CN108912105A - A kind of double carbazole compounds symmetrically replaced and its application - Google Patents
A kind of double carbazole compounds symmetrically replaced and its application Download PDFInfo
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Abstract
The invention belongs to field of organic electroluminescent materials, the double carbazole compounds and its application that one kind symmetrically replaces are disclosed.The double carbazole compounds disclosed in this invention symmetrically replaced have structure shown in formula (I), are a kind of material of main parts containing double carbazole groups, carrier balance.Using the compound of the present invention as the material of main part of OLED device, the cut-in voltage of device is lower, and luminous efficiency is higher.Moreover, because the structure of compound provided by the present invention is symmetrical substitution, compared to the form of Asymmetrical substitute, synthesis step is easy, thereby reduces synthesis loss and purification is lost, be conducive to industrialized production and reduce cost.
Description
Technical field
The invention belongs to field of organic electroluminescent materials, in particular to a kind of double carbazole compounds symmetrically replaced and its
Using.
Background technique
In organic electroluminescence device technical field, can be realized by different modes efficiently, the high life shine, for
The luminescent layer of emission spectrum, one way in which are exactly that the promotion of efficiency and service life is carried out in the form of host-guest system.
It is efficient luminous in order to realize, reverse energy passback of the energy from guest materials to material of main part is avoided, simultaneously
Triplet exciton is limited to luminescent layer, the triplet energy level of material of main part should be greater than the triplet energy level of dopant material.When
When the triplet energy level of material of main part is less than the triplet energies of dopant material, it will occur from dopant material to material of main part energy
The phenomenon that grade anti-transition, so as to cause luminous efficiency reduction.Therefore, it for luminous material layer, needs high thermal stability and is higher than
The material of main part of dopant material triplet energies.
In the prior art, most of material of main part is hole-transporting type material of main part or electron-transporting type material of main part.By
In the imbalance of carrier transmission performance, this unipolar material of main part unfavorable narrow recombination region easy to form.In general,
When using hole-transporting type material of main part, charge recombination zone can be generated in luminescent layer and electron-transport bed boundary, and working as makes
When with electron-transporting type material of main part, charge recombination zone can be generated in luminescent layer and hole transport bed boundary.However weak load
It is unfavorable to the luminous efficiency of organic luminescent device to flow unbalanced charge in transport factor and luminescent layer.Meanwhile organic electroluminescence phosphorus
This narrow charge recombination zone of optical device, can accelerate T-T annihilation process, decline so as to cause luminous efficiency,
Especially under current density condition.In order to avoid this effect, the strategy generallyd use is：(1) two luminescent layers are used,
In one layer use hole-transporting type material of main part, another luminescent layer use electron-transporting type material of main part；(2) by hole transport
Type and the mixing of electron-transporting type material of main part are placed in single luminescent layer.However, both strategies become the preparation of device
Complexity, and mixed material of main part will lead to the problem of mutually separating.
In recent years, there is the hole of balance and the material of main part of electronic carrier ability, led in organic electro phosphorescent device
Domain has attracted people's note that this kind of material not only improves the performance of device, is simplified the structure of device, thus
With larger demand degree.
Summary of the invention
The double carbazole compounds symmetrically replaced the purpose of the present invention is to provide one kind and its application, this kind of compound are one
The material of main part of kind carrier balance.
The purpose of the present invention is achieved through the following technical solutions：
Embodiments of the present invention provide a kind of double carbazole compounds symmetrically replaced, with knot shown in formula (I)
Structure：
Wherein,
N1、N2、N3、N4N atom or CRx are each independently represented, and Rx indicates hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkane
Base, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 virtue sulphur
Base, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amido；
X, Y each independently represents N atom or CRy, wherein Ry indicate hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl,
C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 arylthio,
C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amido；
R indicates deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkanamine
Base, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 arylthio, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryl
Oxygroup, C3-C72 heteroarylthio or C4-C72 heteroaryl amido.
Optionally, R has structure shown in formula (II) or (III)：
Wherein,
Ar1、Ar2Each independently represent C1-C24 alkyl, C6-C72 aryl, C3-C72 heteroaryl；Ar1And Ar2It is not attached to
Or Ar1And Ar2It is connected by singly-bound, double bond, carbon atom or hetero atom；
M1、M2、M3、M4N atom or CRz are each independently represented, and Rz indicates hydrogen atom, D-atom, halogen atom, C1-
C24 alkyl, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72
Arylthio, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amine
Base；
Z indicates oxygen atom, sulphur atom, sulfuryl, sulfoxide group, NRm, CRnRo, SiRpRq or BRr,
And Rm, Rn, Ro, Rp, Rq, Rr each independently represent C1-C24 alkyl, C6-C72 aryl or C3-C72 heteroaryl.
Optionally, the connection Ar1And Ar2Carbon atom be one or two, the carbon atom by hydrogen atom, D-atom,
C1-C12 alkyl, C6-C36 aryl or C3-C36 heteroaryl replace；The hetero atom is oxygen atom, sulphur atom, silicon atom, nitrogen original
Son or boron atom, the sulphur atom are not substituted or are replaced by one or two oxygen atom, the silicon atom, nitrogen-atoms or boron
Atom is replaced by hydrogen atom, D-atom, C1-C12 alkyl, C6-C36 aryl or C3-C36 heteroaryl.
Optionally, R has selected from one of following structure：
Wherein,
R1-R16Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18
Aryl, C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R21-R26Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18
Aryl, C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R31-R34Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18
Aryl, C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R101-R106Each independently represent C1-C12 alkyl, C6-C18 aryl or C3-C18 heteroaryl；
R201-R205Each independently represent C1-C12 alkyl, C6-C18 aryl or C3-C18 heteroaryl.
Still optionally further, R has one of following structure：
Wherein,
R210、R220、R230、R240、R250、R260、R310、R320、R340Each independently represent hydrogen atom, D-atom, methyl,
Ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, 3,5-dimethylphenyl, pyridyl group, naphthalene, carbazyl or carboline base；
R2010Indicate methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, 3,5-dimethylphenyl, pyridyl group or
Naphthalene.
Optionally, the double carbazole compounds symmetrically replaced provided by embodiments of the present invention, have selected from it is following it
One structure：
Embodiments of the present invention also provide the above-mentioned double carbazole compounds symmetrically replaced in organic electroluminescence device
Application.
In terms of existing technologies, the double carbazole compounds symmetrically replaced provided by embodiments of the present invention lead to
It crosses in 2 introducing substituent groups of carbazole, obtains a kind of master of carrier balance symmetrically replacing, containing pyridine and carbazole group
Body material.Using compound provided by embodiments of the present invention, as the material of main part of OLED device, the unlatching electricity of device
Press lower, luminous efficiency is higher.Moreover, because the structure of compound provided by embodiments of the present invention is pyridine two sides pair
Generation is weighed, compared to the form of Asymmetrical substitute, synthesis step is easy, thereby reduces synthesis loss and purification loss, favorably
In industrialized production and reduce cost.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment to of the invention each
Specific embodiment is explained in detail.However, it will be understood by those skilled in the art that in each embodiment party of the present invention
In formula, many technical details are proposed in order to make reader more fully understand the present invention.But even if without these technical details
And various changes and modifications based on the following respective embodiments, each claim skill claimed of the present invention also may be implemented
Art scheme.Compound
In certain specific embodiments of the invention, a kind of double carbazole compounds symmetrically replaced are provided, are had
Structure shown in formula (I)：
Wherein,
N1、N2、N3、N4N atom or CRx are each independently represented, and Rx indicates hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkane
Base, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 virtue sulphur
Base, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amido；
X, Y each independently represents N atom or CRy, wherein Ry indicate hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl,
C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 arylthio,
C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amido；
R indicates deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkanamine
Base, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 arylthio, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryl
Oxygroup, C3-C72 heteroarylthio or C4-C72 heteroaryl amido.
In certain specific embodiments of the invention, R has structure shown in formula (II) or (III)：
Wherein,
Ar1、Ar2Each independently represent C1-C24 alkyl, C6-C72 aryl, C3-C72 heteroaryl；Ar1And Ar2It is not attached to
Or Ar1And Ar2It is connected by singly-bound, double bond, carbon atom or hetero atom；
M1、M2、M3、M4N atom or CRz are each independently represented, and Rz indicates hydrogen atom, D-atom, halogen atom, C1-
C24 alkyl, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72
Arylthio, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amine
Base；
Z indicates oxygen atom, sulphur atom, sulfuryl, sulfoxide group, NRm, CRnRo, SiRpRq or BRr,
And Rm, Rn, Ro, Rp, Rq, Rr each independently represent C1-C24 alkyl, C6-C72 aryl or C3-C72 heteroaryl.
In certain specific embodiments of the invention, the connection Ar1And Ar2Carbon atom be one or two, it is described
Carbon atom is replaced by hydrogen atom, D-atom, C1-C12 alkyl, C6-C36 aryl or C3-C36 heteroaryl；The hetero atom is oxygen
Atom, sulphur atom, silicon atom, nitrogen-atoms or boron atom, the sulphur atom are not substituted or are taken by one or two oxygen atom
In generation, the silicon atom, nitrogen-atoms or boron atom are by hydrogen atom, D-atom, C1-C12 alkyl, C6-C36 aryl or C3-C36 heteroaryl
Base replaces.
In certain specific embodiments of the invention, R has selected from one of following structure：
Wherein,
R1-R16Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18
Aryl, C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R21-R26Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18
Aryl, C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R31-R34Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18
Aryl, C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R101-R106Each independently represent C1-C12 alkyl, C6-C18 aryl or C3-C18 heteroaryl；
R201-R205Each independently represent C1-C12 alkyl, C6-C18 aryl or C3-C18 heteroaryl.
In certain specific embodiments of the invention, R has one of following structure：
Wherein,
R210、R220、R230、R240、R250、R260、R310、R320、R340Each independently represent hydrogen atom, D-atom, methyl,
Ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, 3,5-dimethylphenyl, pyridyl group, naphthalene, carbazyl or carboline base；
R2010Indicate methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, 3,5-dimethylphenyl, pyridyl group or
Naphthalene.
In certain specific embodiments of the invention, double carbazoles for symmetrically replacing provided by embodiments of the present invention
Compound has selected from one of following structure：
General synthetic routes：
Specific embodiments of the present invention also provide the preparation method of the above-mentioned double carbazole compounds symmetrically replaced, through as follows
Universal synthesis method (Syn-1) synthesis：
Wherein, S1, S2 each independently represent reaction leaving group, reaction leaving group be it is diversified, citing and
It is unrestricted, fluorine atom, chlorine atom, bromine atom, iodine atom, boric acid base group, borate group may be selected；Other groups definition
It is identical to lead to formula (I) with the application.Above-mentioned reaction leaving group, when leaving away during the reaction, it may be possible to it is electrically charged, such as fluorine original
Son is mostly left away in the form of anion when leaving away.
Specific reaction condition is not limited, citing such as temperature, the type of solvent and dosage, the type of catalyst and
Dosage, the type of co-catalyst and dosage, the type of alkali and dosage, the dosage of water, the feed ratio of reaction substrate and sequence, in the industry
Those skilled in the art easily can reasonably be promoted from the embodiment in the embodiment of the present invention, and the general foundation of selection can
With pertinent literature, patent and the books with reference to organic synthesis.It is related to coupling reaction, can preferentially refers to suzuki reaction and crow
The related data of Germania reaction；It is related to alkylated reaction, it can be preferentially with reference to a pair gram alkylated related data.
Synthesize example：
The preparation method of disclosed compound of present invention provided below.But present disclosure is not intended to be limited to institute herein
The method of narration it is any.Those skilled in the art can easily modify described method or utilize different sides
Method prepares the one or more of disclosed compound.Following aspect is merely exemplary, and is not intended to limit in the disclosure
The range of appearance.Temperature, catalyst, concentration, reactant composition and other process conditions are changeable, and match for desired
Object is closed, present disclosure those skilled in the art can readily select suitable reactant and condition.
Abbreviation meaning in the embodiment of the present invention：PE：Petroleum ether；DCM：Methylene chloride；EA：Ethyl acetate；CDCl3, deuterium
For chloroform；MeTHF：Methyltetrahydrofuran.
Embodiment 1:Synthesize 2,6- (2- (carbazole -9- base)-carbazole -9- base)-pyridine (H1)
At room temperature, 2,6- (2- bromine carbazole -9- base) pyridine 340mg, carbazole 200mg, iodate are sequentially added into reaction flask
Cuprous 11mg, Trans- cyclohexanediamine 15mg, potassium phosphate 320mg are eventually adding toluene 10ml, open stirring, nitrogen replacement
It is system to be warming up to 110 DEG C, for 24 hours, cooling, after system is filtered, filtrate contracting is dry for insulation reaction, crosses silicagel column, washes after 3 times
De- agent EA:PE=1:20, eluent is concentrated to get white solid 400mg, yield 89%.
1H NMR(400MHz,Solvent：DMSO-d6)δppm 7.08-7.18(m,2H)7.24-7.41(m,10H)
7.46-7.53(m,2H)7.57(d,2H)7.80-7.89(m,1H)7.90-7.97(m,4H)8.06-8.24(m,8H)8.14-
8.23(m,4H).Mass spectrum m/z=741.
Embodiment 2：Synthesize 2,6- (2- (1-N- carboline -9- base)-carbazole -9- base)-pyridine (H2)
At room temperature, 2,6- (2- bromine carbazole -9- base) pyridine 567mg, 1-N- carboline 338mg is sequentially added into reaction flask,
Cuprous iodide 19mg, Trans- cyclohexanediamine 23mg, potassium phosphate 530mg are eventually adding toluene 16ml, open stirring, and nitrogen is set
After changing system 3 times, system is warming up to 110 DEG C, for 24 hours, cooling, after system is filtered, filtrate contracting is dry for insulation reaction, crosses silica gel
Column, eluant, eluent EA:PE=1:3, eluent is concentrated to get white solid 632mg, yield 85%.
1H NMR(400MHz,DMSO-d6)δppm 7.11-7.17(m,2H)7.30-7.38(m,4H)7.42-7.56(m,
8H)7.64-7.69(m,2H)7.80-7.84(m,1H)7.93-7.98(m,2H)8.03-8.07(m,2H)8.10-8.18(m,
4H)8.22-8.27(m,2H)8.31-8.39(m,2H)8.44-8.50(m,2H).Mass spectrum m/z=743.
Embodiment 3：Synthesize 2,6- (2- (3,6- di-t-butyl carbazole -9- base)-carbazole -9- base)-pyridine (H3)
At room temperature, 2,6- (2- bromine carbazole -9- base) pyridine 232mg, 3,6- di-t-butyl clicks are sequentially added into reaction flask
Azoles 240mg, cuprous iodide 8mg, Trans- cyclohexanediamine 15mg, potassium phosphate 254mg are eventually adding toluene 18ml, open stirring,
After nitrogen is replaced system 3 times, system is warming up to 110 DEG C, for 24 hours, cooling, after system is filtered, filtrate contracting is dry, mistake for insulation reaction
Silicagel column, eluant, eluent EA:PE=1:10, eluent is concentrated to get white solid 347mg, yield 88%.
1H NMR(400MHz,DMSO-d6)δppm 1.46(s,36H)7.18-7.28(m,6H)7.30-7.36(m,6H)
7.46-7.52(m,2H)7.54-7.59(m,2H)7.81-7.88(m,1H)7.91-7.97(m,4H)8.02-8.07(m,4H)
8.14-8.17(m,2H)8.19-8.23(m,2H).Mass spectrum m/z=965.
Embodiment 4：Synthesize 2,6- (2- (dibenzofurans -4- base)-carbazole -9- base)-pyridine (H4)
At room temperature, 2,6- (2- bromine carbazole -9- base) pyridine 567mg, 4- dibenzofurans boron is sequentially added into reaction flask
Sour 424mg, tetra-triphenylphosphine palladium 100mg, potassium phosphate 500mg are eventually adding toluene 20ml, purified water 2ml, open stirring, nitrogen
After gas is replaced system 3 times, system is warming up to 110 DEG C, for 24 hours, cooling will filter insulation reaction after system liquid separation, and filtrate contracting is dry,
Cross silicagel column, eluant, eluent DCM:PE=1:10, eluent is concentrated to get white solid 594mg, yield 80%.
1H NMR(400MHz,DMSO-d6)δppm 6.94–7.04(m,2H)7.23(d,2H)7.28-7.40(m,8H)
7.40-7.46(m,2H)7.50-7.56(m,4H)7.58-7.63(m,2H)7.84-7.94(m,6H)8.04-8.13(m,6H)。
Mass spectrum m/z=743.
Compounds property detection
Above compound is dissolved in MeTHF, room temperature measures photoluminescence spectra, obtains the first singlet level S1 energy
Grade measures photoluminescence spectra in low temperature 77K, obtains the first triplet energy level T1 energy level.By compound under a nitrogen atmosphere with
The heating of 10K/min speed, obtains glass transition temperature Tg.The optics and thermodynamic data result that the above method measures see the table below 1：
The optics and thermodynamic data of 1 compound of table
| Compound name | S1(eV) | T1(eV) | Tg(℃) |
| H1 | 3.53 | 2.88 | 163 |
| H2 | 3.63 | 3.01 | 159 |
| H3 | 3.57 | 2.92 | 139 |
| H4 | 3.55 | 2.82 | 124 |
Can see from the data in table 1, the T1 energy level of compound prepared by embodiment of the present invention is higher, can
With dark blue photodoping material；In addition, its glass transition temperature is higher, it has been more than 120 degree, to joule when being conducive to improve long-term work
The tolerance of heat reduces the aging that heats up caused by long term device work.
Organic light emitting diode device
A specific embodiment of the invention also provides a kind of organic light emitting diode device, the organic light emitting diode device
Include carbazole compound in above-described embodiment.
In some specific embodiments provided by the present invention, the double carbazole compounds symmetrically replaced of the invention are organic
Hole mobile material, material of main part or guest materials in LED device.It is used preferably as material of main part.
Organic light emitting diode device preparation example
The production of device involved in the present invention may be selected under type such as and carried out using the preparation method of industry routine：First
Suitable anode is selected, for introducing hole, anode surface can be deposited the work function that other materials changes anode, then be deposited
Organic layer then proceedes to evaporation cathode, plays the role of introducing electronics.
The organic layer can be one layer, be also possible to multilayer.Further, organic layer includes hole transmission layer, is shone
Layer and electron transfer layer.The hole transmission layer can also have the function of hole function of injecting, electronic blocking or exciton blocking function
Can, the electron transfer layer can also have the function of electronics injecting function, hole barrier or exciton blocking function, the luminescent layer
It can be doped structure.When the luminescent layer is doped structure, by the high referred to as material of main part of weight percent, by weight percent
It is known as guest materials than low.Material of main part can be only a kind of, or a variety of.When using doped structure, object material
The doping ratio of material is 0.1-49.9%, preferably 0.5-20%.
It citing but does not limit, using material of the present invention as material of main part, can prepare as follows：
Cleaned ito glass substrate is placed in vacuum chamber, is evacuated to 10-5Pa, is deposited the 2 of one layer of 10nm, and 3,6,
7,10,11- six cyano-Isosorbide-5-Nitrae, 5,8,9,12- six azepine benzophenanthrenes (HAT-CN) continue to be deposited 4,4 ', the 4 "-three of one layer of 20nm
(1- naphthylphenyl amino) triphenylamine (1-TNATA) continues 9,9- (1,3- phenyl) two carbazoles that one layer of 10nm is deposited
(mCP)；Continue two (2,4 difluorobenzene yl pyridines)-four (1- pyrazolyl) boric acid iridium (FIr6) and this hair of one layer of 30nm of total vapor deposition
The luminescent layer of bright compound, doping concentration 8wt%；The TmPyPB for continuing that one layer of 50nm is deposited is as electron transfer layer；Continue
The lithium fluoride of one layer of 1nm is deposited, continues the aluminium electrode that one layer of 100nm is deposited.
The excellent performance of material in order to further illustrate the present invention only will be of the invention using identical device preparation method
Compound replaces with compound (C1).
The external quantum efficiency (EQE) of measurement device, cut-in voltage (Von), data see the table below 2：
2 quantum efficiency of table and cut-in voltage data
| EQE | Von | |
| H1 | 10.1 | 3.3 |
| H2 | 11.1 | 3.5 |
| H3 | 12.4 | 3.9 |
| H4 | 9.8 | 3.5 |
| C1 | 9.3 | 4.9 |
It can see from 2 data of table, the device using compound provided by the present invention as luminescent layer, luminous efficiency
Compound that is higher, replacing compared to 3, luminous efficiency improves at least 5%, in addition, the cut-in voltage drop-out value of device connects
Nearly 3V.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention,
And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (8)
1. double carbazole compounds that one kind symmetrically replaces, with structure shown in formula (I)：
Wherein,
N1、N2、N3、N4Each independently represent N atom or CRx, and Rx indicate hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl,
C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 arylthio,
C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amido；
X, Y each independently represents N atom or CRy, and wherein Ry indicates hydrogen, deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24
Alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 arylthio, C7-C72
Aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amido；
R indicates deuterium, fluorine, chlorine, bromine, iodine, C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-
C72 aryl, C6-C72 aryloxy group, C6-C72 arylthio, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy,
C3-C72 heteroarylthio or C4-C72 heteroaryl amido.
2. the double carbazole compounds according to claim 1 symmetrically replaced, which is characterized in that R has formula (II) or (III)
Shown in structure：
Wherein,
Ar1、Ar2Each independently represent C1-C24 alkyl, C6-C72 aryl, C3-C72 heteroaryl；Ar1And Ar2Be not attached to or
Ar1And Ar2It is connected by singly-bound, double bond, carbon atom or hetero atom；
M1、M2、M3、M4N atom or CRz are each independently represented, and Rz indicates hydrogen atom, D-atom, halogen atom, C1-C24 alkane
Base, C1-C24 alkoxy, C1-C24 alkylthio group, C2-C24 alkylamino radical, C6-C72 aryl, C6-C72 aryloxy group, C6-C72 virtue sulphur
Base, C7-C72 aryl amine, C3-C72 heteroaryl, C3-C72 heteroaryloxy, C3-C72 heteroarylthio or C4-C72 heteroaryl amido；
Z indicates oxygen atom, sulphur atom, sulfuryl, sulfoxide group, NRm, CRnRo, SiRpRq or BRr,
And Rm, Rn, Ro, Rp, Rq, Rr each independently represent C1-C24 alkyl, C6-C72 aryl or C3-C72 heteroaryl.
3. the double carbazole compounds according to claim 2 symmetrically replaced, which is characterized in that the connection Ar1And Ar2's
Carbon atom is one or two, and the carbon atom is miscellaneous by hydrogen atom, D-atom, C1-C12 alkyl, C6-C36 aryl or C3-C36
Aryl replaces；The hetero atom be oxygen atom, sulphur atom, silicon atom, nitrogen-atoms or boron atom, the sulphur atom be substituted or
Person is replaced by one or two oxygen atom, the silicon atom, nitrogen-atoms or boron atom by hydrogen atom, D-atom, C1-C12 alkyl,
C6-C36 aryl or C3-C36 heteroaryl replace.
4. the double carbazole compounds according to claim 3 symmetrically replaced, which is characterized in that R has selected from one of following
Structure：
Wherein,
R1-R16Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18 aryl,
C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R21-R26Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18 aryl,
C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R31-R34Each independently represent hydrogen atom, D-atom, fluorine atom, C1-C6 alkyl, C1-C6 alkoxy, C6-C18 aryl,
C3-C18 heteroaryl, C7-C18 aryl amine, C4-C18 heteroaryl amido, C6-C18 aryloxy group or C3-C18 heteroaryloxy；
R101-R106Each independently represent C1-C12 alkyl, C6-C18 aryl or C3-C18 heteroaryl；
R201-R205Each independently represent C1-C12 alkyl, C6-C18 aryl or C3-C18 heteroaryl.
5. the double carbazole compounds according to claim 4 symmetrically replaced, which is characterized in that R has one of following knot
Structure：
Wherein,
R210、R220、R230、R240、R250、R260、R310、R320、R340Each independently represent hydrogen atom, D-atom, methyl, ethyl,
Propyl, butyl, amyl, hexyl, phenyl, tolyl, 3,5-dimethylphenyl, pyridyl group, naphthalene, carbazyl or carboline base；
R2010Indicate methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, tolyl, 3,5-dimethylphenyl, pyridyl group or naphthalene.
6. the double carbazole compounds according to claim 1 symmetrically replaced, which is characterized in that have selected from one of following
Structure：
7. double carbazole compounds the answering in organic electroluminescence device of any of claims 1-6 symmetrically replaced
With.
8. application according to claim 7, which is characterized in that the double carbazole compounds symmetrically replaced are described organic
Hole mobile material, material of main part or guest materials in electroluminescent device.
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