Organic electroluminescent compound and application thereof

Abstract

The invention relates to the technical field of display, in particular to an organic electroluminescent compound and application thereof. The organic electroluminescent compound provided by the invention has a structure shown as follows: # imgabs0 #, so that an organic electroluminescent device containing the organic electroluminescent compound has relatively low driving voltage, relatively high luminous efficiency and relatively long service life.

Description

Technical Field

[0001] The present invention relates to the field of display technology, and in particular to an organic electroluminescent compound and application thereof. Background Art

[0002] Organic electroluminescent devices such as organic electroluminescent diodes (OLEDs) convert electrical energy into light by applying power to organic electroluminescent materials, and generally include an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the organic electroluminescent device may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescent auxiliary layer, an electron blocking layer, a luminescent layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and the materials used in the organic layer are generally divided into hole injection materials, hole transport materials, hole auxiliary materials, luminescent auxiliary materials, electron blocking materials, luminescent materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. according to their functions. In an organic electroluminescent device, the luminescence mechanism is: under the drive of an external electric field, electrons and holes are injected into the organic electron transport layer and the hole transport layer by the cathode and the anode, respectively, and excitons are compounded in the organic luminescent layer, and the excitons radiatively transition back to the ground state and emit light.

[0003] At present, the existing organic electroluminescent materials have poor structural stability, poor matching between the HOMO and LUMO energy levels of the existing organic electroluminescent materials and the adjacent energy levels, and unbalanced carrier mobility. As a result, the organic electroluminescent devices containing the organic electroluminescent materials have high driving voltage, low luminous efficiency and short life, which seriously limits the application of organic electroluminescent devices. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of poor structural stability of existing organic electroluminescent materials, poor matching between HOMO and LUMO energy levels and adjacent energy levels, and unbalanced carrier mobility, which result in high driving voltage, low luminous efficiency and short life of organic electroluminescent devices containing the organic electroluminescent materials, and further provide an organic electroluminescent compound and its application.

[0005] Definitions of substituent terms in this invention:

[0006] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0007] As used in the present invention, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0008] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a group derived from a monocyclic hydrocarbon or a polycyclic hydrocarbon having 1 to 30 ring main chain carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0009] In the present invention, aryl and arylene groups include monocyclic, polycyclic or condensed-ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures. Aryl groups include but are not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene groups include but are not limited to phenylene, biphenylene, terphenylene, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0010] In the present invention, heteroaryl and heteroarylide include monocyclic, polycyclic or condensed ring heteroaryl, and the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. Heteroaryl includes, but is not limited to, furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzo thiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof; heteroarylene includes but is not limited to furanyl, phenylene thio, pyrroleyl yl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, benzofuranyl, benzothiophenylene, isobenzofuranyl, dibenzofuranyl, dibenzothiophenylene, benzimidazolyl, oxazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, acridinyl, and derivatives thereof.

[0011] As used in the present invention, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0012] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0013] In the present invention, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms is any integer within the defined range. For example, C6-C30 aromatic group, the number of carbon atoms representing the aromatic group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0014] In the present invention, Indicates a connection key.

[0015] The scheme adopted by the present invention is as follows:

[0016] The present invention provides an organic electroluminescent compound having the structure of the following formula 1:

[0017]

[0018] Among them, X 1 , X 2 Each independently selected from O, S, Se;

[0019] L is a self-connecting bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group;

[0020] Z 1 Selected from N and CR Z1 , Z 2 Selected from N and CR Z2 , Z 3 Selected from N and CR Z3 , Z 4 Selected from N and CR Z4 , Z 5 Selected from N and CR Z5 ;

[0021] R Z1 -R Z5 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R X1 -R X5Each exists independently, or two adjacent rings are connected to form Ring A, wherein Ring A is a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring;

[0022] The substituents in the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C1-C30 alkyl group, substituted C3-C30 cycloalkyl group, substituted C6-C30 aryl group, substituted C3-C30 heteroaryl group, substituted C6-C30 aromatic ring and substituted C3-C30 heteroaromatic ring are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl group, C3-C12 cycloalkyl group, C6-C30 aryl group and C3-C30 heteroaromatic group.

[0023] It is understood that the organic electroluminescent compound in the present invention has the following structure:

[0024]

[0025] The substitution may be made on the ring C or the ring D.

[0026] Preferably, L is selected from a linking bond, a substituted or unsubstituted C6-C12 arylene group, a substituted or unsubstituted C3-C12 heteroarylene group;

[0027] Preferably, in the Z 1 -Z 5 middle,

[0028] Z 1 N, Z 2 N, Z 3 CR Z3 , Z 4 CR Z4 , Z 5 CR Z5 ; R Z3 , R Z4 , R Z5 Each exists independently, or R Z3 , R Z4 Connected into ring A, or R Z3 , R Z4 connected to form ring A; or,

[0029] Z 1 N, Z 3 N, Z 2 CR Z2 , X 4 CR Z4 , X 5 CR Z5 ; R Z2, R Z4 , R Z5 Each exists independently, or R Z2 , R Z5 connected to form ring A; or,

[0030] Z 1 N, Z 2 N, Z 3 N, Z 4 CR Z4 , Z 5 CR Z5 ;

[0031] Wherein, Ring A is a substituted or unsubstituted C6-C20 aromatic ring, or a substituted or unsubstituted C3-C20 heteroaromatic ring;

[0032] R Z2 -R Z5 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C20 heteroaryl;

[0033] The substituents in the substituted C6-C12 arylene group, substituted C3-C12 heteroarylene group, substituted C6-C20 aromatic ring, substituted C3-C20 heteroaromatic ring, substituted C1-C12 alkyl group, substituted C3-C20 cycloalkyl group and substituted C6-C25 aromatic group are each independently selected from one or a combination of at least two of the C1-C6 alkyl group, the C3-C12 cycloalkyl group, the C6-C25 aromatic group and the C3-C25 heteroaromatic group.

[0034] Preferably, L is selected from a linking bond, a substituted or unsubstituted phenylene group, a substituted or substituted naphthylene group;

[0035] Preferably, R X1 -R X5 Each is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted B group;

[0036] Wherein the B group is selected from one of the following groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, phenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, pyridylphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl and benzonaphthothiophenyl;

[0037] Preferably, ring A is selected from substituted or unsubstituted C6-C12 aromatic rings;

[0038] The substituents in the substituted phenylene, substituted naphthylene, substituted B group, substituted or C6-C12 aromatic ring are selected from one or a combination of deuterium, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, C3-C12 heteroaryl;

[0039] Preferably, L is selected from a linker, a phenylene group, and a naphthylene group;

[0040] Preferably, R X1 -R X5 Each independently selected from phenyl, naphthyl, biphenyl, phenyl, terphenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridylphenyl, phenylpyridyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl and benzonaphthofuranyl;

[0041] Preferably, Z 1 N, Z 3 N, Z 2 CR Z2 , X 4 CR Z4 , X 5 CR Z5 ; R Z2 , R Z4 , R Z5 Each exists independently, or R Z2 , R Z5 connected to form ring A; or,

[0042] Z 1 N, Z 2 N, Z 3 N, Z 4 CR Z4 , Z 5 CR Z5 ;

[0043] Wherein, ring A is selected from a benzene ring.

[0044] Preferably,

[0045] X 1 , X 2 Selected from O.

[0046] Preferably, the organic electroluminescent compound is selected from one of the following compounds 1 to 283:

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054] The present invention also provides an organic electroluminescent material, comprising the organic electroluminescent compound mentioned above.

[0055] The present invention also provides an organic electroluminescent device, which comprises a cathode, an anode and an organic layer located between the cathode and the anode, wherein the organic layer comprises the organic electroluminescent compound or the organic electroluminescent material described above.

[0056] Preferably, the organic layer comprises an electron transport layer, and the electron transport layer comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material.

[0057] Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the above-mentioned organic electroluminescent compound or the above-mentioned organic electroluminescent material.

[0058] Optionally, the material of the light-emitting layer includes a host material and a guest material; the host material includes the above-mentioned organic electroluminescent compound.

[0059] In an embodiment of an organic electroluminescent device of the present invention, the organic layer is composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer stacked in sequence, and the organic electroluminescent device also includes a substrate, which is located on the surface of the anode facing away from the cathode.

[0060] The present invention also provides the use of the above-mentioned organic electroluminescent device in optical fiber equipment, lighting equipment, electronic photographic photosensitive body equipment, photoelectric converter, organic solar cell, switch element equipment, organic light-emitting field effect transistor, image sensor or dye laser.

[0061] In the present invention, the synthesis path of the organic electroluminescent compound comprises the following steps:

[0062] 1. Synthesis of intermediate nA

[0063]

[0064] 2. Synthesis of organic electroluminescent compounds

[0065]

[0066] X 1 -X 2 Each independently selected from O or S, Se,

[0067] L is selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group,

[0068] Z 1 Selected from N and CR Z1 , Z 2 Selected from N and CR Z2 , Z 3 Selected from N and CR Z3 , Z 4 Selected from N and CR Z4 , Z 5 Selected from N and CR Z5 , R Z1 -R Z5 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R X1 -R X5 They exist independently or are connected to form ring A, and the ring A is a substituted or unsubstituted C6-C30 aromatic ring, and a substituted or unsubstituted C3-C30 heteroaromatic ring.

[0069] Beneficial effects of the present invention:

[0070] The organic electroluminescent compound provided by the present invention is based on the structure of Formula 1, and the energy level matching degree of the organic electroluminescent compound is improved by adjusting the structure of the substituent; the organic electroluminescent compound can be structurally modified to improve the stacking between materials, and a planar rigid structure is adopted, which is beneficial for the organic electroluminescent compound to show high electron mobility and improve the stability of the device. When the organic electroluminescent material provided by the present invention is used as an electron transport material or a main material of an organic electroluminescent device, it has the characteristics of high carrier mobility, thereby improving the luminous efficiency of the device; the HOMO and LUMO energy levels of the organic electroluminescent compound have a high matching degree with the adjacent energy levels, so that the organic electroluminescent compound obtains higher stability and the carrier mobility is more balanced, thereby making the organic electroluminescent device containing the organic electroluminescent compound have lower driving voltage, higher luminous efficiency and longer life. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0072] Figure 1 A structural diagram of an organic electroluminescent device in an embodiment of the device of the present invention;

[0073] 1-substrate; 2-anode; 3-hole injection layer; 4-hole transport layer; 5-light-emitting layer; 6-electron transport layer; 7-electron injection layer; 8-cathode. DETAILED DESCRIPTION

[0074] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0075] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0076] The term "organic electroluminescent material" in the present disclosure means a material that can be used in an organic electroluminescent device and can contain at least one compound. If necessary, the organic electroluminescent material can be contained in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material can be a hole injection material, a hole transport material, a hole auxiliary material, a luminescence auxiliary material, an electron blocking material, a luminescent material (containing a host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0077] The term "multiple organic electroluminescent materials" in the present disclosure means one or more organic electroluminescent materials comprising a combination of at least two compounds, which may be included in any layer constituting an organic electroluminescent device. It may mean both a material contained in an organic electroluminescent device before (e.g., before vapor deposition) and a material contained in an organic electroluminescent device after (e.g., after vapor deposition). For example, a plurality of organic electroluminescent materials may be a combination of at least two compounds, which may be included in at least one of the following: a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescent auxiliary layer, an electron blocking layer, a luminescent layer, an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. At least two compounds may be included in the same layer or in different layers, and may be mixed-evaporated or co-evaporated, or may be evaporated individually.

[0078] Some intermediate synthesis

[0079] Synthesis of intermediate 1-A:

[0080]

[0081] Synthesis of intermediate 1-A-1: Take a 100 ml three-necked round-bottom flask and put in a stirrer. Under nitrogen protection, add the raw material 1-Aa, i.e. 1-bromo-2-chloro-9-methoxydibenzo[b,d]furan (1mmol), tetrahydrofuran (10mmol) in sequence, cool to minus 78 degrees Celsius, slowly add n-butyl lithium (1.2mmol) at this temperature, slowly warm to room temperature after the addition is completed, and react for 1 hour. Cool to minus 78 degrees Celsius again, slowly add N,N-dimethylformamide (DMF) (1.2mmol) at this temperature, slowly warm to room temperature, and react for 2 hours. After the reaction is completed, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate 1-A-1 (yield 72%).

[0082] Synthesis of intermediate 1-A-2: Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate 1-A-1 (1 mmol), benzofuran-3-ylboronic acid (1 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL) in sequence, heat to 90 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate 1-A-2 (yield 64%).

[0083] Synthesis of intermediate 1-A-3: Take a 100 ml three-necked round-bottom flask and put in a stirrer. Under nitrogen protection, add the raw material methoxymethyltriphenylphosphine chloride (1.8 mmol), potassium tert-butoxide (2.5 mmol), tetrahydrofuran (10 mL) in sequence, cool to minus 15 degrees Celsius, stir for 30 minutes, and then slowly add the tetrahydrofuran solution of intermediate 1-A-2 dropwise, react at minus 15 degrees Celsius for 30 minutes, then warm to room temperature and react for 2 hours. After the reaction is completed, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate 1-A-3 (yield 80%).

[0084] Synthesis of intermediate 1-A-4: Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add ferric chloride (0.1 mmol), calcium chloride (0.3 mmol), and 1,2-dichloroethane (10 mL) in sequence, raise the temperature to 90 degrees Celsius, and then slowly add a 1,2-dichloroethane solution of intermediate 1-A-3 (1 mmol) dropwise, and react at 90 degrees Celsius for 5 hours. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate 1-A-4 (yield 76%).

[0085] Synthesis of intermediate 1-A-5: Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate 1-A-4 (1 mmol) and dichloromethane (10 mL) in sequence, cool to 0 degrees Celsius, and slowly add a dichloromethane solution of boron tribromide (2M / L, 1.2 mmol). After the addition is complete, return to room temperature and continue to react for 3 hours. After the reaction is completed, the reaction system is slowly added dropwise to deionized water to quench, extracted with dichloromethane, and the organic phase is dried over anhydrous magnesium sulfate. The solvent is removed using a rotary evaporator, and the crude product is separated by column chromatography (ethyl acetate: n-hexane = 4:50) to obtain intermediate 1-A-5 (yield 75%).

[0086] Synthesis of intermediate 1-A-6: Take a 100 ml three-necked round-bottom flask and put in a stirrer. Under nitrogen protection, add intermediate 1-A-5 (1 mmol), triethylamine (2 mmol), and dichloromethane (10 mL) in sequence, cool to 0 degrees Celsius, and then slowly add trifluoromethanesulfonic anhydride (1.2 mmol). After the addition is complete, return to room temperature and continue to react for 3 hours. After the reaction is completed, the reaction system is slowly added dropwise to deionized water to quench, extracted with dichloromethane, and the organic phase is dried over anhydrous magnesium sulfate. The solvent is removed using a rotary evaporator, and the crude product is separated by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate 1-A-6 (yield 72%).

[0087] Synthesis of intermediate 1-A: Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate 1-A-6 (1 mmol), bis(boronate) (1.1 mmol), 1,4-dioxane (10 mL), Pd(dppf)Cl2 (0.03 mmol), potassium acetate (2.5 mmol) in sequence, heat to 100 degrees Celsius, react for 5 hours, and after the reaction is completed, cool to room temperature, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, use a rotary evaporator to remove the solvent, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate 1-A (yield 80%).

[0088] Synthesis of intermediates 2-A to 6-A:

[0089] The preparation methods of intermediates 2-A to 6-A are as described in the preparation steps of intermediate 1-A, except that 1-Aa substituted with methoxy groups at different positions is used as the reaction raw material;

[0090] The specific structures of intermediates 2-A to 6-A are as follows:

[0091]

[0092] Example 1

[0093] This embodiment provides an organic electroluminescent compound N-4. The preparation method of the organic electroluminescent compound N-4 specifically comprises the following steps:

[0094]

[0095] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate 1-A (1 mmol), 4-B, i.e. 2-chloro-4,6-diphenyl-1,3,5-triazine (0.9 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL) in sequence, heat to 90 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and the crude product is purified twice by recrystallization from o-dichlorobenzene to obtain compound N-4 (yield 52%).

[0096] Elemental analysis: C 37 H 21 Theoretical value of N3O2: C, 82.36; H, 3.92; N, 7.79; O, 5.93; Found value: C, 82.39; H, 3.96; N, 7.72; HRMS (ESI) m / z [M+H]+: Theoretical value: 539.16; Found value: 540.21.

[0097] Example 2

[0098] This embodiment provides an organic electroluminescent compound N-21. The preparation method of the organic electroluminescent compound N-21 specifically comprises the following steps:

[0099]

[0100] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate 3-A (1 mmol), 21-B, i.e. 2-chloro-4-(dibenzo[b, d]furan-1-yl)-6-phenyl-1,3,5-triazine (0.9 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL) in sequence, heat to 90 degrees Celsius and react for 5 hours. After the reaction is completed, cool to room temperature, filter, rinse the filter cake twice with deionized water and twice with ethanol, and the crude product is purified twice by recrystallization from o-dichlorobenzene to obtain compound N-21 (yield 55%).

[0101] Elemental analysis: C 43 H 23 Theoretical value of N3O3: C, 82.02; H, 3.68; N, 6.67; O, 7.62; Found value: C, 82.10; H, 3.66; N, 6.62; HRMS (ESI) m / z [M+H]+: Theoretical value: 629.17; Found value: 630.43.

[0102] Example 3

[0103] This embodiment provides an organic electroluminescent compound N-146. The preparation method of the organic electroluminescent compound N-146 is similar to the preparation method of the organic electroluminescent compound N-4 in Example 1, except that 4-A is used instead of 1-A, and 146-B is used instead of 4-B to obtain compound N-146 (yield 48%).

[0104] The reaction of the preparation process is as follows:

[0105]

[0106] Elemental analysis: C 47 H 25 Theoretical value of N3O3: C, 83.05; H, 3.71; N, 6.18; O, 7.06; Found value: C, 83.12; H, 3.70; N, 6.11; HRMS (ESI) m / z [M+H]+: Theoretical value: 679.19; Found value: 680.65.

[0107] Example 4

[0108] This embodiment provides an organic electroluminescent compound N-200. The preparation method of the organic electroluminescent compound N-200 is similar to the preparation method of the organic electroluminescent compound N-4 in Example 1, except that 6-A is used instead of 1-A, and 200-B is used instead of 4-B to obtain compound N-200 (yield 48%).

[0109] The reaction of the preparation process is as follows:

[0110]

[0111] Elemental analysis: C 43 H 25 Theoretical value of N3O2: C, 83.88; H, 4.09; N, 6.83; O, 5.20; Found value: C, 83.91; H, 4.12; N, 6.76; HRMS (ESI) m / z [M+H]+: Theoretical value: 615.19; Found value: 616.43.

[0112] Example 5

[0113] This embodiment provides an organic electroluminescent compound N-257. The preparation method of the organic electroluminescent compound N-257 is similar to the preparation method of the organic electroluminescent compound N-4 in Example 1, except that 3-A is used instead of 1-A, and 257-B is used instead of 4-B to obtain compound N-257 (yield 48%).

[0114] The reaction of the preparation process is as follows:

[0115]

[0116] Elemental analysis: C 40 H 22 Theoretical value of N2O2: C, 85.39; H, 3.94; N, 4.98; O, 5.69; Found value: C, 85.42; H, 3.95; N, 4.93; HRMS (ESI) m / z [M+H]+: Theoretical value: 562.17; Found value: 563.46.

[0117] Example 6

[0118] This embodiment provides an organic electroluminescent compound N-267. The preparation method of the organic electroluminescent compound N-267 is similar to the preparation method of the organic electroluminescent compound N-4 in Example 1, except that 5-A is used instead of 1-A, and 267-B is used instead of 4-B to obtain compound N-267 (yield 57%).

[0119] The reaction of the preparation process is as follows:

[0120]

[0121] Elemental analysis: C 40 H 22 Theoretical value of N2O2: C, 85.39; H, 3.94; N, 4.98; O, 5.69; Found value: C, 85.45; H, 3.91; N, 4.93; HRMS (ESI) m / z [M+H]+: Theoretical value: 562.17; Found value: 563.83.

[0122] The preparation method of Example 7-23 is similar to that of Example 1. The intermediates used in Example 7-23 and the products obtained are shown in Table 1 below.

[0123] Table 1

[0124]

[0125]

[0126]

[0127]

[0128] The characterization data of the products prepared in Examples 7-23 are shown in Table 2:

[0129] Table 2

[0130]

[0131]

[0132] Device Examples 1-28 and Device Comparative Example 1

[0133] The organic electroluminescent devices provided in device examples 1-28 and device comparative example 1 are as follows: Figure 1 As shown, it includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8 which are sequentially stacked on a substrate 1, and its device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0134] The materials for manufacturing the organic electroluminescent device are as follows:

[0135]

[0136] The preparation of the organic electroluminescent device comprises the following steps:

[0137] 1) Substrate cleaning:

[0138] The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (the volume ratio of acetone to ethanol is 1:1), baked in a clean environment until the moisture is completely removed, and then cleaned with ultraviolet light and ozone.

[0139] 2) Preparation of organic layer:

[0140] Transfer the ITO transparent substrate to the evaporation equipment and evacuate to 1×10 -6 Up to 2×10 -4 Pa, 10nm hole injection layer (HIL) / 80nm hole transport layer (HTL) / 30nm light emitting layer (EML) / 30nm electron transport layer (ETL) / 1nm electron injection layer (EIL) / 90nm thick cathode (Al) were evaporated on the anode in sequence.

[0141] in:

[0142] The material of the hole injection layer (HIL) is a mixture of HATCN and HT, wherein the mass ratio of HATCN to HT is 3:97; the evaporation is carried out by co-evaporation;

[0143] The material of the hole transport layer (HTL) is HT;

[0144] Light-emitting layer (EML): vacuum evaporation of light-emitting materials by co-evaporation, the specific materials and mass ratios are shown in Table 3;

[0145] Electron transport layer (ETL): vacuum evaporation of electron transport material by co-evaporation (specific materials and mass ratios are shown in Table 3);

[0146] The material of the electron injection layer (EIL) is LiQ;

[0147] The thickness and material of each layer are shown in Table 3.

[0148] Table 3

[0149]

[0150]

[0151]

[0152]

[0153] The embodiments in Table 3 refer to device embodiments, and the comparative examples refer to device comparative examples, wherein, taking the ETL layer in Example 1 as an example, the "4" in "4:LiQ" refers to compound N-4, and the other numbers in the table correspond to the corresponding compounds; taking the EML layer in Example 6 as an example, the "4" in "CBP:4:(piq)2Ir(acac)" refers to compound N-4, and the other numbers in the table correspond to the corresponding compounds.

[0154] Test Case

[0155] The organic electroluminescent devices obtained from device examples 1 to 28 and comparative example 1 in the device examples were tested.

[0156] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system;

[0157] Test conditions: Photoelectric properties Test conditions: Current density is 10mA / cm 2 .

[0158] Life test: current density is 50mA / cm 2 , record the time (in hours) when the device brightness drops to 95% of the original brightness.

[0159] The device performance test results are shown in Table 4:

[0160] Table 4

[0161]

[0162]

[0163] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. An organic electroluminescent compound, characterized in that: It has the structure of Formula 1: Among them, X 1 , X 2 Each independently selected from O, S, Se; L is a self-connecting bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group; Z 1 Selected from N and CR Z1 , Z 2 Selected from N and CR Z2 , Z 3 Selected from N and CR Z3 , Z 4 Selected from N and CR Z4 , Z 5 Selected from N and CR Z5 ; R Z1 -R Z5 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R X1 -R X5 Each exists independently, or two adjacent rings are connected to form Ring A, wherein Ring A is a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring; The substituents in the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C1-C30 alkyl group, substituted C3-C30 cycloalkyl group, substituted C6-C30 aryl group, substituted C3-C30 heteroaryl group, substituted C6-C30 aromatic ring and substituted C3-C30 heteroaromatic ring are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl group, C3-C12 cycloalkyl group, C6-C30 aryl group and C3-C30 heteroaromatic group.

2. The organic electroluminescent compound according to claim 1, characterized in that L is selected from a connecting bond, a substituted or unsubstituted C6-C12 arylene group, and a substituted or unsubstituted C3-C12 heteroarylene group; Preferably, in the Z 1 -Z 5 middle, Z 1 N, Z 2 N, Z 3 CR Z3 , Z 4 CR Z4 , Z 5 CR Z5 ; R Z3 , R Z4 , R Z5 Each exists independently, or R Z3 , R Z4 Connected into ring A, or R Z3 , R Z4 connected to form ring A; or, Z 1 N, Z 3 N, Z 2 CR Z2 , X 4 CR Z4 , X 5 CR Z5 ; R Z2 , R Z4 , R Z5 Each exists independently, or R Z2 , R Z5 connected to form ring A; or, Z 1 N, Z 2 N, Z 3 N, Z 4 CR Z4 , Z 5 CR Z5 ; Wherein, Ring A is a substituted or unsubstituted C6-C20 aromatic ring, or a substituted or unsubstituted C3-C20 heteroaromatic ring; R Z2 -R Z5 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C20 heteroaryl; The substituents in the substituted C6-C12 arylene group, substituted C3-C12 heteroarylene group, substituted C6-C20 aromatic ring, substituted C3-C20 heteroaromatic ring, substituted C1-C12 alkyl group, substituted C3-C20 cycloalkyl group and substituted C6-C25 aromatic group are each independently selected from one or a combination of at least two of the C1-C6 alkyl group, the C3-C12 cycloalkyl group, the C6-C25 aromatic group and the C3-C25 heteroaromatic group.

3. The organic electroluminescent compound according to claim 1 or 2, characterized in that: L is selected from a linking bond, a substituted or unsubstituted phenylene group, and a substituted or substituted naphthylene group; Preferably, R X1 -R X5 Each is independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted B group; Wherein the B group is selected from one of the following groups: phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, phenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, pyridylphenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl and benzonaphthothiophenyl; Preferably, ring A is selected from substituted or unsubstituted C6-C12 aromatic rings; The substituents in the substituted phenylene, substituted naphthylene, substituted B group, substituted or C6-C12 aromatic ring are selected from one or a combination of deuterium, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, C3-C12 heteroaryl; Preferably, L is selected from a linker, a phenylene group, and a naphthylene group; Preferably, R X1 -R X5 Each independently selected from phenyl, naphthyl, biphenyl, phenyl, terphenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridylphenyl, phenylpyridyl, dimethylfluorenyl, diphenylfluorenyl, dibenzofuranyl, dibenzothiophenyl and benzonaphthofuranyl; Preferably, Z 1 N, Z 3 N, Z 2 CR Z2 , X 4 CR Z4 , X 5 CR Z5 ; R Z2 , R Z4 , R Z5 Each exists independently, or R Z2 , R Z5 connected to form ring A; or, Z 1 N, Z 2 N, Z 3 N, Z 4 CR Z4 , Z 5 CR Z5 ; Wherein, ring A is selected from a benzene ring.

4. The organic electroluminescent compound according to any one of claims 1 to 3, characterized in that: X 1 , X 2 Selected from O.

5. The organic electroluminescent compound according to any one of claims 1 to 4, characterized in that: The organic electroluminescent compound is selected from one of the following compounds 1 to 283:

6. An organic electroluminescent material, characterized in that: The organic electroluminescent compound comprises the organic electroluminescent compound according to any one of claims 1 to 5.

7. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic layer located between the cathode and the anode, wherein the organic layer comprises the organic electroluminescent compound according to any one of claims 1 to 6 or the organic electroluminescent material according to claim 6.

8. The organic electroluminescent device according to claim 7, characterized in that: The organic layer comprises an electron transport layer, and the electron transport layer comprises the organic electroluminescent compound according to any one of claims 1 to 5 or the organic electroluminescent material according to claim 6.

9. The organic electroluminescent device according to claim 7 or 8, characterized in that: The organic layer comprises a light-emitting layer, and the light-emitting layer comprises the organic electroluminescent compound according to any one of claims 1 to 5 or the organic electroluminescent material according to claim 6.

10. Use of the organic electroluminescent device according to any one of claims 7 to 9 in optical fiber equipment, lighting equipment, electrophotographic photoreceptor equipment, photoelectric converters, organic solar cells, switching element equipment, organic light-emitting field effect transistors, image sensors or dye lasers.

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