A fused ring compound and use thereof

Abstract

The application relates to the technical field of light-emitting materials and devices, and discloses a fused ring compound and application thereof, wherein the structure general formula of the fused ring organic material is shown as formula (I). The fused ring compound has high rigidity, a stable structure and high light-emitting performance, and can utilize singlet and triplet excitons to emit light at the same time. The fused ring compound can be applied to the preparation of an organic electroluminescent device, and the device obtained by the application has a low turn-on voltage, high light-emitting brightness, excellent power efficiency and external quantum efficiency, and exhibits excellent electroluminescent performance.

Description

Technical Field

[0001] This invention relates to the field of luminescent materials and devices, and more specifically, to a fused ring compound and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a new generation of display technology with significant advantages such as high efficiency, energy saving, environmental protection and flexible display. They are expected to replace traditional liquid crystal display technology and be widely used in the display and lighting fields, with a very promising development prospect.

[0003] OLED devices resemble a sandwich structure, consisting of a cathode, an anode, and an organic functional layer in between. When a voltage is applied across the electrodes, positive and negative charges are injected from the anode and cathode, respectively, then flow through the functional layers, ultimately recombine in the emissive layer to form excitons and emit light. The performance of OLED devices largely depends on the emissive layer material. Currently, emissive materials can be mainly classified into three categories: fluorescent, phosphorescent, and delayed-fluorescence materials. The development of organic light-emitting materials, from traditional fluorescent materials to phosphorescent and delayed-fluorescence materials, has significantly improved device performance, greatly driving the advancement of OLED technology. However, with the increasing demands of the display industry, the requirements for the performance of organic light-emitting materials are also rising, and the current level of material development is still insufficient to meet the application needs of OLEDs.

[0004] Therefore, the development of high-performance organic light-emitting materials is of particular importance. Summary of the Invention

[0005] In view of this, the present invention proposes a fused ring compound and its application, aiming to solve the problems in the current technology.

[0006] This invention proposes a fused-ring organic material, the general structural formula of which is shown in formula (I):

[0007]

[0008] Where X is C or N;

[0009] Y is either C or S. When Y is C, i is 1; when Y is S, i is 2.

[0010] R is each independently one of hydrogen, halogen, cyano, substituted or unsubstituted C1-C30 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 aliphatic chain aminyl, substituted or unsubstituted C4-C30 cyclic aliphatic chain aminyl, substituted or unsubstituted C6-C30 aryl aminyl, substituted or unsubstituted C3-C30 heteroaryl aminyl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C60 aryl boryl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl.

[0011] Preferably, the fused ring organic compound has a structure as shown in formula (II), formula (III) or formula (IV):

[0012]

[0013]

[0014] In formula (II), formula (III) or formula (IV), R1, R2, R3, R4, R5, R6, R7, R8, R9 are each independently one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C2-C30 aliphatic chain aminyl, substituted or unsubstituted C4-C30 cyclic aliphatic chain aminyl, substituted or unsubstituted C6-C30 aryl aminyl, substituted or unsubstituted C3-C30 heteroaryl aminyl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C60 aryl boryl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl.

[0015] Preferably, R1, R2, R3, R4, R5, R6, R7, R8, R9 are each independently methyl, ethyl, methoxy, cyano, halogen, t-butyl, phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, chrysenyl, fluoranthenyl, xanthenyl, pyronyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, biphenyl, terphenyl, triphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, triindenyl, isotriindenyl, spirotrindenyl, spiroisotriindenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, pyridimidazolyl, pyrazimidazolyl, quinoximidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazanthrenyl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazachrysenyl, pyrazinyl, phenoxazinyl, phenothiazinyl, naphthidinyl, azacarbazolyl, benzocarbolinyl, phenanthrolineyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, diphenylboron, dimethylboron, dipentafluorophenylboron, and di(2,4,6-triisopropylphenyl)boron.

[0016] Preferably, the fused ring organic compound has the following structure:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] The present application also provides an application of any of the above fused ring organic compounds, comprising at least one of the following:

[0025] A1) an application of any of the above fused ring organic compounds in preparing an organic light-emitting material;

[0026] A2) an application of any of the above fused ring organic compounds in preparing a light-emitting device;

[0027] A3) an application of any of the above fused ring organic compounds in preparing an organic electronic device;

[0028] A4) an application of any of the above fused ring organic compounds in a light-emitting device as at least one light-emitting functional layer.

[0029] Preferably, the organic electronic device is an organic electroluminescent device, an optical sensor, a solar cell, an illumination element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, a sheet-type scanner or electronic paper.

[0030] The present application also provides a light-emitting device comprising an anode, a light-emitting functional layer and a cathode;

[0031] wherein the light-emitting functional layer comprises any of the above fused ring organic compounds.

[0032] Preferably, the light-emitting device is an organic electroluminescent device.

[0033] Preferably, the light-emitting functional layer comprises a hole transport layer, a hole blocking layer, a light-emitting layer, an electron transport layer and an electron blocking layer.

[0034] The light-emitting functional layer comprises any of the above fused ring organic compounds.

[0035] Preferably, the material of the anode is one or more of indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2) and zinc oxide (ZnO).

[0036] Preferably, the material of the cathode is preferably one or more of magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In) and magnesium-silver (Mg-Ag).

[0037] Preferably, the hole transport zone is a single-layer hole transport layer or a multi-layer hole transport layer; wherein the single-layer hole transport layer comprises a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds; and the multi-layer hole transport layer comprises one or more layers of a hole injection layer (HIL), a hole transport layer (HTL) and an electron blocking layer (EBL).

[0038] Preferably, the light-emitting layer comprises light-emitting dyes (i.e. dopants) emitting different wavelengths of light.

[0039] More preferably, the light-emitting layer further comprises a sensitizer and a host material.

[0040] More preferably, the light-emitting layer is preferably a single-color light-emitting layer emitting red, green, blue and the like single color;

[0041] The single-color light-emitting layers of multiple different colors are arranged in a planar manner according to a pixel pattern, or are stacked together to form a color light-emitting layer.

[0042] When the light-emitting layers of different colors are stacked together, they are separated from each other or connected to each other.

[0043] More preferably, the light-emitting layer is a single-color light-emitting layer with the function of emitting different colors at the same time.

[0044] Preferably, the electron transport zone is a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds.

[0045] More preferably, the electron transport zone is a structure comprising one or more layers of an electron injection layer (EIL), an electron transport layer (ETL) and a hole blocking layer (HBL).

[0046] The preparation process of the organic electroluminescent device is as follows: sequentially depositing an anode, a hole transport layer, a light-emitting layer, an electron transport layer and a cathode on a substrate, and then performing packaging.

[0047] Preferably, in the preparation process of the light-emitting layer, a host material is co-evaporated with the fused-ring organic compound involved in the present application, or only a single fused-ring organic compound is evaporated.

[0048] The present application also provides a light-emitting material, which comprises any of the fused-ring organic compounds described above.

[0049] Compared with the prior art, the present application has the following advantages:

[0050] Firstly, the fused-ring organic compounds disclosed in the present application have unique molecular structures and electronic properties, which enable them to exhibit excellent performance in the preparation of organic light-emitting materials, light-emitting devices, and organic electronic devices. Their unique optoelectronic properties make these compounds ideal choices for the preparation of high-efficiency, stable, and color-rich light-emitting devices.

[0051] Secondly, by applying the fused-ring organic compounds of the present application to light-emitting devices, significant improvements in device performance can be achieved. For example, in organic electroluminescent devices, these compounds can serve as key components of the light-emitting functional layer, thereby improving the luminous efficiency, color purity, and stability of the device. Moreover, due to their low excitation energy and high fluorescence quantum yield, these compounds can also achieve high-brightness emission at a lower driving voltage, thereby helping to reduce the energy consumption of the device.

[0052] Furthermore, the fused-ring organic compounds of the present application also have good solubility and film-forming properties, which make them easy to handle and process during the preparation process. Through solution methods, vacuum evaporation methods, or other suitable processes, these compounds can be conveniently introduced into the structure of light-emitting devices, thereby enabling mass production and commercialized application of the devices.

[0053] In addition, the light-emitting materials of the present application, due to the inclusion of the aforementioned fused-ring organic compounds, also have excellent light-emitting performance. These light-emitting materials can be widely applied in various display and lighting fields, such as flat-panel displays, flexible displays, lighting fixtures, etc.

[0054] In summary, the fused-ring organic compounds and their applications of the present application have significant technical advantages and innovations, and are expected to bring new breakthroughs and progress to the development of organic light-emitting materials and light-emitting devices. BRIEF DESCRIPTION OF DRAWINGS

[0055] Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The accompanying drawings are included to provide a description of the preferred embodiments and are not intended to limit the scope of the application. Moreover, like reference numerals designate like parts throughout the several views in the drawings. In the drawings:

[0056] Figure 1 is a synthetic route of compound C01;

[0057] Figure 2 is a synthetic route of compound C45;

[0058] Figure 3 is a synthetic route of compound C46;

[0059] Figure 4 is a synthetic route of compound C50;

[0060] Figure 5 Synthetic route of compound C51;

[0061] Figure 6 Synthetic route of compound C52;

[0062] Figure 7 Synthetic route of compound C53;

[0063] Figure 8 Synthetic route of compound C54;

[0064] Figure 9 Synthetic route of compound C55;

[0065] Figure 10 Synthetic route of compound C56;

[0066] Figure 11 Spectrum of an organic electroluminescent device prepared using compound C01 of Example 1;

[0067] Figure 12 Spectrum of an organic electroluminescent device prepared using compound C45 of Example 2;

[0068] Figure 13 Spectrum of an organic electroluminescent device prepared using compound C46 of Example 3. DETAILED DESCRIPTION

[0069] Exemplary embodiments of the present disclosure will be described in detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it is to be understood that the present disclosure can be embodied in various forms without being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present disclosure to those skilled in the art. It should be noted that the embodiments in the present disclosure and the features in the embodiments can be combined with each other without conflict, and the present disclosure will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0070] Synthesis of compound C01 of Example 1

[0071] The synthetic route of compound C01 is shown in Figure 1 .

[0072] 1. Synthesis of intermediate 1

[0073] Dimethyl 2-bromoisophthalate (10 mmol), phenothiazine (12 mmol), copper powder (1 mmol), copper iodide (1 mmol), potassium carbonate (20 mmol) were added to a two-necked flask, purged with nitrogen three times, 2,2,6,6-tetramethyl-3,5-heptanedione (1 mmol) and dibutyl ether (100 mL) were added, and the temperature was raised to 160 °C for 24 h. After cooling to room temperature, the reaction solution was poured into a large amount of water, extracted with dichloromethane, concentrated, and passed through a column to obtain yellow intermediate 1 in 73% yield.1H NMR (500 MHz, DMSO-d6) δ 8.24 (d, J = 7.8 Hz, 2H), 7.83 (t, J = 7.8 Hz, 1H), 6.98 - 6.92 (m, 2H), 6.84 - 6.78 (m, 4H), 5.81 - 5.76 (m, 2H), 3.66 (s, 6H);13C NMR (125 MHz, DMSO-d6) δ 164.24, 142.42, 138.04, 136.82, 136.45, 127.52, 126.59, 122.91, 122.76, 118.41, 115.56, 53.32.

[0074] 6.72 (m, 4H), 5.81 - 5.76 (m, 2H), 3.66 (s, 6H);13C NMR (125 MHz, DMSO-d6) δ 164.24, 142.42, 138.04, 136.82, 136.45, 127.52, 126.59, 122.91, 122.76, 118.41, 115.56, 53.32.

[0075] 2. Synthesis of Intermediate 2

[0076] Intermediate 1 (5 mmol) was added to a two-necked flask, NaOH (50 mmol), tetrahydrofuran (70 mL) and water (30 mL) were added, and refluxed for 12 h. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and the pH was adjusted to acidic by adding dilute hydrochloric acid to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, purged with nitrogen three times, added with oxalyl chloride (15 mmol), dichloromethane (50 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops). After refluxing for 4 h, tin tetrachloride (15 mmol) was added, and the reaction was continued for 4 h. After the reaction was completed, the reaction solution was poured into a NaOH solution, and washed with water and dichloromethane several times in turn. The product was dried to obtain red intermediate 2 in 75% yield.1H NMR (500 MHz, Methylene Chloride-d2) δ 9.67 (d, J = 7.3 Hz, 2H), 8.96 (d, J = 7.8 Hz, 2H), 8.45 (s, 1H), 8.18 - 7.97 (m, 4H).

[0077] 3. Synthesis of Compound C01

[0078] Intermediate 2 (2 mmol) was added to two flasks, glacial acetic acid (20 mL), dichloromethane (20 mL) and 30% concentration of hydrogen peroxide (5 mL) were added, and the reaction was refluxed under air for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water, and after suction filtration, it was washed with dichloromethane several times to obtain compound C01 with a yield of 80%.1H NMR (500 MHz, DMSO-d6) δ 8.95 (d, J = 7.5 Hz, 2H), 8.93-8.89 (m, 2H), 8.85-8.81 (m, 2H), 8.05-7.96 (m, 3H). Synthesis of compound C45 of Example 2.

[0079] Synthesis of compound C45 of Example 2

[0080] The synthesis route of compound C45 is shown in Figure 2

[0081] 1. Synthesis of intermediate 3

[0082] 5-bromo-2-iodoisophthalic acid dimethyl ester (10 mmol), phenothiazine (12 mmol), copper powder (1 mmol), cuprous iodide (1 mmol), potassium carbonate (20 mmol) were added to two flasks, nitrogen was replaced for 3 times, 2,2,6,6-tetramethyl-3,5-heptanedione (1 mmol) and dibutyl ether (100 mL) were added, and the reaction was heated to 160°C for 24 hours. After cooling to room temperature, the reaction solution was poured into a large amount of water, extracted with dichloromethane, concentrated and powdered to obtain yellow intermediate 3 with a yield of 82%.1H NMR (500 MHz, DMSO-d6) δ 8.41 (s, 2H), 7.01-6.95 (m, 2H), 6.86-6.75 (m, 4H), 5.90-5.84 (m, 2H), 3.66 (s, 6H);13C NMR (125 MHz, DMSO-d6) δ 165.53, 142.70, 137.65, 135.59, 134.37, 130.35, 127.44, 126.53, 122.68, 118.28, 115.36, 53.05.

[0083] 2. Synthesis of intermediate 4

[0084] ​Compound 3 (5 mmol) was added to two flasks, purged with nitrogen 3 times, N,N- dimethylformamide (50 mL) and bromosuccinimide (15 mmol) were added and the reaction was allowed to proceed for 2 hours. After this time the reaction was allowed to warm to room temperature and continue for 2 hours. After the reaction was complete the reaction was poured into a large volume of water and extracted with dichloromethane. The reaction was concentrated and passed through a plug of silica to give yellow intermediate 4 in 72% yield.1H NMR (500 MHz, DMSO-d6) δ 8.45 (s, 2H), 7.21 (d, J = 2.3 Hz, 2H), 7.01 - 6.96 (m, 2H), 5.79 (d, J = 8.8 Hz, 2H), 3.71 (s, 6H);13C NMR (125 MHz, DMSO-d6) δ 163.94, 141.48, 138.56, 136.09, 135.71, 130.33, 128.49, 123.33, 120.35, 117.27, 114.39, 53.49.

[0085] 3. Synthesis of intermediate 5

[0086] Intermediate 4 (3 mmol), 4-tert-butylphenylboronic acid (9 mmol), tetrakis(triphenyl- phosphine)palladium (0.15 mmol), potassium carbonate (6 mmol) were added to two flasks, purged with nitrogen 3 times. Toluene (60 mL) and water (20 mL) were added and the reaction was allowed to reflux for 12 hours. After the reaction was complete the reaction was poured into a large volume of water and extracted with dichloromethane. The reaction was concentrated and passed through a plug of silica to give yellow intermediate 5 in 70% yield.1H NMR (400 MHz, DMSO-d6) δ 8.50 (s, 2H), 7.81 (d, J = 8.3 Hz, 2H), 7.64 - 7.57 (m, 2H), 7.51 (d, J = 8.4 Hz, 4H), 7.42 (d, J = 8.4 Hz, 4H), 7.28 (d, J = 2.2 Hz, 2H), 7.17 - 7.11 (m, 2H), 5.96 (d, J = 8.6 Hz, 2H), 3.73 (s, 6H), 1.36 (s, 9H), 1.29 (s, 18H);13C NMR (100 MHz, DMSO-d6) δ 166.21, 152.09, 149.97, 141.70, 136.24, 134.91, 134.77, 134.47, 133.07, 127.34, 126.60, 126.09, 126.00, 125.43, 124.24, 118.81, 115.83, 110.85, 109.06, 53.22, 34.92, 34.68, 31.56, 31.53.

[0087] 4. Synthesis of intermediate 6

[0088] Intermediate 5 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added, and the reaction was refluxed for 12 h. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and the pH was adjusted to acidic by adding dilute hydrochloric acid to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, replaced with nitrogen for 3 times, and oxalyl chloride (6 mmol), dichloromethane (30 mL) and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 h, tin tetrachloride (6 mmol) was added, and the reaction was continued for 4 h. After the reaction was completed, the reaction solution was poured into a NaOH solution, and washed with water and dichloromethane several times in turn. The product was dried to obtain red intermediate 6 with a yield of 55%.1H NMR (500 MHz, Methylene Chloride-d2) δ 9.16 (s, 2H), 8.43 (d, J = 2.3 Hz, 2H), 7.80 (d, J = 7.9 Hz, 2H), 7.64 (d, J = 8.0 Hz, 4H), 7.60 - 7.56 (m, 4H), 7.56 - 7.51 (m, 4H), 1.41 (s, 9H), 1.39 (s, 18H).

[0089] 5. Synthesis of compound C45

[0090] Intermediate 6 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL) and 30% concentration hydrogen peroxide (3 mL) were added, and the reaction was refluxed for 12 h under air. After the reaction was completed, the reaction solution was poured into a large amount of water, extracted with dichloromethane, dried by rotary evaporation and powdered on a column to obtain compound C45 with a yield of 80%.1H NMR (500 MHz, Chloroform-d) δ 9.09 (s, 2H), 9.03 (d, J = 2.5 Hz, 2H), 8.77 (d, J = 2.5 Hz, 2H), 7.75 - 7.71 (m, 6H), 7.59 - 7.55 (m, 6H), 1.44 (s, 18H), 1.43 (s, 9H);13C NMR (125 MHz, CDC13) δ 174.91, 152.56, 152.20, 138.90, 138.39, 136.47, 134.00, 133.44, 132.91, 132.66, 131.18, 128.00, 126.89, 126.79, 126.45, 126.35, 125.47, 123.51, 123.14, 34.82, 34.77, 31.35.

[0091] Example 3 Synthesis of compound C46

[0092] The synthesis route of compound C46 is as followsFigure 3 as shown.

[0093] 1. Synthesis of Intermediate 7

[0094] Intermediate 4 (3 mmol), 3,5-di-tert-butylphenylboronic acid (9 mmol), tetrakis(triphenylphosphine)palladium (0.15 mmol), potassium carbonate (6 mmol) were added to a two-necked flask and replaced with nitrogen three times. Toluene (60 mL) and water (20 mL) were added and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water, extracted with dichloromethane, concentrated and passed through a column to obtain yellow intermediate 7 with a yield of 63%.1H NMR (400 MHz, Methylen Chloride-d2) δ 8.46 (s, 2H), 7.60 (d, J = 1.7 Hz, 2H), 7.54 (s, 1H), 7.36 - 7.31 (m, 6H), 7.29 (d, J = 2.1 Hz, 2H), 7.16 - 7.11 (m, 2H), 6.02 (d, J = 8.0 Hz, 2H), 3.74 (s, 6H), 1.39 (s, 18H), 1.32 (s, 36H);13C NMR (100 MHz, CD2Cl2) δ 168.46, 154.68, 154.05, 145.96, 144.64, 141.53, 140.48, 138.97, 138.69, 137.72, 136.42, 128.83, 127.55, 125.80, 124.81, 124.06, 123.59, 121.74, 118.73, 56.08, 38.11, 37.93, 34.58.

[0095] 2. Synthesis of Intermediate 8

[0096] Intermediate 7 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added, and the reaction was refluxed for 12 h. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and the pH was adjusted to acidic by adding dilute hydrochloric acid to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, replaced with nitrogen for 3 times, and oxalyl chloride (6 mmol), dichloromethane (30 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 h, tin tetrachloride (6 mmol) was added, and the reaction was continued for 4 h. After the reaction was completed, the reaction solution was poured into a NaOH solution, and washed with water and dichloromethane several times in turn. The product was dried to obtain red intermediate 8 in a yield of 60%.1H NMR (500 MHz, Methy lene Ch l oride-d2) δ 9.23 (s, 2H), 8.50 (d, J = 2.5 Hz, 2H), 7.68 (t, J = 2.1 Hz, 4H), 7.56 (s, 1H), 7.54 (s, 6H), 1.44 (s, 18H), 1.42 (s, 36H).

[0097] 3. Synthesis of compound C46

[0098] Intermediate 8 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL), and 30% concentration hydrogen peroxide (3 mL) were added, and the reaction was refluxed for 12 h under air. After the reaction was completed, the reaction solution was poured into a large amount of water, extracted with dichloromethane, and concentrated to pass through a column to obtain yellow solid compound C46 in a yield of 75%.1H NMR (500 MHz, Ch loroform-d) δ 9.33 (s, 2H), 9.23 (d, J = 2.5 Hz, 2H), 8.96 (d, J = 2.5 Hz, 2H), 7.69 (d, J = 1.7 Hz, 2H), 7.62 (d, J = 1.8 Hz, 4H), 7.61 - 7.58 (m, 3H), 1.45 (s, 18H), 1.45 (s, 36H);13C NMR (125 MHz, CDC13) δ 175.65, 152.23, 152.12, 140.74, 140.16, 137.11, 136.86, 136.41, 133.57, 133.28, 131.87, 128.63, 125.85, 123.99, 123.63, 123.45, 123.17, 121.72, 121.65, 35.17, 31.54.

[0099] Example 4 Synthesis of compound C50

[0100] The synthesis route of compound C50 is shown in Figure 4 .

[0101] 1. Synthesis of Intermediate 9

[0102] Intermediate 4 (3 mmol), carbazole (9 mmol), tris(dibenzylideneacetone)dipalladium (0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 mmol), sodium tert-butoxide (6 mmol) were added to a two-necked flask and purged with nitrogen three times. Toluene (60 mL) was added and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain Intermediate 9. MS = 886.3.

[0103] 2. Synthesis of Intermediate 10

[0104] Intermediate 9 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added and the reaction was refluxed for 12 hours. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and dilute hydrochloric acid was added to adjust the pH to acidic to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, purged with nitrogen three times, and oxalyl chloride (6 mmol), dichloromethane (30 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 hours, stannic chloride (6 mmol) was added and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was poured into a NaOH solution and washed with water and dichloromethane several times. The product was dried to obtain Intermediate 10. MS = 822.3.

[0105] 3. Synthesis of Compound C50

[0106] Intermediate 10 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL), and 30% concentration hydrogen peroxide (3 mL) were added and the reaction was refluxed under air for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain yellow solid Compound C50. MS = 854.2.

[0107] Example 5 Synthesis of Compound 51

[0108] The synthesis route of Compound 51 is shown in Figure 5 .

[0109] 1. Synthesis of Intermediate 11

[0110] Intermediate 4 (3 mmol), 4-methylcarbazole (9 mmol), tris(dibenzylideneacetone)dipalladium (0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 mmol), sodium tert-butoxide (6 mmol) were added to a two-necked flask and purged with nitrogen three times. Toluene (60 mL) was added and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain intermediate 11. MS = 970.4.

[0111] 2. Synthesis of intermediate 12

[0112] Intermediate 11 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added and the reaction was refluxed for 12 hours. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and dilute hydrochloric acid was added to adjust the pH to acidic to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, purged with nitrogen three times, and oxalyl chloride (6 mmol), dichloromethane (30 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 hours, stannic chloride (6 mmol) was added and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was poured into a NaOH solution and washed with water and dichloromethane several times. The product was dried to obtain intermediate 12. MS = 906.3.

[0113] 3. Synthesis of compound C51

[0114] Intermediate 12 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL), and 30% hydrogen peroxide (3 mL) were added and the reaction was refluxed for 12 hours under air. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain yellow solid compound C51. MS = 938.3.

[0115] Example 6 Synthesis of compound C52

[0116] The synthesis route of compound C52 is shown in Figure 6 .

[0117] 1. Synthesis of intermediate 13

[0118] Intermediate 4 (3 mmol), 4-tert-butylcarbazole (9 mmol), tris(dibenzylideneacetone)dipalladium (0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 mmol), sodium tert-butoxide (6 mmol) were added to a two-necked flask and purged with nitrogen three times. Toluene (60 mL) was added and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain intermediate 13. MS = 1222.6.

[0119] 2. Synthesis of intermediate 14

[0120] Intermediate 13 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added and the reaction was refluxed for 12 hours. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and dilute hydrochloric acid was added to adjust the pH to acidic to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, purged with nitrogen three times, and oxalyl chloride (6 mmol), dichloromethane (30 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 hours, stannic chloride (6 mmol) was added and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was poured into a NaOH solution and washed with water and dichloromethane several times. The product was dried to obtain intermediate 14. MS = 1158.6.

[0121] 3. Synthesis of compound C52

[0122] Intermediate 14 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL), and 30% hydrogen peroxide (3 mL) were added and the reaction was refluxed for 12 hours under air. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain yellow solid compound C52. MS = 1190.6.

[0123] Example 7 Synthesis of compound C53

[0124] The synthesis route of compound C53 is shown in Figure 7 .

[0125] 1. Synthesis of intermediate 15

[0126] Intermediate 4 (3 mmol), diphenylamine (9 mmol), tris(dibenzylideneacetone)dipalladium (0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 mmol), sodium tert-butoxide (6 mmol) were added to a two-necked flask and purged with nitrogen three times. Toluene (60 mL) was added and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain intermediate 15. MS = 892.3.

[0127] 2. Synthesis of intermediate 16

[0128] Intermediate 15 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added and the reaction was refluxed for 12 hours. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and dilute hydrochloric acid was added to adjust the pH to acidic to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, purged with nitrogen three times, and oxalyl chloride (6 mmol), dichloromethane (30 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 hours, tin tetrachloride (6 mmol) was added and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was poured into a NaOH solution and washed with water and dichloromethane several times. The product was dried to obtain intermediate 16. MS = 828.3.

[0129] 3. Synthesis of compound C53

[0130] Intermediate 16 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL), and 30% hydrogen peroxide (3 mL) were added and the reaction was refluxed for 12 hours under air. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain yellow solid compound C53. MS = 860.3.

[0131] Example 8 Synthesis of compound C54

[0132] The synthesis route of compound C54 is shown in Figure 8

[0133] 1. Synthesis of intermediate 17

[0134] ​Intermediate 4 (3 mmol), 4-tert-butyl diphenylamine (9 mmol), tris(dibenzylideneacetone)dipalladium (0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 mmol), sodium tert-butoxide (6 mmol) were added to a two-necked flask and purged with nitrogen three times. Toluene (60 mL) was added and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain intermediate 17. MS = 1128.7.

[0135] 2. Synthesis of intermediate 18

[0136] Intermediate 17 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added and the reaction was refluxed for 12 hours. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and dilute hydrochloric acid was added to adjust the pH to acidic to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, purged with nitrogen three times, and oxalyl chloride (6 mmol), dichloromethane (30 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 hours, stannic chloride (6 mmol) was added and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was poured into a NaOH solution and washed with water and dichloromethane several times. The product was dried to obtain intermediate 18. MS = 1164.7.

[0137] 3. Synthesis of compound C54

[0138] Intermediate 18 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL), and 30% hydrogen peroxide (3 mL) were added and the reaction was refluxed for 12 hours under air. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain yellow solid compound C54. MS = 1196.7.

[0139] Example 9 Synthesis of compound C55

[0140] The synthesis route of compound C55 is shown in Figure 9 .

[0141] 1. Synthesis of intermediate 19

[0142] Intermediate 4 (3 mmol), 4-methyldiphenylamine (9 mmol), tris(dibenzylideneacetone)dipalladium (0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 mmol), sodium tert-butoxide (6 mmol) were added to a two-necked flask and purged with nitrogen three times. Toluene (60 mL) was added and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain intermediate 19. MS = 976.4.

[0143] 2. Synthesis of intermediate 20

[0144] Intermediate 19 (2 mmol) was added to a two-necked flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added and the reaction was refluxed for 12 hours. After the reaction was completed, the tetrahydrofuran was removed by distillation under reduced pressure, and dilute hydrochloric acid was added to adjust the pH to acidic to precipitate a yellow solid. After drying in a vacuum oven, it was added to a two-necked flask, purged with nitrogen three times, and oxalyl chloride (6 mmol), dichloromethane (30 mL), and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After refluxing for 4 hours, stannic chloride (6 mmol) was added and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was poured into a NaOH solution and washed with water and dichloromethane several times. The product was dried to obtain intermediate 20. MS = 912.4.

[0145] 3. Synthesis of compound C55

[0146] Intermediate 20 (1 mmol) was added to a two-necked flask, glacial acetic acid (10 mL), dichloromethane (10 mL), and 30% hydrogen peroxide (3 mL) were added and the reaction was refluxed for 12 hours under air. After the reaction was completed, the reaction solution was poured into a large amount of water and extracted with dichloromethane. The product was concentrated and passed through a column to obtain yellow solid compound C55. MS = 944.4.

[0147] Example 10 Synthesis of compound C56

[0148] The synthesis route of compound C56 is shown in Figure 10 .

[0149] 1. Synthesis of intermediate 21

[0150] Intermediate 4 (3 mmol), acridine (9 mmol), tris(dibenzylideneacetone)dipalladium (0.15 mmol), tri-tert-butylphosphine tetrafluoroborate (0.15 mmol), sodium tert-butoxide (6 mmol) were added into a two-neck flask, and replaced by nitrogen for 3 times. Toluene (60 mL) was added, and the reaction was refluxed for 12 hours. After the reaction was completed, the reaction solution was poured into a large amount of water, extracted with dichloromethane, concentrated, and columned to obtain intermediate 21. MS = 1012.4.

[0151] 2. Synthesis of intermediate 22

[0152] Intermediate 21 (2 mmol) was added into a two-neck flask, NaOH (20 mmol), tetrahydrofuran (30 mL) and water (10 mL) were added, and the reaction was refluxed for 12 hours. After the reaction was completed, the tetrahydrofuran was removed by rotary evaporation under reduced pressure, and the pH was adjusted to acidic by adding dilute hydrochloric acid to precipitate a yellow solid. After drying in a vacuum oven, it was added into a two-neck flask, replaced by nitrogen for 3 times, and oxalyl chloride (6 mmol), dichloromethane (30 mL) and a catalytic amount of N,N-dimethylformamide (3-4 drops) were added. After the reaction was refluxed for 4 hours, tin tetrachloride (6 mmol) was added, and the reaction was continued for 4 hours. After the reaction was completed, the reaction solution was poured into a NaOH solution, and washed with water and dichloromethane in turn for several times. The product was dried to obtain intermediate 22. MS = 948.4.

[0153] 3. Synthesis of compound C56

[0154] Intermediate 22 (1 mmol) was added into a two-neck flask, glacial acetic acid (10 mL), dichloromethane (10 mL) and 30% hydrogen peroxide (3 mL) were added, and the reaction was refluxed for 12 hours under air. After the reaction was completed, the reaction solution was poured into a large amount of water, extracted with dichloromethane, concentrated, columned to obtain yellow solid compound C56. MS = 980.4.

[0155] Test Example 1

[0156] The photophysical properties of the fused ring organic compounds prepared in Examples 1-10 in solution were determined. The determination method was as follows: the fused ring organic compounds prepared in Examples 1-10 were dissolved in a spectroscopic pure toluene solution, and a 1×10 -5 concentration solution was prepared, and the absorption, emission spectrum and fluorescence quantum yield of the compound in toluene solution were determined by ultraviolet-visible absorption spectrum, fluorescence spectrum and absolute quantum efficiency tester.

[0157] The determination results are shown in Table 1.

[0158] Table 1

[0159]

[0160] Example 1

[0161] The condensed ring compound prepared in Examples 1-3 was used to fabricate an organic electroluminescent device. The fabrication process was as follows: the functional layer materials were evaporated onto the ITO thin film by an evaporation device at a pressure less than 5 x 10 -4 Pa. The evaporation deposition rate of the organic material, LiF and aluminum was 0.1 A / s, 0.1 A / s and 10 A / s, respectively. and The un-encapsulated device was tested for its properties in a room temperature, air environment. The EL spectrum was measured by a Photo research PR-745, the current density- drive voltage- luminance (J-V-L) curve and the emitted CIE color coordinates were tested by a Keithley 2420 combined with a PIN-25D silicon photodiode device, and then the current and power efficiency were calculated. The external quantum efficiency of the device was calculated assuming that the OLED emission was Lambertian.

[0162] Figure 1 The spectrum of the organic electroluminescent device of Example 1 is shown in Figure 1. The emission peak is at 426 nm and the half-peak width is 56 nm.

[0163] Figure 2 The spectrum of the organic electroluminescent device of Example 2 is shown in Figure 2. The emission peak is at 468 nm and the half-peak width is 38 nm.

[0164] Figure 3 The spectrum of the organic electroluminescent device of Example 3 is shown in Figure 3. The emission peak is at 464 nm and the half-peak width is 40 nm.

[0165] Finally, it should be noted that the above examples are merely used to illustrate the technical solutions of the present application but not to limit it. Although the present application has been described in detail with reference to the above examples, those skilled in the art should understand that the specific implementation of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the present application, and any modification or replacement should be covered in the protection scope of the claims of the present application.

Claims

1. A fused ring organic material characterized in that, The structure general formula of the fused ring organic material is shown as formula (II): wherein X is C or N; R1, R2, R3 are the same and are hydrogen, phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzphenanthryl, pyrenyl, chrysenyl, coronenyl, fluoranthenyl, fluorantenyl, pyromellithenyl, pentacenyl, benzopyrenyl, biphenyl, biphenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydropyrenyl, tetrahydropyrenyl, cis or trans indenofluorenyl, triindenyl, isotriindenyl, spirotrindenyl, spiroisotriindenyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, benzothiophenyl, isobenzothiophenyl, dibenzothiophenyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridyl, phenanthridyl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, indazolyl, benzimidazolyl, naphthimidazolyl, phenanthroimidazolyl, pyridimidazolyl, quinoxalimidazolyl, benzoxazolyl, naphthoxazolyl, anthroxazolyl, phenanthroxazolyl, benzothiazolyl, benzopyridazinyl, benzopyrimidinyl, quinoxalyl, 1,5-diazaanthracenyl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetrazachrysenyl, phenoxazinyl, phenothiazinyl, naphthidinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, benzotriazolyl, benzothiadiazolyl.

2. The fused ring organic compound according to claim 1, wherein The structure formula of the fused ring organic compound is: 。 3. Use of the fused ring organic compound according to any one of claims 1 to 2, characterized in that, At least one of the following is included: A1) Use of the fused ring organic compound of any one of claims 1-2 in the preparation of an organic light emitting material; A2) Use of the fused ring organic compound of any one of claims 1-2 in the preparation of a light emitting device; A3) Use of the fused ring organic compound of any one of claims 1-2 in the preparation of an organic electronic device; A4) Use of the fused ring organic compound of any one of claims 1-2 in a light emitting device as at least one light emitting functional layer.

4. Use according to claim 3, characterized in that, The organic electronic device is an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, a sheet type scanner or electronic paper.

5. A light-emitting device, characterized in that, The light emitting device comprises an anode, a light emitting functional layer and a cathode; wherein the light emitting functional layer comprises the fused ring organic compound of any one of claims 1-2.

6. The light emitting device of claim 5, wherein, The light emitting device is an organic electroluminescent device.

7. The light emitting device of claim 6, wherein the first and second light emitting devices are arranged in a vertical stack. The light emitting functional layer comprises a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer and an electron blocking layer; The light emitting functional layer comprises the fused ring organic compound of any one of claims 1-2.

8. A luminescent material, characterized by The light emitting material comprises the fused ring organic compound of any one of claims 1-2.

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