A compound with a fluoranthene-bis-five-membered ring as a parent core and its application

Abstract

The present invention belongs to the technical field of organic electroluminescent materials and relates to a compound with a fluoranthene-bis-pentacyclic ring as a parent core and its application. The present invention provides a class of compounds with a fluoranthene-bis-pentacyclic ring as a parent core, a large condensed ring stereo structure formed with two fluoranthene-bis-pentacyclic rings as the central skeleton, and a derivative compound formed by modification with specific groups. The compound has appropriate energy levels and color coordinates, good color purity, a high glass transition temperature, is not easy to crystallize, has good thermal stability and film-forming properties, can be used as a blue light dopant and host in organic electroluminescent devices, can reduce the driving voltage of the device, and improve the luminous efficiency and life of the device. The compound provided by the present invention is used as an organic light-emitting material, and its preparation method is simple, the raw materials are readily available, and it is suitable for industrial production and application.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescent materials and relates to a compound with a fluoranthene-bis(five-membered) ring as a parent nucleus and application thereof. Background Art

[0002] Organic electroluminescent devices (OLEDs), as a new display technology, offer unique advantages such as self-luminescence, wide viewing angles, low energy consumption, high efficiency, thinness, rich colors, fast response speed, wide operating temperature range, low driving voltage, the ability to fabricate flexible, bendable, and transparent display panels, and environmental friendliness. They are suitable for applications in flat-panel displays and next-generation lighting, as well as as backlights for LCDs. OLEDs have already gained industrial application, with widespread adoption in mobile phone displays and other display screens, and their future application in larger sizes is expected. However, their current low efficiency and short lifespan are significant limitations, severely restricting their application. While red and green devices have achieved the required lifespan and efficiency for commercial applications, blue devices currently offer good color coordinates but still face room for improvement in color purity. Most importantly, their low lifespan limits their development. While blue phosphorescent devices can address the shortcomings of blue fluorescent devices, they rely on expensive metal complexes such as iridium and platinum, significantly increasing commercialization costs. The design and development of new blue-emitting materials to further improve device efficiency, stability, and achieve ideal color purity remain hot research topics in the industry. Summary of the Invention

[0003] The skeleton structure of the fluoranthene-bis(pentacyclic) ring has high thermal stability due to its large conjugated stereo structure within the molecule. The compound constructed by modification with specific groups can obtain a more appropriate frontier orbital energy level and can achieve blue light emission. When applied to organic electroluminescent devices, it can improve the efficiency and life of the devices and is expected to be industrially applied.

[0004] The present invention aims to provide a compound with a fluoranthene-bis(pentacyclic) ring skeleton, which fully utilizes the stereostructure formed by its large conjugation and is further modified with different groups at specific substitution positions. This compound can be applied as a host or a luminescent material in an organic electroluminescent device, which can significantly improve the device performance of the organic electroluminescent device and achieve the goals of high efficiency and long life.

[0005] In one aspect, the present invention relates to a compound having a structure as shown in formula (I),

[0006] ;

[0007] wherein X is selected from one of O, C(CH3)2, NR1, S, and Si(CH3)2;

[0008] Y is selected from one of O, C(CH3)2, NR1, S, and Si(CH3)2;

[0009] Ar1, Ar2, Ar3 or R1 are independently selected from one of arylene, heteroaryl or aryl;

[0010] The number of carbon atoms of Ar1, Ar2, Ar3 or R1 is 6 to 30;

[0011] The heteroatom in the heteroaryl group is selected from at least one of N, O, and S.

[0012] In another aspect, the present invention relates to a compound having a structure as shown in formula (II),

[0013] ;

[0014] wherein X is selected from one of O, C(CH3)2, NR1, S, and Si(CH3)2;

[0015] Y is selected from one of O, C(CH3)2, NR1, S, and Si(CH3)2;

[0016] Ar1, Ar2, Ar3 or R1 are independently selected from one of arylene, heteroaryl or aryl;

[0017] The number of carbon atoms of Ar1, Ar2, Ar3 or R1 is 6 to 30;

[0018] The heteroatom in the heteroaryl group is selected from at least one of N, O, and S.

[0019] Further, in the compounds provided by the present invention, the Ar1, Ar2, Ar3 or R1 are independently selected from any one or more combinations of hydrogen, deuterium, halogen, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, pyrenyl, peryl, biphenyl, furyl, thienyl, pyridyl, pyrrolyl, pyranyl, pyrimidinyl, triazinyl, pyrazinyl, quinolyl, quinoxalinyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, dibenzocarbazolyl, isoquinoxalinyl, fluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, benzocarbazolyl, triphenylenyl, silafluorenyl, and N-phenyl;

[0020] The Ar1, Ar2, Ar3 or R1 are independently substituted or unsubstituted.

[0021] Specifically, among the compounds provided by the present invention, the compounds have the structure shown in any one of compounds 1 to 150,

[0022]

[0023] On the other hand, the present invention relates to an intermediate for synthesizing the compound, selected from intermediate 1-1, intermediate 1-2, intermediate 2-1, intermediate 3-1, intermediate 3-2, intermediate 3-3, intermediate 4-1, intermediate 5-1, intermediate 6-1, intermediate 7-1, intermediate 8-1, intermediate 9-1, intermediate 10-1;

[0024] .

[0025] In another aspect, the present invention relates to the use of the compound as a fluorescent host material and / or a luminescent material in an organic electroluminescent device.

[0026] On the other hand, the present invention relates to the use of the compound as a fluorescent host material and / or a luminescent material in an organic electroluminescent display device.

[0027] In another aspect, the present invention relates to an organic electroluminescent device comprising a hole transport layer, wherein the hole transport layer comprises at least one compound among the above compounds.

[0028] The compounds, luminescent materials prepared from the compounds, and luminescent devices prepared from the luminescent materials can all be used in organic electroluminescent devices and display devices. It should be noted that the luminescent materials or host materials and luminescent devices all contain the compounds provided by the present invention, but this does not limit the scope of use of the compounds provided by the present invention. The compounds may also be used in the manufacture of other devices. Therefore, any manufacture or use using the compounds provided by the present invention as raw materials should fall within the scope of protection determined by the present invention.

[0029] Compared with the prior art, the technical solution provided by the present invention has at least the following beneficial effects or advantages.

[0030] This invention introduces specific groups at specific positions to modify the fluoranthenyl bipentacyclic ring, improving the spatial configuration of the core structure. The resulting material is a typical fluorescent material, improving device efficiency and lifespan. Experimental verification shows that this series of compounds exhibits excellent performance as both the host and luminescent materials in organic electroluminescent devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solution of the present invention, the following is a brief introduction to the drawings involved in the description of the embodiments. Obviously, the drawings in the description are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without any creative work.

[0032] Figure 1 The figure is a schematic structural diagram of an organic electroluminescent element provided in an embodiment of the present invention.

[0033] Explanation of the accompanying figures: 1 is a substrate, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. DETAILED DESCRIPTION

[0034] The following examples illustrate the technical solutions of the present invention, but the present invention is not limited to the following examples. The experimental methods and detection methods described in each example are conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.

[0035] Preparation Example

[0036] The following are the synthesis methods of some intermediates and compounds. The synthesis methods of the remaining intermediates and compounds can be easily synthesized by those skilled in the art by referring to similar methods.

[0037] Synthesis of intermediate 1-1:

[0038]

[0039] Synthesis of intermediate 1-1-2:

[0040] Under nitrogen, a three-necked flask was charged with intermediate 1-1-1 (100.0 g, 532 mmol), 2,3-dibromodibenzofuran (194.4 g, 600 mmol), Pd2(dba)3 (tris(dibenzylideneacetone)dipalladium, 6.1 g, 6.6 mmol), P(t-Bu)3 (tri-tert-butylphosphine, 2 g, 10 mmol), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene, 7.6 g, 50 mmol), and DMF (N,N-dimethylformamide, 600 mL). The reaction was stirred and refluxed at 150°C for 40 h. After the reaction was complete, the reaction solution was cooled to room temperature, dichloromethane (500 ml) was added, and the mixture was washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 132.7 g of intermediate 1-1-2 in an 81% yield.

[0041] Synthesis of intermediate 1-1-3:

[0042] Under nitrogen protection, intermediate 1-1-2 (100.0 g, 325 mmol), NBS (N-bromosuccinimide, 57.8 g, 325 mmol), and chloroform (400 mL) were added to a three-necked flask and stirred for 3 h at room temperature. The mixture was washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate and concentrated. The organic phase was purified by silica gel column to obtain 97.8 g of intermediate 1-1-3 with a yield of 78%.

[0043] Synthesis of intermediate 1-1-4:

[0044] Under nitrogen protection, intermediate 1-1-3 (90.0 g, 233 mmol), 4-bromo-2-fluorophenylboronic acid (50.8 g, 233 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 2.7 g, 2.33 mmol), K2CO3 (potassium carbonate, 128.6 g, 932 mmol), TBAB (tetrabutylammonium bromide, 7.5 g, 23.3 mmol), toluene (400 mL), ethanol (200 mL), and water (100 mL) were added to a three-necked flask. The mixture was stirred at 80 °C for 10 h, then cooled to room temperature and washed with water until pH = 7. The organic phase was dried and concentrated over anhydrous magnesium sulfate and purified on a silica gel column to obtain 89.5 g of intermediate 1-1-4 with a yield of 80%.

[0045] Synthesis of intermediate 1-1:

[0046] Under nitrogen, intermediate 1-1-4 (30.0 g, 62.5 mmol), K2CO3 (34.5 g, 250 mmol), and DMF (300 mL) were added to a three-necked flask and reacted at 140°C for 2 h. After cooling to room temperature, the reaction solution was poured into water with stirring to precipitate a solid. After filtration, the filter cake was completely dissolved in toluene and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 20.7 g of intermediate 1-1 in a 72% yield.

[0047] Synthesis of intermediate 1-2:

[0048]

[0049]

[0050] The synthesis of intermediate 1-2-1 was carried out by referring to the synthesis method of intermediate 1-1-2, except that intermediate 2,3-dibromodibenzofuran was replaced by intermediate 2,3,7-tribromodibenzofuran, with a yield of 79%.

[0051] The synthesis of intermediate 1-2-2 was carried out by referring to the synthesis method of intermediate 1-1-3, except that intermediate 1-1-2 was replaced by intermediate 1-2-1, with a yield of 82%.

[0052] The synthesis of intermediate 1-2-3 was carried out by referring to the synthesis method of intermediate 1-1-4, except that intermediate 1-1-3 was replaced by intermediate 1-2-2, with a yield of 80%.

[0053] The synthesis of intermediate 1-2 was carried out according to the synthesis method of intermediate 1-1, except that intermediate 1-1-4 was replaced by intermediate 1-2-3, with a yield of 70%.

[0054] Synthesis of intermediate 2-1:

[0055]

[0056] The synthesis of intermediate 2-1-2 was carried out by referring to the synthesis method of intermediate 1-1-2, except that intermediate 1-1-1 was replaced by intermediate 2-1-1, with a yield of 76%.

[0057] The synthesis of intermediate 2-1-3 was carried out by referring to the synthesis method of intermediate 1-1-3, except that intermediate 1-1-2 was replaced by intermediate 2-1-2, with a yield of 80%.

[0058] The synthesis of intermediate 2-1-4 was carried out by referring to the synthesis method of intermediate 1-1-4, except that intermediate 1-1-3 was replaced by intermediate 2-1-3, with a yield of 86%.

[0059] The synthesis of intermediate 2-1 was carried out according to the synthesis method of intermediate 1-1, except that intermediate 1-1-4 was replaced by intermediate 2-1-4, with a yield of 69%.

[0060] Synthesis of intermediate 3-1:

[0061]

[0062]

[0063] Synthesis of intermediate 3-1-2:

[0064] Under nitrogen, a three-necked flask was charged with intermediate 3-1-1 (100.0 g, 357.1 mmol), methyl 2-bromobenzoate (77 g, 360 mmol), Pd(PPh3)4 (tetrakis(triphenylphosphine)palladium, 4.1 g, 3.57 mmol), potassium carbonate (197 g, 754.4 mmol), TBAB (tetrabutylammonium bromide, 2.3 g, 7.1 mmol), toluene (400 mL), ethanol (200 mL), and purified water (100 mL). The reaction mixture was heated to 80°C and stirred for 8 h. After the reaction was complete, the reaction mixture was cooled to room temperature and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 108.3 g of intermediate 3-1-2 in an 82% yield.

[0065] Synthesis of intermediate 3-1-3:

[0066] Under nitrogen, intermediate 3-1-2 (100.0 g, 270.3 mmol) and tetrahydrofuran (200 mL) were added to a three-necked flask. Methylmagnesium bromide (1.0 M in tetrahydrofuran, 710 mL) was slowly added dropwise with stirring at 24°C. After the addition was complete, the temperature was raised to 50°C and the reaction was continued for 6 h. The reaction solution was cooled to 24°C and quenched with aqueous ammonium chloride. The pH was adjusted to 3 with dilute hydrochloric acid and the mixture was washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 76 g of intermediate 3-1-3 in a 76% yield.

[0067] Synthesis of intermediate 3-1-4:

[0068] Under nitrogen, intermediate 3-1-3 (50.0 g, 135.0 mmol), methanesulfonic acid (31.9 g, 270.0 mmol), and toluene (300 mL) were added to a three-necked flask and heated to 108°C for 3 h. The reaction solution was cooled to room temperature and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 42.8 g of intermediate 3-1-4 in an 87% yield.

[0069] Synthesis of intermediate 3-1-5:

[0070] Under nitrogen, intermediate 3-1-4 (40.0 g, 113.6 mmol) and tetrahydrofuran (300 mL) were added to a three-necked flask. The temperature was cooled to -78°C, butyl lithium was added dropwise, and the reaction was incubated for 1 h. Trimethyl borate (23.7 g, 227.2 mmol) was then added dropwise. The reaction was incubated for 1 h, then naturally warmed to 24°C and the reaction was continued for 2 h. After the reaction was completed, the reaction was quenched with aqueous ammonium chloride solution, the pH was adjusted to 3 with dilute hydrochloric acid, and the mixture was washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 32.5 g of intermediate 3-1-5 in a yield of 79%.

[0071] The synthesis of intermediate 3-1-6 refers to the synthesis method of intermediate 3-1-2, replacing intermediate 3-1-1 and methyl 2-bromobenzoate with intermediate 3-1-5 and methyl 1-iodo-4-bromo-2-benzoate, with a yield of 87%.

[0072] The synthesis of intermediate 3-1-7 was carried out by referring to the synthesis method of intermediate 3-1-3, except that intermediate 3-1-2 was replaced by intermediate 3-1-6, with a yield of 80%.

[0073] The synthesis of intermediate 3-1 was carried out by referring to the synthesis method of intermediate 3-1-4, except that intermediate 3-1-3 was replaced by intermediate 3-1-7, with a yield of 68%.

[0074] Synthesis of intermediate 3-2:

[0075]

[0076] The synthesis of intermediate 3-2-2 was carried out by referring to the synthesis method of intermediate 3-1-2, except that intermediate 3-1-1 was replaced by intermediate 3-2-1, with a yield of 80%.

[0077] The synthesis of intermediate 3-2-3 was carried out by referring to the synthesis method of intermediate 3-1-3, except that intermediate 3-1-2 was replaced by intermediate 3-2-2, with a yield of 79%.

[0078] The synthesis of intermediate 3-2-4 was carried out by referring to the synthesis method of intermediate 3-1-4, except that intermediate 3-1-3 was replaced by intermediate 3-2-3, with a yield of 88%.

[0079] The synthesis of intermediate 3-2-5 was carried out by referring to the synthesis method of intermediate 3-1-5, except that intermediate 3-1-4 was replaced by intermediate 3-2-4, with a yield of 73%.

[0080] The synthesis of intermediate 3-2-6 was carried out by referring to the synthesis method of intermediate 3-1-6, except that intermediate 3-1-5 was replaced by intermediate 3-2-5, with a yield of 83%.

[0081] The synthesis of intermediate 3-1-7 was carried out by referring to the synthesis method of intermediate 3-1-7, replacing intermediate 3-1-6 with intermediate 3-2-6, with a yield of 82%.

[0082] The synthesis of intermediate 3-2 was carried out according to the synthesis method of intermediate 3-1, except that intermediate 3-1-7 was replaced by intermediate 3-2-7, with a yield of 64%.

[0083] Synthesis of intermediate 3-3:

[0084]

[0085] The synthesis of intermediate 3-3-2 was carried out by referring to the synthesis method of intermediate 3-1-5, except that intermediate 3-1-4 was replaced by intermediate 3-3-1, with a yield of 76%.

[0086] The synthesis of intermediate 3-3-3 was carried out by referring to the synthesis method of intermediate 3-1-2, except that intermediate 3-1-1 was replaced by intermediate 3-3-2, with a yield of 78%.

[0087] The synthesis of intermediate 3-3-4 was carried out by referring to the synthesis method of intermediate 3-1-3, except that intermediate 3-1-2 was replaced by intermediate 3-3-3, with a yield of 82%.

[0088] The synthesis of intermediate 3-3-5 was carried out by referring to the synthesis method of intermediate 3-1-4, except that intermediate 3-1-3 was replaced by intermediate 3-3-4, with a yield of 75%.

[0089] The synthesis of intermediate 3-3-6 was carried out by referring to the synthesis method of intermediate 1-1-3, except that intermediate 1-1-2 was replaced by intermediate 3-3-5, with a yield of 82%.

[0090] The synthesis of intermediate 3-3-7 was carried out by referring to the synthesis method of intermediate 3-1-6, except that intermediate 3-1-5 was replaced by intermediate 3-3-6, with a yield of 79%.

[0091] The synthesis of intermediate 3-3-8 was carried out by referring to the synthesis method of intermediate 3-1-7, except that intermediate 3-1-6 was replaced by intermediate 3-3-7, with a yield of 80%.

[0092] The synthesis of intermediate 3-3 was carried out according to the synthesis method of intermediate 3-1, except that intermediate 3-1-7 was replaced by intermediate 3-3-8, with a yield of 66%.

[0093] Synthesis of intermediate 4-1:

[0094]

[0095] The synthesis of intermediate 4-1-2 was carried out by referring to the synthesis method of intermediate 3-1-2, except that intermediate 3-1-1 was replaced by intermediate 4-1-1, with a yield of 78%.

[0096] The synthesis of intermediate 4-1-3 was carried out by referring to the synthesis method of intermediate 3-1-3, except that intermediate 3-1-2 was replaced by intermediate 4-1-2, with a yield of 80%.

[0097] The synthesis of intermediate 4-1-4 was carried out by referring to the synthesis method of intermediate 3-1-4, except that intermediate 3-1-3 was replaced by intermediate 4-1-3, with a yield of 82%.

[0098] The synthesis of intermediate 4-1-5 was carried out by referring to the synthesis method of intermediate 3-1-5, except that intermediate 3-1-4 was replaced by intermediate 4-1-4, with a yield of 70%.

[0099] The synthesis of intermediate 4-1-6 was carried out by referring to the synthesis method of intermediate 3-1-6, except that intermediate 3-1-5 was replaced by intermediate 4-1-5, with a yield of 80%.

[0100] The synthesis of intermediate 4-1-7 was carried out by referring to the synthesis method of intermediate 3-1-7, except that intermediate 3-1-6 was replaced by intermediate 4-1-6, with a yield of 79%.

[0101] The synthesis of intermediate 4-1 was carried out according to the synthesis method of intermediate 3-1, except that intermediate 3-1-7 was replaced by intermediate 4-1-7, with a yield of 66%.

[0102] Synthesis of intermediate 5-1:

[0103]

[0104] Synthesis of intermediate 5-1-2:

[0105] Under nitrogen, a three-necked flask was charged with intermediate 3-1-1 (100.0 g, 357.1 mmol), 2-bromonitrobenzene (71.8 g, 357.1 mmol), tetrakis(triphenylphosphine palladium) (4.1 g, 3.57 mmol), potassium carbonate (197 g, 754.4 mmol), TBAB (tetrabutylammonium bromide, 2.3 g, 7.1 mmol), toluene (400 mL), ethanol (200 mL), and water (100 mL). The mixture was stirred at 80°C for 5 h. After the reaction was complete, the reaction solution was cooled to room temperature and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 104.5 g of intermediate 5-1-2 in an 82% yield.

[0106] Synthesis of intermediate 5-1-3:

[0107] Under nitrogen, intermediate 5-1-2 (100.0 g, 280.1 mmol), PPh3 (triphenylphosphine, 131 g, 500 mmol), and o-dichlorobenzene (200 mL) were added to a three-necked flask and heated with stirring at 160°C for 20 h. After cooling the reaction solution to room temperature (24°C), n-heptane was added to precipitate white crystals. After filtration, the crystals were recrystallized from toluene to obtain 72 g of intermediate 5-1-3 in a 79% yield.

[0108] Synthesis of intermediate 5-1-4:

[0109] Under nitrogen, a three-necked flask was charged with intermediate 5-1-3 (50.0 g, 153.8 mmol), iodobenzene (51.0 g, 250 mmol), Pd2(dba)3 (1.4 g, 1.54 mmol), P(t-Bu)3 (1 g, 5 mmol), DBU (1,8-diazabicyclo[5.4.0]undec-7-ene, 15.2 g, 100 mmol), and toluene (300 mL). The reaction was heated to 90°C for 2 h. The reaction solution was cooled to room temperature and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 54.3 g of intermediate 5-1-4 in an 88% yield.

[0110] Synthesis of intermediate 5-1-5:

[0111] Under nitrogen, intermediate 5-1-4 (40.0 g, 99.8 mmol) and tetrahydrofuran (300 mL) were added to a three-necked flask. The temperature was cooled to -78°C, butyl lithium was added dropwise, and the reaction was incubated for 1 h. Trimethyl borate (31.1 g, 299.4 mmol) was then added dropwise. The reaction was incubated for 1 h, then naturally warmed to room temperature and the reaction was continued for 2 h. After the reaction was completed, the reaction was quenched with aqueous ammonium chloride, the pH was adjusted to 3 with dilute hydrochloric acid, and the mixture was washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, concentrated, and purified on a silica gel column to obtain 30.8 g of intermediate 5-1-5 in a yield of 75%.

[0112] The synthesis of intermediate 5-1-6 was carried out according to the synthesis method of intermediate 5-1-2, except that intermediate 3-1-1 and 2-bromonitrobenzene were replaced by intermediate 5-1-5 and 1-iodo-4-bromo-2-nitrobenzene, with a yield of 85%.

[0113] The synthesis of intermediate 5-1-7 was carried out by referring to the synthesis method of intermediate 5-1-3, except that intermediate 5-1-2 was replaced by intermediate 5-1-6, with a yield of 80%.

[0114] The synthesis of intermediate 5-1 was carried out by referring to the synthesis method of intermediate 5-1-4, except that intermediate 5-1-3 was replaced by intermediate 5-1-7, with a yield of 68%.

[0115] Synthesis of intermediate 6-1:

[0116]

[0117] The synthesis of intermediate 6-1-2 was carried out according to the synthesis method of intermediate 5-1-2, except that intermediate 3-1-1 was replaced by intermediate 4-1-1, with a yield of 73%.

[0118] The synthesis of intermediate 6-1-3 was carried out by referring to the synthesis method of intermediate 5-1-3, except that intermediate 5-1-2 was replaced by intermediate 6-1-2, with a yield of 79%.

[0119] The synthesis of intermediate 6-1-4 was carried out by referring to the synthesis method of intermediate 5-1-4, except that intermediate 5-1-3 was replaced by intermediate 6-1-3, with a yield of 83%.

[0120] The synthesis of intermediate 6-1-5 was carried out by referring to the synthesis method of intermediate 5-1-5, except that intermediate 5-1-4 was replaced by intermediate 6-1-4, with a yield of 74%.

[0121] The synthesis of intermediate 6-1-6 was carried out by referring to the synthesis method of intermediate 5-1-6, except that intermediate 5-1-5 was replaced by intermediate 6-1-5, with a yield of 81%.

[0122] The synthesis of intermediate 6-1-7 was carried out by referring to the synthesis method of intermediate 5-1-7, except that intermediate 5-1-6 was replaced by intermediate 6-1-6, with a yield of 73%.

[0123] The synthesis of intermediate 6-1 was carried out according to the synthesis method of intermediate 5-1, except that intermediate 5-1-7 was replaced by intermediate 6-1-7, with a yield of 68%.

[0124] Synthesis of intermediate 7-1:

[0125]

[0126] The synthesis of intermediate 7-1-1 was carried out according to the synthesis method of intermediate 1-1-4, except that intermediate 1-1-3 was replaced by intermediate 4-1-4, with a yield of 70%.

[0127] The synthesis of intermediate 7-1 was carried out by referring to the synthesis method of intermediate 1-1, except that intermediate 1-1-4 was replaced by intermediate 7-1-1, with a yield of 64%.

[0128] Synthesis of intermediate 8-1:

[0129]

[0130] The synthesis of intermediate 8-1-1 was carried out according to the synthesis method of intermediate 3-1-5, except that intermediate 3-1-4 was replaced by intermediate 2-1-3, with a yield of 80%.

[0131] The synthesis of intermediate 8-1-2 was carried out according to the synthesis method of intermediate 3-1-6, except that intermediate 3-1-5 was replaced by intermediate 8-1-1, with a yield of 75%.

[0132] The synthesis of intermediate 8-1-3 was carried out according to the synthesis method of intermediate 3-1-7, except that intermediate 3-1-6 was replaced by intermediate 8-1-2, with a yield of 74%.

[0133] The synthesis of intermediate 8-1 was carried out according to the synthesis method of intermediate 3-1, except that intermediate 3-1-7 was replaced by intermediate 8-1-3, with a yield of 70%.

[0134] Synthesis of intermediate 9-1:

[0135]

[0136] The synthesis of intermediate 9-1-1 was carried out according to the synthesis method of intermediate 3-1-5, except that intermediate 3-1-4 was replaced by intermediate 1-1-3, with a yield of 84%.

[0137] The synthesis of intermediate 9-1-2 was carried out according to the synthesis method of intermediate 3-1-6, except that intermediate 3-1-5 was replaced by intermediate 9-1-1, with a yield of 79%.

[0138] The synthesis of intermediate 9-1-3 was carried out by referring to the synthesis method of intermediate 3-1-7, except that intermediate 3-1-6 was replaced by intermediate 9-1-2, with a yield of 77%.

[0139] The synthesis of intermediate 9-1 was carried out according to the synthesis method of intermediate 3-1, except that intermediate 3-1-7 was replaced by intermediate 9-1-3, with a yield of 76%.

[0140] Synthesis of intermediate 10-1:

[0141]

[0142] The synthesis of intermediate 10-1-1 was carried out according to the synthesis method of intermediate 1-1-4, except that intermediate 1-1-3 was replaced by intermediate 3-1-4. The yield was 76%.

[0143] The synthesis of intermediate 10-1 was carried out by referring to the synthesis method of intermediate 1-1, replacing intermediate 1-1-4 with intermediate 10-1-1, with a yield of 68%.

[0144] Synthesis of compound 1

[0145]

[0146] Under argon, a three-necked reaction flask was charged with intermediate 1-2 (12 g, 26.0 mmol), intermediate 2-biphenylboronic acid (4.2 g, 28.0 mmol), tetrakis(triphenylphosphine palladium) (0.75 g, 3.57 mmol), potassium carbonate (14.4 g, 104.0 mmol), TBAB (tetrabutylammonium bromide, 2.1 g, 6.5 mmol), toluene (100 mL), ethanol (50 mL), and water (25 mL). The mixture was stirred at 80°C for 8 h. After completion of the reaction, the reaction solution was cooled to room temperature (24°C) and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, and the filtrate was passed through a silica gel column, concentrated, and recrystallized from a toluene / ethanol mixture in a certain ratio to obtain 9.6 g of compound 1, with a yield of 70%.

[0147] The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 534.1620 [M+H] + ; Calculated for C40H22O2: C, 89.8667; O, 5.9853; H, 4.1480; Found: C, 89.8678; O, 5.9866; H, 4.1456.

[0148] Synthesis of compound 8

[0149]

[0150] Referring to the synthesis method of compound 1, intermediate 1-2 and 2-biphenylboronic acid were replaced with intermediate 9-2 and dibenzofuran-4-boronic acid, with a yield of 79%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 574.1933 [M+H] + ; Calculated for C43H26O2: C, 89.8716; O, 5.5680; H, 4.5605; Found: C, 89.8757; O, 5.5669; H, 4.5574.

[0151] Synthesis of compound 14

[0152]

[0153] Referring to the synthesis method of compound 1, intermediates 1-2 and 2-biphenylboronic acid were replaced with intermediates 10-2 and 9-phenanthreneboronic acid, with a yield of 80%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 584.2140 [M+H] + ; Calculated for C45H28O: C, 92.4369; O, 2.7362; H, 4.8269; Found: C, 92.4380; O, 2.7352; H, 4.8268.

[0154] Synthesis of compound 22

[0155]

[0156] Referring to the synthesis method of compound 1, intermediates 1-2 and 2-biphenylboronic acid were replaced with intermediates 4-2 and 10-phenyl-9-anthraceneboronic acid, resulting in a yield of 74%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 686.2974 [M+H] + ; Calculated for C54H38: C, 94.4236; H, 5.5764; Found: C, 94.4269; H, 5.5731.

[0157] Synthesis of compound 25

[0158]

[0159] Referring to the synthesis method of compound 1, intermediate 1-2 and 2-biphenylboronic acid were replaced with intermediate 2-2 and 10-phenyl-9-anthraceneboronic acid, resulting in a yield of 78%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 634.1933 [M+H]+ ; Calculated for C48H26O2: C, 90.8299; H, 5.0412; O, 4.1290; Found: C, 90.8254; H, 5.0426; O, 4.1320.

[0160] Synthesis of compound 28

[0161]

[0162] Referring to the synthesis method of compound 1, intermediates 1-2 and 2-biphenylboronic acid were replaced with intermediates 8-2 and 9,9-dimethylfluorene-2-boronic acid, with a yield of 70%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 600.2453 [M+H] + ; Calculated for C46H32O: C, 91.9677; H, 5.3692; O, 2.6631; Found: C, 91.9668; H, 5.3691; O, 2.6641.

[0163] Synthesis of compound 39

[0164]

[0165] Referring to the synthesis method of compound 1, intermediate 1-2 and 2-biphenylboronic acid were replaced with intermediate 5-3 and (4,6-diphenyl-1,3,5-triazin-2-yl)boronic acid, resulting in a yield of 71%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 763.2736 [M+H] + ; Calculated for C55H33N5: C, 86.4775; N, 9.1680; H, 4.3545; Found: C, 86.4780; N, 9.1682; H, 4.3538.

[0166] Synthesis of compound 46

[0167]

[0168] Referring to the synthesis method of compound 1, intermediate 1-2 and 2-biphenylboronic acid were replaced with intermediate 1-1 and 9,9-dimethylfluorene-1-boronic acid, with a yield of 73%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 574.1933 [M+H] + ; Calculated for C43H26O2: C, 89.8716; O, 5.5680; H, 4.5605; Found: C, 89.8732; O, 5.5676; H, 4.5592.

[0169] Synthesis of compound 61

[0170]

[0171] Referring to the synthesis method of compound 1, intermediate 1-2 and 2-biphenylboronic acid were replaced with intermediate 3-2 and dibenzofuran-4-boronic acid, resulting in a yield of 69%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 600.2453 [M+H] + ; Calculated for C46H32O: C, 91.9677; O, 2.6631; H, 5.3692; Found: C, 91.9689; O, 2.6620; H, 5.3691.

[0172] Synthesis of compound 86

[0173]

[0174] Under argon, a three-necked flask was charged with intermediate 3-1 (10.0 g, 19.5 mmol), N,N-diphenylamine (3.4 g, 20 mmol), Pd2(dba)3 (0.9 g, 1 mmol), P(t-Bu)3 (0.6 g, 3 mmol), sodium tert-butoxide (7.5 g, 78 mmol), and toluene (150 mL). The reaction mixture was heated to 110°C and stirred under reflux for 4 h. After completion of the reaction, the mixture was cooled to room temperature and washed with water until neutral. The organic phase was dried over anhydrous magnesium sulfate, and the filtrate was passed through a silica gel column. The column solution was concentrated and purified by recrystallization from toluene / ethanol to obtain 8.8 g of compound 86 in a 75% yield.

[0175] The mass spectrometry results of the obtained sample are: HR-MS (APCI): m / z 601.2769 [M+H] + ; Calculated for C46H35N: C, 91.8100; N, 2.3275; H, 5.8625; Found: C, 91.8119; N, 2.3263; H, 5.8618.

[0176] Synthesis of compound 94

[0177]

[0178] Referring to the synthesis method of compound 1, intermediates 1-2 and 2-biphenylboronic acid were replaced with intermediates 3-3 and 3-(2-naphthyl)phenylboronic acid, resulting in an 80% yield. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 636.2817 [M+H] +; Calculated value for C50H36: C, 94.3018; H, 5.6982; Found: C, 94.3042; H, 5.6958.

[0179] Synthesis of compound 135

[0180]

[0181] Referring to the synthesis method of compound 1, intermediate 1-2 and 2-biphenylboronic acid were replaced with intermediate 2-1 and 8-(4-phenylboronic acid)benzo[b]naphtho[1,2-d]furan, with a yield of 69%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 674.1882 [M+H] + ; Calculated for C50H26O3: C, 89.0027; H, 3.8841; O, 7.1132; Found: C, 89.0023; H, 3.8844; O, 7.1133.

[0182] Synthesis of compound 137

[0183]

[0184] Referring to the synthesis method of compound 1, intermediate 1-2 and 2-biphenylboronic acid were replaced with intermediate 2-2 and 8-(3-phenylboronic acid)benzo[b]naphtho[1,2-d]furan, with a yield of 70%. The mass spectrometry results of the obtained sample were: HR-MS (APCI): m / z 674.1882 [M+H] + ; Calculated for C50H26O3: C, 89.0027; H, 3.8841; O, 7.1132; Found: C, 89.0024; H, 3.8842; O, 7.1134.

[0185] Example

[0186] Device Example 1

[0187] This device embodiment provides an organic electroluminescent device, the structure of which is as follows: Figure 1 As shown, it includes a substrate 1, an anode layer 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9 and a cathode layer 10 stacked in sequence.

[0188] Among them, the material of the anode layer 2 is indium tin oxide (ITO) with a high work function, the material of the hole injection layer 3 is HAT-CN, with a thickness of 5nm; the material of the first hole transport layer 4 is NPB, with a thickness of 50nm; the material of the second hole transport layer 5 is TCTA, with a thickness of 15nm; the light-emitting layer 6 uses ADN as the main material and compound 1 as the light-emitting material, with a doping mass ratio of 3% and a thickness of 30nm; the material of the hole blocking layer 7 is TPBI, with a thickness of 10nm; the material of the electron transport layer 8 is ET-1, with a thickness of 35nm; the material of the electron injection layer 9 is Liq, with a thickness of 2nm; the material of the cathode layer is Al, with a thickness of 100nm.

[0189] The basic material structures used in each functional layer of the device are as follows:

[0190]

[0191] The specific preparation steps of the above-mentioned organic electroluminescent device are as follows:

[0192] 1) Clean the ITO anode on the transparent glass or plastic substrate by ultrasonic cleaning with deionized water, acetone, and ethanol for 20 minutes each, and then perform plasma treatment in an oxygen atmosphere for 5 minutes;

[0193] 2) On the ITO anode layer, a hole injection layer material HAT-CN is deposited by vacuum evaporation with a thickness of 5 nm. This layer serves as the hole injection layer.

[0194] 3) Vacuum evaporation of a hole transport material NPB to a thickness of 50 nm on the hole injection layer, which serves as the first hole transport layer;

[0195] 4) Vacuum evaporation of TCTA, a hole transport material, to a thickness of 15 nm on the first hole transport layer NPB serves as the second hole transport layer.

[0196] 5) On the second hole transport layer, a light-emitting layer was co-deposited by vacuum evaporation, using ADN as the host material and compound 1 as the light-emitting material, with a doping mass ratio of 3% and a thickness of 30 nm;

[0197] 6) On top of the light-emitting layer, a hole-blocking material TPBI is deposited by vacuum evaporation with a thickness of 10 nm. This layer serves as a hole-blocking layer.

[0198] 7) On the hole blocking layer, the electron transport material ET-1 is evaporated by vacuum evaporation to a thickness of 35 nm. This layer serves as the electron transport layer.

[0199] 8) On the electron transport layer, the electron injection material Liq is evaporated by vacuum evaporation with a thickness of 2 nm. This layer serves as the electron injection layer;

[0200] 9) On the electron injection layer, cathode Al is deposited by vacuum evaporation with a thickness of 100 nm. This layer serves as the cathode conductive electrode.

[0201] Device Examples 2 to 20

[0202] The implementation process is the same as that of device embodiment 1, except that the light-emitting material is replaced by other developed compounds instead of compound 1.

[0203] Device Comparison

[0204] The implementation process is the same as that of device embodiment 1, except that BD01 is used as the light-emitting material instead of compound 1.

[0205] Device Examples 21 to 38

[0206] The implementation process is the same as that of the device control example, except that the main material is replaced by other developed compounds instead of ADN, and BD01 is used as the light-emitting material instead of compound 1.

[0207] The components of the different devices prepared in device embodiments 1 to 38 of the present invention and the comparative example are shown in Table 1.

[0208] Table 1: Comparison of organic electroluminescent device components of various device examples

[0209]

[0210] Each group of organic electroluminescent devices was connected to the cathode and anode using a known driving circuit. The voltage-efficiency-current density relationship of the OLED devices was tested using a standard method using a Keithley 2400 power supply and a PR670 photometer. The device life was tested using a constant current method with a constant current density of 10 mA / cm 2 The time it takes for the brightness to decay to 90% of the initial brightness is the LT90 life of the device.

[0211] Taking the test data of the starting voltage V, brightness efficiency and life LT90 of the device comparison as 1, the starting voltage V, brightness efficiency and life LT90 of device embodiments 1-38 are the relative values ​​of their respective test data and the test data of the device comparison. The test results are shown in Table 2.

[0212] Table 2: Comparison of performance results of organic electroluminescent devices in each group

[0213]

[0214] As can be seen from Table 2, the compounds provided by the present invention are applied as luminescent materials to OLED devices, and the performance is improved. For example, compound 14 in device embodiment 6, as a blue light material, has significantly improved luminous efficiency and service life compared with BD01 in the comparative example, with luminous efficiency increased by 39% and service life increased by 12%; compound 39 in device embodiment 30, as a blue light host material, has improved luminous efficiency and service life compared with ADN in the comparative example. It can be seen that the compounds of the present invention have a large intramolecular conjugated stereo structure, a more suitable HOMO / LUMO, a narrow half-peak width, and better color purity. Compared with existing materials applied to OLED light-emitting devices, the photoelectric properties such as luminous efficiency and service life of the device are all good, and the synthesis process of the material is simple, which has great application value in the application of OLED devices and has good industrialization prospects.

[0215] Currently, the blue light-emitting materials used in OLED products are still traditional fluorescent materials. Compared with green and red light-emitting materials, blue light-emitting materials still suffer from low efficiency and unsatisfactory lifespan. The design and development of new blue light-emitting materials to further improve device efficiency, stability, and achieve ideal color purity remains a hot topic in the industry. Currently, traditional blue fluorescent materials struggle to achieve the same efficiency and lifespan as red and green light-emitting devices. Numerous factors must be adjusted and balanced to achieve truly high-efficiency devices. Currently, it is difficult to simultaneously reduce the starting voltage and improve other performance characteristics. The search for superior blue light-emitting materials remains a key factor in driving the development of the OLED industry. This invention modifies a fluoranthene-bis(pentacyclic) core skeleton by attaching simple groups such as aryl and heteroaryl groups at fixed substitution positions to produce novel compounds. These compounds, modified with specific groups, possess suitable frontier orbital energy levels. These innovative compounds exhibit excellent performance as both the host and luminescent materials in organic electroluminescent (OLED) devices.

[0216] Obviously, those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if such changes and modifications of the present invention fall within the scope of the claims and their equivalents, such changes and modifications are intended to be included.

[0217] The embodiments described above are some of the embodiments of the present invention, rather than all of them. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but rather merely represents selected embodiments of the present invention. All other embodiments obtained without creative effort and through deduction and substitution by a person of ordinary skill in the art based on the concept of the present invention are within the scope of protection of the present invention.

Claims

1. A compound, characterized in that Having the structure shown in formula (I), ； wherein X is selected from one of O, C(CH3)2, and NR1; Y is selected from one of O, C(CH3)2, and NR1; The Ar1, Ar2, Ar3 or R1 are independently selected from any one of hydrogen, deuterium, halogen, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, pyrimidinyl, triazine, carbazolyl, dibenzofuranyl, dibenzothiophenyl, 9,9-diphenylfluorenyl, spirofluorenyl and N-phenylcarbazole.

2. A compound characterized in that Having the structure shown in formula (II), ； wherein X is selected from one of O, C(CH3)2, and NR1; Y is selected from one of O, C(CH3)2, and NR1; The Ar1, Ar2, Ar3 or R1 are independently selected from any one of hydrogen, deuterium, halogen, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, pyrimidinyl, triazine, carbazolyl, dibenzofuranyl, dibenzothiophenyl, 9,9-diphenylfluorenyl, spirofluorenyl and N-phenylcarbazole.

3. A compound characterized in that Having the structure shown in any one of compounds 1 to 150, 4. Use of the compound according to any one of claims 1 to 3 as a fluorescent host material and / or a luminescent material in an organic electroluminescent device.

5. Use of the compound according to any one of claims 1 to 3 as a fluorescent host material and / or a luminescent material in an organic electroluminescent display device.

6. An organic electroluminescent device comprising a hole transport layer, characterized in that: The hole transport layer comprises at least one compound selected from the group consisting of the compounds according to claim 1 .

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