Organic electroluminescent material and application thereof

Abstract

According to the organic electroluminescent material and the application thereof provided by the invention, the organic electroluminescent compound is used as the organic electroluminescent material, so that an organic electroluminescent device has low driving voltage, high current efficiency and relatively long service life.

Description

Technical Field

[0001] The invention belongs to the field of organic electroluminescent materials and relates to an organic electroluminescent material and an application thereof. Background Art

[0002] An electroluminescent device (EL device) is a self-luminous display device having the advantages that it provides a wider viewing angle, a greater contrast ratio and a faster response time. The first organic EL device was developed by Eastman Kodak in 1987 by using small aromatic diamine molecules and aluminum complexes as materials for forming the light-emitting layer (see Appl. Phys. Lett.

[0003] An organic electroluminescent device (OLED) converts electrical energy into light by applying power to an organic electroluminescent material, and generally includes an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of an OLED 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, an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. The materials used in the organic layer can be divided into hole injection materials, hole transport materials, hole auxiliary materials, luminescent auxiliary materials, electron blocking materials, luminescent materials (including host materials and dopant materials), electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, and the like according to their functions. In an OLED, holes from an anode and electrons from a cathode are injected into a luminescent layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. The organic light-emitting compound moves to an excited state by energy and emits light when the organic light-emitting compound returns to a ground state from an excited state.

[0004] The most important factor that determines the luminous efficiency in OLED is the luminescent material. The luminescent material is required to have the following characteristics: high quantum efficiency, high electron and hole mobility, and uniformity and stability of the luminescent material layer formed. The luminescent material is divided into blue, green and red luminescent materials according to the luminescent color, and further includes yellow or orange luminescent materials. In addition, in terms of function, the luminescent material can be divided into a host material and a dopant material. Recently, an urgent task is to develop OLEDs with high efficiency and long life. Specifically, considering the EL characteristics required for medium and large OLED panels, it is urgent to develop highly excellent luminescent materials that are superior to conventional materials. For this reason, as a solid solvent and energy emitter, the host material should preferably have high purity and a suitable molecular weight for deposition under vacuum. In addition, the host material is required to have a high glass transition temperature and a pyrolysis temperature to achieve thermal stability, high electrochemical stability, to achieve long life, easy formability of amorphous thin films, good adhesion to adjacent layers, and immobility between layers.

[0005] Currently, phosphorescent materials, which provide excellent luminous efficiency in clear panels, are mainly used in organic electroluminescent devices. In many applications such as TV and lighting equipment, OLED life is insufficient, and there is still a need for high-efficiency OLEDs. Typically, the higher the brightness of the OLED, the shorter the life of the OLED. Therefore, in order to maintain the high resolution of the display for long-term use, new luminescent materials showing high luminous efficiency and long life are needed. Summary of the invention

[0006] In view of the deficiencies of the prior art, an object of the present invention is to provide an organic electroluminescent material and application thereof.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In one aspect, the present invention provides an organic electroluminescent material having a structure as shown in Formula I:

[0009]

[0010] Wherein L1 and L2 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group,

[0011] X1 is selected from O, S or Se, X2 is NAr,

[0012] Y1 is selected from N and CR Y1 , Y2 is selected from N and CR Y2 , Y 3 Selected from N and CR Y3 , Y 4 Selected from N and CR Y4 ,

[0013] R Y1 -R Y4 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 Y1 -R Y4 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;

[0014] R1 and R2 are 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,

[0015] Ar is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

[0016] a and b are each independently selected from an integer of 0-3 (e.g., 0, 1, 2 or 3);

[0017] The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 aromatic ring, substituted C3-C30 heteroaromatic ring, substituted C6-C30 arylene and substituted C3-C30 heteroarylene are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl or C3-C30 heteroaryl.

[0018] Preferably, L1 and L2 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C25 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0019] Preferably, R1 and R2 are selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C3-C25 heteroaryl;

[0020] Preferably, R Y1 -R Y4 R is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C25 heteroaryl; Y1 -R Y5 Each exists independently, or two adjacent rings are connected to form Ring A, wherein Ring A is a substituted or unsubstituted C6-C25 aromatic ring, and a substituted or unsubstituted C3-C25 heteroaromatic ring;

[0021] Preferably, Ar is selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C25 heteroaryl,

[0022] Preferably, the substituents in the substituted C1-C10 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted C6-C25 arylene, substituted C6-C25 aromatic ring, substituted C1-C25 alkyl, substituted C3-C25 cycloalkyl, substituted C6-C25 aryl, substituted C3-C25 heteroaryl, substituted C6-C25 aromatic ring, substituted C3-C25 heteroaromatic ring, substituted C6-C30 aromatic ring, 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, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl.

[0023] Preferably, L1 and L2 are each independently selected from the following connecting, substituted or unsubstituted groups: phenylene, naphthylene, phenanthrenyl, anthracene, biphenylene.

[0024] Preferably, Ar is selected from the group consisting of substituted or unsubstituted phenyl, naphthyl, benzofuranyl, biphenyl, benzothiophenyl, pyridyl, pyrimidyl, terphenyl or binaphthyl.

[0025] Preferably, L1 and L2 are each independently selected from a linker, a phenylene group, and a naphthylene group.

[0026] Preferably, Ar is selected from phenyl, naphthyl, benzofuranyl, biphenyl, benzothienyl, pyridyl or pyrimidinyl.

[0027] Preferably, in Y1-Y4, Y1 is N, Y2 is N, and Y3 is CR Y3 , Y4 is CR Y4 , or Y1 is N, Y3 is N, Y2 is CR Y2 , Y4 is CR Y4 , R Y2 , R Y4 Each exists independently, or R Y2 , R Y4 connected to form ring A; or Y1 is N, Y2 is N, Z 3 N, Y4 is CR Y4 ; or Y2 is N, Y3 is N, Y1 is CR Y1 , Y4 is CR Y4 , R Y1 , R Y4 Each exists independently, or R Y1 , R Y4 Connect into ring A.

[0028] Preferably, R Y2 -R Y4Each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenanthrenyl, yl, anthracenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, pyrimidyl, phenylpyridyl, pyridylphenyl, pyrimidylphenyl, phenylpyrimidyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzofuranyl Benzo[3,2-b]benzofuranyl, benzo[4,5]thienyl[3,2-b]benzofuranyl, benzo[b]benzo[4,5]selenobenzo[2,3-d]thienyl, benzo[4,5]selenobenzo[3,2-b]benzofuranyl; the substituent is selected from one or a combination of two of hydrogen, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl or C3-C12 heteroaryl.

[0029] Preferably, ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, and a substituted or unsubstituted indene ring; and the substituents in the substituted benzene ring, substituted naphthalene ring, substituted anthracene ring, substituted phenanthrene ring, substituted benzothiophene ring, substituted benzofuran ring, and substituted indene ring are selected from one or a combination of two of hydrogen, a C1-C6 alkyl group, a C3-C30 cycloalkyl group, a C5-C12 aryl group, and a C3-C12 heteroaryl group.

[0030] Preferably, R Y2 -R Y4 Each independently selected from phenyl, biphenyl, naphthyl, 1-4-[0-1-4-1]-1, 1-6-[0-1 ...

[0031] Preferably, ring A is selected from a benzene ring or a naphthalene ring.

[0032] Preferably, in formula I: Labeled as 1-a; 1-a is selected from one of the following structures:

[0033]

[0034]

[0035] The wavy line represents the attachment site of the group.

[0036] Preferably, in formula I: Labeled as 1-b; 1-b is selected from one of the following structures:

[0037]

[0038]

[0039] The wavy line represents the attachment site of the group.

[0040] Preferably, in formula I: Marked as formula 1-c; formula 1-c is selected from one of the following structures:

[0041]

[0042]

[0043] The wavy line represents the attachment site of the group.

[0044] Preferably, the organic electroluminescent material is selected from any one of the following compounds:

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052] Definitions of substituent terms:

[0053] The term "halogen" as used in the present invention may include fluorine, chlorine, bromine or iodine.

[0054] 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.

[0055] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a cycloalkane 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.

[0056] In the present invention, the 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, including but not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthrenyl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0057] In the present invention, the heteroaryl and heteroarylene groups include monocyclic, polycyclic or condensed-ring heteroaryl groups. The rings may be interrupted by short non-aromatic units. The heteroatoms include nitrogen, oxygen and sulfur. Including but 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, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof.

[0058] 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.

[0059] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0060] 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.

[0061] In the present invention, the arc line across the ring structure in the structure of Formula I represents that the substitution connection position of the group can be any connectable position on the ring.

[0062] In the present invention, the organic compound represented by formula I can be prepared by the following synthetic route:

[0063]

[0064] Y1 is selected from N and CR Y1 , Y2 is selected from N and CR Y2 , Y 3 Selected from N and CR Y3 , Y4 Selected from N and CR Y4 ,

[0065] R Y1 -R Y4 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 Y1 -R Y4 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;

[0066] X1 is selected from O, S or Se, X2 is NAr,

[0067] L1 and L2 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group,

[0068] R1 and R2 are 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,

[0069] Ar is selected from substituted or unsubstituted C6-C30 aryl groups,

[0070] The substituents of the substituted C6-C30 arylene group, substituted C6-C30 aryl group and substituted C3-C30 heteroaryl group 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 heteroaryl group.

[0071] In another aspect, the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound as described above.

[0072] On the other hand, the present invention provides an organic electroluminescent device, which comprises a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode, and the material of the organic layer comprises one or a combination of at least two of the organic electroluminescent compounds described above.

[0073] Preferably, the organic layer comprises one or more of a hole injection layer, a first hole transport layer, a light-emitting layer, an electron buffer layer, an electron transport layer, and an electron injection layer, and the material of the organic layer comprises one or a combination of at least two of the compounds described above.

[0074] Preferably, the organic layer comprises an electron transport layer, and the electron transport layer comprises one or a combination of at least two of the organic electroluminescent compounds described above.

[0075] Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises one or a combination of at least two of the organic electroluminescent compounds described above.

[0076] In another aspect, the present invention provides a product comprising the organic electroluminescent device as described above.

[0077] Preferably, the product is used in optoelectronics, medicine, biotechnology, optical fiber, lighting equipment, electronic photographic photoreceptor, photoelectric converter, organic solar cell, switching element, organic light emitting field effect transistor, image sensor or dye laser.

[0078] Compared with the prior art, the present invention has the following beneficial effects:

[0079] The organic electroluminescent compound of the present invention is used as an organic electroluminescent material to enable the organic electroluminescent device to have a low driving voltage (below 3.95V, even as low as below 3.55V), a high current efficiency (above 15Cd / A) and a long life (lifetime of more than 172h, even up to more than 260h). BRIEF DESCRIPTION OF THE DRAWINGS

[0080] Figure 1 is a schematic structural diagram of the organic electroluminescent device of the present invention;

[0081] Among them, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode. DETAILED DESCRIPTION

[0082] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0083] Synthesis Example

[0084] The following compounds can be obtained by commercial purchase or conventional reagent products that can be obtained by conventional experimental steps or conditions described in literature in the field:

[0085]

[0086]

[0087]

[0088]

[0089] Synthesis Example 1

[0090] Synthesis of Compound N-2

[0091]

[0092] Step 1:

[0093] Take a 100 ml three-necked round-bottom flask and put in a stirrer and a reflux tube. Under nitrogen protection, add the intermediate INT-1-3 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (0.8 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 tetrahydrofuran, and obtain the intermediate N-2-1 (yield 86%). Step 2:

[0094] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate N-2-1 (1 mmol), intermediate INT-2-1 (1.1 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, 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-2 (yield 45%).

[0095] Elemental analysis: C 47 H 28 N4O theoretical value: C, 84.92; H, 4.25; N, 8.43; O, 2.41 Found value: C, 84.89; H, 4.43; N, 8.54; HRMS (ESI) m / z [M+H]+: theoretical value: 664.23; found value: 665.44.

[0096] Synthesis Example 2

[0097] Synthesis of Compound N-5

[0098]

[0099] Step 1:

[0100] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add the intermediate INT-1-13 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (0.8 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 tetrahydrofuran to obtain the intermediate N-5-1 (yield 88%).

[0101] Step 2:

[0102] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate N-5-1 (1 mmol), intermediate INT-2-1 (1.1 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, 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-5 (yield 43%).

[0103] Elemental analysis: C 47 H 28 N4S theoretical value: C, 82.92; H, 4.15; N, 8.23; S, 4.71 Found value: C, 82.87; H, 4.33; N, 8.45; S, 4.76; HRMS (ESI) m / z [M+H]+: theoretical value: 680.20; found value: 681.45.

[0104] Synthesis Example 3

[0105] Synthesis of Compound N-13

[0106]

[0107] Step 1:

[0108] Take a 100 ml three-necked round-bottom flask and put in a stirrer and a reflux tube. Under nitrogen protection, add the intermediate INT-1-52 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (0.8 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 tetrahydrofuran, and obtain the intermediate N-13-1 (yield 79%). Step 2:

[0109] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate N-13-1 (1 mmol), intermediate INT-2-1 (1.1 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, 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-13 (yield 51%).

[0110] Elemental analysis: C 47 H 28 N4O theoretical value: C, 84.92; H, 4.25; N, 8.43; O, 2.41 Found value: C, 84.95; H, 4.24; N, 8.40; HRMS (ESI) m / z [M+H]+: theoretical value: 664.23; found value: 665.67.

[0111] Synthesis Example 4

[0112] Synthesis of compound N-70:

[0113]

[0114] Step 1:

[0115] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add the intermediate INT-2-21 (1 mmol), 2,4-dichloroquinazole (0.8 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 tetrahydrofuran to obtain the intermediate N-70-1 (yield 83%).

[0116] Step 2:

[0117] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate N-70-1 (1 mmol), intermediate INT-1-8 (1.1 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, filter, rinse the filter cake twice with deionized water, rinse twice with ethanol, and the crude product is purified twice by recrystallization from o-dichlorobenzene to obtain compound N-70 (yield 55%).

[0118] Elemental analysis: C 45 H 26 N4O theoretical value: C, 84.62; H, 4.10; N, 8.77; O, 2.50 Found value: C, 84.68; H, 4.15; N, 8.69; HRMS (ESI) m / z [M+H]+: theoretical value: 638.21; found value: 639.43.

[0119] Synthesis Example 5

[0120] Synthesis of compound N-116:

[0121]

[0122] Step 1:

[0123] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add the intermediate INT-2-43 (1 mmol), 2,4-dichlorobenzo[h]quinazoline (0.8 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 tetrahydrofuran to obtain the intermediate N-116-1 (yield 76%).

[0124] Step 2:

[0125] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate N-116-1 (1 mmol), intermediate INT-1-1 (1.1 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, 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-116 (yield 54%).

[0126] Elemental analysis: C 56 H 31 Theoretical value of N3O2: C, 86.47; H, 4.02; N, 5.40; O, 4.11 Found value: C, 86.41; H, 4.06; N, 5.42; HRMS (ESI) m / z [M+H]+: Theoretical value: 777.24; Found value: 778.56.

[0127] Synthesis Example 6

[0128] Synthesis of Compound N-197

[0129]

[0130] Step 1:

[0131] Take a 100 ml three-necked round-bottom flask and put in a stirrer and a reflux tube. Under nitrogen protection, add the intermediate INT-1-1 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (0.8 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 tetrahydrofuran, and obtain the intermediate N-197-1 (yield 79%). Step 2:

[0132] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate N-197-1 (1 mmol), intermediate SM-197 (0.8 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 tetrahydrofuran to obtain intermediate N-197-2 (yield 76%).

[0133] Step 3:

[0134] Take a 100 ml three-necked round-bottom flask and put in a stirring bar and a reflux tube. Under nitrogen protection, add intermediate N-197-2 (1 mmol), intermediate INT-2-11 (1.1 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, 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-197 (yield 49%).

[0135] Elemental analysis: C 57 H 34 N4O theoretical value: C, 86.56; H, 4.33; N, 7.08; O, 2.02. Found value: C, 86.61; H, 4.36; N, 7.01; HRMS (ESI) m / z [M+H]+: theoretical value: 790.27; found value: 791.43.

[0136] The preparation methods of Examples 7-22 are similar to those of Example 1, except that different starting materials are used for the reactions.

[0137] The intermediates used in Examples 7-22 and the products obtained are shown in Table 1 below:

[0138] Table 1

[0139]

[0140]

[0141]

[0142] The characterization data of the products prepared in Examples 7-22 are shown in Table 2:

[0143] Table 2

[0144]

[0145]

[0146] Application Example 1-24 and Comparative Application Example 1-2

[0147] The following application examples 1-24 and comparative application examples 1-2 provide different OLEDs, such as Figure 1As shown, they all have the following layer structure: substrate 1 (coated glass substrate with indium tin oxide (ITO) as anode 2) / hole injection layer 3 (HIL) / hole transport layer 4 (HTL) / light-emitting layer 5 (EML) / electron transport layer 6 (ETL) / electron injection layer 7 (EIL), and finally cathode 8.

[0148] The materials used are as follows:

[0149]

[0150] The preparation of the organic electroluminescent device comprises the following steps:

[0151] (1) Substrate cleaning: 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%), rinsed in deionized water, ultrasonically degreased in an acetone: ethanol mixed solvent (volume ratio 1:1), baked in a clean environment until the water is completely removed, and then cleaned with ultraviolet light and ozone.

[0152] (2) Evaporation of organic light-emitting functional layer:

[0153] The glass substrate with the anode layer is placed in a vacuum chamber and evacuated to 1×10 -6 Up to 2×10 -4 Pa, vacuum evaporating a mixture of HATCN and HT on the above anode layer film, wherein the mass ratio of HATCN to HT is 3:97, as a hole injection layer, and the evaporation thickness is 10 nm;

[0154] A hole transport layer (made of HT) is evaporated on the hole injection layer, with a thickness of 80 nm.

[0155] The light-emitting layer is deposited on the hole transport layer. The specific preparation method is: vacuum-deposit the light-emitting host material (the materials are shown in Table 1) and the guest material (piq)2Ir(acac) in a co-evaporation manner, and the total film thickness of the deposition is 30 nm;

[0156] An electron transport layer is evaporated on the light-emitting layer. The specific preparation method is as follows: vacuum evaporation of electron transport material (the material is shown in Table 1) is performed in a co-evaporation manner, and the total film thickness of the evaporation is 30 nm;

[0157] An electron injection layer (made of LiQ) is vacuum-deposited on the electron transport layer, with a total film thickness of 1 nm.

[0158] Al was evaporated on the electron injection layer, and the total film thickness of the evaporated layer was 90 nm.

[0159] The parameters of each layer in the device, its material, thickness, etc. are shown in Table 3 below:

[0160] Table 3

[0161]

[0162]

[0163]

[0164] Device performance test:

[0165] Test sample: organic electroluminescent device provided in Application Example 1-25 and Comparative Application Example 1-2;

[0166] Test 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 K 2400 digital source meter system;

[0167] Test conditions: Photoelectric properties Test conditions: Current density is 10mA / cm 2 ;

[0168] Life test: current density is 50mA / cm 2 , record the time (in hours) when the device brightness drops to 95% of the original brightness;

[0169] The test results are shown in Table 4 below:

[0170] Table 4

[0171]

[0172]

[0173] As can be seen from Table 1, the organic material provided in the embodiment of the present invention can match the corresponding light-emitting layer and has a certain electron transmission ability. At the same time, the evaporation temperature of the material is correspondingly reduced in the device preparation, which is beneficial to the preparation of the device. It can be seen from Comparative Example 2 that the direct connection between N in the benzocarbazole group and the triazine group will offset the electron-withdrawing ability of the molecule, which is not conducive to its application as a light-emitting main material. After the structure is modified by the present invention, the application of the device has been greatly improved, with outstanding substantive characteristics and significant progress.

[0174] In summary, the present invention provides a new organic electroluminescent material. The use of this material improves the stability of the device. When the organic electroluminescent material provided by the present invention is used as the electron transport material or the main material of the organic electroluminescent device, it has the advantages of high carrier mobility, improved device luminous efficiency and good thermal stability.

[0175] The organic electroluminescent compound of the present invention is used as an organic electroluminescent material to enable the organic electroluminescent device to have a low driving voltage (below 3.95V, even as low as below 3.55V), a high current efficiency (above 15Cd / A) and a long life (lifetime of more than 172h, even up to more than 260h).

[0176] The applicant declares that the present invention illustrates the organic compounds and applications of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of the raw materials selected by the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An organic electroluminescent material having a structure shown in Formula I: Wherein L1 and L2 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, X1 is selected from O, S or Se, X2 is NAr, Y1 is selected from N and CR Y1 , Y2 is selected from N and CR Y2 , Y 3 Selected from N and CR Y3 , Y 4 Selected from N and CR Y4 , R Y1 -R Y4 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 Y1 -R Y4 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; R1 and R2 are 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, Ar is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, a and b are each independently selected from integers from 0 to 3; The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C6-C30 aryl, substituted C3-C30 heteroaryl, substituted C6-C30 aromatic ring, substituted C3-C30 heteroaromatic ring, substituted C6-C30 arylene and substituted C3-C30 heteroarylene are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl or C3-C30 heteroaryl.

2. The organic electroluminescent compound according to claim 1, characterized in that L1 and L2 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C25 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Preferably, R1 and R2 are selected from hydrogen, deuterium, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted or unsubstituted C6-C25 aryl or substituted or unsubstituted C3-C25 heteroaryl; Preferably, R Y1 -R Y4 R is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C25 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C25 heteroaryl; Y1 -R Y5 Each exists independently, or two adjacent rings are connected to form Ring A, wherein Ring A is a substituted or unsubstituted C6-C25 aromatic ring, and a substituted or unsubstituted C3-C25 heteroaromatic ring; Preferably, Ar is selected from substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C3-C25 heteroaryl; Preferably, the substituents in the substituted C1-C10 alkyl, substituted or unsubstituted C3-C18 cycloalkyl, substituted C6-C25 arylene, substituted C6-C25 aromatic ring, substituted C1-C25 alkyl, substituted C3-C25 cycloalkyl, substituted C6-C25 aryl, substituted C3-C25 heteroaryl, substituted C6-C25 aromatic ring, substituted C3-C25 heteroaromatic ring, substituted C6-C30 aromatic ring, 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, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl.

3. The organic electroluminescent compound according to claim 1 or 2, characterized in that: L1 and L2 are each independently selected from the following groups: connecting bonds, substituted or unsubstituted: phenylene, naphthylene, phenanthrenyl, anthracene, biphenylene; Preferably, Ar is selected from the group consisting of substituted or unsubstituted phenyl, naphthyl, benzofuranyl, biphenyl, benzothiophenyl, pyridyl, pyrimidyl, terphenyl or binaphthyl; Preferably, L1 and L2 are each independently selected from a linker, a phenylene group or a naphthylene group; Preferably, Ar is selected from phenyl, naphthyl, benzofuranyl, biphenyl, benzothienyl, pyridyl or pyrimidinyl; Preferably, in Y1-Y4, Y1 is N, Y2 is N, and Y3 is CR Y3 , Y4 is CR Y4 , or Y1 is N, Y3 is N, Y2 is CR Y2 , Y4 is CR Y4 , R Y2 , R Y4 Each exists independently, or R Y2 , R Y4 connected to form ring A; or Y1 is N, Y2 is N, Z 3 N, Y4 is CR Y4 ; or Y2 is N, Y3 is N, Y1 is CR Y1 , Y4 is CR Y4 , R Y1 , R Y4 Each exists independently, or R Y1 , R Y4 Connected into ring A; Preferably, R Y2 -R Y4 Each independently selected from hydrogen, deuterium, halogen, substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenanthrenyl, yl, anthracenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, pyrimidyl, phenylpyridyl, pyridylphenyl, pyrimidylphenyl, phenylpyrimidyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolylphenyl, phenylcarbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenylphenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzofuranyl Benzo[3,2-b]benzofuranyl, benzo[4,5]thienyl[3,2-b]benzofuranyl, benzo[b]benzo[4,5]selenobenzo[2,3-d]thienyl, benzo[4,5]selenobenzo[3,2-b]benzofuranyl; the substituent is selected from one or a combination of two of hydrogen, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl or C3-C12 heteroaryl; Preferably, Ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, and a substituted or unsubstituted indene ring; the substituents in the substituted benzene ring, substituted naphthalene ring, substituted anthracene ring, substituted phenanthrene ring, substituted benzothiophene ring, substituted benzofuran ring, and substituted indene ring are selected from one or a combination of two of hydrogen, a C1-C6 alkyl group, a C3-C30 cycloalkyl group, a C5-C12 aryl group, and a C3-C12 heteroaryl group; Preferably, R Y2 -R Y4 Each independently selected from phenyl, biphenyl, naphthyl, 1-difluoro-1, 1-difluoro-2, ...3, 1-difluoro-4, 1-difluoro-5, 1-difluoro-6, 1-difluoro-7, 1-difluoro-8, 1-difluoro-9, 1-difluoro-10, 1-difluoro-11, 1-difluoro-12, 1-difluoro-13, 1- Preferably, ring A is selected from a benzene ring or a naphthalene ring.

4. The organic electroluminescent compound according to any one of claims 1 to 3, characterized in that: In formula I: Labeled as 1-a; 1-a is selected from one of the following structures: The wavy line represents the attachment site of the group.

5. The organic electroluminescent compound according to any one of claims 1 to 4, characterized in that: In formula I: Labeled as 1-b; 1-b is selected from one of the following structures: The wavy line represents the attachment site of the group.

6. The organic electroluminescent compound according to any one of claims 1 to 5, characterized in that: In formula I: Marked as formula 1-c; formula 1-c is selected from one of the following structures: The wavy line represents the attachment site of the group.

7. The organic electroluminescent material according to any one of claims 1 to 6, characterized in that: The organic electroluminescent material is selected from any one of the following compounds:

8. An organic electroluminescent material, characterized in that: Contains the organic electroluminescent compound as claimed in any one of claims 1 to 7.

9. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a first electrode, a second electrode, and an organic layer disposed between the first electrode and the second electrode, wherein a material of the organic layer comprises one or a combination of at least two of the organic electroluminescent compounds described in any one of claims 1 to 7; Preferably, the organic layer comprises one or more of a hole injection layer, a first hole transport layer, a light emitting layer, an electron buffer layer, an electron transport layer, and an electron injection layer, and the material of the organic layer comprises one or a combination of at least two of the compounds described in any one of claims 1 to 7; Preferably, the organic layer comprises an electron transport layer, and the electron transport layer comprises one or a combination of at least two of the organic electroluminescent compounds according to any one of claims 1 to 7; Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises one or a combination of at least two of the organic electroluminescent compounds according to any one of claims 1 to 7.

10. A product, characterized in that It comprises the organic electroluminescent device as claimed in claim 9.

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