An organic material composition and its application

Abstract

The present invention provides an organic material composition and application thereof. The organic material composition, through the coordination of compounds contained therein, enables a device to have lower driving voltage, higher current efficiency and longer life when used as an organic functional layer material.

Description

Technical Field

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

[0002] Organic light emitting diodes (OLED) have recently attracted attention due to the increased demand for flat panel displays. The organic layer of an organic OLED 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. The materials used in the organic layer may be 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. depending on their functions. In an organic OLED device, holes from the anode and electrons from the cathode are injected into the 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 by the energy when the organic light-emitting compound returns to the ground state from the excited state.

[0003] The most important factor for OLED light-emitting performance is the light-emitting material, which needs to have high quantum efficiency, high electron mobility and high hole mobility, and the light-emitting material needs to be uniform and stable. Therefore, in this field, the development of light-emitting materials is extremely important. Summary of the invention

[0004] In view of the deficiencies in the prior art, an object of the present invention is to provide an organic material composition and application thereof.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In one aspect, the present invention provides an organic material composition, comprising at least one compound of the structure shown in Formula 1 and at least one compound of the structure shown in Formula 2.

[0007]

[0008] Wherein, R is 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,

[0009] R 1 Selected from -L 1 Ar 1 , R2 Selected from -L 2 Ar 2 , R 3 Selected from -L 3 Ar 3 , R 4 Selected from -L 4 Ar 4 ,

[0010] L 1 -L 4 are each independently selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group,

[0011] Ar 1 -Ar 4 Each is independently selected from hydrogen, deuterium, halogen, cyano, and substituted or unsubstituted C3-C60 heteroaryl;

[0012]

[0013] Ar 10 is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl,

[0014] L 10 is selected from a connecting bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group,

[0015] R 10 -R 17 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted with —O— or —S— in a non-adjacent O atom or S atom, substituted or unsubstituted C2-C30 alkenyl, C2-C30 alkenyl in which one or more methylene groups are substituted with —O— or —S— in a non-adjacent O atom or S atom, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryloxy,

[0016] R 10 -R 17 Each exists independently or two to four adjacent ones are linked to form Ring A, and Ring A is a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring.

[0017] Preferably, in Formula 1, Ar 1 -Ar 4 At least one is selected from the group represented by formula a: Formula a,

[0018] X 1 Select from N or CR X1 , X 2 Select from N or CR X2 , X 3 Select from N or CR X3 , X 4 Select from N or CR X4 , X 5 Select from N or CR X5 ,

[0019] R X1 -R X5 are each independently selected from hydrogen, deuterium, 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 ones are connected to form a ring, and the ring is a benzene ring;

[0020] Preferably, X 1 Select from N, X 2 Select from N, X 3 Selected from CR X3 , X 4 Selected from CR X4 , X 5 Selected from CR X5 ;

[0021] Preferably, X 1 Select from N, X 3 Select from N, X 2 Selected from CR X2 , X 4 Selected from CR X4 , X 5 Selected from CR X5 ;

[0022] Preferably, X 1 Select from N, X 2 Select from N, X 3 Select from N, X 4 Selected from CR X4 , X 5 Selected from CR X5 ;

[0023] Preferably, the group represented by formula a is selected from R X5 Same as the above definition, no further elaboration is given here;

[0024] Preferably, the group represented by formula a is selected from R X2 Same as the above definition, no further details will be given here.

[0025] Preferably, in Formula 1, the R X1 -R X5 Each is independently selected from hydrogen, deuterium, and substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolyl-substituted phenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl-substituted phenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl.

[0026] Preferably, in Formula 1, the R 1 , R 2 , R 3 , R 4 At least one selected from hydrogen;

[0027] Preferably, the R 1 , R 2 , R 3 , R 4 At least two items are selected from hydrogen;

[0028] Preferably, the R 1 , R 2 , R 3 , R 4 Three of them are selected from hydrogen;

[0029] Preferably, the R 2 Selected from L 2 Ar 2 , R 1 , R 3 , R 4 are all selected from hydrogen;

[0030] Preferably, the R 3 Selected from L 3 Ar 3 , R 1 , R 2 , R 4 are all selected from hydrogen;

[0031] Preferably, R is selected from the following substituted or unsubstituted groups: phenyl, biphenyl.

[0032] Preferably, L 1 -L4 Each is independently selected from the following groups which are connecting, substituted or unsubstituted: phenylene, naphthylene, biphenylene, terphenylene.

[0033] Preferably, the compound of the structure shown in Formula 1 is selected from the following compounds,

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044] Where D stands for deuterium.

[0045] Preferably, in Formula 2, the ring A is a substituted or unsubstituted benzene ring;

[0046] Preferably, the compound of the structure shown in Formula 2 is a compound having any of the following structures:

[0047]

[0048] Preferably, the ring A is a substituted or unsubstituted indene ring, indole ring, benzofuran ring, naphthofuran ring, benzothiophene ring, naphthothiophene ring, benzoindole ring, or naphthoindole ring;

[0049] Preferably, R 10 -R 17 Adjacent to The black dot is a fused bond.

[0050] Y is selected from O, S, CR Y5 R Y6 NL Y7 R Y7 ,

[0051] R Y1 , R Y2 , RY3 , R Y4 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted by -O- or -S- in a non-adjacent O atom or S atom, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C30 aryloxy,

[0052] R Y1 , R Y2 , R Y3 , R Y4 Each exists independently or two adjacent rings are connected to form a benzene ring or a naphthalene ring.

[0053] R Y5 , R Y6 Each is independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl,

[0054] R Y7 is selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryloxy,

[0055] L Y7 a connecting bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group;

[0056] Preferably, the compound of the structure shown in Formula 2 is a compound having any of the following structures:

[0057]

[0058] Preferably, Ar 10 , R Y7Each independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl substituted naphthyl, naphthyl substituted phenyl, anthracenyl, phenanthryl, triphenylenyl, pyridyl, dibenzofuranyl, dibenzothienyl, carbazolyl, phenyl substituted carbazolyl, pyridyl substituted carbazolyl, naphthyl substituted carbazolyl, biphenyl substituted carbazolyl, dibenzofuran substituted phenyl, dibenzothiophene substituted phenyl, dimethylfluorenyl, diphenyl substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothienyl, benzocarbazolyl, dibenzocarbazolyl;

[0059] Preferably, R 10 -R 17 , R Y1 -R Y4 each independently selected from hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, anthracenyl, phenanthryl, triphenylenyl, pyridyl, dibenzofuranyl, dibenzothienyl, dibenzofuran-substituted phenyl, dibenzothienyl substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothienyl, R 10 -R 17 , R Y1 -R Y4 Each exists independently or two adjacent ones are connected to form a benzene ring or a naphthalene ring;

[0060] Preferably, R Y5 , R Y6 Each independently selected from methyl, phenyl, or R Y5 , R Y6 Connect to form a fluorene group;

[0061] Preferably, L 10 , L Y7 Each is independently selected from a linker, a phenylene group, a biphenylene group, and a naphthylene group;

[0062] Preferably, Selected from the following substituted or unsubstituted groups:

[0063]

[0064]

[0065] The wavy lines represent the attachment sites of the groups.

[0066] In the present invention, when the group as described above carries a substituent, the substituent is independently selected from deuterium, halogen, cyano, nitro, unsubstituted or R'-substituted C1~C4 straight or branched alkyl, unsubstituted or R'-substituted C6~C20 aryl, unsubstituted or R'-substituted C3~C20 heteroaryl, C6~C20 aromatic amine; R' is selected from deuterium, halogen, cyano or nitro.

[0067] Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl or spirobifluorenyl;

[0068] Preferably, the heteroaryl group is selected from pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazolyl or dibenzocarbazolyl;

[0069] Preferably, the alkyl group is selected from methyl, ethyl, propyl, tert-butyl, cyclohexyl or adamantyl.

[0070] Preferably, the compound of the structure shown in Formula 2 is selected from the following compounds:

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080] Preferably, the weight ratio of the compound with the structure shown in Formula 1 to the compound with the structure shown in Formula 2 in the organic material composition is 1:9-9:1, for example, 1:9, 2:8, 3:7, 4:6, 5:5, 6:4, 7:3, 8:2 or 9:1, etc., preferably 2:8-8:2, more preferably 3:7-7:3, and further preferably 4:6-6:4.

[0081] As used in the present invention, the term "organic electroluminescent material" refers to a material that can be used in an organic electroluminescent element and can contain at least one compound. If necessary, the organic electroluminescent material can be contained in any layer constituting the organic electroluminescent element. For example, the organic electroluminescent material can be a hole injection material, a hole transport material, an electron blocking material, a luminescent auxiliary material, a luminescent layer material (including a main material and a doping material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0082] As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0083] 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.

[0084] 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.

[0085] 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.

[0086] In the present invention, the heteroaryl and heteroarylene group 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.

[0087] Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, 9,9'-dimethylfluorenyl, 9,9'-diphenylfluorenyl or spirobifluorenyl.

[0088] Preferably, the heteroaryl group is selected from dibenzofuranyl, dibenzothiophenyl, carbazolyl, triazine, pyridyl, pyrimidinyl, imidazolyl, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, naphthoimidazolyl, naphthoxazolyl, naphthothiazolyl, phenanthroimidazolyl, phenanthroxazolyl, phenanthrothiazolyl, quinoxalinyl, quinazolinyl, indolecarbazolyl, oxazolyl, indolefluorenyl, benzothienopyrazinyl, benzothienopyrimidinyl, benzofuranopyrazinyl, benzofuranopyrimidinyl, indolepyrazinyl, indolepyrimidinyl, indenopyrazinyl, indenopyrimidinyl, spiro(fluorene-9,1'-indenyl)pyrazinyl, spiro(fluorene-9,1'-indenyl)pyrimidinyl, benzofuranocarbazolyl or benzothienocarbazolyl.

[0089] As used in the present invention, the term "C6-C30 aryloxy" refers to a monovalent substituent represented by ZO-, wherein Z represents an aryl group having 6 to 30 carbon atoms. Examples of such aryloxy include, but are not limited to, phenoxy, naphthoxy, diphenoxy, and the like.

[0090] As used in the present invention, the term "C1-C30 alkoxy group" refers to a monovalent substituent represented by Z'O-, wherein Z' represents an alkyl group having 1 to 30 carbon atoms.

[0091] 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.

[0092] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0093] In the present invention, "two adjacent groups are connected to form a ring" means that two substituents in adjacent positions in the same ring or adjacent rings can be connected to each other through chemical bonds to form a ring. The present invention does not limit the specific way of connecting to form a ring (for example, connecting through a single bond, connecting through a benzene ring, connecting through a naphthalene ring, connecting through a Thick, through Thick, through Thick, through Thick, through Thick and; indicates a condensed position), and has the same meaning as the following when referring to the same description

[0094] 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-C60 aromatic group, the number of carbon atoms representing the aromatic group can be any integer within the range of 6-60, for example 6, 8, 10, 15, 20, 30, 35, 40, 45, 50, 55 or 60, etc.

[0095] In the present invention, the organic compounds substituted at various positions are prepared by the following synthetic route:

[0096]

[0097] R 5” is chlorine, R 5’ for X is halogen, preferably chlorine or bromine;

[0098]

[0099] R 6” is chlorine, R 6’ for X is halogen, preferably chlorine or bromine;

[0100]

[0101] R 7” is chlorine, R 7’ for X is halogen, preferably chlorine or bromine;

[0102]

[0103] R 8” is chlorine, R 8’ for X is halogen, preferably chlorine or bromine.

[0104] In another aspect, the present invention provides an organic electroluminescent material, which comprises the organic material composition as described above.

[0105] In another aspect, the present invention provides the use of the organic material composition or the organic electroluminescent material as described above in the preparation of an optical device;

[0106] Preferably, the optical device comprises any one of an organic electroluminescent device, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching device, a light emitting electrochemical cell, an organic laser diode or an organic photoreceptor.

[0107] In another aspect, the present invention provides an organic electroluminescent device, comprising an anode and a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the organic material composition or the organic electroluminescent material as described above.

[0108] Preferably, the organic layer comprises a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer stacked in sequence from the anode side to the cathode side;

[0109] Preferably, the material of the light-emitting layer comprises a host material and a guest material, and the host material comprises the organic material composition or the organic electroluminescent material as described above.

[0110] Preferably, the guest material comprises a phosphorescent dopant, and the phosphorescent dopant comprises a complex containing a transition metal.

[0111] In another aspect, the present invention provides an organic electroluminescent device, comprising the organic electroluminescent device as described above.

[0112] Compared with the prior art, the present invention has the following beneficial effects:

[0113] The organic material composition of the present invention can improve the electron transport properties of the main material and further improve the electron-hole binding rate by combining at least one compound with a structure represented by formula (1) and at least one compound with a structure represented by formula (2), thereby improving the luminous efficiency of the organic electroluminescent diode and extending its service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0114] Figure 1 A schematic structural diagram of an organic electroluminescent device provided for an application example of the present invention, wherein 1 is an anode, 2 is a hole injection layer, 3 is a hole transport layer, 4 is a light-emitting layer, 5 is an electron transport layer, 6 is an electron injection layer, and 7 is a cathode. DETAILED DESCRIPTION

[0115] 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 to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0116] Preparation Example

[0117]

[0118] Synthesis of 1B: 1A (10 mmol), nitrobenzene (10 mmol), potassium hydroxide (22 mmol) and cuprous thiocyanate (1 mmol), anhydrous tetrahydrofuran (10 ml) were placed in a 25 ml three-necked flask, and nitrogen was replaced three times. The mixture was heated to 90 degrees Celsius under nitrogen protection. The reaction was completed after 48 hours, and water was added to quench the reaction. The system was extracted with ethyl acetate and the organic solvent was removed by rotary evaporation. The crude product was separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain 1B (1.34 g, yield 49%).

[0119] Synthesis of 1B': 2-bromo-4-chlorobenzaldehyde (10 mmol), bipyraclostrobin (12 mmol), potassium acetate (100 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.2 mmol), 1,-dioxane (25 ml) were added into a 50 ml three-necked flask, replaced with nitrogen, heated to 100 degrees Celsius under nitrogen protection, quenched with water after the reaction was completed, extracted with dichloromethane, and the crude product was separated by column chromatography (dichloromethane:n-hexane (volume ratio 1:50)) to obtain 1B' (1.7 g, yield 64%)

[0120] Synthesis of 1C: 1B (10 mmol), 1B' (10 mmol), sodium bicarbonate (20 mmol), tetrakistriphenylphosphine palladium (0.2 mmol), tetrahydrofuran (20 ml), water (10 ml) were placed in a 50 ml three-necked flask, replaced with nitrogen, and heated to 60 ° C under nitrogen protection to react overnight. After the reaction was completed, water was added to quench, dichloromethane was extracted, and the organic solvent was removed by rotary evaporation. The crude product was separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain 1C (3.06 g, yield 92%).

[0121] Synthesis of 1D: 1C (10 mmol), (methoxymethyl) triphenylphosphine chloride (20 mmol), tetrahydrofuran (10 ml) were added to a 50 ml three-necked flask, the temperature was lowered to 0 degrees Celsius, potassium tert-butoxide (2 mmol) was dissolved in 5 ml tetrahydrofuran, nitrogen was replaced, and potassium tert-butoxide solution was added dropwise at 0 degrees Celsius under nitrogen protection. After the addition was completed, the reaction was stirred for half an hour. After the reaction was completed, water was added to quench, dichloromethane was extracted, and the organic solvent was removed by rotary evaporation. The crude product was separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain 1D (1.8 g, yield 50%).

[0122] Synthesis of 1E: In a 25 ml three-necked flask, 1E (1 mmol) and hexafluoroisopropanol (5 ml) were added, cooled to 0 degrees Celsius, replaced with nitrogen, and trifluoromethanesulfonic acid (1 ml) was added dropwise under nitrogen protection. The reaction was continued to stir for half an hour, and the crude product was separated by column chromatography (ethyl acetate:n-hexane (volume ratio 1:50)) to obtain 1E (0.24 g, yield 73%).

[0123] Synthesis of 1F: 1E (10 mmol), biboric acid pinacol ester (12 mmol), sodium acetate (20 mmol), tris(dibenzylideneacetone)dipalladium (0.5 mmol) and 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (1.5 mmol) were placed in a 50 ml three-necked round-bottom flask, and 1,4-dioxane (20 ml) was added, and nitrogen was replaced three times. Under nitrogen protection, the reaction was heated to 100°C. After the reaction was completed, water was added to quench, dichloromethane was extracted, and the organic solvent was removed by rotary evaporation. The crude product was separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain 1F (3.24 g, yield 77%).

[0124] Synthesis of compound 1: Take a 100 ml three-necked round-bottom flask and put a stirring bar and a reflux tube in it. After drying, fill it with nitrogen and add 1F (10 mmol), 1G (10 mmol, CAS 1689576-03-1 ), sodium bicarbonate (23mmol), tetrakistriphenylphosphine palladium (0.5mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (0.5mmol), toluene (25ml), ethanol (7ml) and water (7ml), replaced with nitrogen three times. Under nitrogen protection, the temperature was raised to 80℃ for 8 hours. After the reaction, it was extracted with ethyl acetate. The obtained extract was dried by adding magnesium sulfate, filtered and dried by spin drying. The crude product was purified by chromatography (ethyl acetate: n-hexane (volume ratio 1:10)) to obtain compound 1 (4.13g, yield 69%).

[0125] Elemental analysis: C 41 H 26 N6 theoretical value: C, 81.71; H, 4.35; N, 13.94; found value: C, 81.78; H, 4.33; N, 13.89; HRMS (ESI) m / z [M+H]+: theoretical value: 602.22; found value: 603.40.

[0126]

[0127] Synthesis of 1B" is the same as that of 1B', except that 2-bromo-5-chlorobenzaldehyde is used instead of 2-bromo-4-chlorobenzaldehyde to obtain 1B" (1.60 g, yield 60%).

[0128] Synthesis of 10C: The same as the synthesis of 1C, except that 4-chloro-2-formylphenylboronic acid pinacol ester was used instead of 5-chloro-2-formylphenylboronic acid pinacol ester to obtain 10C (2.13 g, yield 64%).

[0129] Synthesis of 10D: The synthesis was the same as that of 1D, except that 10C was used instead of 1C to obtain 10D (3.21 g, yield 89%).

[0130] Synthesis of 10E: The same as the synthesis of 1E, except that 10D was used instead of 1D, to obtain 10E (0.16 g, yield 48%).

[0131] Synthesis of 10F: The same as the synthesis of 1F, except that 10E was used instead of 1E, to obtain 10F (4.00 g, yield 95%).

[0132] Synthesis of 10: The synthesis was the same as that of compound 1, except that 10F was used instead of 1F, and 10G was used instead of 1G, to obtain compound 10 (4.70 g, yield 78%).

[0133] Elemental analysis: C 41 H 26 N6 theoretical value: C, 81.71; H, 4.35; N, 13.94; found value: C, 81.73; H, 4.37; N, 13.90; HRMS (ESI) m / z (M+): theoretical value: 602.22; found value: 603.29.

[0134] The raw materials 1 and 2 in Table 1 were used as raw materials and the corresponding products were prepared according to the above method as shown in Table 1. The structural characterization data of the products are shown in Table 2.

[0135] Table 1

[0136]

[0137]

[0138] Table 2

[0139]

[0140]

[0141]

[0142] Synthesis of 1': In a 25 ml three-necked flask, nitrogen was introduced, 1'-A (1 mmol), compound 1'-B (1 mmol), sodium tert-butoxide (2 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.02 mmol), 50% tri-tert-butylphosphine solution (0.1 mmol) and toluene 8 mL were added, and then refluxed and stirred. After the reaction was completed, it was cooled to room temperature, and the organic layer was extracted with ethyl acetate and H2O. The extracted organic layer was dried over MgSO4 and filtered. The filtrate was concentrated under reduced pressure, and the crude product was separated by column chromatography (ethyl acetate: n-hexane (volume ratio 1:50)) to obtain compound 1' (0.40 g, yield: 62%).

[0143] Elemental analysis: C 48 H 31 N3 theoretical value: C, 88.72; H, 4.81; N, 6.47; found value: C, 88.76; H, 4.79; N, 6.45; HRMS (ESI) m / z [M+H] + : Theoretical value: 649.25; measured value: 650.33.

[0144] The raw materials 1 and 2 in Table 3 were used as raw materials and the corresponding products were prepared according to the above method as shown in Table 3. The structural characterization data of the products are shown in Table 4.

[0145] Table 3

[0146]

[0147]

[0148] Table 4

[0149]

[0150] Application Examples

[0151] Provided is an organic electroluminescent device having a structure as Figure 1 As shown, it has the following layer structure: substrate (indium tin oxide (ITO, as anode 1) coated glass substrate) / hole injection layer 2 (HIL) / hole transport layer 3 (HTL) / light emitting layer 4 (EML) / electron transport layer 5 (ETL) / electron injection layer 6 (EIL), and finally cathode 7.

[0152] The materials needed to make OLEDs are as follows:

[0153]

[0154] The preparation of the organic electroluminescent device comprises the following steps:

[0155] (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.

[0156] (2) Evaporation of organic light-emitting functional layer:

[0157] 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 NDP-9 and HT on the above anode layer film, wherein the mass ratio of NDP-9 to HT is 3:97, as a hole injection layer, and the evaporation thickness is 10 nm;

[0158] A hole transport layer is evaporated on the hole injection layer, and the evaporated film thickness is 80nm;

[0159] The light-emitting layer is deposited on the hole transport layer. The specific preparation method is as follows: vacuum-deposit the light-emitting host material (the materials used are shown in Table 5) and the guest material in a co-evaporation manner, and the total film thickness of the deposition is 30 nm;

[0160] An electron transport layer is deposited on the electron buffer layer. The specific preparation method is as follows: BPhen and LiQ are vacuum deposited in a co-evaporation manner, and the total film thickness of the deposition is 30 nm;

[0161] An electron injection layer is vacuum-deposited on the electron transport layer, and the total thickness of the evaporated layer is 1 nm;

[0162] Al was evaporated on the electron injection layer, and the total film thickness of the evaporated layer was 80 nm.

[0163] The parameters of each layer in the device, its material, thickness and so on are shown in Table 5.

[0164] Table 5

[0165]

[0166]

[0167]

[0168] Device performance test:

[0169] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR650 spectrum scanning luminance meter and a Keithley K 2400 digital source meter system;

[0170] Photoelectric characteristics test conditions: current density is 10mA / cm 2 .

[0171] Life test: current density is 50mA / cm 2 , record the time (in hours) when the device brightness drops to 98% of the original brightness.

[0172] The device performance test results are shown in Table 6:

[0173] Table 6

[0174]

[0175]

[0176] As can be seen from Table 6, the electron and hole transport capabilities of a single host compound are different. The use of an organic material composition can improve the electron transport characteristics, further improve the electron and hole combination rate, thereby improving the luminous efficiency of the organic electroluminescent diode and extending the service life. When the organic material composition is used as an organic functional layer material, the device can have a lower driving voltage (below 3.90V), a higher current efficiency (above 18Cd / A) and a longer life (above 45h).

[0177] The applicant declares that the present invention illustrates the organic material composition and its application 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 various raw materials of the product of 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 material composition, comprising at least one compound of the structure shown in Formula 1 and at least one compound of the structure shown in Formula 2, in, R is selected from substituted or unsubstituted phenyl, the substituent is deuterium, R1, R2, R4 are selected from hydrogen, R 3 Selected from -L 3 Ar 3 , L 3 is a connecting bond or a phenylene group, Ar 3 Selected from the group represented by formula a: X 1 Select from N, X 2 Select from N, X 3 Selected from CR X3 or N, X 4 Selected from CR X4 , X 5 Selected from CR X5 ; R X3 -R X5 are each independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C12-C30 heteroaryl, R X3 -R X5 Each exists independently, or two adjacent ones are connected to form a ring, and the ring is a benzene ring; Ar 10 is selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C12-C30 heteroaryl, L 10 Select from the connection key, R 10 -R 17 are each independently selected from hydrogen, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, R 10 -R 17 Each exists independently or two to four adjacent rings are linked 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 are each independently selected from deuterium, unsubstituted or R'-substituted C1-C4 straight or branched chain alkyl; R' is selected from deuterium.

2. The organic material composition according to claim 1, characterized in that: X 1 Select from N, X 2 Select from N, X 3 Selected from CR X3 , X 4 Selected from CR X4 , X 5 Selected from CR X5 .

3. The organic material composition according to claim 1, characterized in that: X 1 Select from N, X 2 Select from N, X 3 Select from N, X 4 Selected from CR X4 , X 5 Selected from CR X5 .

4. The organic material composition according to claim 1, characterized in that: The group represented by formula a is selected from 5. The organic material composition according to claim 1, characterized in that: In Formula 1, the R X3 -R X5 Each is independently selected from hydrogen, deuterium, and substituted or unsubstituted phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbazolyl-substituted phenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl-substituted phenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl.

6. The organic material composition according to claim 1, characterized in that: The compound of the structure shown in Formula 1 is selected from the following compounds: Where D stands for deuterium.

7. The organic material composition according to claim 1, characterized in that: In Formula 2, the ring A is a substituted or unsubstituted benzene ring.

8. The organic material composition according to claim 1, characterized in that: The compound of the structure shown in Formula 2 is a compound having any of the following structures:

9. The organic material composition according to claim 1, characterized in that: The ring A is a substituted or unsubstituted indene ring, indole ring, benzofuran ring, naphthofuran ring, benzothiophene ring, naphthothiophene ring, benzindole ring or naphthoindole ring.

10. The organic material composition according to claim 1, characterized in that: R 10 -R 17 Adjacent to The black dot is a fused bond. Y is selected from O, S, CR Y5 R Y6 NL Y7 R Y7 , R Y1 , R Y2 , R Y3 , R Y4 Each is independently selected from hydrogen, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C6-C30 aryloxy, R Y1 , R Y2 , R Y3 , R Y4 Each exists independently or two adjacent rings are connected to form a benzene ring or a naphthalene ring. R Y5 , R Y6 Each is independently selected from substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, R Y7 is selected from substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C6-C30 aryloxy, L Y7 a connecting bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group.

11. The organic material composition according to claim 1, characterized in that: The compound of the structure shown in Formula 2 is a compound having any of the following structures:

12. The organic material composition according to claim 10, characterized in that: Ar 10 , R Y7 Each is independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl substituted naphthyl, naphthyl substituted phenyl, anthracenyl, phenanthryl, triphenylenyl, pyridyl, dibenzofuranyl, dibenzothienyl, carbazolyl, phenyl substituted carbazolyl, pyridyl substituted carbazolyl, naphthyl substituted carbazolyl, biphenyl substituted carbazolyl, dibenzofuran substituted phenyl, dibenzothiophene substituted phenyl, dimethylfluorenyl, diphenyl substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothienyl, benzocarbazolyl, dibenzocarbazolyl.

13. The organic material composition according to claim 10, characterized in that: R 10 -R 17 , R Y1 -R Y4 each independently selected from hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, anthracenyl, phenanthryl, triphenylenyl, pyridyl, dibenzofuranyl, dibenzothienyl, dibenzofuran-substituted phenyl, dibenzothienyl substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothienyl, R 10 -R 17 , R Y1 -R Y4 They can exist independently or be connected to form a benzene ring or a naphthalene ring.

14. The organic material composition according to claim 10, characterized in that: R Y5 , R Y6 Each independently selected from methyl, phenyl, or R Y5 , R Y6 Connect to form a fluorenyl group.

15. The organic material composition according to claim 10, characterized in that: L 10 , L Y7 Each is independently selected from a linker, a phenylene group, a biphenylene group, and a naphthylene group.

16. The organic material composition according to claim 1, characterized in that: select The wavy lines represent the attachment sites of the groups.

17. The organic material composition according to claim 1, characterized in that: When the group carries a substituent, the substituent is independently selected from deuterium, unsubstituted or R'-substituted C1-C4 straight or branched alkyl; R' is selected from deuterium.

18. The organic material composition according to claim 1, characterized in that: The aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl or spirobifluorenyl.

19. The organic material composition according to claim 1, characterized in that: The heteroaryl group is selected from pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl substituted carbazolyl, pyridyl substituted carbazolyl, naphthyl substituted carbazolyl, biphenyl substituted carbazolyl, dibenzofuran substituted phenyl, dibenzothiophene substituted phenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazolyl or dibenzocarbazolyl.

20. The organic material composition according to claim 1, characterized in that: The alkyl group is selected from methyl, ethyl, propyl or tert-butyl.

21. The organic material composition according to claim 1, characterized in that: The compound of the structure shown in Formula 2 is selected from the following compounds:

22. The organic material composition according to claim 1, characterized in that: The weight ratio of the compound represented by the structure of Formula 1 to the compound represented by the structure of Formula 2 is 1:9-9:

1.

23. The organic material composition according to claim 22, characterized in that: The weight ratio of the compound represented by the structure of Formula 1 to the compound represented by the structure of Formula 2 is 2:8-8:

2.

24. The organic material composition according to claim 23, characterized in that: The weight ratio of the compound represented by the structure of Formula 1 to the compound represented by the structure of Formula 2 is 3:7-7:

3.

25. The organic material composition according to claim 24, characterized in that: The weight ratio of the compound represented by Formula 1 to the compound represented by Formula 2 is 4:6-6:

4.

26. An organic electroluminescent material, characterized in that: The organic electroluminescent material comprises the organic material composition according to any one of claims 1 to 25.

27. Use of the organic material composition according to any one of claims 1 to 25 or the organic electroluminescent material according to claim 26 in the preparation of an optical device.

28. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode and a cathode, and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises the organic material composition according to any one of claims 1 to 25 or the organic electroluminescent material according to claim 26.

29. The organic electroluminescent device according to claim 28, characterized in that: The organic layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer which are sequentially stacked from the anode side to the cathode side.

30. The organic electroluminescent device according to claim 29, characterized in that: The material of the light-emitting layer comprises a host material and a guest material, wherein the host material comprises the organic material composition according to any one of claims 1 to 25 or the organic electroluminescent material according to claim 26.

31. The organic electroluminescent device according to claim 30, characterized in that: The guest material includes a phosphorescent dopant, and the phosphorescent dopant includes a complex containing a transition metal.

32. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises the organic electroluminescent device according to any one of claims 28 to 31.

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