CN106397341A - Phenazine derivative, method for preparing same and application of phenazine derivative - Google Patents
Phenazine derivative, method for preparing same and application of phenazine derivative Download PDFInfo
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- CN106397341A CN106397341A CN201610817266.4A CN201610817266A CN106397341A CN 106397341 A CN106397341 A CN 106397341A CN 201610817266 A CN201610817266 A CN 201610817266A CN 106397341 A CN106397341 A CN 106397341A
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- IGGDKDTUCAWDAN-UHFFFAOYSA-N C=Cc1c(cccc2)c2ccc1 Chemical compound C=Cc1c(cccc2)c2ccc1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- WSSZHJBCUKRIOR-BSXYJMEJSA-N C[C@H](C1C=CC=CC11)c2ccccc2N1c(cc1)ccc1-c1cc2nc(cc(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c3)c3nc2cc1-c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 Chemical compound C[C@H](C1C=CC=CC11)c2ccccc2N1c(cc1)ccc1-c1cc2nc(cc(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c(-c(cc3)ccc3-[n]3c(cccc4)c4c4c3cccc4)c3)c3nc2cc1-c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2 WSSZHJBCUKRIOR-BSXYJMEJSA-N 0.000 description 1
- QPUYECUOLPXSFR-UHFFFAOYSA-N Cc1c(cccc2)c2ccc1 Chemical compound Cc1c(cccc2)c2ccc1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
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- H—ELECTRICITY
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
- H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a phenazine derivative, a method for preparing the same and application of the phenazine derivative, and relates to the technical field of organic photoelectric materials. The phenazine derivative, the method and the application have the advantages that molecular structure designs are optimized, accordingly, the phenazine derivative is high in light extraction efficiency, can be used for preparing organic electroluminescence devices and particularly can be used as a light extraction material in the organic electroluminescence devices, and the light emitting efficiency of OLED (organic light emitting diode) devices can be effectively improved and is superior to the light emitting efficiency of existing common OLED devices; the method is simple, and raw materials for the phenazine derivative are easily available.
Description
Technical field
The present invention relates to organic photoelectrical material technical field and in particular to a kind of phenazene derivative and preparation method thereof and should
With.
Background technology
1963, the first observed such as Pope of New York Univ USA arrived the electroluminescent of anthracene, hereafter, organic electroluminescent
This new technique has progressed into the visual field of scientist.Due to universal higher, the organic electroluminescence of the initial device drive voltage making
Light and be once once not considered practical value.Until 1987, Tang of Kodak etc. utilized 8-hydroxyquinoline aluminum
With the aromatic diamine with hole transport performance, being prepared for brightness under 10V voltage using ultrathin film technology is 1000cd/
m2Green organic electrofluorescence device (organic light-emitting devices, OLEDs), achieve breakthrough enter
Exhibition is so that the research of OLED has worldwide obtained widely carrying out rapidly.Hereafter people to have developed various performances excellent
Good OLED material, and by the different designs to device architecture, and the optimization to performances such as device lifetime, efficiency, accelerate
The commercialization process of OLED.
Through the development of nearly 30 years, OLED was applied in display and lighting field, but so far, OLED is still
Do not obtain universalness application, the life-span of device, cost, efficiency etc. are all the developing bottlenecks of OLED, and light extraction efficiency is shadow
Ring one of most critical factor of device efficiency.Although the internal quantum efficiency of OLED is already close to 100%, external quantum efficiency
But only have about 20% about, most light is due to substrate mode loss, surface plasma loss and the factors such as waveguiding effect
It is limited in inside luminescent device, result in a large amount of energy losses.In order to improve the light extraction efficiency of device, using light removing layer
(Capping Layer, CPL) is effective method at present.Light removing layer can reduce the surface plasma of metal electrode
Bulk effect, reaches the effect adjusting light direction and light extraction efficiency.But, prepare one layer of CPL material not only needs to increase material more
The cost budgeting of material is in addition it is also necessary to increase an individually evaporation chamber, this improves the preparation cost of OLED.
Content of the invention
In view of this, it is an object of the invention to provide a kind of phenazene derivative and its preparation method and application.The present invention
Described phenazene derivative is not only a class light and takes out material, and has hole transport function, can be simultaneously as hole transmission layer
With light removing layer, improve the luminous efficiency of device, and greatly save the preparation cost of device.
The invention provides a kind of phenazene derivative is it is characterised in that structure formula (I) is as follows：
Wherein, X is the aryl amine of substituted or unsubstituted C6-C60 or the condensed hetero ring of substituted or unsubstituted C6-C60.
Preferably, described X is the thick of the aryl amine of substituted or unsubstituted C6-C40 or substituted or unsubstituted C6-C40
Heterocycle.
Preferably, described X is the aryl amine of substituted or unsubstituted C12-C36 or substituted or unsubstituted C12-C36
Condensed hetero ring.
Still more preferably, described phenazene derivative is any one in structure shown in TM1-TM26：
The present invention also provides a kind of preparation method of phenazene derivative, including：
Compound shown in intermediate shown in formula (A) and formula (B) is obtained formula through coupling reaction under nitrogen protection
(I) phenazene derivative：
Wherein, X is the aryl amine of substituted or unsubstituted C6-C60 or the condensed hetero ring of substituted or unsubstituted C6-C60.
Present invention also offers application in organic electroluminescence device for the above-mentioned phenazene derivative.
Preferably, described organic electroluminescence device includes anode, negative electrode, organic matter layer and light removing layer, organic matter layer
Comprise hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer
In at least one of which；
Described phenazene derivative is contained in described smooth removing layer.
Preferably, described smooth removing layer and hole transmission layer contain described phenazene derivative simultaneously.
The present invention also provides a kind of display device, containing described organic electroluminescence device.
The invention provides a kind of phenazene derivative, this phenazene derivative has structure shown in formula I, is greater band gap
Organic material, does not substantially absorb in visible light wave range, can simultaneously as hole mobile material and light take out materials application in
In OLED, this phenazene derivative is taken out, as light, the transmitance that layer material can improve half transmitting electrode, improve OLED
The external quantum efficiency of device it is seen that in optical range transmitance reach more than 80%；Described phenazene derivative is passed simultaneously as hole
Defeated layer and light removing layer are applied in OLED, not only increase the luminous efficiency of device moreover it is possible to effectively save cost.
Specific embodiment
With reference to specific embodiment, the invention will be further elaborated, but the present invention is not limited to following embodiment party
Formula.
Present invention firstly provides a kind of phenazene derivative, structural formula is：
Wherein, X is the aryl amine of substituted or unsubstituted C6-C60 or the condensed hetero ring of substituted or unsubstituted C6-C60.
Preferably, X is the aryl amine of substituted or unsubstituted C6-C40 or the condensed hetero ring of substituted or unsubstituted C6-C40；
Optionally, the structure of X is as follows：
It is furthermore preferred that X is the thick of the aryl amine of substituted or unsubstituted C12-C36 or substituted or unsubstituted C12-C36
Heterocycle.
Most preferably, the structure of X is as follows：
Specifically, described phenazene derivative is preferably selected from any one in structure shown in following TM1-TM26：
Present invention also offers the preparation method of described phenazene derivative, including：
Compound shown in compound shown in formula (A) and formula (B) is obtained formula through coupling reaction under nitrogen protection
(I) phenazene derivative shown in：
Wherein, X is the aryl amine of substituted or unsubstituted C6-C60 or the condensed hetero ring of substituted or unsubstituted C6-C60.
According to the present invention, the intermediate shown in formula (A) prepares according to method as follows：
In the presence of catalyst, reaction obtains the intermediate shown in formula (A) to 3,4- dibromo aniline shown in formula A-1.
The present invention has no particular limits to the reaction condition of said method, using well-known to those skilled in the art anti-
Answer condition.
According to the present invention, by the intermediate shown in formula (A) with the compound shown in formula (B) under nitrogen protection through being coupled
Reaction obtains the phenazene derivative shown in formula I, and the present invention does not have special restriction to described coupling reaction, using this area skill
Coupling reaction known to art personnel, this preparation method is simple, and raw material is easy to get.
Invention further provides application in organic electroluminescence device for the described phenazene derivative.Described has
Organic electroluminescence devices include anode, negative electrode, organic matter layer and light removing layer, and organic matter layer comprises hole injection layer, hole passes
At least one of which in defeated layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；Preferably described
Described phenazene derivative is contained, more preferably described smooth removing layer and hole transmission layer contain described fen simultaneously in light removing layer
Oxazine derivatives.
Using device architecture preferably, specially：Using transparent glass as anode；NPB or described phenazene derivative
(any one in TM1-TM26) is as hole transmission layer；TCTA adulterates as luminescent layer, or as main body with phosphor material
(mass concentration of doping is 0.5～30.0%) is as luminescent layer；TPBI is as electron transfer layer；Using Al layer as negative electrode；?
Afterwards described phenazene derivative (any one in TM1-TM26) is deposited with above-mentioned negative electrode, as light removing layer.Above-mentioned
Device employ phenazene derivative of the present invention (any one in TM1-TM26) as light removing layer or simultaneously as
Light removing layer and hole transmission layer, are significantly improved compared with traditional devices luminous efficiency：The luminous efficiency of above-mentioned device exists
Between 48cd/A～62cd/A, the luminous efficiency of traditional devices is 30cd/A.
Described organic electroluminescence device can be used for the application neck such as flat faced display, lighting source, direction board, signal lighties
Domain.
Invention still further provides a kind of display device, including described organic electroluminescence device.
More fully explain the present invention by following examples, but so as not to limit the present invention.Base in this description
On plinth, those of ordinary skill in the art are possible to real in disclosed gamut in the case of not paying creative work
Apply the present invention and preparation other compounds according to the present invention.
Embodiment 1：The preparation of intermediate A
Add 3, the 4- dibromo aniline (compound A-1) of 125g (0.5mol) in there-necked flask, add 3.5g
(0.005mol) bis-triphenylphosphipalladium palladium dichloride, 276g (1mol) Disilver carbonate, 32.2g (0.1mol) tetrabutyl ammonium bromide and
The dimethylformamide of 500ml, rouses O while stirring2, it is warming up to 100 DEG C simultaneously, react 20 minutes under this condition.To react
System pours stirring in a large amount of frozen water into, is then extracted with ethyl acetate, and organic faciess use distilled water and saturated common salt water washing successively,
With anhydrous sodium sulfate drying, filter out solid residue, last vacuum distillation removes solvent, obtain the intermediate A of 238g, yield is
96%.Mass spectrum m/z：495.88 (value of calculation：495.79).Theoretical elemental content (%) C12H4Br4N2：C,29.07；H,0.81；
Br,64.47；N,5.65.Actual measurement constituent content (%)：C,28.93；H,0.77；Br,64.36；N,5.41.The above results confirm
Acquisition product is target product.
Embodiment 2：The synthesis of compound TM1
The tetrakis triphenylphosphine palladium mixture of the intermediate A of 495mg (1mmol) and 231mg (0.2mmol) is added 10ml
Remove in the toluene of air, in N2Under protection, system is heated to 60 DEG C, stirs 5 minutes.Sequentially add 1272mg in system
(4.4mmol) triphenylamine -4- boric acid, 2.5ml remove the ethanol of air and the aqueous sodium carbonate of the 2M of 5ml removal air,
Stir 24 hours at 80 DEG C.Reaction system is poured in a large amount of water, is extracted with dichloromethane.Organic layer uses saturated aqueous common salt successively
And water washing, it is dried with anhydrous magnesium sulfate, vacuum distillation.Residual solids are through column chromatography (hexanes/ch=4:4, V/V) pure
After change, recrystallization in hexane/chloroform mixed solution, obtain the compound TM1 of 853mg (0.74mmol), yield is 74%.Matter
Spectrum m/z：1153.64 (value of calculation：1153.42).Theoretical elemental content (%) C84H60N6：C,87.47；H,5.24；N,7.29.Real
Survey constituent content (%)：C,87.35；H,5.16；N,7.16.The above results confirm that obtaining product is target product.
Embodiment 3：The synthesis of compound TM2
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- carbazole -9- base phenylboric acid, other steps are equal
Same as Example 2, obtain compound TM2.Mass spectrum m/z：1145.57 (value of calculation：1145.35).Theoretical elemental content (%)
C84H52N6：C,88.09；H,4.58；N,7.34.Actual measurement constituent content (%)：C,87.96；H,4.41；N,7.28.The above results
Confirm that obtaining product is target product.
Embodiment 4：The synthesis of compound TM3
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- [two (4- tolyl) amine] phenyl] boric acid,
Other steps are all same as Example 2, obtain compound TM3.Mass spectrum m/z：1265.69 (value of calculation：1265.63).Theoretical unit
Cellulose content (%) C92H76N6：C,87.31；H,6.05；N,6.64.Actual measurement constituent content (%)：C,87.26；H,5.98；N,
6.54.The above results confirm that obtaining product is target product.
Embodiment 5：The synthesis of compound TM4
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- [two (4- methoxyphenyl) amido] benzene boron
Acid, other steps are all same as Example 2, obtain compound TM4.Mass spectrum m/z：1392.74 (value of calculation：1392.64).Theoretical
Constituent content (%) C92H76N6O8：C,79.29；H,5.50；N,6.03；O,9.18.Actual measurement constituent content (%)：C,79.15；H,
5.36；N,5.89；O,9.04.The above results confirm that obtaining product is target product.
Embodiment 6：The synthesis of compound TM5
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar B- [4- (1,1 '-biphenyl) -4- anilino-] benzene
Boric acid, other steps are all same as Example 2, obtain compound TM5.Mass spectrum m/z：1457.94 (value of calculation：1457.80).Reason
Argument cellulose content (%) C108H76N6：C,88.98；H,5.25；N,5.76.Actual measurement constituent content (%)：C,88.85；H,5.13；
N,5.64.The above results confirm that obtaining product is target product.
Embodiment 7：The synthesis of compound TM6
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- (dibiphenylyl -4- amino) phenylboric acid, its
His step is all same as Example 2, obtains compound TM6.Mass spectrum m/z：1762.41 (value of calculation：1762.18).Theoretical elemental
Content (%) C132H92N6：C,89.97；H,5.26；N,4.77.Actual measurement constituent content (%)：C,89.92；H,5.17；N,4.66.
The above results confirm that obtaining product is target product.
Embodiment 8：The synthesis of compound TM7
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- (phenyl [1,1 ':4 ', 1 "-terphenyl] -4-
Amido) phenylboric acid, other steps are all same as Example 2, obtain compound TM7.Mass spectrum m/z：1762.32 (value of calculation：
1762.18).Theoretical elemental content (%) C132H92N6：C,89.97；H,5.26；N,4.77.Actual measurement constituent content (%)：C,
89.86；H,5.14；N,4.63.The above results confirm that obtaining product is target product.
Embodiment 9：The synthesis of compound TM8
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar B- [4- bis- (4 '-methyl biphenyl) -4- amido]
Phenylboric acid, other steps are all same as Example 2, obtain compound TM8.Mass spectrum m/z：1874.67 (value of calculation：1874.40).
Theoretical elemental content (%) C140H108N6：C,89.71；H,5.81；N,4.48.Actual measurement constituent content (%)：C,89.65；H,
5.73；N,4.31.The above results confirm that obtaining product is target product.
Embodiment 10：The synthesis of compound TM9
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar two-(4 '-pentylbiphenyl -4- base) amido benzene boron
Acid, other steps are all same as Example 2, obtain compound TM9.Mass spectrum m/z：2098.95 (value of calculation：2098.82).Theoretical
Constituent content (%) C156H140N6：C,89.27；H,6.72；N,4.00.Actual measurement constituent content (%)：C,89.15；H,6.63；N,
3.84.The above results confirm that obtaining product is target product.
Embodiment 11：The synthesis of compound TM10
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- [1,1'- biphenyl] -4- base (9,9- diformazan
Base -9H- fluorenes -2- base) amido phenylboric acid, other steps are all same as Example 2, obtain compound TM10.Mass spectrum m/z：
1922.58 (value of calculation：1922.44).Theoretical elemental content (%) C144H108N6：C,89.97；H,5.66；N,4.37.Actual measurement unit
Cellulose content (%)：C,89.85；H,5.54；N,4.31.The above results confirm that obtaining product is target product.
Embodiment 12：The synthesis of compound TM11
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- [two (9,9- dimethyl -9H- fluorenes -2- bases)
Amido] phenylboric acid, other steps are all same as Example 2, obtain compound TM11.Mass spectrum m/z：2082.78 (value of calculation：
2082.69).Theoretical elemental content (%) C156H124N6：C,89.96；H,6.00；N,4.04.Actual measurement constituent content (%)：C,
89.84；H,5.96；N,3.98.The above results confirm that obtaining product is target product.
Embodiment 13：The synthesis of compound TM12
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- (14,15- dihydro -14,14,15,15- four
Methyl -7H- two indeno [1,2-c:2 ', 1 '-g] carbazole -7- base) phenylboric acid, other steps are all same as Example 2, are changed
Compound TM12.Mass spectrum m/z：2074.77 (value of calculation：2074.63).Theoretical elemental content (%) C156H116N6：C,90.31；H,
5.64；N,4.05.Actual measurement constituent content (%)：C,90.24；H,5.58；N,4.02.The above results confirm that obtaining product is target
Product.
Embodiment 14：The synthesis of compound TM13
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- ([1,1 '-biphenyl] -4- base [1,1 '：4’
1 "-terphenyl] -4- amido) phenylboric acid, other steps are all same as Example 2, obtain compound TM13.Mass spectrum m/z：
2066.63 (value of calculation：2066.57).Theoretical elemental content (%) C156H108N6：C,90.67；H,5.27；N,4.07.Actual measurement unit
Cellulose content (%)：C,90.54；H,5.23；N,3.96.The above results confirm that obtaining product is target product.
Embodiment 15：The synthesis of compound TM14
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- [two ([1,1 ':4 ', 1 "-terphenyl] -4-
Base) amido] phenylboric acid, other steps are all same as Example 2, obtain compound TM14.Mass spectrum m/z：2370.98 (value of calculation：
2370.95).Theoretical elemental content (%) C180H124N6：C,91.18；H,5.27；N,3.54.Actual measurement constituent content (%)：C,
91.11；H,5.16；N,3.44.The above results confirm that obtaining product is target product.
Embodiment 16：The synthesis of compound TM15
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- ([1,1 '-biphenyl] -4- base [1,1 ':3’,
1 "-terphenyl] -5 '-amido) phenylboric acid, other steps are all same as Example 2, obtain compound TM15.Mass spectrum m/z：
2066.68 (value of calculation：2066.57).Theoretical elemental content (%) C156H108N6：C,90.67；H,5.27；N,4.07.Actual measurement unit
Cellulose content (%)：C,90.53；H,5.19；N,4.01.The above results confirm that obtaining product is target product.
Embodiment 17：The synthesis of compound TM16
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- [two ([1,1 ':3 ', 1 "-terphenyl] -5 ' -
Base) amido] phenylboric acid, other steps are all same as Example 2, obtain compound TM16.Mass spectrum m/z：2370.84 (value of calculation：
2370.95).Theoretical elemental content (%) C180H124N6：C,91.18；H,5.27；N,3.54.Actual measurement constituent content (%)：C,
91.06；H,5.14；N,3.33.The above results confirm that obtaining product is target product.
Embodiment 18：The synthesis of compound TM17
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- ([1,1 ':3 ', 1 "-terphenyl] -4- base
[1,1’:4 ', 1 "-terphenyl] -4- amido) phenylboric acid, other steps are all same as Example 2, obtain compound TM17.Mass spectrum
m/z：2371.41 (value of calculation：2370.95).Theoretical elemental content (%) C180H124N6：C,91.18；H,5.27；N,3.54.Real
Survey constituent content (%)：C,91.06；H,5.16；N,3.48.The above results confirm that obtaining product is target product.
Embodiment 19：The synthesis of compound TM18
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- (N- (naphthalene -1- base)-N- anilino-) benzene boron
Acid, other steps are all same as Example 2, obtain compound TM18.Mass spectrum m/z：1353.77 (value of calculation：1353.65).Reason
Argument cellulose content (%) C100H68N6：C,88.73；H,5.06；N,6.21.Actual measurement constituent content (%)：C,88.65；H,4.97；
N,6.13.The above results confirm that obtaining product is target product.
Embodiment 20：The synthesis of compound TM19
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- (N- (1- naphthyl)-N- (2- naphthyl) amido)
Phenylboric acid, other steps are all same as Example 2, obtain compound TM19.Mass spectrum m/z：1553.96 (value of calculation：
1553.88).Theoretical elemental content (%) C116H76N6：C,89.66；H,4.93；N,5.41.Actual measurement constituent content (%)：C,
89.54；H,4.83；N,5.29.The above results confirm that obtaining product is target product.
Embodiment 21：The synthesis of compound TM20
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- (2- naphthyl) anilino- phenylboric acid, other steps
Rapid all same as Example 2, obtain compound TM20.Mass spectrum m/z：1353.79 (value of calculation：1353.65).Theoretical elemental content
(%) C100H68N6：C,88.73；H,5.06；N,6.21.Actual measurement constituent content (%)：C,88.64；H,4.97；N,6.08.Above-mentioned
Result confirms that obtaining product is target product.
Embodiment 22：The synthesis of compound TM21
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar 4- (two -1- naphtyl phenyl amine bases) phenylboric acid, its
His step is all same as Example 2, obtains compound TM21.Mass spectrum m/z：1553.97 (value of calculation：1553.88).Theoretical elemental
Content (%) C116H76N6：C,89.66；H,4.93；N,5.41.Actual measurement constituent content (%)：C,89.48；H,4.87；N,5.36.
The above results confirm that obtaining product is target product.
Embodiment 23：The synthesis of compound TM22
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar [(1- naphthyl)-(4- phenylnaphthalene -1- base) amine
Base] phenylboric acid, other steps are all same as Example 2, obtain compound TM22.Mass spectrum m/z：1858.44 (value of calculation：
1858.27).Theoretical elemental content (%) C140H92N6：C,90.49；H,4.99；N,4.52.Actual measurement constituent content (%)：C,
90.35；H,4.69；N,4.37.The above results confirm that obtaining product is target product.
Embodiment 24：The synthesis of compound TM23
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar [(phenanthrene -9- base)-(4- phenylnaphthalene -1- base) amine
Base] phenylboric acid, other steps are all same as Example 2, obtain compound TM23.Mass spectrum m/z：2058.84 (value of calculation：
2058.50).Theoretical elemental content (%) C156H100N6：C,91.02；H,4.90；N,4.08.Actual measurement constituent content (%)：C,
90.87；H,4.85；N,3.95.The above results confirm that obtaining product is target product.
Embodiment 25：The synthesis of compound TM24
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar [(naphthalene -1- base)-(phenanthrene -9- base) amido] benzene boron
Acid, other steps are all same as Example 2, obtain compound TM24.Mass spectrum m/z：1754.33 (value of calculation：1754.12).Reason
Argument cellulose content (%) C132H84N6：C,90.38；H,4.83；N,4.79.Actual measurement constituent content (%)：C,90.25；H,4.74；
N,4.56.The above results confirm that obtaining product is target product.
Embodiment 26：The synthesis of compound TM25
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar two-(phenanthrene -9- base) amido phenylboric acids, other steps
Rapid all same as Example 2, obtain compound TM25.Mass spectrum m/z：1954.22 (value of calculation：1954.35).Theoretical elemental content
(%) C148H92N6：C,90.96；H,4.74；N,4.30.Actual measurement constituent content (%)：C,90.88；H,4.66；N,4.14.Above-mentioned
Result confirms that obtaining product is target product.
Embodiment 27：The synthesis of compound TM26
Triphenylamine -4- boric acid in embodiment 2 is replaced with equimolar two (4- phenyl-naphthalene -1- base) amido phenylboric acid,
Other steps are all same as Example 2, obtain compound TM26.Mass spectrum m/z：2162.77 (value of calculation：2162.65).Theoretical unit
Cellulose content (%) C164H108N6：C,91.08；H,5.03；N,3.89.Actual measurement constituent content (%)：C,90.94；H,4.95；N,
3.71.The above results confirm that obtaining product is target product.
Embodiment 28：The preparation of luminescent device 1
Selection transparent glass is anode, is dried as in vacuum chamber, is evacuated to 5 × 10-5Pa after ultrasonic cleaning,
On above-mentioned anode substrate, as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation NPB, and evaporation thickness is 60nm.In sky
In the transport layer of cave, as luminescent layer, doping content is 15wt% to vacuum evaporation TCTA/FIrpic, and evaporation rate is 0.005nm/s,
Evaporation thickness is 30nm.On luminescent layer, as electron transfer layer, evaporation rate is 0.01nm/s to vacuum evaporation TPBI, and evaporation is thick
Spend for 60nm.As negative electrode, thickness is 200nm to vacuum evaporation Al layer on the electron transport layer.Last evaporation TM2ization on negative electrode
As light removing layer, evaporation rate is 0.1nm/s to compound, and evaporation thickness is 60nm.This device blue light-emitting, luminous efficiency is
48cd/A.
Embodiment 29：The preparation of luminescent device 2
Selection transparent glass is anode, is dried as in vacuum chamber, is evacuated to 5 × 10-5Pa after ultrasonic cleaning,
On above-mentioned anode substrate, as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation NPB, and evaporation thickness is 60nm.In sky
In the transport layer of cave, as luminescent layer, doping content is 15wt% to vacuum evaporation TCTA/FIrpic, and evaporation rate is 0.005nm/s,
Evaporation thickness is 30nm.On luminescent layer, as electron transfer layer, evaporation rate is 0.01nm/s to vacuum evaporation TPBI, and evaporation is thick
Spend for 60nm.As negative electrode, thickness is 200nm to vacuum evaporation Al layer on the electron transport layer.Last evaporation TM10 on negative electrode
As light removing layer, evaporation rate is 0.1nm/s to compound, and evaporation thickness is 60nm.This device blue light-emitting, luminous efficiency is
51cd/A.
Embodiment 30：The preparation of luminescent device 3
Selection transparent glass is anode, is dried as in vacuum chamber, is evacuated to 5 × 10-5Pa after ultrasonic cleaning,
On above-mentioned anode substrate, as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation NPB, and evaporation thickness is 60nm.In sky
In the transport layer of cave, as luminescent layer, doping content is 15wt% to vacuum evaporation TCTA/FIrpic, and evaporation rate is 0.005nm/s,
Evaporation thickness is 30nm.On luminescent layer, as electron transfer layer, evaporation rate is 0.01nm/s to vacuum evaporation TPBI, and evaporation is thick
Spend for 60nm.As negative electrode, thickness is 200nm to vacuum evaporation Al layer on the electron transport layer.Last evaporation TM19 on negative electrode
As light removing layer, evaporation rate is 0.1nm/s to compound, and evaporation thickness is 60nm.This device blue light-emitting, luminous efficiency is
57cd/A.
Embodiment 31：The preparation of luminescent device 4
Selection transparent glass is anode, is dried as in vacuum chamber, is evacuated to 5 × 10-5Pa after ultrasonic cleaning,
On above-mentioned anode substrate, as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation NPB, and evaporation thickness is 60nm.In sky
In the transport layer of cave, as luminescent layer, doping content is 15wt% to vacuum evaporation TCTA/FIrpic, and evaporation rate is 0.005nm/s,
Evaporation thickness is 30nm.On luminescent layer, as electron transfer layer, evaporation rate is 0.01nm/s to vacuum evaporation TPBI, and evaporation is thick
Spend for 60nm.As negative electrode, thickness is 200nm to vacuum evaporation Al layer on the electron transport layer.Last evaporation TM25 on negative electrode
As light removing layer, evaporation rate is 0.1nm/s to compound, and evaporation thickness is 60nm.This device blue light-emitting, luminous efficiency is
54cd/A.
Embodiment 32：The preparation of luminescent device 5
Selection transparent glass is anode, is dried as in vacuum chamber, is evacuated to 5 × 10-5Pa after ultrasonic cleaning,
On above-mentioned anode substrate, as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation TM2 compound, and evaporation thickness is
60nm.On hole transmission layer, as luminescent layer, doping content is 15wt% to vacuum evaporation TCTA/FIrpic, and evaporation rate is
0.005nm/s, evaporation thickness is 30nm.On luminescent layer, as electron transfer layer, evaporation rate is vacuum evaporation TPBI
0.01nm/s, evaporation thickness is 60nm.As negative electrode, thickness is 200nm to vacuum evaporation Al layer on the electron transport layer.Finally exist
On negative electrode, as light removing layer, evaporation rate is 0.1nm/s to evaporation TM2 compound, and evaporation thickness is 60nm.This device turns blue
Light, luminous efficiency is 62cd/A.
Comparative example：The preparation of luminescent device 6
Selection transparent glass is anode, is dried as in vacuum chamber, is evacuated to 5 × 10-5Pa after ultrasonic cleaning,
On above-mentioned anode substrate, as hole transmission layer, evaporation rate is 0.1nm/s to vacuum evaporation NPB, and evaporation thickness is 60nm.In sky
In the transport layer of cave, as luminescent layer, doping content is 15wt% to vacuum evaporation TCTA/FIrpic, and evaporation rate is 0.005nm/s,
Evaporation thickness is 30nm.On luminescent layer, as electron transfer layer, evaporation rate is 0.01nm/s to vacuum evaporation TPBI, and evaporation is thick
Spend for 60nm.As negative electrode, thickness is 200nm to last vacuum evaporation Al layer on the electron transport layer.This device blue light-emitting, lights
Efficiency is 30cd/A.
| Luminescent device | Luminous efficiency (cd/A) |
| 1 | 48 |
| 2 | 51 |
| 3 | 57 |
| 4 | 54 |
| 5 | 62 |
| 6 | 30 |
Result above shows, the phenazene derivative of the present invention takes out layer material as light, is applied to organic electroluminescence
In part, luminous efficiency is high, is luminous organic material of good performance.
Obviously, the explanation of above example is only intended to help and understands the method for the present invention and its core concept.Should refer to
Go out, for the those of ordinary skill of described technical field, under the premise without departing from the principles of the invention, can also be to this
Bright carry out some improve and modify, these improve and modify also fall in the protection domain of the claims in the present invention.
Claims (9)
1. a kind of phenazene derivative is it is characterised in that structure formula (I) is as follows：
Wherein, X is the aryl amine of substituted or unsubstituted C6-C60 or the condensed hetero ring of substituted or unsubstituted C6-C60.
2. a kind of phenazene derivative according to claim 1 is it is characterised in that X is substituted or unsubstituted C6-C40
Aryl amine or the condensed hetero ring of substituted or unsubstituted C6-C40.
3. a kind of phenazene derivative according to claim 1 is it is characterised in that X is substituted or unsubstituted C12-C36
Aryl amine or the condensed hetero ring of substituted or unsubstituted C12-C36.
4. a kind of phenazene derivative according to any one of claim 1-3 is it is characterised in that described phenazene derivative is
Any one in compound TM1-TM26：
5. the preparation method of the phenazene derivative described in any one of claim 1-4 is it is characterised in that include：
Compound shown in intermediate shown in formula (A) and formula (B) is obtained formula I institute through coupling reaction under nitrogen protection
The phenazene derivative showing：
Wherein, X is the aryl amine of substituted or unsubstituted C6-C60 or the condensed hetero ring of substituted or unsubstituted C6-C60.
6. application in organic electroluminescence device for the phenazene derivative described in claim 1-4 any one.
7. application in organic electroluminescence device for the phenazene derivative according to claim 6 is it is characterised in that described
Organic electroluminescence device includes anode, negative electrode, organic matter layer and light removing layer, and organic matter layer comprises hole injection layer, hole
At least one of which in transport layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；Described light
Containing the phenazene derivative described in any one of claim 1-4 in removing layer.
8. application in organic electroluminescence device for the phenazene derivative according to claim 7 is it is characterised in that described
Light removing layer and hole transmission layer are simultaneously containing the phenazene derivative described in any one of claim 1-4.
9. a kind of display device is it is characterised in that include the organic electroluminescence device any one of claim 6-8.
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| CN111072578A (en) * | 2019-11-25 | 2020-04-28 | 武汉华星光电半导体显示技术有限公司 | P-type dopant and organic light emitting diode |
| CN111378437A (en) * | 2018-12-26 | 2020-07-07 | 创王光电股份有限公司 | Organic electroluminescent compounds and organic electroluminescent device comprising the same |
| CN113292551A (en) * | 2021-06-16 | 2021-08-24 | 吉林奥来德光电材料股份有限公司 | Capping layer material, preparation method thereof, organic electroluminescent device and display device |
| CN113801102A (en) * | 2021-10-11 | 2021-12-17 | 上海交通大学 | Phenazinyl-based compound and preparation method and application thereof |
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