CN106699780A - Aromatic amine derivative as well as preparation method and application thereof - Google Patents
Aromatic amine derivative as well as preparation method and application thereof Download PDFInfo
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- 0 *C(c(nccc1)c1Br)=O Chemical compound *C(c(nccc1)c1Br)=O 0.000 description 5
- ICHBEMJRNBQZRQ-UHFFFAOYSA-N Bc1ccccn1 Chemical compound Bc1ccccn1 ICHBEMJRNBQZRQ-UHFFFAOYSA-N 0.000 description 1
- QBJZZZRKQOJYOM-UHFFFAOYSA-N Clc(c1c2cccn1)c(cccn1)c1c2[Ar] Chemical compound Clc(c1c2cccn1)c(cccn1)c1c2[Ar] QBJZZZRKQOJYOM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides an aromatic amine derivative as well as a preparation method and application thereof, and relates to the technical field of organic photoelectric materials. By introducing a fluorenylidene, subindenofluorene or spirobifluorene structure, the conjugation degree of a system is improved, and the thermal stability of the aromatic amine derivative obtained by the invention is enabled to be high; the aromatic amine derivative can be used for producing an organic electroluminescence device, particularly can serves as a hole-transport material in the organic electroluminescence device and shows the advantages of high luminous efficiency and long service life; the organic electroluminescence device produced by using the aromatic amine derivatives is superior to a common OLED (Organic Light Emitting Diode) device. The invention also provides the preparation method of the aromatic amine derivatives, which is simple; raw materials are easy to obtain.
Description
Technical field
The present invention relates to organic photoelectrical material technical field, and in particular to a kind of aromatic amine analog derivative and its preparation side
Method and application.
Background technology
The history of electroluminescent organic molecule can trace back to early 1960s.However, Organic Light Emitting Diode
The important breakthrough of (organic light-emitting diodes, OLEDs) research be Kodak in 1987 Deng Qingyun and
Steve VanSlyke et al. have invented a research group of vacuum vapour deposition and nineteen ninety Cambridge University, and to solve conjugation poly-
The problems of dissolution of compound.Research based on forefathers, is produced by in-depth study and development are first commercial based on OLED display
Product are produced at the end of the nineties.Organic electroluminescence device with energy-conservation, fast response time, colour stable, environment due to fitting
The features such as Ying Xingqiang, radiationless, light weight, thickness of thin so that its application market is quite varied.
What the generation of organic electroluminescent was leaned on is the weight of the carrier (electronics and hole) transmitted in organic electroluminescence material
Group.It is well known that the electric conductivity of organic material is very poor, and there is no what is continued unlike inorganic semiconductor, in organic semiconductor
Can band, the transmission of carrier conventional jump theory is described, i.e., under the driving of an electric field, electronics is being excited or is being injected into point
In the lumo energy of son, the purpose of electric charge transmission is reached via the lumo energy for jumping to another molecule.
With developing rapidly for photoelectric communication in recent years and MultiMedia Field, organic optoelectronic material has turned into modern society
The core of information and electronic industry.But, the research in the field still has some key issues not solved really, the device longevity
Order short, luminous efficiency low as its wide variety of bottleneck of restriction.
The content of the invention
It is an object of the invention to provide a kind of aromatic amine analog derivative and its preparation method and application, what the present invention was provided
Organic compound thermal stability is high, preparation method simple, the organic luminescent device being made up of the compound, shows luminous effect
Rate is high, the advantage of long lifespan, is the luminous organic material of function admirable.
Present invention firstly provides a kind of aromatic amine analog derivative, structural formula is：
Wherein, Ar be selected from the substituted or unsubstituted aryl of C6~C50, the substituted or unsubstituted condensed ring of C10~C30,
One kind in the substituted or unsubstituted condensed hetero ring of C8~C30；R be selected from the substituted or unsubstituted aryl of C6~C50, C10~
In the substituted or unsubstituted condensed ring of C30, the substituted or unsubstituted condensed hetero ring of C8~C30, the aromatic series amino of C6~C30
It is a kind of.
Preferably, the Ar be selected from the substituted or unsubstituted aryl of C6~C30, C10~C30 it is substituted or unsubstituted
Condensed ring；R is selected from the substituted or unsubstituted aryl of C6~C50, the substituted or unsubstituted condensed ring of C10~C30, C6~C30
One kind in aromatic series amino.
Preferably, the Ar is selected from fluorenylidene, sub- indeno fluorenyl or the fluorenyl of spiral shell two.
Preferably, the R be selected from phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, xenyl, terphenyl, indenyl, pyrrole radicals,
Pyridine radicals, thienyl, furyl, indyl, quinolyl, imidazole radicals, thiazolyl, oxazolyl, fluorenylidene, sub- indeno fluorenyl or spiral shell
Two fluorenyls.
Preferably, the aromatic amine analog derivative is selected from any one in structure shown in following TM1~TM16：
The present invention also provides a kind of preparation method of aromatic amine analog derivative, and syntheti c route is as follows：
Wherein, Ar be selected from the substituted or unsubstituted aryl of C6~C50, the substituted or unsubstituted condensed ring of C10~C30,
One kind in the substituted or unsubstituted condensed hetero ring of C8~C30；R be selected from the substituted or unsubstituted aryl of C6~C50, C10~
In the substituted or unsubstituted condensed ring of C30, the substituted or unsubstituted condensed hetero ring of C8~C30, the aromatic series amino of C6~C30
It is a kind of.
The present invention also provides application of the aromatic amine analog derivative in organic electroluminescence device.
Preferably, the organic electroluminescence device includes anode, negative electrode and organic matter layer, contains in the organic matter layer
Aromatic amine analog derivative described in any one.
Preferably, the aromatic amine analog derivative is used to prepare the hole transmission layer of organic electroluminescence device.
Beneficial effects of the present invention:
Present invention firstly provides a kind of aromatic amine analog derivative, the aromatic amine analog derivative has structure shown in formula I,
By introducing fluorenylidene, sub- indeno fluorenyl or the fluorenyl structure of spiral shell two, the conjugated degree of system is increased, obtained by making the present invention
Aromatic amine analog derivative thermal stability is high, can be used to prepare organic electroluminescence device, especially as organic electroluminescence hair
Hole mobile material in optical device, shows that luminous efficiency is high, long lifespan advantage, better than existing conventional OLED.This
Invention also provides a kind of preparation method of aromatic amine analog derivative, and the preparation method is simple, raw material is easy to get, and disclosure satisfy that industry
The need for changing development.Aromatic amine analog derivative of the present invention has good application effect in OLED luminescent devices, with good
Good industrialization prospect.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Present invention firstly provides a kind of aromatic amine analog derivative, structural formula is：
Wherein, Ar be selected from the substituted or unsubstituted aryl of C6~C50, the substituted or unsubstituted condensed ring of C10~C30,
One kind in the substituted or unsubstituted condensed hetero ring of C8~C30；R be selected from the substituted or unsubstituted aryl of C6~C50, C10~
In the substituted or unsubstituted condensed ring of C30, the substituted or unsubstituted condensed hetero ring of C8~C30, the aromatic series amino of C6~C30
It is a kind of.
Preferably Ar is selected from substituted or unsubstituted aryl, the substituted or unsubstituted condensed ring of C10~C30 of C6~C30；
R is selected from substituted or unsubstituted aryl, the substituted or unsubstituted condensed ring of C10~C30, the aromatic series of C6~C30 of C6~C50
One kind in amino.
According to the present invention, in described substituted aryl, the condensed ring of substitution, the condensed hetero ring of substitution, replace the choosing of base independence
From alkyl, alkoxy, amino, halogen, cyano group, nitro, hydroxyl or sulfydryl.
Further preferably Ar is selected from fluorenylidene, sub- indeno fluorenyl or the fluorenyl of spiral shell two.
Most preferably R1Phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, xenyl, terphenyl, indenyl, pyrroles are selected from selected from R
Base, pyridine radicals, thienyl, furyl, indyl, quinolyl, imidazole radicals, thiazolyl, oxazolyl, fluorenylidene, sub- indeno fluorenyl
Or the fluorenyl of spiral shell two.
Specifically, the aromatic amine analog derivative is preferably selected from any one in structure shown in following TM1~TM16：
The present invention also provides a kind of preparation method of aromatic amine analog derivative, and syntheti c route is as follows：
Wherein, Ar be selected from the substituted or unsubstituted aryl of C6~C50, the substituted or unsubstituted condensed ring of C10~C30,
One kind in the substituted or unsubstituted condensed hetero ring of C8~C30；R be selected from the substituted or unsubstituted aryl of C6~C50, C10~
In the substituted or unsubstituted condensed ring of C30, the substituted or unsubstituted condensed hetero ring of C8~C30, the aromatic series amino of C6~C30
It is a kind of.
According to the present invention, the compound shown in intermediate A is prepared according to method as follows：
Under nitrogen protection, halides obtain intermediate A with triisopropyl borate ester reaction.
According to the present invention, the compound shown in intermediate C is prepared according to method as follows：
Substrate departs from via coupling reaction, methoxyl group and the displacement reaction of ketone group obtains intermediate B.Under nitrogen protection,
Tetra-triphenylphosphine palladium is catalyst, and in the case that potassium carbonate is alkali, intermediate B is obtained with boronic acid compounds through Suzuki coupling reactions
To intermediate C.
According to the present invention, the compound shown in target product is prepared according to method as follows：
Under nitrogen protection, triphenylphosphine palladium is catalyst, and in the case that potassium carbonate is alkali, intermediate C is passed through with intermediate A
Target product is obtained by Suzuki coupling reactions.
According to the present invention, compound and synthesis target product shown in synthetic intermediate C are to pass through under nitrogen protection
Coupling reaction is obtained, and the present invention does not have special limitation to the coupling reaction, using idol well-known to those skilled in the art
Connection reaction, the preparation method is simple, and raw material is easy to get.
The present invention also provides application of the aromatic amine analog derivative in organic electroluminescence device, virtue of the invention
Fragrant race's amine derivant can be applied as hole mobile material in terms of organic electroluminescence device, the organic electroluminescence
Luminescent device include anode, negative electrode and organic matter layer, organic matter layer comprising hole injection layer, hole transmission layer, electronic barrier layer,
At least one of which in luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；At least one of which in the organic matter layer
Contain aromatic amine analog derivative described above.The aromatic amine analog derivative can specifically be sent out as organic electroluminescence is prepared
The hole transmission layer of optical device.The device architecture of use is preferably specially：BH1 and BD1 is used as luminescent layer material, and Alq3 is used as electricity
Sub- transport materials, described aromatic amine analog derivative is used as hole transmission layer material, is used to manufacture construction same as below
Organic luminescent device：Aromatic amine analog derivative/BH1 described in ITO/:BD1/Alq3/LiF/Al.The organic electroluminescent
Device can be used for the application fields such as flat-panel monitor, lighting source, direction board, signal lamp.
The present invention has no particular limits to the raw material employed in following examples, can be for commercially available prod or using this
Preparation method known to art personnel is prepared.
Embodiment A：
(A1)：The preparation of intermediate A 1
Take bromo- 9, the 9- dimethyl fluorenes (14.8g, 42.4mmol) of 2,7- bis- to be added in there-necked flask, add THF100mL, nitrogen
Gas shielded, -78 DEG C are stirred 30 minutes, are subsequently adding n-BuLi (2.5M) 21mL, are reacted 1 hour, add the isopropyl of boric acid three
Ester 14g, low-temp reaction 1 hour, gradually recovers room temperature.Last handling process, adds 2M hydrochloric acid to make solution pH value for 4-5 in system,
A point liquid is stood, aqueous layer with ethyl acetate extraction merges organic layer, is spin-dried for, and obtains intermediate A 1 (9.5g, yield 80%).
Mass spectrum m/z：282.16 (calculated values：282.12).Theoretical elemental content (%) C15H16B2O4：C,63.91；H,
5.72；B,7.67；O, 22.70 actual measurements constituent content (%)：C,63.91；H,5.71；B,7.68；O,22.70.The above results are demonstrate,proved
The real product that obtains is target product.
(A2)：The preparation of intermediate A 2
The bromo- 9,9- dimethyl fluorenes of 2,7- bis- in embodiment A1 are replaced with into the bromo- 9,9- diphenyl of equimolar 2,7- bis-
Fluorenes, other steps are identical with embodiment A1, obtain intermediate A 2.Mass spectrum m/z：406.16 (calculated values：406.15).Theoretical unit
Cellulose content (%) C25H20B2O4：C,73.95；H,4.96；B,5.33；O, 15.76 actual measurements constituent content (%)：C,73.94；H,
4.96；B,5.33；O,15.77.The above results confirm that it is target product to obtain product.
(A3)：The preparation of intermediate A 3
Bromo- 9, the 9- dimethyl fluorenes of 2,7- bis- in embodiment A1 are replaced with into the bromo- fluorenes of 9,9- spiral shells two of equimolar 2,7- bis-,
Other steps are identical with embodiment A1, obtain intermediate A 3.Mass spectrum m/z：404.16 (calculated values：404.14).Theoretical elemental
Content (%) C25H18B2O4：C,74.32；H,4.49；B,5.35；O, 15.84 actual measurements constituent content (%)：C,74.32；H,
4.48；B,5.36；O,15.84.The above results confirm that it is target product to obtain product.
(A4)：The preparation of intermediate A 4
The bromo- 9,9- dimethyl fluorenes of 2,7- bis- in embodiment A1 are replaced with into the bromo- 6,6,12,12- of equimolar 2,8- bis-
Tetramethyl indeno [1,2-b] fluorenes, other steps are identical with embodiment A1, obtain intermediate A 4.Mass spectrum m/z：398.16 (calculate
Value：398.19).Theoretical elemental content (%) C24H24B2O4：C,72.41；H,6.08；B,5.43；O, 16.08 actual measurement constituent contents
(%)：C,72.42；H,6.07；B,5.44；O,16.08.The above results confirm that it is target product to obtain product.
Embodiment B：
The preparation of intermediate B
3- pyridine boronic acids (0.1mol) are dissolved in 300mL absolute ethers, -78 DEG C of the dry ice bath, in the condition of starvation
Under, the butyl lithium (2.5M) of 44mL is added, stirring reaction 1 hour adds the bromo- pyridine carboxylic acid methyl esters (0.1mol) of 2-, reaction 2
Hour, after be gradually raised to 15~25 DEG C, add water terminating reaction.A point liquid, branch vibration layer, water layer acetic acid are carried out to product
Ethyl ester is extracted, and merges organic phase, is spin-dried for organic solvent, and white solid B-1 (yield 51%) is obtained by silica gel column chromatography.
B-1 (41.5mmol) is dissolved in the tetrahydrofuran of 300mL, 0 DEG C is cooled to, mixed liquor LTMP (LTMP are added
As the tetrahydrofuran of 500mL dissolves the 2,2,6,6- tetramethyl piperidines of 0.13mol butyl lithiums and 0.14mol at 0 DEG C) after
Stirring reaction 2 hours at 0 DEG C.200mL water terminating reactions are added, be spin-dried for for organic layer by branch vibration layer, and column chromatography obtains solid B-2
(yield 54%).
Accurately weigh B-2 (10g, 47.8mmol) to be added in reaction bulb, add 200mL acetonitriles, then weigh 30g trichlorine oxygen
Phosphorus is slowly dropped in reaction bulb, and slow after completion of dropping to be warmed up to 60 DEG C, the reaction time is 5 hours.After completion of the reaction, add
Water carefully go out by extraction, then places substantial amounts of saturated solution of sodium carbonate tune pH value to 7-8, adds dichloromethane, extracts three times, is spin-dried for
Obtain solid and be intermediate B (7.5g, yield 63%).
Mass spectrum m/z：247.97 (calculated values：247.99).Theoretical elemental content (%) C12H6Cl2N2：C,57.86；H,
2.43；Br,28.47；N, 11.25 actual measurements constituent content (%)：C,57.85；H,2.43；Br,28.48；N,11.24.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
Embodiment C：
(C1) preparation of intermediate C1
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to phenyl boric acid
The solution of (22.3g, 183mmol) and intermediate B (45.8g, 185mmol) in degassing tetrahydrofuran (500mL), and should
Mixture is heated 4 hours under reflux.The reactant mixture is cooled to room temperature, rotation afterwards removes solvent.Via silica gel column chromatography
Obtain intermediate C1 (49.5g, theoretical value 70%).
Mass spectrum m/z：290.05 (calculated values：290.06).Theoretical elemental content (%) C18H11ClN2：C,74.36；H,
3.81；Cl,12.19；N, 9.63 actual measurements constituent content (%)：C,74.36；H,3.81；Cl,12.17；N,9.65.The above results
Confirm that it is target product to obtain product.
(C2) preparation of intermediate C2
Phenyl boric acid in embodiment C1 is replaced with it is equimolar to tert-butylbenzeneboronic acid, other steps with embodiment C1
It is identical, obtain intermediate C2.Mass spectrum m/z：346.13 (calculated values：346.12).Theoretical elemental content (%) C22H19ClN2：C,
76.18；H,5.52；Cl,10.22；N, 8.08 actual measurements constituent content (%)：C,76.19；H,5.52；Cl,10.22；N,8.07.
The above results confirm that it is target product to obtain product.
(C3) preparation of intermediate C3
Phenyl boric acid in embodiment C1 is replaced with into equimolar 1- naphthalene boronic acids, other steps are identical with embodiment C1,
Obtain intermediate C3.Mass spectrum m/z：340.05 (calculated values：340.08).Theoretical elemental content (%) C22H13ClN2：C,77.53；
H,3.84；Cl,10.40；N, 8.22 actual measurements constituent content (%)：C,77.51；H,3.85；Cl,10.41；N,8.23.Above-mentioned knot
Fruit confirms that it is target product to obtain product.
(C4) preparation of intermediate C4
By tri-butyl phosphine (toluene solution of the 1.0M of 3mL, 7.32mmol), palladium (0.4g, 1.83mmol) and uncle
Sodium butoxide (22.8g, 238mmol) is added to intermediate B (45.3g, 183mmol) and diphenylamines (30.9g, 183mmol) de-
Solution in gas toluene (500mL), and the mixture is heated 2 hours under reflux.The reactant mixture is cooled to room
Temperature, filters with dilution with toluene and via diatomite.By filtrate water dilution, and extracted with toluene, and merge organic phase,
It is evaporated under vacuo.The residue is filtered via silica gel, intermediate C4 (76.7g, theory is recrystallized to give
Value 80%).
Mass spectrum m/z：381.12 (calculated values：381.10).Theoretical elemental content (%) C24H16ClN3：C,75.49；H,
4.22；Cl,9.28；N, 11.00 actual measurements constituent content (%)：75.47；H,4.24；Cl,9.28；N,11.01.The above results are demonstrate,proved
The real product that obtains is target product.
Embodiment D：
(D1) synthesis of compound TM1：
Tetra-triphenylphosphine palladium (2.1g, 1.83mmol) and potassium carbonate (75.7g, 549mmol) are added to intermediate A 1
The solution of (51.6g, 183mmol) and intermediate C1 (111.4g, 384mmol) in degassing tetrahydrofuran (500mL), and will
The mixture is heated 10 hours under reflux.The reactant mixture is cooled to room temperature, rotation afterwards removes solvent.Via silica gel column layer
Analysis obtains target product TM1 (49.5g, theoretical value 65%).
Mass spectrum m/z：702.25 (calculated values：702.28).Theoretical elemental content (%) C51H34N4：C,87.15；H,4.88；
N, 7.97 actual measurements constituent content (%)：C,87.16；H,4.87；N,7.97.The above results confirm that it is target product to obtain product.
Following compound is obtained in a similar fashion：
Embodiment D2:Mass spectrum m/z：826.35 (calculated values：826.31).Theoretical elemental content (%) C61H38N4：C,
88.59；H,4.63；N, 6.77 actual measurements constituent content (%)：C,88.58；H,4.64；N,6.78.The above results confirm to be produced
Thing is target product.
Embodiment D3:Mass spectrum m/z：824.27 (calculated values：824.29).Theoretical elemental content (%) C61H36N4：C,
88.81；H,4.40；N, 6.79 actual measurements constituent content (%)：C,88.81；H,4.41；N,6.78.The above results confirm to be produced
Thing is target product.
Embodiment D4:Mass spectrum m/z：818.35 (calculated values：818.34).Theoretical elemental content (%) C60H42N4：C,
87.99；H,5.17；N, 6.84 actual measurements constituent content (%)：C,87.97；H,5.18；N,6.85.The above results confirm to be produced
Thing is target product.
Embodiment D5:Mass spectrum m/z：814.43 (calculated values：814.40).Theoretical elemental content (%) C59H50N4：C,
86.94；H,6.18；N, 6.87 actual measurements constituent content (%)：C,86.96；H,6.17；N,6.87.The above results confirm to be produced
Thing is target product.
Embodiment D6:Mass spectrum m/z：938.45 (calculated values：938.43).Theoretical elemental content (%) C69H54N4：C,
88.24；H,5.80；N, 5.97 actual measurements constituent content (%)：C,88.24；H,5.82；N,5.96.The above results confirm to be produced
Thing is target product.
Embodiment D7:Mass spectrum m/z：936.40 (calculated values：936.42).Theoretical elemental content (%) C69H52N4：C,
88.43；H,5.59；N, 5.98 actual measurements constituent content (%)：C,88.43；H,5.59；N,5.98.The above results confirm to be produced
Thing is target product.
Embodiment D8:Mass spectrum m/z：930.46 (calculated values：930.47).Theoretical elemental content (%) C68H58N4：C,
87.71；H,6.28；N, 6.02 actual measurements constituent content (%)：C,87.72；H,6.26；N,6.02.The above results confirm to be produced
Thing is target product.
Embodiment D9:Mass spectrum m/z：802.35 (calculated values：802.31).Theoretical elemental content (%) C59H38N4：C,
88.25；H,4.77；N, 6.98 actual measurements constituent content (%)：C,88.24；H,4.77；N,6.99.The above results confirm to be produced
Thing is target product.
Embodiment D10:Mass spectrum m/z：926.33 (calculated values：926.34).Theoretical elemental content (%) C69H42N4：C,
89.39；H,4.57；N, 6.04 actual measurements constituent content (%)：C,89.38；H,4.56；N,6.06.The above results confirm to be produced
Thing is target product.
Embodiment D11:Mass spectrum m/z：924.35 (calculated values：924.33).Theoretical elemental content (%) C69H40N4：C,
89.59；H,4.36；N, 6.06 actual measurements constituent content (%)：C,89.58；H,4.36；N,6.06.The above results confirm to be produced
Thing is target product.
Embodiment D12:Mass spectrum m/z：918.35 (calculated values：918.37).Theoretical elemental content (%) C68H46N4：C,
88.86；H,5.04；N, 6.10 actual measurements constituent content (%)：C,88.85；H,5.03；N,6.12.The above results confirm to be produced
Thing is target product.
Embodiment D13:Mass spectrum m/z：884.35 (calculated values：884.36).Theoretical elemental content (%) C63H44N6：C,
85.49；H,5.01；N, 9.50 actual measurements constituent content (%)：C,85.47；H,5.01；N,9.52.The above results confirm to be produced
Thing is target product.
Embodiment D14:Mass spectrum m/z：1008.37 (calculated values：1008.39).Theoretical elemental content (%) C73H48N6：C,
86.88；H,4.79；N, 8.33 actual measurements constituent content (%)：C,86.88；H,4.78；N,8.34.The above results confirm to be produced
Thing is target product.
Embodiment D15:Mass spectrum m/z：1006.35 (calculated values：1006.38).Theoretical elemental content (%) C73H46N6：C,
87.05；H,4.60；N, 8.34 actual measurements constituent content (%)：C,87.05；H,4.61；N,8.35.The above results confirm to be produced
Thing is target product.
Embodiment D16:Mass spectrum m/z：1000.42 (calculated values：1000.43).Theoretical elemental content (%) C72H52N6：C,
86.37；H,5.23；N, 8.39 actual measurements constituent content (%)：C,86.37；H,5.24；N,8.38.The above results confirm to be produced
Thing is target product.
Contrast Application Example：
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and is exposed 30 minutes under ultraviolet light,
Then processed 10 minutes with plasma.The ito substrate after treatment is then put into evaporated device.One layer of 30nm's of evaporation first
NPB as hole transmission layer, followed by luminescent layer evaporation, the BD1 of mixing evaporation BH1 and 5%, the then Alq3 of evaporation 30nm
As electron transfer layer, 0.5nmLiF is then deposited with again, then the metal Al of evaporation 60nm.
Application Example 1
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and is exposed 30 minutes under ultraviolet light,
Then processed 10 minutes with plasma.The ito substrate after treatment is then put into evaporated device.One layer of 30nm's of evaporation first
TM3 as hole transmission layer, followed by luminescent layer evaporation, the BD1 of mixing evaporation BH1 and 5%, the then Alq3 of evaporation 30nm
As electron transfer layer, 0.5nmLiF is then deposited with again, then the metal Al of evaporation 60nm.
Application Example 2
Change the TM3 in Application Example 1 into TM7.
Application Example 3
Change the TM3 in Application Example 1 into TM11.
Application Example 4
Change the TM3 in Application Example 1 into TM15.
OLED is produced as follows：
Contrast Application Example：ITO/NPB/BH1:BD1/Alq3/LiF/Al；
Application Example 1：ITO/TM3/BH1:BD1/Alq3/LiF/Al；
Application Example 2：ITO/TM7/BH1:BD1/Alq3/LiF/Al；
Application Example 3：ITO/TM11/BH1:BD1/Alq3/LiF/Al；
Application Example 4：ITO/TM15/BH1:BD1/Alq3/LiF/Al；
Under 1000nits, Nan dian Yao device result is as follows：
| Device | Luminous efficiency | Driving voltage | Life-span (T80) |
| Contrast Application Example | 55.2cd/A | 4.7V | 35hours |
| Application Example 1 | 62.3cd/A | 4.5V | 213hours |
| Application Example 2 | 62.1cd/A | 4.3V | 223hours |
| Application Example 3 | 62.2cd/A | 4.4V | 245hours |
| Application Example 4 | 64.2cd/A | 4.4V | 265hours |
Result above shows that aromatic amine analog derivative of the invention is applied in organic electroluminescence device, especially
As hole mobile material, show that luminous efficiency is high, long lifespan advantage, be 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 the technical field, under the premise without departing from the principles of the invention, can also be to this hair
Bright to carry out some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (9)
1. a kind of aromatic amine analog derivative, it is characterised in that structural formula is as shown in formula I：
Wherein, Ar be selected from the substituted or unsubstituted aryl of C6~C50, the substituted or unsubstituted condensed ring of C10~C30, C8~
One kind in the substituted or unsubstituted condensed hetero ring of C30；R is selected from the substituted or unsubstituted aryl of C6~C50, C10~C30
One kind in substituted or unsubstituted condensed ring, the substituted or unsubstituted condensed hetero ring of C8~C30, the aromatic series amino of C6~C30.
2. a kind of aromatic amine analog derivative according to claim 1, it is characterised in that Ar is selected from the substitution of C6~C30
Or the substituted or unsubstituted condensed ring of unsubstituted aryl, C10~C30；R be selected from C6~C50 substituted or unsubstituted aryl,
One kind in the substituted or unsubstituted condensed ring of C10~C30, the aromatic series amino of C6~C30.
3. a kind of aromatic amine analog derivative according to claim 1, it is characterised in that Ar is selected from fluorenylidene, sub- indeno
Fluorenyl or the fluorenyl of spiral shell two.
4. a kind of aromatic amine analog derivative according to claim 1, it is characterised in that R be selected from phenyl, naphthyl, anthryl,
Phenanthryl, pyrenyl, xenyl, terphenyl, indenyl, pyrrole radicals, pyridine radicals, thienyl, furyl, indyl, quinolyl, imidazoles
Base, thiazolyl, oxazolyl, fluorenylidene, sub- indeno fluorenyl or the fluorenyl of spiral shell two.
5. a kind of aromatic amine analog derivative according to claim 1, it is characterised in that the aromatic amine analog derivative
Selected from any one in structure shown in following TM1~TM16：
6. the preparation method of the aromatic amine analog derivative described in any one of claim 1-5, it is characterised in that by following road
Line synthesis obtains the analog derivative containing aromatic amine：
Wherein, Ar be selected from the substituted or unsubstituted aryl of C6~C50, the substituted or unsubstituted condensed ring of C10~C30, C8~
One kind in the substituted or unsubstituted condensed hetero ring of C30；R is selected from the substituted or unsubstituted aryl of C6~C50, C10~C30
One kind in substituted or unsubstituted condensed ring, the substituted or unsubstituted condensed hetero ring of C8~C30, the aromatic series amino of C6~C30.
7. application of the aromatic amine analog derivative described in claim 1-5 any one in organic electroluminescence device.
8. application of the aromatic amine analog derivative according to claim 7 in organic electroluminescence device, its feature exists
In the organic electroluminescence device includes anode, negative electrode and organic matter layer, and Claims 1 to 5 is contained in the organic matter layer
Aromatic amine analog derivative described in any one.
9. application of the aromatic amine analog derivative according to claim 8 in organic electroluminescence device, its feature exists
In the organic layer includes hole transmission layer, and the aromatic amine described in any one of Claims 1 to 5 is contained in hole transmission layer
Analog derivative.
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| WO2008127004A1 (en) * | 2007-04-13 | 2008-10-23 | Gracel Display Inc. | Electroluminescent compounds with high efficiency and organic light-emitting diode using the same |
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| WO2008127004A1 (en) * | 2007-04-13 | 2008-10-23 | Gracel Display Inc. | Electroluminescent compounds with high efficiency and organic light-emitting diode using the same |
| KR20130098228A (en) * | 2012-02-27 | 2013-09-04 | 주식회사 엘지화학 | Organic light emitting diode |
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