CN110183332A - A kind of aromatic derivant comprising polycyoalkane and the organic electroluminescence device comprising the derivative - Google Patents

A kind of aromatic derivant comprising polycyoalkane and the organic electroluminescence device comprising the derivative Download PDF

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CN110183332A
CN110183332A CN201910523543.4A CN201910523543A CN110183332A CN 110183332 A CN110183332 A CN 110183332A CN 201910523543 A CN201910523543 A CN 201910523543A CN 110183332 A CN110183332 A CN 110183332A
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carbon atom
atom number
substituted
unsubstituted
group
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CN110183332B (en
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马天天
冯震
杨雷
李红燕
沙荀姗
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Shaanxi Lighte Optoelectronics Material Co Ltd
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Abstract

The present invention relates to a kind of aromatic derivant comprising polycyoalkane and comprising the organic electroluminescence device of the derivative, shown in the following chemical formula I of structure:

Description

A kind of aromatic derivant comprising polycyoalkane and the Organic Electricity comprising the derivative Electroluminescence device
Technical field
The invention belongs to electroluminescent technology field more particularly to a kind of aromatic derivants and packet comprising polycyoalkane Organic electroluminescence device containing the derivative.
Background technique
In recent years, organic electroluminescence device (OLED:Organic electroluminescent device) is as new Generation display technology progresses into the visual field of people.Common are organic electroluminescence devices is by anode, cathode and in cathode One layer or more of organic layer is arranged between anode to constitute.When yin-yang the two poles of the earth apply voltage, two electrodes generate electric field, in electric field Under the action of, the electronics of cathode side is moved to luminescent layer, and anode-side is also moved to luminescent layer, and the two is combined in luminescent layer and formed Exciton, exciton are in excitation state and release energy outward, and releasing energy from excitation state becomes process that ground state releases energy to outgoing Light.Therefore, improving electrons and holes in OLED device in conjunction with property is vital.
In general, when organic electroluminescence device is driven at high temperature, it may appear that driving voltage rises, luminous efficiency reduces And the problems such as lost of life, cause the performance of organic electroluminescence device to decline.To solve the above-mentioned problems, many materials are met the tendency of And it gives birth to.Such as: a kind of CN201680002336.1 is related to adamantane derivative and its organic electroluminescence is given out light device comprising base Plate, the cathode being vaporized on substrate, anode, and the organic layer of vapor deposition between a cathode and an anode, wherein organic layer includes hole Transport layer, and hole transmission layer includes such as flowering structureAdamantane derivative.
Although the technology is still currently, the electroluminescent organic material of a large amount of function admirables developed successively There are many problems, for example in order to improve luminous efficiency, need suitable organic layer by triplet state in organic electroluminescence device Exciton is enclosed in luminescent layer；When being driven in applied at elevated temperature environment in order to avoid device, it may appear that driving voltage rises, shines The problems such as efficiency reduction and the lost of life, how to design the better material of new performance and be adjusted, so that all device energy Enough achieve the effect that reduce voltage, improve efficiency and the service life, is always those skilled in the art's urgent problem to be solved.
Summary of the invention
It is an object of the invention to overcome the problems of the prior art, it is derivative to provide a kind of aromatic series comprising polycyoalkane Object and organic electroluminescence device comprising the derivative, the derivative can be used as the injection of the hole in organic electroluminescence device Layer, hole transmission layer, electronic barrier layer etc. have lower driving voltage, higher luminous efficiency and service life.
The technical solution adopted by the present invention is that: shown in the following chemical formula I of the structure of the aromatic derivant:
Wherein, Ar1Alkyl, substituted or unsubstituted carbon atom number 3- selected from substituted or unsubstituted carbon atom number 1-20 20 naphthenic base, the aryl that substituted or unsubstituted carbon atom number is 6-40 and substituted or unsubstituted carbon atom number are 1- One of 40 heteroaryl；
Ar2And Ar3Identical or different, the substituted or unsubstituted carbon atom number being independently selected from is 6-40 aryl, takes Generation or unsubstituted carbon atom number 1-40 heteroaryl, replace or do not take the alkyl that substituted or unsubstituted carbon atom number is 1-35 Alkynyl that alkenyl that the carbon atom number in generation is 2-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon Heterocyclylalkyl that naphthenic base that atomicity is 3-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon Aralkyl that atomicity is 7-40, substituted or unsubstituted carbon atom number are one of heteroarylalkyl of 2-40；
A is the polycyoalkane comprising hexatomic ring, and n is the integer more than or equal to 1.
Further, A is selected from such as flowering structure:
To include hexatomic ring naphthenic base and Ar1The breaking portion of formed singly-bound.
Further, the substitution refers to by deuterium, cyano, nitro, halogen, hydroxyl, the alkyl that carbon atom number is 1-40 Group, the group of naphthene base of carbon atom number 3-40, the alkenyl group of carbon atom number 2-40, carbon atom number 2-40 alkynyl group, The heterocycloalkyl of carbon atom number 2-40, the aromatic alkyl group of carbon atom number 7-40, carbon atom number 2-40 heteroarylalkyl base Group, the aryl group of carbon atom number 6-40, the heteroaryl groups of carbon atom number 1-40, carbon atom number 1-40 alkoxy base, The alkylamino radicals of carbon atom number 1-40, the fragrant amino group of carbon atom number 6-40, carbon atom number be 1-40 alkylthio radicals, The arylalkylamino group of carbon atom number 7-40, the heteroaryl amino group of carbon atom number 1-24, the alkyl first that carbon atom number is 1-45 The aryloxy group or carbon that arylsilyl groups group that silyl group, carbon atom number are 6-50, carbon atom number are 6-30 Atomicity is the substitution of 6-30 arylthio group, instead of at least one of substituent group or compound hydrogen.
Further, Ar1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted xenyl, substituted or unsubstituted Terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substitution or not Substituted pyrenyl, substituted or unsubstituted indenyl, substituted or unsubstituted camomile ring group, replaces substituted or unsubstituted phenanthryl Or it is unsubstitutedOne of base, phonetic substituted or unsubstituted piperidinyl, substituted or unsubstituted pyridyl group.
Further, Ar1A and N is connected by singly-bound.
Further, the aromatic derivant includes:
A kind of organic electroluminescence device, including anode and cathode, and one layer or more between anode and cathode Organic layer, at least one layer includes aromatic derivant described in any of the above one in organic layer.
Further, organic layer includes hole injection layer, hole transmission layer, the hair set gradually from anode to cathode direction Photosphere, electron transfer layer and electron injecting layer；Coating is provided on cathode.
Further, the hole transmission layer includes aromatic derivant.
Further, the hole transmission layer includes: the first hole transmission layer and the second hole transmission layer；
Wherein, the first hole transmission layer is set on hole injection layer；Second hole transmission layer is set to the first hole biography On defeated layer；Luminescent layer is located on the second hole transmission layer.
Compared with prior art, the invention has the benefit that
It in the structure of the compounds of this invention based on hexa-atomic cycloalkane, is spread out comprising the aromatic series that polycyoalkane is skeleton Biology, compared with general substituent group, linear paraffin or monocycle alkane, the polycyoalkane comprising hexatomic ring shows more excellent Stability and high-fire resistance；Cyclic alkane has high complexity stereochemical structure, can be substantially compared to the general substituent group such as aryl It reduces due to molecule rotation, movement, and shakes brought energy loss, meanwhile, stereochemical structure is but also it being capable of shape At stable condensed ring；The asymmetric class polycyoalkane in part, while having reduction molecular symmetry to reduce molecular stacks to mention The feature of high material filming.Therefore, these polycyoalkanes comprising hexatomic ring can be improved in organic electroluminescence device and have The stability of machine layer.
Aromatic derivant of the present invention is used in organic electroluminescence device, can show that in 450-780nm range Interior optical wavelength, polycyoalkane derivative of the invention are that will have the characteristics such as hole injection, hole transport and electronic blocking Each functional characteristic molecule be combined, formed comprising hexatomic ring polycyoalkane aromatic derivant, as organic Has excellent stability and high-fire resistance when electroluminescent device, with the device phase for not using aromatic derivant of the present invention Than driving voltage of the present invention, current efficiency and external quantum efficiency and service life have obtained apparent improvement, and voltage reduces about 1-2V, luminous efficiency improve at least about 30%, and service life can extend 3.6 times.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of aromatic derivant of the invention；
Fig. 2 is the schematic cross-section of the organic electroluminescence device of an embodiment of the invention；
Fig. 3 is the schematic cross-section of the organic electroluminescence device of an embodiment of the invention.
Specific embodiment
In the present invention, hole characteristic refer to the hole formed in the anode easily by injection luminescent layer, and due to The characteristic transmitted in luminescent layer according to the transport properties of HOMO level.
Characteristic electron refers to the electronics formed in the cathode easily by injection luminescent layer, and due to according to LUMO level The characteristic transmitted in luminescent layer of transport properties.
Compound for organic electroluminescence device includes following compound, which can shine or inject And/or it works in transmission electronics, and can also act as the light emitting host containing appropriate dopant.In other words, for having The compound of organic electroluminescence devices may be used as phosphorescence or fluorescent host material, blue-light-emitting dopant material or electron-transport Material.
A kind of compound for organic electroluminescence device of embodiment according to the present invention is used as organic layer, and It its life characteristic that can improve organic electroluminescence device, efficiency characteristic, electrochemical stability and thermal stability and reduces Driving voltage.
Another aspect of the present invention is to provide a kind of organic light emission of aromatic derivant comprising the polycyoalkane Device makes it have lower driving voltage, higher luminous efficiency and service life.
Aromatic derivant of the invention, in compound structure based on hexa-atomic cycloalkane, derive containing polycyclic The triarylamine of alkane.The present invention is will to be used as hole injection, the hole of organic electroluminescent comprising the polycyoalkane of hexatomic ring Transmission material, compared with general substituent group, linear paraffin or monocycle alkane, the polycyoalkane comprising hexatomic ring shows more excellent Good stability and high-fire resistance.Especially bicyclic [2.2.2] octane, bicyclic [2.2.1] heptane, tricyclic [3.3.1.13,6] are pungent Alkane, tricyclic [3.3.1.1 3,7] octane, tricyclic [3.3.1.0 3,7] nonane, tricyclic [4.3.1.03,8] decane these have height The cyclic alkane for spending complexity stereochemical structure, compared to the general substituent group such as aryl can substantially reduce due to molecule rotation, Movement, and shake brought energy loss.Meanwhile stereochemical structure is but also it is capable of forming stable condensed ring.Wherein The asymmetric class polycyoalkane in part, e.g., tricyclic [3.3.1.1 3,7] octane and tricyclic [3.3.1.0 3,7] nonane etc. have simultaneously Having reduces molecular symmetry to reduce molecular stacks to improve the feature of material filming.Therefore, these include hexatomic ring Polycyoalkane can be improved the stability of organic layer in organic electroluminescence device.
Aromatic derivant of the present invention, structure is as shown in chemical formula I:
Wherein, Ar1Alkyl, substituted or unsubstituted carbon atom number 3- selected from substituted or unsubstituted carbon atom number 1-20 Aryl that 20 naphthenic base, substituted or unsubstituted carbon atom number are 6-40, substituted or unsubstituted carbon atom number are 1-40's One of heteroaryl；Ar1A and N is connected by singly-bound.
Preferably, Ar1Selected from substituted or unsubstituted phenyl, substituted or unsubstituted xenyl, substituted or unsubstituted Terphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substitution do not take The pyrenyl in generation, substituted or unsubstituted phenanthryl, substituted or unsubstituted indenyl, substituted or unsubstituted camomile ring group, replace or It is unsubstitutedOne of base, phonetic substituted or unsubstituted piperidinyl, substituted or unsubstituted pyridyl group.
Ar2、Ar3Identical or different, the substituted or unsubstituted carbon atom number being independently selected from is 6-40 aryl, takes Generation or unsubstituted carbon atom number 1-40 heteroaryl, replace or do not take the alkyl that substituted or unsubstituted carbon atom number is 1-35 Alkynyl that alkenyl that the carbon atom number in generation is 2-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon Heterocyclylalkyl that naphthenic base that atomicity is 3-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon Aralkyl that atomicity is 7-40, substituted or unsubstituted carbon atom number are one of heteroarylalkyl of 2-40；
A is the polycyoalkane comprising hexatomic ring, be can be selected from such as flowering structure:
N is the integer more than or equal to 1.
To include hexatomic ring naphthenic base and Ar1The breaking portion of formed singly-bound.
" substitution " refers to that by deuterium, cyano, nitro, halogen, hydroxyl, carbon atom number be the alkyl group of 1-40, carbon atom number The group of naphthene base of 3-40, the alkenyl group of carbon atom number 2-40, the alkynyl group of carbon atom number 2-40, carbon atom number 2-40 Heterocycloalkyl, the aromatic alkyl group of carbon atom number 7-40, the heteroaralkyl group of carbon atom number 2-40, carbon atom number 6-40 Aryl group, the heteroaryl groups of carbon atom number 1-40, the alkoxy base of carbon atom number 1-40, carbon atom number 1-40 alkane Amino group, the fragrant amino group of carbon atom number 6-40, the virtue that carbon atom number is the alkylthio radicals of 1-40, carbon atom number 7-40 Alkylamino radicals, the heteroaryl amino group of carbon atom number 1-24, aIkylsilyl groups group, the carbon atom that carbon atom number is 1-45 The aryloxy group or carbon atom number that arylsilyl groups group that number is 6-50, carbon atom number are 6-30 are 6-30 arylthio Group replaces, instead of A, Ar1、Ar2And Ar3At least one hydrogen of middle compound or substituent group, A, Ar1、Ar2And Ar3Substituent group It is same or different.
In the present specification, when it is in addition provide specific definition when, " miscellaneous " refer in a functional group include 1 to 3 hetero atoms in the group being made of B, N, O, S and P and remaining be carbon.
Alkyl group can be " the saturated alkyl group " of no any double or triple bonds.Alkyl group can be branch, Straight chain or cyclic alkyl radical.
" alkenyl group " refers to the functional group of at least one carbon-to-carbon double bond of at least two carbon, " alkynyl group " refer to The functional group of at least one carbon-carbon triple bond of few two carbon.
" aryl group " includes monocycle or fused polycycle (that is, the ring for sharing adjacent carbon atom pair) group.
" heteroaryl groups " refer to the hetero atom including 1 to 3 in the group being made of N, O, S and P and remaining is carbon Aryl group.When heteroaryl groups are fused rings, each ring may include 1 to 3 hetero atom.
Hereinafter, organic electroluminescence device is specifically described.
The organic electroluminescence device of other embodiment according to the present invention includes anode, cathode and between anode At least one or more organic layer between cathode, and at least one organic layer may include a kind of reality according to the present invention Apply the aromatic derivant for organic electroluminescence device of mode.
Fig. 1 and 2 is to spread out comprising a kind of aromatic series for organic electroluminescence device of embodiment according to the present invention The sectional view of the organic electroluminescence device of biology.
Referring to Figures 1 and 2, according to a kind of embodiment organic electroluminescence device and comprising being placed between anode and cathode At least one layer of organic layer.
Anode includes preferably facilitating hole and being injected into organic layer have big work function with anode material (work function, work function) material.Anode material specific example include: metal such as nickel, platinum, vanadium, chromium, copper, zinc and gold or Their alloy；Metal oxide such as zinc oxide, indium oxide, tin indium oxide (ITO) and indium zinc oxide (IZO)；Combined metal With oxide such as ZnO:Al or SnO2:Sb；Or conducting polymer for example poly- (3 methyl thiophene), poly- [3,4- (ethylidene -1,2- two Oxygroup) thiophene] (PEDT), polypyrrole and polyaniline, but not limited to this.Preferably include comprising tin indium oxide (indium tin oxide, Indium tin oxide) transparent electrode of (ITO) as anode.
Cathode includes following cathode material, contributes to material with small work function of the electron injection into organic layer Material.The specific example of cathode material include: metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminium, silver, tin and lead or they Alloy；Or multilayer material such as LiF/Al, Liq/Al, LiO2/ Al, LiF/Ca, LiF/Al and BaF2/ Ca, but not limited to this.It is excellent Choosing includes the metal electrode comprising aluminium as cathode.
Referring to fig. 2, organic layer includes hole injection layer, hole transmission layer, the hair set gradually from anode to cathode direction Photosphere, electron transfer layer and electron injecting layer；Referring to Fig. 3, hole transmission layer includes: that the first hole transmission layer and the second hole pass Defeated layer, the first hole transmission layer are set on hole injection layer；Second hole transmission layer is set on the first hole transmission layer；Hair Photosphere is located on the second hole transmission layer, and the first hole transmission layer and the second hole transmission layer all include aromatic derivant.
Hereinafter, by embodiment (cycloalkane+aryl amine), the present invention is described in more detail.But following implementations Example be only illustration of the invention, and and the non-limiting present invention.
The synthesis of compound 1
250mL round-bottomed flask is added in bicyclic [2,2,1] heptane (10.0g, 104.0mmol) and trifluoroacetic acid (100mL) In, concentrated nitric acid (0.3g) is added under stirring condition, is warming up to 45~50 DEG C, in being stirred 4 hours in air atmosphere；It is removed under reduced pressure three Fluoroacetic acid is added 10% potassium hydroxide-ethanol solution (90mL) into remaining mixture, stirs 1 hour；Ethyl alcohol is removed under reduced pressure, to Methylene chloride is added in bottle, washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Use dichloromethane Alkane/normal heptane carries out silica gel column chromatography purification to product as eluent, obtains white crystalline intermediate 1-A-1 (4.7g； 40%).
By bromo- 9, the 9- dimethyl fluorene (11.4g, 41.9mmol) of intermediate compound I-A-1 (4.7g, 41.9mmol), 2- and dichloro Methane (50mL) be added 100mL round-bottomed flask in, under the conditions of nitrogen protection, in -35~-40 DEG C of dropwise addition trifluoromethanesulfonic acids (9.4g, 62.9mmol)；After being added dropwise, keeps low temperature to stir 4 hours, be warmed to room temperature, 10% hydroxide is slowly added dropwise into reaction solution Sodium water solution is to neutrality；Organic phase is separated, using washing twice, using anhydrous magnesium sulfate drying, solvent is removed under reduced pressure in organic phase Obtain crude product；Use normal heptane to carry out silica gel column chromatography purification to product as eluent, obtains white solid intermediate compound I-A (7.8g；51%).
By 4- bromo biphenyl (10.0g, 42.9mmol), 2- amino -9,9- dimethyl fluorene (9.9g, 47.2mmol), three (two Asias Benzylacetone) two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.9mmol) and Sodium tert-butoxide (6.2g, 64.4mmol) is added in toluene (100mL), and 105-110 DEG C is heated under nitrogen protection, stirs 1 hour； It is cooled to room temperature, reaction solution twice, is added filtrate after magnesium sulfate dries, filters through short silicagel column, decompression removes using washing Remove solvent；Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtains light gray solid intermediate compound I-B (12.5g, 81%).
By intermediate compound I-A (7.8g, 21.2mmol), intermediate compound I-B (7.7g, 21.2mmol), three (dibenzalacetones) Two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.8mmol) and sodium tert-butoxide (4.1g, 42.5mmol) is added in toluene (60mL), and 105-110 DEG C is heated under nitrogen protection, stirs 12 hours；Then cool down 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； Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains compound as white solid I (6.2g, 45%) (formula 65).Mass spectrum: m/z=648.4 (M+H)+
The synthesis of compound 2
Bicyclic [2,2,2] octane (10.0g, 90.7mmol) and trifluoroacetic acid (80mL) are added in 250mL round-bottomed flask, Concentrated nitric acid (0.2g) is added under stirring condition, is warming up to 45~50 DEG C, in being stirred 3 hours in air atmosphere；Trifluoro is removed under reduced pressure Acetic acid is added 10% potassium hydroxide-ethanol solution (80mL) into remaining mixture, stirs 1 hour；Ethyl alcohol is removed under reduced pressure, to bottle Middle addition methylene chloride, washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Using methylene chloride/ Normal heptane carries out silica gel column chromatography purification to product as eluent, obtains white solid intermediate II-A-1 (5.0g； 44%).
By intermediate II-A-1 (5.0g, 39.6mmol), 4- bromo biphenyl (9.2g, 39.6mmol) and methylene chloride (50mL) It is added in 100mL round-bottomed flask, under the conditions of nitrogen protection, in -20~-15 DEG C of dropwise addition trifluoromethanesulfonic acids (8.9g, 59.4mmol)； After being added dropwise, keeps low temperature to stir 6 hours, be warmed to room temperature, 10% sodium hydrate aqueous solution is slowly added dropwise into reaction solution extremely It is neutral；Organic phase is separated, organic phase twice, using anhydrous magnesium sulfate drying, is removed under reduced pressure solvent and obtains crude product using washing；Make It uses normal heptane to carry out silica gel column chromatography purification to product as eluent, obtains white crystal intermediate II-A (6.5g； 48%).
By 2- bromo biphenyl (10.0g, 42.9mmol), 2- amino -9,9- dimethyl fluorene (9.9g, 47.2mmol), three (two Asias Benzylacetone) two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.9mmol) and Sodium tert-butoxide (6.2g, 64.4mmol) is added in toluene (100mL), and 105-110 DEG C is heated under nitrogen protection, stirs 2 hours； It is cooled to room temperature, reaction solution twice, is added filtrate after magnesium sulfate dries, filters through short silicagel column, decompression removes using washing Remove solvent；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains gray solid intermediate II-B (11.0g, 71%).
By intermediate II-A (6.5g, 19.0mmol), intermediate II-B (6.9g, 19.0mmol), three (dibenzylidenes third Ketone) two palladiums (0.3g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.8mmol) and sodium tert-butoxide (3.7,38.1mmol) it is added in toluene (50mL), 105-110 DEG C is heated under nitrogen protection, stir 18 hours；Then cool down 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； Recrystallization purification is carried out to crude product using dichloromethane/ethyl acetate system, obtains compound as white solid II (7.6g, 64%) (formula 58).Mass spectrum: m/z=622.3 (M+H)+
The synthesis of compound 3
Bicyclic [3.2.1] octane (8.0g, 72.6mmol) and trifluoroacetic acid (100mL) are added in 250mL round-bottomed flask, Concentrated nitric acid (0.5g) is added under stirring condition, is warming up to 50~55 DEG C, in being stirred 3 hours in air atmosphere；Trifluoro is removed under reduced pressure Acetic acid is added 10% potassium hydroxide-ethanol solution (80mL) into remaining mixture, stirs 1 hour；Ethyl alcohol is removed under reduced pressure, to bottle Middle addition methylene chloride, washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Using ethyl acetate/ Normal heptane carries out silica gel column chromatography purification to product as eluent, obtains white needles intermediate III-A-1 (4.5g； 49%).
By bromo- 9, the 9- dimethyl fluorene (9.7g, 35.7mmol) of intermediate III-A-1 (4.5g, 35.7mmol), 2- and dichloro Methane (50mL) be added 100mL round-bottomed flask in, under the conditions of nitrogen protection, in -20~-15 DEG C of dropwise addition trifluoromethanesulfonic acids (8.0g, 53.5mmol)；After being added dropwise, keeps low temperature to stir 3 hours, be warmed to room temperature, 10% hydroxide is slowly added dropwise into reaction solution Sodium water solution is to neutrality；Organic phase is separated, using washing twice, using anhydrous magnesium sulfate drying, solvent is removed under reduced pressure in organic phase Obtain crude product；Use normal heptane to carry out silica gel column chromatography purification to product as eluent, obtains light gray solid intermediate III-A(8.2g；60%).
By 2- bromo biphenyl (10.0g, 42.9mmol), 4- aminobphenyl (8.0g, 47.2mmol), three (dibenzalacetones) Two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.9mmol) and sodium tert-butoxide (6.2g, 64.4mmol) is added in toluene (100mL), and 105-110 DEG C is heated under nitrogen protection, stirs 1 hour；It is cooled to room Temperature, reaction solution twice, are added filtrate after magnesium sulfate dries, filters through short silicagel column using washing, solvent are removed under reduced pressure；Make Recrystallization purification is carried out to crude product with methylene chloride/ethanol system, obtains white solid intermediate III-B (12.1g, 88%).
By intermediate III-A (8.2g, 21.5mmol), intermediate III-B (6.9g, 21.5mmol), three (dibenzylidenes third Ketone) two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 0.9mmol) and sodium tert-butoxide (4.1,43.0mmol) it is added in toluene (70mL), 105-110 DEG C is heated under nitrogen protection, stir 24 hours；Then cool down 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； Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains compound as white solid III (7.1g, 53%) (formula 56).Mass spectrum: m/z=622.3 (M+H)+
The synthesis of compound 4
Bicyclic [3.3.1] nonane (10.0g, 80.5mmol) and trifluoroacetic acid (100mL) are added in 50mL round-bottomed flask, Nitric acid (0.2g) is added under stirring condition, is warming up to 45~50 DEG C, in being stirred 8 hours in air atmosphere；Trifluoro second is removed under reduced pressure Acid is added 10% potassium hydroxide-ethanol solution (80mL) into remaining mixture, stirs 0.5 hour；Ethyl alcohol is removed under reduced pressure, to bottle Middle addition methylene chloride, washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Using ethyl acetate/ Normal heptane carries out silica gel column chromatography purification to product as eluent, obtains white crystal intermediate compound IV-A-1 (3.9g； 35%).
Intermediate compound IV-A-1 (3.9g, 27.8mmol), bromobenzene (4.4g, 27.8mmol) and methylene chloride (40mL) are added In 100mL round-bottomed flask, under the conditions of nitrogen protection, in -25~-20 DEG C of dropwise addition trifluoromethanesulfonic acids (6.3g, 41.7mmol)；It is added dropwise After, it keeps low temperature to stir 4 hours, is warmed to room temperature, 10% sodium hydrate aqueous solution is slowly added dropwise into reaction solution to neutrality； Organic phase is separated, organic phase twice, using anhydrous magnesium sulfate drying, is removed under reduced pressure solvent and obtains crude product using washing；Using just Heptane carries out silica gel column chromatography purification to product as eluent, obtains faint yellow solid intermediate compound IV-A (5.1g；66%).
By the bromo- 9- phenyl carbazole (15.0g, 46.6mmol) of 2-, 4- aminobphenyl (8.7g, 51.2mmol), three (two benzal Benzylacetone) two palladiums (0.4g, 0.5mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.9mmol) and uncle Sodium butoxide (6.7g, 69.8mmol) is added in toluene (150mL), and 105-110 DEG C is heated under nitrogen protection, stirs 1.5 hours； It is cooled to room temperature, reaction solution twice, is added filtrate after magnesium sulfate dries, filters through short silicagel column, decompression removes using washing Remove solvent；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains white solid intermediate compound IV-B (14.0g, 73%).
By intermediate compound IV-A (5.1g, 18.3mmol), intermediate compound IV-B (7.5g, 18.3mmol), three (dibenzylidenes third Ketone) two palladiums (0.3g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.7mmol) and sodium tert-butoxide (3.5,36.5mmol) it is added in toluene (40mL), 105-110 DEG C is heated under nitrogen protection, stir 12 hours；Then cool down 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； Recrystallization purification is carried out to crude product using dichloromethane/ethyl acetate system, obtains compound as white solid IV (8.0g, 72%) (formula 78).Mass spectrum: m/z=609.3 (M+H)+
The synthesis of compound 5
Bicyclic [4.3.0] nonane (10.0g, 80.5mmol) and trifluoroacetic acid (120mL) are added in 50mL round-bottomed flask, Nitric acid (0.5g) is added under stirring condition, is warming up to 40~45 DEG C, in being stirred 6 hours in air atmosphere；Trifluoro second is removed under reduced pressure Acid is added 10% potassium hydroxide-ethanol solution (100mL) into remaining mixture, stirs 0.5 hour；Ethyl alcohol is removed under reduced pressure, to Methylene chloride is added in bottle, washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Use dichloromethane Alkane/normal heptane carries out silica gel column chromatography purification to product as eluent, obtains light yellow solid intermediate V-A-1 (5.7g； 51%).
By intermediate V-A-1 (5.7g, 40.7mmol), 4- bromo biphenyl (9.5g, 40.7mmol) and methylene chloride (60mL) It is added in 100mL round-bottomed flask, under the conditions of nitrogen protection, in -20~-15 DEG C of dropwise addition trifluoromethanesulfonic acids (9.2g, 61.0mmol)； After being added dropwise, keeps low temperature to stir 6 hours, be warmed to room temperature, 10% sodium hydrate aqueous solution is slowly added dropwise into reaction solution extremely It is neutral；Organic phase is separated, organic phase twice, using anhydrous magnesium sulfate drying, is removed under reduced pressure solvent and obtains crude product using washing；Make It uses normal heptane to carry out silica gel column chromatography purification to product as eluent, obtains white solid intermediate V-A (6.4g； 44%).
By bromo- 9, the 9- dimethyl fluorene (12.0g, 43.9mmol) of 2-, 2- amino -9,9- dimethyl fluorene (10.1g, 48.3mmol), tris(dibenzylideneacetone) dipalladium (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.9mmol) and sodium tert-butoxide (6.3g, 65.9mmol) are added in toluene (120mL), are heated under nitrogen protection It 105-110 DEG C, stirs 2.5 hours；It is cooled to room temperature, twice using washing, being added after magnesium sulfate dries, filters will filter for reaction solution Solvent is removed under reduced pressure by short silicagel column in liquid；Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtains ash Color solid intermediate V-B (15.2g, 84%).
By intermediate V-A (6.4g, 18.0mmol), intermediate V-B (7.2g, 18.0mmol), three (dibenzalacetones) Two palladiums (0.3g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.7mmol) and sodium tert-butoxide (3.5,36.0mmol) it is added in toluene (50mL), 105-110 DEG C is heated under nitrogen protection, stir 12 hours；Then cool down 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； Recrystallization purification is carried out to crude product using toluene/n-heptane system, obtains compound as white solid V (6.8g, 56%) (formula 75). Mass spectrum: m/z=676.4 (M+H)+
The synthesis of compound 6
250mL round-bottomed flask is added in bicyclic [4.4.0] decane (11.0g, 79.6mmol) and trifluoroacetic acid (110mL) In, nitric acid (0.3g) is added under stirring condition, is warming up to 50~55 DEG C, in being stirred 4 hours in air atmosphere；Trifluoro is removed under reduced pressure Acetic acid is added 10% potassium hydroxide-ethanol solution (90mL) into remaining mixture, stirs 1 hour；Ethyl alcohol is removed under reduced pressure, to bottle Middle addition methylene chloride, washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Using methylene chloride/ Normal heptane carries out silica gel column chromatography purification to product as eluent, obtains white solid intermediate VI-A-1 (4.4g； 36%).
Intermediate VI-A-1 (4.4g, 28.5mmol), bromobenzene (4.5g, 28.5mmol) and methylene chloride (45mL) are added In 100mL round-bottomed flask, under the conditions of nitrogen protection, in -15~-10 DEG C of dropwise addition trifluoromethanesulfonic acids (6.4g, 42.8mmol)；It is added dropwise After, it keeps low temperature to stir 8 hours, is warmed to room temperature, 10% sodium hydrate aqueous solution is slowly added dropwise into reaction solution to neutrality； Organic phase is separated, organic phase twice, using anhydrous magnesium sulfate drying, is removed under reduced pressure solvent and obtains crude product using washing；Using just Heptane carries out silica gel column chromatography purification to product as eluent, obtains white powder intermediate VI-A (5.1g；61%).
By 3- bromine dibenzofurans (10.0g, 40.5mmol), 4- aminobphenyl (7.5g, 44.5mmol), three (two benzal Benzylacetone) two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.8mmol) and uncle Sodium butoxide (5.8g, 60.7mmol) is added in toluene (100mL), and 105-110 DEG C is heated under nitrogen protection, stirs 1 hour；It is cold But to room temperature, reaction solution twice, is added filtrate after magnesium sulfate dries, filters through short silicagel column, is removed under reduced pressure using washing Solvent；Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtain white solid intermediate VI-B (10.4g, 77%).
By intermediate VI-A (5.1g, 17.4mmol), intermediate VI-B (5.8g, 17.4mmol), three (dibenzylidenes third Ketone) two palladiums (0.3g, 0.3mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.7mmol) and sodium tert-butoxide (3.3,34.8mmol) it is added in toluene (40mL), 105-110 DEG C is heated under nitrogen protection, stir 16 hours；Then cool down 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； Recrystallization purification is carried out to crude product using dichloroethanes/n-heptane system, obtains compound as white solid VI (6.6g, 69%) (formula 68).Mass spectrum: m/z=548.3 (M+H)+
The synthesis of compound 7
By tricyclic [3.3.1.03,7] nonane (10.0g, 81.8mmol) and trifluoroacetic acid (100mL) be added 250mL round bottom and burn In bottle, nitric acid (0.2g) is added under stirring condition, is warming up to 45~50 DEG C, in being stirred 6 hours in air atmosphere；It is removed under reduced pressure three Fluoroacetic acid is added 10% potassium hydroxide-ethanol solution (100mL) into remaining mixture, stirs 1.5 hours；Second is removed under reduced pressure Methylene chloride is added into bottle for alcohol, and washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Use two Chloromethanes/normal heptane carries out silica gel column chromatography purification to product as eluent, obtains white powder intermediate VII-A-1 (5.1g；45%).
By intermediate VII-A-1 (5.1g, 36.9mmol), 4- bromo biphenyl (8.6g, 36.9mmol) and methylene chloride (50mL) be added 100mL round-bottomed flask in, under the conditions of nitrogen protection, in -20~-15 DEG C of dropwise addition trifluoromethanesulfonic acids (8.3g, 55.4mmol)；After being added dropwise, keeps low temperature to stir 6 hours, be warmed to room temperature, 10% hydroxide is slowly added dropwise into reaction solution Sodium water solution is to neutrality；Organic phase is separated, using washing twice, using anhydrous magnesium sulfate drying, solvent is removed under reduced pressure in organic phase Obtain crude product；Use normal heptane to carry out silica gel column chromatography purification to product as eluent, obtains light gray solid intermediate VII-A(6.9g；53%).
By 3- bromine dibenzofurans (10.0g, 40.5mmol), bromo- 9, the 9- dimethyl fluorene (9.3g, 44.5mmol) of 2-, three (dibenzalacetone) two palladium (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.8mmol) and sodium tert-butoxide (5.8g, 60.7mmol) is added in toluene (100mL), is heated to 105-110 under nitrogen protection DEG C, it stirs 2 hours；It is cooled to room temperature, twice using washing, addition magnesium sulfate passes through filtrate after drying, filtering short reaction solution Solvent is removed under reduced pressure in silicagel column；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, is obtained light yellow solid Body intermediate VII-B (12.1g, 80%).
By intermediate VII-A (6.9g, 19.5mmol), intermediate VII-B (7.3g, 19.5mmol), three (dibenzylidenes third Ketone) two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.8mmol) and sodium tert-butoxide (3.8,39.1mmol) it is added in toluene (60mL), 105-110 DEG C is heated under nitrogen protection, stir 14 hours；Then cool down 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； Recrystallization purification is carried out to crude product using dichloromethane/ethyl acetate system, obtain compound as white solid VII (7.0g, 55%) (formula 76).Mass spectrum: m/z=648.3 (M+H)+
The synthesis of compound 8
By tricyclic [3.3.1.13,6] decane (10.0g, 73.4mmol) and trifluoroacetic acid (100mL) be added 250mL round bottom and burn In bottle, nitric acid (0.3g) is added under stirring condition, is warming up to 45~50 DEG C, in being stirred 4 hours in air atmosphere；It is removed under reduced pressure three Fluoroacetic acid is added 10% potassium hydroxide-ethanol solution (80mL) into remaining mixture, stirs 1 hour；Ethyl alcohol is removed under reduced pressure, to Methylene chloride is added in bottle, washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Use acetic acid second Ester/normal heptane carries out silica gel column chromatography purification to product as eluent, obtains buff powder intermediate VIII-A-1 (4.6g；41%).
Intermediate VIII-A-1 (4.6g, 30.2mmol), bromobenzene (4.7g, 30.2mmol) and methylene chloride (50mL) are added Enter in 100mL round-bottomed flask, under the conditions of nitrogen protection, in -20~-15 DEG C of dropwise addition trifluoromethanesulfonic acids (6.8g, 45.3mmol)；Drop After adding, keeps low temperature to stir 8 hours, be warmed to room temperature, 10% sodium hydrate aqueous solution is slowly added dropwise into reaction solution into Property；Organic phase is separated, organic phase twice, using anhydrous magnesium sulfate drying, is removed under reduced pressure solvent and obtains crude product using washing；It uses Normal heptane carries out silica gel column chromatography purification to product as eluent, obtains white solid intermediate VIII-A (6.0g； 68%).
By 3- bromodiphenylthiophene (12.0g, 45.6mmol), 4- aminobphenyl (8.5g, 50.2mmol), three (two benzal Benzylacetone) two palladiums (0.4g, 0.5mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.4g, 0.9mmol) and uncle Sodium butoxide (6.6g, 68.4mmol) is added in toluene (120mL), and 105-110 DEG C is heated under nitrogen protection, stirs 1.5 hours； It is cooled to room temperature, reaction solution twice, is added filtrate after magnesium sulfate dries, filters through short silicagel column, decompression removes using washing Remove solvent；Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtains pale brownish solid Intermediate VIII-B (13.9g, 87%).
By intermediate VIII-A (6.0g, 20.6mmol), intermediate VIII-B (7.2g, 20.6mmol), three (dibenzylidenes Acetone) two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.3g, 0.8mmol) and the tert-butyl alcohol Sodium (4.0,41.2mmol) is added in toluene (50mL), and 105-110 DEG C is heated under nitrogen protection, stirs 12 hours；It is then cold But to room temperature, reaction solution is removed under reduced pressure molten using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column Agent；Recrystallization purification is carried out to crude product using toluene/n-heptane system, obtains compound as white solid VIII (6.8g, 59%) (formula 66).Mass spectrum: m/z=562.3 (M+H)+
The synthesis of compound 9
By tricyclic [4.3.1.03,8] decane (12.0g, 88.1mmol) and trifluoroacetic acid (120mL) be added 250mL round bottom and burn In bottle, nitric acid (0.5g) is added under stirring condition, is warming up to 50~55 DEG C, in being stirred 5 hours in air atmosphere；It is removed under reduced pressure three Fluoroacetic acid is added 10% potassium hydroxide-ethanol solution (100mL) into remaining mixture, stirs 0.5 hour；Second is removed under reduced pressure Methylene chloride is added into bottle for alcohol, and washing is twice, dry using anhydrous magnesium sulfate, and solvent is removed under reduced pressure and obtains crude product；Use second Acetoacetic ester/normal heptane carries out silica gel column chromatography purification to product as eluent, obtains light yellow solid intermediate compound I X-A-1 (6.0g；45%).
By bromo- 9, the 9- dimethyl fluorene (10.8g, 39.4mmol) of intermediate VIII-A-1 (6.0g, 39.4mmol), 2- and two Chloromethanes (60mL) is added in 100mL round-bottomed flask, under the conditions of nitrogen protection, in -35~-30 DEG C of dropwise addition trifluoromethanesulfonic acids (8.9g,59.1mmol)；After being added dropwise, keeps low temperature to stir 3 hours, be warmed to room temperature, 10% is slowly added dropwise into reaction solution Sodium hydrate aqueous solution is to neutrality；Organic phase is separated, twice using washing, dry using anhydrous magnesium sulfate, decompression removes organic phase Solvent is gone to obtain crude product；Use normal heptane to carry out silica gel column chromatography purification to product as eluent, obtains in white solid Mesosome IX-A (9.1g；57%).
By 2- bromonaphthalene (10.0g, 48.3mmol), 4- aminobphenyl (9.0g, 53.1mmol), three (dibenzalacetones) two Palladium (0.4g, 0.5mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.5g, 1.0mmol) and sodium tert-butoxide (7.0g, 72.4mmol) is added in toluene (100mL), and 105-110 DEG C is heated under nitrogen protection, stirs 0.5 hour；It is cooled to Room temperature, reaction solution twice, are added filtrate after magnesium sulfate dries, filters through short silicagel column using washing, solvent are removed under reduced pressure； Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtains white solid intermediate compound I X-B (10.8g, 76%).
By intermediate compound I X-A (9.1g, 22.3mmol), intermediate compound I X-B (6.6g, 22.3mmol), three (dibenzylidenes third Ketone) two palladiums (0.4g, 0.4mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.4g, 0.9mmol) and sodium tert-butoxide (4.3,44.7mmol) it is added in toluene (70mL), 105-110 DEG C is heated under nitrogen protection, stir 16 hours；Then cool down 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； Recrystallization purification is carried out to crude product using dichloromethane/ethyl acetate system, obtains compound as white solid IX (7.5g, 54%) (formula 60).Mass spectrum: m/z=622.3 (M+H)+
Manufacture organic electroluminescence device
Implementation column 1: red 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 process Plate utilizes UV ozone and O2:N2Plasma is surface-treated, with increase anode (experimental substrate) work function and it is clear Except dross.
On experimental substrate (anode) vacuum evaporation m-MTDATA with formed with a thickness of with a thickness ofHole injection Layer (HIL), and hole injection layer be deposited NPB, formed with a thickness ofThe first hole transmission layer (HT1).
The vacuum evaporation compound 1 on the first hole transmission layer, formed with a thickness ofThe second hole transmission layer (HT2)。
4,4'-N, N'-dicarbazole-biphenyl (referred to as " CBP ") conduct are deposited on the second hole transmission layer Main body, while adulterating Ir (acac) (piq)2, 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 transfer layer (ETL), by LiQ vapor deposition on the electron transport layer with formed with a thickness ofElectron injecting layer (EIL), then by magnesium (Mg) and Silver-colored (Ag) is mixed with the evaporation rate of 1:9, vacuum evaporation on electron injecting layer, formed with a thickness ofCathode.
In addition, on above-mentioned cathode as be deposited with a thickness ofN- (4- (9H- carbazole -9- base) phenyl) -4'- (9H- carbazole -9- base)-N- phenyl-[1,1'- biphenyl] -4- amine is formed coating (CPL), to complete organic hair of top emitting The manufacture of optical device.
Embodiment 2-5
Other than respectively using compound shown in table 1 when forming the second hole transmission layer (HT2), using with reality Apply the identical method of example 1 production organic electroluminescence device.
I.e. embodiment 2 makes organic electroluminescence device using compound 2, and embodiment 3 makes Organic Electricity using compound 3 Electroluminescence device, embodiment 4 make organic electroluminescence device using compound 4, and embodiment 5 is made organic of compound 5 Electroluminescent device, device performance are shown in Table 1.
1~comparative example of comparative example 2
In the comparative example 1-2, in addition to used NPD and TPD as the second hole transmission layer alternative compounds 1 it Outside, organic electroluminescence device is manufactured with method same as Example 1.
Comparative example 3
Other than not formed second hole transmission layer this point, prepared using method identical with above-described embodiment 1 organic Electroluminescent cell, device performance are shown in Table 1.
That is comparative example NPD manufactures organic electroluminescence device, and comparative example 2 manufactures organic electroluminescence device, device using TPD Part performance is shown in Table 1.
To organic electroluminescence device prepared above, in 20mA/cm2Under conditions of analyze the performance of device, knot Fruit is shown in the following table 1.
Organic electroluminescence device test performance made from table 1 embodiment 1-5 and comparative example 1-3
Embodiment Compound Volt(V) Cd/A EQE T95(h) Color
Embodiment 1 Compound 1 3.55 33.82 22.64 400 Red
Embodiment 2 Compound 2 3.61 32.89 22.55 410 Red
Embodiment 3 Compound 3 3.82 30.79 23.95 470 Red
Embodiment 4 Compound 4 3.89 31.93 25.54 390 Red
Embodiment 5 Compound 5 3.78 30.89 23.91 372 Red
Comparative example 1 NPD 4.54 26.00 19.71 210 Red
Comparative example 2 TPD 5.32 25.40 18.50 230 Red
Comparative example 3 - 4.32 18.30 14.64 189 Red
Reference table 1 is it is found that embodiment 1-5 passes the compounds of this invention 1-5 as the second hole of organic electroluminescence device Defeated layer material, compared with comparative example 1-2, driving voltage (Vlot), current efficiency (Cd/A) and external quantum efficiency (EQE) and Service life (T95) has obtained apparent improvement, and service life can extend one times.
Compared with comparative example, embodiment compound is used for organic electroluminescence device, and voltage reduces about 1-2V, and shine effect Rate improves at least about 30%.
From embodiment 1-5 with comparative example 3 as can be seen that the compounds of this invention is organic as the second hole transmission layer (HT2) Compared with the organic electroluminescence device without the second hole transmission layer (HT2), voltage (V) is obviously dropped electroluminescent device It is low, current efficiency (Cd/A) and external quantum efficiency (EQE) is significantly improved and the service life (T95) is also improved.
Compared with comparative example, embodiment shows lower driving voltage and increased efficiency.
Specifically, compared with comparative example 1 to 3, Examples 1 and 2 show excellent efficiency, voltage and service life.
Implementation column 6: blue organic electroluminescent 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 process Plate utilizes UV ozone and O2:N2Plasma is surface-treated, with increase anode (experimental substrate) work function and it is clear Except dross.
On experimental substrate (anode) vacuum evaporation m-MTDATA with formed with a thickness ofHole injection layer (HIL), And the vacuum evaporation compound 6 on hole injection layer, with formed with a thickness ofThe first hole transmission layer (HT1).
Be deposited TCTA on the first hole transmission layer, formed with a thickness ofThe second hole transmission layer (HT2).
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- diyl Amine), 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 transfer layer (ETL), by LiQ vapor deposition on the electron transport layer with formed with a thickness ofElectron injecting layer (EIL), then by magnesium (Mg) and Silver-colored (Ag) is mixed with the evaporation rate of 1:9, vacuum evaporation on electron injecting layer, formed with a thickness ofCathode.
In addition, on above-mentioned cathode as be deposited with a thickness ofN- (4- (9H- carbazole -9- base) phenyl) -4'- (9H- carbazole -9- base)-N- phenyl-[1,1'- biphenyl] -4- amine is formed coating (CPL), to complete organic luminescent device Manufacture.
Embodiment 7-9
Other than respectively using compound shown in table 2 when forming the first hole transmission layer (HT1), using with reality Apply the identical method of example 6 production organic electroluminescence device.
I.e. embodiment 7 makes organic electroluminescence device using compound 7, and embodiment 8 makes Organic Electricity using compound 8 Electroluminescence device, embodiment 9 make organic electroluminescence device performance using compound 9 and are shown in Table 2.
4~comparative example of comparative example 6
In the 4~comparative example of comparative example 5, in addition to having used NPB, NPD, TPD to substitute as the first hole transmission layer Except compound 6, organic electroluminescence device is manufactured with method same as Example 6.
I.e. comparative example 4 manufactures organic electroluminescence device using NPB, and comparative example 5 manufactures organic electroluminescence using NPD Part, comparative example 6 manufacture organic electroluminescence device using TPD, and device performance is shown in Table 2.
To organic electroluminescence device obtained above, in 20mA/cm2Under conditions of analyze the performance of device, knot Fruit is shown in the following table 2.
2 embodiment 6-9 of table and comparative example 4-6 organic electroluminescence device test performance
Embodiment Compound Volt(V) Cd/A EQE% T95(h) Color
Embodiment 6 Compound 6 4.0 6.7 14.3 200 Blue
Embodiment 7 Compound 7 4.1 6.8 14.6 210 Blue
Embodiment 8 Compound 8 3.9 6.9 14.9 198 Blue
Embodiment 9 Compound 9 4.2 7.2 15.1 209 Blue
Comparative example 4 NPB 5.6 6.2 9.2 75 Blue
Comparative example 5 NPD 5.0 6.0 8.9 68 Blue
Comparative example 6 TPD 5.5 5.6 6.9 59 Blue
Reference table 2, in the case that the compound of the present invention is used as the first hole transmission layer (HT1) by embodiment 6-10, with Compound in comparative example 4-6 is compared, voltage (V), and current efficiency (Cd/A) and external quantum efficiency (EQE) get a promotion, the service life (T95) significant improvement is showed.
Compared with comparative example 4-6, the organic electroluminescence device made using the compounds of this invention, especially compound 8, Compared with NPD, voltage reduces 1.1V, and external quantum efficiency improves 67%, this is very significant for blue-light device It is promoted.
For OLED device (i.e. organic electroluminescence device), to its effect (such as in terms of EQE) even if improvement There was only a few percent in data, still, this improve is also highly significant.
Specifically, external quantum efficiency (EQE) can be calculated according to following formula, such as EQE=projects the photon of component Number/injection number of electrons；In another example EQE=light emission rate * internal quantum (light emission rate is less than 1).
For blue-light device, luminescent layer is fluorescent material, and fluorescent material is that singlet exciton shines, in Portion's quantum efficiency is up to 25%.And when externally shining, other originals such as loss of the light caused by the device architectures such as coupling Cause causes external quantum efficiency to be centainly lower than 25%, so that its efficiency is usually lower because 25% exciton can only be utilized.
Therefore, the device made using the compounds of this invention, having reduces driving voltage, improves luminous efficiency and extension The characteristic of 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 change The organic electroluminescence device for closing object has lower driving voltage, higher luminous efficiency and better service life.
Above embodiments are the further explanation to the compound of the present invention, and range is claimed simultaneously in invention of the invention It is not limited to this.For those skilled in the art, remembered not departing to invent in claimed range Under 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 invention It encloses.

Claims (10)

1. a kind of aromatic derivant comprising polycyoalkane, it is characterised in that: the structure of the aromatic derivant is chemical as follows Shown in formula I:
Wherein, Ar1Alkyl, substituted or unsubstituted carbon atom number 3-20 selected from substituted or unsubstituted carbon atom number 1-20 Naphthenic base, the aryl that substituted or unsubstituted carbon atom number is 6-40 and substituted or unsubstituted carbon atom number are 1-40's One of heteroaryl；
Ar2And Ar3It is identical or different, the substituted or unsubstituted carbon atom number being independently selected from be 6-40 aryl, replace or Unsubstituted carbon atom number 1-40 heteroaryl, the alkyl, substituted or unsubstituted that substituted or unsubstituted carbon atom number is 1-35 Alkynyl that alkenyl that carbon atom number is 2-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon atom Heterocyclylalkyl that naphthenic base that number is 3-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon atom Aralkyl that number is 7-40, substituted or unsubstituted carbon atom number are one of heteroarylalkyl of 2-40；
A is the polycyoalkane comprising hexatomic ring, and n is the integer more than or equal to 1.
2. a kind of aromatic derivant comprising polycyoalkane according to claim 1, it is characterised in that: A is selected from as follows Structure:
To include hexatomic ring naphthenic base and Ar1The breaking portion of formed singly-bound.
3. a kind of aromatic derivant comprising polycyoalkane according to claim 1, it is characterised in that: the substitution Refer to by deuterium, cyano, nitro, halogen, hydroxyl, the naphthenic base base that carbon atom number is the alkyl group of 1-40, carbon atom number 3-40 Group, the alkenyl group of carbon atom number 2-40, the alkynyl group of carbon atom number 2-40, carbon atom number 2-40 heterocycloalkyl, The aromatic alkyl group of carbon atom number 7-40, the heteroaralkyl group of carbon atom number 2-40, carbon atom number 6-40 aryl group, carbon The heteroaryl groups of atomicity 1-40, the alkoxy base of carbon atom number 1-40, the alkylamino radicals of carbon atom number 1-40, carbon are former The fragrant amino group of subnumber 6-40, arylalkylamino group, the carbon that carbon atom number is the alkylthio radicals of 1-40, carbon atom number 7-40 The virtue that aIkylsilyl groups group that the heteroaryl amino group of atomicity 1-24, carbon atom number are 1-45, carbon atom number are 6-50 The aryloxy group or carbon atom number that base silyl-group, carbon atom number are 6-30 are that 6-30 arylthio group replaces, generation For at least one of substituent group or compound hydrogen.
4. a kind of aromatic derivant comprising polycyoalkane according to claim 1, it is characterised in that: Ar1Selected from substitution Or unsubstituted phenyl, substituted or unsubstituted xenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted fluorenes Base, substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted phenanthrene It is base, substituted or unsubstituted indenyl, substituted or unsubstituted camomile ring group, substituted or unsubstitutedBase, phonetic substitution do not take One of the piperidinyl in generation, substituted or unsubstituted pyridyl group.
5. a kind of aromatic derivant comprising polycyoalkane according to claim 1, it is characterised in that: Ar1Pass through singly-bound Connect A and N.
6. a kind of aromatic derivant comprising polycyoalkane according to claim 1, it is characterised in that: the fragrance Race's derivative includes:
7. a kind of organic electroluminescence device, it is characterised in that: including anode and cathode, and between anode and cathode One layer or more organic layer, at least one layer includes aromatic derivant as claimed in any one of claims 1 to 6 in organic layer.
8. a kind of organic electroluminescence device according to claim 7, it is characterised in that: organic layer includes from anode to yin Hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and the electron injecting layer that extreme direction is set gradually；It is set on cathode It is equipped with coating.
9. a kind of organic electroluminescence device according to claim 8, it is characterised in that: the hole transmission layer includes There is the aromatic derivant.
10. a kind of organic electroluminescence device according to claim 8, it is characterised in that: the hole transmission layer includes: First hole transmission layer and the second hole transmission layer；
Wherein, first hole transmission layer is set on the hole injection layer；Second hole transmission layer is set to institute It states on the first hole transmission layer；The luminescent layer is located on second hole transmission layer.
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