CN109336834A - A kind of aryl amine derivatives and its organic electroluminescence device - Google Patents
A kind of aryl amine derivatives and its organic electroluminescence device Download PDFInfo
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Abstract
The present invention provides a kind of aryl amine derivatives and its organic electroluminescence device, is related to organic optoelectronic materials technology.The present invention connects fluorenes class deriveding group in triaryl amine main structure and big steric group obtains a kind of aryl amine derivatives, it is with good cavity transmission ability, thermal stability, it is easy to form a film, it synthesizes simple to operation, it can be applied in organic electroluminescence device as hole transmission layer, it is poor that hole mobile material thermostabilization in organic electroluminescence device can effectively be solved, it is not easy to form a film, device light emitting efficiency is low and serious problem of roll-offing, organic luminescent device have the advantages that driving voltage is low, luminous efficiency is high, the service life is long.
Description
Technical field
The present invention relates to organic photoelectrical material technical field more particularly to a kind of aryl amine derivatives and its organic electroluminescent
Device.
Background technique
From 1987, Deng Qingyun of Kodak et al. used Alq using the method for vacuum deposition plated film3As hair
Photosphere is successfully realized low-voltage 10V, high brightness 1000cd/m2Green emission, device efficiency 1.5lm/W, the service life is in 100h
More than, this behave makes electroluminescent organic material and device be provided with the possibility of practicability, to drive organic material
Research boom in this electroluminescent field, by development in more than 30 years, organic electroluminescence device efficiency obtained biggish
Promoted, and because its with self-luminous, visual angle is wide, all solidstate, true color, reaction speed are fast, high brightness, low driving voltage, thickness
It spends thin, light weight, the features such as large scale and curved panel can be made, organic electroluminescence device is got in monitor market
Carry out more applications, becomes current most potential panel display technologies.
The principle of organic electroluminescent: apply external voltage at cathode and an anode both ends, electronics enters electronics by cathode and passes
Defeated layer, hole enter hole transmission layer by anode, and electrons and holes are compounded to form exciton in luminescent layer, and exciton is excitation state, no
Stablize, final exciton radiation transistion returns to ground state and shines.
Classical its structure of organic electroluminescence device is sandwich structure, generally comprises cathode, anode and in the two
Between organic matter layer.Its organic matter layer substantially may include hole injection layer, hole transmission layer, shine auxiliary layer, luminescent layer, sky
One of cave barrier layer, electron transfer layer, electron injecting layer are a variety of, wherein electron injecting layer, electron transfer layer, hole resistance
Barrier, shine auxiliary layer, hole injection layer and hole transmission layer, and effect is mainly equilbrium carrier injection so that electronics with
Hole effectively combines in luminescent layer and forms exciton, and then shines, and improves luminous efficiency.
Wherein, hole mobile material is mainly used to improve the balance of the injection and transmission in device hole, to improve device
Efficiency and service life, hole mobile material need to have following four conditions: a) good hole mobility；B) good film-forming property；c)
Heat-resistant stability is good；D) HOMO energy level size is suitable, drops low start voltage, guarantees that hole can have effective injection.Function admirable
Hole mobile material can reduce the energy barrier in the injection process of hole so that hole injection efficiency improve, to realize
Efficiency, service life and the raising of brightness of device.Hole mobile material plays an important role in organic electroluminescence device.
All in all, the direction of the following organic electroluminescence device is to develop high efficiency, high brightness, long-life, low cost
White light parts and full color display device, but the technological industrialization process still faces many critical issues, wherein hole passes
Defeated material mainly uses tri-arylamine group compound and diphenyl amine compound, but it is not easy film forming and thermal stability is poor, leads to device
The reduction of part efficiency and the shortening in service life, therefore develop the sky that a kind of hole transport performance is excellent, is easy to form a film, thermal stability is good
Hole transport materials, and then the efficiency of device, service life are improved, become current main task.
Summary of the invention
The object of the present invention is to provide a kind of aryl amine derivatives and its organic electroluminescence device, arylamine provided by the invention
Derivative has good cavity transmission ability, and good film-forming property, thermal stability is good, can effectively reduce the energy in the injection process of hole
Potential barrier is measured, improves the injection and efficiency of transmission in hole, synthetic method is simple to operation, has using prepared by the aryl amine derivatives
There is organic electroluminescence devices good luminous efficiency and service life to show.
The present invention provides a kind of aryl amine derivatives, and general formula of molecular structure is as shown in chemical formula I:
Wherein, L1、L2、L3Independently selected from singly-bound, substituted or unsubstituted C6~C30 arlydene, substituted or unsubstituted
Any one in C3-C30 inferior heteroaryl；A is selected from the thick aryl of substituted or unsubstituted C12~C30；B, which is selected from, to be replaced or does not take
The thick aryl of the C6~C30 in generation；R1、R2、R3、R4Independently selected from C1-C10 alkyl, substituted or unsubstituted C6~C30 aryl, take
Generation or unsubstituted C6~C30 aryl amine, substituted or unsubstituted C3~C30 heteroaryl in any one, R1With R2It can connect
Cyclization, R3With R4Cyclization can be connected；M is selected from integer of 1 to 3, and n is selected from 0 to 2 integer, and p is selected from 0 to 2 integer；
Ar is selected from group as follows:
C, D is independently selected from substituted or unsubstituted C6~C24 aryl；R5Selected from substituted or unsubstituted C1-C10 alkane
Base, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted C7~C30 aralkyl, substituted or unsubstituted C6~
Any one in C24 aryl amine, substituted or unsubstituted C6~C24 heteroaryl；A is selected from 0 to 6 integer；X, Y is independently selected
From singly-bound, NR6、CR7R8, any one in O, S, C and/or D can connect cyclization with X and/or Y；Q is selected from 0 or 1；R6、R7、
R8Independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted
C6~C24 aryl amine, substituted or unsubstituted C6~C24 aryloxy group, substituted or unsubstituted C6~C24 arylthio, replace or
Any one in unsubstituted C3~C24 heteroaryl, R7、R8Cyclization can be connected.
Preferably, any one of Ar in group as follows:
Preferably, A is selected from substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl
In any one；B is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenanthryl, takes
Generation or unsubstituted anthryl in any one.
Preferably, R1、R2、R3、R4It does not take independently selected from methyl, ethyl, isopropyl, tert-butyl, sec-butyl, substitution or
The following group in generation: phenyl, naphthalene, anthryl, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, thienyl, benzofuranyl,
Benzothienyl, dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, quinolyl, isoquinolyl, is rattled away at dibenzofuran group
Piperazine base, pyrazinyl, quinoxalinyl, quinazolyl, indyl, any one in azepine carbazyl, wherein R1With R2It can connect into
Ring, R3With R4Cyclization can be connected.
Preferably, L1、L2、L3Independently selected from any one in singly-bound or group as follows:
Further preferably, any one of A in naphthalene, anthryl, phenanthryl, B appointing in phenyl, naphthalene, anthryl, phenanthryl
It anticipates one kind.
Most preferably, any one of aryl amine derivatives of the present invention in chemical structure as follows:
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes cathode, anode
And the one or more organic matter layers being placed between two electrode, the organic matter layer contain arylamine of the present invention and spread out
Biology.
Preferably, organic matter layer of the present invention includes hole transmission layer, is contained in hole transmission layer of the present invention
Any aryl amine derivatives.
Beneficial effects of the present invention:
The present invention provides a kind of aryl amine derivatives and its organic electroluminescence device.The present invention is in triaryl amine main structure
Fluorenes class deriveding group and big steric group are connected, to obtain aromatic amino-derivative of the present invention.
Tertiary aromatic amine structure itself due to there is the nitrogen-atoms containing lone pair electrons, make in external electric field by the electronics on nitrogen-atoms
With lower generation great-jump-forward transmit, molecule thus generate hole, to realize the back transfer in hole, triaryl amine itself has well
Cavity transmission ability；Fluorenes class deriveding group triplet with higher, is easy to the transmission in hole；Virtue of the present invention
Amine derivative connects fluorene kind derivative group and big steric group in triaryl amine main structure, on non-planar molecular structure basis
On increase geometric configuration, form the biggish Star-shaped of steric hindrance, unique structure is conducive to the transmission in hole, from
And obtain higher hole transport efficiency.
The molecular weight of fluorenes class and big steric group is larger, improves the molecular weight of aryl amine derivatives of the present invention and divides
Sub-volume, aryl amine derivatives glass transition temperature with higher of the present invention, is not easy to crystallize, good thermal stability.
The present invention obtains steric hindrance by connecting fluorenes class deriveding group and big steric group in triaryl amine main structure
Biggish Star-shaped reduces the coplanarity of molecule, is easy to form a film.
Aryl amine derivatives of the present invention have good cavity transmission ability, can be applied to organic electroluminescence device
It is middle to be used as hole transmission layer, hole migration efficiency can be effectively improved, and it is easy to form a film, thermal stability is good, can effectively improve device
The efficiency and service life of part.Organic electroluminescence device using aryl amine derivatives of the present invention preparation has good hair
Light efficiency and service life performance.
Aryl amine derivatives preparation method of the present invention is simple, and raw material is easy to get, and can satisfy industrialization demand.
Specific embodiment:
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, art technology
Personnel's every other embodiment obtained without making creative work, belongs to protection scope of the present invention.
Aryl of the present invention refers to remove a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule after, be left the total of univalent perssad
Claiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but
It is without being limited thereto.
Heteroaryl of the present invention be the heteroaromatic being made of carbon and hetero atom core carbon on remove a hydrogen atom, be left
The general name of univalent perssad, the hetero atom include but is not limited to oxygen, sulphur, nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl
Or fused ring heteroaryl, embodiment may include carbazyl, acridinyl, benzothienyl, benzofuranyl, dibenzofuran group, two
Benzothienyl, carbazyl etc., but not limited to this.
The present invention provides a kind of aryl amine derivatives, and general formula of molecular structure is as shown in chemical formula I:
Wherein, L1、L2、L3Independently selected from singly-bound, substituted or unsubstituted C6~C30 arlydene, substituted or unsubstituted
Any one in C3-C30 inferior heteroaryl；A is selected from the thick aryl of substituted or unsubstituted C12~C30；B, which is selected from, to be replaced or does not take
The thick aryl of the C6~C30 in generation；R1、R2、R3、R4Independently selected from C1-C10 alkyl, substituted or unsubstituted C6~C30 aryl, take
Generation or unsubstituted C6~C30 aryl amine, substituted or unsubstituted C3~C30 heteroaryl in any one, R1With R2It can connect
Cyclization, R3With R4Cyclization can be connected；M is selected from integer of 1 to 3, and n is selected from 0 to 2 integer, and p is selected from 0 to 2 integer；
Ar is selected from group as follows:
C, D is independently selected from substituted or unsubstituted C6~C24 aryl；R5Selected from substituted or unsubstituted C1-C10 alkane
Base, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted C7~C30 aralkyl, substituted or unsubstituted C6~
Any one in C24 aryl amine, substituted or unsubstituted C6~C24 heteroaryl；A is selected from 0 to 6 integer；X, Y is independently selected
From singly-bound, NR6、CR7R8, any one in O, S, C and/or D can connect cyclization with X and/or Y；Q is selected from 0 or 1；R6、R7、
R8Independently selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted
C6~C24 aryl amine, substituted or unsubstituted C6~C24 aryloxy group, substituted or unsubstituted C6~C24 arylthio, replace or
Any one in unsubstituted C3~C24 heteroaryl, R7、R8Cyclization can be connected.
According to the present invention, the substituted alkyl, substituted aryl, substituted thick aryl, substituted heteroaryl, replace
Aralkyl, substituted aryl amine, substituted arlydene, substituted inferior heteroaryl, substituted aryloxy group, substituted arylthio,
Described in substituent group independently selected from deuterium, cyano, halogen, C1~C10 alkyl, C6~C24 aryl or C3~C24 heteroaryl, it is excellent
Be selected as methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, naphthalene, xenyl, phenanthryl, anthryl, triphenylene, carbazyl,
Furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuran group, dibenzothiophene, acridinyl, phenoxazine
It is base, phenothiazinyl, 9,9-dimethylacridan base, fluorenyl, 9,9- dimethyl fluorenyl, pyridyl group, pyrimidine radicals, any in triazine radical
It is a kind of.
Preferably, any one of Ar in group as follows:
Preferably, A is selected from substituted or unsubstituted naphthalene, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl
In any one；B is selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted phenanthryl, takes
Generation or unsubstituted anthryl in any one.
Preferably, R1、R2、R3、R4It does not take independently selected from methyl, ethyl, isopropyl, tert-butyl, sec-butyl, substitution or
The following group in generation: phenyl, naphthalene, anthryl, phenanthryl, acridinyl, fluorenyl, carbazyl, furyl, thienyl, benzofuranyl,
Benzothienyl, dibenzothiophene, pyridyl group, pyrimidine radicals, triazine radical, quinolyl, isoquinolyl, is rattled away at dibenzofuran group
Piperazine base, pyrazinyl, quinoxalinyl, quinazolyl, indyl, any one in azepine carbazyl, wherein R1With R2It can connect into
Ring, R3With R4Cyclization can be connected.
Preferably, L1、L2、L3Independently selected from any one in singly-bound or group as follows:
Further preferably, any one of A in naphthalene, anthryl, phenanthryl, B appointing in phenyl, naphthalene, anthryl, phenanthryl
It anticipates one kind.
Most preferably, as an example, it is not particularly limited, a kind of aryl amine derivatives of the present invention are selected from as followsization
Learn any one in structure:
The present invention reacts to obtain aryl amine derivatives of the present invention by a series of Suzuki reaction and Buchwald,
Synthetic route is as follows:
1, raw material r-1, r-2, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains intermediate I -1；
2, raw material r-3, r-4, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains intermediate I -2；
3, raw material r-5, r-6, with Pd (PPh3)4For catalyst, K2CO3For alkali, reaction obtains intermediate I -3；
4, intermediate I -1, I -2, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, and reaction obtains centre
Body I -4；
5, intermediate I -4, I -3, with Pd2(dba)3、P(t-Bu)3For catalyst, NaOBu-t is alkali, and reaction obtains chemical combination
Object I.
The present invention limitation not special to above-mentioned reaction be using popular response well-known to those skilled in the art
Can, the preparation method is simple, easily operated.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device includes cathode, anode
And the one or more organic matter layers being placed between two electrode, the organic matter layer contain arylamine of the present invention and spread out
Biology.
Organic matter layer of the present invention is selected from hole injection layer, hole transmission layer, luminescent layer, and (light emitting host adulterates object
Form or single substance form are as luminescent layer), hole blocking layer, electron transfer layer, at least one of electron injecting layer.
Preferably, the organic matter layer includes hole transmission layer, is contained in hole transmission layer of the present invention any
Aryl amine derivatives.
Hole transmission layer can be single layer structure, be also possible to include the first hole transmission layer and the second hole transmission layer
Double-layer structure, the second hole transmission layer is close to luminescent layer.Aryl amine derivatives of the present invention can do the hole transmission layer of single layer,
The first hole transmission layer of double-layer structure hole transmission layer can also be done.
Its structure of organic electroluminescence device of the present invention is preferred are as follows: substrate/anode/hole injection layer/hole passes
Defeated layer/luminescent layer/hole blocking layer/electron transfer layer/electron injecting layer/cathode.However, the structure of organic electroluminescence device
It is without being limited thereto.Organic electroluminescence device of the present invention can be carried out according to the characteristic of device parameter requirements and material selection and
Combination, can also add or omit part organic layer.
Organic electroluminescence device structure of the present invention is further preferably are as follows: ITO is as transparent anode；2-TNATA conduct
Hole injection layer；Aryl amine derivatives of the present invention are as hole transmission layer；CBP/Ir(ppy)3As luminescent layer substance；BAlq
As hole blocking layer；Alq3As electron transfer layer；LiF is used as electron injecting layer；Al is used as cathode.
Aryl amine derivatives of the present invention are used as hole transmission layer, to manufacture the organic electroluminescence of construction same as below
Luminescent device:
ITO/2-TNATA/ aryl amine derivatives/CBP:Ir (ppy) of the present invention3/BAlq/Alq3/LiF/Al。
Aryl amine derivatives of the present invention are used as the first hole transmission layer, to manufacture the organic of construction same as below
Electroluminescent device:
ITO/2-TNATA/ aryl amine derivatives/NPB/CBP:Ir (ppy) of the present invention3/BAlq/Alq3/LiF/Al。
Organic electroluminescence device of the present invention can be widely applied to Display panel, lighting source, flexibility OLED, electronics
The fields such as paper, Organophotoreceptor or Organic Thin Film Transistors, direction board, signal lamp.
The synthesis of [embodiment 1] compound 1
Step1: addition 3- amino -11,11- dimethyl -11H- benzfluorene (2.59g, 10mmol), 3- are bromo- in reactor
11,11- dimethyl -11H- benzfluorenes (3.23g, 10mmol), Pd2(dba)3(0.21g, 0.25mmol), P (t-Bu)3
(0.18g, 0.84mmol), NaOt-Bu (2.8g, 25mmol), toluene solution 100mL react for 24 hours under the conditions of 100 DEG C, reaction knot
Shu Houyong ether and water extract organic phase, organic layer MgSO4Dry, condensed organic crosses column chromatography, is recrystallized to give centre
Body 1-1 (3.96g, 79%).
Step2: intermediate 1-1 (5.02g, 10mmol), the bromo- 10- phenyl -10H- phenoxazine of 3- are added in reactor
(3.38g, 10mmol), Pd2(dba)3(0.21g, 0.25mmol), P (t-Bu)3(0.18g, 0.84mmol), NaOt-Bu
((2.8g, 25mmol), toluene solution 100mL reacts for 24 hours under the conditions of 100 DEG C, organic with ether and water extraction after reaction
Phase, organic layer MgSO4Dry, condensed organic crosses column chromatography, is recrystallized to give compound 1 (5.69g, 75%).
The synthesis of [embodiment 2] compound 6
Compound 6 (5.14g, 77%) is obtained according to the synthetic method of 1 compound 1 of embodiment.
The synthesis of [embodiment 3] compound 24
Compound 24 (5.23g, 80%) is obtained according to the synthetic method of 1 compound 1 of embodiment.
The synthesis of [embodiment 4] compound 35
Compound 35 (5.19g, 70%) is obtained according to the synthetic method of 1 compound 1 of embodiment.
The synthesis of [embodiment 5] compound 132
Step1: under condition of nitrogen gas, 9,9- dimethyl fluorene -2- boric acid (2.38g, 10mmol), Isosorbide-5-Nitrae-are added into reactor
Dibromobenzene (2.34g, 10mmol), tetra-triphenylphosphine palladium (0.12g, 0.1mmol), sodium carbonate (4.14g, 30mmol), toluene
100mL, ethyl alcohol 20mL and distilled water 20mL are stirred at reflux reaction 3h.Distilled water stops reaction after reaction terminates, and filters, will
Filter cake is dissolved in ethyl acetate, crosses diatomite, and extraction merges organic phase, and with anhydrous MgSO4It is dry, it is concentrated under reduced pressure, ties again
Crystalline substance obtains intermediate 132-1 (2.90g, 83%).
Step2: 2 amino -11,11- dimethyl -11H- benzfluorenes (2.59g, 10mmol), intermediate are added in reactor
132-1 (3.49g, 10mmol), Pd2(dba)3(0.21g, 0.25mmol), P (t-Bu)3(0.18g, 0.84mmol), NaOt-Bu
(2.8g, 25mmol), toluene solution 100mL reacts for 24 hours under the conditions of 100 DEG C, organic with ether and water extraction after reaction
Phase, organic layer MgSO4Dry, condensed organic crosses column chromatography, is recrystallized to give intermediate 132-2 (4.24g, 81%).
Step3: in reactor be added intermediate 132-2 (5.28g, 10mmol), raw material r132-1 (4.11g, 10mmol),
Pd2(dba)3(0.21g, 0.25mmol), P (t-Bu)3(0.18g, 0.84mmol), NaOt-Bu (2.8g, 25mmol), toluene are molten
Liquid 100mL reacts for 24 hours under the conditions of 100 DEG C, extracts organic phase, organic layer MgSO with ether and water after reaction4It is dry,
Condensed organic crosses column chromatography, is recrystallized to give compound 132 (6.18g, 72%).
The synthesis of [embodiment 6] compound 158
Compound 158 (5.34g, 81%) is obtained according to the synthetic method of 1 compound 1 of embodiment.
The synthesis of [embodiment 7] compound 180
Compound 180 (4.95g, 82%) is obtained according to the synthetic method of 1 compound 1 of embodiment.
The aryl amine derivatives FD-MS value of synthesis of the embodiment of the present invention is as shown in table 1.
[table 1]
| Embodiment | FD-MS |
| Embodiment 1 | M/z=758.35 (C56H42N2O=758.33) |
| Embodiment 2 | M/z=667.27 (C50H37NO=667.29) |
| Embodiment 3 | M/z=653.30 (C50H39N=653.31) |
| Embodiment 4 | M/z=740.35 (C56H40N=740.32) |
| Embodiment 5 | M/z=858.39 (C65H47NO=858.37) |
| Embodiment 6 | M/z=659.30 (C49H41NO=659.32) |
| Embodiment 7 | M/z=603.28 (C46H37N=603.29 |
[comparative example 1] device prepares embodiment:
Ito glass substrate is placed in distilled water and is cleaned 2 times, it is ultrasonic washing 30 minutes, different after distilled water cleans
Ultrasonic washing is later dry in order for propyl alcohol, acetone, methanol equal solvent, is transferred in plasma washing machine, by above-mentioned base
Plate washs 5 minutes, is sent in evaporator.
Hole injection layer 2-TNATA/60nm, hole transmission layer are successively deposited on the ito transparent electrode having had been prepared for
Compound N PB/60nm, vapor deposition main body CBP: doping Ir (ppy)310% mixing/30nm, hole blocking layer BAlq/10nm, electricity
Sub- transport layer Alq3/ 30nm, electron injecting layer LiF/0.2nm, cathode Al/150nm.
[embodiment 8] device prepares embodiment:
The compound N PB of the hole transmission layer of comparative example 1 is changed to the compound 1 of embodiment 1.
[embodiment 9] device prepares embodiment:
The compound N PB of the hole transmission layer of comparative example 1 is changed to the compound 6 of embodiment 2.
[embodiment 10] device prepares embodiment:
The compound N PB of the hole transmission layer of comparative example 1 is changed to the compound 24 of embodiment 3.
[embodiment 11] device prepares embodiment:
The compound N PB of the hole transmission layer of comparative example 1 is changed to the compound 35 of embodiment 4.
[embodiment 12] device prepares embodiment:
The compound N PB of the hole transmission layer of comparative example 1 is changed to the compound 132 of embodiment 5.
[embodiment 13] device prepares embodiment:
The compound N PB of the hole transmission layer of comparative example 1 is changed to the compound 158 of embodiment 6.
[embodiment 14] device prepares embodiment:
The compound N PB of the hole transmission layer of comparative example 1 is changed to the compound 180 of embodiment 7.
The characteristics of luminescence test result such as table 2 of luminescent device prepared by 8-14 of the embodiment of the present invention and comparative example 1
It is shown: [table 2]
The above result shows that aryl amine derivatives of the invention are applied in organic electroluminescence device, especially as sky
Cave transport layer, organic electroluminescence device have the advantages that driving voltage is low, luminous efficiency is high, long service life, the present invention
Aryl amine derivatives be luminous organic material of good performance.
It should be pointed out that the present invention is particularly described with individual embodiments, but before not departing from the principle of the invention
It puts, ordinary skill people can carry out the improvement on various forms or details to the present invention, these improvement also fall into this hair
In bright protection scope.
Claims (9)
1. a kind of aryl amine derivatives, which is characterized in that its general formula of molecular structure is as shown in chemical formula I:
Wherein, L1、L2、L3Independently selected from singly-bound, substituted or unsubstituted C6~C30 arlydene, substituted or unsubstituted C3-
Any one in C30 inferior heteroaryl；A is selected from the thick aryl of substituted or unsubstituted C12~C30；B is selected from substituted or unsubstituted
The thick aryl of C6~C30；R1、R2、R3、R4Independently selected from C1-C10 alkyl, substituted or unsubstituted C6~C30 aryl, replace or
Any one in unsubstituted C6~C30 aryl amine, substituted or unsubstituted C3~C30 heteroaryl, R1With R2It can connect into
Ring, R3With R4Cyclization can be connected；M is selected from integer of 1 to 3, and n is selected from 0 to 2 integer, and p is selected from 0 to 2 integer；
Ar is selected from group as follows:
C, D is independently selected from substituted or unsubstituted C6~C24 aryl；R5Selected from substituted or unsubstituted C1-C10 alkyl, replace
Or unsubstituted C6~C24 aryl, substituted or unsubstituted C7~C30 aralkyl, substituted or unsubstituted C6~C24 arylamine
Any one in base, substituted or unsubstituted C6~C24 heteroaryl；A is selected from 0 to 6 integer；X, Y independently selected from singly-bound,
NR6、CR7R8, any one in O, S, C and/or D can connect cyclization with X and/or Y；Q is selected from 0 or 1；R6、R7、R8Independently
Selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6~C24 aryl, substituted or unsubstituted C6~C24
It is aryl amine, substituted or unsubstituted C6~C24 aryloxy group, substituted or unsubstituted C6~C24 arylthio, substituted or unsubstituted
Any one in C3~C24 heteroaryl, R7、R8Cyclization can be connected.
2. a kind of aryl amine derivatives according to claim 1, which is characterized in that Ar is any in group as follows
It is a kind of:
3. a kind of aryl amine derivatives according to claim 1, which is characterized in that A is selected from substituted or unsubstituted naphthalene, takes
Generation or unsubstituted anthryl, substituted or unsubstituted phenanthryl in any one；B is selected from substituted or unsubstituted phenyl, substitution
Or any one in unsubstituted naphthalene, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl.
4. a kind of aryl amine derivatives according to claim 1, which is characterized in that R1、R2、R3、R4Independently selected from methyl, second
Base, isopropyl, tert-butyl, sec-butyl, substituted or unsubstituted following group: phenyl, naphthalene, anthryl, phenanthryl, acridinyl, fluorenes
Base, carbazyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuran group, dibenzothiophene, pyridine
Base, pyrimidine radicals, triazine radical, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, quinoxalinyl, quinazolyl, indyl, azepine
Any one in carbazyl, wherein R1With R2Cyclization, R can be connected3With R4Cyclization can be connected.
5. a kind of aryl amine derivatives according to claim 1, which is characterized in that L1、L2、L3Independently selected from singly-bound or such as
Descend any one in shown group:
6. a kind of aryl amine derivatives according to claim 1, which is characterized in that A appointing in naphthalene, anthryl, phenanthryl
It anticipates one kind, any one of B in phenyl, naphthalene, anthryl, phenanthryl.
7. a kind of aryl amine derivatives according to claim 1, which is characterized in that the aryl amine derivatives are selected from as follows
Any one in chemical structure:
8. a kind of organic electroluminescence device, which is characterized in that the organic electroluminescence device includes cathode, anode and is placed in
One or more organic matter layers between two electrode, it is described in any item that the organic matter layer contains claim 1~7
Aryl amine derivatives.
9. a kind of organic electroluminescence device according to claim 8, which is characterized in that the organic matter layer includes sky
Cave transport layer contains the described in any item aryl amine derivatives of claim 1~7 in hole transmission layer.
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