some embodiments of the present invention, Ar 8 Selected from any of the following general formulas:

[0029] .

[0030] In some embodiments of the present invention, Ar 8 It is a phenyl group.

[0031] In some embodiments of the present invention, the Ar structure 7 and Ar 3 -Ar 4 The conjugate structure in the plane is located on the same side of the center of the helical ring, and Ar 7 and Ar 3 -Ar 4 There are intramolecular π-π stacking interactions between the π-conjugated planes of the planar conjugated structure at a distance of 3.39~3.43 Å.

[0032] In some embodiments of the present invention, the spirocyclic sterically hindered triarylamine compound includes any one of the following S-1 to S-96:

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040] A second aspect of this invention provides a method for preparing a spirocyclic sterically hindered triarylamine compound, the synthetic route of which is shown below:

[0041] .

[0042] X and Y are each independently selected from single bonds, O and N-Ar bonds. 8 Any one of the following, and X and Y are not both O; Z is Br or Cl; Ar 8 Selected from any one of substituted or unsubstituted phenyl, naphthyl, dibenzofuranyl, and para-biphenyl; Ar 1 ~Ar 4 Each is independently selected from any one of substituted or unsubstituted phenyl, naphthyl, dibenzofuranyl, and carbazoleyl; Ar 5 and Ar 6 Each is independently selected from any one of substituted or unsubstituted phenyl, naphthyl, dibenzofuranyl, and carbazoleyl; M is selected from any one of Cl, I, or OTf; Ar 7 It is selected from any one of substituted or unsubstituted naphthyl, phenanthryl, carbazolyl, dibenzofuranyl, arylbenzofuranyl, and arylbenzoindolyl; the substituents in each substituted group are independently selected from any one of deuterium, fluorine, cyano, phenyl, naphthyl, dibenzofuranyl, and carbazolyl.

[0043] In some embodiments of the present invention, in step one, the molar ratio of the compound of general formula (II) and tris(dibenzylacetone)palladium is 1:(0.03~0.06); the reaction conditions in step one are: reaction temperature of 80 ℃~120 ℃ and reaction time of 1~2 h.

[0044] In some embodiments of the present invention, the raw materials in step one include an alkali, and the molar ratio of the compound of general formula (II) to the alkali is 1:(1~4); the alkali may be selected from one or more of alkali metal or alkaline earth metal alkoxides, carbonates, phosphates, hydrides or alkylsilylamino salts.

[0045] In some embodiments of the present invention, the alkali in step one is selected from any one of lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, cesium carbonate, potassium carbonate, potassium phosphate, or sodium hydride.

[0046] In some embodiments of the present invention, the reaction in step one is carried out in a solvent environment, and the organic solvent used is any one of toluene, dioxane, xylene and a mixed solvent of toluene-N,N'-dimethylformamide (volume ratio of 10:1 to 5:1).

[0047] In some embodiments of the present invention, in step two, the molar ratio of the compound of general formula (III) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) is 1:(0.01~0.03); the reaction conditions in step two are: a reaction temperature of 80 ℃~100 ℃ and a reaction time of 2~6 h.

[0048] In some embodiments of the present invention, the raw materials in step two include an alkali, and the molar ratio of the general formula (III) compound to the alkali is 1:(1~4); the alkali may be selected from one or more of alkali metal or alkaline earth metal alkoxides, carbonates, phosphates, hydrides or alkylsilylamino salts.

[0049] In some embodiments of the present invention, the alkali in step two is selected from any one of lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, cesium carbonate, potassium carbonate, potassium phosphate, or sodium hydride.

[0050] In some embodiments of the present invention, the reaction in step two is carried out in a solvent environment, and the organic solvent used is any one of toluene, dioxane, xylene and a mixed solvent of toluene-N,N'-dimethylformamide (volume ratio of 10:1 to 5:1).

[0051] A third aspect of this invention provides the application of a spirocyclic sterically hindered triarylamine compound in the preparation of organic electronic devices.

[0052] The spirocyclic sterically hindered triarylamine compound is used in organic electronic devices as one or more of the hole transport layer, auxiliary layer, or light-emitting layer.

[0053] In some embodiments of the present invention, the organic electronic device includes, from bottom to top, an anode, a hole injection layer, a hole transport layer, a B Prime layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode. By comparing the organic electronic device prepared using the spirocyclic sterically hindered triarylamine compound obtained in some embodiments of the present invention as the B Prime layer material with a control group device prepared using the existing commercial material TAPC, it is shown that an organic electronic device with longer operating life, higher thermal stability, and better process adaptability than existing materials can be achieved at a lower evaporation temperature, demonstrating the application prospects of the spirocyclic sterically hindered triarylamine compound provided by the present invention in the preparation of organic electronic devices.

[0054] Beneficial effects:

[0055] Applying compounds with the specific structures described above to such devices is expected to bring about the following synergistic optimization benefits:

[0056] 1) Improved thermal stability and process adaptability: The rigid spiro ring structure of the compound is conducive to the formation of stable amorphous films. Its high thermal stability is expected to allow the deposition of high-quality films at lower temperatures, thereby reducing process energy consumption, reducing thermal damage and widening the process window.

[0057] 2) Optimize device lifetime: As a B Prime layer material, this compound helps to balance the carrier distribution near the light-emitting layer and limit the exciton recombination region, which may slow down the device aging process and extend the operating lifetime.

[0058] 3) Maintaining excellent optoelectronic performance: While achieving the above-mentioned potential process and stability advantages, the compound is well matched with adjacent functional layers in terms of energy level, which can ensure that the device has core optoelectronic performance such as low driving voltage and high efficiency. Attached Figure Description

[0059] The present invention will be further described in detail below with reference to the accompanying drawings, and the advantages of the present invention in the above and / or other aspects will become clearer.

[0060] Figure 1 This is the proton NMR spectrum of compound S-1 prepared in Example 1 of the present invention.

[0061] Figure 2 This is the carbon spectrum of compound S-1 prepared in Example 1 of the present invention.

[0062] Figure 3 This is a schematic diagram of the structure of the S-1 single crystal in Embodiment 11 of the present invention.

[0063] Figure 4 This is a schematic diagram of the molecular stacking of the S-1 single crystal in Embodiment 11 of the present invention.

[0064] Figure 5 The images show the ultraviolet absorption spectra of the compounds synthesized in Examples 1, 2, 3, 6, and 9 of this invention.

[0065] Figure 6 The images show the fluorescence emission spectra of the compounds synthesized in Examples 1, 2, 3, 6, and 9 of this invention. Detailed Implementation

[0066] The present invention will be further described in detail below with reference to specific embodiments, and the advantages of the present invention in the above and / or other aspects will become clearer.

[0067] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; the reagents and materials described are commercially available unless otherwise specified.

[0068] Example 1:

[0069] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-1 and its preparation method. The structural formula of S-1 is as follows:

[0070]

[0071] S-1

[0072] The synthesis route for S-1 is as follows:

[0073]

[0074] The specific preparation steps are as follows:

[0075] Step 1: Synthesis of compound a

[0076] A 250 mL double-necked flask was washed and dried. 2-Chlorospirodifluorene (1.78 g, 5.06 mmol), 4-(dibenzo-p-b,d]furan-4-yl)aniline (1.31 g, 5.06 mmol), and toluene (24 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 4 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.97 g, 10.12 mmol), S-Phos (0.13 g, 0.3 mmol), and tris(dibenzylacetone)palladium (0.14 g, 0.15 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After the reaction was complete, the mixture was cooled to room temperature, and water and toluene were added to extract the mixture. The organic layer was collected and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 25 mL of toluene by heating, concentrated to twice its volume, cooled to crystallize, and dried under vacuum at 80 °C to obtain a high-purity intermediate compound a (2.6 g), with a yield of 90%, as a white solid.

[0077] The NMR characterization data of compound a are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.19 – 8.13 (m,1H), 8.08 – 8.02 (m, 1H), 7.96 – 7.91 (m, 1H), 7.82 (ddd, J = 16.3, 6.8, 1.4Hz, 3H), 7.68 – 7.63 (m, 1H), 7.57 – 7.51 (m, 2H), 7.50 – 7.30 (m, 10H), 7.34– 7.28 (m, 2H), 7.23 – 7.15 (m, 3H), 6.86 (dd, J = 7.1, 1.4 Hz, 1H), 6.79(dd, J = 7.0, 1.4 Hz, 2H), 6.67 (s, 1H). 13C NMR (125 MHz, DMSO-d6) δ 155.77,153.16, 143.69, 143.32, 142.60, 140.81, 139.05, 137.92, 137.87, 134.61,130.94, 129.09, 129.04, 128.53, 128.52, 128.28, 127.22, 126.46, 126.08,125.87, 125.47, 125.10, 124.66, 122.83, 122.42, 122.38, 122.22, 121.82, 120.90, 120.39, 120.28, 119.88, 116.75, 111.65, 64.61.

[0078] Step 2: Synthesis of compound S-1

[0079] A 100 mL double-necked flask was washed and dried. Intermediate a (1.00 g, 1.74 mmol), 1-bromonaphthalene (1.44 g, 6.97 mmol), and toluene (12 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and about 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.34 g, 3.54 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.039 g, 0.055 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 6 hours. After the reaction was complete, the mixture was cooled to room temperature, and water and toluene were added to extract the mixture. The organic layer was collected and dried over anhydrous sodium sulfate. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1) to obtain the crude product. The crude product was dissolved in about 10 mL of toluene by heating, concentrated to twice its volume, cooled and crystallized, and dried under vacuum at 80 °C to obtain 0.71 g of high-purity product S-1, with a yield of 80%, which was a white solid.

[0080] Figure 1 This is the proton NMR spectrum of compound S-1. Figure 2 The carbon spectrum of compound S-1 is shown below, along with the specific NMR characterization data: 1HNMR (500 MHz, CD2Cl2) δ 8.01 (dt, J = 7.6, 1.0 Hz, 1H), 7.95 (dd, J = 7.5, 1.0Hz, 1H), 7.93 – 7.88 (m, 3H), 7.69 – 7.56 (m, 5H), 7.54 – 7.45 (m, 3H), 7.45– 7.30 (m, 9H), 7.17 – 7.10 (m, 4H), 7.10 – 7.07 (m, 1H), 7.03 (td, J = 7.5,1.1 Hz, 2H), 6.83 (d, J = 8.5 Hz, 2H), 6.68 (dd, J = 7.5, 1.1 Hz, 2H), 6.66(s, 1H), 6.34 (dt, J = 7.7, 0.9 Hz, 2H), 6.27 (d, J = 8.5 Hz, 2H), 5.39 –5.32 (m, 5H). 13 C NMR (126 MHz, CD2Cl2) δ 156.01, 153.13, 150.60, 150.44,146.62, 145.73, 143.59, 142.88, 140.34, 134.93, 130.63, 129.72, 129.04,128.83, 128.22, 128.13, 128.01, 127.67, 127.32, 127.16, 126.26, 126.18,125.36, 125.26, 125.19, 124.76, 124.44, 124.43, 124.15, The NMR data (123.21, 123.01, 122.88, 122.75, 121.88, 120.84, 120.62, 119.95, 118.96, 117.77, 111.64, 65.63) show a high degree of correspondence and reasonableness between these NMR data and the basic structural characteristics of compound S-1.

[0081] Example 2:

[0082] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-2 and its preparation method. The structural formula of S-2 is as follows:

[0083]

[0084] S-2

[0085] The synthesis route for S-2 is as follows:

[0086]

[0087] The specific preparation steps are as follows:

[0088] Step 1: Synthesis of compound b

[0089] A 250 mL double-necked flask was washed and dried. 1-Bromo-9,9'-spirobis[9H-fluorene] (2 g, 5.06 mmol), 4-(dibenzo[b,d]furan-4-yl)aniline (1.31 g, 5.06 mmol), and toluene (24 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 4 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.97 g, 10.12 mmol), S-Phos (0.13 g, 0.3 mmol), and tris(dibenzylacetone)palladium (0.14 g, 0.15 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 25 mL of toluene by heating, concentrated to twice its volume, cooled and crystallized, and dried under vacuum at 80 °C to obtain a high-purity intermediate compound b (2.74 g), with a yield of 90%, as a white solid.

[0090] The NMR characterization data of compound b are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.19 – 8.13 (m,1H), 8.08 – 8.02 (m, 1H), 7.96 – 7.91 (m, 1H), 7.82 (ddd, J = 16.3, 6.8, 1.4Hz, 3H), 7.68 – 7.63 (m, 1H), 7.57 – 7.51 (m, 2H), 7.50 – 7.30 (m, 10H), 7.34– 7.28 (m, 2H), 7.23 – 7.15 (m, 3H), 6.86 (dd, J = 7.1, 1.4 Hz, 1H), 6.79(dd, J = 7.0, 1.4 Hz, 2H), 6.67 (s, 1H). 13C NMR (125 MHz, DMSO-d6) δ 155.77,153.16, 143.69, 143.32, 142.60, 140.81, 139.05, 137.92, 137.87, 134.61,130.94, 129.09, 129.04, 128.53, 128.52, 128.28, 127.22, 126.46, 126.08,125.87, 125.47, 125.10, 124.66, 122.83, 122.42, 122.38, 122.22, 121.82, 120.90, 120.39, 120.28, 119.88, 116.75, 111.65, 64.61.

[0091] Step 2: Synthesis of compound S-2

[0092] A 100 mL double-necked flask was washed and dried. Intermediate b (1.00 g, 1.74 mmol), 8-bromonaphtho[2,1-b]benzofuran (0.52 g, 1.74 mmol), and toluene (12 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.33 g, 3.48 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.037 g, 0.052 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 6 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 10 mL of toluene by heating, concentrated to twice its volume, cooled and crystallized, and dried under vacuum at 80 °C to obtain 1.09 g of high-purity product S-2, with a yield of 79.1%, as a white solid.

[0093] The NMR characterization data of compound S-2 are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.00 – 7.91 (m,1H), 7.90 – 7.78 (m, 1H), 7.68 – 7.54 (m, 1H), 7.57 – 7.51 (m, 1H), 7.50 –7.28 (m, 4H), 7.26 – 7.19 (m, 1H), 6.80 (td, J = 7.0, 1.4 Hz, 1H).13 C NMR(125 MHz, DMSO-d6) δ 155.77, 153.16, 145.25, 143.81, 143.15, 142.92, 140.19,139.76, 139.20, 139.02, 136.56, 132.47, 132.21, 130.89, 130.42, 129.47,129.05, 129.04, 129.02, 128.53, 128.52, 127.95, 127.22, 127.15, 126.98,126.77, 126.46, 126.16, The NMR data (126.06, 125.83, 125.40, 125.10, 124.84, 124.59, 124.12, 123.96, 123.70, 123.65, 122.83, 122.42, 122.38, 122.22, 121.96, 121.82, 120.90, 120.11, 116.10, 111.65, and 63.39) show a high degree of correspondence and reasonableness between these NMR data and the basic characteristics of the structural formula of compound S-2.

[0094] Example 3:

[0095] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-21 and its preparation method. The structural formula of S-21 is as follows:

[0096]

[0097] S-21

[0098] The S-21 synthesis route is as follows:

[0099]

[0100] The specific preparation steps are as follows:

[0101] Step 1: Synthesis of compound c

[0102] A 250 mL double-necked flask was washed and dried. 1'-bromo-9H-spiro[fluorene-9,9'-oxazanthene] (2 g, 5.06 mmol), 4-(dibenzo[b,d]furan-1-yl)aniline (1.31 g, 5.06 mmol), and toluene (24 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 4 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.97 g, 10.12 mmol), S-Phos (0.13 g, 0.3 mmol), and tris(dibenzylacetone)dipalladium (0.14 g, 0.15 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 25 mL of toluene by heating, concentrated to twice its volume, cooled to crystallize, and dried under vacuum at 80 °C to obtain a high-purity intermediate compound c (2.74 g), with a yield of 90%, as a white solid.

[0103] The NMR characterization data of compound c are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.03 (dd, J =9.0, 1.4 Hz, 1H), 7.84 (dd, J = 6.9, 1.2 Hz, 2H), 7.66 – 7.58 (m, 3H), 7.54(ddd, J = 9.7, 7.1, 1.1 Hz, 2H), 7.47 (ddd, J = 8.8, 6.8, 1.3 Hz, 1H), 7.41 (td, J = 6.8, 1.3 Hz, 2H), 7.38 – 7.33 (m, 1H), 7.36 – 7.28 (m, 4H), 7.25 –7.18 (m, 1H), 7.19 (s, 2H), 7.20 – 7.15 (m, 2H), 7.16 (dd, J = 7.1, 1.5 Hz, 1H), 6.99 (dd, J = 7.0, 1.2 Hz, 1H), 6.85 (dd, J = 7.2, 1.3 Hz, 2H), 6.71(dd, J = 6.6, 1.5 Hz, 1H), 6.22 (s, 1H). 13C NMR (125 MHz, DMSO-d6) δ 156.90,155.35, 152.54, 151.01, 145.73, 143.22, 142.64, 139.79, 135.10, 132.29,129.41, 129.05, 129.00, 128.93, 127.28, 127.22, 126.82, 126.34, 126.16,125.12, 124.96, 124.94, 123.41, 122.32, 121.65, 121.04, 119.66, 116.95, 116.51, 115.66, 113.21, 112.04, 110.74, 109.91, 54.27.

[0104] Step 2: Synthesis of compound S-21

[0105] A 100 mL double-necked flask was washed and dried. Intermediate C (1.00 g, 1.74 mmol), 5-bromonaphtho[2,1-b]benzofuran (0.52 g, 1.74 mmol), and toluene (12 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.33 g, 3.48 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.037 g, 0.052 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 4 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 10 mL of toluene by heating, concentrated to twice its volume, cooled and crystallized, and dried under vacuum at 80 °C to obtain 1.09 g of high-purity product S-21, with a yield of 79.1%, as a white solid.

[0106] The NMR characterization data of compound S-21 are as follows: 1H NMR (500 MHz, DMSO-d6) δ 8.10 – 7.99(m, 2H), 7.84 (dd, J = 6.9, 1.3 Hz, 1H), 7.66 – 7.57 (m, 2H), 7.57 – 7.15 (m,7H), 6.97 (ddd, J = 12.4, 6.7, 1.3 Hz, 1H), 6.85 (dd, J = 7.2, 1.4 Hz, 1H). 13 C NMR (125 MHz, DMSO-d6) δ 157.28, 156.90, 155.35, 154.05, 153.55, 151.02,145.93, 145.39, 144.05, 141.91, 139.79, 135.22, 131.55, 130.85, 129.81,129.41, 128.93, 128.65, 128.19, 127.28, 127.22, 127.16, 126.89, 126.82,126.68, 126.32, 126.16, 125.15, The NMR data (125.12, 124.82, 124.44, 124.43, 123.92, 123.87, 123.41, 122.32, 122.21, 121.65, 121.04, 119.87, 119.11, 116.49, 115.73, 115.66, 113.77, 112.04, 112.00, 110.74, 110.47, 101.83, and 52.78) show a high degree of correspondence and reasonableness between these NMR data and the basic characteristics of the structural formula of compound S-21.

[0107] Example 4:

[0108] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-25 and its preparation method. The structural formula of S-25 is as follows:

[0109]

[0110] S-25

[0111] The S-25 synthesis route is as follows:

[0112]

[0113] The specific preparation steps are as follows:

[0114] Step 1: Synthesis of compound d

[0115] A 250 mL double-necked flask was washed and dried. 1-Bromo-9H-spiro[fluorene-9,9'-oxazanthene] (2 g, 5.06 mmol), 4-(dibenzo[b,d]furan-4-yl)aniline (1.31 g, 5.06 mmol), and toluene (24 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 4 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.97 g, 10.12 mmol), S-Phos (0.13 g, 0.3 mmol), and tris(dibenzylacetone)dipalladium (0.14 g, 0.15 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 25 mL of toluene by heating, concentrated to twice its volume, cooled and crystallized, and dried under vacuum at 80 °C to obtain a high-purity intermediate compound d (2.68 g), with a yield of 88%, as a white solid.

[0116] The NMR data characterization of compound d are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.19 – 8.13 (m,1H), 8.08 – 8.02 (m, 0H), 7.96 – 7.91 (m, 0H), 7.80 (dd, J = 6.6, 1.4 Hz,0H), 7.67 – 7.62 (m, 0H), 7.57 – 7.51 (m, 1H), 7.50 – 7.28 (m, 5H), 7.25 –7.15 (m, 3H), 7.08 – 6.95 (m, 2H), 6.86 (dd, J = 7.2, 1.4 Hz, 0H). 13C NMR(125 MHz, DMSO-d6) δ 155.77, 153.16, 150.86, 150.79, 145.49, 142.63, 140.89,139.02, 138.12, 130.94, 130.15, 129.38, 129.08, 128.62, 128.54, 128.28,126.96, 126.46, 126.34, 126.33, 126.08, 125.87, 125.49, 125.40, 125.15,125.10, 122.83, 122.42, 122.38, 122.22, 121.82, 120.39, 119.86, 116.68, 116.48, 116.31, 111.65, 48.33.

[0117] Step 2: Synthesis of compound S-25

[0118] A 100 mL double-necked flask was washed and dried. Intermediate d (1.00 g, 1.70 mmol), 1-bromonaphthalene (0.70 g, 3.40 mmol), and toluene (12 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and about 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.33 g, 3.40 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.037 g, 0.052 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 4 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1) to obtain the crude product. The crude product was dissolved in about 10 mL of toluene by heating, concentrated to twice its volume, cooled and crystallized, and dried under vacuum at 80 °C to obtain 1.19 g of high-purity product S-25, with a yield of 81.2%, which was a white solid.

[0119] The NMR characterization data of compound S-25 are as follows: 1H NMR (500 MHz, DMSO-d6) δ 8.16 (dd, J =8.9, 1.5 Hz, 1H), 8.08 – 8.02 (m, 1H), 7.96 – 7.91 (m, 1H), 7.85 – 7.77 (m,2H), 7.61 – 7.28 (m, 10H), 7.25 – 7.15 (m, 4H), 7.14 – 7.09 (m, 1H), 7.08 –6.95 (m, 2H), 6.80 (dd, J = 7.2, 1.4 Hz, 1H). 13 C NMR (125 MHz, DMSO-d6) δ155.77, 153.16, 150.87, 150.80, 145.43, 145.28, 142.74, 140.05, 139.51,137.57, 134.82, 133.80, 130.35, 129.47, 129.38, 129.13, 129.05, 128.62,128.43, 128.31, 127.18, 127.02, 126.96, 126.46, 126.43, 126.32, 126.16,125.83, The NMR data (125.69, 125.60, 125.15, 125.10, 124.84, 124.19, 124.14, 124.04, 123.91, 122.83, 122.42, 122.38, 122.22, 121.82, 120.44, 116.46, 116.30, 116.18, 111.65, and 47.26) show a high degree of correspondence and reasonableness between these NMR data and the basic characteristics of the structural formula of compound S-25.

[0120] Example 5:

[0121] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-33 and its preparation method. The structural formula of S-33 is as follows:

[0122]

[0123] S-33

[0124] The S-33 synthesis route is as follows:

[0125]

[0126] Step 1: Synthesis of compound e

[0127] A 250 mL double-necked flask was washed and dried. 1-Bromo-9H-spiro[fluorene-9,9'-oxazanthene] (2 g, 5.06 mmol), 4-(dibenzo[b,d]furan-1-yl)aniline (1.31 g, 5.06 mmol), and toluene (24 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 4 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.97 g, 10.12 mmol), S-Phos (0.13 g, 0.3 mmol), and tris(dibenzylacetone)dipalladium (0.14 g, 0.15 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 25 mL of toluene (12 times its volume) by heating, concentrated to 2 times its volume, cooled to crystallize, and dried under vacuum at 80 °C to obtain a high-purity intermediate compound e (2.74 g), with a yield of 90%, as a white solid.

[0128] The NMR characterization data of compound e are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 7.67 – 7.58 (m,2H), 7.54 (ddd, J = 9.7, 7.1, 1.1 Hz, 1H), 7.50 – 7.38 (m, 1H), 7.40 – 7.31(m, 2H), 7.35 – 7.28 (m, 2H), 7.25 – 7.15 (m, 3H), 6.98 (dd, J = 7.0, 1.2 Hz,1H). 13 C NMR (125 MHz, DMSO-d6) δ 156.90, 155.35, 150.79, 145.49, 142.87,140.89, 139.02, 138.12, 135.10, 132.29, 130.15, 129.38, 129.08, 129.05,128.62, 128.54, 127.28, 126.96, 126.82, 126.34, 125.40, 125.15, 125.12,123.41, 122.32, 121.65, 120.40, 119.86, 119.66, 116.68, 116.48, 115.66, 112.04, 110.74, 48.33.

[0129] Step 2: Synthesis of compound S-33

[0130] A 100 mL double-necked flask was washed and dried. Intermediate e (1.00 g, 1.70 mmol), 6-chloronaphtho[2,1-b]benzofuran (0.86 g, 3.40 mmol), and toluene (12 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.33 g, 3.40 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.037 g, 0.052 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 4 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 10 mL of toluene by heating, concentrated to twice its volume, cooled and crystallized, and dried under vacuum at 80 °C to obtain 1.43 g of high-purity product S-33, with a yield of 82%, as a white solid.

[0131] The NMR characterization data of compound S-33 are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.05 – 7.99(m, 1H), 7.66 – 7.28 (m, 8H), 7.26 – 7.15 (m, 2H), 7.08 – 6.95 (m, 1H). 13CNMR (125 MHz, DMSO-d6) δ 156.90, 156.54, 155.35, 150.87, 150.80, 145.92,145.43, 144.22, 140.04, 138.60, 137.57, 135.22, 134.02, 133.56, 130.91,130.51, 130.33, 129.83, 129.38, 129.13, 128.62, 128.14, 127.87, 127.62,127.28, 126.96, 126.82, 126.32, The NMR data (125.73, 125.61, 125.60, 125.25, 125.15, 125.12, 125.07, 124.26, 123.94, 123.83, 123.79, 123.41, 122.82, 122.32, 121.87, 121.65, 120.44, 117.71, 116.46, 116.30, 116.13, 115.66, 112.04, 111.19, 110.74, and 47.34) show a high degree of correspondence and reasonableness between these NMR data and the basic characteristics of the structural formula of compound S-33.

[0132] Example 6:

[0133] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-43 and its preparation method. The structural formula of S-43 is as follows:

[0134]

[0135] S-43

[0136] The synthesis route for the S-43 is as follows:

[0137]

[0138] Step 1: Synthesis of compound f

[0139] A 250 mL double-necked flask was washed and dried. 1'-Bromo-10-phenyl-10H-spiro[acridin-9,9'-oxazanthene] (2.54 g, 5.06 mmol), 6-(4-aminonaphthyl-1-yl)dibenzo[b,d]furan (1.57 g, 5.06 mmol), and toluene (24 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 4 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.97 g, 10.12 mmol), S-Phos (0.12 g, 0.3 mmol), and tris(dibenzylacetone)dipalladium (0.14 g, 0.15 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 25 mL of toluene by heating, concentrated to twice its volume, cooled to crystallize, and dried under vacuum at 80 °C to give intermediate compound f (3.19 g), yield 86.4%, as a white solid.

[0140] The NMR characterization data of compound f are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.19 – 8.13 (m,1H), 8.11 – 8.02 (m, 2H), 7.96 – 7.90 (m, 2H), 7.80 (dd, J = 6.6, 1.4 Hz,1H), 7.59 – 7.42 (m, 5H), 7.38 (td, J = 8.9, 1.5 Hz, 1H), 7.35 – 7.28 (m,3H), 7.28 – 6.98 (m, 17H), 6.87 (dd, J = 7.1, 1.1 Hz, 1H), 6.76 (dd, J = 7.0,1.1 Hz, 1H). 13C NMR (125 MHz, DMSO-d6) δ 155.87, 153.80, 151.87, 150.09,144.12, 142.64, 141.23, 140.27, 139.80, 132.53, 132.38, 131.80, 130.47,129.54, 129.50, 129.28, 129.01, 128.47, 128.08, 127.97, 127.89, 127.88,127.25, 127.06, 126.73, 126.46, 125.84, 125.61, 125.49, 124.99, 124.71, 124.53, 124.38, 123.00, 122.83, 122.30, 122.20, 121.82, 121.42, 121.35, 119.95, 116.35, 116.26, 114.51, 111.65, 109.84, 50.37.

[0141] Step 2: Synthesis of compound S-43

[0142] A 100 mL double-necked flask was washed and dried. Intermediate f (1.00 g, 1.37 mmol), 4-iododibenzo[b,d]furan (0.81 g, 2.74 mmol), and toluene (10 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and about 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.26 g, 2.74 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.031 g, 0.044 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 4 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried with anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1) to obtain the crude product. The crude product was dissolved in about 8 mL of toluene by heating, concentrated to about twice its volume, cooled and crystallized, filtered, and dried under vacuum at 80 °C to obtain a high-purity product S-43 (1.19 g), with a yield of 81.8%, which was a white solid.

[0143] The NMR characterization data of compound S-43 are as follows: 1H NMR (500 MHz, DMSO-d6) δ 8.19 – 8.11(m, 1H), 8.08 – 7.99 (m, 1H), 7.93 (ddd, J = 7.9, 6.2, 1.0 Hz, 1H), 7.85 –7.78 (m, 1H), 7.65 – 7.55 (m, 1H), 7.54 – 7.42 (m, 2H), 7.42 – 7.18 (m, 5H), 7.18 – 7.08 (m, 1H), 7.11 – 6.96 (m, 3H). 13 C NMR (125 MHz, DMSO-d6) δ 155.87,155.31, 153.80, 152.81, 150.10, 148.50, 144.12, 141.62, 140.52, 140.21,139.74, 135.16, 132.73, 132.58, 132.51, 130.47, 129.54, 129.48, 129.28,128.47, 128.14, 128.08, 128.03, 127.89, 127.63, 127.25, 127.14, 127.06, 127.02, 126.92, 126.54, 126.46, 125.84, 125.13, 125.07, 124.94, 124.88, 124.63, 124.25, 123.98, 123.90, 123.43, 123.00, 122.91, 122.83, 122.47, 122.30, 122.20, 121.82, 121.43, 121.35, 121.33, 120.29, 116.85, 116.35, 111.65, 111.25, 110.67, 49.21. The NMR data show that the NMR data is highly consistent with and reasonable in relation to the basic characteristics of the structural formula of compound S-43.

[0144] Example 7:

[0145] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-50 and its preparation method. The structural formula of S-50 is as follows:

[0146]

[0147] S-50

[0148] The synthesis route of the S-50 is as follows:

[0149]

[0150] Step 1: Synthesis of compound g

[0151] A 100 mL double-necked flask was washed and dried. 1-Bromo-10-phenyl-10H-spiro[acridin-9,9'-fluorene] (1.00 g, 2.06 mmol), 4-(dibenzo[b,d]furan-4-yl)aniline (0.53 g, 2.06 mmol), and toluene (10 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 2 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and potassium tert-butoxide (0.46 g, 4.12 mmol), S-Phos (0.05 g, 0.12 mmol), and tris(dibenzylacetone)dipalladium (0.06 g, 0.062 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 10 mL of toluene by heating, concentrated to about twice its volume, cooled to crystallize, filtered, and dried under vacuum at 80 °C to give the intermediate compound g (1.18 g), with a yield of 86%, as a white solid.

[0152] The NMR characterization data of compound g are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.19 – 8.13 (m,1H), 8.08 – 8.02 (m, 1H), 7.96 – 7.91 (m, 1H), 7.84 (dd, J = 6.9, 1.2 Hz,2H), 7.80 (dd, J = 6.6, 1.4 Hz, 1H), 7.57 – 7.51 (m, 2H), 7.50 – 7.28 (m,7H), 7.25 (s, 1H), 7.26 – 7.19 (m, 1H), 7.22 – 7.14 (m, 4H), 7.12 – 7.02 (m,2H), 7.06 – 6.93 (m, 2H), 6.85 (dd, J = 7.2, 1.3 Hz, 2H), 6.74 (dd, J = 4.9, 2.4 Hz, 1H), 6.01 (s, 1H). 13C NMR (125 MHz, DMSO-d6) δ 155.77, 153.16,146.83, 144.96, 144.55, 143.63, 142.49, 140.75, 139.83, 130.94, 130.47,129.16, 129.04, 128.88, 128.28, 128.08, 127.25, 127.23, 127.09, 126.88,126.46, 126.08, 126.05, 125.87, 125.10, 124.28, 122.83, 122.42, 122.38, 122.22, 121.82, 121.18, 121.00, 120.96, 120.39, 116.25, 114.16, 111.65, 54.80.

[0153] Step 2: Synthesis of compound S-50

[0154] A 100 mL double-necked flask was washed and dried. Intermediate g (1.18 g, 1.77 mmol), 8-bromophenanthrene (0.91 g, 3.54 mmol), and toluene (13 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1.3 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.34 g, 3.54 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.040 g, 0.057 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 6 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1) to obtain the crude product. The crude product was dissolved in about 10 mL of toluene by heating, concentrated to about twice its volume, cooled and crystallized, filtered, and dried under vacuum at 80 °C to obtain a high-purity product S-50 (1.50 g) with a yield of 83%, which was a white solid.

[0155] The NMR characterization data of compound S-50 are as follows: 1H NMR (500 MHz, DMSO-d6) δ 8.00 – 7.91(m, 1H), 7.90 – 7.78 (m, 1H), 7.68 – 7.51 (m, 2H), 7.50 – 7.14 (m, 5H), 7.12– 6.93 (m, 2H), 6.85 (dd, J = 7.2, 1.4 Hz, 1H), 6.80 – 6.74 (m, 1H). 13 C NMR(125 MHz, DMSO-d6) δ 155.77, 153.16, 147.10, 146.23, 145.59, 144.82, 144.56,142.83, 140.75, 139.83, 132.47, 132.21, 130.89, 130.47, 129.47, 129.40,129.16, 129.05, 129.04, 128.53, 128.08, 127.96, 127.30, 127.25, 127.23,127.15, 126.98, 126.96, The NMR data (126.77, 126.46, 126.16, 126.06, 125.83, 125.10, 124.71, 124.28, 124.12, 123.70, 123.69, 123.38, 122.83, 122.42, 122.38, 122.22, 121.96, 121.82, 121.20, 121.18, 120.91, 118.26, 111.65, and 53.36) show a high degree of correspondence and reasonableness between these NMR data and the basic characteristics of the structural formula of compound S-50.

[0156] Example 8:

[0157] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-72 and its preparation method. The structural formula of S-72 is as follows:

[0158]

[0159] S-72

[0160] The synthesis route for the S-72 is as follows:

[0161]

[0162] Step 1: Synthesis of compound h

[0163] A 100 mL double-necked flask was washed and dried. 1'-Chloro-10-phenylspiro[acridin-9,9'-fluorene] (1.00 g, 2.26 mmol), 6-(4-aminonaphthyl-1-yl)dibenzo[b,d]furan (0.70 g, 2.26 mmol), and toluene (11 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 2 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and potassium tert-butoxide (0.51 g, 4.52 mmol), S-Phos (0.05 g, 0.13 mmol), and tris(dibenzylacetone)palladium (0.06 g, 0.062 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 10 mL of toluene by heating, concentrated to about twice its volume, cooled to crystallize, filtered, and dried under vacuum at 80 °C to obtain a high-purity intermediate compound h (1.41 g), with a yield of 87%, as a white solid.

[0164] The NMR characterization data of compound h are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.10 (dd, J =7.8, 1.4 Hz, 1H), 8.03 (dd, J = 9.0, 1.3 Hz, 1H), 7.92 (dd, J = 7.6, 1.5 Hz,1H), 7.64 (ddd, J = 6.7, 5.2, 1.3 Hz, 2H), 7.61 (d, J = 8.3 Hz, 1H), 7.58 –7.49 (m, 3H), 7.52 – 7.28 (m, 11H), 7.28 – 7.21 (m, 3H), 7.17 (td, J = 7.6,1.4 Hz, 3H), 7.12 – 7.04 (m, 3H), 7.07 – 6.99 (m, 3H), 6.96 (dd, J = 7.7, 1.3Hz, 2H), 6.86 (dd, J = 7.2, 1.3 Hz, 1H). 13C NMR (125 MHz, DMSO-d6) δ 156.95,155.03, 146.53, 144.44, 141.65, 140.70, 140.69, 138.88, 138.82, 138.00,132.93, 131.82, 130.53, 130.47, 130.18, 129.09, 129.05, 128.59, 128.49,128.08, 128.06, 127.97, 127.30, 127.25, 126.91, 126.82, 126.79, 126.50, 125.56, 125.49, 125.29, 124.65, 124.38, 124.20, 122.51, 121.64, 121.19, 121.15, 121.14, 120.75, 116.70, 116.15, 115.66, 112.04, 110.79, 48.72.

[0165] Step 2: Synthesis of compound S-72

[0166] A 100 mL double-necked flask was washed and dried. Intermediate h (1.00 g, 1.40 mmol), 10-iodobenzo[b]naphtho[2,1-d]furan (0.96 g, 2.80 mmol), and toluene (10 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1.0 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.27 g, 2.80 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.031 g, 0.044 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 6 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 8 mL of toluene by heating, concentrated to about twice its volume, cooled to crystallize, filtered, and dried under vacuum at 80 °C to obtain high-purity product S-72 (1.33 g), with a yield of 83%, as a white solid.

[0167] The NMR characterization data of compound S-72 are as follows: 1H NMR (500 MHz, DMSO-d6) δ 8.13 (ddd, J= 19.3, 8.3, 1.3 Hz, 1H), 7.91 (ddd, J = 15.8, 7.7, 1.3 Hz, 1H), 7.85 – 7.75(m, 1H), 7.70 – 7.28 (m, 8H), 7.28 – 7.14 (m, 3H), 7.12 – 7.04 (m, 1H), 7.07– 6.93 (m, 2H). 13 C NMR (125 MHz, DMSO-d6) δ 156.95, 155.03, 150.02, 147.43,146.56, 144.44, 141.39, 140.70, 140.69, 139.92, 137.85, 137.32, 135.17,134.65, 132.99, 132.85, 130.96, 130.47, 130.31, 130.06, 129.79, 129.10,129.05, 128.61, 128.15, 128.08, 128.05, 127.74, 127.50, 127.46, 127.44, 127.25, 127.15, 126.98, 126.82, 126.78, 126.73, 126.61, 126.55, 126.50, 125.58, 124.92, 124.78, 124.65, 124.56, 124.20, 124.02, 123.97, 123.04, 122.82, 122.54, 122.51, 121.76, 121.64, 121.19, 121.15, 120.76, 119.40, 116.19, 116.15, 115.66, 112.04, 110.79, 47.99. As can be seen from the NMR data, the NMR data corresponds highly with and is reasonable to the basic characteristics of the structural formula of compound S-72.

[0168] Example 9:

[0169] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-74 and its preparation method. The structural formula of S-74 is as follows:

[0170]

[0171] S-74

[0172] The synthesis route for the S-74 is as follows:

[0173]

[0174] Step 1: Synthesis of compound i

[0175] A 100 mL double-necked flask was washed and dried. 1-Bromo-10,10'-diphenyl-10H,10'H-9,9'-spirodi[acridinium] (1.00 g, 1.73 mmol), 4-(dibenzo[b,d]furan-4-yl)aniline (0.45 g, 1.73 mmol), and toluene (8.5 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1.7 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.33 g, 3.46 mmol), S-Phos (0.04 g, 0.10 mmol), and tris(dibenzylacetone)dipalladium (0.05 g, 0.052 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried with anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 8.5 mL of toluene by heating, concentrated to about twice its volume, cooled to crystallize, filtered, and dried under vacuum at 80 °C to give a high-purity intermediate compound i (1.13 g), in 86% yield, as a white solid.

[0176] The NMR characterization data of compound i are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.16 (dd, J =8.9, 1.6 Hz, 1H), 8.08 – 8.02 (m, 1H), 7.96 – 7.91 (m, 1H), 7.80 (dd, J =6.6, 1.4 Hz, 1H), 7.57 – 7.51 (m, 2H), 7.47 (ddd, J = 8.9, 6.7, 1.3 Hz, 1H), 7.44 – 7.35 (m, 2H), 7.35 – 7.22 (m, 8H), 7.23 (d, J = 6.0 Hz, 1H), 7.24 –7.18 (m, 1H), 7.21 – 7.15 (m, 2H), 7.13 – 6.98 (m, 13H), 6.74 (dd, J = 6.2,1.1 Hz, 1H), 5.96 (s, 1H). 13C NMR (125 MHz, DMSO-d6) δ 155.77, 153.16, 144.59,144.57, 144.44, 143.89, 142.49, 140.37, 140.29, 139.76, 132.54, 132.15,132.09, 130.94, 130.59, 130.53, 130.47, 129.31, 129.25, 129.20, 128.84,128.50, 128.43, 128.41, 128.28, 128.15, 128.08, 127.34, 127.30, 127.25, 126.46, 126.08, 125.87, 125.10, 124.61, 124.56, 124.51, 122.83, 122.42, 122.38, 122.22, 121.82, 121.21, 121.20, 120.39, 116.26, 114.06, 111.65, 49.75.

[0177] Step 2: Synthesis of compound S-74

[0178] A 100 mL double-necked flask was washed and dried. Intermediate I (1.00 g, 1.32 mmol), 11-chlorobenzo[b]naphtho[1,2-d]furan (0.67 g, 2.64 mmol), and toluene (9 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.25 g, 2.64 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.029 g, 0.041 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 6 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 8 mL of toluene by heating, concentrated to about twice its volume, cooled to crystallize, filtered, and dried under vacuum at 80 °C to obtain high-purity product S-74 (1.31 g), with a yield of 83.6%, as a white solid.

[0179] The NMR characterization data of compound S-74 are as follows: 1H NMR (500 MHz, Chloroform-d) δ 7.97 – 7.86 (m, 1H), 7.58 – 7.49 (m, 2H), 7.49 – 7.19 (m, 8H), 7.12 – 6.98 (m, 5H), 6.80 – 6.74 (m, 1H). 13 C NMR (125 MHz, Common NMR Solvents) δ 156.12, 155.77,153.87, 153.16, 145.19, 145.12, 144.59, 144.44, 144.14, 142.05, 140.34,140.26, 139.78, 132.69, 132.40, 132.35, 130.59, 130.53, 130.47, 129.66,129.50, 129.47, 129.37, 129.31, 129.25, 129.20, 129.12, 129.05, 128.50, 128.43, 128.41, 128.15, 128.08, 127.96, 127.87, 127.80, 127.34, 127.30, 127.25, 126.63, 126.46, 126.40, 126.16, 125.83, 125.69, 125.10, 124.79, 124.61, 124.56, 124.51, 122.83, 122.42, 122.38, 122.22, 121.82, 121.21, 121.20, 121.12, 120.24, 119.56, 118.28, 118.20, 111.65, 108.89, 107.12, 48.91. As can be seen from the NMR data, the NMR data corresponds highly with and is reasonable to the basic characteristics of the structural formula of compound S-74.

[0180] Example 10:

[0181] This embodiment provides a sterically hindered spirocyclic triarylamine compound S-85 and its preparation method. The structural formula of S-85 is as follows:

[0182]

[0183] S-85

[0184] The synthesis route for the S-85 is as follows:

[0185]

[0186] Step 1: Synthesis of compound j

[0187] A 100 mL double-necked flask was washed and dried. N-phenylspiro[acridinyl-9,9'-oxazanthene] (molecular weight 502.4, 1.00 g, 1.99 mmol), 4-(dibenzo[b,d]furan-4-yl)aniline (molecular weight 259.31, 0.52 g, 1.99 mmol), and toluene (8.5 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1.7 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 50 °C, and sodium tert-butoxide (0.38 g, 3.98 mmol), S-Phos (0.05 g, 0.12 mmol), and tris(dibenzylacetone)dipalladium (0.06 g, 0.060 mmol) were added sequentially. The reaction mixture was heated to reflux for 2 hours. After cooling to below 50 °C, water and toluene were added to extract the mixture. The organic layer was collected, dried with anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1). The crude product was dissolved in about 8.5 mL of toluene at elevated temperature, concentrated to about twice its volume, cooled to crystallize, filtered, and dried under vacuum at 80 °C to give a high-purity intermediate compound j (1.16 g), in 86% yield, as a white solid.

[0188] The NMR characterization data of compound j are as follows: 1 H NMR (500 MHz, DMSO-d6) δ 8.19 – 8.13 (m,0H), 8.08 – 8.02 (m, 0H), 7.96 – 7.91 (m, 0H), 7.80 (dd, J = 6.6, 1.4 Hz,0H), 7.57 – 7.51 (m, 1H), 7.50 – 6.95 (m, 12H), 6.74 (dd, J = 6.2, 1.1 Hz,0H). 13C NMR (125 MHz, DMSO-d6) δ 155.77, 153.16, 150.38, 149.91, 144.68,144.26, 143.87, 142.47, 140.44, 132.38, 130.94, 130.47, 129.54, 129.28,128.84, 128.47, 128.28, 128.08, 127.93, 127.89, 127.25, 126.70, 126.61,126.46, 126.08, 125.87, 125.44, 125.10, 125.00, 123.43, 122.83, 122.42, 122.38, 122.22, 121.82, 121.35, 120.39, 116.44, 116.42, 116.35, 114.30, 111.65, 48.17.

[0189] Step 2: Synthesis of compound S-85

[0190] A 100 mL double-necked flask was washed and dried. Intermediate J (1.00 g, 1.47 mmol), 1-bromonaphthalene (0.61 g, 2.94 mmol), and toluene (10 mL) were added. Under nitrogen protection, the mixture was heated to reflux, and approximately 1 mL of toluene was distilled off at atmospheric pressure to remove water. The system was then cooled to 85 °C, and sodium tert-butoxide (0.29 g, 2.94 mmol) and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.032 g, 0.045 mmol) were added sequentially. The reaction mixture was heated to 99–102 °C and reacted for 4 hours. After the reaction was complete, the mixture was cooled to below 50 °C, and water and toluene were added to extract the mixture. The organic layer was collected, dried over anhydrous sodium sulfate, and the solvent was removed under vacuum. The crude product was purified by column chromatography (neutral alumina, petroleum ether: dichloromethane = 20:1) to obtain the crude product. The crude product was dissolved in about 9 mL of toluene by heating, concentrated to about twice its volume, cooled and crystallized, filtered, and dried under vacuum at 80 °C to obtain a high-purity product S-85 (0.96 g) with a yield of 81%, which was a white solid.

[0191] The NMR characterization data of compound S-85 are as follows: 1H NMR (500 MHz, DMSO-d6) δ 8.16 (dd, J =8.9, 1.5 Hz, 1H), 8.08 – 8.02 (m, 2H), 7.96 – 7.91 (m, 1H), 7.85 – 7.77 (m,3H), 7.61 – 7.42 (m, 6H), 7.42 – 7.37 (m, 1H), 7.40 – 7.26 (m, 4H), 7.28 –7.18 (m, 8H), 7.18 – 6.95 (m, 10H), 6.80 – 6.74 (m, 2H). 13 C NMR (125 MHz, DMSO-d6) δ 155.77, 153.16, 150.36, 149.90, 145.41, 145.19, 144.25, 144.19,142.69, 140.42, 134.82, 132.58, 130.47, 129.54, 129.47, 129.36, 129.28,129.05, 128.47, 128.43, 128.30, 128.08, 127.89, 127.25, 127.18, 127.02,126.88, 126.81, The NMR data (126.46, 126.43, 126.16, 125.83, 125.44, 125.10, 125.00, 124.71, 124.19, 124.14, 124.04, 122.83, 122.42, 122.38, 122.22, 121.82, 121.35, 121.19, 118.40, 116.42, 116.35, 111.65, and 47.10) show a high degree of correspondence and reasonable consistency with the basic characteristics of the structural formula of compound S-85.

[0192] Example 11:

[0193] Compound S-1 prepared in Example 1 was dissolved in hot xylene, and the solvent was slowly evaporated to obtain colorless bulk single crystals. X-ray diffraction analysis of the S-1 single crystals was performed using a Bruker D8 Venture diffractometer. Figure 3 This is a schematic diagram of the structure of S-1 single crystal. Figure 4 This is a schematic diagram of the molecular stacking structure of S-1 single crystal, from... Figure 3 and Figure 4As can be seen, Example 1 successfully prepared a Q-type spirocyclic sterically hindered triarylamine compound with a specific crystal stacking structure. Its naphthyl and fluorenyl segments are located on the same side of the spirocyclic center and the Pi conjugated planes are opposite each other, with an intramolecular π-π stacking effect at a distance of 3.39~3.43 Å.

[0194] Example 12:

[0195] This embodiment characterizes the photophysical properties of the spirocyclic sterically hindered triarylamine compounds prepared in Examples 1 to 10. The specific method is as follows: each compound was dissolved in anhydrous and oxygen-free toluene to prepare a solution of approximately 1 × 10⁻⁶. -5 A dilute solution of M was used for UV-Vis absorption spectroscopy measurements, and approximately 1×10⁻⁶. -6 A dilute solution of M was used for fluorescence emission spectroscopy to eliminate the influence of concentration on the spectrum. Tests were performed at room temperature using a fluorescence spectrometer equipped with an integrating sphere. The absorption spectrum was scanned in the range of 250–600 nm, while the emission spectra were recorded at their respective maximum absorption wavelengths.

[0196] Figure 5 The images show the UV absorption spectra of the compounds synthesized in Examples 1, 2, 3, 6, and 9. Figure 6 Table 1 shows the fluorescence emission spectra of the compounds synthesized in Examples 1, 2, 3, 6, and 9. Table 1 also shows the UV absorption and fluorescence emission data of the compounds synthesized in Examples 1-10. Figure 5 and Figure 6 Based on the data in Table 1, it can be seen that:

[0197] The maximum absorption wavelength (λ) of all compounds in toluene solution max Located in the ultraviolet region of 342–362 nm, its ground state exhibits a wide bandgap, consistent with the basic characteristics of deep blue light-emitting materials. Its maximum fluorescence emission wavelength (λ...) em Located in the blue light region of 398~422 nm, this confirms the potential of this type of material as a blue light emitting material.

[0198] The differences between the absorption and emission wavelengths of the compounds reflect the influence of the fine molecular structure (such as the different aromatic amine acceptors and linker sites in the examples) on the energy levels of the leading molecular orbitals and the characteristics of electronic transitions. For example, the absorption spectra of Examples 3, 6, 8, and 9 show a relative blue shift, while the absorption of Examples 1, 4, and 10 shows a relative red shift. This difference may be related to slight variations in the intensity of the electronic push-pull effect of the donor-acceptor units within the molecule and the overall degree of conjugation.

[0199] Stokes shift is a key parameter characterizing the degree of relaxation in excited states. Data show that ∆λ is tunable in the range of 46–77 nm for different compounds. Example 7 exhibits the largest Stokes shift (77 nm), indicating that its molecule may have undergone more significant geometric relaxation or stronger intramolecular charge transfer in the excited state. In contrast, Examples 2 and 6 show smaller Stokes shifts (48 nm and 46 nm), suggesting that their excited states have a geometry or electronic distribution closer to the ground state, which may be beneficial for obtaining narrower emission spectra.

[0200] Table 1. UV absorption and fluorescence emission data of the compounds synthesized in Examples 1-10

[0201]

[0202] Example 13:

[0203] This embodiment describes the fabrication and performance verification of an OLED device using a sterically hindered triarylamine compound. The OLED device fabricated in this embodiment has the following stacking order from bottom to top: anode (ITO), hole injection layer (P-type doped HTL), hole transport layer (HTL), B Prime layer, light-emitting layer (BH:BD), hole blocking layer (HBL), electron transport layer (ETL:LiQ), electron injection layer (Yb), and cathode (Mg:Ag).

[0204] The specific preparation steps are as follows:

[0205] Step 1: Substrate cleaning and pretreatment

[0206] A glass substrate with an ITO (copper tin oxide) anode was selected and ultrasonically cleaned for 15 minutes each with detergent, deionized water, acetone, and isopropanol in sequence. After drying with nitrogen, it was treated with ultraviolet ozone for 20 minutes.

[0207] Step 2: Device fabrication

[0208] The pretreated substrate is transferred into a vacuum evaporation chamber (vacuum degree ≤ 5 × 10⁻⁶). -4 Pa), and then sequentially deposit each functional layer:

[0209] The hole injection layer was made of P-type doped material HAT-CN with a thickness of 5 nm. The evaporation process parameters were: evaporation temperature 260~300 ℃, evaporation rate 0.8-1.2 Å / s.

[0210] The hole transport layer is made of HTL material NPB with a thickness of 30 nm. The evaporation process parameters are: evaporation temperature 240~260 ℃, evaporation rate 1.0~1.5 Å / s.

[0211] The B Prime layer is composed of N-[4-(dibenzo[b,d]furan-4-yl)phenyl]-9,9-spirodi[9H-fluorene]-2-amine, prepared in Example 1 of this invention, with a thickness of 20 nm. The vapor deposition process parameters are: vapor deposition temperature 196 ℃, evaporation rate 0.5 Å / s.

[0212] The luminescent layer is formed by dual-source co-evaporation of the host material BH and dopant BD (taking CBP and Ir(ppy)3 as an example), with a doping ratio of 8 wt% and a thickness of 30 nm. The evaporation process parameters are as follows: host (CBP) evaporation temperature 250~280 °C, evaporation rate 0.8~1.2 Å / s; dopant (Ir(ppy)3) evaporation temperature 220~250 °C, evaporation rate controlled proportionally (approximately 0.06~0.10 Å / s).

[0213] The hole-blocking layer is made of HBL material (e.g., BAlq or TmPyPB) with a thickness of 5 nm. The evaporation process parameters are: evaporation temperature 240~260 °C, evaporation rate 0.5~1.0 Å / s.

[0214] The electron transport layer is made of LiQ-doped ETL material (e.g., TPBi doped with 30 wt% LiQ) with a thickness of 40 nm. The evaporation process parameters are as follows: TPBi evaporation temperature 250~270 °C, evaporation rate 0.8~1.2 Å / s; LiQ evaporation temperature 190~220 °C, evaporation rate controlled proportionally (approximately 0.2~0.4 Å / s).

[0215] The electron injection layer is made of metallic Yb with a thickness of 1 nm. The evaporation process parameters are: evaporation temperature 200~300 °C, evaporation rate 0.1~0.3 Å / s.

[0216] The cathode was formed by dual-source co-evaporation of magnesium (Mg) and silver (Ag) to create a Mg:Ag alloy (mass ratio 10:1) with a thickness of 100 nm. The evaporation process parameters were: Mg evaporation temperature 380~450 °C, evaporation rate 1.2~1.8 Å / s; Ag evaporation temperature 800~900 °C, evaporation rate 0.1~0.2 Å / s.

[0217] A set of four parallel devices was prepared according to the above preparation method. Simultaneously, a control group device was prepared by replacing the B Prime layer with commercially available TAPC material, which has a purity >99.0% (HPLC) and was purchased from McLean (catalog number: B803940-1g). The thickness of the B Prime layer in the control device was 20 nm, and the evaporation process parameters were: evaporation temperature 204 °C, evaporation rate 0.5 Å / s.

[0218] At a current density of 10 mA / cm2 The current-voltage-luminance characteristics and lifetime of the device fabricated in this embodiment and the control group were tested under the following conditions. Using a spectral scanning luminance meter equipped with an integrating sphere and a source measurement unit, the current-voltage-luminance characteristics, electroluminescence spectrum, current efficiency, and external quantum efficiency of the device were tested at room temperature. Device lifetime testing was conducted under constant current drive conditions, with an initial luminance of 1000 cd / m². 2 The experiment was conducted in an environment where the brightness decayed to 96% and 95% of its initial value, and the time was recorded as LT96 and LT95, respectively.

[0219] Table 2 Performance comparison between the device fabricated in this embodiment and the control group device

[0220]

[0221] Table 2 compares the performance of the device prepared in this embodiment with that of the control group. As can be seen from Table 2, the device based on N-[4-(dibenzo[b,d]furan-4-yl)phenyl]-9,9-spirodi[9H-fluorene]-2-amine described in this invention exhibits key photoelectric parameters such as turn-on voltage and luminous efficiency comparable to the reference device. This sterically hindered triarylamine compound achieves the aforementioned performance at a lower deposition temperature (196 °C) by 8 °C, indicating superior thermal stability and process adaptability. In accelerated aging tests, the device using this compound showed better LT95 and LT96 lifetimes than the reference device, demonstrating a longer operating life.

[0222] This embodiment demonstrates that the compound N-[4-(dibenzo[b,d]furan-4-yl)phenyl]-9,9-spirobis[9H-fluorene]-2-amine of the present invention is suitable as a B Prime layer material for OLED devices, which maintains excellent photoelectric performance and exhibits better working life while reducing the process temperature.

[0223] This invention provides a sterically hindered spirocyclic triarylamine compound, its preparation method, and its application. Many methods and approaches exist for implementing this technical solution; the above description is merely a preferred embodiment of the invention. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this invention, and these improvements and modifications should also be considered within the scope of protection of this invention. All components not explicitly stated in this embodiment can be implemented using existing technologies.

Claims

1. A sterically hindered spirocyclic triarylamine compound, characterized in that, The general formula of the sterically hindered triarylamine compound is shown in formula (I): ； Formula (I) X and Y are each independently selected from single bonds, O and N-Ar bonds. 8 Any one of the following, and X and Y are not both 0 at the same time; Ar 1 ~Ar 6 Each is independently selected from any one of substituted or unsubstituted phenyl, naphthyl, dibenzofuranyl and carbazoleyl; Ar 7 It is selected from any one of naphthyl, phenanthryl, carbazolyl, dibenzofuranyl, arylbenzofuranyl and arylbenzoindolyl, whether substituted or unsubstituted; Ar 8 Selected from any one of substituted or unsubstituted phenyl, naphthyl, dibenzofuranyl and para-biphenyl; Ar 1 ~Ar 8 Each substituent in the substituted group is independently selected from any one of deuterium, fluorine, cyano, phenyl, naphthyl, dibenzofuranyl, and carbazoleyl.

2. The sterically hindered triarylamine compound according to claim 1, characterized in that, Ar 1 ~Ar 6 Each is independently selected from any of the following general formulas: ； Among them, Ar 9 Existence or non-existence; when Ar 9 When it exists, it is selected from any of the following general formulas: 。 3. The sterically hindered triarylamine compound according to claim 1 or 2, characterized in that, The general formula of the spirocyclic sterically hindered triarylamine compound is selected from any one of the following formulas I-1 to I-8: 。 4. The sterically hindered triarylamine compound according to claim 3, characterized in that, Ar 7 Selected from any of the following general formulas: ； Among them, Ar 10 Existence or non-existence; when Ar 10 When it exists, it is selected from any of the following general formulas: .

5. The sterically hindered triarylamine compound according to claim 3, characterized in that, Ar 8 Selected from any of the following general formulas: 。 6. The sterically hindered triarylamine compound according to claim 1, characterized in that, The general formula of the spirocyclic sterically hindered triarylamine compound is selected from any one of formulas S-1 to S-96: ； ； ； ； ； ； 。 7. The method for preparing the spirocyclic sterically hindered triarylamine compound according to any one of claims 1 to 6, characterized in that, The synthetic route of the preparation method is shown below: 。 8. The preparation method according to claim 7, characterized in that, In step one, the molar ratio of the compound of general formula (II) and tris(dibenzylacetone)palladium is 1:(0.03~0.06); the reaction conditions in step one are: reaction temperature of 80 ℃~120 ℃ and reaction time of 1~2 h.

9. The preparation method according to claim 7, characterized in that, In step two, the molar ratio of the general formula (III) compound and dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) is 1:(0.01~0.03); the reaction conditions in step two are: a reaction temperature of 80 ℃~100 ℃ and a reaction time of 2~6 h.

10. The use of the spirocyclic sterically hindered triarylamine compound according to any one of claims 1 to 6 in the preparation of organic electronic devices, characterized in that, The spirocyclic sterically hindered triarylamine compound is used in organic electronic devices as one or more of the hole transport layer, auxiliary layer, or light-emitting layer.

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