Luminescent compound containing sulfuryl and anthracene units as well as preparation method and application of luminescent compound

Abstract

The invention provides a luminescent compound containing sulfuryl and anthracene units as well as a preparation method and application of the luminescent compound. The luminescent compound containing sulfuryl and anthracene units comprises a sulfuryl unit, an anthracene unit and a donor unit, the sulfonyl unit and the donor unit are respectively connected to two sides of the anthracene unit; the number of carbon atoms of the luminescent compound containing sulfuryl and anthracene unit is 20-100, preferably 30-60; preferably, the structure of the anthracene unit is that the donor unit is a structure with relatively good hole transport capability. The prepared luminescent compound containing sulfuryl and anthracene units can emit light in an excited state through hybridization local charge transfer, the utilization rate of excitons is improved, and the luminescent compound can be used for preparing a high-efficiency blue light organic light-emitting diode.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials technology, and more specifically, to a luminescent compound containing sulfone and anthracene units, its preparation method, and its application. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have attracted widespread attention due to their advantages such as flexibility, ultra-thinness, wide viewing angle, active emission, high efficiency, low voltage driving, and ease of large-area device fabrication. OLED research began in the 1960s. In 1987, Qingyun Tang and others at Kodak in the United States developed an OLED device with a sandwich structure, achieving a brightness of 1000 cd / m² under a 10V DC driving voltage. -2 This has led to a revolutionary development in OLED research.

[0003] Organic light-emitting diodes (OLEDs) are primarily used in novel displays and solid-state lighting. While they are widely used in novel displays, their application in solid-state lighting still requires further development. The light-emitting material is the core of OLEDs, determining not only the color of the emitted light but also, to a large extent, the device's efficiency and lifespan. To achieve a high color rendering index (CRI) full-color display panel, organic light-emitting materials in red, green, and blue are needed. Significant progress has been made in red and green light emission, but high-efficiency blue fluorescent materials are still relatively scarce. Therefore, developing novel, high-performance blue light-emitting materials is an important research direction for OLEDs.

[0004] First-generation fluorescent materials can only utilize 25% of singlet excitons for luminescence, while 75% of triplet excitons return to the ground state via nonradiative transitions. The theoretical limit of external quantum efficiency is 5%, far from meeting the requirements and significantly limiting their luminescence performance. To address the low exciton utilization problem, phosphorescent materials utilizing triplet excitons for luminescence, thermally activated delayed fluorescence (TADF) materials based on triplet anti-intersystem crossing, and TTA fluorescent materials based on triplet-triplet annihilation upconversion have been developed. However, the first two types of materials rarely achieve high efficiency with blue color coordinates CIEy < 0.15. Furthermore, these two types of materials face a severe efficiency roll-off problem, hindering practical applications. TTA fluorescent materials, by fusing two triplet excitons to form a singlet exciton, achieve an exciton utilization of only 62.5%. While the TTA mechanism increases exciton utilization to some extent, it also results in the loss of 37.5% of triplet excitons.

[0005] Therefore, it is necessary to develop a new type of fluorescent material that can achieve antisystem crossing from high triplet energy level to singlet energy level, realize 100% utilization of excitons, and obtain high-performance blue fluorescent material. Summary of the Invention

[0006] To address the technical problems existing in the prior art, the present invention provides a luminescent compound containing sulfone and anthracene units, its preparation method, and its application.

[0007] This application provides a D-π-A type luminescent small molecule compound containing sulfone and anthracene. Anthracene has high photoluminescence efficiency and bipolar transport characteristics, good electrochemical and thermal stability. The sulfone unit acts as an electron acceptor unit, and anthracene acts as a π bridge. The donor unit has good hole transport capability and is connected to both sides of the sterically hindered anthracene unit. The donor and acceptor units in the constructed molecule have a large torsion angle, realizing a charge transfer of moderate intensity, and thus forming a hybrid local charge transfer excited state (HLCT). It can realize anti-system crossing from high-energy triplet state to singlet state and achieve nearly 100% exciton utilization.

[0008] The luminescent compounds containing sulfone and anthracene units prepared in this application can emit light through hybridized local charge transfer excited states, thereby improving exciton utilization and can be used to prepare high-efficiency blue organic light-emitting diodes.

[0009] One objective of this invention is to provide a luminescent compound containing sulfone and anthracene units, comprising a sulfone unit, an anthracene unit, and a donor unit; the sulfone unit and the donor unit are respectively connected to both sides of the anthracene unit; the sulfone unit is... The anthracene unit is The donor unit has a structure with good hole transport capability; the number of carbon atoms in the luminescent compound containing sulfone and anthracene units is 20 to 100.

[0010] In a preferred embodiment of the present invention,

[0011] The luminescent compound containing sulfone and anthracene units has 30 to 60 carbon atoms; and / or,

[0012] The donor unit has one of the following structures:

[0013] In a preferred embodiment of the present invention,

[0014] The luminescent compound containing sulfone and anthracene units has one of the following structural formulas:

[0015]

[0016] A second objective of this invention is to provide a method for preparing a luminescent compound containing sulfone and anthracene units, comprising method A or

[0017] Method B;

[0018] Method A includes the following steps:

[0019] (1) Reacting a starting material including haloanthracene or its derivatives with pinacol diboronic acid ester to obtain intermediate product one;

[0020] (2) Reacting the raw materials, including haloarylthiophene and peroxide, to obtain intermediate product II;

[0021] (3) React the raw materials including intermediate product one and intermediate product two to obtain intermediate product three;

[0022] (4) The luminescent compound is obtained by reacting the raw material, including the intermediate tri, with a haloaryl amine;

[0023] Method B includes the following steps:

[0024] (I) Reaction of a haloanthracene or its derivatives with an acridine compound yields intermediate I;

[0025] (II) Reacting the raw material including intermediate product I with pinacol diboronate to obtain intermediate product II;

[0026] (III) Reacting a raw material including a haloarylthiophene and a peroxide yields intermediate product III;

[0027] (IV) The luminescent compound is obtained by reacting the raw materials, including intermediate product II and intermediate product III.

[0028] In a preferred embodiment of the present invention,

[0029] Step (1),

[0030] The haloanthracene is 9,10-dibromoanthracene or 2,6-dibromoanthracene;

[0031] The molar ratio of the haloanthracene or its derivative to pinacol diboronate is 1:(2-4), preferably (2.2-2.6);

[0032] Step (2),

[0033] The haloarylthiophene is 2-bromodibenzothiophene;

[0034] The molar ratio of the haloarylthiophene to the peroxide is 1:(10-60), preferably 1:(30-40);

[0035] Step (3),

[0036] The molar ratio of intermediate product one to intermediate product two is 1:(1-2), preferably 1:(1-1.2);

[0037] Step (4),

[0038] The haloaryl amine is one of the following compounds;

[0039]

[0040]

[0041] The molar ratio of the haloaryl amine to intermediate tri is 1:(1-2), preferably 1:(1.1-1.3).

[0042] In a preferred embodiment of the present invention,

[0043] Step (1),

[0044] The raw materials also include solvent A, catalyst A, and strong base-weak acid salt A; preferably,

[0045] Solvent A is at least one of 1,4-dioxane, toluene, and N,N-dimethylformamide;

[0046] The catalyst A is a palladium catalyst, more preferably at least one of 1,1'-bis(diphenylphosphine)ferrocene palladium(II) chloride and tris(dibenzylideneacetone) dipalladium;

[0047] The strong base weak acid salt A is at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate.

[0048] The ratio of the volume of solvent A to the total mass of the reaction raw materials in step (1) is 1 to 20 ml solvent / 1 mmol reactant, preferably 1 to 5 ml solvent / 1 mmol reactant;

[0049] The molar ratio of catalyst A to the total molar ratio of reactants in step (1) is (0.001-0.1):1, preferably (0.005-0.03):1;

[0050] The ratio of the molar amount of the strong base-weak acid salt A to the total molar amount of the reactants is (0.5-10):1, preferably (1-4):1;

[0051] The reaction temperature is 80–120℃;

[0052] The reaction time is 12–36 hours;

[0053] The intermediate product requires post-processing, preferably including extraction and separation.

[0054] Step (2),

[0055] The raw materials also include solvent B; preferably,

[0056] Solvent B is acetic acid;

[0057] The volume ratio of solvent B to the total mass of the reaction raw materials in step (2) is 0.1 to 10 ml solvent / 1 mmol reactant, preferably 0.2 to 1 ml solvent / 1 mmol reactant;

[0058] The reaction temperature is 60–100℃;

[0059] The reaction time is 2 to 4 hours;

[0060] Intermediate product 2 requires post-processing, preferably including extraction and separation.

[0061] Step (3),

[0062] The raw materials also include solvent C, catalyst C, and strong base-weak acid salt C; preferably,

[0063] The solvent C is at least one of toluene, tetrahydrofuran, and deionized water;

[0064] The catalyst C is a palladium catalyst, more preferably tetratriphenylphosphine palladium;

[0065] The strong base weak acid salt C is at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate.

[0066] The ratio of the volume of solvent C to the total mass of the reaction raw materials in step (3) is 1 to 40 ml solvent / 1 mmol reactant, preferably 5 to 20 ml solvent / 1 mmol reactant;

[0067] The mass ratio of the catalyst C to the total mass of the reaction raw materials in step (3) is (0.001-0.1):1, preferably (0.01-0.05):1;

[0068] The ratio of the molar amount of the strong base-weak acid salt C to the total molar amount of the reactants is (0.5-10):1, preferably (1-4):1;

[0069] The reaction temperature is 80–100℃;

[0070] The reaction time is 24–48 hours;

[0071] Intermediate product 3 requires post-processing, preferably including extraction and separation.

[0072] Step (4),

[0073] The raw materials also include solvent D, catalyst D, and strong base-weak acid salt D; preferably,

[0074] The solvent D is at least one of toluene, tetrahydrofuran, and deionized water;

[0075] The catalyst D is a palladium catalyst, more preferably tetratriphenylphosphine palladium;

[0076] The strong base weak acid salt D is at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate.

[0077] The ratio of the volume of solvent D to the total mass of the reaction raw materials in step (4) is 1 to 40 ml solvent / 1 mmol reactant, preferably 5 to 20 ml solvent / 1 mmol reactant;

[0078] The mass ratio of the catalyst D to the total mass of the reaction raw materials in step (4) is (0.001-0.2):1, preferably (0.01-0.05):1;

[0079] The ratio of the molar amount of the strong base-weak acid salt D to the total molar amount of the reactants is (0.5-10):1, preferably (1-4):1;

[0080] The reaction temperature is 80–100℃;

[0081] The reaction time is 24–48 hours;

[0082] The reaction products need to be post-processed, and preferably, the post-processing includes extraction and separation.

[0083] Steps (1) to (4) are all carried out under a protective gas atmosphere, wherein the protective gas is at least one of nitrogen or an inert gas.

[0084] In a preferred embodiment of the present invention,

[0085] Step (I),

[0086] The haloanthracene is 9,10-dibromoanthracene or 2,6-dibromoanthracene;

[0087] The acridine compound is at least one selected from 9,10-dihydro-9,9-dimethylacridine and 9,10-dihydro-9,9-diphenylacridine;

[0088] The molar ratio of the haloanthracene or its derivative to the acridine compound is 1:(0.5-2), preferably 1:(0.8-1.2);

[0089] Step (II),

[0090] The molar ratio of intermediate product I to pinacol diboronate is 1:(1-2), preferably 1:(1.1-1.3);

[0091] Step (III),

[0092] The haloarylthiophene is 2-bromodibenzothiophene;

[0093] The molar ratio of the haloarylthiophene to the peroxide is 1:(10-60), preferably 1:(30-40);

[0094] Step (Ⅳ),

[0095] The molar ratio of intermediate product III to intermediate product II is 1:(1-2), preferably 1:(1.1-1.3).

[0096] In a preferred embodiment of the present invention,

[0097] Step (I),

[0098] The raw materials also include solvent E, catalyst E, ligand E, and organic base E;

[0099] Preferably,

[0100] The solvent E is at least one of toluene, tetrahydrofuran, and water;

[0101] The catalyst E is a palladium catalyst, more preferably tris(dibenzylacetone)dipalladium;

[0102] The ligand E is tri-tert-butylphosphine;

[0103] The organic base E is at least one of sodium tert-butoxide and potassium tert-butoxide;

[0104] The volume ratio of solvent E to the total molar amount of reactants in step (I) is 0.5–40 ml solvent / 1 mmol reactant, preferably 1–10 ml solvent / 1 mmol reactant;

[0105] The molar ratio of catalyst E to the total molar ratio of reactants in step (Ⅰ) is (0.001-0.2):1, preferably (0.01-0.05):1;

[0106] The molar ratio of the ligand E to the total molar ratio of the reactants in step (Ⅰ) is (0.01-0.2):1, preferably (0.03-0.06):1;

[0107] The molar ratio of the organic base E to the total molar ratio of the reaction raw materials in step (Ⅰ) is (0.5-3):1, preferably (1-1.5):1;

[0108] The reaction temperature is 100–140℃;

[0109] The reaction time is 8–12 hours;

[0110] Intermediate product I requires post-processing, preferably including extraction and separation.

[0111] Step (II),

[0112] The raw materials also include solvent F, catalyst F, and strong base-weak acid salt F; preferably,

[0113] The solvent F is at least one of 1,4-dioxane, toluene, and N,N-dimethylformamide;

[0114] The catalyst F is a palladium catalyst, more preferably at least one of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride and tris(dibenzylacetone)palladium dichloride;

[0115] The strong base weak acid salt F is at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate.

[0116] The volume ratio of solvent F to the total molar amount of reactants in step (II) is 0.5–40 ml solvent / 1 mmol reactant, preferably 1–10 solvent / 1 mmol reactant;

[0117] The mass ratio of the catalyst F to the total molar mass of the reaction raw materials in step (II) is (0.001-0.2):1, preferably (0.01-0.03):1;

[0118] The molar ratio of the strong base-weak acid salt F to the total molar ratio of the reaction raw materials in step (II) is (1-10):1, preferably (2-4):1;

[0119] The reaction temperature is 80–120℃;

[0120] The reaction time is 12–36 hours;

[0121] Intermediate product II requires post-processing, preferably including extraction and separation.

[0122] Step (III),

[0123] The raw materials also include solvent G; preferably,

[0124] The solvent G is acetic acid;

[0125] The volume ratio of solvent G to the total molar amount of reactants in step (III) is 0.1–10 ml solvent / 1 mmol reactant, preferably 0.2–1 ml solvent / 1 mmol reactant;

[0126] The reaction temperature is 60–100℃;

[0127] The reaction time is 2 to 4 hours;

[0128] Intermediate product III requires post-processing, preferably including extraction and separation.

[0129] Step (Ⅳ),

[0130] The raw materials also include solvent H, catalyst H, and strong base-weak acid salt H; preferably,

[0131] The solvent H is at least one of toluene, tetrahydrofuran, and deionized water;

[0132] The catalyst H is a palladium catalyst, more preferably tetraphenylphosphine palladium;

[0133] The strong base weak acid salt H is at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate.

[0134] The ratio of the volume of solvent H to the total molar amount of the reaction raw materials in step (IV) is 1 to 40 ml solvent / 1 mmol reactant, preferably 5 to 20 ml solvent / 1 mmol reactant;

[0135] The mass ratio of the catalyst H to the total molar mass of the reaction raw materials in step (Ⅳ) is (0.001-0.2):1, preferably (0.01-0.05):1.

[0136] The reaction temperature is 80–100℃;

[0137] The reaction time is 24–48 hours;

[0138] The reaction products need to be post-processed, and preferably, the post-processing includes extraction and separation.

[0139] Steps (I) to (IV) are all carried out under a protective gas atmosphere, wherein the protective gas is at least one of nitrogen and an inert gas.

[0140] A third objective of this invention is to provide a luminescent compound containing sulfone and anthracene units obtained by the above preparation method.

[0141] The fourth objective of this invention is to provide an application of a luminescent compound containing sulfone and anthracene units in an organic electroluminescent device.

[0142] In a preferred embodiment of the present invention,

[0143] The organic electroluminescent device has the following structure from bottom to top: an anode, a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, and a cathode; the light-emitting layer contains the luminescent compound containing sulfone groups and anthracene units as described in claim 1, 2, or 7.

[0144] In a preferred embodiment of the present invention,

[0145] The organic light-emitting layer is a pure film of a light-emitting compound containing sulfone and anthracene units, or a mixed film doped with a light-emitting compound containing sulfone and anthracene units and a host material.

[0146] Preferably, the proportion of the luminescent compound containing sulfone and anthracene units in the organic light-emitting layer is not less than 2 wt%, for example, 5 wt% or 10 wt%;

[0147] The main material is 9'-(1,3-phenyl)bis-9H-carbazole (mCP);

[0148] The organic electroluminescent device is obtained by sequentially assembling a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, and a cathode on the anode.

[0149] Preferably,

[0150] The anode is indium tin oxide glass;

[0151] The hole injection layer is molybdenum trioxide or 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN);

[0152] The hole transport layer is 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline], 4,4',4”-tris(carbazole-9-yl)triphenylamine or N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine;

[0153] The organic light-emitting layer is the light-emitting compound and an optional host material;

[0154] The electron transport layer is 1,3,5-tris(3-pyridyl-3-phenyl)benzene (TmPyPB) or 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene;

[0155] The electron injection layer is lithium fluoride;

[0156] The cathode is aluminum;

[0157] Assembly is performed using vacuum evaporation.

[0158] More preferably,

[0159] The resistance of the anode is 10 to 20 Ω;

[0160] The anode is subjected to ultrasonic cleaning and plasma treatment before assembly;

[0161] The thickness of the hole injection layer is 3–50 nm;

[0162] The thickness of the hole transport layer is 5–80 nm;

[0163] The thickness of the organic light-emitting layer is 5–50 nm;

[0164] The thickness of the electron transport layer is 5–50 nm;

[0165] The thickness of the electron injection layer is 0.7–2 nm;

[0166] The thickness of the cathode is 80–110 nm.

[0167] The principle of this invention is as follows: using sulfone groups as acceptor units and anthracene as π-bridges, and selecting different donor units, novel donor-acceptor type blue fluorescent molecules are constructed. These molecules exhibit high fluorescence quantum yield, high hole mobility, and high electron mobility with a relatively balanced electron-hole mobility. They also possess a moderate degree of charge transfer, enabling hybrid local charge transfer state (HLCT) luminescence and improving exciton utilization. Furthermore, these molecules have an asymmetric structure, which can suppress molecular aggregation and reduce exciton quenching.

[0168] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0169] (1) The present invention provides a class of luminescent small molecules containing sulfone groups as acceptors and anthracene as π bridges, and different donor units are replaced. The acceptor unit and the donor unit are coupled on both sides of the anthracene unit respectively, and there is a large twist angle between the acceptor and donor units to form a hybrid local charge transfer excited state (HLCT) luminescence, thereby achieving high exciton utilization.

[0170] (2) The present invention provides a class of luminescent small molecules containing sulfone groups as acceptor units and anthracene as π bridges, and different donor units can be replaced. By adjusting the hole transport capability and charge transfer degree of different donors, the emission spectrum can be changed and the anti-system crossing from triplet exciton to singlet state can be improved.

[0171] (3) The present invention provides a type of D-π-A molecule with sulfone group as acceptor and anthracene as π bridge, which has good hole and electron transport capabilities and bipolar transport characteristics. Attached Figure Description

[0172] Figure 1 The absorption spectra of the luminescent compound containing sulfone and anthracene units prepared in Example 6 in solution and thin film are shown.

[0173] Figure 2 The small molecule absorption spectra of the luminescent compounds containing sulfone groups and anthracene units prepared in Example 2 in solution and thin film are shown.

[0174] Figure 3The emission spectra of the luminescent compound containing sulfone and anthracene units prepared in Example 6 in solution and thin film are shown.

[0175] Figure 4 The emission spectra of the luminescent compound containing sulfone and anthracene units prepared in Example 2 are shown in solution and thin film.

[0176] above Figures 1-4 In the figure, Film represents the thin film of the aforementioned luminescent compound, while the other curves represent solutions of the aforementioned luminescent compound prepared in different solvents, with a solution concentration of 10. -5 mol / L, Toluene is toluene, EA is ethyl acetate, THF is tetrahydrofuran, DCM is dichloromethane, and Acetone is acetone;

[0177] Figure 5 Electrochemical diagram of the oxidation and reduction potentials of the luminescent compound containing sulfone and anthracene units prepared in Example 6 under thin film;

[0178] Figure 6 Electrochemical diagram of the oxidation and reduction potentials of the luminescent compound containing sulfone and anthracene units prepared in Example 2 under thin film;

[0179] Figure 7 Thermal stability test diagram of the luminescent compound containing sulfone and anthracene units prepared in Example 6;

[0180] Figure 8 The thermal stability test diagram of the luminescent compound containing sulfone and anthracene units prepared in Example 2;

[0181] Figure 9 Thermal stability test diagram of the luminescent compound containing sulfone and anthracene units prepared in Example 6;

[0182] Figure 10 The thermal stability test diagram of the luminescent compound containing sulfone and anthracene units prepared in Example 2;

[0183] Figure 11 External quantum efficiency-brightness diagram of the undoped device prepared in Example 13;

[0184] Figure 12 The electroluminescence spectrum of the undoped device prepared in Example 13;

[0185] Figure 13 The image shows the electroluminescence spectrum of the doped device prepared in Example 14. Detailed Implementation

[0186] The present invention will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0187] All raw materials used in the examples were commercially available.

[0188] Sources of some of the main raw materials: purchased from Dongguan Fu'an Optoelectronic Technology Co., Ltd., Anhui Zesheng Technology Co., Ltd., and Guangzhou Chemical Reagent Factory.

[0189] Test method:

[0190] Absorption spectroscopy testing:

[0191] The absorption spectra of the test material in solution and thin film were measured, with a solution concentration of 10. -5 mol / L; UV light source, Guangzhou Biaoqi Optoelectronic Technology Development Co., Ltd., instrument model ZWH212148;

[0192] Emission spectroscopy test:

[0193] The emission spectra of the test material were measured in solution and thin film form, with a solution concentration of 10. -5 mol / L; UV light source, Guangzhou Biaoqi Optoelectronic Technology Development Co., Ltd., instrument model ZWH212148;

[0194] Electrochemical testing:

[0195] The oxidation and reduction potentials of the material under thin films were measured using cyclic voltammetry; electrochemical analyzer, Shanghai Chenhua Instrument Co., Ltd., CHI630E, scan rate 0.1 V / s. -1 .

[0196] Thermal stability testing of materials:

[0197] Thermogravimetric analysis showed that the heating rate of the Netzsch TG209 was 25 °C / min. -1 Differential scanning calorimeter, model Netzsch DSC204.

[0198] Example 1

[0199]

[0200] (1) Synthesis of compound 1 (intermediate product 1):

[0201] In a 2L round-bottom flask, 150.0 mmol of 9,10-dibromoanthracene, 375.0 mmol of pinacol diborate, 750.0 mmol of potassium acetate, and 4.5 mmol of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were added. Then, 1250.0 mL of 1,4-dioxane was added as the reaction solvent. The mixture was evacuated three times and heated to 100°C for 24 hours under nitrogen protection. After the reaction was completed, the mixture was cooled to room temperature, and the product was extracted three times with ethyl acetate and water. The product was dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent, yielding a white solid product with a yield of 80%. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0202] (2) Synthesis of compound 2 (intermediate product 2):

[0203] 150.0 mmol of 2-bromodibenzothiophene and 1250.0 mL of acetic acid were added to a 3 L round-bottom flask. The mixture was purged three times and reacted at 60 °C under nitrogen protection for 1 hour. Then, 600 mL of 30% H₂O₂ was added, and the temperature was raised to 80 °C and reacted for 3 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted three times with dichloromethane and water. The extract was dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 92% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0204] (3) Synthesis of compound 3 (intermediate product 3)

[0205] In a 2L round-bottom flask, compound 1 (50.0 mmol), compound 2 (55.0 mmol), potassium carbonate (246.0 mmol), tetraphenylphosphine palladium (1.5 mmol), 300.0 mL deionized water, 300.0 mL tetrahydrofuran, and 600.0 mL toluene were added, and the mixture was purged three times under nitrogen protection at 90°C for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 75% yield. 1 H NMR,13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0206] (4) Preparation of compound M1:

[0207] The structural formula and synthetic route of compound M1 are shown below, and the specific synthetic method is as follows:

[0208]

[0209] In a 100 mL round-bottom flask, N-4-bromophenyl-N-naphth-2-ylaniline (1.5 mmol), compound 3 (1.7 mmol), potassium carbonate (7.4 mmol), tetrakis(triphenylphosphine)palladium (45.0 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 85% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0210] Example 2

[0211] The preparation of intermediates one through three is the same as in Example 1.

[0212] Preparation of compound M2:

[0213] The structural formula and synthetic route of compound M2 are shown below, and the specific synthetic method is as follows:

[0214]

[0215] Synthesis of compound M2:

[0216] In a 100 mL round-bottom flask, 1.5 mmol of 3-bromo-N-phenylcarbazole, 1.7 mmol of compound 3, 7.7 mmol of potassium carbonate, 47.0 μmol of tetraphenylphosphine palladium, 10.0 mL of deionized water, 10.0 mL of tetrahydrofuran, and 20.0 mL of toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 88% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0217] Example 3

[0218] The preparation of intermediates one through three is the same as in Example 1.

[0219] Preparation of compound M3:

[0220] The structural formula and synthetic route of compound M3 are shown below, and the specific synthetic method is as follows:

[0221]

[0222] Synthesis of compound M3:

[0223] In a 100 mL round-bottom flask, 1.3 mmol of 4-bromo-5'-phenyl-1,1':3',1”-terphenyl, 1.4 mmol of compound 3, 6.5 mmol of potassium carbonate, 39.0 μmol of tetraphenylphosphine palladium, 10.0 mL of deionized water, 10.0 mL of tetrahydrofuran, and 20.0 mL of toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature and extracted three times with dichloromethane and water. The extract was dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 90% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0224] Example 4

[0225] The preparation of intermediates one through three is the same as in Example 1.

[0226] Preparation of compound M4:

[0227] The structural formula and synthetic route of compound M4 are shown below, and the specific synthetic method is as follows:

[0228]

[0229] Synthesis of Compound 7 (Haloaromatic Amine)

[0230] In a 250 mL round-bottom flask, 25.0 mmol of 9,10-phenanthroquinone, 25.0 mmol of 4-bromobenzaldehyde, 125.0 mmol of ammonium acetate, and 100.0 mmol of aniline were added. Then, 150.0 mL of acetic acid was added to the flask. The mixture was evacuated three times and reacted at 120 °C for 3 hours under nitrogen protection. After the reaction was complete, the mixture was cooled to room temperature. The mixture was extracted three times with dichloromethane and water, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 88% yield.

[0231] Synthesis of compound M4:

[0232] Compound 7 (1.8 mmol), compound 3 (2.0 mmol), potassium carbonate (9.0 mmol), tetraphenylphosphine palladium (54.0 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added to a 100 mL round-bottom flask. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 84% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0233] Example 5

[0234] The preparation of intermediates one through three is the same as in Example 1.

[0235] Preparation of compound M5:

[0236] The structural formula and synthetic route of compound M5 are shown below, and the specific synthetic method is as follows:

[0237]

[0238] In a 100 mL round-bottom flask, compound 4-bromotriphenylamine (1.5 mmol), compound 3 (1.7 mmol), potassium carbonate (7.8 mmol), tetraphenylphosphine palladium (54.0 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 86% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0239] Example 6

[0240] The preparation of intermediates one through three is the same as in Example 1.

[0241] Preparation of compound M6

[0242] The structural formula and synthetic route of compound M6 are shown below, and the specific synthetic method is as follows:

[0243]

[0244] In a 100 mL round-bottom flask, compound 9-(3-chlorophenyl)-9H-carbazole (1.8 mmol), compound 3 (2.0 mmol), potassium carbonate (9.0 mmol), tetraphenylphosphine palladium (54.0 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 82% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product. 1 H NMR(500MHz,Chloroform-d)δ8.16(d,J=8.6Hz,2H),8.10(t,J=8.1Hz,1H),7. 96–7.82(m,6H),7.78–7.55(m,10H),7.51–7.41(m,6H),7.31(t,J=6.8Hz,2H).

[0245] Example 7

[0246] Preparation of compound M7:

[0247] The structural formula and synthetic route of compound M7 are shown below, and the specific synthetic method is as follows:

[0248]

[0249] (1) Synthesis of compound 8 (intermediate product I):

[0250] 9,10-Dihydro-9,9-dimethylacridine (10.0 mmol), 9,10-dibromoanthracene (10.0 mmol), sodium tert-butoxide (25.0 mmol), the catalyst tridibenzylacetone dipalladium (Pd2(dba)3, 0.5 mmol), and the ligand tritert-butylphosphine (1.0 mmol), along with 100 mL of toluene, were added to a 250 mL three-necked flask. The mixture was purged three times and heated to 120 °C under nitrogen protection for 10 hours. After the reaction was complete, the mixture was cooled to room temperature, and the product was extracted with ethyl acetate, washed three times with saturated sodium chloride solution, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent, yielding a white solid product in 70% yield. 1 H NMR, 13 The results of C NMR, MS and elemental analysis indicate that the obtained compound is the target product.

[0251] Synthesis of compound 9 (intermediate product II):

[0252] Compound 8 (5.0 mmol), pinacol diborate (6.0 mmol), potassium acetate (25.0 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (149.0 μmol) were added, and then 60 mL of 1,4-dioxane was used as the reaction solvent. The mixture was purged three times under nitrogen protection and heated to 100 °C for 24 hours. After the reaction, the mixture was cooled to room temperature, and the product was extracted three times with ethyl acetate and water. The extract was dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 81% yield. ¹H NMR, ¹³C NMR, MS, and elemental analysis showed that the obtained compound was the target product.

[0253] The synthesis of compound 2 (intermediate product III) is the same as in Example 1.

[0254] Synthesis of compound M7:

[0255] Compound 2 (1.7 mmol), compound 9 (1.9 mmol), potassium carbonate (8.5 mmol), tetraphenylphosphine palladium (51.0 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added to a 100 mL round-bottom flask. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 88% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0256] Example 8

[0257] Preparation of compound M8:

[0258] The structural formula and synthetic route of compound M8 are shown below, and the specific synthetic method is as follows:

[0259]

[0260] Synthesis of Compound 10 (Intermediate I):

[0261] 9,10-Dihydro-9,9-diphenylacridine (10.0 mmol), 9,10-dibromoanthracene (10.0 mmol), sodium tert-butoxide (25.0 mmol), the catalyst tris(dibenzylacetone)palladium (Pd2(dba)3, 0.5 mmol), and the ligand tri-tert-butylphosphine (1.0 mmol) were added to 50.0 mL of toluene. The mixture was stirred and heated to 120 °C for 10 hours. After the reaction was complete, the product was extracted with ethyl acetate, washed three times with saturated sodium chloride solution, dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent to obtain a white solid product in 68% yield. 1 H NMR, 13 The results of C NMR, MS and elemental analysis indicate that the obtained compound is the target product.

[0262] Synthesis of Compound 11 (Intermediate II):

[0263] Compound 10 (4.0 mmol), pinacol diborate (5.0 mmol), potassium acetate (21.0 mmol), and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (122.0 μmol) were added as the reaction solvent. Then, 50.0 mL of 1,4-dioxane was used as the reaction solvent. The mixture was purged three times under nitrogen protection and heated to 100 °C for 24 hours. After the reaction, the mixture was cooled to room temperature, and the product was extracted three times with ethyl acetate and water. The extract was dried over anhydrous sodium sulfate, filtered, and the solvent was evaporated using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixed solvent as the eluent, yielding a white solid product in 83% yield. ¹H NMR, ¹³C NMR, MS, and elemental analysis results indicated that the obtained compound was the target product.

[0264] The synthesis of compound 2 (intermediate product III) is the same as in Example 1.

[0265] Synthesis of compound M8:

[0266] Compound 2 (1.7 mmol), compound 11 (2.0 mmol), potassium carbonate (8.5 mmol), tetraphenylphosphine palladium (51.0 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added to a 100 mL round-bottom flask. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 90% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0267] Example 9

[0268] The preparation of intermediates one through three is the same as in Example 1.

[0269] Preparation of compound M9:

[0270] The structural formula and synthetic route of compound M9 are shown below, and the specific synthetic method is as follows:

[0271]

[0272] In a 100 mL round-bottom flask, 9-(4-bromophenyl)-3,6-di-tert-butyl-9H-carbazole (1.4 mmol), compound 3 (1.7 mmol), potassium carbonate (7.0 mmol), tetraphenylphosphine palladium (42.0 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 90% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0273] Example 10

[0274] The preparation of intermediates one through three is the same as in Example 1.

[0275] Preparation of compound M10:

[0276] The structural formula and synthetic route of compound M10 are shown below, and the specific synthetic method is as follows:

[0277]

[0278] In a 100 mL round-bottom flask, 2'-bromo-10-phenyl-10H-spiro[acridin-9,9'-fluorene] (1.6 mmol), compound 3 (1.9 mmol), potassium carbonate (8.1 mmol), tetraphenylphosphine palladium (49 μmol), 10 mL deionized water, 10 mL tetrahydrofuran, and 20 mL toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 83% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0279] Example 11

[0280] The preparation of intermediates one through three is the same as in Example 1.

[0281] Preparation of compound M11:

[0282] The structural formula and synthetic route of compound M11 are shown below, and the specific synthetic method is as follows:

[0283]

[0284] In a 100 mL round-bottom flask, 1.8 mmol of 3-bromo-phenothiazine, 2.2 mmol of compound 3, 9.0 mmol of potassium carbonate, 54.0 μmol of tetraphenylphosphine palladium, 10.0 mL of deionized water, 10.0 mL of tetrahydrofuran, and 20.0 mL of toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 91% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0285] Example 12

[0286] The preparation of intermediates one through three is the same as in Example 1.

[0287] Preparation of compound M12:

[0288] The structural formula and synthetic route of compound M12 are shown below, and the specific synthetic method is as follows:

[0289]

[0290] In a 100 mL round-bottom flask, 2-chloro-9,9-dimethylfluorene (2.2 mmol), compound 3 (2.6 mmol), potassium carbonate (11.0 mmol), tetraphenylphosphine palladium (65.6 μmol), 10.0 mL deionized water, 10.0 mL tetrahydrofuran, and 20.0 mL toluene were added. The mixture was purged three times and reacted at 90 °C under nitrogen protection for 36 hours. After the reaction was complete, the mixture was cooled to room temperature, extracted three times with dichloromethane and water, and dried over anhydrous sodium sulfate. The dried solution was filtered, and the solvent was evaporated to dryness using a rotary evaporator to obtain the crude product. The crude product was purified by silica gel chromatography using a petroleum ether / dichloromethane mixture as the eluent, yielding a white solid product in 86% yield. 1 H NMR, 13 CNMR, MS and elemental analysis results indicate that the obtained compound is the target product.

[0291] Absorption spectroscopy testing:

[0292] The absorption spectra of the test material in solution and thin film were measured, with a solution concentration of (10). -5 The absorption peaks of the material are located at 323 nm, 332 nm, 374 nm, and 396 nm.

[0293] Figure 1 This is the absorption spectrum of Example 6. Figure 2 This is the absorption spectrum of Example 2. Figures 1-2 As can be seen, the absorption peaks of the compounds are mainly characteristic peaks of carbazole and anthracene.

[0294] Spectral testing of the emission:

[0295] The emission spectra of the test material were measured in solution and thin film form, with a solution concentration of (10). -5 The test results show that the emission spectrum gradually broadens and redshifts as the solvent polarity increases.

[0296] Figure 3 This is the emission spectrum of Example 6. Figure 4 This is the emission spectrum of Example 2. Figures 3-4 As can be seen, both materials exhibit blue light emission wavelengths, and the emission wavelengths of the materials in different solvents show that they exhibit obvious hybridized local charge transfer excited states.

[0297] Electrochemical testing:

[0298] The oxidation and reduction potentials of the material under thin films were tested using cyclic voltammetry.

[0299] Figure 5 These are the oxidation and reduction potentials of Example 6. Figure 6 These are the oxidation and reduction potentials of Example 2. Figures 5-6 The HOMO and LUMO energy levels of the material can be calculated.

[0300] Thermal stability testing of materials:

[0301] Figure 7 The temperature at which 5% weight loss occurred in Example 6 was 426°C. Figure 8 The temperature at which 5% weight loss occurred in Example 2 was 489°C. Figure 9 The glass transition temperature of Example 6 is 169°C. Figure 10 The glass transition temperature of Example 2 is 124°C. Figures 7-10 The test results show that M6 and M2 have high decomposition temperatures and glass transition temperatures, and both materials exhibit good thermal stability.

[0302] Example 13

[0303] Fabrication of undoped organic light-emitting diodes:

[0304] A pre-made indium tin oxide (ITO) glass with a sheet resistance of 15Ω was ultrasonically cleaned sequentially with acetone, detergent, deionized water, and isopropanol, followed by plasma treatment for 10 minutes. Then, in a vacuum evaporation apparatus, a 5nm thick layer of molybdenum trioxide (MoO3) was sequentially deposited on the ITO surface as a hole injection layer, a 25nm thick layer of 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline (TAPC)] as a hole transport layer, a 20nm thick layer of sulfone- and anthracene-containing luminescent molecules as a luminescent layer, a 40nm thick layer of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) as an electron transport layer, a 1nm thick layer of lithium fluoride (LiF) as an electron injection layer, and a 100nm thick layer of aluminum (Al) as a cathode. The device structure is: ITO / MoO3 / TAPC / M1~M3 / TPBi / LiF / Al. The luminescent small molecules containing sulfone groups and anthracene are compounds M1, M2, and M3, respectively.

[0305] The electroluminescence data of the fabricated undoped devices are listed in Table 1.

[0306] Table 1: Performance of Organic Light-Emitting Devices Based on Undoped Emitting Layers

[0307]

[0308] Table 1 shows that the OLED devices fabricated from these materials all exhibit very low turn-on voltages, high brightness, and high current efficiency. The maximum external quantum efficiencies of M1, M2, and M3 are 9.4%, 11.3%, and 8.5%, respectively. Lifetime testing revealed high lifetimes, with LT50 values ​​of 600 hours, 454 hours, and 520 hours, respectively. Exciton utilization rates were 84%, 88%, and 77%, respectively. The high exciton utilization rate indicates the involvement of triplet excitons. Based on transient magnetic field effect testing, triplet-triplet excitons were ruled out. The annihilation effect was observed through low-temperature phosphorescence testing, revealing a large energy level difference between S1 and T1, with the energy difference being much greater than 0.3 eV. This ruled out the thermal activation delay effect. The smaller energy level difference between T2 and S1 provided a channel for reverse intersystem crossing, allowing triplet excitons to participate in the interaction. This indicates that thermal exciton interaction led to the ultra-high efficiency. The emission wavelengths were 454 nm, 434 nm, and 445 nm, respectively. It was found that these materials all exhibit pure blue light emission. Undoped devices prepared from these materials have excellent performance and are conducive to industrial application.

[0309] Figure 11 The graph shows the external quantum efficiency and brightness of the undoped device implemented in Figure 13. The results show that the material has a high external quantum efficiency.

[0310] Figure 12The emission spectrum of the undoped device in Example 13 does not change with voltage.

[0311] Example 14

[0312] Fabrication of doped organic light-emitting diodes:

[0313] Take a pre-made indium tin oxide (ITO) glass with a sheet resistance of 15Ω, and clean it ultrasonically with acetone, detergent, deionized water and isopropanol in sequence, followed by plasma treatment for 10 minutes. Then, in a vacuum evaporation apparatus, a 5 nm thick layer of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzphenanthrene (HATCN) was sequentially deposited on the ITO surface as a hole injection layer, a 25 nm thick layer of 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC) as a hole transport layer, a 20 nm thick mixed film of 9'-(1,3-phenyl)bis-9H-carbazole (mCP) (90% by mass) and luminescent small molecules containing sulfones and anthracene (10% by mass) as a luminescent layer, a 40 nm thick layer of 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) as an electron transport layer, a 1 nm thick layer of lithium fluoride (LiF) as an electron injection layer, and a 100 nm thick layer of aluminum (Al) as a cathode. The device structure is: ITO / HATCN / TAPC / mCP:M4~M6(10%) / TPBi / LiF / Al. The luminescent small molecules containing sulfone groups and anthracene are compounds M4, M5, and M6, respectively.

[0314] Figure 13 The image shows the electroluminescence spectrum of the doped device prepared in Example 14. The emission spectrum does not change with voltage. The doped device emits light at wavelengths of 470 nm, 432 nm, and 442 nm, with color coordinates of (0.15, 0.14), (0.15, 0.08), and (0.15, 0.11), exhibiting standard blue light emission. The external quantum efficiencies after doping are 15.5%, 12.4%, and 14.5%, respectively; the maximum luminance is 14500 cd. . m -2 16300cd . m -2 12386cd . m -2 The maximum current efficiency is 13.5 cd.A. -1 15.3cd.A -1 14.9cd.A -1Lifetime tests were conducted, and the results showed that the device had a high lifetime: LT50 was 965 hours, 885 hours, and 643 hours, with exciton utilization rates of 90%, 88%, and 93%, respectively. It can be seen that the efficiency of the device was greatly improved after doping.

Claims

1. A luminescent compound containing a sulfone group and anthracene unit, comprising a sulfone group unit, an anthracene unit, and a donor unit; the sulfone group unit and the donor unit are respectively connected to both sides of the anthracene unit; wherein the sulfone group unit is... The anthracene unit is The donor unit has a hole transport capability; the luminescent compound containing sulfone and anthracene units has 20 to 100 carbon atoms.

2. The luminescent compound containing sulfone and anthracene units as described in claim 1, characterized in that: The luminescent compound containing sulfone and anthracene units has 30 to 60 carbon atoms; and / or, The donor unit has one of the following structures:

3. The luminescent compound containing sulfone and anthracene units as described in claim 1, characterized in that: The luminescent compound containing sulfone and anthracene units has one of the following structural formulas:

4. A method for preparing a luminescent compound containing a sulfone group and anthracene unit as described in any one of claims 1 to 3, comprising method A or method B; Method A includes the following steps: (1) Reacting a starting material including haloanthracene or its derivatives with pinacol diboronic acid ester to obtain intermediate product one; (2) Reacting the raw materials, including haloarylthiophene and peroxide, to obtain intermediate product II; (3) React the raw materials including intermediate product one and intermediate product two to obtain intermediate product three; (4) The luminescent compound is obtained by reacting the raw material, including the intermediate tri, with a haloaryl amine; Method B includes the following steps: (I) Reacting a haloanthracene or its derivatives with an acridine compound to give intermediate product I; (II) Reacting the raw material including intermediate product I with pinacol diboronate to obtain intermediate product II; (III) Reacting a raw material including a haloarylthiophene and a peroxide yields intermediate product III; (IV) The luminescent compound is obtained by reacting the raw materials, including intermediate product II and intermediate product III.

5. The method for preparing the luminescent compound containing sulfone and anthracene units as described in claim 4, characterized in that: Step (1), The haloanthracene is 9,10-dibromoanthracene or 2,6-dibromoanthracene; and / or, The molar ratio of the haloanthracene or its derivative to pinacol diboronate is 1:(2-4), preferably (2.2-2.6); and / or, Step (2), The haloarylthiophene is 2-bromodibenzothiophene; and / or... The molar ratio of the haloarylthiophene to the peroxide is 1:(10-60), preferably 1:(30-40); and / or, Step (3), The molar ratio of intermediate product one to intermediate product two is 1:(1-2), preferably 1:(1-1.2); and / or, Step (4), The haloaryl amine is one of the following compounds; And / or, The molar ratio of the haloaryl amine to intermediate tri is 1:(1-2), preferably 1:(1.1-1.3).

6. The method for preparing the luminescent compound containing sulfone and anthracene units as described in claim 4, characterized in that: Step (1), The raw materials also include solvent A, catalyst A, and strong base-weak acid salt A; preferably, Solvent A is at least one selected from 1,4-dioxane, toluene, and N,N-dimethylformamide; and / or... The catalyst A is a palladium catalyst, more preferably at least one of 1,1'-bis(diphenylphosphino)ferrocene palladium(II) dichloride and tris(dibenzylacetone)dipalladium; and / or The strong base-weak acid salt A is at least one selected from potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate; and / or, The volume ratio of solvent A to the total mass of the reactants in step (1) is 1–20 ml solvent / 1 mmol reactant, preferably 1–5 ml solvent / 1 mmol reactant; and / or, The molar ratio of catalyst A to the total molar ratio of reactants in step (1) is (0.001–0.1):1, preferably (0.005–0.03):1; and / or, The molar ratio of the strong base-weak acid salt A to the total molar ratio of the reactants is (0.5–10):1, preferably (1–4):1; and / or, The reaction temperature is 80–120°C; and / or, The reaction time is 12–36 hours; and / or, The intermediate product requires post-processing, preferably including extraction, separation; and / or... Step (2), The raw materials also include solvent B; preferably, The solvent B is acetic acid; and / or, The volume ratio of solvent B to the total mass of the reactants in step (2) is 0.1–10 ml solvent / 1 mmol reactant, preferably 0.2–1 ml solvent / 1 mmol reactant; and / or, The reaction temperature is 60–100℃; and / or, The reaction time is 2–4 hours; and / or, Intermediate product two requires post-processing, preferably including extraction, separation; and / or... Step (3), The raw materials also include solvent C, catalyst C, and strong base-weak acid salt C; preferably, The solvent C is at least one of toluene, tetrahydrofuran, and deionized water; and / or, The catalyst C is a palladium catalyst, more preferably tetraphenylphosphine palladium; and / or, The strong base-weak acid salt C is at least one selected from potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate; and / or, The volume ratio of solvent C to the total mass of the reactants in step (3) is 1–40 ml solvent / 1 mmol reactant, preferably 5–20 ml solvent / 1 mmol reactant; and / or, The mass ratio of the catalyst C to the total mass of the reaction raw materials in step (3) is (0.001–0.1):1, preferably (0.01–0.05):1; and / or, The molar ratio of the strong base-weak acid salt C to the total molar ratio of the reactants is (0.5–10):1, preferably (1–4):1; and / or, The reaction temperature is 80–100℃; and / or, The reaction time is 24–48 hours; and / or, Intermediate product three requires post-processing, preferably including extraction, separation; and / or... Step (4), The raw materials also include solvent D, catalyst D, and strong base-weak acid salt D; preferably, The solvent D is at least one of toluene, tetrahydrofuran, and deionized water; and / or, The catalyst D is a palladium catalyst, more preferably tetrakis(triphenylphosphine)palladium; and / or, The strong base-weak acid salt D is at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate; and / or, The volume ratio of solvent D to the total mass of the reactants in step (4) is 1–40 ml solvent / 1 mmol reactant, preferably 5–20 ml solvent / 1 mmol reactant; and / or, The mass ratio of catalyst D to the total mass of the reaction raw materials in step (4) is (0.001–0.2):1, preferably (0.01–0.05):1; and / or, The molar ratio of the strong base-weak acid salt D to the total molar ratio of the reactants is (0.5–10):1, preferably (1–4):1; and / or, The reaction temperature is 80–100℃; and / or, The reaction time is 24–48 hours; and / or, The reaction products require post-processing, preferably including extraction, separation; and / or, Steps (1) to (4) are all carried out under a protective gas atmosphere, wherein the protective gas is at least one of nitrogen or an inert gas.

7. The method for preparing the luminescent compound containing sulfone and anthracene units as described in claim 4, characterized in that: Step (I), The haloanthracene is 9,10-dibromoanthracene or 2,6-dibromoanthracene; and / or, The acridine compound is at least one selected from 9,10-dihydro-9,9-dimethylacridine and 9,10-dihydro-9,9-diphenylacridine; and / or, The molar ratio of the haloanthracene or its derivative to the acridine compound is 1:(0.5-2), preferably 1:(0.8-1.2); and / or, Step (II), The molar ratio of intermediate product I to pinacol diboronate is 1:(1-2), preferably 1:(1.1-1.3); and / or, Step (III), The haloarylthiophene is 2-bromodibenzothiophene; and / or... The molar ratio of the haloarylthiophene to the peroxide is 1:(10-60), preferably 1:(30-40); and / or, Step (Ⅳ), The molar ratio of intermediate product III to intermediate product II is 1:(1-2), preferably 1:(1.1-1.3).

8. The method for preparing the luminescent compound containing sulfone and anthracene units as described in claim 4, characterized in that: Step (I), The raw materials also include solvent E, catalyst E, ligand E, and organic base E; Preferably, The solvent E is at least one of toluene, tetrahydrofuran, and water; and / or, The catalyst E is a palladium catalyst, more preferably tris(dibenzylacetone)dipalladium; and / or, The ligand E is tri-tert-butylphosphine; and / or... The organic base E is at least one of sodium tert-butoxide and potassium tert-butoxide; and / or The volume ratio of solvent E to the total molar amount of reactants in step (I) is 0.5–40 ml solvent / 1 mmol reactant, preferably 1–10 ml solvent / 1 mmol reactant; and / or, The molar ratio of catalyst E to the total molar ratio of reactants in step (I) is (0.001–0.2):1, preferably (0.01–0.05):1; and / or, The molar ratio of the ligand E to the total molar ratio of the reactants in step (I) is (0.01–0.2):1, preferably (0.03–0.06):1; and / or, The molar ratio of the organic base E to the total molar ratio of the reactants in step (I) is (0.5–3):1, preferably (1–1.5):1; and / or, The reaction temperature is 100–140℃; and / or, The reaction time is 8–12 hours; and / or, Intermediate product I requires post-processing, preferably including extraction, separation; and / or, Step (II), The raw materials also include solvent F, catalyst F, and strong base-weak acid salt F; preferably, The solvent F is at least one selected from 1,4-dioxane, toluene, and N,N-dimethylformamide; and / or The catalyst F is a palladium catalyst, more preferably at least one of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride and tris(dibenzylacetone)palladium; and / or The strong base-weak acid salt F is at least one selected from potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate; and / or, The volume ratio of solvent F to the total molar amount of reactants in step (II) is 0.5–40 ml solvent / 1 mmol reactant, preferably 1–10 solvent / 1 mmol reactant; and / or, The mass ratio of catalyst F to the total molar mass of the reactants in step (II) is (0.001–0.2):1, preferably (0.01–0.03):1; and / or, The molar ratio of the strong base-weak acid salt F to the total molar ratio of the reactants in step (II) is (1-10):1, preferably (2-4):1; and / or, The reaction temperature is 80–120°C; and / or, The reaction time is 12–36 hours; and / or, Intermediate product II requires post-processing, preferably including extraction, separation; and / or, Step (III), The raw materials also include solvent G; preferably, The solvent G is acetic acid; and / or, The volume ratio of solvent G to the total molar amount of reactants in step (III) is 0.1–10 ml solvent / 1 mmol reactant, preferably 0.2–1 ml solvent / 1 mmol reactant; and / or, The reaction temperature is 60–100℃; and / or, The reaction time is 2–4 hours; and / or, Intermediate product III requires post-processing, preferably including extraction, separation; and / or... Step (Ⅳ), The raw materials also include solvent H, catalyst H, and strong base-weak acid salt H; preferably, The solvent H is at least one of toluene, tetrahydrofuran, and deionized water; and / or, The catalyst H is a palladium catalyst, more preferably tetraphenylphosphine palladium; and / or, The strong base-weak acid salt H is at least one of potassium acetate, potassium carbonate, sodium carbonate, sodium acetate, sodium phosphate, and sodium bicarbonate; and / or, The volume ratio of solvent H to the total molar amount of reactants in step (IV) is 1–40 ml solvent / 1 mmol reactant, preferably 5–20 ml solvent / 1 mmol reactant; and / or, The mass ratio of catalyst H to the total molar mass of the reactants in step (IV) is (0.001–0.2):1, preferably (0.01–0.05):1; and / or, The reaction temperature is 80–100℃; and / or, The reaction time is 24–48 hours; and / or, The reaction products require post-processing, preferably including extraction, separation; and / or, Steps (I) to (IV) are all carried out under a protective gas atmosphere, wherein the protective gas is at least one of nitrogen and an inert gas.

9. A luminescent compound containing sulfone and anthracene units, obtained by the preparation method according to any one of claims 4 to 8.

10. The use of a luminescent compound containing sulfone and anthracene units as described in any one of claims 1 to 3, 9 in an organic electroluminescent device.

11. The application as described in claim 10, characterized in that: The organic electroluminescent device has the following structure from bottom to top: an anode, a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, and a cathode; the light-emitting layer contains the luminescent compound containing sulfone groups and anthracene units as described in claim 1, 2, or 7.

12. The application as described in claim 11, characterized in that: The organic light-emitting layer is a pure film of a light-emitting compound containing sulfone and anthracene units, or a mixed film doped with a light-emitting compound containing sulfone and anthracene units and a host material. Preferably, the proportion of the luminescent compound containing sulfone and anthracene units in the organic light-emitting layer is not less than 2 wt%; and / or, The main material is 9'-(1,3-phenyl)bis-9H-carbazole (mCP); and / or, The organic electroluminescent device is obtained by sequentially assembling a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, an electron injection layer, and a cathode on the anode. More preferably, The anode is indium tin oxide glass; and / or, The hole injection layer is molybdenum trioxide or 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HATCN); and / or, The hole transport layer is 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline], 4,4',4”-tris(carbazole-9-yl)triphenylamine, or N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine; and / or The organic light-emitting layer is the light-emitting compound and an optional host material; and / or, The electron transport layer is 1,3,5-tris(3-pyridyl-3-phenyl)benzene (TmPyPB) or 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene; and / or, The electron injection layer is lithium fluoride; and / or, The cathode is aluminum; and / or, Assembly is performed using vacuum evaporation. More preferably, The resistance of the anode is 10–20 Ω; and / or, The anode is subjected to ultrasonic cleaning and plasma treatment before assembly; and / or, The thickness of the hole injection layer is 3–50 nm; and / or, The thickness of the hole transport layer is 5–80 nm; and / or, The thickness of the organic light-emitting layer is 5–50 nm; and / or, The thickness of the electron transport layer is 5–50 nm; and / or, The thickness of the electron injection layer is 0.7–2 nm; and / or, The thickness of the cathode is 80–110 nm.

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