CN106083861B - A kind of electroluminescent organic material, application and device - Google Patents
A kind of electroluminescent organic material, application and device Download PDFInfo
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Abstract
The present invention relates to a kind of electroluminescent organic materials, as shown in lower formula (I):Wherein, Ar1Group is conjugated for tri-arylamine group.It selects pyrazine and quinoxaline as parent, on rigid carbon skeleton is coplanar at one, is conducive to electronics and hole transport, by introducing alkynyl, cyano, improves the electronic transmission performance of pyrazine simultaneously quinoxaline；By introducing the tri-arylamine group compound with good hole transport performance on alkynyl, it is made to have both hole and electronic transmission performance.Therefore, electroluminescent organic material hole with higher and electronic transmission performance, stronger oxidation resistance, and higher glass transition temperature, good amorphous thin film easy to form, it can be used in field of organic electroluminescence, and the luminescent layer and/or electron transfer layer and/or hole transmission layer as organic material use.
Description
Technical field
The present invention relates to the technical field of luminous organic material more particularly to a kind of electroluminescent organic material, using and
Its device.
Background technique
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology can both be used to make
New display product is made, production novel illumination product is can be used for, is expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is very extensive.
Structure of the OLED luminescent device like sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it
Between organic functional material, various different function materials are overlapped mutually depending on the application collectively constitutes OLED luminescent device together.
As current device, when the two end electrodes application voltage to OLED luminescent device, and pass through electric field action organic layer functional material
Positive and negative charge in film layer, positive and negative charge is further compound in luminescent layer, i.e. generation OLED electroluminescent.
Linking arm of the acetylene bond as conjugated bridge in organic conjugate system, has the advantage that the introducing of (i) acetylene bond, can drop
Low system HOMO and lumo energy, and lumo energy reduction is more significant, system energy gap becomes smaller.Thus infer, the introducing of acetylene bond can
With the oxidation resistance of reinforcing material and electron injection ability；It therefore can be using different structure unit and connection type to such
Compound energy level of frontier orbital and energy level difference are effectively adjusted, and influence of the different regulative modes to HOMO and LUMO
Degree is not also identical.(ii) introducing of acetylene bond, so that the ionization energy of most compounds decreases, and electron affinity energy is then significant
Increase, ionization energy is consistent with energy level of frontier orbital variation tendency with the variation tendency of electron affinity energy, further demonstrates alkynes
The introducing of key can significantly improve the injectability of electronics；(iii) introducing of block key, hole and electron mobility have significantly
Increase, this is because the introducing of alkynyl enables hole and electron recombination significantly to reduce；(iv) increase the length of conjugated system
Degree, the hole of compound and electron mobility also increase.The result shows that the introducing of acetylene bond and end group and conjugated bridge change
Become the photoelectric properties that can effectively adjust such compound.
Quinoxaline derivatives are a kind of good electron transport materials, can be used for field of organic electroluminescence, meanwhile, quinoline
Oxazoline derivates have n-type conduction property, while there is good thermal stability, mechanical performance and antioxygenic property etc..Pyrrole
Piperazine and quinoxaline derivatives increase rigid plane compared with quinoxaline derivatives, improve its electron transport ability, while cyanogen
The introducing of base increases the electron affinity of parent, substantially increases its transmittability.
Summary of the invention
It is stronger technical problem to be solved by the invention is to provide a kind of hole with higher and electronic transmission performance
The electroluminescent organic material of oxidation resistance.
The technical scheme to solve the above technical problems is that a kind of electroluminescent organic material, by lower formula (I)
It is shown:
Wherein, Ar1Group is conjugated for tri-arylamine group.
The beneficial effects of the present invention are: selecting pyrazine, simultaneously for quinoxaline as parent, rigid carbon skeleton is coplanar at one
On, be conducive to electronics and hole transport, by introducing alkynyl, cyano, improve the electronic transmission performance of pyrazine and quinoxaline；It is logical
The tri-arylamine group compound for introducing on alkynyl and there is good hole transport performance is crossed, it is made to have both hole and electron-transporting
Energy.Therefore, electroluminescent organic material hole with higher and electronic transmission performance, stronger oxidation resistance, and
Higher glass transition temperature, good amorphous thin film easy to form, can be used in field of organic electroluminescence, as having
The luminescent layer and/or electron transfer layer and/or hole transmission layer of machine material use.
Based on the above technical solution, the present invention can also be improved as follows.
Further, the carbon atom number in the tri-arylamine group conjugation group is 6~60.
Further, the tri-arylamine group conjugation group is selected from N- phenyl carbazole, triphenylamine, diphenylbenzidine, N- phenyl
Any one in carbazole derivates, triphenylamine derivative or diphenylbenzidine derivative.
Further, the N- phenyl carbazole derivative includes N- (4- methoxyphenyl) carbazole, the triphenylamine derivative
Including 4- methoxyphenyl benzidine, the diphenylbenzidine derivative includes two-(4- methoxyphenyl) aniline.
The present invention also provides a kind of preparation methods of electroluminescent organic material comprising following steps:
S1: putting into there-necked flask for 1,2,4,5- benzene, four amine hydrochlorate, oxalic acid and water, after nitrogen displacement, back flow reaction, and room temperature
It filters and dries, obtain intermediate A；
S2: by intermediate A, phosphorus oxychloride, after nitrogen displacement, temperature reaction, after completion of the reaction, quenching reaction is filtered
Khaki solid purifies and dries to obtain intermediate B；
S3: using intermediate B as substrate, being added ferricyanic acid and tetrahydrofuran, back flow reaction, after completion of the reaction quenching reaction,
It purifies and dries to obtain intermediate C fine work；
S4: intermediate C fine work, 2- methyl -3- alkynyl -2- butanol and triethylamine are put into there-necked flask, nitrogen displacement, investment
Two triphenyl phosphorus close palladium chloride, triphenyl phosphorus and cuprous iodide, temperature reaction and largely salt out, and after completion of the reaction, are cooled to room
Toluene is added in temperature, filters desalination, and filtrate is washed to neutrality, and desolventizing obtains vitreous solid, obtains intermediate through column chromatographic purifying
D fine work；
S5: putting into there-necked flask for intermediate D fine work, potassium hydroxide, and distilling apparatus is built in solvent-free direct temperature reaction,
The acetone that reaction generates is evaporated off, until solvent-free steam, stops reaction, is cooled to room temperature, toluene dissolution is washed to neutrality, takes off dry
After solvent, is chromatographed and refined using column, obtain intermediate E fine work；
S6: intermediate E, N- phenyl -3- bromine carbazole and triethylamine are put into there-necked flask, nitrogen displacement puts into two triphenyls
Phosphorus closes palladium chloride, triphenyl phosphorus and cuprous iodide, nitrogen displacement, and temperature reaction is largely salted out, after completion of the reaction, is cooled to
Toluene is added in room temperature, filters desalination, and filtrate is washed to neutrality, and desolventizing obtains vitreous solid, and column chromatographs to obtain shown in formula (I)
Compound fine work.
Further, in the step S1,1, the molar ratio of 2,4,5- benzene, four amine hydrochlorate and oxalic acid is 1: 2.0~3.0,
It is 1: 3.0~8.0 that the additive amount of water, which meets 1,2,4,5- benzene, four amine hydrochlorate and the mass ratio of water,；In the step S2, three
It is 1: 20.0~30.0 that the additive amount of chlorethoxyfos, which meets intermediate A and the molar ratio of phosphorus oxychloride,；In the step S3, cyanogen iron
It is 1: 2.0~3.0 that the additive amount of acid, which meets intermediate B and the molar ratio of ferricyanic acid, and the additive amount of tetrahydrofuran meets intermediate B
Mass ratio with tetrahydrofuran is 1: 5.0~20.0；In the step S4, the additive amount of 2- methyl -3- alkynyl -2- butanol is full
The molar ratio of sufficient intermediate C and 2- methyl -3- alkynyl -2- butanol is 1: 2.0~5.0, and the additive amount of triethylamine meets intermediate C
Mass ratio with triethylamine is 1: 5.0~20.0, and the additive amount that two triphenyl phosphorus close palladium chloride meets intermediate C and two triphenyls
The molar ratio that phosphorus closes palladium chloride is 1: 0.001~0.03, and the additive amount of triphenyl phosphorus meets mole of intermediate C and triphenyl phosphorus
Than being 1: 0.002~0.08, the additive amount of cuprous iodide meet the molar ratio of intermediate C and cuprous iodide be 1: 0.002~
0.08；In the step S5, it is 1: 3.0~10.0 that potassium hydroxide additive amount, which meets intermediate D and the molar ratio of potassium hydroxide,；
In the step S6, it is 1 that the additive amount of N- phenyl -3- bromine carbazole, which meets intermediate E and the molar ratio of N- phenyl -3- bromine carbazole,
: 2.0~5.0, it is 1: 5.0~20.0 that the additive amount of triethylamine, which meets intermediate E and the mass ratio of triethylamine, and two triphenyl phosphorus close
It is 1: 0.001~0.03 that the additive amount of palladium chloride, which meets intermediate E and the molar ratio of two triphenyl phosphorus conjunction palladium chloride, triphenyl phosphorus
Additive amount to meet the molar ratio of intermediate E and triphenyl phosphorus be 1: 0.002~0.08, the additive amount of cuprous iodide meets intermediate
The molar ratio of body E and cuprous iodide is 1: 0.002~0.08.
Further, the reflux time in the step S1 is 3.0~10.0 hours；Heating in the step S2 is anti-
It is 5.0~20.0 hours between seasonable；Reflux time in the step S3 is 3.0~10.0 hours；In the step S4
The temperature reaction time be 3.0~10.0 hours；The temperature reaction time in the step S6 is 3.0~15.0 hours.
Beneficial effect using above-mentioned further scheme is.
Further, the temperature reaction temperature in the step S2 is 80.0~160.0 DEG C；Heating in the step S4 is anti-
Answering temperature is 80.0~120.0 DEG C；Reaction temperature in the step S5 is 50.0~90.0 DEG C；Liter in the step S6
Warm reaction temperature is 80.0~120.0 DEG C.
The present invention also provides a kind of electroluminescent organic materials as described above as in organic electroluminescence device
The application of at least one functional layer.
The present invention also provides a kind of organic electroluminescence devices comprising transparent substrate layer, anode layer, hole injection
Layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；Wherein, on the transparent substrate layer according to
It is secondary to be stacked with the anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode
Layer；Wherein, the electron transfer layer contains electroluminescent organic material described in any of the above embodiments.
The beneficial effects of the present invention are: electroluminescent material provided by the invention is with higher as electron transfer layer
Current efficiency and external quantum efficiency；Hole with higher and electronic transmission performance simultaneously, stronger oxidation resistance, and it is higher
Glass transition temperature, and good amorphous thin film easy to form makes manufacturing cost lower, at room temperature preferable stability
So that device work is more stable, service life is longer；In addition, being made due to its hole with higher and electronic transmission performance
It obtains and is used as electronics and/or hole mobile material, can significantly reduce driving voltage, there is high carrier mobility, improve electronics
Efficiency.
Detailed description of the invention
Fig. 1 is the structural schematic diagram for the organic electroluminescence device that the embodiment of the present invention three provides；
Fig. 2 is ITO/Mo O3(10nm)/NPB (50nm)/Formula one: Ir (piq) 2:(acac) (6wt%,
30nm)/BCP (10nm)/TPBI (30nm)/LiF (1nm)/Al (120nm) electroluminescent spectrum；
Fig. 3 is ITO/Mo O3(10nm)/NPB (50nm)/Formula two: Ir (piq) 2:(acac) (6wt%,
30nm)/BCP (10nm)/TPBI (30nm)/LiF (1nm)/Al (120nm) electroluminescent spectrum.
In attached drawing, parts list represented by the reference numerals are as follows:
1, transparent substrate layer, 2, anode layer, 3, hole injection layer, 4, hole transmission layer, 5, luminescent layer, 6, electron-transport
Layer, 7, electron injecting layer, 8, cathode layer.
Specific embodiment
The principle and features of the present invention will be described below with reference to the accompanying drawings, and the given examples are served only to explain the present invention, and
It is non-to be used to limit the scope of the invention.It should be noted that in the absence of conflict, in embodiments herein and embodiment
Feature can be combined with each other.
Embodiment one
A kind of electroluminescent organic material is present embodiments provided, as shown in lower formula (I):
Wherein, Ar1Group is conjugated for tri-arylamine group.
Preferably, the carbon atom number in tri-arylamine group conjugation group is 6~60.It is further preferred that tri-arylamine group
It is conjugated group and is selected from N- phenyl carbazole, triphenylamine, diphenylbenzidine, N- phenyl carbazole derivative, triphenylamine derivative or two
Any one in phenyl benzidine derivative.N- phenyl carbazole derivative therein is specially N- (4- methoxyphenyl) click
Azoles, triphenylamine derivative are specially 4- methoxyphenyl benzidine, and diphenylbenzidine derivative is specially two-(4- methoxyl groups
Phenyl) aniline.
The electroluminescent organic material concretely any one of following formula one into formula ten:
Electroluminescent organic material provided in this embodiment selects pyrazine and quinoxaline is as parent, and rigid carbon skeleton exists
One it is coplanar on, be conducive to electronics and hole transport, by introducing alkynyl, cyano, improve the electronics of pyrazine and quinoxaline
Transmission performance；By on alkynyl introduce have good hole transport performance tri-arylamine group compound, make its have both hole and
Electronic transmission performance.Therefore, electroluminescent organic material hole with higher and electronic transmission performance, it is stronger anti-oxidant
Ability and higher glass transition temperature, good amorphous thin film easy to form can be used in organic electroluminescent neck
Domain, luminescent layer and/or electron transfer layer and/or hole transmission layer as organic material use.
Embodiment two
Present embodiments provide a kind of preparation method of electroluminescent organic material, used 1,2,4 in the present embodiment,
5- tetramino hydrochloride, oxalic acid, phosphorus oxychloride, H4Fe(CN)6, 2- methyl -3- alkynyl -2- butanol, triethylamine, two triphenyl phosphorus
Close palladium chloride, potassium hydroxide, triaryl amine bromine band object Chemical market can buy at home.
A kind of preparation method of electroluminescent organic material provided in this embodiment, specifically includes the following steps:
S1: putting into there-necked flask for 1,2,4,5- benzene, four amine hydrochlorate, oxalic acid and water, after nitrogen displacement, back flow reaction, and room temperature
It filters and dries, obtain intermediate A；
S2: by intermediate A, phosphorus oxychloride, after nitrogen displacement, temperature reaction, after completion of the reaction, quenching reaction is filtered
Khaki solid purifies and dries to obtain intermediate B；
S3: using intermediate B as substrate, ferricyanic acid is added and tetrahydrofuran (THF), back flow reaction are quenched after completion of the reaction
Reaction, purifies and dries to obtain intermediate C fine work；
S4: intermediate C fine work, 2- methyl -3- alkynyl -2- butanol and triethylamine are put into there-necked flask, nitrogen displacement, investment
Two triphenyl phosphorus close palladium chloride, triphenyl phosphorus and cuprous iodide, temperature reaction and largely salt out, and after completion of the reaction, are cooled to room
Toluene is added in temperature, filters desalination, and filtrate is washed to neutrality, and desolventizing obtains vitreous solid, obtains intermediate through column chromatographic purifying
D fine work；
S5: putting into there-necked flask for intermediate D fine work, potassium hydroxide, and distilling apparatus is built in solvent-free direct temperature reaction,
The acetone that reaction generates is evaporated off, until solvent-free steam, stops reaction, is cooled to room temperature, toluene dissolution is washed to neutrality, takes off dry
After solvent, is chromatographed and refined using column, obtain intermediate E fine work；
S6: intermediate E, N- phenyl -3- bromine carbazole and triethylamine are put into there-necked flask, nitrogen displacement puts into two triphenyls
Phosphorus closes palladium chloride, triphenyl phosphorus and cuprous iodide, nitrogen displacement, and temperature reaction is largely salted out, after completion of the reaction, is cooled to
Toluene is added in room temperature, filters desalination, and filtrate is washed to neutrality, and desolventizing obtains vitreous solid, and column chromatographs to obtain shown in formula (I)
Compound fine work.
In conjunction with above-mentioned electroluminescent organic material preparation method the step of, the synthetic route of the electroluminescent organic material
It is specific as follows:
For convenient for having a clear understanding of the specific method for preparing electroluminescent organic material, ten kinds provided with embodiment one are organic
For electroluminescent material, what following embodiments provided above-mentioned ten kinds of electroluminescent organic materials has preparation method.
Embodiment one
The embodiment gives the preparation side of electroluminescent organic material shown in the formula one that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A:
Four amine hydrochlorate of 85.2g (0.3mol) 1,2,4,5- benzene, 56.7g (0.63mol) oxalic acid and 300g water are put into three
Mouth bottle, after leading to nitrogen 20min, back flow reaction 7hr, a large amount of yellow particle shape solids are insoluble, and room temperature is filtered and dried, and is obtained
88.6g intermediate A, yield 100%, product dissolubility is poor, can not carry out purity test, directly feed intake.
The preparation of intermediate B:
88.6g (theoretical amount 0.3mol) intermediate A, 1103.0g phosphorus oxychloride are warming up to 130 after leading to nitrogen 20min
DEG C reaction 12hr, TLC show only a product point, solvent use petroleum ether: ethyl acetate 1: 1, stop react, by system
It is poured slowly into 5000g ice water, very exothermic, hydrolysis finishes, and filters to obtain khaki solid；Using Soxhlet extractor, using four
Hydrogen furans (THF) solvent extracts, and obtains yellow clarified solution, and desolventizing to remaining 100g solvent is cooled to -10 DEG C, filters
And 28.7g intermediate B is dried to obtain, HPLC purity is 99.5%, yield 30.2%, with 1,2,4,5- benzene, four amine hydrochlorate meter.
The compound, molecular formula C are identified using HPLC-MS10H2C14N4, detected value [M+1]+=321.13, calculated value 319.96.
The preparation of intermediate C:
Using 28.7g (0.09mol) intermediate B as substrate, 38.8g (0.18mol) ferricyanic acid and 350.0g tetrahydro furan is added
Mutter (THF), back flow reaction 8hr, is down to room temperature, and 30.3g (0.54mol) potassium hydroxide aqueous solution is added dropwise, and filters, filtrate layered,
Washing, toluene aqueous phase extracted are incorporated into organic phase, and organic phase desolventizing obtains intermediate C crude product 13.2g, chromatographs to obtain 8.9g through column
Intermediate C fine work, single step yield are 33.3%, purity 98.3%.The compound, molecular formula are identified using HPLC-MS
C12H2C12N6, detected value [M+1]+=302.13, calculated value 301.09.
The preparation of intermediate D:
By 8.9g (0.029mol) intermediate C fine work, 7.5g (0.089mol) 2- methyl -3- alkynyl -2- butanol and 90.0g
Triethylamine puts into there-necked flask, nitrogen displacement 20min, and investment 0.104g (0.149mmol) two triphenyl phosphorus closes palladium chloride, 0.078g
(0.297mmol) triphenyl phosphorus and 0.0565g (0.0297mmol) cuprous iodide, nitrogen displacement 20min are warming up to 100 DEG C, instead
4hr is answered, is largely salted out, TLC shows that intermediate C without residue, is cooled to room temperature, 100g toluene is added, filter desalination, filtrate water
It is washed till neutrality, desolventizing obtains vitreous solid 14.7g, and column chromatographs to obtain 10.3g intermediate D fine work, and single step yield is 87.1%,
Purity is 97.5%.The compound, molecular formula C are identified using HPLC-MS22H16N6O2, detected value [M+1]+=397.67, meter
Calculation value 396.40.
The preparation of intermediate E:
10.3g (25.8mmol) intermediate D fine work, 7.2g (0.13mol) potassium hydroxide are put into there-necked flask, it is solvent-free straight
It connects and is warming up to 90 DEG C, system is viscous liquid, builds distilling apparatus, and the acetone that reaction generates is evaporated off and stops until solvent-free steam
It only reacts, is cooled to room temperature, toluene dissolution is washed to neutrality, after taking off dry solvent, is chromatographed and is refined using column, obtained among 6.6g
Body E fine work, single step yield 91.3%, HPLC purity are 98.3%.The compound, molecular formula are identified using HPLC-MS
C16H4N6, detected value [M+1]+=281.44, calculated value 280.24.
The preparation of product:
6.6g (23.5mmol) intermediate E, 15.9g (49.4mmol) N- phenyl -3- bromine carbazole and 50.0g triethylamine are thrown
Enter there-necked flask, nitrogen displacement 20min, investment 0.165g (0.235mmol) two triphenyl phosphorus closes palladium chloride, 0.123g
(0.470mmol) triphenyl phosphorus and 0.0896g (0.470mmol) cuprous iodide, nitrogen displacement 20min are warming up to 110 DEG C, instead
6hr is answered, is largely salted out, TLC shows that intermediate E without residue, is cooled to room temperature, 100g toluene is added, filter desalination, filtrate water
It is washed till neutrality, desolventizing obtains vitreous solid 17.2g, and column chromatographs to obtain 4.5g product fine work, and single step yield is 81.5%, purity
It is 97.5%.The compound, molecular formula C are identified using HPLC-MS52H26N8, detected value [M+1]+=763.99, calculated value
762.82。
The distillation of Formula one weighs the crude product of 10.0g Formula one, and in vacuum sublimation instrument, distillation parameter is
Distil vacuum degree 2 × 10-5Pa, three area's temperature of distillation are 275 DEG C, and two area's temperature of distillation are 180 DEG C, and one area's temperature of distillation is 110
DEG C, established temperature is gradient increased temperature, and every 15min increases 50 DEG C, after being increased to target temperature, and heat preservation distillation 5.0hr, distillation is altogether
Fine work 8.3g, HPLC:99.9% are obtained, distillation yield is 83.0%.
Embodiment two
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula two that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, when reacts referring to the material in embodiment one
Journey changes the N- phenyl -3- bromine carbazole in one step of preparation of product into N- (4- methoxyl group -1- phenyl) -3- bromine carbazole, can obtain
Two compound represented of formula provided to embodiment one.
Embodiment three
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula three that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
It changes the N- phenyl -3- bromine carbazole in one step of preparation of product into 4- (9- carbazyl) bromobenzene, the offer of embodiment one is provided
Three compound represented of formula.
Embodiment four
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula four that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
It changes the N- phenyl -3- bromine carbazole in one step of preparation of product into 4- (3,6- dimethoxy -9- carbazyl) bromobenzene, can be obtained
Four compound represented of formula that embodiment one provides.
Embodiment five
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula five that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
It changes the N- phenyl -3- bromine carbazole in one step of preparation of product into 4- (N, N- diphenyl) amido bromobenzene, embodiment can be obtained
One five compound represented of formula provided.
Embodiment six
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula six that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
Change the N- phenyl -3- bromine carbazole in one step of preparation of product into 4- (N, N- bis- (4- methoxyphenyl)) amido bromobenzene
Six compound represented of formula of the offer of embodiment one is provided.
Embodiment seven
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula seven that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
It changes the N- phenyl -3- bromine carbazole in one step of preparation of product into 4 '-(N, N- diphenyl) amido -4- bromo biphenyls, can be obtained
Seven compound represented of formula that embodiment one provides.
Embodiment eight
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula eight that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
Change the N- phenyl -3- bromine carbazole in one step of preparation of product into 4- (N- (p-methoxyphenyl)-N- (4- xenyl)) amido
Eight compound represented of formula of the offer of embodiment one can be obtained in bromobenzene.
Embodiment nine
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula nine that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
It changes the N- phenyl -3- bromine carbazole in one step of preparation of product into 4 '-(N, N- diphenyl) amido -2- bromo biphenyls, can be obtained
Nine compound represented of formula that embodiment one provides.
Embodiment ten
Present embodiment gives the preparation side of electroluminescent organic material shown in the formula ten that preparation embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical as embodiment one, referring to expecting when reaction process in embodiment one,
Change the N- phenyl -3- bromine carbazole in one step of preparation of product into 3- (N- (p-methoxyphenyl)-N- (4- xenyl)) amido
Ten compound represented of formula of the offer of embodiment one can be obtained in bromobenzene.
According to electroluminescent organic material prepared by method described in embodiment one to embodiment ten, that is, prepare
The formula one that embodiment one provides is to ten compound represented of formula, as 1~formula of following formula, 10 compound represented, 1~formula of formula 10
The MS data of shown compound are as shown in table 1.
Table 1
The preparation method of the electroluminescent organic material provided through this embodiment can get hole with higher and electricity
Sub- transmission performance, the electroluminescent organic material of stronger oxidation resistance and higher glass transition temperature, by the Organic Electricity
Electroluminescent material is used as the luminescent layer and/or electron transfer layer and/or hole transmission layer of electronic device, can significantly be reduced
Driving voltage has high carrier mobility, improves electronic efficiency.
Embodiment three
A kind of electroluminescent organic material as described in embodiment one is present embodiments provided as organic electroluminescence
The application of at least one functional layer in part.
The present embodiment additionally provides a kind of organic electroluminescence device comprising transparent substrate layer 1, anode 2, hole injection
Layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and cathode layer 8；Wherein, in the transparent substrate
The anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injection have been sequentially stacked on layer 1
Layer 7 and cathode 8；Wherein, the electron transfer layer 6 contains described in any item organic electroluminescence materials described in embodiment one
Material.
The organic electroluminescence device can be prepared according to art processes, method particularly includes: in high vacuum conditions, passing through
MoO is successively deposited on electro-conductive glass (tin indium oxide) substrate of over cleaning3, hole transmission layer, luminescent layer, BCP, electron-transport
Layer, the Al of the LiF and 120nm of 1nm.The mode that vacuum evaporation can be used is deposited, and is easy to get when by material film
Even film layer, and pin hole not easily generated.Device as shown in Figure 1 is made with this method.Following give is mentioned using embodiment one
The formula one of confession to ten compound represented of formula is as device different function layer and manufactured device 1 is to device 10.
Device embodiments 1, one compound represented of formula that the luminescent layer of the device embodiments 1 uses embodiment one to provide.
ITO/Mo O3(10nm)/NPB (50nm)/Formula one: Ir (piq) 2:(acac) (6wt%, 30nm)/BCP
(10nm)/TPBI(30nm)/LiF(1nm)/Al(120nm).Electroluminescent spectrum is by Potoresearch company of the U.S.
The measurement of PR-705 spectrum device, all measurements are completed in atmosphere at room temperature environment, and spectrogram is shown in Fig. 2.
Device embodiments 2, two compound represented of formula that the luminescent layer of the device embodiments 2 uses embodiment one to provide.
ITO/Mo O3(10nm)/NPB (50nm)/Formula two: Ir (piq) 2:(acac) (6wt%, 30nm)/BCP
(10nm)/TPBI(30nm)/LiF(1nm)/Al(120nm).Electroluminescent spectrum is by Potoresearch company of the U.S.
The measurement of PR-705 spectrum device, all measurements are completed in atmosphere at room temperature environment, and spectrogram is shown in Fig. 3.
The electron transfer layer of device embodiments 3, the device embodiments 3 uses chemical combination shown in the formula three of the offer of embodiment one
Object.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula three (30nm)/LiF
(1nm)/Al(120nm)。
The electron transfer layer of device embodiments 4, the device embodiments 4 uses chemical combination shown in the formula four of the offer of embodiment one
Object.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula four (30nm)/LiF
(1nm)/Al(120nm)。
The electron transfer layer of device embodiments 5, the device embodiments 5 uses chemical combination shown in the formula five of the offer of embodiment one
Object.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula five (30nm)/LiF
(1nm)/Al(120nm)。
The electron transfer layer of device embodiments 6, the device embodiments 6 uses chemical combination shown in the formula six of the offer of embodiment one
Object.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula six (30nm)/LiF
(1nm)/Al(120nm)。
The hole transmission layer of device embodiments 7, the device embodiments 7 uses chemical combination shown in the formula seven of the offer of embodiment one
Object.
ITO/Mo O3(10nm)/Formula seven (30nm)/Alq3(30nm)/BCP(10nm)/TPBI(30nm)/LiF
(1nm)/Al(120nm)。
The hole transmission layer of device embodiments 8, the device embodiments 8 uses chemical combination shown in the formula eight of the offer of embodiment one
Object.
ITO/Mo O3(10nm)/Formula eight (30nm)/Alq3(30nm)/BCP(10nm)/TPBI(30nm)/LiF
(1nm)/Al(120nm)。
The hole transmission layer of device embodiments 9, the device embodiments 9 uses chemical combination shown in the formula nine of the offer of embodiment one
Object.
ITO/Mo O3(10nm)/Formula nine (30nm)/Alq3(30nm)/BCP(10nm)/TPBI(30nm)/LiF
(1nm)/Al(120nm)。
Device embodiments 10, the hole transmission layer of the device embodiments 10 uses to be changed shown in the formula ten of the offer of embodiment one
Close object.
ITO/Mo O3(10nm)/Formula ten (30nm)/Alq3(30nm)/BCP(10nm)/TPBI(30nm)/LiF
(1nm)/Al(120nm)。
Current versus brightness-voltage characteristic of device is measured by the source keithley with corrected silicon photoelectric diode
What system (keithley236 source measure unit) was completed, the performance number of device embodiments 1 to device embodiments 10
According to being shown in Table 2.
The performance data of 2 device of table
The compound provided using embodiment one is sent out as device embodiments 1 obtained by luminescent layer and device embodiments 2
Feux rouges is penetrated, maximum current efficiency reaches 8.2cd/A, and maximum external quantum efficiency reaches 11.5%, and (Jilin Normal University is learned with document
Report: natural science edition, 2011,4,44-46) Devices Electroluminescent performance comparison, made with the compound that embodiment one provides
There are apparent advantage, strong operability in terms of brightness, colour efficiency, purity for the performance of device made from functional layer.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of electroluminescent organic material, which is characterized in that by shown in following formula (I):
Wherein, Ar1It is conjugated group for tri-arylamine group,
The tri-arylamine group conjugation group is selected from N- phenyl carbazole, triphenylamine, diphenylbenzidine, N- (4- methoxyphenyl) click
Azoles, 4- methoxyphenyl benzidine, any one in two-(4- methoxyphenyl) aniline.
2. electroluminescent organic material according to claim 1, which is characterized in that in the tri-arylamine group conjugation group
Carbon atom number is 6~60.
3. a kind of preparation method of the described in any item electroluminescent organic materials of claim 1 to 2, which is characterized in that including
Following steps:
S1: 1,2,4,5- benzene, four amine hydrochlorate, oxalic acid and water are put into there-necked flask, after nitrogen displacement, back flow reaction, room temperature is filtered
And dry, obtain intermediate A；
S2: by intermediate A, phosphorus oxychloride, after nitrogen displacement, temperature reaction through quenching reaction, then filters after completion of the reaction
Khaki solid purifies and dries to obtain intermediate B；
S3: using intermediate B as substrate, addition ferricyanic acid and tetrahydrofuran, back flow reaction, after completion of the reaction, through quenching reaction, then
It purifies and dries to obtain intermediate C fine work；
S4: intermediate C fine work, 2- methyl -3- alkynyl -2- butanol and triethylamine are put into there-necked flask, nitrogen displacement, investment two or three
Phenyl phosphorus closes palladium chloride, triphenyl phosphorus and cuprous iodide, temperature reaction and largely salts out, and after completion of the reaction, is cooled to room temperature,
Toluene is added, filters desalination, filtrate is washed to neutrality, and desolventizing obtains vitreous solid, obtains intermediate D essence through column chromatographic purifying
Product；
S5: intermediate D fine work, potassium hydroxide are put into there-necked flask, solvent-free direct temperature reaction is built distilling apparatus, is evaporated off
The acetone generated is reacted, until solvent-free steam, stops reaction, is cooled to room temperature, toluene dissolution is washed to neutrality, takes off dry solvent
Afterwards, it is chromatographed and is refined using column, obtain intermediate E fine work；
S6: intermediate E, N- phenyl -3- bromine carbazole and triethylamine are put into there-necked flask, nitrogen displacement, two triphenyl phosphorus of investment close
Palladium chloride, triphenyl phosphorus and cuprous iodide, nitrogen displacement, temperature reaction largely salt out, and after completion of the reaction, are cooled to room temperature,
Toluene is added, filters desalination, filtrate is washed to neutrality, and desolventizing obtains vitreous solid, and column chromatographs to obtain chemical combination shown in formula (I)
The fine work of object.
4. the preparation method of electroluminescent organic material according to claim 3, which is characterized in that in the step S1
In, the molar ratio of 1,2,4,5- benzene, four amine hydrochlorate and oxalic acid is 1:2.0~3.0, and the additive amount of water meets 1,2,4,5- benzene four
The mass ratio of amine hydrochlorate and water is 1:3.0~8.0；
In the step S2, the additive amount of phosphorus oxychloride meet intermediate A and phosphorus oxychloride molar ratio be 1:20.0~
30.0；
In the step S3, it is 1:2.0~3.0, tetrahydro that the additive amount of ferricyanic acid, which meets intermediate B and the molar ratio of ferricyanic acid,
It is 1:5.0~20.0 that the additive amount of furans, which meets intermediate B and the mass ratio of tetrahydrofuran,；
In the step S4, the additive amount of 2- methyl -3- alkynyl -2- butanol meets intermediate C and 2- methyl -3- alkynyl -2-
The molar ratio of butanol is 1:2.0~5.0, the additive amount of triethylamine meet intermediate C and triethylamine mass ratio be 1:5.0~
20.0, it is 1 that the additive amount that two triphenyl phosphorus close palladium chloride, which meets intermediate C and the molar ratio of two triphenyl phosphorus conjunction palladium chloride:
0.001~0.03, it is 1:0.002~0.08, iodate that the additive amount of triphenyl phosphorus, which meets intermediate C and the molar ratio of triphenyl phosphorus,
It is 1:0.002~0.08 that cuprous additive amount, which meets intermediate C and the molar ratio of cuprous iodide,；
In the step S5, it is 1:3.0~10.0 that potassium hydroxide additive amount, which meets intermediate D and the molar ratio of potassium hydroxide,；
In the step S6, the additive amount of N- phenyl -3- bromine carbazole meets mole of intermediate E Yu N- phenyl -3- bromine carbazole
Mass ratio than meeting intermediate E and triethylamine for the additive amount of 1:2.0~5.0, triethylamine is 1:5.0~20.0, two triphens
It is 1:0.001~0.03 that the additive amount that base phosphorus closes palladium chloride, which meets intermediate E and two triphenyl phosphorus to close the molar ratio of palladium chloride, three
It is 1:0.002~0.08 that the additive amount of phenyl phosphorus, which meets intermediate E and the molar ratio of triphenyl phosphorus, and the additive amount of cuprous iodide is full
Sufficient intermediate E and the molar ratio of cuprous iodide are 1:0.002~0.08.
5. the preparation method of electroluminescent organic material according to claim 4, which is characterized in that in the step S1
Reflux time is 3.0~10.0 hours；The temperature reaction time in the step S2 is 5.0~20.0 hours；The step
Reflux time in rapid S3 is 3.0~10.0 hours；The temperature reaction time in the step S4 is 3.0~10.0 small
When；The temperature reaction time in the step S6 is 3.0~15.0 hours.
6. the preparation method of electroluminescent organic material according to claim 5, which is characterized in that in the step S2
Temperature reaction temperature is 80.0~160.0 DEG C；Temperature reaction temperature in the step S4 is 80.0~120.0 DEG C；The step
Reaction temperature in rapid S5 is 50.0~90.0 DEG C；Temperature reaction temperature in the step S6 is 80.0~120.0 DEG C.
7. a kind of described in any item electroluminescent organic materials of claim 1 to 2 as in organic electroluminescence device extremely
The application of a few functional layer.
8. a kind of organic electroluminescence device, which is characterized in that passed including transparent substrate layer, anode layer, hole injection layer, hole
Defeated layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；Wherein, it is sequentially stacked on the transparent substrate layer
State anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；Wherein, described
Electron transfer layer contains electroluminescent organic material described in any one of the claims 1 to 2.
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