CN109748802A - A kind of organic electroluminescent compounds and preparation method and organic electroluminescence device - Google Patents
A kind of organic electroluminescent compounds and preparation method and organic electroluminescence device Download PDFInfo
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Abstract
The present invention relates to luminophor technical fields, and in particular to a kind of organic electroluminescent compounds and preparation method and organic electroluminescence device.Ideal material is obtained in order to solve the problems, such as conventional hole transmission material, the present invention proposes to introduce arylamine and aromatic radical, heteroaryl solution to the position 9- of fluorenes.Hole injection capacity/transmittability, high power efficiency, long-life are obtained by introducing arylamine；By introducing aryl, heteroaryl obtains appropriate glass transition temperature, to obtain good organic electroluminescent compounds.The device of compound preparation provided by the present invention has splendid current efficiency and power efficiency and long-life.The preparation method of organic electroluminescent compounds provided by the invention, simple and easy, yield is high, is suitable for industrialized production.
Description
Technical field
The present invention relates to luminophor technical fields, and in particular to a kind of organic electroluminescent compounds and preparation method and has
Organic electroluminescence devices.
Background technique
El light emitting device (EL device) is automatic luminous device, the advantage is that it provides wider visual angle, biggish
Contrast ratio and faster response time.
Organic EL element is the self-emission device that following principle is utilized: by applying electric field, utilizing what is injected by anode
Hole makes fluorescent substance shine with the recombination energy by cathode injected electrons.It has the following structure: anode, cathode and Jie
In organic layer between the two.In order to improve the efficiency and stability of organic EL element, organic layer includes having different materials
Multilayer, such as hole injection layer (HIL), hole transmission layer (HTL), luminescent layer, electron transfer layer (ETL) and electron injecting layer
(EIL)。
Hole can be changed to the hole transport efficiency, luminous efficiency, service life etc. of luminescent layer in its hole-transporting layer.Therefore,
Using copper phthalocyanine (CuPc), 4,4 '-bis- [N- (1- naphthalene)-N- phenyl amino] biphenyl (NPB), N, N '-diphenyl-N, N '-are bis-
(3- aminomethyl phenyl)-(1,1 '-biphenyl) -4,4 '-diamines (TPD) etc. are used as hole mobile material.However, using these materials
There are still problems in terms of quantum efficiency and service life for organic el device.
Summary of the invention
The invention solves in the prior art the technical issues of, provide it is a kind of have splendid current efficiency and power efficiency with
And the organic electroluminescent compounds and preparation method and organic electroluminescence device of long-life.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
A kind of organic electroluminescent compounds, structural formula are as follows:
Wherein:
Ar1、Ar2、Ar3The C1-C30 alkyl for being substituted or being unsubstituted is each independently represented, is substituted or is unsubstituted
C6-C30 aryl or the C3-C30 heteroaryl that is substituted or is unsubstituted；
Or connect with adjacent substituents and to form monocycle or polycyclic, specially C3-C30 aliphatic ring or aromatic ring, carbon
The replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of atom；
And Ar1、Ar2、Ar3It is not simultaneously identical aryl；
It is preferred that the Ar1、Ar2It each independently represents the C6-C25 aryl for being substituted or being unsubstituted or is substituted or not
C6~C24 the heteroaryl being substituted, Ar3It indicates the C6-C18 aryl that is substituted or is unsubstituted or is substituted or is unsubstituted
C4-C15 heteroaryl；The further preferred Ar1、Ar2Each independently represent the C12-C20 aryl for being substituted or being unsubstituted
Or the C12-C18 heteroaryl for being substituted or being unsubstituted, Ar3Indicate the C10-C14 aryl for being substituted or being unsubstituted or through taking
Generation or the C5-C11 heteroaryl being unsubstituted；Wherein the substituent group is methyl, phenyl, cyano or isopropyl；
L is the C1-C30 alkyl for being substituted or being unsubstituted, the C6-C30 aryl for being substituted or being unsubstituted or is substituted
Or the C1-C30 heteroaryl being unsubstituted；The preferred benzene of L or deuterated benzene；
R1、R2Hydrogen is each independently represented, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, is substituted or is unsubstituted
C1-C30 alkyl, the C1-C30 alkoxy for being substituted or being unsubstituted, the C3-C30 naphthenic base for being substituted or being unsubstituted, through taking
Generation or the C3-C30 cycloalkenyl being unsubstituted, are substituted or are unsubstituted the C3-C7 Heterocyclylalkyl for being substituted or being unsubstituted
C6-C30 aryl, C3-C30 the heteroaryl ,-NR for being substituted or being unsubstituted3R4、-SiR5R6R7、-SR8、-OR9、-COR10、-B
(OR11)(OR12)；It is preferred that R1、R2For isopropyl, methyl, hydrogen；
Or R1And R2It connect to form the monocycle for being substituted or being unsubstituted or polycyclic, specially C3-C30 with adjacent substituents
Aliphatic ring or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；Preferably naphthalene, anthracene
Or pyrene；
R3To R12It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or be unsubstituted
C6-C30 aryl or the C3-C30 heteroaryl for being substituted or being unsubstituted；
Or connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or polycyclic, specially C3-C30 aliphatic
Ring or aromatic ring；A, b each independently represents integer 1 to 4, and preferably a, b is 1.
In the above-mentioned technical solutions, the R1、R2The C1-C30 alkane for each independently representing hydrogen, being substituted or being unsubstituted
Base, alkenyl or alkynyl.
In the above-mentioned technical solutions, the Ar1、Ar2It is each independently selected from the substituent group with flowering structure:
Wherein, " * " represents any position on the substituent group that can be connect with the N atom in chemical formula 1；
The Ar3Selected from the substituent group of flowering structure:
Wherein, " * " represents any position and can connect with the five-membered ring in chemical formula 1；
The above-mentioned Ar listed1、Ar2And Ar3The alkyl of C1-C5 can also be connected on substituent group, as methyl, ethyl,
Isopropyl；
In the above-mentioned technical solutions, any one of the organic electroluminescent compounds in following structures:
The present invention also provides a kind of preparation methods of organic electroluminescent compounds, comprising the following steps:
The preparation of step 1, intermediate 1
It is added after compound 2 and tetrahydrofuran in the reaction vessel, makes the container cooling under nitrogen atmosphere, then
N-BuLi is added dropwise in mixture, after stirring mixture, is stirred at room temperature reaction, it is cooling, it will be dissolved in
Compound 1 in tetrahydrofuran is added dropwise in said mixture, after addition, reaction temperature is made to be warming up to room temperature, and after
It is continuous to be stirred to react, then aqueous ammonium chloride solution is added in reaction solution to complete reaction, and be extracted with ethyl acetate anti-
Solution is answered, then using the dry organic layer through extracting of magnesium sulfate, and solvent is removed using rotary evaporator, with tubing string color
Spectrometry purifies surplus materials and obtains intermediate 1；
The preparation of the compound of structure shown in step 2, chemical formula 1
After intermediate 1, compound 3 and methylene chloride are added in reaction vessel, air is sufficiently displaced from three times with nitrogen,
The boron trifluoride ether being dissolved in methylene chloride is added dropwise in said mixture, after reaction is stirred at room temperature, is used
Distilled water is quenched, and mixture is extracted with dichloromethane, and then using the organic layer of the dry extraction of sodium sulphate, and uses rotation
Rotatable evaporator removes solvent, obtains 1 compound represented of chemical formula with column chromatography eluting surplus materials；
Wherein R1、R2、Ar1、Ar2、Ar3, L and a and b as defined in above-mentioned chemical formula 1, and Hal indicates halogen.
In the above-mentioned technical solutions, the step 1 specifically includes the following steps:
It is added after compound 2 and 200mL tetrahydrofuran in the reaction vessel, makes the container cooling under nitrogen atmosphere
To -78 DEG C, then by n-BuLi, it is added dropwise in said mixture, it, will after being stirred mixture 30 minutes at -78 DEG C
It is stirred at room temperature 3 hours, and is cooled to -78 DEG C, hereafter, will be dissolved in the compound in 200mL tetrahydrofuran 1 dropwise
It is added in mixture, after addition, reaction temperature is made to be warming up to room temperature, and stir mixture 16 hours, then by ammonium chloride
Aqueous solution is added in reaction solution to complete reaction, and reaction solution is extracted with ethyl acetate, then dry using magnesium sulfate
The dry organic layer through extracting, and using rotary evaporator remove solvent, with column chromatography purify surplus materials acquisition in
Mesosome 1.
In the above-mentioned technical solutions, the step 2 specifically includes the following steps:
After compound 3, intermediate 1 and 500L methylene chloride are added in reaction vessel, air is sufficiently displaced from nitrogen
Three times, it will be dissolved in the boron trifluoride ether in 100mL methylene chloride, be added dropwise in mixture, is stirred at room temperature mixed
It after closing object 2 hours, is quenched with distilled water, and mixture is extracted with dichloromethane, then having using the dry extraction of sodium sulphate
Machine layer, and solvent is removed using rotary evaporator, chemical combination shown in chemical formula 1 is obtained with column chromatography eluting surplus materials
Object.
The present invention also provides a kind of organic electroluminescences of compound comprising structure shown in chemical formula 1 of the present invention
Part.
The organic electroluminescence device includes:
First electrode, second electrode and the organic matter layer being placed between two electrode, wherein wrapped in the organic matter layer
Compound containing structure shown in chemical formula 1；The compound of structure shown in chemical formula 1 can be single form or and other materials
It is mixed in organic matter layer.I.e. above compound may include individual organic electroluminescent chemical combination according to the present invention
Object, or can further comprise the conventional material for being generally used for electroluminescent organic material.
One in first and second electrode is anode, and the other is cathode.The organic matter layer includes to shine
Layer, and further include at least one and be selected from hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer, hole
The layer of the group of barrier layer and electronic barrier layer composition.
It may include organic electroluminescent according to the present invention at least one of luminescent layer and hole transmission layer
Close object.
Wherein, the organic matter layer includes at least hole injection layer, hole transmission layer, had both had hole injection but also with sky
It transmits technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and both has electronics biography in cave
It is defeated but also with one or more of electron injection technical ability layer.
" organic matter layer " refers to disposing between organic electroluminescence device first electrode and second electrode in the present invention
The term of whole layers.
When the compound of the structure shown in the chemical formula 1 is present in the luminescent layer in the organic matter layer, 1 institute of chemical formula
Show that the compound of structure can be used as light emitting host or be entrained in other fluorescent hosts；
The compound of the structure shown in the chemical formula 1 is present in hole transmission layer or hole injection in the organic matter layer
When layer, the compound of structure shown in the chemical formula 1 can be used as hole transmission layer, hole injection layer and both have hole note
Enter but also with hole transport functional layer.
Of the present invention includes that the device of the compound preparation of structure shown in chemical formula 1 can be used for organic illuminator
Part (OLED), organic photovoltaic cell (OSC), Electronic Paper (e-Paper), Organophotoreceptor (OPC) or Organic Thin Film Transistors
(OTFT)。
Device of the present invention can be by the methods of film vapor deposition, electron beam evaporation, physical vapour deposition (PVD) in substrate
Upper evaporation metal and conductive oxide and their alloy form anode, can also use spin-coating (spin-
Coating) or strip takes the lead to be deposited；It can also be using molding (tape-casting), scraping blade method (doctor-blading), silk
The methods of wire mark brush (Screen-Printing), ink jet printing or thermal imaging (Thermal-Imaging) reduce number of plies manufacture.
The beneficial effects of the present invention are:
The present invention is provided to the hole mobile materials for solving the problems, such as traditional technology in organic el device.Traditional sky
Hole transport materials are substantially based on triaryl derivative.Although it is with cavity transmission ability and low driving voltage, in order to
It obtains suitable glass transition temperature and has to introduce a large amount of substituent group in its structure and promote its molecular weight.But this
Sample but reduces triplet energies or LUMO energy, so as to cause the deterioration of organic electroluminescence device.Ideal hole transport material
Material needs high glass transition temperature, Hole injection capacity and cavity transmission ability and suitable triplet energies and LUMO energy
Amount.Therefore, ideal material is obtained in order to solve the problems, such as conventional hole transmission material, the present invention is proposed to fluorenes
9- introducing arylamines and aromatic radical, heteroaryl solution.Hole injection capacity/transmission energy is obtained by introducing arylamine
Power, high power efficiency, long-life；By introducing aryl, heteroaryl obtains appropriate glass transition temperature, to obtain high-quality
Organic electroluminescent compounds.
The device of compound preparation provided by the present invention has splendid current efficiency and power efficiency and long-life.
The preparation method of organic electroluminescent compounds provided by the invention, simple and easy, yield is high, is suitable for industrialized production.
Specific embodiment
The present invention provides a kind of organic electroluminescent compounds, and structural formula is as follows:
Wherein: Ar1、Ar2、Ar3It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or not
The C6-C30 aryl being substituted or the C3-C30 heteroaryl for being substituted or being unsubstituted；Or it is connect with adjacent substituents and to form monocycle
Or polycyclic, specially C3-C30 aliphatic ring or aromatic ring, carbon atom is replaceable to be selected from nitrogen, oxygen and sulphur at least one
Hetero atom；And Ar1、Ar2、Ar3It is not simultaneously identical aryl；It is preferred that the Ar1、Ar2It each independently represents and is substituted or not
The C6-C25 aryl being substituted or the C6~C24 heteroaryl for being substituted or being unsubstituted, Ar3What expression was substituted or was unsubstituted
C6-C18 aryl or the C4-C15 heteroaryl for being substituted or being unsubstituted；The further preferred Ar1、Ar2It each independently represents
The C12-C20 aryl for being substituted or being unsubstituted or the C12-C18 heteroaryl for being substituted or being unsubstituted, Ar3Expression is substituted
Or the C10-C14 aryl being unsubstituted or the C5-C11 heteroaryl for being substituted or being unsubstituted；Wherein the substituent group be methyl,
Phenyl, cyano or isopropyl；L is the C1-C30 alkyl for being substituted or being unsubstituted, the C6-C30 for being substituted or being unsubstituted virtue
Base or the C3-C30 heteroaryl for being substituted or being unsubstituted；The preferred benzene of L or deuterated benzene；R1、R2Each independently represent hydrogen, deuterium, halogen
Element, cyano, carboxyl, nitro, hydroxyl, the C1-C30 alkyl for being substituted or being unsubstituted, the C1-C30 for being substituted or being unsubstituted
Alkoxy, the C3-C30 naphthenic base for being substituted or being unsubstituted, the C3-C30 cycloalkenyl for being substituted or being unsubstituted, be substituted or
The C3-C7 Heterocyclylalkyl that is unsubstituted, the C6-C30 aryl for being substituted or being unsubstituted, the C3-C30 for being substituted or being unsubstituted
Heteroaryl ,-NR3R4、-SiR5R6R7、-SR8、-OR9、-COR10、-B(OR11)(OR12)；It is preferred that R1、R2For isopropyl, methyl, hydrogen；
Or R1And R2It connect to form the monocycle for being substituted or being unsubstituted or polycyclic with adjacent substituents, specially C3-C30 aliphatic ring
Or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；Preferably naphthalene, anthracene or pyrene；R3Extremely
R12The C6-C30 aryl or warp for each independently representing the C1-C30 alkyl for being substituted or being unsubstituted, being substituted or being unsubstituted
The C3-C30 heteroaryl for replacing or being unsubstituted；Or it is connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or more
Ring, specially C3-C30 aliphatic ring or aromatic ring；A, b each independently represents integer 1 to 4, and preferably a, b is 1.
It is preferred that the R1、R2C1-C30 alkyl, alkenyl or the alkynes for each independently representing hydrogen, being substituted or being unsubstituted
Base.
Further preferably, the Ar1、Ar2It is each independently selected from the substituent group with flowering structure:
Wherein, " * " represents any position on the substituent group that can be connect with the N atom in chemical formula 1；
The Ar3Selected from the substituent group of flowering structure:
Wherein, " * " represents any position and can connect with the five-membered ring in chemical formula 1；The above-mentioned Ar listed1、Ar2With
Ar3The alkyl of C1-C5 can also be connected on substituent group, such as methyl, ethyl, isopropyl.
Most preferably, any one of the organic electroluminescent compounds in following structures:
The present invention also provides a kind of preparation methods of organic electroluminescent compounds, comprising the following steps:
The preparation of step 1, intermediate 1
It is added after compound 2 and tetrahydrofuran in the reaction vessel, makes the container cooling under nitrogen atmosphere, then
N-BuLi is added dropwise in mixture, after stirring mixture, is stirred at room temperature reaction, it is cooling, it will be dissolved in
Compound 1 in tetrahydrofuran is added dropwise in said mixture, after addition, reaction temperature is made to be warming up to room temperature, and after
It is continuous to be stirred to react, then aqueous ammonium chloride solution is added in reaction solution to complete reaction, and be extracted with ethyl acetate anti-
Solution is answered, then using the dry organic layer through extracting of magnesium sulfate, and solvent is removed using rotary evaporator, with tubing string color
Spectrometry purifies surplus materials and obtains intermediate 1；
The preparation of the compound of structure shown in step 2, chemical formula 1
After intermediate 1, compound 3 and methylene chloride are added in reaction vessel, air is sufficiently displaced from three times with nitrogen,
The boron trifluoride ether being dissolved in methylene chloride is added dropwise in said mixture, after reaction is stirred at room temperature, is used
Distilled water is quenched, and mixture is extracted with dichloromethane, and then using the organic layer of the dry extraction of sodium sulphate, and uses rotation
Rotatable evaporator removes solvent, obtains 1 compound represented of chemical formula with column chromatography eluting surplus materials；
Wherein R1、R2、Ar1、Ar2、Ar3, L and a and b as defined in above-mentioned chemical formula 1, and Hal indicates halogen.
It is preferred that the step 1 specifically includes the following steps:
It is added after compound 2 and 200mL tetrahydrofuran in the reaction vessel, makes the container cooling under nitrogen atmosphere
To -78 DEG C, then by n-BuLi, it is added dropwise in said mixture, it, will after being stirred mixture 30 minutes at -78 DEG C
It is stirred at room temperature 3 hours, and is cooled to -78 DEG C, hereafter, will be dissolved in the compound in 200mL tetrahydrofuran 1 dropwise
It is added in mixture, after addition, reaction temperature is made to be warming up to room temperature, and stir mixture 16 hours, then by ammonium chloride
Aqueous solution is added in reaction solution to complete reaction, and reaction solution is extracted with ethyl acetate, then dry using magnesium sulfate
The dry organic layer through extracting, and using rotary evaporator remove solvent, with column chromatography purify surplus materials acquisition in
Mesosome 1.
It is preferred that the step 2 specifically includes the following steps:
After compound 3, intermediate 1 and 500L methylene chloride are added in reaction vessel, air is sufficiently displaced from nitrogen
Three times, it will be dissolved in the boron trifluoride ether in 100mL methylene chloride, be added dropwise in mixture, is stirred at room temperature mixed
It after closing object 2 hours, is quenched with distilled water, and mixture is extracted with dichloromethane, then having using the dry extraction of sodium sulphate
Machine layer, and solvent is removed using rotary evaporator, chemical combination shown in chemical formula 1 is obtained with column chromatography eluting surplus materials
Object.
The present invention also provides a kind of organic electroluminescents of compound comprising structure shown in chemical formula 1 of the present invention
Device.
The organic electroluminescence device includes: first electrode, second electrode and is placed in organic between two electrode
Nitride layer, wherein include the compound of structure shown in chemical formula 1 in the organic matter layer；The compound of structure shown in chemical formula 1
It can be single form or be mixed in organic matter layer with other materials.I.e. above compound may include individual basis
Organic electroluminescent compounds of the invention, or can further comprise the conventional material for being generally used for electroluminescent organic material.
One in first and second electrode is anode, and the other is cathode.The organic matter layer includes to shine
Layer, and further include at least one and be selected from hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer, hole
The layer of the group of barrier layer and electronic barrier layer composition.
It may include organic electroluminescent according to the present invention at least one of luminescent layer and hole transmission layer
Close object.
Wherein, the organic matter layer includes at least hole injection layer, hole transmission layer, had both had hole injection but also with sky
It transmits technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and both has electronics biography in cave
It is defeated but also with one or more of electron injection technical ability layer.
" organic matter layer " refers to disposing between organic electroluminescence device first electrode and second electrode in the present invention
The term of whole layers.
When the compound of the structure shown in the chemical formula 1 is present in the luminescent layer in the organic matter layer, 1 institute of chemical formula
Show that the compound of structure can be used as light emitting host or be entrained in other fluorescent hosts；
The compound of the structure shown in the chemical formula 1 is present in hole transmission layer or hole injection in the organic matter layer
When layer, the compound of structure shown in the chemical formula 1 can be used as hole transmission layer, hole injection layer and both have hole note
Enter but also with hole transport functional layer.
Of the present invention includes that the device of the compound preparation of structure shown in chemical formula 1 can be used for organic illuminator
Part (OLED), organic photovoltaic cell (OSC), Electronic Paper (e-Paper), Organophotoreceptor (OPC) or Organic Thin Film Transistors
(OTFT)。
Device of the present invention can be by the methods of film vapor deposition, electron beam evaporation, physical vapour deposition (PVD) in substrate
Upper evaporation metal and conductive oxide and their alloy form anode, can also use spin-coating (spin-
Coating) or strip takes the lead to be deposited；It can also be using molding (tape-casting), scraping blade method (doctor-blading), silk
The methods of wire mark brush (Screen-Printing), ink jet printing or thermal imaging (Thermal-Imaging) reduce number of plies manufacture.
Embodiment 1: prepare compound 1
It is added after bromobenzene (60mmol) and 200mL tetrahydrofuran in the reaction vessel, makes the appearance under nitrogen atmosphere
Device is cooled to -78 DEG C.Then n-BuLi (2.5M, 60mmol) is slowly added dropwise in mixture.It is stirred at -78 DEG C
After mixture 30 minutes, it is stirred at room temperature 3 hours, and be cooled to -78 DEG C.Hereafter, 200mL tetrahydro furan will be dissolved in
The 9-Fluorenone (60mmol) muttered slowly is added dropwise in mixture.After addition, reaction temperature is made slowly to be warming up to room temperature, and
And stirring mixture 16 hours.Then aqueous ammonium chloride solution is added in reaction solution to complete reaction, and with acetic acid second
Ester extracts reaction solution.Then using the dry organic layer through extracting of magnesium sulfate, and solvent is removed using rotary evaporator.
With column chromatography purify surplus materials obtain compound 1-1 (11.94g, yield 77%, MW:258.42).
It in reaction vessel is added in compound 1-1 (45mmol), intermediate 2-1 (46mmol) and 500L methylene chloride
Afterwards, air is sufficiently displaced from three times with nitrogen.By the boron trifluoride ether (46mmol) being dissolved in 100mL methylene chloride slowly by
Drop is added in mixture.It after mixture being stirred at room temperature 2 hours, is quenched, and is extracted with dichloromethane mixed with distilled water
Close object.Then using the organic layer of the dry extraction of sodium sulphate, and solvent is removed using rotary evaporator.It is pure with column chromatography
Change surplus materials and obtains compound 1 (26.52g, yield 87%, 677.52).
Embodiment 2: prepare compound 4
Prepare compound 4 according to the method for embodiment 1, (yield 85%, MW:753.12).It is different from embodiment 1 it
It is in and replaces intermediate 1-1 in use intermediate 1-4.
Embodiment 3: prepare compound 19
Prepare compound 19 according to the method for embodiment 1, (yield 78%, MW:789.35).With the difference of embodiment 1
Place is to replace intermediate 1-1 using intermediate 1-19, using intermediate 2-19 instead of intermediate 2-1.
Embodiment 4: prepare compound 24
Prepare compound 24 according to the method for embodiment 1, (yield 83%, MW:727.88).With the difference of embodiment 1
Place is to replace intermediate 1-1 using intermediate 1-4, using intermediate 2-24 instead of intermediate 2-1.
Embodiment 5: prepare compound 33
Prepare compound 33 according to the method for embodiment 1, (yield 79%, MW:767.33).With the difference of embodiment 1
Place is to replace intermediate 1-1 using intermediate 1-4, using intermediate 2-33 instead of intermediate 2-1.
Embodiment 6: prepare compound 41
Prepare compound 41 according to the method for embodiment 1, (yield 85%, MW:768.40.).With the difference of embodiment 1
Place is to replace intermediate 1-1 using intermediate 1-4, using intermediate 2-41 instead of intermediate 2-1.
Embodiment 7: prepare compound 52
Prepare compound 52 according to the method for embodiment 1, (yield 86%, MW:803.34).With the difference of embodiment 1
Place is to replace intermediate 1-1 using intermediate 1-4, using intermediate 2-52 instead of intermediate 2-1.
Embodiment 8: prepare compound 62
Prepare compound 62 according to the method for embodiment 1, (yield 77%, MW:693.22).With the difference of embodiment 1
Place is to replace intermediate 1-1 using intermediate 1-62, using intermediate 2-62 instead of intermediate 2-1.
Embodiment 9: prepare compound 77
Prepare compound 77 according to the method for embodiment 1, (yield 81%, MW:754.23).With the difference of embodiment 1
Place is to replace intermediate 1-1 using intermediate 1-77, using intermediate 2-77 instead of intermediate 2-1.
Embodiment 10: organic electroluminescence device of the manufacture containing compound 1
It is by coating layer thicknessIto glass substrate be placed in distilled water and clean 2 times, ultrasonic washing 30 minutes,
It is cleaned repeatedly with distilled water 2 times, ultrasonic washing 10 minutes, after distilled water cleans, isopropanol, acetone, methanol equal solvent
It is dry after ultrasonic washing in order, it is transferred in plasma washing machine, aforesaid substrate is washed 5 minutes, vapor deposition is sent to
In machine.The 4,4' for being 50nm by evaporation thickness on the ito transparent electrode having had been prepared for, 4 "-three [2- naphthylphenyl amino] three
Phenyl amine (2-TNATA) is used as hole injection layer.Then by compound 1 on the hole injection layer of formation vacuum evaporation thickness
For the hole transmission layer of 30nm.Then the blue material of main part 9,10- bis- that evaporation thickness is 30nm on above-mentioned hole transmission layer
(2- naphthalene) anthracene (ADN) and bis- (4,6- difluorophenyl pyridinato-N, the C2) pyridinecarboxylics of dopant material close iridium (FIrpic).Main body material
The weight ratio of material and dopant material is 95:5.Then on above-mentioned luminescent layer vacuum evaporation with a thickness of 40nm TPBi as hole
Barrier layer and electron transfer layer.Vacuum evaporation is on above-mentioned electron transfer layer with a thickness of 0.5nm lithium fluoride (LiF), as electronics
Implanted layer.The aluminium that last evaporation thickness is 150nm completes the preparation of organic electroluminescence device with this as cathode.To
The performance characteristics of luminescence of the device arrived is tested, and measurement uses KEITHLEY2400 type source measuring unit, and CS-2000 spectroradio is bright
Degree meter, to evaluate driving voltage, light emission luminance, luminous efficiency.
Embodiment 11: organic electroluminescence device of the manufacture containing compound 4
Compound 1 in embodiment 10 is replaced into compound 4, other methods are identical, and production contains the organic of compound 4
Electroluminescent device.
Embodiment 12: organic electroluminescence device of the manufacture containing compound 19
Compound 1 in embodiment 10 is replaced into compound 19, other methods are identical, make having containing compound 19
Organic electroluminescence devices.
Embodiment 13: organic electroluminescence device of the manufacture containing compound 24
Compound 1 in embodiment 10 is replaced into compound 24, other methods are identical, make having containing compound 24
Organic electroluminescence devices.
Embodiment 14: organic electroluminescence device of the manufacture containing compound 33
Compound 1 in embodiment 10 is replaced into compound 33, other methods are identical, make having containing compound 33
Organic electroluminescence devices.
Embodiment 15: organic electroluminescence device of the manufacture containing compound 41
Compound 1 in embodiment 10 is replaced into compound 41, other methods are identical, make having containing compound 41
Organic electroluminescence devices.
Embodiment 16: organic electroluminescence device of the manufacture containing compound 52
Compound 1 in embodiment 10 is replaced into compound 52, other methods are identical, make having containing compound 52
Organic electroluminescence devices.
Embodiment 17: organic electroluminescence device of the manufacture containing compound 62
Compound 1 in embodiment 10 is replaced into compound 62, other methods are identical, make having containing compound 62
Organic electroluminescence devices.
Embodiment 18: organic electroluminescence device of the manufacture containing compound 77
Compound 1 in embodiment 10 is replaced into compound 77, other methods are identical, make having containing compound 77
Organic electroluminescence devices.
Comparative example 1:
According to the method for embodiment 10, the material of hole transmission layer is replaced into N'- bis- (1- naphthalene)-N by compound 1,
N'- diphenyl-(1,1'- biphenyl) -4,4'- diamines (NPD).
Table 1 is the characteristics of luminescence test knot of the compound of preparation of the embodiment of the present invention and the luminescent device of a-NPD preparation
Fruit.
Table 1
It can be seen that compound provided by the invention has suitable glass transition temperature from upper table, by the compound of the present invention
The luminous efficiency of device as hole transmission layer preparation and service life have relative to the device prepared by NPD as hole transmission layer
It is significant to improve.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of organic electroluminescent compounds, which is characterized in that its structural formula is as follows:
Wherein:
Ar1、Ar2、Ar3It each independently represents the C1-C30 alkyl for being substituted or being unsubstituted, be substituted or be unsubstituted
C6-C30 aryl or the C3-C30 heteroaryl for being substituted or being unsubstituted；；
Or connect with adjacent substituents and to form monocycle or polycyclic, specially C3-C30 aliphatic ring or aromatic ring, carbon atom
The replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one；
And Ar1、Ar2、Ar3It is not simultaneously identical aryl；
L is the C1-C30 alkyl for being substituted or being unsubstituted, the C6-C30 aryl for being substituted or being unsubstituted or is substituted or not
C3~C30 the heteroaryl being substituted；
R1、R2Each independently represent hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, the C1-C30 for being substituted or being unsubstituted
Alkyl, the C3-C30 naphthenic base for being substituted or being unsubstituted, is substituted or not the C1-C30 alkoxy for being substituted or being unsubstituted
The C3-C30 cycloalkenyl that is substituted, the C3-C7 Heterocyclylalkyl for being substituted or being unsubstituted, the C6-C30 for being substituted or being unsubstituted
Aryl, C3-C30 the heteroaryl ,-NR for being substituted or being unsubstituted3R4、-SiR5R6R7、-SR8、-OR9、-COR10、-B(OR11)
(OR12)；
Or R1And R2It connect to form the monocycle for being substituted or being unsubstituted or polycyclic with adjacent substituents, specially C3-C30 alicyclic ring
Race's ring or aromatic ring, the replaceable hetero atom that nitrogen, oxygen and sulphur are selected from least one of carbon atom；
R3To R12Each independently represent the C1-C30 alkyl for being substituted or being unsubstituted, the C6-C30 for being substituted or being unsubstituted
Aryl or the C3-C30 heteroaryl for being substituted or being unsubstituted；
Or connect with adjacent substituents and to form the monocycle for being substituted or being unsubstituted or polycyclic, specially C3-C30 aliphatic ring or
Aromatic ring；
A, b each independently represents integer 1 to 4.
2. organic electroluminescent compounds according to claim 1, which is characterized in that the R1、R2It each independently represents
C1-C30 alkyl, the alkenyl or alkynyl for being substituted or being unsubstituted.
3. organic electroluminescent compounds according to claim 1, which is characterized in that the Ar1、Ar2Table each independently
C6~C24 the heteroaryl for showing the C6-C25 aryl for being substituted or being unsubstituted or being substituted or being unsubstituted, Ar3Expression is substituted
Or the C6-C18 aryl being unsubstituted or the C4-C15 heteroaryl for being substituted or being unsubstituted.
4. organic electroluminescent compounds according to claim 1, which is characterized in that the Ar1、Ar2Table each independently
The C12-C18 heteroaryl for showing the C12-C20 aryl for being substituted or being unsubstituted or being substituted or being unsubstituted, Ar3It indicates through taking
Generation or the C10-C14 aryl being unsubstituted or the C5-C11 heteroaryl for being substituted or being unsubstituted.
5. organic electroluminescent compounds according to claim 4, which is characterized in that the substituent group be methyl, phenyl,
Cyano or isopropyl.
6. organic electroluminescent compounds according to claim 1, which is characterized in that the Ar1、Ar2It selects each independently
From with the substituent group of flowering structure:
Wherein, " * " represents any position on the substituent group that can be connect with the N atom in chemical formula 1；
The Ar3Selected from the substituent group of flowering structure:
Wherein, " * " represents any position and can connect with the five-membered ring in chemical formula 1.
7. organic electroluminescent compounds according to claim 1, which is characterized in that it is any in following structures
One:
8. the preparation method of organic electroluminescent compounds described in -7 any one according to claim 1, which is characterized in that including with
Lower step:
The preparation of step 1, intermediate 1
It is added after compound 2 and tetrahydrofuran in the reaction vessel, makes the container cooling under nitrogen atmosphere, it then will just
Butyl lithium is added dropwise in mixture, after stirring mixture, is stirred at room temperature reaction, cooling, will be dissolved in tetrahydro
Compound 1 in furans is added dropwise in said mixture, after addition, reaction temperature is made to be warming up to room temperature, and continue to stir
Reaction is mixed, then aqueous ammonium chloride solution is added in reaction solution to complete reaction, and it is molten that reaction is extracted with ethyl acetate
Liquid then using the dry organic layer through extracting of magnesium sulfate, and removes solvent using rotary evaporator, uses column chromatography
It purifies surplus materials and obtains intermediate 1；
The preparation of the compound of structure shown in step 2, chemical formula 1
After intermediate 1, compound 3 and methylene chloride are added in reaction vessel, air is sufficiently displaced from three times with nitrogen, it will be molten
Boron trifluoride ether of the solution in methylene chloride is added dropwise in said mixture, after reaction is stirred at room temperature, with distillation
Water quenching is gone out, and mixture is extracted with dichloromethane, then using the organic layer of the dry extraction of sodium sulphate, and using rotary
Evaporator removes solvent, obtains 1 compound represented of chemical formula with column chromatography eluting surplus materials；
Wherein Hal indicates halogen.
9. the preparation method of organic electroluminescent compounds according to claim 8, which is characterized in that the step 1 is specifically wrapped
Include following steps:
Be added after compound 2 and 200mL tetrahydrofuran in the reaction vessel, make under nitrogen atmosphere the container be cooled to-
78 DEG C, then by n-BuLi, be added dropwise in said mixture, after being stirred mixture 30 minutes at -78 DEG C, by its
It stirs 3 hours at room temperature, and is cooled to -78 DEG C, hereafter, the compound 1 being dissolved in 200mL tetrahydrofuran is added dropwise
Into mixture, after addition, reaction temperature is made to be warming up to room temperature, and stir mixture 16 hours, then by ammonium chloride solution
Liquid is added in reaction solution to complete reaction, and reaction solution is extracted with ethyl acetate, then using the dry warp of magnesium sulfate
The organic layer of extraction, and using rotary evaporator remove solvent, with column chromatography purify surplus materials acquisition intermediate
1；
The step 2 specifically includes the following steps:
After compound 3, intermediate 1 and 500L methylene chloride are added in reaction vessel, air is sufficiently displaced from three times with nitrogen,
It will be dissolved in the boron trifluoride ether in 100mL methylene chloride, be added dropwise in mixture, mixture 2 is stirred at room temperature
It after hour, is quenched with distilled water, and mixture is extracted with dichloromethane, the organic layer then extracted using sodium sulphate drying,
And solvent is removed using rotary evaporator, obtains 1 compound represented of chemical formula with column chromatography eluting surplus materials.
10. a kind of organic electroluminescence device comprising organic electroluminescent compounds described in claim 1-7 any one.
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