CN109593042A - A kind of electroluminescent organic material and the organic electroluminescence device comprising it - Google Patents

Abstract

The present invention provides a kind of electroluminescent organic material and the organic electroluminescence device comprising it, belongs to electroluminescent technology field.The present invention introduces adamantane as new core group, changes molecular conformation, reduce the symmetry of structure on the basis of bis- (triarylamine) symmetrical structures, to promote material filming；Adamantane group itself has biggish steric hindrance and rigid structure, while its unconjugated molecular structure will not influence the electron energy level of triarylamine, ensure that the hole transport performance of material；The compound of the group of the present invention containing adamantane has excellent hole transport performance, it can be used for making organic electroluminescence device, especially as the hole transport layer material in organic electroluminescence device, the luminous efficiency and service life of organic luminescent device can be effectively improved.

Description

A kind of electroluminescent organic material and the organic electroluminescence device comprising it

Technical field

The present invention relates to a kind of electroluminescent organic material and its as organic electroluminescence device hole-transporting layer materialThe application of material, and in particular to electroluminescent organic material and the organic electroluminescence device comprising it belong to electroluminescent field.

Background technique

Electroluminescent (Electroluminescence), and electroluminescence can be claimed, abbreviation EL is by being added in two electrodesVoltage generate electric field, by electric field excite electronics hit the centre of luminescence, and be led to electronics transition between energy level, variation, answerConjunction leads to a kind of luminous physical phenomenon.In recent years, organic electroluminescence device (OLED:OrganicElectroluminescent device) visual field of people is progressed into as display technology of new generation.OLED is one kind by moreThe electroluminescent device that layer organic thin film structure is formed, organic film therein are using vapor deposition, vapor deposition or spin coating proceeding in baseThe film of the luminous organic material formed on plate.Compared with traditional display technology, in voltage characteristic, light emission luminance, shine effectRate, chromaticness, response speed and appreciative perspective etc. very advantageous, and it is at low cost, therefore possess vast market prospect.

In order to improve brightness, efficiency and the service life of organic electroluminescence device, multilayered structure is usually used in the devices.ThisA little multilayered structures include: hole injection layer (hole injection layer), hole transmission layer (hole transportLayer), electronic barrier layer ((electron-blocking layer), luminescent layer (emitting layer) and electron-transportLayer (electron transport layer) etc..These organic layers, which have, improves carrier (hole and electronics) in each stratum boundaryInjection efficiency between face, the ability that equilbrium carrier transmits between the layers, to improve the brightness and efficiency of device.

Although the technology is still currently, the electroluminescent organic material of a large amount of function admirables developed successivelyThere are many problems, how to design the better material of new performance and are adjusted, so that all devices can reach reduction electricityIt presses, improve efficiency effect with the service life, be always those skilled in the art's urgent problem to be solved.

Summary of the invention

The purpose of the present invention is to provide a kind of with high-fire resistance and excellent chemical stability and can be used as skyThe electroluminescent organic material of cave implanted layer, hole transporting layer or electronic blocking layer material etc..

Another object of the present invention is to provide a kind of organic luminescent device comprising the electroluminescent organic material, toolsThere are lower driving voltage, higher luminous efficiency and service life.

To achieve the above object, the present invention adopts the following technical scheme that:

A kind of electroluminescent organic material, the structural formula of the material as described in chemical formula 1:

Ar₁、Ar₂、Ar₅With Ar₆It is identical or different, it is separately 1-20 selected from substituted or unsubstituted carbon atom numberAlkyl, substituted or unsubstituted carbon atom number be 2-20 alkenyl, substituted or unsubstituted carbon atom number be 2-24 alkynyl,Heterocyclylalkyl that naphthenic base that substituted or unsubstituted carbon atom number is 3-20, substituted or unsubstituted carbon atom number are 2-20,Heteroarylalkyl that aralkyl that substituted or unsubstituted carbon atom number is 7-30, substituted or unsubstituted carbon atom number are 2-30,Aryl that substituted or unsubstituted carbon atom number is 6-30, substituted or unsubstituted carbon atom number are one in the heteroaryl of 1-30Kind；

Ar₃And Ar₄It is identical or different, separately selected from singly-bound, the Asia that substituted or unsubstituted carbon atom number is 1-20The sub- alkynes that alkenylene that alkyl, substituted or unsubstituted carbon atom number are 2-20, substituted or unsubstituted carbon atom number are 2-24The heterocycle that ring alkylidene that base, substituted or unsubstituted carbon atom number are 3-20, substituted or unsubstituted carbon atom number are 2-20Sub- aralkyl that alkylidene, substituted or unsubstituted carbon atom number are 7-30, substituted or unsubstituted carbon atom number are 2-30'sArlydene that miscellaneous Asia aralkyl, substituted or unsubstituted carbon atom number are 6-30, substituted or unsubstituted carbon atom number are 1-30Heteroarylidene, the ring alkenylene of substituted or unsubstituted carbon atom number 3-15, substituted or unsubstituted carbon atom number 2-15One of miscellaneous alkenylene, miscellaneous alkynylene of substituted or unsubstituted carbon atom number 2-15；

The Ar₁、Ar₂、Ar₃、Ar₄、Ar₅With Ar₆Substituent group it is identical or different, and separately be selected from deuterium, cyanogenBase, nitro, halogen, hydroxyl, the alkyl of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon atom number 3-20Naphthenic base, the alkenyl of substituted or unsubstituted carbon atom number 2-20, substituted or unsubstituted carbon atom number 2-24 alkynyl, takeGeneration or the Heterocyclylalkyl of unsubstituted carbon atom number 2-20, substituted or unsubstituted carbon atom number 7-20 aralkyl, replace orThe aryl, substituted or unsubstituted of the heteroarylalkyl of unsubstituted carbon atom number 2-20, substituted or unsubstituted carbon atom number 6-20The heteroaryl of carbon atom number 1-20, the alkoxy of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon it is formerSubnumber is the alkylthio group of 1-20, the alkylamino of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon atom numberThe fragrant amino of 6-20, the heteroaryl amino of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon atom number 7-20Arylalkylamino, substituted or unsubstituted carbon atom number be the aIkylsilyl groups of 1-20, substituted or unsubstituted carbon atom numberFor the arylsilyl groups of 6-24, substituted or unsubstituted carbon atom number be 6-20 aryloxy group, substituted or unsubstituted carbon it is formerSubnumber is one of 6-20 arylthio.

A further improvement of the present invention lies in that the Ar₁、Ar₂、Ar₅With Ar₆It is identical or different, separately it is selected fromHeteroarylalkyl that aralkyl that substituted or unsubstituted carbon atom number is 7-30, substituted or unsubstituted carbon atom number are 2-30,Aryl that substituted or unsubstituted carbon atom number is 6-30, substituted or unsubstituted carbon atom number are one in the heteroaryl of 1-30Kind.

A further improvement of the present invention lies in that the Ar₃、Ar₄The Asia for being 6-30 selected from substituted or unsubstituted carbon atom numberThe Asia that heteroarylidene that aryl, substituted or unsubstituted carbon atom number are 1-30, substituted or unsubstituted carbon atom number are 7-30Aralkyl, substituted or unsubstituted carbon atom number are one of miscellaneous sub- aralkyl of 2-30.

A further improvement of the present invention lies in that the chemical formula 1 is such as one of flowering structure:

A further improvement of the present invention lies in that the Ar₃、Ar₄Selected from substituted or unsubstituted phenyl, substituted or unsubstitutedXenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted dimethyl fluorenyl,One of substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiophene.

A kind of organic electroluminescence device, including cathode, anode and one layer or more between the cathode and anodeOrganic layer, at least one layer of in one layer or more organic layer between the cathode and anode includes electroluminescent hair described in claim 1Luminescent material.

A further improvement of the present invention lies in that the organic layer is selected from hole injection layer, hole transmission layer, electronic blockingLayer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer.

A further improvement of the present invention lies in that the organic matter layer comprising electroluminescent material described in claim 1 is skyCave transport layer.

Compared with prior art, the invention has the benefit that

1. the present invention introduces adamantane as new core base on the basis of bis- (triarylamine) symmetrical structuresGroup, changes molecular conformation, reduces the symmetry of structure, to promote material filming；

2. adamantane group itself has biggish steric hindrance and rigid structure, while its unconjugated molecular structure is notThe electron energy level that will affect triarylamine ensure that the hole transport performance of material；

3. the adamantane group in molecular center position can also be by the protective effect of two sides triarylamine, can be oneDetermine degree inhibition its isomerization/dehydrogenation reaction occurs at high temperature, to improve the purity and device performance of material；

4. the compound of the group of the present invention containing adamantane has excellent hole transport performance, can be used for making organicElectroluminescent device can effectively improve organic hair especially as the hole transport layer material in organic electroluminescence deviceThe luminous efficiency and service life of optical device.

Detailed description of the invention

Fig. 1 is the structural schematic diagram of electroluminescent organic material of the invention.

Specific embodiment

Hereinafter, by embodiment, the present invention is described in more detail.But following embodiments are only examples of the inventionShow, and and the non-limiting present invention.

Referring to Fig. 1, a kind of electroluminescent organic material of the invention, the structural formula of the material as described in chemical formula 1:

Ar₁、Ar₂、Ar₅With Ar₆It is identical or different, it is separately 1-20 selected from substituted or unsubstituted carbon atom numberAlkyl, substituted or unsubstituted carbon atom number be 2-20 alkenyl, substituted or unsubstituted carbon atom number be 2-24 alkynyl,Heterocyclylalkyl that naphthenic base that substituted or unsubstituted carbon atom number is 3-20, substituted or unsubstituted carbon atom number are 2-20,Heteroarylalkyl that aralkyl that substituted or unsubstituted carbon atom number is 7-30, substituted or unsubstituted carbon atom number are 2-30,Aryl that substituted or unsubstituted carbon atom number is 6-30, substituted or unsubstituted carbon atom number are one in the heteroaryl of 1-30Kind；

Ar₃And Ar₄It is identical or different, separately selected from singly-bound, the Asia that substituted or unsubstituted carbon atom number is 1-20The sub- alkynes that alkenylene that alkyl, substituted or unsubstituted carbon atom number are 2-20, substituted or unsubstituted carbon atom number are 2-24The heterocycle that ring alkylidene that base, substituted or unsubstituted carbon atom number are 3-20, substituted or unsubstituted carbon atom number are 2-20Sub- aralkyl that alkylidene, substituted or unsubstituted carbon atom number are 7-30, substituted or unsubstituted carbon atom number are 2-30'sArlydene that miscellaneous Asia aralkyl, substituted or unsubstituted carbon atom number are 6-30, substituted or unsubstituted carbon atom number are 1-30Heteroarylidene, the ring alkenylene of substituted or unsubstituted carbon atom number 3-15, substituted or unsubstituted carbon atom number 2-15One of miscellaneous alkenylene, miscellaneous alkynylene of substituted or unsubstituted carbon atom number 2-15；

The Ar₁、Ar₂、Ar₃、Ar₄、Ar₅With Ar₆Substituent group it is identical or different, and separately be selected from deuterium, cyanogenBase, nitro, halogen, hydroxyl, the alkyl of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon atom number 3-20Naphthenic base, the alkenyl of substituted or unsubstituted carbon atom number 2-20, substituted or unsubstituted carbon atom number 2-24 alkynyl, takeGeneration or the Heterocyclylalkyl of unsubstituted carbon atom number 2-20, substituted or unsubstituted carbon atom number 7-20 aralkyl, replace orThe aryl, substituted or unsubstituted of the heteroarylalkyl of unsubstituted carbon atom number 2-20, substituted or unsubstituted carbon atom number 6-20The heteroaryl of carbon atom number 1-20, the alkoxy of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon it is formerSubnumber is the alkylthio group of 1-20, the alkylamino of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon atom numberThe fragrant amino of 6-20, the heteroaryl amino of substituted or unsubstituted carbon atom number 1-20, substituted or unsubstituted carbon atom number 7-20Arylalkylamino, substituted or unsubstituted carbon atom number be the aIkylsilyl groups of 1-20, substituted or unsubstituted carbon atom numberFor the arylsilyl groups of 6-24, substituted or unsubstituted carbon atom number be 6-20 aryloxy group, substituted or unsubstituted carbon it is formerSubnumber is one of 6-20 arylthio.

Specifically, the Ar₁、Ar₂、Ar₅With Ar₆It is identical or different, separately it is selected from substituted or unsubstituted carbonHeteroarylalkyl that aralkyl that atomicity is 7-30, substituted or unsubstituted carbon atom number are 2-30, substituted or unsubstituted carbonAryl that atomicity is 6-30, substituted or unsubstituted carbon atom number are one of heteroaryl of 1-30.

Specifically, the Ar₃、Ar₄Selected from the arlydene that substituted or unsubstituted carbon atom number is 6-30, replaces or do not takeSub- aralkyl that heteroarylidene that the carbon atom number in generation is 1-30, substituted or unsubstituted carbon atom number are 7-30, substitution or notSubstituted carbon atom number is one of miscellaneous sub- aralkyl of 2-30.

Specifically, the chemical formula 1 is such as one of flowering structure:

Heretofore described Ar₃、Ar₄Selected from substituted or unsubstituted phenyl, substituted or unsubstituted xenyl, substitution orUnsubstituted terphenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted dimethyl fluorenyl, substituted or unsubstituted twoOne of benzofuranyl, substituted or unsubstituted dibenzothiophene.

A kind of organic electroluminescence device based on above-mentioned electroluminescent organic material, including cathode, anode and in instituteOne layer or more organic layer possessed by stating between cathode and anode, it is at least one layer of comprising upper in described one layer or more of organic layerThe electroluminescent material stated.

The organic layer includes hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electronicsTransport layer and electron injecting layer.

Organic matter layer comprising the electroluminescent organic material is hole transmission layer.

" alkyl " unsubstituted in the present invention refers to that carbon atom number is the alkyl of 1-20, is 1-20 comprising carbon atom numberStraight chained alkyl or carbon atom number be 1-6 branched alkyl.For example, methyl, ethyl, propyl, isobutyl group, sec-butyl, amyl,Isopentyl, base etc..Substituted carbon atom number be 1-20 alkyl refer at least one hydrogen atom by D-atom, F, Cl, I, CN,Hydroxyl, nitro, amino etc. replace.

Unsubstituted alkenyl in the present invention, the carbon atom number referred to are the alkenyl of 2-20, the carbon comprising carbon-carbon double bondAtomicity is the alkenyl of the straight chain of 2-20, or the alkenyl comprising the branch that carbon atom number is 1-6.Such as: vinyl, acrylic,Allyl, isopropenyl, 2- cyclobutenyl etc..The alkenyl that substituted carbon atom number is 2-20 refers at least one hydrogen atom by deuterium originalSon, F, Cl, I, CN, hydroxyl, nitro, amino etc. replace.Unsubstituted alkynyl in the present invention, the carbon atom number referred to are 2-24 alkynyl, the carbon atom number comprising triple carbon-carbon bonds are the straight-chain alkynyl of 2-24, or the alkynes comprising the branch that carbon atom number is 1-7Base.Such as: acetenyl, 2-propynyl etc..The alkynyl that substituted carbon atom number is 2-24 refers at least one hydrogen atom by deuterium originalSon, F, Cl, I, CN, hydroxyl, nitro, amino etc. replace.

Unsubstituted aryl in the present invention, the carbon atom number referred to are the aryl of 6-30.Such as: phenyl, naphthalene, pyreneBase, dimethyl fluorenyl, anthryl, phenanthryl,Base, camomile ring group, acenaphthenyl, xenyl, benzo anthryl, two fluorenyl of spiral shell, base, indenylDeng.Substituted carbon atom number be 6-30 aryl refer at least one hydrogen atom by D-atom, F, Cl, I, CN, hydroxyl, nitro,Amino etc. replaces.

Unsubstituted aralkyl in the present invention refers to that carbon atom number is the aralkyl of 7-30.Such as: tolyl, diformazanBase fluorenyl etc..Substituted carbon atom number be 7-30 aralkyl refer at least one hydrogen atom by D-atom, F, Cl, I, CN,Hydroxyl, nitro, amino etc. replace.

The unsubstituted heteroaryl of the present invention refers to that carbon atom number is the heteroaryl of 2-30.Such as: pyridyl group, pyrazinyl,Pyrimidine radicals, pyridazinyl, triazine radical, quinolyl, indyl, carbazyl, dibenzofuran group, dibenzothiophene, dibenzo seleniumPheno base etc..Substituted carbon atom number be 2-30 heteroaryl refer at least one hydrogen atom by D-atom, F, Cl, I, CN, hydroxyl,Nitro, amino etc. replace.

The unsubstituted naphthenic base of the present invention refers to that carbon atom number is the naphthenic base of 3-20.Such as: cyclopropyl, cyclobutyl,Cyclopenta, cyclohexyl, norborny, adamantyl etc..Substituted carbon atom number is that the naphthenic base of 3-20 refers at least oneHydrogen atom is replaced by D-atom, F, Cl, I, CN, hydroxyl, nitro, amino etc..

The synthesis of compound 1

1,3- adamantane glycol (5.0g, 29.7mmol) and bromobenzene (10.3g, 65.4mmol) are dissolved in methylene chlorideIn (70mL), under the conditions of 0 DEG C of nitrogen protection, it is slowly added dropwise trifluoromethanesulfonic acid (11.2g, 74.3mmol), after insulated and stirred 8hIt is warmed to room temperature, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that pH value=7 of reaction solution.Then liquid separation, it is organicIt is mutually dry using magnesium sulfate is added after washing, solvent is removed under reduced pressure；Using normal heptane as mobile phase, using silica gel column chromatography to thickIt after product are purified, is recrystallized using methylene chloride/n-heptane system, obtains 6.8g white solid intermediate 1-A, yieldIt is 51%.

By 2 bromo toluene (10.0g, 58.5mmol), 2- amino -9,9- dimethyl fluorene (13.5g, 64.3mmol), three (twoBENZYLIDENE ACETONE) two palladiums (1.1g, 1.2mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.1g, 2.3mmol) withAnd sodium tert-butoxide (8.4g, 87.7mmol) is added in toluene (150mL), is heated to reflux temperature under nitrogen protection, stirs 2h；It is then cooled to room temperature, using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column, decompression removes reaction solutionRemove solvent；Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtains 11.3g light yellow solid intermediate 1-B, yield 65%.

By intermediate 1-A (6.8g, 15.2mmol), 1-B (10.0g, 33.5mmol), tris(dibenzylideneacetone) dipalladium(0.6g, 0.6mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.5g, 1.2mmol) and sodium tert-butoxide (4.4g,It 45.7mmol) is added in toluene (50mL), is heated to reflux temperature under nitrogen protection, stir 16h；Then it is cooled to room temperature,Solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Use dichloroEthane carries out recrystallization purification to crude product, obtains 5.6g compound as white solid 1, yield 42%.Mass spectrum: m/z=883.5 (M+H⁺)

The synthesis of compound 2

By bromo- 9, the 9- dimethyl fluorene (15.0g, 54.9mmol) of 2-, 4- aminobphenyl (10.2g, 60.4mmol), three (twoBENZYLIDENE ACETONE) two palladiums (1.0g, 1.1mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.0g, 2.2mmol) withAnd sodium tert-butoxide (7.9g, 82.4mmol) is added in toluene (200mL), is heated to reflux temperature under nitrogen protection, stirs 2h；It is then cooled to room temperature, using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column, decompression removes reaction solutionRemove solvent；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains 14.4g white solid intermediate 2-B, yield 73%.

By intermediate 1-A (5.0g, 11.2mmol), 2-B (8.9g, 24.7mmol), tris(dibenzylideneacetone) dipalladium(0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 0.9mmol) and sodium tert-butoxide (3.2g,It 33.6mmol) is added in toluene (50mL), is heated to reflux temperature under nitrogen protection, stir 12h；Then it is cooled to room temperature,Solid is obtained by filtration, solid is dry after washing using water and ethyl alcohol；Recrystallization purification is carried out to crude product using dichloroethanes, is obtained6.8g compound as white solid 2, yield 60%.Mass spectrum: m/z=1007.5 (M+H⁺)

The synthesis of compound 3

By bromo- 9, the 9- dimethyl fluorene (15.0g, 54.9mmol) of 2-, 2- aminobphenyl (10.2g, 60.4mmol), three (twoBENZYLIDENE ACETONE) two palladiums (1.0g, 1.1mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.0g, 2.2mmol) withAnd sodium tert-butoxide (7.9g, 82.4mmol) is added in toluene (200mL), is heated to reflux temperature under nitrogen protection, stirs 5h；It is then cooled to room temperature, using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column, decompression removes reaction solutionRemove solvent；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains 11.9g pale brownish solid Intermediate3-B, yield 60%.

By intermediate 1-A (5.0g, 11.2mmol), 3-B (8.9g, 24.7mmol), tris(dibenzylideneacetone) dipalladium(0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 0.9mmol) and sodium tert-butoxide (3.2g,It 33.6mmol) is added in toluene (50mL), is heated to reflux temperature under nitrogen protection, stir 16h；Then it is cooled to room temperature,Solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Use dichloroMethane carries out recrystallization purification to crude product, obtains 5.2g compound as white solid 3, yield 46%.Mass spectrum: m/z=1007.5(M+H⁺)

The synthesis of compound 4

1,3- adamantane glycol (5.0g, 29.7mmol) and 2 bromo toluene (11.2g, 65.4mmol) are dissolved in methylene chlorideIn (70mL), under the conditions of 0 DEG C of nitrogen protection, it is slowly added dropwise trifluoromethanesulfonic acid (11.2g, 74.3mmol), after insulated and stirred 8hIt is warmed to room temperature, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that pH value=7 of reaction solution.Then liquid separation, it is organicIt is mutually dry using magnesium sulfate is added after washing, solvent is removed under reduced pressure；Using normal heptane as mobile phase, using silica gel column chromatography to thickIt after product are purified, is recrystallized using methylene chloride/n-heptane system, obtains 6.0g white solid intermediate 4-A, yieldIt is 43%.

By bromobenzene (10g, 63.7mmol), 2- amino -9,9- dimethyl fluorene (14.7g, 70.1mmol), three (dibenzylidenesAcetone) two palladiums (1.2g, 1.3mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.2g, 2.5mmol) and tertiary fourthSodium alkoxide (9.2g, 95.5mmol) is added in toluene (150mL), and reflux temperature is heated under nitrogen protection, stirs 2h；Then cool downTo room temperature, solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtains 14.5g white solid intermediate 4-B, yield is80%.

By intermediate 4-A (6.0g, 12.7mmol), 4-B (7.9g, 27.8mmol), tris(dibenzylideneacetone) dipalladium(0.5g, 0.5mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 1.0mmol) and sodium tert-butoxide (3.6g,It 38.0mmol) is added in toluene (50mL), is heated to reflux temperature under nitrogen protection, stir 16h；Then it is cooled to room temperature,Solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Use dichloroMethane/n-heptane system carries out recrystallization purification to crude product, obtains 6.1g compound as white solid 4, yield 55%.Mass spectrum:M/z=883.5 (M+H⁺)

The synthesis of compound 5

1,3- adamantane glycol (5.0g, 29.7mmol) and 2- bromofluorobenzene (11.4g, 65.4mmol) are dissolved in methylene chlorideIn (80mL), under the conditions of 0 DEG C of nitrogen protection, it is slowly added dropwise trifluoromethanesulfonic acid (11.2g, 74.3mmol), after insulated and stirred 12hIt is warmed to room temperature, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that pH value=7 of reaction solution.Then liquid separation, it is organicIt is mutually dry using magnesium sulfate is added after washing, solvent is removed under reduced pressure；Use silica gel column chromatography to thick by mobile phase of normal heptaneIt after product are purified, is recrystallized using methylene chloride/n-heptane system, obtains 8.1g white solid intermediate 5-A, yieldIt is 57%.

By intermediate 5-A (4.0g, 8.3mmol), 4-B (5.2g, 18.2mmol), tris(dibenzylideneacetone) dipalladium(0.3g, 0.3mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.7mmol) and sodium tert-butoxide (2.4g,It 24.9mmol) is added in toluene (30mL), is heated to reflux temperature under nitrogen protection, stir 12h；Then it is cooled to room temperature,Solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Use dichloroEthane carries out recrystallization purification to crude product, obtains 6.1g compound as white solid 5, yield 83%.Mass spectrum: m/z=891.5 (M+H⁺)

The synthesis of compound 6

1,3- adamantane glycol (5.0g, 29.7mmol) and 4- bromo biphenyl (15.2g, 65.4mmol) are dissolved in methylene chlorideIn (100mL), under the conditions of 0 DEG C of nitrogen protection, it is slowly added dropwise trifluoromethanesulfonic acid (11.2g, 74.3mmol), after insulated and stirred 4hIt is warmed to room temperature, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that pH value=7 of reaction solution.Then by reaction solutionSolid is obtained by filtration, solid is dry after washing using water and ethyl alcohol, carries out recrystallization purification to solid crude product using methylene chloride, obtainsTo 7.7g white solid intermediate 6-A, yield 43%.

By 2- bromonaphthalene (15.0g, 72.4mmol), 2-aminotoluene (8.5g, 79.7mmol), three (dibenzalacetones) twoPalladium (1.3g, 1.4mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.4g, 2.9mmol) and sodium tert-butoxide(10.4g, 108.7mmol) is added in toluene (200mL), is heated to reflux temperature under nitrogen protection, stirs 3h；Then cool downTo room temperature, solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains 13.1g white solid intermediate 6-B, yield is78%.

By intermediate 6-A (7.7g, 12.9mmol), 6-B (6.6g, 28.3mmol), tris(dibenzylideneacetone) dipalladium(0.5g, 0.5mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 1.0mmol) and sodium tert-butoxide (3.7g,It 38.6mmol) is added in toluene (60mL), is heated to reflux temperature under nitrogen protection, stir 20h；Then it is cooled to room temperature,Solid is obtained after reaction solution filtering, is dried after being washed using water and ethyl alcohol；Recrystallization purification then is carried out to crude product using toluene, is obtainedTo 5.4g compound as white solid 6, yield 46%.Mass spectrum: m/z=903.5 (M+H⁺)

The synthesis of compound 7

1,3- adamantane glycol (5.0g, 29.7mmol) and 2- bromine dibenzofurans (16.2g, 65.4mmol) are dissolved in twoIn chloromethanes (100mL), under the conditions of subzero 10 DEG C of nitrogen protections, trifluoromethanesulfonic acid (11.2g, 74.3mmol) is slowly added dropwise,It is warmed to room temperature after insulated and stirred 4h, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that pH value=7 of reaction solution,Solid is obtained by filtration, solid is dry after washing using water and ethyl alcohol, carries out recrystallization purification to crude product using methylene chloride, obtains9.2g white solid intermediate 7-A, yield 49%.

By bromobenzene (10.0g, 63.7mmol), 4- aminobphenyl (11.9g, 70.1mmol), three (dibenzalacetones) twoPalladium (1.2g, 1.3mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.2g, 2.5mmol) and sodium tert-butoxide(9.2g, 95.5mmol) is added in toluene (150mL), and reflux temperature is heated under nitrogen protection, stirs 1h；Then it is cooled to roomSolvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in temperature, reaction solution；It usesMethylene chloride/ethanol system carries out recrystallization purification to crude product, obtains 11.7g light yellow solid intermediate 7-B, and yield is75%.

By intermediate 7-A (9.2g, 14.7mmol), 7-B (7.9g, 32.3mmol), tris(dibenzylideneacetone) dipalladium(0.5g, 0.6mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.5g, 1.2mmol) and sodium tert-butoxide (4.2g,It 44.1mmol) is added in toluene (80mL), is heated to reflux temperature under nitrogen protection, stir 8h；It is then cooled to room temperature, insteadSolid is obtained after answering liquid to filter, is dried after being washed using water and ethyl alcohol；Recrystallization purification then is carried out to crude product using dichloroethanes,Obtain 7.0g compound as white solid 7, yield 50%.Mass spectrum: m/z=955.4 (M+H⁺)

The synthesis of compound 8

1,3- adamantane glycol (5.0g, 29.7mmol) and 2- bromodiphenylthiophene (xxg, xxmmol) are dissolved in dichloromethaneIt in alkane (100mL), under the conditions of subzero 10 DEG C of nitrogen protections, is slowly added dropwise trifluoromethanesulfonic acid (11.2g, 74.3mmol), keeps the temperatureIt is warmed to room temperature after stirring 6h, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that pH value=7 of reaction solution, filteringSolid is obtained, solid is dry after washing using water and ethyl alcohol, carries out recrystallization purification to crude product using dichloroethanes, it is white to obtain 7.6gColor solid intermediate 8-A, yield 39%.

By 2 bromo toluene (15.0g, 87.7mmol), aniline (9.0g, 96.5mmol), tris(dibenzylideneacetone) dipalladium(1.6g, 1.8mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.7g, 3.5mmol) and sodium tert-butoxide(12.6g, 131.5mmol) is added in toluene (200mL), is heated to reflux temperature under nitrogen protection, stirs 1h；Then cool downTo room temperature, solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；It the use of methylene chloride/normal heptane is after eluent carries out silica gel column chromatography purification to crude product, to be recrystallized, obtained using ethyl alcoholTo 10.2g pale brownish solid Intermediate 8-B, yield 63%.

By intermediate 8-A (7.6g, 11.5mmol), 8-B (4.7g, 25.4mmol), tris(dibenzylideneacetone) dipalladium(0.4g, 0.5mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 0.9mmol) and sodium tert-butoxide (3.3g,It 34.6mmol) is added in toluene (60mL), is heated to reflux temperature under nitrogen protection, stir 12h；Then it is cooled to room temperature,Solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Use dichloroMethane/n-heptane system carries out recrystallization purification to crude product, obtains 4.7g compound as white solid 8, yield 47%.Mass spectrum:M/z=863.4 (M+H⁺)

The synthesis of compound 9

1,3- adamantane glycol (5.0g, 29.7mmol) and 2- bromonaphthalene (13.5g, 65.4mmol) are dissolved in methylene chlorideIn (80mL), under the conditions of subzero 20 DEG C of nitrogen protections, trifluoromethanesulfonic acid (11.2g, 74.3mmol), insulated and stirred is slowly added dropwiseIt is warmed to room temperature after 4h, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that pH value=7 of reaction solution, are obtained by filtrationSolid, solid is dry after being washed using water and ethyl alcohol, carries out recrystallization purification to crude product using methylene chloride, and it is solid to obtain 6.9g whiteBody intermediate 9-A, yield 42%.

By 2 bromo toluene (10.0g, 58.5mmol), 4- aminobphenyl (10.9g, 64.3mmol), three (dibenzylidenes thirdKetone) two palladiums (1.1g, 1.2mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (1.1g, 2.3mmol) and the tert-butyl alcoholSodium (8.4g, 87.7mmol) is added in toluene (150mL), is heated to reflux temperature under nitrogen protection, stirs 2h；Then cool downTo room temperature, solid is obtained after reaction solution filtering, is dried after being washed using water and ethyl alcohol；Then crude product is recrystallized using toluenePurification, obtains 7.0g compound as white solid 9, yield 50%.

By intermediate 9-A (6.9g, xxmmol), 9-B (7.2g, 27.8mmol), tris(dibenzylideneacetone) dipalladium(0.5g, 0.5mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 1.0mmol) and sodium tert-butoxide (3.6g,It 37.9mmol) is added in toluene (60mL), is heated to reflux temperature under nitrogen protection, stir 16h；Then it is cooled to room temperature,Solvent is removed under reduced pressure using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column in reaction solution；Use dichloroEthane system carries out recrystallization purification to crude product, obtains 6.1g compound as white solid 9, yield 53%.Mass spectrum: m/z=903.5(M+H⁺)

The synthesis of compound 10

1,3- adamantane glycol (5.0g, 29.7mmol) and the bromo- 9,9- dimethyl fluorene (17.9g, 65.4mmol) of 2- is moltenIn methylene chloride (100mL), under the conditions of subzero 10 DEG C of nitrogen protections, be slowly added dropwise trifluoromethanesulfonic acid (11.2g,74.3mmol), it is warmed to room temperature after insulated and stirred 4h, 2mol/L sodium hydrate aqueous solution is added dropwise into reaction solution, so that reaction solutionPH value=7.Then liquid separation, organic phase is dry using magnesium sulfate is added after washing, and solvent is removed under reduced pressure；It is flowing with normal heptanePhase after being purified using silica gel column chromatography to crude product, is recrystallized using methylene chloride/n-heptane system, is obtained8.9g white solid intermediate 10-A, yield 44%.

By intermediate 10-A (8.9g, 13.1mmol), diphenylamines (4.9g, 29mmol), tris(dibenzylideneacetone) dipalladium(0.5g, 0.5mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 1.0mmol) and sodium tert-butoxide (3.8g,It 39.3mmol) is added in toluene (70mL), is heated to reflux temperature under nitrogen protection, stir 6h；It is then cooled to room temperature, insteadIt answers liquid using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column, solvent is removed under reduced pressure；Use toluene pairCrude product carries out recrystallization purification, obtains 6.9g compound as white solid 10, yield 62%.Mass spectrum: m/z=855.5 (M+H⁺)

Embodiment 1: production organic electroluminescence device

Anode is prepared by following procedure: will be with a thickness ofIto substrate (healthy and free from worry manufacture) be cut into 40mm ×The size of 40mm × 0.7mm is prepared into the experiment base with cathode, anode and insulating layer pattern using photo-mask processPlate utilizes UV ozone and O₂:N₂Plasma is surface-treated, with increase anode (experimental substrate) work function and it is clearExcept dross.

On experimental substrate (anode) vacuum evaporation m-MTDATA with formed with a thickness of hole injection layer (HIL), andOn hole injection layer vacuum evaporation compound 1 with formed with a thickness ofHole transmission layer (HTL).

Be deposited TCTA on the hole transport layer, formed with a thickness ofElectronic barrier layer (EBL).

It regard α, β-AND as main body, while adulterating 4,4'- (3,8- bis- (N, the N- diphenyl benzenes of diphenyl pyrene -1,6- diylAmine), form with a thickness ofLuminescent layer (EML).

DBimiBphen and LiQ is mixed and is deposited with the weight ratio of 1:1 and is formdThick electron transportLayer (ETL), by LiQ vapor deposition on the electron transport layer with formed with a thickness ofElectron injecting layer (EIL), then by magnesium (Mg)Mixed with silver-colored (Ag) with the ratio of 9:1, vacuum evaporation on electron injecting layer, formed with a thickness ofCathode.

In addition, as N- (4- (9H- carbazole -9- base) the phenyl) -4'- being deposited with a thickness of 65nm on above-mentioned cathode(9H- carbazole -9- base)-N- phenyl-[1,1'- biphenyl] -4- amine is formed coating (CPL), to complete organic luminescent deviceManufacture.

Embodiment 2-10

Other than respectively using compound shown in table 1 when forming hole transmission layer, utilization is same as Example 1Method make organic electroluminescence device.

I.e. embodiment 2 makes organic electroluminescence device using compound 2, and embodiment 3 makes Organic Electricity using compound 3Corresponding compound 4-10 production organic electroluminescence device is respectively adopted in electroluminescence device, embodiment 4-10, and device performance is shown inTable 1.

1~comparative example of comparative example 3

In the embodiment 1, in addition to having used NPB, compound A and compound B as hole transporting layer substitutionizationIt closes except object 1, manufactures organic electroluminescence device with method same as Example 1.

I.e. comparative example 1 manufactures organic electroluminescence device using NPB, and comparative example 2 is using compound A manufacture organic electroluminescence hairOptical device, comparative example 3 manufacture organic electroluminescence device using compound B, and device performance is shown in Table 1.

To organic electroluminescence device prepared above, in 10mA/cm²Under conditions of analyze the performance of device, knotFruit is shown in the following table 1.

1 device performance of table

Embodiment	Compound	V	lm/W	Cd/A	Cd/m2	Color	EQE (%)	T50(hr)
									1	Compound 1	3.95	5.7	7.1	772.3	Blue	14.4	3000
2	Compound 2	3.90	6	7.4	745.2	Blue	14.7	3050
									3	Compound 3	3.88	6.1	7.5	758.9	Blue	14.9	2900
4	Compound 4	3.89	5.5	6.9	751.8	Blue	13.8	3300
									5	Compound 5	3.89	6.2	7.7	724.5	Blue	14.9	2900
6	Compound 6	3.88	5.3	6.9	728.4	Blue	13.3	3400
									7	Compound 7	3.89	5.4	7.0	734.7	Blue	13.8	3100
8	Compound 8	3.89	6	7.4	717.7	Blue	14.4	3000
									9	Compound 9	3.87	5.2	6.4	730.1	Blue	13.1	3400
10	Compound 10	3.90	6	7.4	732.4	Blue	14.7	2980
									Comparative example 1	NPB	4.00	5.6	6.5	549	Blue	6.9	1650
Comparative example 2	Compound A	4.10	6.0	6.7	627	Blue	10.9	2600
									Comparative example 3	Compound B	3.91	5.7	6.8	665.5	Blue	10.9	2850

Reference table 1, in the case that the compound of the present invention is used as hole transporting layer by embodiment 1-10, with comparative example 1-3Compound compare, voltage (V), current efficiency (Cd/A), brightness (Cd/m²) and external quantum efficiency (EQE) and half-life(T50) better characteristics is showed.Therefore, the device made using the compounds of this invention, having reduces driving voltage, improvesLuminous efficiency and the characteristic to prolong the service life.

In conclusion the compounds of this invention to be used as to the hole transmission layer of organic electroluminescence device, so that including the changeThe organic electroluminescence device for closing object has lower driving voltage, higher luminous efficiency and better service life.

According to the table 1 of the result of the organic electroluminescent device of the embodiment it is found that the compound of the present invention is in bis- (three virtuesBase amine) on the basis of symmetrical structure, adamantane is introduced as new core group, changes molecular conformation, reduction finishesThe symmetry of structure.When being used as hole transporting material, the hole transport performance of material can be further promoted.It therefore, can be withManufacture the organic electroluminescence device with excellent characteristics such as driving voltage, luminous efficiency, external quantum efficiency and half-life.

Above embodiments are the further explanation to the compound of the present invention, and range is claimed simultaneously in invention of the inventionIt is not limited to this.For those skilled in the art, remembered not departing to invent in claimed rangeUnder the range of the technical idea of the invention carried, the various supplements and deformation carry out to the present invention also belong to protection model of the inventionIt encloses.

Claims (9)

1. a kind of electroluminescent organic material, which is characterized in that the structural formula of the material as described in chemical formula 1:

Ar₁、Ar₂、Ar₅With Ar₆Alkane that is identical or different, being separately 1-20 selected from substituted or unsubstituted carbon atom numberAlkynyl that alkenyl that base, substituted or unsubstituted carbon atom number are 2-20, substituted or unsubstituted carbon atom number are 2-24 replacesOr unsubstituted carbon atom number be 3-20 naphthenic base, substituted or unsubstituted carbon atom number be 2-20 Heterocyclylalkyl, replaceOr unsubstituted carbon atom number be 7-30 aralkyl, substituted or unsubstituted carbon atom number be 2-30 heteroarylalkyl, replaceOr unsubstituted carbon atom number be 6-30 aryl, substituted or unsubstituted carbon atom number be one of heteroaryl of 1-30；

Ar₃And Ar₄It is identical or different, separately selected from singly-bound, the alkylene that substituted or unsubstituted carbon atom number is 1-20Alkynylene that alkenylene that base, substituted or unsubstituted carbon atom number are 2-20, substituted or unsubstituted carbon atom number are 2-24,The heterocycle alkylene that ring alkylidene that substituted or unsubstituted carbon atom number is 3-20, substituted or unsubstituted carbon atom number are 2-20The miscellaneous Asia that sub- aralkyl that base, substituted or unsubstituted carbon atom number are 7-30, substituted or unsubstituted carbon atom number are 2-30Arlydene that aralkyl, substituted or unsubstituted carbon atom number are 6-30, substituted or unsubstituted carbon atom number are the miscellaneous of 1-30The miscellaneous Asia of arlydene, the ring alkenylene of substituted or unsubstituted carbon atom number 3-15, substituted or unsubstituted carbon atom number 2-15One of alkenyl, miscellaneous alkynylene of substituted or unsubstituted carbon atom number 2-15.

2. electroluminescent organic material according to claim 1, which is characterized in that the Ar₁、Ar₂、Ar₃、Ar₄、Ar₅AndAr₆Substituent group it is identical or different, and separately be selected from deuterium, cyano, nitro, halogen, hydroxyl, substituted or unsubstituted carbonThe alkyl of atomicity 1-20, the naphthenic base of substituted or unsubstituted carbon atom number 3-20, substituted or unsubstituted carbon atom number 2-20 alkenyl, the alkynyl of substituted or unsubstituted carbon atom number 2-24, substituted or unsubstituted carbon atom number 2-20 heterocycle alkaneBase, the aralkyl of substituted or unsubstituted carbon atom number 7-20, substituted or unsubstituted carbon atom number 2-20 heteroarylalkyl, takeThe aryl of generation or unsubstituted carbon atom number 6-20, the heteroaryl of substituted or unsubstituted carbon atom number 1-20, substitution do not takeIt is the alkoxy of the carbon atom number 1-20 in generation, the alkylthio group that substituted or unsubstituted carbon atom number is 1-20, substituted or unsubstitutedThe alkylamino of carbon atom number 1-20, the fragrant amino of substituted or unsubstituted carbon atom number 6-20, substituted or unsubstituted carbon atomNumber the heteroaryl amino of 1-20, the arylalkylamino of substituted or unsubstituted carbon atom number 7-20, substituted or unsubstituted carbon atom numberThe arylsilyl groups, substituted or unsubstituted for being 6-24 for the aIkylsilyl groups of 1-20, substituted or unsubstituted carbon atom numberCarbon atom number be 6-20 aryloxy group, substituted or unsubstituted carbon atom number be one of 6-20 arylthio.

3. electroluminescent organic material according to claim 1, which is characterized in that the Ar₁、Ar₂、Ar₅With Ar₆It is identicalOr it is different, it is separately former selected from the aralkyl, substituted or unsubstituted carbon that substituted or unsubstituted carbon atom number is 7-30Aryl that heteroarylalkyl that subnumber is 2-30, substituted or unsubstituted carbon atom number are 6-30, substituted or unsubstituted carbon atomNumber is one of the heteroaryl of 1-30.

4. electroluminescent organic material according to claim 1, which is characterized in that the Ar₃、Ar₄It does not take selected from substitution orHeteroarylidene that arlydene that the carbon atom number in generation is 6-30, substituted or unsubstituted carbon atom number are 1-30 replaces or does not takeSub- aralkyl that the carbon atom number in generation is 7-30, substituted or unsubstituted carbon atom number are one in the miscellaneous sub- aralkyl of 2-30Kind.

5. electroluminescent organic material according to claim 1, which is characterized in that the chemical formula 1 is as in flowering structureOne kind:

6. electroluminescent organic material according to claim 1, which is characterized in that the Ar₃、Ar₄It does not take selected from substitution orThe phenyl in generation, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthalene, substitutionOr in unsubstituted dimethyl fluorenyl, substituted or unsubstituted dibenzofuran group, substituted or unsubstituted dibenzothiopheneOne kind.

7. a kind of organic electroluminescence device, have including cathode, anode and one layer or more between the cathode and anodeMachine layer, which is characterized in that at least one layer of comprising described in claim 1 in one layer or more organic layer between the cathode and anodeElectroluminescent material.

8. organic electroluminescence device according to claim 7, which is characterized in that the organic layer includes hole injectionLayer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer.

9. organic electroluminescence device according to claim 7, which is characterized in that comprising described in claim 1 electroluminescentThe organic matter layer of luminescent material is hole transmission layer.