Bipolar optoelectronic material and applications thereof

Abstract

The application relates to the technical field of organic photoelectricity, and particularly discloses a bipolar photoelectric material and application thereof, the bipolar photoelectric material has the following general formula: in the general formula, R1 is hydrogen, an aromatic hydrocarbon and derivatives thereof, an electron-donor carbazole and derivatives thereof, a phenoxazine and derivatives thereof, or an acridine and derivatives thereof; R2 is an aromatic hydrocarbon and derivatives thereof, an electron-donor carbazole and derivatives thereof, a phenoxazine and derivatives thereof, or an acridine and derivatives thereof; and R3 is an aromatic hydrocarbon and derivatives thereof, an electron-donor carbazole and derivatives thereof, a phenoxazine and derivatives thereof, or an acridine and derivatives thereof; the hydrogen in R1 can be partially replaced by deuterium or fully replaced by deuterium or not replaced by deuterium; the bipolar photoelectric material is introduced with a diphenyl sulfone thiophene sulfoxide electron-deficient group as a light-emitting unit and an electron-withdrawing unit in a molecular structure, the introduction of the group can improve the carrier mobility of the material, is beneficial to charge balance, and is further beneficial to obtaining high light-emitting efficiency.

Description

Technical Field

[0001] This application relates to the field of organic optoelectronic technology, and more specifically, to a bipolar optoelectronic material and its applications. Background Technology

[0002] Organic light-emitting materials have significant application value in fields such as electroluminescence, biological detection, and signal identification. Especially in the field of electroluminescence, organic light-emitting diodes (OLEDs) based on organic light-emitting materials have been gradually applied to high-end displays and solid-state lighting devices. These devices have advantages such as wide color gamut, high contrast, and thin and light appearance, and some have even been developed into foldable and rollable products.

[0003] Currently, organometallic complexes such as iridium / platinum are among the best light-emitting materials for fabricating high-efficiency organic light-emitting diodes (OLEDs). This is because the heavy metal centers can promote intersystem crossings between singlet and triplet states, utilizing excitons generated by complete electrical excitation to achieve 100% internal quantum efficiency. However, heavy metals are non-renewable and expensive, and organometallic complex light-emitting materials are costly and difficult to recycle. To address these issues, thermally activated delayed fluorescence materials without precious metals have emerged.

[0004] Thermally activated delayed fluorescence (TEF) materials, utilizing the property of thermally activated reverse intersystem crossing, can achieve rational utilization of triplet excitons, ultimately potentially achieving 100% internal quantum efficiency in organic light-emitting diodes (OLEDs), thus attracting increasing attention. However, currently reported TEF materials suffer from limitations such as limited variety and low luminous efficiency, particularly deep blue / blue light TEF materials, which typically have luminous efficiency not exceeding 80%. Holes in organic semiconductor materials often have high mobility, making them the majority carriers in organic electroluminescent devices, thus electrons become relatively minority carriers, resulting in poor charge balance. However, based on the luminescence process and mechanism of organic electroluminescence, the charge balance among carriers is of paramount importance for improving device efficiency and other performance characteristics. Based on the above, this application provides a bipolar optoelectronic material and its application. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this application provides a bipolar optoelectronic material and its applications.

[0006] On the one hand, this application provides a bipolar optoelectronic material, which adopts the following technical solution:

[0007] A bipolar optoelectronic material, wherein the bipolar optoelectronic material has the following general formula:

[0008]

[0009] In the general formula: R1 is hydrogen, aromatic hydrocarbons and their derivatives, electron donor carbazole and its derivatives, phenoxazine and its derivatives, or acridine and its derivatives;

[0010] R2 is an aromatic hydrocarbon or its derivative, an electron donor carbazole or its derivative, a phenoxazine or its derivative, or an acridine or its derivative;

[0011] R3 is an aromatic hydrocarbon and its derivatives, an electron donor carbazole and its derivatives, a phenoxazine and its derivatives, or an acridine and its derivatives;

[0012] The hydrogen in R1 may be partially deuterated, fully deuterated, or not deuterated.

[0013] Preferably, R1, R2, and R3 are selected from different types of substituents.

[0014] Preferably, the bipolar optoelectronic material has the following general formula:

[0015]

[0016] Secondly, this application provides an application of a bipolar optoelectronic material, employing the following technical solution:

[0017] An application of a bipolar optoelectronic material, wherein the bipolar optoelectronic material is used in organic electroluminescent devices or organic field-effect transistors.

[0018] In summary, this application has the following beneficial effects:

[0019] This application introduces electron-deficient dibenzothiophene sulfone groups into the molecular structure as both luminescent and electron-withdrawing units. The introduction of these groups improves carrier mobility and promotes charge balance, thereby contributing to high luminescence efficiency. Furthermore, introducing nitrogen atoms into the dibenzothiophene sulfone further enhances the charge balance of the material.

[0020] The bipolar optoelectronic material of this application has a narrow spectral absorption range and high carrier mobility, and can be applied to organic electroluminescent devices or organic field-effect transistors. As a light-emitting layer, electron transport layer or other functional layer, it can be connected with electron-donating groups and bridged to construct a D-π-A bipolar structure to obtain a high-efficiency organic electroluminescent device or organic field-effect transistor. Detailed Implementation

[0021] The present application will be further described in detail below with reference to the embodiments.

[0022] Examples 1-5 provide a bipolar optoelectronic material.

[0023] Example 1

[0024] Synthesis of a bipolar optoelectronic material NDPT-1:

[0025]

[0026] Synthesis of NDPT-1-M1: Methyl 3-amino-2-naphtho[2,1-b]thiophene-formate (25.7 g, 100 mmol) and sodium cyanate aqueous solution (100 ml, containing 13 g of sodium cyanate, 200 mol) were mixed and added dropwise (at a dropping rate of 20 ml / min) to 200 ml of 50% glacial acetic acid aqueous solution. The mixture was stirred at room temperature for 5 h, resulting in a white solid. The solid was filtered and dissolved in 100 ml of 2N sodium hydroxide solution. The reaction was cooled to 0 °C, and the solution was acidified with hydrochloric acid until a solid precipitated. The solid was then filtered and dried to obtain NDPT-1-M1. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-1-M1 are as follows: 1 H NMR (400MHz, CDCl3) δ11.40 (s, 1H), 11.34 (s, 1H), 8.54 (s, 1H), 7.99 (s, 1H), 7.80-7.78 (d, 2H), 7.61 (s, 1H), 7.53 (s, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 14 H8N2O2S, 268.29, found: 268.03. Elemental Analysis: C, 62.68; H, 3.01; N, 10.44; O, 11.93; S, 11.95.

[0027] Synthesis of NDPT-1-M2: NDPT-1-M1 (13.41 g, 50 mmol) was added to a reaction flask, followed by phosphorus oxychloride (27.40 mL, 300 mmol). Under stirring at room temperature, N,N-dimethylaniline (19.24 mL, 150 mol) was added dropwise (at a dropping rate of 30 mL / min). The mixture was heated to reflux at 153 °C for 5 h. Heating was stopped, and the mixture was cooled and poured into 300 mL of ice water, precipitating a solid. The solid was filtered, and the upper filter cake was the crude NDPT-1-M2. The crude product was purified by column chromatography using petroleum ether and ethyl acetate (V / V = 3:1) as eluents. The eluent containing NDPT-1-M2 was collected, and the organic solvent was removed under reduced pressure. After drying, NDPT-1-M2 was obtained. The 1H NMR spectrum and high-resolution mass spectrometry of NDPT-1-M2 are as follows: 1 H NMR (400MHz, CDCl3) δ8.54 (s, 1H), 7.99 (s, 1H), 7.80-7.78 (d, 2H), 7.61 (s, 1H), 7.53 (s, 1H). HRMS(ESI,Positive)(m / z):[M] +Calculated for:C 14 H6Cl2N2S, 305.18, found: 305.04. Elemental Analysis: C, 55.10; H, 1.98; Cl, ​​23.23; N, 9.18; S, 10.51.

[0028] Synthesis of NDPT-1-M3: To a mixed solution of NDPT-1-M2 (15.25 g, 50 mmol) and diiodomethane (40.2 g, 150 mmol) in acetonitrile (400 mL), tert-butyl nitrite (17.7 g, 150 mmol) was added dropwise (at a dropping rate of 4.5 g / min). Under nitrogen protection, the mixture was stirred at 60 °C for 30 min, then at 80 °C for 4 h. After cooling to room temperature, the mixture was concentrated, and water was added (…). The residue was diluted with 100 ml of ethyl acetate and extracted twice with 100 ml of ethyl acetate each time. The extract was washed with Na₂S₂O₃ aqueous solution and saturated brine (30 ml). The organic phases were separated and combined, dried over Na₂SO₄, and concentrated to obtain crude NDPT-1-M3. The crude product was purified by column chromatography using silica gel column chromatography (petroleum ether:ethyl acetate, V / V = 10:1). The eluent containing NDPT-1-M3 was collected, and the organic solvent was removed to obtain NDPT-1-M3. The 1H NMR spectrum and high-resolution mass spectrometry of NDPT-1-M3 are as follows: 1 H NMR (400MHz, CDCl3) δ8.54 (s, 1H), 7.99 (s, 1H), 7.80-7.78 (d, 2H), 7.61 (s, 1H), 7.53 (s, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 14 H6ClIN2S, 396.63, found: 396.51. Elemental Analysis: C, 42.40; H, 1.52; Cl, ​​8.94; I, 32.00; N, 7.06; S, 8.08.

[0029] Synthesis of NDPT-1-M4: NDPT-1-M3 (19.83 g, 50 mmol), potassium acetate (9.8 g, 100 mmol), L-co-p-amino acid (0.57 g, 0.5 mmol), and toluene (150 mL) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Then, phenylboronic acid (5.4 g, 45 mmol) and bis(dibenzylacetone)palladium (0.28 g, 0.5 mmol) were added. The mixture was refluxed at 110 °C for 6 h. After the reaction solution was brought to room temperature, it was extracted with ethyl acetate and water. The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain crude NDPT-1-M4. The crude product was purified by column chromatography using silica gel column chromatography (petroleum ether:ethyl acetate, V / V = 20:1). The eluent containing NDPT-1-M4 was collected, and the organic solvent was removed to obtain NDPT-1-M4. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-1-M4 are as follows: 1 H NMR (400MHz, CDCl3) δ 8.54 (s, 1H), 7.99 (s, 1H), 7.84 (dd, 2H), 7.80-7.78 (d, 2H), 7.61 (s, 1H), 7.53 (m, 3H), 7.49 (s, 1H). HRMS(ESI,Positive)(m / z):[M] + Calcdfor:C 20 H 11 ClN2S, 346.83, found: 346.77. Elemental Analysis: C, 69.26; H, 3.20; Cl, ​​10.22; N, 8.08; S, 9.24.

[0030] Synthesis of NDPT-1-M5: NDPT-1-M4 (17.34 g, 50 mmol), potassium carbonate (20.7 g, 150 mmol), tetrabutylammonium chloride (1.38 g, 0.5 mmol), and 1,4-dioxane (120 ml) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Then, benzimidazole borate (13.89 g, 55 mmol) and 1,1′-bis(di-phenylphosphino)ferrocene palladium chloride (0.4 g, 0.5 mmol) were added. The reaction mixture was refluxed at 88℃ for 12 h (5 mmol), and after the reaction solution was brought to room temperature, it was extracted with ethyl acetate (150 ml each time) and water (150 ml each time, three times). The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain crude NDPT-1-M5. The crude product was purified by column chromatography using silica gel column chromatography (petroleum ether: ethyl acetate, V / V = 14:1). The eluent containing NDPT-1-M5 was collected, and the organic solvent was removed to obtain NDPT-1-M5. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-1-M5 are as follows: 1H NMR (400MHz, CDCl3) δ8.56 (d, 1H), 8.54 (s, 1H), 7.99 (s, 1H), 7.96 (m, 4H), 7.84 (dd, 2H), 7.84 (d, 2H ), 7.80-7.78(d, 4H), 7.62-7.61(d, 2H), 7.53(m, 4H), 7.49-7.48(m, 2H), 7.38(m, 2H), 7.28(dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 39 H 24 N4S,580.71,found:580.51. Elemental Analysis: C, 80.67; H, 4.17; N, 9.65; S, 5.52.

[0031] Synthesis of NDPT-1-M6: NDPT-1-M5 (14.5 g, 25 mmol) and anhydrous ethanol (80 ml) were added to a glass reaction flask, followed by ferric oxide (0.57 g, 0.25 mmol). The mixture was stirred until dissolved, and then 30% hydrogen peroxide (22.6 g, 200 mmol) was added dropwise (at a dropping rate of 5.5 g / min). The mixture was stirred at 75 °C for 4 h, then allowed to return to room temperature. The reaction solution was filtered and washed successively with methanol and 10% hydrochloric acid, completing one washing operation. This washing operation was repeated three times in total. The solution was then dried to obtain NDPT-1-M6. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-1-M6 are as follows: 1 H NMR (400MHz, CDCl3) δ8.97 (d, 1H), 8.57-8.56 (d, 2H), 8.15 (d, 1H), 8.08 (d, 1H), 7.96 (m, 4H), 7.84 (dd, 2H) , 7.81 (d, 1H), 7.62 (d, 1H), 7.59 (dd, 1H), 7.53-7.52 (m, 4H), 7.49-7.48 (m, 3H), 7.38 (m, 2H), 7.28 (dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 39 H 24 N4O2S, 612.71, found: 612.54. Elemental Analysis: C, 76.45; H, 3.95; N, 9.14; O, 5.22; S, 5.23.

[0032] Synthesis of NDPT-1-M7: NDPT-1-M6 (14.5 g, 25 mmol) and chlorobenzene (100 ml) were added to a reaction flask. Then, dibromohydantoin (14 g, 25 mmol) was added in two batches (7 g each, 10 min apart). The temperature was controlled below 50°C during the addition process (45°C in this example). After the addition was complete, the temperature was raised to 80°C and reacted for 6 h. After the reaction solution was brought back to room temperature, it was poured into a 10% hydrochloric acid aqueous solution, followed by filtration. The resulting filter cake was washed with methanol and dried to obtain NDPT-1-M7. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-1-M7 are as follows: 1 H NMR (400MHz, CDCl3) δ8.96 (d, 1H), 8.64 (s, 1H), 8.56 (d, 1H), 8.23 ​​(d, 1H), 7.96 (m, 4H), 7.84 (dd, 2H), 7.81 (d, 1H), 7.63-7.62 (d, 2H), 7.59 (dd, 1H), 7.53-7.52 (m, 3H), 7.49-7.48 (m, 3H), 7.38 (m, 2H), 7.28 (dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 39 H 23 BrN4O2S, 691.60, found: 691.29. Elemental Analysis: C, 67.73; H, 3.35; Br, 11.55; N, 8.10; O, 4.63; S, 4.64.

[0033] Synthesis of NDPT-1: NDPT-1-M7 (13.82 g, 25 mmol), potassium carbonate (10.35 g, 75 mmol), tetrabutylammonium bromide (1.61 g, 0.5 mmol), toluene (120 ml), and water (6 ml) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Then, (4-(phenanthrene-9-yl)phenyl)boronic acid (17.88 g, 60 mmol) and 1,1′-bis(di-phenylphosphino)ferrocene palladium chloride (0.4 g, 0.5 mmol) were added. The mixture was refluxed at 110 °C for 20 h. After the reaction solution was brought to room temperature, it was extracted with ethyl acetate (120 ml once) and water (120 ml three times each time). The organic phase was dried with anhydrous sodium sulfate and concentrated to obtain crude NDPT-1. The crude product was recrystallized from acetone, and the resulting solid was dried after filtration to obtain NDPT-1. The proton NMR spectrum and high-resolution mass spectra of NDPT-1 were analyzed as follows: 1H NMR (400MHz, CDCl3) δ9.08 (d, 1H), 9.02 (d, 1H), 8.95 (d, 1H), 8.84 (s, 1H), 8.56 (s, 1H), 8.27 (d, 1H), 8.05 (s, 1H), 7.90 (dd, 1H), 7.81 (d, 1H), 7.70-7.68(m, 2H), 7.64-7.62(m, 4H), 7.53-7.52(m, 4H), 7.49-7.48(m, 3H), 7.46(dd, 1H), 7.38(m, 2H), 7.28(dd, 1H), 7.25(dd, 4H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 59 H 36 N4O2S,865.02,found:865.02. Elemental Analysis: C, 81.92; H, 4.20; N, 6.48; O, 3.70; S, 3.71.

[0034] Example 2

[0035] Synthesis of a bipolar optoelectronic material NDPT-2:

[0036]

[0037] Compared to the synthesis of NDPT-1 in Example 1, steps 1 to 7 remain unchanged, except that (4-(phenanthrene-9-yl)phenyl)boronic acid in step 8 is replaced with 9-phenanthreneboronic acid. The remaining steps are unchanged to obtain NDPT-2. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-2 are as follows: 1 H NMR (400MHz, CDCl3) δ9.08 (d, 1H), 9.02 (d, 1H), 8.95 (d, 1H), 8.84 (s, 1H), 8.79 (d, 1H), 8.56 (s, 1H), 8.05 (s, 1H), 7.96 (m, 4H), 7.90 (dd, 1H), 7.84(dd, 2H), 7.70-7.68(m, 2H), 7.64-7.61(m, 4H), 7.53-7.52(m, 4H), 7.49-7.48(m, 3H), 7.46(dd, 1H), 7.38(m, 2H), 7.28(dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 53 H 32N4O2S,788.93,found:788.77. Elemental Analysis: C, 80.69; H, 4.09; N, 7.10; O, 4.06; S, 4.06.

[0038] Example 3

[0039] Synthesis of a bipolar optoelectronic material NDPT-3:

[0040]

[0041] Synthesis of NTPD-3-M1: Methyl 3-amino-2-naphtho[2,1-b]thiophene formate (25.7 g, 100 mmol) and sodium cyanate aqueous solution (100 ml, containing 13 g of sodium cyanate, 200 mol) were mixed and added dropwise (at a dropping rate of 20 ml / min) to 200 ml of 50% glacial acetic acid aqueous solution. The mixture was stirred at room temperature for 5 h, resulting in a white solid. The solid was filtered and dissolved in 100 ml of 2N sodium hydroxide solution. The reaction was cooled to 0 °C, and the solution was acidified with hydrochloric acid until a solid precipitated. The solid was then filtered and dried to obtain NDPD-3-M1. The proton NMR spectrum and high-resolution mass spectrometry of NDPD-3-M1 are as follows: 1 H NMR (400MHz, CDCl3) δ11.40 (s, 1H), 11.34 (s, 1H), 8.54 (s, 1H), 7.99 (s, 1H), 7.80-7.78 (d, 2H), 7.61 (s, 1H), 7.53 (s, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 14 H8N2O2S, 268.29, found: 268.03. Elemental Analysis: C, 62.68; H, 3.01; N, 10.44; O, 11.93; S, 11.95.

[0042] Synthesis of NTPD-3-M2: NTPD-3-M1 (13.4 g, 50 mmol) and dichloromethane (120 ml) were added to a reaction flask. Then, N-bromosuccinimide (9.79 g, 55 mmol) was added in two batches (4.895 g each, 10 min apart). The temperature during the addition process was controlled below 50°C (45°C in this example). After the addition was complete, the reaction mixture was reacted at 50°C for 12 hours. After the reaction mixture was brought to room temperature, it was poured into ice water and then filtered. The resulting filter cake was washed with acetone and dried to obtain NTPD-3-M2. The proton NMR spectrum and high-resolution mass spectrometry of NTPD-3-M2 are as follows: 1H NMR (400MHz, CDCl3) δ 11.40 (s, 1H), 11.34 (s, 1H), 8.97 (d, 1H), 8.15 (s, 1H), 7.84 (dd, 1H), 7.59 (d, 1H), 7.48 (dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 14 H7BrN2O2S, 347.19, found: 347.07. Elemental Analysis: C, 48.43; H, 2.03; Br, 23.01; N, 8.07; O, 9.22; S, 9.23.

[0043] Synthesis of NTPD-3-M3: NTPD-3-M2 (13.41 g, 50 mmol) was added to a reaction flask, followed by phosphorus oxychloride (27.40 ml, 300 mmol). Under stirring at room temperature, N,N-dimethylaniline (19.24 ml) was added dropwise (at a dropping rate of 30 ml / min). The mixture was heated to reflux at 153 °C for 5 h. Heating was stopped, and the mixture was cooled and poured into 300 ml of ice water, precipitating a solid. The solid was filtered, and the upper filter cake was the crude NTPD-3-M3. The crude product was purified by column chromatography using petroleum ether and ethyl acetate (V / V = 3:1) as eluents. The eluent containing NTPD-3-M3 was collected, and the organic solvent was removed under reduced pressure. After drying, NTPD-3-M3 was obtained. The 1H NMR spectrum and high-resolution mass spectrometry of NTPD-3-M3 are as follows: 1 H NMR (400MHz, CDCl3) δ 8.97 (d, 1H), 8.15 (s, 1H), 7.84 (dd, 1H), 7.59 (d, 1H), 7.48 (dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 14 H5BrCl2N2S, 384.07, found: 384.07. Elemental Analysis: C, 43.78; H, 1.31; Br, 20.80; Cl, ​​18.46; N, 7.29; S, 8.35.

[0044] Synthesis of NTPD-3-M4: NTPD-3-M3 (19.83 g, 50 mmol), potassium acetate (9.8 g, 100 mmol), L-co-amino acid (0.57 g, 0.5 mmol), and toluene (150 ml) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Then, phenylboronic acid (5.4 g, 45 mmol) and bis(dibenzylacetone)palladium (0.28 g, 0.5 mmol) were added. The mixture was refluxed at 110 °C for 6 h. After the reaction solution was brought to room temperature, it was extracted with ethyl acetate (150 ml once) and water (150 ml each time, three extractions). The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain crude NTPD-3-M4. The crude product was purified by column chromatography using silica gel column chromatography (petroleum ether: ethyl acetate, V / V = 20:1). The eluent containing NTPD-3-M4 was collected, and the organic solvent was removed to obtain NDPT-1-M4. The proton NMR spectrum and high-resolution mass spectra of NTPD-3-M4 were analyzed as follows: 1 H NMR (400MHz, CDCl3) δ 8.97 (d, 1H), 8.15 (s, 1H), 7.84 (m, 3H), 7.59 (d, 1H), 7.53 (dd, 2H), 7.49-7.48 (dd, 2H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 20 H 10 BrClN2S, 425.73, found: 425.44. Elemental Analysis: C, 56.43; H, 2.37; Br, 18.77; Cl, ​​8.33; N, 6.58; S, 7.53.

[0045] Synthesis of NTPD-3-M5: NTPD-3-M4 (17.34 g, 50 mmol), potassium carbonate (20.7 g, 150 mmol), tetrabutylammonium chloride (1.38 g, 0.5 mmol), and 1,4-dioxane (120 ml) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Subsequently, benzimidazole borate (13.89 g, 55 mmol) and 1,1′-bis(di-phenylphosphino)ferrocene palladium chloride (0.4 g, 0.5 mmol) were added. The reaction mixture (5 mmol) was refluxed at 88℃ for 12 h. After the reaction solution was brought to room temperature, it was extracted with ethyl acetate (120 ml each time) and water (120 ml each time, three times). The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain crude NTPD-3-M5. The crude product was purified by column chromatography using silica gel column chromatography (petroleum ether:ethyl acetate, V / V = 14:1). The eluent containing NTPD-3-M5 was collected, and the organic solvent was removed to obtain NTPD-3-M5. The proton NMR spectrum and high-resolution mass spectrometry of NTPD-3-M5 are as follows: 1 H NMR (400MHz, CDCl3) δ 8.97 (d, 1H), 8.35 (d, 2H), 8.15 (s, 1H), 7.84 (m, 3H), 7.59 (d, 1H), 7.53 (dd, 2H), 7.50-7.48 (m, 5H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 26 H 15 BrN2S, 467.38, found: 467.03. Elemental Analysis: C, 66.82; H, 3.24; Br, 17.10; N, 5.99; S, 6.86.

[0046] Synthesis of NTPD-3-M6: NTPD-3-M5 (13.82 g, 25 mmol), potassium carbonate (10.35 g, 75 mmol), tetrabutylammonium bromide (1.61 g, 0.5 mmol), toluene (120 ml), and water (6 ml) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Then, (4-(phenanthrene-9-yl)phenyl)boronic acid (17.88 g, 60 mmol) and 1,1′-bis(di-phenylphosphino)ferrocene palladium chloride (0.4 g, 0.5 mmol) were added. The mixture was refluxed at 110 °C for 20 h. After the reaction solution was brought to room temperature, it was extracted with ethyl acetate (120 ml once) and water (120 ml three times each time). The organic phase was dried with anhydrous sodium sulfate and concentrated to obtain crude NTPD-3-M6. The crude product was recrystallized from acetone, and the resulting solid was dried after filtration to obtain NTPD-3-M6. The proton NMR spectrum and high-resolution mass spectra of NTPD-3-M6 were analyzed as follows:1 H NMR (400MHz, CDCl3) δ9.08 (d, 1H), 8.97 (d, 2H), 8.84 (s, 1H), 8.35 (d, 2H), 8.27 (s, 1H), 8.05 (s, 1H), 7.90 (d, 1H), 7.84 ( d, 2H), 7.75 (d, 1H), 7.70-7.68 (m, 2H), 7.64-7.63 (dd, 2H), 7.59 (dd, 2H), 7.53 (dd, 2H), 7.50-7.49 (m, 4H), 7.25 (m, 4H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 46 H 28 N2S, 640.80, found: 640.64. Elemental Analysis: C, 86.22; H, 4.40; N, 4.37; S, 5.00.

[0047] Synthesis of NTPD-3: NTPD-3-M6 (14.5 g, 25 mmol) and anhydrous ethanol (80 mL) were added to a glass reaction flask, followed by ferric oxide (0.57 g, 0.25 mmol). The mixture was stirred until dissolved, and then 30% hydrogen peroxide (22.6 g, 200 mmol) was added dropwise (at a dropping rate of 5.5 g / min). The mixture was stirred at 75 °C for 4 h, then allowed to return to room temperature. The reaction solution was filtered and washed successively with methanol and 10% hydrochloric acid, completing one washing operation. This washing operation was repeated three times in total. The solution was then dried to obtain NTPD-3. The proton NMR spectrum and high-resolution mass spectrometry of NTPD-3 are as follows: 1 H NMR (400MHz, CDCl3) δ9.08 (d, 1H), 9.02 (s, 1H), 8.95 (d, 2H), 8.84 (s, 1H), 8.35 (d, 2H), 8.27 (s, 1H), 8.05 (s, 1H), 7.90 (d, 1H), 7.84 ( d, 2H), 7.70 (d, 1H), 7.68 (dd, 1H), 7.64-7.63 (dd, 2H), 7.61 (d, 1H), 7.53-7.52 (dd, 3H), 7.50-7.49 (m, 4H), 7.46 (d, 1H), 7.25 (m, 4H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 46 H 28N2O2S, 672.80, found: 672.63. Elemental Analysis: C, 82.12; H, 4.19; N, 4.16; O, 4.76; S, 4.77.

[0048] Example 4

[0049] Synthesis of a bipolar optoelectronic material NTPD-4:

[0050]

[0051] Compared to the synthesis of NDPT-1 in Example 1, steps 1 to 4 remain unchanged, and the remaining steps are as follows:

[0052] Synthesis of NDPT-4-M5: NDPT-1-M4 (17.34 g, 50 mmol), potassium carbonate (20.7 g, 150 mmol), tetrabutylammonium chloride (1.38 g, 0.5 mmol), and 1,4-dioxane (120 ml) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Subsequently, naphthaleneborate (13.89 g, 55 mmol) and 1,1′-bis(di-phenylphosphino)ferrocene palladium chloride (0.4 g, 0.5 ml) were added. The reaction mixture was refluxed at 88℃ for 12 h. After the reaction solution was brought to room temperature, it was extracted with ethyl acetate (120 ml each time) and water (120 ml each time, three times). The organic phase was dried over anhydrous sodium sulfate and concentrated to obtain crude NDPT-4-M5. The crude product was purified by column chromatography using silica gel column chromatography (petroleum ether: ethyl acetate, V / V = 14:1). The eluent containing NDPT-4-M5 was collected, and the organic solvent was removed to obtain NDPT-4-M5. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-4-M5 are as follows: 1 H NMR (400MHz, CDCl3) δ8.97 (d, 1H), 8.54 (dd, 1H), 8.25 (d, 1H), 8.15 (d, 1H), 8.10 (d, 1H), 8.00-7 .99 (m, 2H), 7.84 (d, 2H), 7.80-7.78 (d, 2H), 7.61-7.59 (m, 2H), 7.53-7.52 (m, 4H), 7.49 (dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 30 H 18 N2S, 438.55, found: 438.32. Elemental Analysis: C, 82.16; H, 4.14; N, 6.39; S, 7.31.

[0053] Synthesis of NDPT-4-M6: Synthesis of NDPT-1-M6: NDPT-1-M5 (14.5 g, 25 mmol) and anhydrous ethanol (80 ml) were added to a glass reaction flask, followed by ferric oxide (0.57 g, 0.25 mmol). The mixture was stirred until dissolved, and then 30% hydrogen peroxide (22.6 g, 200 mmol) was added dropwise (dropping rate 5.5 g / min). The mixture was stirred at 75 °C for 4 h, then allowed to return to room temperature. The reaction solution was filtered and washed successively with methanol and 10% hydrochloric acid, completing one washing operation. This washing operation was repeated three times in total. The solution was then dried to obtain NDPT-1-M6. The proton NMR spectrum and high-resolution mass spectrometry of NDPT-1-M6 are as follows: 1 H NMR (400MHz, CDCl3) δ8.97 (d, 2H), 8.57 (dd, 1H), 8.25 (d, 1H), 8.15 (d, 2H), 8.10-8.0 8 (d, 2H), 8.00 (dd, 1H), 7.84 (d, 2H), 7.59 (dd, 2H), 7.53-7.52 (m, 4H), 7.49 (dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 30 H 18 N2O2S, 470.55, found: 470.32. Elemental Analysis: C, 76.58; H, 3.86; N, 5.95; O, 6.80; S, 6.81.

[0054] Synthesis of NDPT-4-M7: NDPT-4-M6 (14.5 g, 25 mmol) and chlorobenzene (100 ml) were added to a reaction flask. Then, dibromohydantoin (14 g, 25 mmol) was added in two batches (7 g each, 10 min apart). The temperature was controlled below 50°C during the addition process (45°C in this example). After the addition was complete, the temperature was raised to 80°C and reacted for 6 h. After the reaction solution was brought to room temperature, it was poured into a 10% hydrochloric acid aqueous solution, followed by filtration. The resulting filter cake was washed with methanol and dried to obtain NTPD-4-M7. The proton NMR spectrum and high-resolution mass spectrometry of NTPD-4-M7 are as follows: 1H NMR (400MHz, CDCl3) δ8.97-8.96 (d, 2H), 8.64 (s, 1H), 8.25-8.23 (d, 2H), 8.15 (d, 1H), 8.10 (d , 1H), 8.00(dd, 1H), 7.84(d, 2H), 7.63(d, 1H), 7.59(dd, 2H), 7.53-7.52(m, 3H), 7.49(dd, 1H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 30 H 17 BrN2O2S, 549.44, found: 549.13. Elemental Analysis: C, 65.58; H, 3.12; Br, 14.54; N, 5.10; O, 5.82; S, 5.84.

[0055] Synthesis of NDPT-4: NDPT-4-M7 (13.82 g, 25 mmol), potassium carbonate (10.35 g, 75 mmol), tetrabutylammonium bromide (1.61 g, 0.5 mmol), toluene (120 ml), and water (6 ml) were added to a glass reaction flask. The mixture was purged with nitrogen three times. Then, (4-(phenanthrene-9-yl)phenyl)boronic acid (17.88 g, 60 mmol) and 1,1′-bis(di-phenylphosphino)ferrocene palladium chloride (0.4 g, 0.5 mmol) were added. The mixture was refluxed at 110 °C for 20 h. After the reaction solution was brought to room temperature, it was extracted with ethyl acetate (150 ml once) and water (150 ml three times each time). The organic phase was dried with anhydrous sodium sulfate and concentrated to obtain crude NDPT-4. The crude product was recrystallized from acetone, and the resulting solid was dried after filtration to obtain NDPT-4. The proton NMR spectrum and high-resolution mass spectra of NDPT-4 were analyzed as follows: 1 H NMR (400MHz, CDCl3) δ9.08 (d, 1H), 9.02 (s, 1H), 8.97-8.95 (m, 2H), 8.84 (d, 1H), 8.27-8.25 (d, 2H), 8.10 (d, 1H), 8.05 (d, 1H), 8.00 (d, 1H), 7. 90(d,1H),7.84(d,2H),7.70-7.68(m,2H),7.64-7.63(d,2H),7.61(s, 1H), 7.59(dd, 1H), 7.53-7.52(m, 4H), 7.49-7.46(dd, 2H), 7.25(d, 4H). HRMS(ESI,Positive)(m / z):[M] + Calculated for:C 50 H30 N2O2S, 722.86, found: 722.52. Elemental Analysis:,83.08;H,4.18;N,3.88;O,4.43;S,4.44.

[0056] Application examples

[0057] To verify whether the properties of the bipolar optoelectronic materials prepared in Examples 1-4 of this application meet the requirements of organic electroluminescent devices, the applicant used the bipolar optoelectronic materials prepared in Examples 1-4 of this application as the main material of the light-emitting layer to prepare organic electroluminescent devices 1-4 and test their corresponding performance.

[0058] The fabrication method of organic electroluminescent devices includes the following steps:

[0059] (1) The glass plate coated with ITO transparent conductive layer was ultrasonically treated in commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in acetone:ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until the moisture was completely removed, cleaned with ultraviolet light and ozone, and bombarded with low-energy cation beam.

[0060] (2) Place the glass substrate with the anode into a vacuum chamber and evacuate to 1×10⁻⁶. -5 -9×10 -3 Pa, HATCN is vacuum-deposited on the above-mentioned anolyte film as the first hole injection layer at a deposition rate of 0.1 nm / s and a total film thickness of 2 nm; then, the second hole injection layer HT01 is deposited at a deposition rate of 0.1 nm / s and a thickness of 50 nm.

[0061] (3) An NPB layer is deposited on the hole injection layer as a hole transport layer at a deposition rate of 0.1 nm / s and a deposition thickness of 25 nm.

[0062] (4) Continue to deposit the bipolar optoelectronic material NTPD-1 provided in Example 1 as the main material on the hole transport layer. The deposition rate is 0.1 nm / s. Ir(piq)2acac is used as the dopant material (i.e. the light-emitting material) with a doping concentration of 5% to form the organic light-emitting layer of the device. The total film thickness of the organic light-emitting layer obtained by deposition is 30 nm.

[0063] (5) A compound BCP is deposited on the organic light-emitting layer as an electron transport layer of the device. The deposition rate is 0.1 nm / s and the deposition film thickness is 30 nm.

[0064] (6) A LiF layer is deposited on top of the electron transport layer as the electron injection layer of the device, with a deposition thickness of 0.5 nm;

[0065] (7) A layer of Al is deposited on top of the electron injection layer as the cathode of the device. The thickness of the deposited film is 130 nm, and the OLED device 1 provided by the present invention is obtained.

[0066] According to the preparation method of OLED device 1, the bipolar optoelectronic material NTPD-1 in step (4) is replaced with bipolar optoelectronic material NTPD-2, bipolar optoelectronic material NTPD-3 and bipolar optoelectronic material NTPD-4 respectively, and then OLED device 2, OLED device 3 and OLED device 4 are obtained respectively.

[0067] Application of comparative examples

[0068] According to the preparation method of OLED device 1, the bipolar optoelectronic material NTPD-1 in step (4) is replaced with comparative compound 1 (structure shown below) to obtain comparative device 1.

[0069]

[0070] Performance testing

[0071] The performance of devices 1-4 and control device 1 prepared above were tested respectively, and the test results are shown in Table 1 below:

[0072] Table 1:

[0073]

[0074] As shown in Table 1 above, the bipolar optoelectronic materials prepared in Examples 1-4 are used to fabricate organic electroluminescent devices. The devices 1-4 prepared have higher current efficiency, and under current density conditions, the operating voltage is significantly lower than that of the comparative device using compound 1 as the organic light-emitting host material.

[0075] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A bipolar optoelectronic material, characterized in that, The bipolar optoelectronic material has the following general formula: 。 2. An application of the bipolar optoelectronic material as described in claim 1, characterized in that, The bipolar optoelectronic material is used in organic electroluminescent devices or organic field-effect transistors.

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