CN110105225A - A kind of electroluminescent organic material and the organic electroluminescence device comprising the material - Google Patents

A kind of electroluminescent organic material and the organic electroluminescence device comprising the material Download PDF

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CN110105225A
CN110105225A CN201910401738.1A CN201910401738A CN110105225A CN 110105225 A CN110105225 A CN 110105225A CN 201910401738 A CN201910401738 A CN 201910401738A CN 110105225 A CN110105225 A CN 110105225A
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substituted
carbon atom
atom number
unsubstituted carbon
unsubstituted
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CN110105225B (en
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马天天
冯震
李红燕
李健
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

A kind of electroluminescent organic material and the organic electroluminescence device comprising the material, new aryl group-dihydro phenanthrene is introduced as one of core group, obtain dihydro phenanthrene derivative, the dihydro phenanthrene derivative possesses biggish molecular weight, material glass transition temperature and decomposition temperature can be promoted, to reinforcing material thermal stability, device lifetime is promoted；The compound of the group containing dihydro phenanthrene has excellent hole transport performance, it can be used for making organic electroluminescence device, it can be used as hole injection layer in organic electroluminescence device, hole transmission layer etc., especially as the hole transport layer material in organic electroluminescence device, improve OLED device in electrons and holes in conjunction with property, so as to which driving voltage is effectively reduced, the luminous efficiency and service life of organic luminescent device are improved.

Description

A kind of electroluminescent organic material and the organic electroluminescence device comprising the material
Technical field
The present invention relates to electroluminescent organic material technical fields, and in particular to a kind of electroluminescent organic material and comprising The organic electroluminescence device of the material.
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 order to improve brightness, efficiency and the service life of organic electroluminescence device, multilayered structure is usually used in the devices.This A little multilayered structures include: hole injection layer (hole injection layer), hole transmission layer (hole transport Layer), electronic barrier layer (electron-blocking layer), luminescent layer (emitting layer) and electron transfer layer (electron transport layer) etc..These organic layers, which have, improves carrier (hole and electronics) in each bed boundary Between injection efficiency, the ability that equilbrium carrier transmits between the layers, to improve the brightness and efficiency of device.
Currently, although the electroluminescent organic material of a large amount of function admirable developed successively, such as: CN201380045022.3 provides the aromatic derivant with 9 ' 9 diphenylfluorenes for skeleton, is used as organic electroluminescent Material.But the fluorenes five-membered ring tension in 9 ' 9 diphenylfluorenes is larger, at high temperature or is electrically excited state and is easy to happen scission of link, thus Reduce organic electroluminescence device performance.Therefore, how to design the better material of new performance to be adjusted, so that all devices Part can achieve the effect that reduce voltage, improve efficiency and the service life, be always those skilled in the art's urgent problem to be solved.
Organic electroluminescence device influences most importantly efficiency, driving voltage and service life, while how to improve device Stability is also very important problem.
Summary of the invention
The purpose of the present invention is to provide a kind of electroluminescent organic material haveing excellent performance containing dihydro phenanthrene.
Another object of the present invention is to provide a kind of organic electroluminescences comprising the electroluminescent organic material Part has 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 is as described in chemical formula 1；
Wherein, arlydene, the substituted or unsubstituted carbon that L is selected from singly-bound, substituted or unsubstituted carbon atom number is 6-40 Atomicity is the heteroarylidene of 1-40；
Ar1、Ar2It is identical or different, separately selected from substituted or unsubstituted carbon atom number be 1-35 alkyl, take Generation or unsubstituted carbon atom number be 2-35 alkenyl, substituted or unsubstituted carbon atom number be 2-35 alkynyl, replace or not Heterocyclylalkyl that naphthenic base that substituted carbon atom number is 3-35, substituted or unsubstituted carbon atom number are 2-35 replaces or not Heteroarylalkyl that aralkyl that substituted carbon atom number is 7-40, substituted or unsubstituted carbon atom number are 2-40 replaces or not The heteroaryl that aryl that substituted carbon atom number is 6-40, substituted or unsubstituted carbon atom number are 1-40；
R1、R2、R3、R4It is identical or different, be separately selected from hydrogen, deuterium, tritium, substituted or unsubstituted carbon atom number Alkenyl that the alkyl of 1-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon atom number are 2-35's The heteroaryl that aryl that alkynyl, substituted or unsubstituted carbon atom number are 6-40, substituted or unsubstituted carbon atom number are 1-40；
R5Selected from empty, hydrogen or singly-bound；
The R1、R2、R3、R4、Ar1、Ar2And the substituent group of L is identical or different, and separately selected from deuterium, cyano, Nitro, halogen, hydroxyl, the alkyl of substituted or unsubstituted carbon atom number 1-40, substituted or unsubstituted carbon atom number 3-40 Naphthenic base, the alkenyl of substituted or unsubstituted carbon atom number 2-40, the alkynyl of substituted or unsubstituted carbon atom number 2-40, substitution Or the Heterocyclylalkyl of unsubstituted carbon atom number 2-40, substituted or unsubstituted carbon atom number 7-40 aralkyl, replace or not The aryl, substituted or unsubstituted of the heteroarylalkyl of substituted carbon atom number 2-40, substituted or unsubstituted carbon atom number 6-40 The heteroaryl of carbon atom number 1-40, the alkoxy of substituted or unsubstituted carbon atom number 1-40, substituted or unsubstituted carbon atom The number alkylamino of 1-40, the fragrant amino of substituted or unsubstituted carbon atom number 6-40, substituted or unsubstituted carbon atom number are 1- 40 alkylthio group, the arylalkylamino of substituted or unsubstituted carbon atom number 7-40, substituted or unsubstituted carbon atom number 1-24 AIkylsilyl groups that heteroaryl amino, substituted or unsubstituted carbon atom number are 1-45, substituted or unsubstituted carbon atom number are The arylsilyl groups of 6-50, aryloxy group, the substituted or unsubstituted carbon atom that substituted or unsubstituted carbon atom number is 6-30 Number is 6-30 arylthio.
A further improvement of the present invention lies in that the structural formula of the electroluminescent organic material such as chemical formula 2 or chemical formula 3 It is shown；
A further improvement of the present invention lies in that the R1、R2、R3、R4It is identical or different, separately selected from hydrogen, substitution Or it unsubstituted methyl, substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted xenyl, takes Generation or unsubstituted naphthalene.
A further improvement of the present invention lies in that the L is selected from singly-bound, substituted or unsubstituted phenyl, substituted or unsubstituted Fluorenyl, substituted or unsubstituted xenyl, substituted or unsubstituted naphthalene.
A further improvement of the present invention lies in that the structure of the chemical formula 1 is specific as follows:
A kind of organic electroluminescence device based on above-mentioned electroluminescent organic material, including anode are set on the anode It is equipped with hole injection layer；
Hole transmission layer is provided on the hole injection layer；
Luminescent layer is provided on the hole transmission layer；
Electron transfer layer is provided on the luminescent layer；
Electron injecting layer is provided on the electron transfer layer；
Cathode is provided on the electron injecting layer；
Wherein, the hole transmission layer includes electroluminescent organic material.
A further improvement of the present invention lies 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 on first hole transmission layer；
The luminescent layer is set on second hole transmission layer.
A further improvement of the present invention lies in that first hole transmission layer or second hole transmission layer include described Electroluminescent organic material.
Compared with prior art, beneficial effects of the present invention:
1. invention introduces new aryl group-dihydro phenanthrenes as one of core group, dihydro phenanthrene possesses non-conjugated six Member ring division center can fine-tune dihedral angle/coplanarity of triarylamine branch phenyl ring, to reach more preferable Molecular orbital energy level and hole mobility balance；
2. dihydro phenanthrene group have it is multiple may replace site, possess better scalability；Pass through the substituent group of optimum choice Combination can make intermolecular being optimal of stack manner, promote material devices performance；
3. dihydro phenanthrene derivative is obtained since present invention introduces new aryl group-dihydro phenanthrenes as one of core group, The dihydro phenanthrene derivative possesses biggish molecular weight, can promote material glass transition temperature and decomposition temperature, thus strengthening material Expect thermal stability, promotes device lifetime；
4. the compound of the group of the invention containing dihydro phenanthrene has excellent hole transport performance, can be used for making organic electroluminescence Luminescent device can be used as hole injection layer in organic electroluminescence device, hole transmission layer etc., especially as Organic Electricity Hole transport layer material in electroluminescence device, improve OLED device in electrons and holes in conjunction with property, so as to effective Driving voltage is reduced, the luminous efficiency and service life of organic luminescent device are improved.
Detailed description of the invention
Fig. 1 is the schematic cross-section of the organic electroluminescence device of an embodiment of the invention；
Fig. 2 is the schematic cross-section of the organic electroluminescence device of an embodiment of the invention.
In figure, 1 is anode, and 2 be hole injection layer, and 3 be hole transmission layer, and 4 be luminescent layer, and 5 be electron transfer layer, and 6 are Electron injecting layer, 7 be cathode, and 8 be coating, and 9 be the first hole transmission layer, and 10 be the second hole transmission layer.
Specific embodiment
Hereinafter, by embodiment, the present invention is described in more detail.But following embodiments are only examples of the invention Show, and and the non-limiting present invention.
Hereinafter, organic electroluminescence device according to one embodiment will be explained.Will mainly provide about in addition to The explanation of the feature other than compound according to one embodiment, and unaccounted part will be according to above description.
The structural formula of electroluminescent organic material provided by the invention is as described in chemical formula 1；
Wherein, arlydene, the substituted or unsubstituted carbon that L is selected from singly-bound, substituted or unsubstituted carbon atom number is 6-40 Atomicity is the heteroarylidene of 1-40；
Ar1、Ar2It is identical or different, separately selected from substituted or unsubstituted carbon atom number be 1-35 alkyl, take Generation or unsubstituted carbon atom number be 2-35 alkenyl, substituted or unsubstituted carbon atom number be 2-35 alkynyl, replace or not Heterocyclylalkyl that naphthenic base that substituted carbon atom number is 3-35, substituted or unsubstituted carbon atom number are 2-35 replaces or not Heteroarylalkyl that aralkyl that substituted carbon atom number is 7-40, substituted or unsubstituted carbon atom number are 2-40 replaces or not The heteroaryl that aryl that substituted carbon atom number is 6-40, substituted or unsubstituted carbon atom number are 1-40；
R1、R2、R3、R4It is identical or different, be separately selected from hydrogen, deuterium, tritium, substituted or unsubstituted carbon atom number Alkenyl that the alkyl of 1-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon atom number are 2-35's The heteroaryl that aryl that alkynyl, substituted or unsubstituted carbon atom number are 6-40, substituted or unsubstituted carbon atom number are 1-40；
R5Selected from empty, hydrogen or singly-bound；
The R1、R2、R3、R4、Ar1、Ar2And the substituent group of L is identical or different, and separately selected from deuterium, cyano, Nitro, halogen, hydroxyl, the alkyl of substituted or unsubstituted carbon atom number 1-40, substituted or unsubstituted carbon atom number 3-40 Naphthenic base, the alkenyl of substituted or unsubstituted carbon atom number 2-40, the alkynyl of substituted or unsubstituted carbon atom number 2-40, substitution Or the Heterocyclylalkyl of unsubstituted carbon atom number 2-40, substituted or unsubstituted carbon atom number 7-40 aralkyl, replace or not The aryl, substituted or unsubstituted of the heteroarylalkyl of substituted carbon atom number 2-40, substituted or unsubstituted carbon atom number 6-40 The heteroaryl of carbon atom number 1-40, the alkoxy of substituted or unsubstituted carbon atom number 1-40, substituted or unsubstituted carbon atom The number alkylamino of 1-40, the fragrant amino of substituted or unsubstituted carbon atom number 6-40, substituted or unsubstituted carbon atom number are 1- 40 alkylthio group, the arylalkylamino of substituted or unsubstituted carbon atom number 7-40, substituted or unsubstituted carbon atom number 1-24 AIkylsilyl groups that heteroaryl amino, substituted or unsubstituted carbon atom number are 1-45, substituted or unsubstituted carbon atom number are The arylsilyl groups of 6-50, aryloxy group, the substituted or unsubstituted carbon atom that substituted or unsubstituted carbon atom number is 6-30 Number is 6-30 arylthio.
Preferably, the structural formula of the electroluminescent organic material is as shown in chemical formula 2 or chemical formula 3；
Preferably, the R1、R2、R3、R4It is identical or different, separately selected from hydrogen, substituted or unsubstituted methyl, Substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted xenyl, substituted or unsubstituted naphthalene Base.
Preferably, L is selected from singly-bound, substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted Xenyl, substituted or unsubstituted naphthalene.
Preferably, the structure of the chemical formula 1 is specific as follows, but is not limited only to this:
A kind of organic electroluminescence device of above-mentioned material, including anode are provided with hole injection layer on the anode；
Hole transmission layer is provided on the hole injection layer；
Luminescent layer is provided on the hole transmission layer；
Electron transfer layer is provided on the luminescent layer；
Electron injecting layer is provided on the electron transfer layer；
Cathode is provided on the electron injecting layer；
Wherein, the hole transmission layer includes electroluminescent organic material.
Preferably, 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 on first hole transmission layer；
The luminescent layer is set on second hole transmission layer.
Preferably, first hole transmission layer or second hole transmission layer include the organic electroluminescence material Material.
Fig. 1 is the schematic cross-section of the organic electroluminescence device of an embodiment of the invention；Fig. 2 is of the invention The schematic cross-section of the organic electroluminescence device of one embodiment.
As shown in Figure 1, organic electroluminescence device according to one embodiment includes anode 1, hole injection layer (HIL) 2, hole transmission layer (HTL) 3, luminescent layer (EML) 4, electron transfer layer (ETL) 5, electron injecting layer (EIL) 6, cathode 7 and covering Layer (CPL) 8.
Under normal conditions, anode 1 selects transparent metal oxide, for example, tin indium oxide (ITO), indium zinc oxide (IZO), Zinc oxide (ZnO) or indium tin zinc oxide (ITZO) etc..
Hole injection layer 2 is arranged on anode 1, and hole transmission layer 2 is arranged on hole injection layer 3, wherein hole transport Layer 3 includes electroluminescent organic material shown in chemical formula 1.
As shown in Fig. 2, hole transmission layer 3 may include the first hole transmission layer (HT1) 9 and the second hole transmission layer (HT2)10.In multiple hole transmission layers, the second hole transmission layer (HT2) 10 and luminescent layer (EML) 4 are neighbouring, specifically, the One hole transmission layer 9 is arranged on hole transmission layer 2, and the second hole transmission layer 10 is arranged on the first hole transmission layer 9, shines Layer 4 is arranged on the second hole transmission layer 10.Wherein, the first hole transmission layer and the second hole transport are from comprising chemical formula 1 Shown in electroluminescent organic material.
Unsubstituted alkyl in the present invention refers to that carbon atom number is the alkyl of the straight chain of 1-35, or includes carbon atom number For the alkyl of the branch of 1-13.For example, methyl, ethyl, propyl, isobutyl group, sec-butyl, amyl, isopentyl, base etc..Replace Carbon atom number be 1-35 alkyl refer to that at least one hydrogen atom is taken by D-atom, F, Cl, I, CN, hydroxyl, nitro, amino etc. Generation.
Unsubstituted alkenyl in the present invention, the carbon atom number referred to are the alkenyl of 2-35, the carbon comprising carbon-carbon double bond Atomicity is the alkenyl of the straight chain of 2-40, or the alkenyl comprising the branch that carbon atom number is 1-13.Such as: vinyl, acrylic, Allyl, isopropenyl, 2- cyclobutenyl etc..The alkenyl that substituted carbon atom number is 2-35 refers at least one hydrogen atom by deuterium original Son, F, Cl, I, CN, hydroxyl, nitro, amino etc. replace.
Unsubstituted alkynyl in the present invention, the carbon atom number referred to are the alkynyl of 2-35, the carbon comprising triple carbon-carbon bonds Atomicity is the alkynyl of the straight chain of 2-35, or the alkynyl comprising the branch that carbon atom number is 1-10.Such as: acetenyl, 2- propine Base etc..Substituted carbon atom number is that the alkynyl of 2-35 refers at least one hydrogen atom by D-atom, F, Cl, I, CN, hydroxyl, nitre Base, amino etc. replace.
Unsubstituted aryl in the present invention, the carbon atom number referred to are the aryl of 6-40.Such as: phenyl, naphthalene, pyrene Base, dimethyl fluorenyl, anthryl, phenanthryl,Base, camomile ring group, acenaphthenyl, xenyl, benzo anthryl, two fluorenyl of spiral shell, base, indenyl Deng.Substituted carbon atom number be 6-40 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 7-40.Such as: tolyl, diformazan Base fluorenyl etc..Substituted carbon atom number be 7-40 aralkyl refer at least one hydrogen atom by D-atom, F, Cl, I, CN, Hydroxyl, nitro, amino etc. replace.
Unsubstituted heteroaryl in the present invention refers to that carbon atom number is the heteroaryl of 2-40.Such as: pyridyl group, pyrazine Base, pyrimidine radicals, pyridazinyl, triazine radical, quinolyl, indyl, carbazyl, dibenzofuran group, dibenzothiophene, dibenzo Selenophen base etc..Substituted carbon atom number is that the heteroaryl of 2-40 refers at least one hydrogen atom by D-atom, F, Cl, I, CN, hydroxyl Base, nitro, amino etc. replace.
Unsubstituted naphthenic base in the present invention refers to that carbon atom number is the naphthenic base of 3-40.Such as: cyclopropyl, ring fourth Base, cyclopenta, cyclohexyl, norborny, adamantyl etc..Substituted carbon atom number is that the naphthenic base of 3-40 refers at least one A hydrogen atom is replaced by D-atom, F, Cl, I, CN, hydroxyl, nitro, amino etc..
It is illustrated below by specific embodiment.
The synthesis of compound 1
By 2 bromo toluene (10.0g, 58.5mmol), 4- chlorophenylboronic acid (11.0g, 70.2mmol), tetra-triphenylphosphine palladium (1.35g, 1.17mmol), potassium carbonate (16.2g, 117mmol), tetrabutylammonium bromide (3.77g, 11.7mmol), toluene (60mL), ethyl alcohol (60mL) and deionized water (60mL) are added in round-bottomed flask, are warming up to 75-80 DEG C under nitrogen protection, stir It mixes 8 hours；Reaction solution is cooled to room temperature, toluene (100mL) is added and is extracted, merges organic phase, uses anhydrous magnesium sulfate It is dried, filters, solvent is removed under reduced pressure；Gained crude product carries out recrystallization purification using methylene chloride/ethanol system, obtains shallow Yellow solid intermediate compound I-A-1 (9.80g, 83%).
By intermediate compound I-A-1 (9.80g, 48.4mmol), N-bromosuccinimide (9.04g, 50.8mmol), azo two Isobutyronitrile (20mg) and carbon tetrachloride (100mL) are added in round-bottomed flask, heat up under nitrogen protection, and small in 77 DEG C of stirrings 2 When；Reaction solution is cooled to room temperature, solvent is removed under reduced pressure；With methylene chloride/normal heptane (1:5) be mobile phase to solid crude product into The purification of row silica gel column chromatography, obtains white solid intermediate compound I-A-2 (6.81g, 50%).
Magnesium rod (0.71g, 29.0mmol) and ether (10mL) are placed in round-bottomed flask dry under nitrogen protection, are added Iodine (10mg).It will be then slowly dropped into flask dissolved with ether (20mL) solution of intermediate compound I-A-2 (6.81g, 24.2mmol), It is warming up to 35 DEG C after being added dropwise, stirs 1 hour；Reaction solution is down to 0 DEG C, be slowly dropped into thereto dissolved with acetone (1.12g, Ether (5mL) solution 19.3mmol) is warming up to 35 DEG C after being added dropwise, stir 2 hours；Reaction solution is cooled to room temperature, to 5% hydrochloric acid is wherein added to pH < 7, stirs 1 hour, ether (50mL) is added and is extracted, merges organic phase, uses anhydrous sulphur Sour magnesium is dried, and solvent is removed under reduced pressure in filtering；Gained crude product is that mobile phase carries out silicon using ethyl acetate/normal heptane (1:5) Rubber column gel column chromatography purity obtains white solid intermediate compound I-A-3 (4.55g, 72%).
By intermediate compound I-A-3 (4.55g, 17.4mmol), trifluoroacetic acid (3.98g, 34.9mmol) and methylene chloride (50mL) is added in round-bottomed flask, and stirred under nitrogen atmosphere 6 hours；And sodium hydrate aqueous solution is added in backward reaction solution and makes Reaction solution pH=8, then liquid separation, organic phase are dried using anhydrous magnesium sulfate, and solvent is removed under reduced pressure in filtering；Gained crude product Using methylene chloride/normal heptane (1:2) carry out silica gel column chromatography purification, obtain white solid intermediate compound I-A (3.80g, 90%).
By 4- bromo biphenyl (10.0g, 42.9mmol), 2- amino -9,9- dimethyl fluorene (9.88g, 47.2mmol), three (two BENZYLIDENE ACETONE) two palladiums (0.39g, 0.43mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.41g, 0.86mmol) and sodium tert-butoxide (6.18g, 64.3mmol) is added in toluene (100mL), is heated to 105- under nitrogen protection 110 DEG C, stir 1h；It is then cooled to room temperature, reaction solution passes through filtrate after being dried, filtered using addition magnesium sulfate after washing short Solvent is removed under reduced pressure in silicagel column；Recrystallization purification is carried out to crude product using methylene chloride/ethanol system, obtains light gray solid Intermediate II-A (13.1g, 84%).
By intermediate compound I-A (3.80g, 15.7mmol), intermediate II-A (5.66g, 15.7mmol), three (dibenzylidenes third Ketone) two palladiums (0.29g, 0.31mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.26g, 0.63mmol) and tertiary fourth Sodium alkoxide (2.26g, 23.5mmol) is added in toluene (30mL), is heated to 105-110 DEG C under nitrogen protection, stirs 16h；Then It is cooled 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 dichloromethane/ethyl acetate system, obtain compound as white solid 1 (5.55g, 62%).Mass spectrum: m/z=568.3 (M+H)+
The synthesis of compound 2
By 2- bromo biphenyl (15.0g, 64.4mmol), 2- amino -9,9- dimethyl fluorene (14.8g, 70.8mmol), three (two BENZYLIDENE ACETONE) two palladiums (0.59g, 0.64mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.61g, 1.29mmol) and sodium tert-butoxide (9.28g, 96.5mmol) is added in toluene (150mL), is heated to 105- under nitrogen protection 110 DEG C, stir 4h；It is then cooled to room temperature, reaction solution passes through filtrate after being dried, filtered using addition magnesium sulfate after washing short Solvent is removed under reduced pressure in silicagel column；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains gray solid Intermediate II-B (18.7g, 80%).
By intermediate compound I-A (5.00g, 20.7mmol), intermediate II-B (7.46g, 20.7mmol), three (dibenzylidenes third Ketone) two palladiums (0.38g, 0.41mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.34g, 0.83mmol) and tertiary fourth Sodium alkoxide (2.98g, 31.0mmol) is added in toluene (40mL), is heated to 105-110 DEG C under nitrogen protection, stirs 20h；Then It is cooled 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 dichloromethane/ethyl acetate system, obtain compound as white solid 2 (6.82g, 58%).Mass spectrum: m/z=568.3 (M+H)+
The synthesis of compound 3
By 2- bromine-N-phenylcarbazole (10.0g, 31.0mmol), 2- aminobphenyl (5.78g, 34.1mmol), three (two Asias Benzylacetone) two palladiums (0.28g, 0.31mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.30g, 0.62mmol) And sodium tert-butoxide (4.47g, 46.6mmol) is added in toluene (100mL), is heated to 105-110 DEG C under nitrogen protection, stirs Mix 3h；Then be cooled to room temperature, reaction solution using being added filtrate after washing after magnesium sulfate dries, filters through short silicagel column, Solvent is removed under reduced pressure；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains white solid intermediate II-C (9.88g, 78%).
By intermediate compound I-A (5.00g, 20.7mmol), intermediate II-C (9.32g, 20.7mmol), three (dibenzylidenes third Ketone) two palladiums (0.38g, 0.41mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.34g, 0.83mmol) and tertiary fourth Sodium alkoxide (2.98g, 31.0mmol) is added in toluene (40mL), is heated to 105-110 DEG C under nitrogen protection, stirs 18h；Then It is cooled 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 dichloroethanes system, obtains compound as white solid 3 (7.90g, 62%).Mass spectrum: M/z=617.3 (M+H)+
The synthesis of compound 4
By the bromo- 2- isopropylbenzene (15.0g, 75.3mmol) of 1-, 4- chlorophenylboronic acid (14.1g, 90.4mmol), four triphenylphosphines Palladium (1.74g, 1.51mmol), potassium carbonate (20.8g, 151mmol), tetrabutylammonium bromide 4.86g, 15.1mmol), toluene (80mL), ethyl alcohol (80mL) and deionized water (80mL) are added in round-bottomed flask, 75-80 DEG C are warming up under nitrogen protection, stirring 16 hours；Reaction solution is cooled to room temperature, be added toluene (150mL) extracted, merge organic phase, using anhydrous magnesium sulfate into Row dries, filters, and solvent is removed under reduced pressure；Gained crude product carries out recrystallization purification using methylene chloride/n-heptane system, obtains Huang Color solid-like intermediate compound I-B-1 (7.89g, 45%).
By intermediate compound I-B-1 (7.89g, 34.2mmol), N-bromosuccinimide (6.69g, 37.6mmol), azo two Isobutyronitrile (20mg) and carbon tetrachloride (100mL) are added in round-bottomed flask, heat up under nitrogen protection, and small in 77 DEG C of stirrings 1 When；Reaction solution is cooled to room temperature, solvent is removed under reduced pressure；With methylene chloride/normal heptane (1:4) be mobile phase to solid crude product into The purification of row silica gel column chromatography, obtains white solid intermediate compound I-B-2 (6.57g, 62%).
Magnesium rod (0.61g, 25.5mmol) and ether (10mL) are placed in round-bottomed flask dry under nitrogen protection, are added Iodine (10mg).It will be then slowly dropped into flask dissolved with ether (15mL) solution of intermediate compound I-B-2 (6.57g, 21.2mmol), It is warming up to 35 DEG C after being added dropwise, stirs 1.5 hours；Reaction solution is down to 0 DEG C, is slowly dropped into thereto dissolved with acetone Ether (5mL) solution of (0.99g, 17.0mmol) is warming up to 35 DEG C after being added dropwise, stir 6 hours；Reaction solution is cooled to 5% hydrochloric acid is added in room temperature thereto, so that reaction solution pH < 7, are stirred 1 hour, ether (50mL) is added and is extracted, is associated with Machine phase, is dried using anhydrous magnesium sulfate, and solvent is removed under reduced pressure in filtering；Gained crude product using ethyl acetate/normal heptane (1: 3) silica gel column chromatography purification is carried out for mobile phase, obtains white solid intermediate compound I-B-3 (4.10g, 67%).
By intermediate compound I-B-3 (4.10g, 14.2mmol), trifluoroacetic acid (3.23g, 28.4mmol) and methylene chloride (40mL) is added in round-bottomed flask, and stirred under nitrogen atmosphere 8 hours；And sodium hydrate aqueous solution is added in backward reaction solution and makes Reaction solution pH=8, then liquid separation, organic phase are dried using anhydrous magnesium sulfate, and solvent is removed under reduced pressure in filtering；Gained crude product Using methylene chloride/normal heptane (1:2) carry out silica gel column chromatography purification, obtain white solid intermediate compound I-B (3.66g, 95%).
By 2- bromine-N-phenylcarbazole (5.00g, 15.5mmol), 4- aminobphenyl (2.89g, 17.1mmol), three (two Asias Benzylacetone) two palladiums (0.14g, 0.16mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.15g, 0.31mmol) And sodium tert-butoxide (2.24g, 23.3mmol) is added in toluene (50mL), is heated to 105-110 DEG C under nitrogen protection, stirring 1h；It is then cooled to room temperature, reaction solution is subtracted using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column Pressure removes solvent；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains light gray solid intermediate II-D (5.44g, 85%).
By intermediate compound I-B (3.50g, 12.9mmol), intermediate II-D (5.31g, 12.9mmol), three (dibenzylidenes third Ketone) two palladiums (0.24g, 0.26mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.21g, 0.52mmol) and tertiary fourth Sodium alkoxide (1.86g, 19.4mmol) is added in toluene (30mL), is heated to 105-110 DEG C under nitrogen protection, stirs 12h；Then It is cooled 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 4 (4.04g, 48%).Matter Spectrum: m/z=645.3 (M+H)+
The synthesis of compound 5
Magnesium rod (1.11g, 46.2mmol) and ether (10mL) are placed in round-bottomed flask dry under nitrogen protection, are added Iodine (10mg).It will be then slowly dropped into flask dissolved with ether (20mL) solution of intermediate compound I-A-2 (10.0g, 35.5mmol), It is warming up to 35 DEG C after being added dropwise, stirs 2 hours；Reaction solution is down to 0 DEG C, is slowly dropped into thereto dissolved with benzophenone Ether (10mL) solution of (4.53g, 24.9mmol) is warming up to 35 DEG C after being added dropwise, stir 8 hours；Reaction solution is cooling To room temperature, 5% hydrochloric acid is added thereto to pH < 7, stirring 1 hour is added ether (100mL) and is extracted, merges organic phase, It is dried using anhydrous magnesium sulfate, filters, solvent is removed under reduced pressure；Gained crude product is stream using ethyl acetate/normal heptane (1:4) It is dynamic mutually to carry out silica gel column chromatography purification, obtain white solid intermediate compound I-C-3 (7.52g, 55%).
By intermediate compound I-C-3 (7.52g, 19.5mmol), trifluoroacetic acid (4.45g, 39.1mmol) and methylene chloride (40mL) is added in round-bottomed flask, and stirred under nitrogen atmosphere 4 hours；And sodium hydrate aqueous solution is added in backward reaction solution and makes Reaction solution pH=8, then liquid separation, organic phase are dried using anhydrous magnesium sulfate, and solvent is removed under reduced pressure in filtering；Gained crude product Using methylene chloride/normal heptane (1:3) carry out silica gel column chromatography purification, obtain white solid intermediate compound I-C (6.49g, 91%).
By intermediate compound I-C (3.00g, 8.18mmol), intermediate II-B (2.96g, 8.18mmol), three (dibenzylidenes third Ketone) two palladiums (0.15g, 0.16mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.13g, 0.33mmol) and tertiary fourth Sodium alkoxide (1.18g, 12.3mmol) is added in toluene (20mL), is heated to 105-110 DEG C under nitrogen protection, stirs 20h；Then It is cooled 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 dichloroethanes/n-heptane system, obtain compound as white solid 5 (3.22g, 61%).Mass spectrum: m/z=692.3 (M+H)+
The synthesis of compound 6
By 2- bromine dibenzofurans (10.0g, 40.5mmol), 4- aminobphenyl (7.53g, 44.5mmol), three (two benzal Benzylacetone) two palladiums (0.37g, 0.40mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.39g, 0.81mmol) with And sodium tert-butoxide (5.83g, 60.7mmol) is added in toluene (100mL), is heated to 105-110 DEG C under nitrogen protection, stirring 2h；It is then cooled to room temperature, reaction solution is subtracted using being added filtrate after magnesium sulfate dries, filters after washing through short silicagel column Pressure removes solvent；Recrystallization purification is carried out to crude product using ethyl acetate/n-heptane system, obtains light gray solid intermediate II-E (11.8g, 87%).
By intermediate compound I-C (4.00g, 10.9mmol), intermediate II-E (3.66g, 10.9mmol), three (dibenzylidenes third Ketone) two palladiums (0.20g, 0.22mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.18g, 0.44mmol) and tertiary fourth Sodium alkoxide (1.57g, 16.4mmol) is added in toluene (30mL), is heated to 105-110 DEG C under nitrogen protection, stirs 12h；Then It is cooled 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 methylene chloride/n-heptane system, obtain compound as white solid 6 (3.98g, 55%).Mass spectrum: m/z=666.3 (M+H)+
The synthesis of compound 7
By intermediate compound I-C (4.50g, 12.3mmol), intermediate II-A (4.43g, 12.3mmol), three (dibenzylidenes third Ketone) two palladiums (0.22g, 0.25mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.20g, 0.49mmol) and tertiary fourth Sodium alkoxide (1.77g, 18.4mmol) is added in toluene (30mL), is heated to 105-110 DEG C under nitrogen protection, stirs 10h；Then It is cooled 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 7 (4.88g, 58%).Matter Spectrum: m/z=692.3 (M+H)+。
The synthesis of compound 8
Magnesium rod (0.81g, 34.1mmol) and ether (10mL) are placed in round-bottomed flask dry under nitrogen protection, are added Iodine (10mg).It will be then slowly dropped into flask dissolved with ether (20mL) solution of intermediate compound I-A-2 (8.0g, 28.4mmol), It is warming up to 35 DEG C after being added dropwise, stirs 3 hours；Reaction solution is down to 0 DEG C, be slowly dropped into thereto dissolved with Fluorenone (4.10g, Ether (20mL) solution 22.7mmol) is warming up to 35 DEG C after being added dropwise, stir 6 hours；Reaction solution is cooled to room temperature, 5% hydrochloric acid is added thereto to pH < 7, stirs 1 hour, ether (100mL) is added and is extracted, organic phase is merged, use is anhydrous Magnesium sulfate is dried, and solvent is removed under reduced pressure in filtering；Gained crude product is mobile phase progress using ethyl acetate/normal heptane (1:2) Silica gel column chromatography purification, obtains white solid intermediate compound I-D-3 (5.40g, 50%).
By intermediate compound I-D-3 (5.40g, 14.1mmol), trifluoroacetic acid (3.22g, 39.1mmol) and methylene chloride (30mL) is added in round-bottomed flask, and stirred under nitrogen atmosphere 2 hours；And sodium hydrate aqueous solution is added in backward reaction solution to pH =8, liquid separation, organic phase is dried using anhydrous magnesium sulfate, and solvent is removed under reduced pressure in filtering；Gained crude product using methylene chloride/ Normal heptane (1:2) carries out silica gel column chromatography purification, obtains white solid intermediate compound I-D (4.19g, 81%).
By intermediate compound I-D (4.00g, 11.0mmol), two-(4- xenyl) amine (3.52g, 11.0mmol), three (two benzal Benzylacetone) two palladiums (0.20g, 0.22mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.18g, 0.44mmol) and Sodium tert-butoxide (1.58g, 16.4mmol) is added in toluene (25mL), is heated to 105-110 DEG C under nitrogen protection, stirs 8h； 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 solution Remove solvent；Recrystallization purification is carried out to crude product using toluene system, obtains compound as white solid 8 (3.35g, 47%).Mass spectrum: M/z=650.3 (M+H)+。
The synthesis of compound 9
By 2- bromine dibenzofurans (15.0g, 60.7mmol), 2- amino -9,9 dimethyl fluorene (14.0g, 66.8mmol), Tris(dibenzylideneacetone) dipalladium (0.56g, 0.61mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.58g, 1.21mmol) and sodium tert-butoxide (8.75g, 91.1mmol) is added in toluene (120mL), is heated to 105- under nitrogen protection 110 DEG C, stir 1h；It is then cooled to room temperature, reaction solution passes through filtrate after being dried, filtered using addition magnesium sulfate after washing short Solvent is removed under reduced pressure in silicagel column；Recrystallization purification is carried out to crude product using methylene chloride/n-heptane system, obtains gray solid Intermediate II-F (18.2g, 80%).
By intermediate compound I-D (5.00g, 13.7mmol), intermediate 2-F (5.14g, 13.7mmol), three (dibenzylidenes third Ketone) two palladiums (0.25g, 0.27mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.23g, 0.55mmol) and tertiary fourth Sodium alkoxide (1.98g, 20.6mmol) is added in toluene (40mL), is heated to 105-110 DEG C under nitrogen protection, stirs 10h；Then It is cooled 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 methylene chloride/n-heptane system, obtain compound as white solid 9 (5.02g, 52%).Mass spectrum: m/z=704.3 (M+H)+。
The synthesis of compound 10
By 2- bromodiphenylthiophene (10.0g, 38.0mmol), 4- aminobphenyl (7.07g, 41.8mmol), three (two benzal Benzylacetone) two palladiums (0.35g, 0.38mmol), 2- dicyclohexyl phosphorus -2,4,6- tri isopropyl biphenyl (0.36g, 0.76mmol) with And sodium tert-butoxide (5.48g, 57.0mmol) is added in toluene (100mL), is heated to 105-110 DEG C under nitrogen protection, stirring 1.5h；Then be cooled to room temperature, reaction solution using being added filtrate after washing after magnesium sulfate dries, filters through short silicagel column, Solvent is removed under reduced pressure；Recrystallization purification is carried out to crude product using dichloromethane/ethyl acetate system, obtains white solid intermediate II-G (11.5g, 86%).
By intermediate compound I-D (4.80g, 13.2mmol), intermediate II-G (4.62g, 13.2mmol), three (dibenzylidenes third Ketone) two palladiums (0.24g, 0.26mmol), 2- dicyclohexyl phosphorus -2,6- dimethoxy-biphenyl (0.22g, 0.53mmol) and tertiary fourth Sodium alkoxide (1.90g, 19.7mmol) is added in toluene (40mL), and 105-110 DEG C is heated under nitrogen protection, stirs 12h；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 10 (4.11g, 46%). Mass spectrum: m/z=680.2 (M+H)+。
Make organic electroluminescence device
Embodiment 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)。
It is deposited 4,4'-N on the second hole transmission layer, and N'-dicarbazole-biphenyl (referred to as " CBP ") conduct 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-transport Layer (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 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.
Other than respectively using compound shown in table 2 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.
I.e. comparative example manufactures organic electroluminescence device using NPD, and comparative example 2 manufactures organic electroluminescence using TPD Part, device performance are 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.
The device performance of table 1 embodiment 1-5 and comparative example 1-3
Embodiment Compound Volt(V) Cd/A EQE T95(h) CIE(x,y)
Embodiment 1 Compound 1 3.58 33.31 22.64 472 (0.677,0.322)
Embodiment 2 Compound 2 3.61 32.80 22.55 510 (0.678,0.321)
Embodiment 3 Compound 3 3.82 33.29 23.95 462 (0.682,0.316)
Embodiment 4 Compound 4 3.98 34.15 20.69 485 (0.680,0.319)
Embodiment 5 Compound 5 3.72 31.12 25.11 468 (0.671,0.328)
Comparative example 1 NPD 5.9 23.15 12.30 280 (0.676,0.323)
Comparative example 2 TPD 6.3 24.22 9.40 310 (0.684,0.314)
Comparative example 3 - 6.1 28.30 9.57 210 (0.683,0.316)
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 1-3, driving voltage (Vlot), current efficiency (Cd/A) and external quantum efficiency (EQE) and Service life, (T95) obtained apparent improvement.
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 1-3, embodiment 1-5 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.
Embodiment 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-transport Layer (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 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 7-10
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 using compound 9, and embodiment 10 is had using the production of compound 10 Organic electroluminescence devices, device performance are shown in Table 2.
4~comparative example of comparative example 6
In the 4~comparative example of comparative example 6, 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.
The device performance of table 2 embodiment 6-10 and comparative example 4-6
Embodiment Compound Volt(V) Cd/A EQE T95(h) CIE(x,y)
Embodiment 6 Compound 6 3.90 7.9 16.3 167 (0.141,0.047)
Embodiment 7 Compound 7 3.88 8.1 16.3 156 (0.142,0.046)
Embodiment 8 Compound 8 4.14 7.2 16.4 173 (0.141,0.047)
Embodiment 9 Compound 9 4.15 7.4 16.5 153 (0.143,0.048)
Embodiment 10 Compound 10 3.95 7.3 15.6 160 (0.142,0.045)
Comparative example 4 NPB 5.20 6.2 10.2 103 (0.140,0.047)
Comparative example 5 NPD 5.00 6.0 10.9 98 (0.141,0.052)
Comparative example 6 TPD 5.5 5.7 6.9 78 (0.140,0.050)
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.
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.
Heat stability testing
Compound 1-10 and NPB, NPD are passed through into high-temperature heat treatment, when testing its glass transition temperature Tg and decomposing 1% Temperature Td, result is as shown in Table 3.
Table 3
Compound Tg(℃) Td 1% (DEG C)
Compound 1 127 368
Compound 2 130 370
Compound 3 128 375
Compound 4 136 405
Compound 5 158 387
Compound 6 145 377
Compound 7 153 390
Compound 8 146 376
Compound 9 129 360
Compound 10 138 400
NPB 100 339
NPD 84 290
Can be seen that the compounds of this invention 1-10 compared with NPB and NPD from the data of table 3, glass transition temperature and point It is higher to solve temperature, there is better thermal stability.
According to 1-table of table 2 of the organic electroluminescence device of the embodiment it is found that the present invention imports dihydro phenanthrene group To novel arylamine compound, when being used as hole transport layer material, the high efficiency of good heat stability can be manufactured, the long-life has Organic electroluminescence devices.
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 (8)

1. a kind of electroluminescent organic material, which is characterized in that the structural formula of the material is as described in chemical formula 1；
Wherein, arlydene, the substituted or unsubstituted carbon atom that L is selected from singly-bound, substituted or unsubstituted carbon atom number is 6-40 Number is the heteroarylidene of 1-40；
Ar1、Ar2It is identical or different, separately selected from substituted or unsubstituted carbon atom number be 1-35 alkyl, replace or It is alkynyl that alkenyl that unsubstituted carbon atom number is 2-35, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted Carbon atom number be 3-35 naphthenic base, substituted or unsubstituted carbon atom number be 2-35 Heterocyclylalkyl, substituted or unsubstituted Carbon atom number be 7-40 aralkyl, substituted or unsubstituted carbon atom number be 2-40 heteroarylalkyl, substituted or unsubstituted Carbon atom number be 6-40 aryl, substituted or unsubstituted carbon atom number be 1-40 heteroaryl；
R1、R2、R3、R4It is identical or different, it is separately 1-35's selected from hydrogen, deuterium, tritium, substituted or unsubstituted carbon atom number Alkynyl that alkenyl that alkyl, substituted or unsubstituted carbon atom number are 2-35, substituted or unsubstituted carbon atom number are 2-35 takes Generation or unsubstituted carbon atom number be 6-40 aryl, substituted or unsubstituted carbon atom number be 1-40 heteroaryl；
R5Selected from empty, hydrogen or singly-bound；
The R1、R2、R3、R4、Ar1、Ar2And the substituent group of L is identical or different, and is separately selected from deuterium, cyano, nitre Base, halogen, hydroxyl, the alkyl of substituted or unsubstituted carbon atom number 1-40, substituted or unsubstituted carbon atom number 3-40 ring Alkyl, the alkenyl of substituted or unsubstituted carbon atom number 2-40, substituted or unsubstituted carbon atom number 2-40 alkynyl, replace or The Heterocyclylalkyl of unsubstituted carbon atom number 2-40, the aralkyl of substituted or unsubstituted carbon atom number 7-40, substitution do not take The heteroarylalkyl of the carbon atom number 2-40 in generation, the aryl of substituted or unsubstituted carbon atom number 6-40, substituted or unsubstituted carbon The heteroaryl of atomicity 1-40, the alkoxy of substituted or unsubstituted carbon atom number 1-40, substituted or unsubstituted carbon atom number The alkylamino of 1-40, the fragrant amino of substituted or unsubstituted carbon atom number 6-40, substituted or unsubstituted carbon atom number are 1-40 Alkylthio group, the arylalkylamino of substituted or unsubstituted carbon atom number 7-40, substituted or unsubstituted carbon atom number 1-24 it is miscellaneous AIkylsilyl groups that fragrant amino, substituted or unsubstituted carbon atom number are 1-45, substituted or unsubstituted carbon atom number are 6- 50 arylsilyl groups, substituted or unsubstituted carbon atom number are the aryloxy group of 6-30, substituted or unsubstituted carbon atom number For 6-30 arylthio.
2. electroluminescent organic material according to claim 1, which is characterized in that the knot of the electroluminescent organic material Structure formula is as shown in chemical formula 2 or chemical formula 3；
3. electroluminescent organic material according to claim 1 or 2, which is characterized in that the R1、R2、R3、R4It is identical or not Together, separately selected from hydrogen, substituted or unsubstituted methyl, substituted or unsubstituted phenyl, substituted or unsubstituted fluorenyl, Substituted or unsubstituted xenyl, substituted or unsubstituted naphthalene.
4. electroluminescent organic material according to claim 1 or 2, which is characterized in that the L be selected from singly-bound, replace or Unsubstituted phenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted xenyl, substituted or unsubstituted naphthalene.
5. electroluminescent organic material according to claim 1, which is characterized in that the structure of the chemical formula 1 is specifically such as Under:
6. a kind of organic electroluminescence device based on electroluminescent organic material described in claim 1, which is characterized in that packet Anode is included, is provided with hole injection layer on the anode；
Hole transmission layer is provided on the hole injection layer；
Luminescent layer is provided on the hole transmission layer；
Electron transfer layer is provided on the luminescent layer；
Electron injecting layer is provided on the electron transfer layer；
Cathode is provided on the electron injecting layer；
Wherein, the hole transmission layer includes electroluminescent organic material.
7. organic electroluminescence device according to claim 6, which is characterized 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 on first hole transmission layer；
The luminescent layer is set on second hole transmission layer.
8. organic electroluminescence device according to claim 6, which is characterized in that first hole transmission layer or described Second hole transmission layer includes the electroluminescent organic material.
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CN114685360A (en) * 2020-12-31 2022-07-01 阜阳欣奕华材料科技有限公司 Carbazole compound, organic electroluminescent device and display device
CN114957188A (en) * 2021-02-26 2022-08-30 阜阳欣奕华材料科技有限公司 Compound, organic electroluminescent device and intermediate compound
CN115611713A (en) * 2022-07-25 2023-01-17 广东工业大学 Synthesis method of 9-benzylated fluorenol derivative
CN115611713B (en) * 2022-07-25 2024-04-02 广东工业大学 Synthesis method of 9-benzylated fluorenol derivative
CN115141173A (en) * 2022-08-17 2022-10-04 浙江虹舞科技有限公司 Compound and organic electroluminescent device comprising the same
CN115724750A (en) * 2022-11-16 2023-03-03 北京八亿时空液晶科技股份有限公司 Spirofluorene derivative and application thereof

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