Boron-nitrogen compound, application thereof and organic electroluminescent device containing compound

Abstract

The invention provides a blue fluorescence luminescent material with high efficiency and long service life and application thereof. The material is optimized through the following structural design: firstly, replacing a triarylamine unit at a boron para-position in DABNA-2 (CAS: 1689553-04-5) with an indole acridine unit, and carrying out monosubstitution or polysubstitution on a carbazole part of the indole acridine unit; and secondly, replacing the biphenyl unit at the boron para-position with a substituted benzothiophene unit. Through the innovative design of the molecular structure, the luminous efficiency of the material and the stability of the device are remarkably improved, and meanwhile, the service life of the device is effectively prolonged.

Description

Technical Field

[0001] The invention relates to the technical field of organic electroluminescence, and in particular to a novel organic compound and application thereof, and an organic electroluminescence device containing the compound. Background Art

[0002] OLED display panels, which are composed of organic light-emitting diodes (OLED), have the advantages of low power consumption, wide color gamut, and high brightness. After nearly ten years of technological iterations, their commercial applications are becoming more and more extensive. Specifically, under the action of the electric field, the electron and hole carriers generated by the cathode and anode of OLED move relative to each other, and meet and recombine into excitons in the light-emitting layer through the electron transport layer and the hole transport layer. The excitons generate photons through radiation, thereby generating visible light. OLED has the characteristics of self-luminescence, wide viewing angle, rollability, and short response time. It has great advantages in large-size and / or flexible ultra-thin panels. It is a new display technology that is rapidly developing and has a high degree of process integration. It has been widely used in display products such as TVs, smart phones, tablets, car displays, and lighting. It will also be further used in creative display products such as large-size displays and flexible screens.

[0003] OLED devices are composed of three colors: red, green, and blue. However, the life of phosphorescent materials for blue light cannot meet commercial requirements. Therefore, blue light materials are still mainly fluorescent materials. Since the exciton utilization rate of fluorescent materials is only 25%, in order to obtain higher efficiency, top-emitting device structures are widely used. That is, under fixed color coordinates, the narrower the intrinsic spectrum of the material, the higher the device efficiency. Therefore, narrow spectrum materials have become an effective solution for scientific researchers to develop high-efficiency blue light materials. Due to the weak electronic properties of boron and nitrogen atoms, boron nitrogen materials (DOI: 10.1002 / adma.201505491) show multiple resonances of the entire molecule, which not only makes the HOMO / LUMO electron cloud distribution more uniform, but also makes the non-radiative vibration of the molecule suppressed to a large extent, so that the half-peak width of the spectrum of the entire molecule is very narrow and has a lower shoulder peak. Summary of the invention

[0004] The present invention mainly designs a high-efficiency, long-life blue fluorescent luminescent material. First, a triarylamine unit in a boron-para-position of DABNA-2 (CAS: 1689553-04-5) is replaced with an indole acridine unit, and the hydrogen on the carbazole part of the indole acridine unit is monosubstituted or polysubstituted. Second, the biphenyl unit in the boron-para-position is replaced with a substituted benzothiophene unit. Specifically, the present invention provides:

[0005] 1) A fused heterocyclic compound, wherein the fused heterocyclic compound is represented by the following general formula (1):

[0006]

[0007] X: O, S, Se

[0008] R1 to R4 are independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted silyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diphenylamine; and adjacent groups may form a ring; a is independently selected from an integer of 0-3, and b and c are independently selected from an integer of 0-4;

[0009] R5 to R6 are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, and R5 and R6 may form a ring, except that R5 and R6 form a ring with fluorene;

[0010] Ar1 to Ar2 are independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl;

[0011] The entire molecule may be deuterated or undeuterated.

[0012] 2) According to the fused heterocyclic compound for an organic electroluminescent device described in 1) above, wherein R1 to R4 independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted phenyl group; preferably tert-butyl, phenyl, o-methylphenyl, or adamantyl.

[0013] 3) According to the fused heterocyclic compound for an organic electroluminescent device described in 1) above, wherein R5 and R6 independently represent a methyl group or a phenyl group, and when R5 and R6 form a ring, the ring structure is preferably a cyclohexyl group.

[0014] 4) According to the fused heterocyclic compound for an organic electroluminescent device described in 1) above, wherein Ar1 and Ar2 are selected from substituted or unsubstituted phenyl groups; preferably tert-butylphenyl, tetramethylnaphthyl, 2-phenyl-4-tert-butylphenyl, and 9,9-dimethylfluorenyl.

[0015] 5) According to the fused heterocyclic compound for an organic electroluminescent device described in 1) above, the "substituted" in the "substituted or unsubstituted" in the compound means that the substituent is independently selected from a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a monovalent alkyl group or a cycloalkyl group having 1 to 10 carbon atoms, a monovalent monocyclic aromatic group or a condensed aromatic group having 6 to 30 carbon atoms, and a monovalent heterocyclic group or a condensed heteroaryl group having 2 to 50 carbon atoms.

[0016] 6) The fused heterocyclic compound for an organic electroluminescent device according to 1) above, wherein the fused heterocyclic compound is selected from the following structures:

[0017]

[0018]

[0019]

[0020]

[0021]

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] 7) An organic electroluminescent device, wherein the organic electroluminescent device comprises an anode, a cathode and at least one organic thin film located between the anode and the cathode, and the organic thin film contains the compound described in any one of 1) to 6) above.

[0034] 8) The organic electroluminescent device according to 7) above, wherein the compound is used as a light-emitting material in the organic electroluminescent device.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows: first, relative to triphenylamine, the indoleacridine unit has good electron-donating properties and rigidity, which can further expand the degree of multiple resonance and improve the radiation rate, thereby improving the efficiency of the device; at the same time, after the hydrogen substitution on the carbazole part of the indoleacridine unit, aggregation can be suppressed and the HOMO / LUMO energy level and luminescence spectrum can be regulated. Secondly, relative to phenyl, the benzothiophene unit has a lower triplet energy level, which can quench excessive triplet excitons, thereby improving the stability of the device. Therefore, by adjusting and optimizing a variety of units, the efficiency and life of the device are effectively improved. In addition, in top-emitting devices, the device efficiency is affected by the spectrum and energy level of the luminescent material. The material of the present invention is more matched with the commercial device structure in terms of spectrum and energy level, thereby obtaining high-efficiency and long-life device performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The drawings described herein are used to provide a further understanding of the present application and constitute a part of the present application. The illustrative embodiments of the present application and their descriptions are used to explain the present application and do not constitute an improper limitation on the present application. In the drawings:

[0037] Figure 1 This is a schematic diagram of the structure of an organic electroluminescent device to which the compound of the present invention is applied, wherein the meanings of the various layers of the device structure are as follows:

[0038] 1. Transparent substrate layer, 2. ITO anode layer, 3. Hole injection layer, 4. Hole transport layer A, 5. Hole transport layer B (or electron blocking layer), 6. Light-emitting layer, 7. Electron transport layer B (or hole blocking layer), 8. Electron transport layer A, 9. Electron injection layer, 10. Cathode reflective electrode layer, 11. Light coupling layer, 12. Packaging cover layer. DETAILED DESCRIPTION

[0039] the term

[0040] In the present invention, the alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is, for example, 1 to 50, preferably 1 to 20, and more preferably 1 to 6. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethylpropyl, 1,1-dimethylpropyl, isohexyl, 4-methylhexyl, and 5-methylhexyl.

[0041] Alkoxy refers to -O-alkyl, wherein the number of carbon atoms is not particularly limited, for example, 1 to 50, preferably 1 to 20, more preferably 1 to 6. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy (eg, n-propoxy and isopropoxy), and tert-butoxy.

[0042] In the present invention, the above-mentioned alkyl or alkoxy group may be substituted. For example, in the fluorinated alkyl group and the fluorinated alkoxy group substituted with fluorine, the number of carbon atoms is not particularly limited, for example, 1 to 20, more preferably 1 to 6. Examples of fluorinated alkyl groups include, but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, and heptafluoropropyl. Examples of fluorinated alkoxy groups include, but are not limited to, trifluoromethoxy, 2,2,2-trifluoroethoxy, and pentafluoroethoxy.

[0043] The cycloalkyl group may be a monocyclic ring or a condensed ring, and the number of carbon atoms therein is not particularly limited, and is, for example, 3 to 50, preferably 3 to 20, and more preferably 3 to 6. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and adamantyl, and cyclohexyl is preferred.

[0044] The aryl group may be a monocyclic or polycyclic aryl group, wherein the number of carbon atoms is not particularly limited, for example, 6 to 50, preferably 6 to 20. Examples of monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl and terphenyl. Examples of polycyclic aryl groups include naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, naphthylene, fluorenyl, acenaphthenyl, triphenylene and fluoranthenyl, but the scope of the present invention is not limited thereto.

[0045] "Heterocyclyl" refers to a cyclic compound group in which one or more atoms in the ring are replaced by heteroatoms other than carbon (such as nitrogen, oxygen, sulfur, etc.). A fused-ring heteroaryl group refers to a cyclic compound group in which at least two rings (at least one of which is an aromatic ring) share one or more carbon atoms, and at least one ring contains one or more heteroatoms. Examples of heterocyclic groups and fused-ring heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, triazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidyl, triazinyl, triazolyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothienyl, dibenzothienyl, benzofuranyl, dibenzofuranyl, thiazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, benzothiazolyl, and phenothiazinyl.

[0046] Silyl is intended to include alkyl-substituted silyl and aryl-substituted silyl. Specific examples of such silyl include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, and dimethylfurylsilyl.

[0047] "Deuterated" or "deuterated or not deuterated" refers to one or more deuterated or fully deuterated.

[0048] The specific synthesis steps are as follows:

[0049] Synthesis Example 1

[0050]

[0051] Synthesis of intermediate M001-1:

[0052] Weigh 3,6-di-tert-butylcarbazole (30.69 g, 110 mmol, C1), 2-fluoro-4-chlorobromobenzene (38.0 g, 100 mmol, C2), cesium carbonate (39.1 g, 120 mmol) in a flask, add 300 mL of dry N,N-dimethylformamide, and purify. Under nitrogen protection, react at 140 ° C for 6 hours. Stop the reaction, cool to room temperature, pour into 600 ml of water, precipitate solids, and filter. Collect the solids, separate and purify on a silica gel column to obtain 39.49 g of product with a yield of 87%. The molecular weight measured by mass spectrometry is m / z = 453.9 (M+H) + ; Synthesis of intermediate M001-2:

[0053] Weigh the intermediate M001-1 (37.22g, 82mmol) and dissolve it in 300mL of anhydrous THF, and stir it at -78℃ for 20 minutes. Under nitrogen protection, add n-butyl lithium in n-hexane solution (38.4mL, 96mmol, 2.5M) to the reaction solution. After the addition is complete, keep stirring at low temperature for 1h. At -78℃, weigh acetone (5.57g, 96mmol, C3) and add it to the reaction solution, return to room temperature naturally, and react for 10h. Add 100mL of water to quench the reaction, extract with ethyl acetate / water three times, collect the organic phase, remove the solvent by rotary evaporation, and separate with silica gel column to obtain the crude product. Dissolve the crude product in 200mL of dichloromethane, stir at room temperature, add boron trifluoride ether (9.6mL, 80mmol) dropwise under nitrogen protection, and stir at room temperature for 1h. Stop the reaction, add sodium carbonate solution to neutralize the reaction solution, and extract with dichloromethane three times. The solvent was removed by rotary evaporation and separated by silica gel column to obtain 26.04 g of intermediate M2 with a yield of 74%. The molecular weight measured by mass spectrometry was m / z=429.2 (M+H) + ;

[0054] Synthesis of intermediate M001-3:

[0055] Weigh the intermediate M001-2 (25.75g, 60mmol), 4-tert-butylaniline (10.73g, 72mmol, C4), tris(dibenzylideneacetone)dipalladium (1.66g, 1.8mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (1.48g, 3.6mmol, S-Phos), and sodium tert-butoxide (11.52g, 120mmol) in a flask, and add 300mL toluene and ventilate. Under nitrogen protection, reflux at 110°C for 20h. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then separate and purify with a silica gel column to obtain about 27.33g of product with a yield of 84%. The molecular weight measured by mass spectrometry is m / z=542.4 (M+H) + ;

[0056] Synthesis of intermediate M001-4:

[0057] Weigh the intermediate M001-3 (27.12g, 50mmol), 1-bromo-5-(tert-butyl)-2,3-dichlorobenzene (14.1g, 50mmol, C5), tris(dibenzylideneacetone)dipalladium (1.66g, 1.5mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (1.43g, 3.0mmol, X-Phos), and sodium tert-butoxide (96.10g, 100mmol) in a flask, and add 300mL toluene and ventilate. Under nitrogen protection, reflux at 110°C for 12h. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then separate and purify with a silica gel column to obtain about 30.24g of product with a yield of 83%. The molecular weight measured by mass spectrometry is m / z=728.8 (M+H) + ; Synthesis of intermediate M001-5:

[0058] Weigh the intermediate M001-4 (29.15g, 40mmol), 4-tert-butylaniline (7.15g, 48mmol, C4), tris(dibenzylideneacetone)dipalladium (1.48g, 1.6mmol), 2-dicyclohexylphosphine-2',6'-dimethoxy-1,1'-biphenyl (1.32g, 3.2mmol, S-Phos), and sodium tert-butoxide (7.68g, 80mmol) in a flask, and add 200mL of xylene and purify. Under nitrogen protection, reflux at 140°C for 20h. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then separate and purify with a silica gel column to obtain about 26.35g of product with a yield of 77%. The molecular weight measured by mass spectrometry is m / z=855.5 (M+H) + ;

[0059] Synthesis of intermediate M001-6:

[0060] Weigh the intermediate M001-5 (25.66g, 30mmol), 3-bromo-5-(tert-butyl)benzo[B]thiophene (9.69g, 36mmol, C6), tri(dibenzylideneacetone)dipalladium (1.66g, 1.5mmol), tri-tert-butylphosphine (6.97g, 3.0mmol), and sodium tert-butoxide (57.66g, 60mmol) in a flask, and add 200mL toluene and ventilate. Under nitrogen protection, reflux at 110°C for 12h. Stop the reaction, cool to room temperature, extract with ethyl acetate and water, and concentrate by rotary evaporation. Then separate and purify with a silica gel column to obtain about 21.93g of product with a yield of 71%. The molecular weight measured by mass spectrometry is m / z=1029.8 (M+H) + ;

[0061] Synthesis of product BD001:

[0062] Weigh the intermediate M001-6 (21.0 g, 20 mmol) and dissolve it in 100 mL of dry xylene. Protect with nitrogen. Add tert-butyl lithium solution (15.4 mL, 30 mmol, 1.3 M) dropwise at -20 ° C, stir at low temperature for 1 hour, and stir at 60 ° C for 1 hour. Return to -20 ° C, add boron tribromide (10.0 g, 40 mmol), stir at low temperature for 1 hour, and stir at room temperature for 2 hours. Add diisopropylethylamine (7.68 g, 60 mmol), heat to 110 ° C and react for 6 hours. Stop the reaction, cool to room temperature, add sodium carbonate solution to neutralize to neutrality, extract with dichloromethane three times, collect the organic phase, spin dry the solvent, separate on a silica gel column, and obtain 3.46 g of yellow solid with a yield of 17%. The molecular weight measured by mass spectrometry is m / z = 1018.6 (M+H) + ;

[0063] Synthesis Example 2

[0064]

[0065] The synthesis conditions of product BD005 are the same as those of product BD001, except that C1 is replaced by C7; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1086.6 (M+H) + .

[0066] Synthesis Example 3

[0067]

[0068] The synthesis conditions of product BD007 are the same as those of product BD001, except that C1 is replaced by C8; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1094.7 (M+H) + .

[0069] Synthesis Example 4

[0070]

[0071] The synthesis conditions of product BD014 are the same as those of product BD001, except that C1 is replaced by C9; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1134.7 (M+H) + .

[0072] Synthesis Example 5

[0073]

[0074] The synthesis conditions of product BD019 are the same as those of product BD001, except that C10 replaces C1, and C11 replaces C3; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1050.4 (M+H) + .

[0075] Synthesis Example 6

[0076]

[0077] The synthesis conditions of product BD022 are the same as those of product BD019, except that C10 is replaced by C12; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1126.6 (M+H) + .

[0078] Synthesis Example 7

[0079]

[0080] The synthesis conditions of product BD032 are the same as those of product BD001, except that C13 replaces C1, and C14 replaces C3; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1140.6 (M+H) + .

[0081] Synthesis Example 8

[0082]

[0083] The synthesis conditions of product BD035 are the same as those of product BD032, except that C15 replaces C13; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1238.7 (M+H) + .

[0084] Synthesis Example 9

[0085]

[0086] The synthesis conditions of product BD042 are the same as those of product BD001, except that C16 replaces C1, and C17 replaces C3; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1176.6 (M+H) + .

[0087] Synthesis Example 10

[0088]

[0089] The synthesis conditions of product BD045 are the same as those of product BD042, except that C18 is used to replace C16; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1102.6 (M+H) + .

[0090] Synthesis Example 11

[0091]

[0092] The synthesis conditions of product BD050 are the same as those of product BD001, except that C1 is replaced by C19; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1018.6 (M+H) + .

[0093] Synthesis Example 12

[0094]

[0095] The synthesis conditions of product BD053 are the same as those of product BD001, except that C20 replaces C1; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1018.6 (M+H) + .

[0096] Synthesis Example 13

[0097]

[0098] The synthesis conditions of product BD057 are the same as those of product BD001, except that C21 replaces C1; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1101.5 (M+H) + .

[0099] Synthesis Example 14

[0100]

[0101] The synthesis conditions of product BD061 are the same as those of product BD001, except that C17 replaces C3 and C22 replaces C6; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1114.6 (M+H) + .

[0102] Synthesis Example 15

[0103]

[0104] The synthesis conditions of product BD005 are the same as those of product BD005, except that C23 replaces C6; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1140.6 (M+H) + .

[0105] Synthesis Example 16

[0106]

[0107] The synthesis conditions of product BD075 are the same as those of product BD001, except that C14 replaces C3 and C24 replaces C5; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1162.6 (M+H) + .

[0108] Synthesis Example 17

[0109]

[0110] The synthesis conditions of product BD077 are the same as those of product BD005, except that C25 replaces C5; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1166.7 (M+H) + .

[0111] Synthesis Example 18

[0112]

[0113] The synthesis conditions of product BD083 are the same as those of product BD005, except that one of the C4 is replaced by C26; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1086.6 (M+H) + .

[0114] Synthesis Example 19

[0115]

[0116] The synthesis conditions of product BD093 are the same as those of product BD001, except that C14 replaces C3 and C27 replaces one of the C4s; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1196.7 (M+H) + .

[0117] Synthesis Example 20

[0118]

[0119] The synthesis conditions of product BD101 are the same as those of product BD001, except that C28 replaces C1, C11 replaces C3, and C29 replaces C6; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1140.7 (M+H) + .

[0120] Synthesis Example 21

[0121]

[0122] The synthesis conditions of product BD106 are the same as those of product BD001, except that one of the C4 is replaced by C30; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1150.7 (M+H) + .

[0123] Synthesis Example 22

[0124]

[0125] The synthesis conditions of product BD106 are the same as those of product BD001, except that one of the C4 is replaced by C31; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1259.7 (M+H) + .

[0126] Synthesis Example 23

[0127]

[0128] The synthesis conditions of product BD114 are the same as those of product BD001, except that C32 is used instead of C1; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1114.6 (M+H) + .

[0129] Synthesis Example 24

[0130]

[0131] The synthesis conditions of product BD118 are the same as those of product BD001, except that C33 is used instead of C1; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1130.6 (M+H) + .

[0132] Synthesis Example 25

[0133]

[0134] The synthesis conditions of product BD128 are the same as those of product BD001, except that C27 replaces one of C4 and C34 replaces C5; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1052.5 (M+H) + .

[0135] Synthesis Example 26

[0136]

[0137] The synthesis conditions of product BD 132 are the same as those of product BD001, except that C35 is used instead of C5; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1096.6 (M+H) + .

[0138] Synthesis Example 27

[0139]

[0140] The synthesis conditions of product BD 134 are the same as those of product BD001, except that one of the C4 is replaced by C37; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1096.6 (M+H) + .

[0141] Synthesis Example 27

[0142]

[0143] The synthesis conditions of product BD 140 are the same as those of product BD001, except that C38 is used instead of C1 and C39 is used instead of C3. The molecular weight measured by liquid chromatography mass spectrometry is m / z=1182.7 (M+H) + .

[0144] Synthesis Example 28

[0145]

[0146] The synthesis conditions of product BD 143 are the same as those of product BD001, except that C40 is used instead of C1 and C41 is used instead of C5. The molecular weight measured by liquid chromatography mass spectrometry is m / z=1072.6 (M+H) + .

[0147] Synthesis Example 29

[0148]

[0149] The synthesis conditions of product BD 148 are the same as those of product BD143, except that C42 is used instead of C40; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1085.6 (M+H) + .

[0150] Synthesis Example 30

[0151]

[0152] The synthesis conditions of product BD 152 are the same as those of product BD001, except that C43 is used instead of C42; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1052.6 (M+H) + .

[0153] Synthesis Example 31

[0154]

[0155] The synthesis conditions of product BD157 are the same as those of product BD075, except that C44 is used instead of C6; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1146.6 (M+H) + .

[0156] Synthesis Example 32

[0157]

[0158] The synthesis conditions of product BD164 are the same as those of product BD157, except that C17 replaces C14 and C45 replaces one of the C4s; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1140.7 (M+H) + .

[0159] Synthesis Example 33

[0160]

[0161] The synthesis conditions of product BD166 are the same as those of product BD001, except that C11 replaces C3 and C46 replaces one of C6; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1040.6 (M+H) + .

[0162] Synthesis Example 34

[0163]

[0164] The synthesis conditions of product BD169 are the same as those of product BD014, except that C44 is used instead of C6; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1118.7 (M+H) + .

[0165] Synthesis Example 35

[0166]

[0167] The synthesis conditions of product BD172 are the same as those of product BD148, except that C47 is used instead of C42, and C44 is used instead of C6; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1020.6 (M+H)+ .

[0168] Synthesis Example 36

[0169]

[0170] The synthesis conditions of product BD176 are the same as those of product BD169, except that C48 replaces C9 and C27 replaces C4; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1118.7 (M+H) + .

[0171] Synthesis Example 37

[0172]

[0173] The synthesis conditions of product BD180 are the same as those of product BD001, except that C49 replaces C6; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1066.6 (M+H) + .

[0174] Synthesis Example 38

[0175]

[0176] The synthesis conditions of product BD185 are the same as those of product BD180, except that C24 replaces C5; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1086.5 (M+H) + .

[0177] Synthesis Example 39

[0178]

[0179] The synthesis conditions of product BD188 are the same as those of product BD001, except that C50 is used to replace C5; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1181.7 (M+H) + .

[0180] Synthesis Example 40

[0181]

[0182] The synthesis conditions of product BD194 are the same as those of product BD005, except that C51 is used to replace C5; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1095.7 (M+H) + .

[0183] Synthesis Example 41

[0184]

[0185] The synthesis conditions of product BD194 are the same as those of product BD001, except that C11 replaces C3 and C52 replaces C5; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1083.6 (M+H) + .

[0186] Synthesis Example 42

[0187]

[0188] The synthesis conditions of product BD199 are the same as those of product BD007, except that C53 is used to replace C5; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1055.6 (M+H) + .

[0189] Synthesis Example 43

[0190]

[0191] The synthesis conditions of product BD203 are the same as those of product BD194, except that C54 replaces C3; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1111.7 (M+H) + .

[0192] Synthesis Example 44

[0193]

[0194] The synthesis conditions of product BD212 are the same as those of product BD203, except that C55 replaces C2, C56 replaces C51, and C57 replaces C6; the molecular weight measured by liquid chromatography-mass spectrometry is m / z=1118.8 (M+H) + .

[0195] Synthesis Example 45

[0196]

[0197] The synthesis conditions of product BD221 are the same as those of product BD212, except that C58 replaces C7 and C59 replaces C4; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1132.0 (M+H) + .

[0198] Synthesis Example 46

[0199]

[0200] The synthesis conditions of product BD229 are the same as those of product BD007, except that C60 replaces C8, C55 replaces C2, C54 replaces C3, C59 replaces C4, C56 replaces C5, and C57 replaces C6; the molecular weight measured by liquid chromatography mass spectrometry is m / z=1178.9 (M+H) + .

[0201] Device Example: Fabrication of Organic Electroluminescent Devices Used as Light Emitting Materials

[0202] A 50 mm × 50 mm × 0.7 mm thick glass substrate with an indium tin oxide / silver / indium tin oxide (ITO / Ag / ITO) anode was ultrasonically cleaned in isopropyl alcohol for 5 minutes. The cleaned glass substrate was mounted on a substrate rack of a vacuum evaporation device and evacuated to 1×10 -5 ~1×10 -6 Pa, before evaporating the organic material, treat with nitrogen plasma for 120 seconds. Then co-evaporate HT and PD as a doped hole injection layer (HIL) on the anode, with a film thickness of 10nm, where the doping concentration of PD is 3%. Evaporate HT on the hole injection layer as a hole transport layer (HTL) with a film thickness of 132nm. Then, evaporate EB on the hole transport layer as an electron blocking layer (EBL) with a film thickness of 5nm. Then, co-evaporate the light-emitting layer (EML) on the electron blocking layer with a film thickness of 20nm; the light-emitting layer (EML) adopts a multi-source co-evaporation method to evaporate the main material and the light-emitting material (BH and BD001) of the light-emitting layer, where the doping concentration of the light-emitting material is 1.5%. Then evaporate HB on the light-emitting layer as a hole blocking layer (HBL) with a film thickness of 5nm. Then on the hole blocking layer, 1:1 co-evaporate the electron transport material (ET) and 8-hydroxyquinoline lithium (Liq) as the electron transport layer (ETL), with a film thickness of 30nm. In addition, LiF was evaporated on the ETL as an electron injection layer (EIL) with a thickness of 1 nm. Then, cathode metal magnesium / silver (Mg / Ag) was co-evaporated on the EIL with a thickness of 13.2 nm, wherein the doping concentration of magnesium was 10%. Finally, CP was evaporated as a light coupling layer (CPL) with a thickness of 70 nm. The fabricated device was transferred to a glove box and encapsulated with a glass cover. The structure of the organic electroluminescent device of Example 1 is shown in FIG. Figure 1 As shown, Figure 1 The stacking order and role of each functional layer are also shown.

[0203] The OLED has the following layer structure in principle: ITO / Ag / ITO substrate / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / luminescent layer (EML) / hole blocking layer (HBL) / electron transport layer (ETL) / electron injection layer (EIL) / cathode / coupling layer (CPL). The exact structure of the OLED is shown in Table 1.

[0204] Table 1 Materials used for OLED

[0205]

[0206]

[0207] Device Example 1 :

[0208] ITO / Ag / ITO / HT:PD(10nm,3%) / HT(132nm) / EB(5nm) / BH:BD001(20nm,1.5%) / HB(5nm) / ET:Liq(30nm,50%) / LiF(1nm) / Ag:Mg(13.2nm,10%) / CP(70nm)

[0209] The only difference between device example 2-46 and device example 1 is that BD001 of the present invention used in the light-emitting layer is replaced with other compounds of the present invention. The obtained device performance test data is shown in Table 2.

[0210] Comparative Examples 1 to 4:

[0211] Compared with device embodiment 1, the difference between this comparative example is that BD001 in the organic electroluminescent device is changed to Ref-1, Ref-2, Ref-3, and Ref-4 which are well-known in the industry and have been commercially applied. The obtained device performance test data are shown in Table 2.

[0212] The OLEDs were characterized by standard methods. For this purpose, the electroluminescence spectrum, half-peak width, current efficiency (measured in cd / A), power efficiency (measured in lm / W) and external quantum efficiency (EQE, measured in %) and color coordinates (CIEx, CIEy) were determined, which were calculated as a function of the luminous density from the current / voltage / luminous density characteristic line (IUL characteristic line) exhibiting Lambertian emission characteristics. The blue light index (BI) is expressed at 10 mA / cm 2 Current efficiency / CIEy under T95, which means the device is at 20mA / cm 2 The FWHM value indicates the working time of the device when the brightness decreases to 95% at the initial brightness of 10mA / cm 2 The device performances of Examples 1 to 32 of the present invention and Comparative Examples 1 to 4 are summarized in Table 2;

[0213] Table 2 Device performance

[0214]

[0215]

[0216] As can be seen from Table 2, compared with the prior art, the use of the material embodiments 1-47 of the present invention has good performance in spectrum narrowing, efficiency and life improvement. Compared with Comparative Example 2, the FWHM of BD065 of device embodiment 15 is narrowed by 0.5nm, the efficiency is improved by 9.1%, and the life is also improved by 21.1%; the performance improvement comes from the large plane of indole acridine, which can increase the rigidity of the molecule, improve the radiation rate and stability. Compared with Comparative Example 3, the FWHM of BD093 of device embodiment 19 is narrowed by nearly 1nm, the efficiency is improved by 13.7%, and the life is also doubled. The performance improvement comes from the greater conjugation of indole acridine relative to indole; the lower T1 energy level suppresses the accumulation of triplet excitons; thereby improving efficiency and life. Compared with Comparative Example 4, the FWHM of BD194 of device embodiment 41 is slightly narrowed, but the efficiency is improved by 19%, and the life is also improved by 24.1%. The performance improvement comes from the spectrum and energy level more matching the device, and the improvement of the stability of the molecule by deuteration.

Claims

1. A fused heterocyclic compound, characterized in that: The fused heterocyclic compound is represented by the following general formula (1): X is selected from O, S, Se; R1 to R4 are independently selected from hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted silyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diphenylamine; and adjacent groups may form a ring; a is independently selected from an integer of 0-3, and b and c are independently selected from an integer of 0-4; R5 to R6 are independently selected from substituted or unsubstituted alkyl, substituted or unsubstituted phenyl, and R5 and R6 may form a ring, except that R5 and R6 form a ring with fluorene; Ar1 to Ar2 are independently selected from substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl; The entire molecule may be deuterated or undeuterated.

2. The fused heterocyclic compound for an organic electroluminescent device according to claim 1, characterized in that: The R1 to R4 each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted phenyl group.

3. The fused heterocyclic compound for an organic electroluminescent device according to claim 1, characterized in that: The R5 and R6 respectively independently represent a methyl group and a phenyl group.

4. The fused heterocyclic compound for an organic electroluminescent device according to claim 1, characterized in that: The Ar1 and Ar2 are independently selected from substituted or unsubstituted phenyl groups.

5. The fused heterocyclic compound for an organic electroluminescent device according to claim 1, characterized in that: The "substituted" in the "substituted or unsubstituted" in the compound means that the substituent is independently selected from a deuterium atom, a tritium atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a monovalent alkyl group or a cycloalkyl group having 1 to 10 carbon atoms, a monovalent monocyclic aromatic group or a condensed aromatic group having 6 to 30 carbon atoms, and a monovalent heterocyclic group or a condensed heteroaryl group having 2 to 50 carbon atoms.

6. The fused heterocyclic compound for an organic electroluminescent device according to claim 1, characterized in that: The fused heterocyclic compound is selected from the following structures:

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and at least one organic thin film between the anode and the cathode, wherein the organic thin film contains the compound according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, characterized in that: The compound is used as a light-emitting material in an organic electroluminescent device.

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