CN106083861A - 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 material, it is by shown in lower formula (I):Wherein, Ar1It is conjugated group for tri-arylamine group.Its select pyrazine quinoxaline as parent, rigidity carbon skeleton all in a copline, beneficially electronics and hole transport, by introducing alkynyl, cyano group, improve the electronic transmission performance of pyrazine quinoxaline；By introducing the tri-arylamine group compound with good hole transport performance on alkynyl so that it is have hole and electronic transmission performance concurrently.Therefore, this electroluminescent organic material has higher hole and electronic transmission performance, stronger oxidation resistance, and higher vitrification point, easily form good amorphous thin film, it can be used in field of organic electroluminescence, uses as the luminescent layer of organic material and/or electron transfer layer and/or hole transmission layer.
Description
Technical field
The present invention relates to the technical field of luminous organic material, particularly relate to a kind of electroluminescent organic material, application and
Its device.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used to make
Make novel display product, it is also possible to be used for making novel illumination product, be expected to substitute existing liquid crystal display and fluorescent lighting,
Application prospect is quite varied.
OLED luminescent device is just as the structure of sandwich, including electrode material film layer, and be clipped in Different electrodes film layer it
Between organic functional material, various difference in functionality materials are overlapped mutually according to purposes and collectively constitute OLED luminescent device together.
As current device, when the two end electrodes applying voltage to OLED luminescent device, and by electric field action organic layer functional material
Positive and negative charge in film layer, positive and negative charge is compound in luminescent layer further, i.e. produces OLED electroluminescent.
Acetylene bond, as the linking arm of 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 notable, system energy gap diminishes.Thus inferring, the introducing of acetylene bond can
Oxidation resistance and electronics injectability with reinforcing material；Therefore different structure unit and connected mode can be used this type of
Compound energy level of frontier orbital and energy level difference effectively regulate, and the impact that different regulative modes is on HOMO and LUMO
Degree also differs.(ii) introducing of acetylene bond so that the ionization energy of most compounds decreases, and electron affinity energy is the most notable
Increase, ionization energy is consistent with energy level of frontier orbital variation tendency with the variation tendency of electron affinity energy, further demonstrate that alkynes
The introducing of key can significantly improve the injectability of electronics；(iii) introducing of block key, hole and electron mobility all have significantly
Increase, this is because the introducing of alkynyl makes hole and electron recombination significantly to reduce；(iv) length of conjugated system is increased
Degree, hole and the electron mobility of compound the most all increase.Result shows, changing of the introducing of acetylene bond and end group and conjugated bridge
Become the photoelectric properties that all can effectively regulate this compounds.
Quinoxaline derivatives is a good electron transport material of class, can be used for field of organic electroluminescence, meanwhile, and quinoline
Oxazoline derivates has n-type conduction property, has good heat stability, mechanical performance and antioxygenic property etc. simultaneously.Pyrrole
Piperazine quinoxaline derivatives relatively quinoxaline derivatives increases rigid plane, improves its electron transport ability, simultaneously cyanogen
The introducing of base adds the electron affinity of parent, substantially increases its transmittability.
Summary of the invention
The technical problem to be solved is to provide a kind of has higher hole and an electronic transmission performance, stronger
The electroluminescent organic material of oxidation resistance.
The technical scheme is that a kind of electroluminescent organic material, it is by lower formula (I)
Shown in:
Wherein, Ar1It is conjugated group for tri-arylamine group.
The invention has the beneficial effects as follows: selecting pyrazine quinoxaline as parent, rigidity carbon skeleton is all a copline
On, beneficially electronics and hole transport, by introducing alkynyl, cyano group, improve the electronic transmission performance of pyrazine quinoxaline；Logical
Cross on alkynyl, introduce the tri-arylamine group compound with good hole transport performance so that it is have hole and electron-transporting concurrently
Energy.Therefore, this electroluminescent organic material has higher hole and an electronic transmission performance, stronger oxidation resistance, and
Higher vitrification point, easily forms good amorphous thin film, and it can be used in field of organic electroluminescence, as having
The luminescent layer of machine material and/or electron transfer layer and/or hole transmission layer use.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the carbon atom number in described tri-arylamine group conjugation group is 6～60.
Further, described tri-arylamine group conjugation group is selected from N-phenyl carbazole, triphenylamine, diphenylbenzidine, N-phenyl
Any one in carbazole derivates, triphenylamine derivative or diphenylbenzidine derivant.
Further, described N-phenyl carbazole derivant includes N-(4-methoxyphenyl) carbazole, described triphenylamine derivative
Including 4-methoxyphenyl benzidine, described diphenylbenzidine derivant includes two-(4-methoxyphenyl) aniline.
Present invention also offers the preparation method of a kind of electroluminescent organic material, it comprises the following steps:
S1: by 1,2,4,5-benzene four amine hydrochlorates, oxalic acid and water put into there-necked flask, after nitrogen displacement, back flow reaction, room temperature
Sucking filtration is also dried, and obtains intermediate A；
S2: by intermediate A, phosphorus oxychloride, after nitrogen displacement, temperature reaction, after completion of the reaction, cancellation is reacted, and sucking filtration obtains
Khaki solid, purification drying obtain intermediate B；
S3: with intermediate B as substrate, adds ferricyanic acid and oxolane, back flow reaction, and cancellation is reacted after completion of the reaction,
Purification drying 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 is replaced, and puts into
Two triphenyl phosphorus close Palladous chloride., triphenyl phosphorus and Hydro-Giene (Water Science)., temperature reaction, salt out in a large number, after completion of the reaction, are cooled to room
Temperature, adds toluene, and sucking filtration desalination, filtrate water is washed till neutrality, and desolventizing obtains vitreous solid, obtains intermediate through column chromatography purification
D fine work；
S5: intermediate D fine work, potassium hydroxide are put into there-necked flask, solvent-free direct temperature reaction, builds distilling apparatus,
Acetone that reaction generate being evaporated off, steams to solvent-free, stopped reaction, be cooled to room temperature, toluene dissolves, and is washed to neutrality, de-dry
After solvent, use column chromatography to refine, obtain intermediate E fine work；
S6: intermediate E, N-phenyl-3-bromine carbazole and triethylamine are put into there-necked flask, nitrogen is replaced, and puts into two triphenyls
Phosphorus closes Palladous chloride., triphenyl phosphorus and Hydro-Giene (Water Science)., and nitrogen is replaced, and temperature reaction salts out in a large number, after completion of the reaction, is cooled to
Room temperature, adds toluene, sucking filtration desalination, and filtrate water is washed till neutrality, and desolventizing obtains vitreous solid, and column chromatography obtains shown in formula (I)
The fine work of compound.
Further, in described step S1,1,2,4,5-benzene four amine hydrochlorate is 1: 2.0～3.0 with the mol ratio of oxalic acid,
The addition of water meets 1, and 2,4,5-benzene four amine hydrochlorates are 1: 3.0～8.0 with the mass ratio of water；In described step S2, three
It is 1: 20.0～30.0 that the addition of chlorethoxyfos meets the mol ratio of intermediate A and phosphorus oxychloride；In described step S3, cyanogen ferrum
It is 1: 2.0～3.0 that the addition of acid meets the mol ratio of intermediate B and ferricyanic acid, and the addition of oxolane meets intermediate B
It is 1: 5.0～20.0 with the mass ratio of oxolane；In described step S4, the addition of 2-methyl-3-alkynyl-2-butanol is full
Foot intermediate C is 1: 2.0～5.0 with the mol ratio of 2-methyl-3-alkynyl-2-butanol, and the addition of triethylamine meets intermediate C
Being 1: 5.0～20.0 with the mass ratio of triethylamine, two triphenyl phosphorus close the addition of Palladous chloride. and meet intermediate C and two triphenyls
It is 1: 0.001～0.03 that phosphorus closes the mol ratio of Palladous chloride., the addition of triphenyl phosphorus meet intermediate C and triphenyl phosphorus mole
Ratio is 1: 0.002～0.08, the addition of Hydro-Giene (Water Science). meet the mol ratio of intermediate C and Hydro-Giene (Water Science). be 1: 0.002～
0.08；In described step S5, it is 1: 3.0～10.0 that potassium hydroxide addition meets the mol ratio of intermediate D and potassium hydroxide；
In described step S6, it is 1 that the addition of N-phenyl-3-bromine carbazole meets the mol ratio of intermediate E and N-phenyl-3-bromine carbazole
: 2.0～5.0, it is 1: 5.0～20.0 that the addition of triethylamine meets the mass ratio of intermediate E and triethylamine, and two triphenyl phosphorus close
The mol ratio that the addition of Palladous chloride. meets intermediate E and two triphenyl phosphorus close Palladous chloride. is 1: 0.001～0.03, triphenyl phosphorus
Addition to meet the mol ratio of intermediate E and triphenyl phosphorus be 1: 0.002～0.08, in the middle of the addition of Hydro-Giene (Water Science). meets
Body E is 1: 0.002～0.08 with the mol ratio of Hydro-Giene (Water Science)..
Further, the reflux time in described step S1 is 3.0～10.0 hours；Intensification in described step S2 is anti-
It is 5.0～20.0 hours between Ying Shi；Reflux time in described step S3 is 3.0～10.0 hours；In described step S4
The temperature reaction time be 3.0～10.0 hours；The temperature reaction time in described step S6 is 3.0～15.0 hours.
Above-mentioned further scheme is used to provide the benefit that.
Further, the temperature reaction temperature in described step S2 is 80.0～160.0 DEG C；Intensification in described step S4 is anti-
Answering temperature is 80.0～120.0 DEG C；Reaction temperature in described step S5 is 50.0～90.0 DEG C；Liter in described step S6
Temperature reaction temperature is 80.0～120.0 DEG C.
Present invention also offers a kind of electroluminescent organic material as above as in organic electroluminescence device
The application of at least one functional layer.
Present invention also offers a kind of organic electroluminescence device, it includes that transparent substrate layer, anode layer, hole are injected
Layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；Wherein, described transparent substrate layer depends on
Secondary it is stacked with described anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode
Layer；Wherein, described electron transfer layer contains the electroluminescent organic material described in any of the above-described item.
The invention has the beneficial effects as follows: the electroluminescent material that the present invention provides has higher as electron transfer layer
Current efficiency and external quantum efficiency；There is higher hole and electronic transmission performance simultaneously, stronger oxidation resistance, and higher
Vitrification point, and easily form good amorphous thin film and make manufacturing cost lower, at room temperature preferable stability
Making device work more stable, service life is longer；Further, since it has higher hole and electronic transmission performance, make
Can must significantly reduce driving voltage as electronics and/or hole mobile material, there is high carrier mobility, improve electronics
Efficiency.
Accompanying drawing explanation
The structural representation of the organic electroluminescence device that Fig. 1 provides for the embodiment of the present invention three；
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 accompanying drawing, the list of parts representated by each label is as follows:
1, transparent substrate layer, 2, anode layer, 3, hole injection layer, 4, hole transmission layer, 5, luminescent layer, 6, electric transmission
Layer, 7, electron injecting layer, 8, cathode layer.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with accompanying drawing, example is served only for explaining the present invention, and
Non-for limiting the scope of the present invention.It should be noted that in the case of not conflicting, in embodiments herein and embodiment
Feature can be mutually combined.
Embodiment one
Present embodiments providing a kind of electroluminescent organic material, it is by shown in lower formula (I):
Wherein, Ar1It is conjugated group for tri-arylamine group.
Preferably, the carbon atom number in this tri-arylamine group conjugation group is 6～60.It is further preferred that tri-arylamine group
Conjugation group is selected from N-phenyl carbazole, triphenylamine, diphenylbenzidine, N-phenyl carbazole derivant, triphenylamine derivative or two
Any one in phenyl benzidine derivative.N-phenyl carbazole derivant therein is specially N-(4-methoxyphenyl) click
Azoles, triphenylamine derivative is specially 4-methoxyphenyl benzidine, and diphenylbenzidine derivant is specially two-(4-methoxyl group
Phenyl) aniline.
Any one in this electroluminescent organic material concretely following formula one to formula ten:
The electroluminescent organic material that the present embodiment provides selects pyrazine quinoxaline all to exist as parent, rigidity carbon skeleton
In one copline, beneficially electronics and hole transport, by introducing alkynyl, cyano group, improve the electronics of pyrazine quinoxaline
Transmission performance；By introducing on alkynyl, there is the tri-arylamine group compound of good hole transport performance so that it is have concurrently hole and
Electronic transmission performance.Therefore, this electroluminescent organic material has higher hole and electronic transmission performance, stronger antioxidation
Ability, and higher vitrification point, easily form good amorphous thin film, and it can be used in organic electroluminescent neck
Territory, uses as the luminescent layer of organic material and/or electron transfer layer and/or hole transmission layer.
Embodiment two
Present embodiments provide the preparation method of a kind of electroluminescent organic material, 1,2,4 used in the present embodiment,
5-tetramino hydrochlorate, oxalic acid, phosphorus oxychloride, H4Fe(CN)6, 2-methyl-3-alkynyl-2-butanol, triethylamine, two triphenyl phosphorus
Conjunction Palladous chloride., potassium hydroxide, triaryl amine bromine band thing all can Chemical market have been bought at home.
The preparation method of a kind of electroluminescent organic material that the present embodiment provides, specifically includes following steps:
S1: by 1,2,4,5-benzene four amine hydrochlorates, oxalic acid and water put into there-necked flask, after nitrogen displacement, back flow reaction, room temperature
Sucking filtration is also dried, and obtains intermediate A；
S2: by intermediate A, phosphorus oxychloride, after nitrogen displacement, temperature reaction, after completion of the reaction, cancellation is reacted, and sucking filtration obtains
Khaki solid, purification drying obtain intermediate B；
S3: with intermediate B as substrate, adds ferricyanic acid and oxolane (THF), back flow reaction, after completion of the reaction cancellation
Reaction, purification drying 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 is replaced, and puts into
Two triphenyl phosphorus close Palladous chloride., triphenyl phosphorus and Hydro-Giene (Water Science)., temperature reaction, salt out in a large number, after completion of the reaction, are cooled to room
Temperature, adds toluene, and sucking filtration desalination, filtrate water is washed till neutrality, and desolventizing obtains vitreous solid, obtains intermediate through column chromatography purification
D fine work；
S5: intermediate D fine work, potassium hydroxide are put into there-necked flask, solvent-free direct temperature reaction, builds distilling apparatus,
Acetone that reaction generate being evaporated off, steams to solvent-free, stopped reaction, be cooled to room temperature, toluene dissolves, and is washed to neutrality, de-dry
After solvent, use column chromatography to refine, obtain intermediate E fine work；
S6: intermediate E, N-phenyl-3-bromine carbazole and triethylamine are put into there-necked flask, nitrogen is replaced, and puts into two triphenyls
Phosphorus closes Palladous chloride., triphenyl phosphorus and Hydro-Giene (Water Science)., and nitrogen is replaced, and temperature reaction salts out in a large number, after completion of the reaction, is cooled to
Room temperature, adds toluene, sucking filtration desalination, and filtrate water is washed till neutrality, and desolventizing obtains vitreous solid, and column chromatography obtains shown in formula (I)
The fine work of compound.
In conjunction with the step of the preparation method of above-mentioned electroluminescent organic material, the synthetic route of this electroluminescent organic material
Specific as follows:
For ease of having a clear understanding of the concrete grammar preparing electroluminescent organic material, ten kinds with embodiment one offer organic
As a example by electroluminescent material, what following embodiment provided above-mentioned ten kinds of electroluminescent organic materials possesses preparation method.
Embodiment one
This embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula one that embodiment one provides
Method, specific as follows:
The preparation of intermediate A:
85.2g (0.3mol) 1,2,4,5-benzene four amine hydrochlorate, 56.7g (0.63mol) oxalic acid and 300g water are put into three
Mouth bottle, after logical nitrogen 20min, back flow reaction 7hr, a large amount of yellow particle shape solids do not dissolve, and room temperature sucking filtration is also dried, and obtains
88.6g intermediate A, yield is 100%, and product dissolubility is poor, it is impossible to carries out purity test, directly feeds intake.
The preparation of intermediate B:
By 88.6g (theoretical amount 0.3mol) intermediate A, 1103.0g phosphorus oxychloride, after logical nitrogen 20min, it is warming up to 130
DEG C reaction 12hr, TLC shows an only product point, developing solvent employing petroleum ether: ethyl acetate 1: 1, stopped reaction, by system
Being poured slowly in 5000g frozen water, very exothermic, hydrolyze complete, sucking filtration obtains khaki solid；Use apparatus,Soxhlet's, use four
Hydrogen furan (THF) solvent extracts, and obtains yellow clear liquor, and desolventizing, to residue 100g solvent, is cooled to-10 DEG C, sucking filtration
And dry to obtain 28.7g intermediate B, and HPLC purity is 99.5%, and yield is 30.2%, with 1, and 2,4,5-benzene four amine hydrochlorate meters.
HPLC-MS is used to identify this compound, molecular formula C10H2C14N4, detected value [M+1]+=321.13, value of calculation 319.96.
The preparation of intermediate C:
With 28.7g (0.09mol) intermediate B as substrate, add 38.8g (0.18mol) ferricyanic acid and 350.0g tetrahydrochysene furan
Mutter (THF), back flow reaction 8hr, is down to room temperature, drips 30.3g (0.54mol) potassium hydroxide aqueous solution, sucking filtration, filtrate layering,
Washing, toluene aqueous phase extracted are incorporated into organic facies, and organic facies desolventizing obtains intermediate C crude product 13.2g, obtains 8.9g through column chromatography
Intermediate C fine work, single step yield is 33.3%, purity 98.3%.HPLC-MS is used to identify this compound, molecular formula
C12H2C12N6, detected value [M+1]+=302.13, value of calculation 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, puts into 0.104g (0.149mmol) two triphenyl phosphorus and closes Palladous chloride., 0.078g
(0.297mmol) triphenyl phosphorus and 0.0565g (0.0297mmol) Hydro-Giene (Water Science)., nitrogen displacement 20min, it is warming up to 100 DEG C, instead
Answering 4hr, salt out in a large number, TLC display intermediate C, without residue, is cooled to room temperature, adds 100g toluene, sucking filtration desalination, filtrate water
Being washed till neutrality, desolventizing obtains vitreous solid 14.7g, and column chromatography obtains 10.3g intermediate D fine work, and single step yield is 87.1%,
Purity is 97.5%.HPLC-MS is used to identify this compound, molecular formula C22H16N6O2, detected value [M+1]+=397.67, meter
Calculation value 396.40.
The preparation of intermediate E:
By 10.3g (25.8mmol) intermediate D fine work, 7.2g (0.13mol) potassium hydroxide put into there-necked flask, solvent-free directly
Connecing and be warming up to 90 DEG C, system is viscous liquid, builds distilling apparatus, and acetone that reaction generate is evaporated off, and steams to solvent-free, stops
Only reaction, is cooled to room temperature, and toluene dissolves, and is washed to neutrality, after de-dry solvent, uses column chromatography to refine, obtains in the middle of 6.6g
Body E fine work, single step yield 91.3%, HPLC purity is 98.3%.HPLC-MS is used to identify this compound, molecular formula
C16H4N6, detected value [M+1]+=281.44, value of calculation 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, put into 0.165g (0.235mmol) two triphenyl phosphorus and close Palladous chloride., 0.123g
(0.470mmol) triphenyl phosphorus and 0.0896g (0.470mmol) Hydro-Giene (Water Science)., nitrogen displacement 20min, it is warming up to 110 DEG C, instead
Answering 6hr, salt out in a large number, TLC display intermediate E, without residue, is cooled to room temperature, adds 100g toluene, sucking filtration desalination, filtrate water
Being washed till neutrality, desolventizing obtains vitreous solid 17.2g, and column chromatography obtains 4.5g product fine work, and single step yield is 81.5%, purity
It is 97.5%.HPLC-MS is used to identify this compound, molecular formula C52H26N8, detected value [M+1]+=763.99, value of calculation
762.82。
The distillation of Formula one, weighs the crude product of 10.0g Formula one, and in vacuum sublimation instrument, distillation parameter is
Distillation vacuum 2 × 10-5Pa, the three district's temperature that distil are 275 DEG C, and the two district's temperature that distil are 180 DEG C, and the district's temperature that distils is 110
DEG C, established temperature is gradient increased temperature, and every 15min raises 50 DEG C, and after being increased to target temperature, insulation distillation 5.0hr, distillation is altogether
Obtaining fine work 8.3g, HPLC:99.9%, distillation yield is 83.0%.
Embodiment two
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula two that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, when reacts with reference to the material in embodiment one
Journey, changes the N-phenyl-3-bromine carbazole in preparation one step of product into N-(4-methoxyl group-1-phenyl)-3-bromine carbazole,
To the compound shown in the formula two that embodiment one provides.
Embodiment three
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula three that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
Change the N-phenyl-3-bromine carbazole in preparation one step of product into 4-(9-carbazyl) bromobenzene, embodiment one offer is i.e. provided
The compound shown in formula three.
Embodiment four
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula four that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
N-phenyl-3-bromine carbazole in preparation one step of product is changed into 4-(3,6-dimethoxy-9-carbazyl) bromobenzene, the most available
The compound shown in formula four that embodiment one provides.
Embodiment five
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula five that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
Change the N-phenyl-3-bromine carbazole in preparation one step of product into 4-(N, N-diphenyl) amido bromobenzene, i.e. can get embodiment
One compound shown in formula five provided.
Embodiment six
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula six that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
Change the N-phenyl-3-bromine carbazole in preparation one step of product into 4-(N, N-bis-(4-methoxyphenyl)) amido bromobenzene,
Obtain the compound shown in formula six that embodiment one provides.
Embodiment seven
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula seven that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
Change the N-phenyl-3-bromine carbazole in preparation one step of product into 4 '-(N, N-diphenyl) amido-4-bromo biphenyls, the most available
The compound shown in formula seven that embodiment one provides.
Embodiment eight
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula eight that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
Change the N-phenyl-3-bromine carbazole in preparation one step of product into 4-(N-(p-methoxyphenyl)-N-(4-xenyl)) amido
Bromobenzene, i.e. can get the compound shown in formula eight that embodiment one provides.
Embodiment nine
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula nine that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
Change the N-phenyl-3-bromine carbazole in preparation one step of product into 4 '-(N, N-diphenyl) amido-2-bromo biphenyls, the most available
The compound shown in formula nine that embodiment one provides.
Embodiment ten
Present embodiment gives the preparation side of the preparation electroluminescent organic material shown in formula ten that embodiment one provides
Method, specific as follows:
The preparation of intermediate A-intermediate E is identical with embodiment one, with reference to embodiment one is expected when course of reaction,
Change the N-phenyl-3-bromine carbazole in preparation one step of product into 3-(N-(p-methoxyphenyl)-N-(4-xenyl)) amido
Bromobenzene, i.e. can get the compound shown in formula ten that embodiment one provides.
The electroluminescent organic material prepared according to the method described in embodiment one to embodiment ten, i.e. prepares
The compound shown in formula one to formula ten that embodiment one provides, is the compound shown in following formula 1～formula 10, formula 1～formula 10
The MS data of shown compound are as shown in table 1.
Table 1
By the preparation method of the electroluminescent organic material that the present embodiment provides, can obtain and there is higher hole and electricity
Sub-transmission performance, stronger oxidation resistance, and the electroluminescent organic material of higher vitrification point, by this Organic Electricity
Electroluminescent material uses as the luminescent layer of electronic device and/or electron transfer layer and/or hole transmission layer, can significantly reduce
Driving voltage, has high carrier mobility, improves electronic efficiency.
Embodiment three
Present embodiments provide a kind of electroluminescent organic material as described in embodiment one as organic electroluminescence
The application of at least one functional layer in part.
The present embodiment additionally provides a kind of organic electroluminescence device, and it includes that transparent substrate layer 1, anode 2, hole are injected
Layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and cathode layer 8；Wherein, at described transparency carrier
Described anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electronics injection it has been sequentially stacked on layer 1
Layer 7 and negative electrode 8；Wherein, described electron transfer layer 6 is containing the organic electroluminescence material described in any one described in embodiment one
Material.
This organic electroluminescence device can be prepared according to art processes, method particularly includes: in high vacuum conditions, at warp
MoO it is deposited with successively on electro-conductive glass (tin indium oxide) substrate of over cleaning3, hole transmission layer, luminescent layer, BCP, electric transmission
Layer, the Al of LiF and 120nm of 1nm.The mode that can use vacuum evaporation is deposited with, and is readily available all during by material film
Even film layer, and be difficult to generate pin hole.Device as shown in Figure 1 is prepared by the method.The following employing embodiment one that gives carries
Device 1 to the device 10 that the compound shown in formula one to formula ten of confession is made as device difference in functionality layer.
Device embodiments 1, the luminescent layer of this device embodiments 1 uses the compound shown in formula one that embodiment one provides.
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.
PR-705 spectrum device is measured, and all measurements all complete in atmosphere at room temperature environment, and spectrogram is shown in Fig. 2.
Device embodiments 2, the luminescent layer of this device embodiments 2 uses the compound shown in formula two that embodiment one provides.
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.
PR-705 spectrum device is measured, and all measurements all complete in atmosphere at room temperature environment, and spectrogram is shown in Fig. 3.
Device embodiments 3, the electron transfer layer of this device embodiments 3 uses the chemical combination shown in formula three that embodiment one provides
Thing.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula three (30nm)/LiF
(1nm)/Al(120nm)。
Device embodiments 4, the electron transfer layer of this device embodiments 4 uses the chemical combination shown in formula four that embodiment one provides
Thing.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula four (30nm)/LiF
(1nm)/Al(120nm)。
Device embodiments 5, the electron transfer layer of this device embodiments 5 uses the chemical combination shown in formula five that embodiment one provides
Thing.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula five (30nm)/LiF
(1nm)/Al(120nm)。
Device embodiments 6, the electron transfer layer of this device embodiments 6 uses the chemical combination shown in formula six that embodiment one provides
Thing.
ITO/Mo O3(10nm)/NPB(50nm)/Alq3(30nm)/BCP (10nm)/Formula six (30nm)/LiF
(1nm)/Al(120nm)。
Device embodiments 7, the hole transmission layer of this device embodiments 7 uses the chemical combination shown in formula seven that embodiment one provides
Thing.
ITO/Mo O3(10nm)/Formula seven (30nm)/Alq3(30nm)/BCP(10nm)/TPBI(30nm)/LiF
(1nm)/Al(120nm)。
Device embodiments 8, the hole transmission layer of this device embodiments 8 uses the chemical combination shown in formula eight that embodiment one provides
Thing.
ITO/Mo O3(10nm)/Formula eight (30nm)/Alq3(30nm)/BCP(10nm)/TPBI(30nm)/LiF
(1nm)/Al(120nm)。
Device embodiments 9, the hole transmission layer of this device embodiments 9 uses the chemical combination shown in formula nine that embodiment one provides
Thing.
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 this device embodiments 10 uses the change shown in formula ten that embodiment one provides
Compound.
ITO/Mo O3(10nm)/Formula ten (30nm)/Alq3(30nm)/BCP(10nm)/TPBI(30nm)/LiF
(1nm)/Al(120nm)。
Current versus brightness-the voltage characteristic of device is to be measured by the keithley source with corrected silicon photoelectric diode
System (keithley236 source measure unit) completes, the performance number of device embodiments 1 to device embodiments 10
According to being shown in Table 2.
The performance data of table 2 device
The compound provided using embodiment one, as the device embodiments 1 obtained by luminescent layer and device embodiments 2, is all sent out
Penetrating HONGGUANG, 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, with embodiment one provide compound make
The performance of device prepared for functional layer has obvious advantage in terms of brightness, colour efficiency, purity, workable.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. an electroluminescent organic material, it is characterised in that shown in lower formula (I):
Wherein, Ar1It is conjugated group for tri-arylamine group.
Electroluminescent organic material the most according to claim 1, it is characterised in that in described tri-arylamine group conjugation group
Carbon atom number is 6～60.
Electroluminescent organic material the most according to claim 2, it is characterised in that described tri-arylamine group conjugation group is selected from
N-phenyl carbazole, triphenylamine, diphenylbenzidine, N-phenyl carbazole derivant, triphenylamine derivative or diphenylbenzidine spread out
Any one in biology.
Electroluminescent organic material the most according to claim 3, it is characterised in that described N-phenyl carbazole derivant includes
N-(4-methoxyphenyl) carbazole, described triphenylamine derivative includes 4-methoxyphenyl benzidine, described diphenylbenzidine
Derivant includes two-(4-methoxyphenyl) aniline.
5. the preparation method of the electroluminescent organic material described in an any one of Claims 1-4, it is characterised in that include
Following steps:
S1: by 1,2,4,5-benzene four amine hydrochlorates, oxalic acid and water put into there-necked flask, after nitrogen displacement, back flow reaction, room temperature sucking filtration
And dry, obtain intermediate A；
S2: by intermediate A, phosphorus oxychloride, after nitrogen displacement, temperature reaction, after completion of the reaction, react through cancellation, then sucking filtration obtains
Khaki solid, purification drying obtain intermediate B；
S3: with intermediate B as substrate, adds ferricyanic acid and oxolane, back flow reaction, after completion of the reaction, reacts through cancellation, then
Purification drying 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 is replaced, and puts into two or three
Phenyl phosphorus closes Palladous chloride., triphenyl phosphorus and Hydro-Giene (Water Science)., temperature reaction, salts out in a large number, after completion of the reaction, is cooled to room temperature,
Adding toluene, sucking filtration desalination, filtrate water is washed till neutrality, and desolventizing obtains vitreous solid, obtains intermediate D essence through column chromatography purification
Product；
S5: intermediate D fine work, potassium hydroxide are put into there-necked flask, solvent-free direct temperature reaction, builds distilling apparatus, be evaporated off
The acetone that reaction generates, steams to solvent-free, stopped reaction, is cooled to room temperature, and toluene dissolves, and is washed to neutrality, de-dry solvent
After, use column chromatography to refine, obtain intermediate E fine work；
S6: intermediate E, N-phenyl-3-bromine carbazole and triethylamine are put into there-necked flask, nitrogen is replaced, and puts into two triphenyl phosphorus and closes
Palladous chloride., triphenyl phosphorus and Hydro-Giene (Water Science)., nitrogen displacement, temperature reaction, salt out in a large number, after completion of the reaction, be cooled to room temperature,
Adding toluene, sucking filtration desalination, filtrate water is washed till neutrality, and desolventizing obtains vitreous solid, and column chromatography obtains the chemical combination shown in formula (I)
The fine work of thing.
The preparation method of electroluminescent organic material the most according to claim 5, it is characterised in that in described step S1
In, 1,2,4,5-benzene four amine hydrochlorate is 1:2.0～3.0 with the mol ratio of oxalic acid, and the addition of water meets 1,2,4,5-benzene four
Amine hydrochlorate is 1:3.0～8.0 with the mass ratio of water；
In described step S2, the addition of phosphorus oxychloride meet the mol ratio of intermediate A and phosphorus oxychloride be 1:20.0～
30.0；
In described step S3, it is 1:2.0～3.0 that the addition of ferricyanic acid meets the mol ratio of intermediate B and ferricyanic acid, tetrahydrochysene
It is 1:5.0～20.0 that the addition of furan meets the mass ratio of intermediate B and oxolane；
In described step S4, the addition of 2-methyl-3-alkynyl-2-butanol meets intermediate C and 2-methyl-3-alkynyl-2-
The mol ratio of butanol is 1:2.0～5.0, the addition of triethylamine meet the mass ratio of intermediate C and triethylamine be 1:5.0～
20.0, it is 1 that the addition of two triphenyl phosphorus conjunction Palladous chloride .s meets the mol ratio of intermediate C and two triphenyl phosphorus conjunction Palladous chloride.:
0.001～0.03, it is 1:0.002～0.08 that the addition of triphenyl phosphorus meets the mol ratio of intermediate C and triphenyl phosphorus, iodate
It is 1:0.002～0.08 that cuprous addition meets the mol ratio of intermediate C and Hydro-Giene (Water Science).；
In described step S5, it is 1:3.0～10.0 that potassium hydroxide addition meets the mol ratio of intermediate D and potassium hydroxide；
In described step S6, the addition of N-phenyl-3-bromine carbazole meet intermediate E and N-phenyl-3-bromine carbazole mole
Ratio is 1:2.0～5.0, and it is 1:5.0～20.0 that the addition of triethylamine meets the mass ratio of intermediate E and triethylamine, two triphens
It is 1:0.001～0.03 that base phosphorus closes the mol ratio that addition meets intermediate E and two triphenyl phosphorus close Palladous chloride. of Palladous chloride., three
It is 1:0.002～0.08 that the addition of phenyl phosphorus meets the mol ratio of intermediate E and triphenyl phosphorus, and the addition of Hydro-Giene (Water Science). is full
Foot intermediate E is 1:0.002～0.08 with the mol ratio of Hydro-Giene (Water Science)..
The preparation method of electroluminescent organic material the most according to claim 6, it is characterised in that in described step S1
Reflux time is 3.0～10.0 hours；The temperature reaction time in described step S2 is 5.0～20.0 hours；Described step
Reflux time in rapid S3 is 3.0～10.0 hours；The temperature reaction time in described step S4 is 3.0～10.0 little
Time；The temperature reaction time in described step S6 is 3.0～15.0 hours.
The preparation method of electroluminescent organic material the most according to claim 7, it is characterised in that in described step S2
Temperature reaction temperature is 80.0～160.0 DEG C；Temperature reaction temperature in described step S4 is 80.0～120.0 DEG C；Described step
Reaction temperature in rapid S5 is 50.0～90.0 DEG C；Temperature reaction temperature in described step S6 is 80.0～120.0 DEG C.
9. the electroluminescent organic material described in an any one of Claims 1-4 as in organic electroluminescence device extremely
The application of a few functional layer.
10. an organic electroluminescence device, it is characterised in that include transparent substrate layer, anode layer, hole injection layer, hole
Transport layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；Wherein, described transparent substrate layer has been sequentially stacked
Described anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer；Wherein, institute
State electron transfer layer and contain the electroluminescent organic material according to any one of the claims 1 to 4.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020098146A1 (en) * | 2018-11-15 | 2020-05-22 | 武汉华星光电半导体显示技术有限公司 | Blue light thermally activated delayed fluorescence material and use thereof |
| CN112898282A (en) * | 2021-01-25 | 2021-06-04 | 常州大学 | D-pi-A type AIE-TADF near-infrared luminescent material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003516A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | Dentritic pattern compound, preparation method and application |
| JP2014011437A (en) * | 2012-07-03 | 2014-01-20 | Kyushu Univ | Organic semiconductor device and chemical compound |
-
2016
- 2016-06-23 CN CN201610466150.0A patent/CN106083861B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003516A (en) * | 2006-01-18 | 2007-07-25 | 中国科学院化学研究所 | Dentritic pattern compound, preparation method and application |
| JP2014011437A (en) * | 2012-07-03 | 2014-01-20 | Kyushu Univ | Organic semiconductor device and chemical compound |
Non-Patent Citations (2)
| Title |
|---|
| B. CHRISTOPHER RINDERSPACHER ET AL.: "The role of aromatic π-bridges in push–pull-chromophores on the transparency-hyperpolarizability tradeoff", 《CHEMICAL PHYSICS LETTERS》 * |
| PEI-YANG GU ET AL.: "Synthesis, physical properties and ion recognition of a novel larger heteroacene with eleven linearly-fused rings and two different types of heteroatom", 《RSC ADVANCES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020098146A1 (en) * | 2018-11-15 | 2020-05-22 | 武汉华星光电半导体显示技术有限公司 | Blue light thermally activated delayed fluorescence material and use thereof |
| CN112898282A (en) * | 2021-01-25 | 2021-06-04 | 常州大学 | D-pi-A type AIE-TADF near-infrared luminescent material and preparation method and application thereof |
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