CN103936792B - Compound containing pyrazole structural unit - Google Patents

Compound containing pyrazole structural unit Download PDF

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CN103936792B
CN103936792B CN201310682801.6A CN201310682801A CN103936792B CN 103936792 B CN103936792 B CN 103936792B CN 201310682801 A CN201310682801 A CN 201310682801A CN 103936792 B CN103936792 B CN 103936792B
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CN103936792A (en
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曹建华
华瑞茂
郭剑
李雅敏
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石家庄诚志永华显示材料有限公司
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Abstract

The invention discloses a compound containing a pyrazole structural unit. A structural general formula of the compound is shown as a formula I. Because that an electrophosphorescent material requires good film-forming performance and a high-efficiency phosphorescence material having short phosphorescence life, by aiming at enhancement of luminescence efficiency and luminescent device performance, the invention provides a series of electrophosphorescent materials of iridium or platinum complex having pyrazole group. The compound has excellent film forming ability and high luminescence efficiency, the raw material is easily available, the compound is simple to prepare, the total yield is high, the cost of phosphorescence material is greatly reduced, and the compound has important application value.

Description

Compound containing pyrazole structural unit

Technical field

The invention belongs to ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field, is related to a kind of compound containing pyrazole structural unit.

Background technology

For organic electroluminescent(Abbreviation OLED)And the research of correlation, it has been found that first early in pope in 1963 et al. The electro optical phenomenon of machine compound monocrystal anthracene.The Kodak in the U.S. in 1987 is made with the method for evaporation organic molecule A kind of amorphous membranous type device, driving voltage is fallen below within 20V.This kind of device is due to ultra-thin, all solidstate, spontaneous Light, brightness height, visual angle width, fast response time, driving voltage is low, small power consumption, bright in luster, contrast is high, technical process is simple, The advantages of good temp characteristic, achievable soft display, flat-panel monitor and area source are can be widely applied to, therefore obtained extensively Ground is studied, develops and use.

Electroluminescent organic material is divided into two big class:Organic electroluminescent fluorescent materials and organic electromechanical phosphorescent material, wherein having Machine electroluminescent fluorescent is the result of singlet excitons Radiation-induced deactivation, different from luminescence generated by light, in Organic Light Emitting Diodes, three lines State exciton and singlet exciton are to generate simultaneously.The generation ratio of generally singlet exciton and triplet excitons is 1:3, and root Prohibit effect according to quantum taboo meter, triplet excitons mainly occur non-radiative decay, minimum to luminous contribution, only singlet swashs Sub- radioluminescence, therefore, for organic/electrostrictive polymer fluorescent device, the basic reason that luminous efficiency is difficult to improve is to send out Photoreduction process is the luminous of singlet exciton.

The content of the invention

It is an object of the invention to provide a kind of compound containing pyrazole structural unit.

The present invention provide the compound containing pyrazole structural unit, its general structure shown in formula I,

In the Formulas I, R1Aliphatic group, 2- dibenzofuran bases selected from C1-C10,2- dibenzothiophen bases, the polycyclic aromatic of C1-C50 The polycyclic aromatic base of the alkyl-substituted C1-C50 of base, C1-C10, the aromatic radical of the C1-C50 containing substituent and contain substituent Pyridine radicals in any one;

In the aromatic radical of the C1-C50 containing substituent and the pyridine radicals containing substituent, substituent is selected from fluorine Any one in atom, methyl, cyano group, trifluoromethoxy and trifluoromethyl;

M is iridium or pt atom;

X is 1,2 or 3;

When X is 1 or 2, RaFor levulinic ketone group, the levulinic ketone group containing substituent, the acetoacetyl, the 2- that replace Pyridinecarboxylic epoxide or the 2- pyridinecarboxylic epoxides containing substituent;

Wherein, in the levulinic ketone group containing substituent and the 2- pyridinecarboxylic epoxides containing substituent, substituent is selected Any one from fluorine atom, the alkyl of C1-C8, the alkoxyl of C1-C8, cyano group and trifluoromethyl;

In the substituted acetoacetyl, substituent is the alkyl-substituted aryl radicals of C1-C10;

When X is 3, RaSelected from 2- (1-R1- 1H- pyrazoles -5- bases) pyridine radicals, wherein, R1Selected from the aliphatic hydrocarbon of C1-C10 Base, 2- dibenzofuran bases, 2- dibenzothiophen bases, the polycyclic aromatic base of C1-C50, the polycyclic aromatic base of the alkyl-substituted C1-C50 of C1-C10, contain Any one in the aromatic radical and the pyridine radicals containing substituent of the C1-C50 of substituted base;

In the aromatic radical of the C1-C50 containing substituent and the pyridine radicals containing substituent, it is former that substituent is selected from fluorine Any one in son, methyl, cyano group, trifluoromethoxy and trifluoromethyl;

Specifically, the R1ForPyridine radicals, naphthyl or

Specifically, compound shown in the Formulas I be Formulas I -1a, Formulas I -1b, Formulas I -1c, Formulas I -2a, Formulas I -2b, Formulas I -2c and In compound shown in Formulas I -3 any one:

Wherein, compound shown in the Formulas I -1a is specially compound shown in DPYPT-AC:

Compound shown in the Formulas I -2a is specially compound shown in DPYIR-AC:

Compound shown in the Formulas I -2c is specially compound shown in DPYIR-PY:

Compound shown in the Formulas I -3 is specially compound shown in DPYIR-DPY:

Formulas I-the 1a, Formulas I -1b, Formulas I -1c, Formulas I -2a, Formulas I -2b, Formulas I -2c, Formulas I -3, DPYPT-AC, DPYIR- In AC, DPYIR-PY and DPYIR-DPY, R1Definition and aforementioned R1Definition it is identical;

R2It is selected from appointing in hydrogen atom, fluorine atom, the alkyl of C1-C8, the alkoxyl of C1-C8, cyano group and trifluoromethyl Meaning is a kind of;

R3It is selected from appointing in hydrogen atom, fluorine atom, the alkyl of C1-C8, the alkoxyl of C1-C8, cyano group and trifluoromethyl Meaning is a kind of;

R4It is the alkyl-substituted aryl radicals of C1-C10;

Wherein, compound shown in the DPYIR-AC is more specifically any one in following compound:

Any one in the more following compound of compound shown in the DPYPT-AC:

Compound shown in the structural formula DPYIR-PY is more specifically any one in following compound:

Compound shown in the structural formula DPYIR-DPY is more specifically any one in following compound:

Additionally, prepared by the luminescent material and compound shown in Formulas I of compound shown in the Formulas I provided containing the invention described above Application in luminescent material, falls within protection scope of the present invention.Wherein, the luminescent material is specially organic electrophosphorescenpolymer and sends out Luminescent material, more specifically organic electroluminescence orange phosphor luminescent material;The emission wavelength of the luminescent material is specially 460- 620nm, specially 594,606,610,612,616,618 or 594-618nm.

The answering in organic electroluminescence device is prepared as luminescent layer of compound shown in the Formulas I provided using the invention described above With and containing compound shown in Formulas I as the organic electroluminescence device of luminescent layer, fall within protection scope of the present invention.Its In, the organic electroluminescence device is specially organic electro-phosphorescent luminescent device, and more specifically organic electroluminescence orange phosphor is sent out Luminescent material;The emission wavelength of the luminescent material is specially 460-620nm, specially 594,606,610,612,616,618 or 594-618nm。

Specifically, the organic electroluminescence device is from the bottom to top successively by transparent substrate, anode, hole injection layer, sky Cave transport layer, organic luminous layer, electron transfer layer and cathode layer composition;

Wherein, the material for constituting the transparent substrate is glass or flexible substrate;

The material for constituting the anode layer is inorganic material or organic conductive polymer;Wherein, the inorganic material is oxygen Change indium tin, zinc oxide, zinc tin oxide, gold, silver or copper;The organic conductive polymer is selected from polythiophene, polyvinylbenzenesulfonic acid At least one in sodium and polyaniline;

The material for constituting the hole injection layer is TDATA;

The structural formula of the TDATA is as follows:

The material for constituting the hole transmission layer is NPB;

The structural formula of the NPB is as follows:

The material for constituting the organic luminous layer is compound and material of main part shown in Formulas I;

Wherein, the material of main part be mCP, CBP, NATZ or

Wherein, the structural formula of mCP, CBP and NATZ is as follows:

The quality of compound shown in Formulas I for main body quality of materials 1-10%, specially 5%;

The material for constituting the electron transfer layer is Alq3, Gaq3 or BPhen;

Wherein, the structural formula of Alq3, Gaq3, BPhen and TPBi is as follows successively:

Constitute any one or any two kinds of compositions of the material of the cathode layer in following elements alloy or under State the fluoride of element:Lithium, magnesium, silver, calcium, strontium, aluminium, indium, copper, Jin Heyin.

Specifically, the thickness of the hole injection layer is 30-50nm, specially 40nm;

The thickness of the hole transmission layer is 5-15nm, specially 10nm;

The thickness of the organic luminous layer is 10-100nm, specially 50nm;

The thickness of the electron transfer layer is 10-30nm, specially 20nm;

The thickness of the cathode layer is 90-110nm, specially 100nm.

Filming performance and the high efficiency phosphorescent material with shorter phosphorescent lifetime that the present invention has been needed based on electromechanical phosphorescent material Material, while improving luminous efficiency, improves the performance of luminescent device, there is provided a series of iridium with pyrazole group or platinum complex Electroluminescent phosphorescence luminescent material.Such compound has film forming into excellent, and the features such as luminous efficiency is high, and raw material is easy to get, and makes Standby easy, overall yield is high, the cost of the phosphor material for substantially reducing, with important using value.

Specific embodiment

With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute State method and be conventional method if no special instructions.The raw material can be obtained if no special instructions from open commercial sources.

Compound shown in the Formulas I that the present invention is provided, its preparation method can be prepared by following reaction equation:

Following embodiments are as follows to the tester and method that OLED material and device carry out performance test:

OLED performance detection condition:

Brightness and chromaticity coordinate:Tested using spectrum scanner PhotoResearch PR-715;

Current density and bright voltage:Tested using digital sourcemeter Keithley2420;

Power efficiency:Tested using NEWPORT1931-C.

The following abbreviation used in embodiment:

THF tetrahydrofurans

N-BuLi positive group lithiums

DCM dichloromethane

(PinB)2Connection boric acid pinacol ester

Pd(PPh3)4Four(Triphenylphosphine)Palladium

DMF-DMA1,1- dimethoxy-N, N- dimethyl methylamine

The preparation of the compound DPYIR-AC-001 of embodiment 1

The first step:(E) preparation of -3- (dimethylamino) -1- (pyridine -2- bases) propylene -1- ketone

The 2- acetylpyridines of 12.1g are dissolved in 150ml toluene, and the DMF-DMA of the lower addition 30ml of stirring, heat temperature raising is returned Stream reaction 24 hours, is cooled to room temperature, and reduced pressure concentration is done, and adds the petroleum ether of 150ml, dispersed with stirring to filter into residue, Filter cake is washed with petroleum ether, obtains intermediate 13g, yellow crystal.

Second step:The preparation of 2- (1- (4- fluorophenyls) -1H- pyrazole-3-yls) pyridine

The 4- fluorine phenylhydrazines mixing of the CJH-1 and 3.6g of 5g, adds the ethanol of 80ml, adds back flow reaction 12 hours, cooling To room temperature, reduced pressure concentration is done, residue over silica gel column separating purification, and ethyl acetate and petroleum ether are eluted, and obtain the CJH- of 6.6g 2, red solid.

3rd step:The preparation of intermediate CJH-5

The IrCl of the CJH-2 and 1.75g of 2.4g3·3H2O is dispersed in the ethylene glycol ethyl ether of 60ml and 20ml water, in nitrogen Under protection, temperature rising reflux reacts 24 hours, is cooled to room temperature, filters, and filter cake is washed with water, is vacuum dried, and obtains the compound of 2.6g CJH-5, brown solid.

4th step:The preparation of compound DPYIR-AC-001

The acetylacetone,2,4-pentanedione of compound CJH-5 and 200mg and the natrium carbonicum calcinatum of 424mg of 1.4g are dispersed in the second of 40ml In glycol ether/acetonitrile, under nitrogen protection, temperature rising reflux reacts 24 hours, is cooled to room temperature, and reactant liquor is poured into water, Extracted with DCM, organic phase is dried, filtered, filtrate reduced in volume is done, and residue by silicagel column is isolated and purified, and obtains the chemical combination of 950mg Thing DPYIR-AC-001, brown solid.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.27-8.36(m,4H),8.11-8.13(d,2H),7.86-7.90(m, 2H),7.52-7.57(m,4H),7.22-7.28(m,4H),7.06-7.12(m,2H),5.00(s,1H),1.66(s,6H)。

(1)Vitrification point(DSC):277.98℃;

(2)UV maximum absorption wavelengths(DCM):250nm,280nm;

(3)Phosphorescent emissions wavelength(DCM):616nm.

The preparation of the compound DPYPT-AC-015 of embodiment 2

The first step:The preparation of 4- hydrazino pyridine hydrochlorides

The ethanol mixing of the 4- chloropyridine hydrochloric acid salts of 3.0g and 85% hydrazine hydrate of 20ml and 20ml, heating reflux reaction 24 hours, room temperature is cooled to, reduced pressure concentration 1/2 adds the dilution of 20ml water, organic with ethyl acetate/THF mixed solutions extraction Mutually it is dried, reduced pressure concentration is done, adds the petroleum ether of 50ml, freezing and crystallizing to filter out precipitation, obtain yellow solid into residue.

Second step:The preparation of compound CJH-2

The 4- hydrazino pyridines mixing of the compound CJH-1 and 3.1g that prepare in the embodiment 1 of 5.0g, adds the second of 80ml Alcohol, heating reflux reaction 12 hours is cooled to room temperature, and reduced pressure concentration is done, residue over silica gel column separating purification, ethyl acetate and Petroleum ether is eluted, and obtains the CJH-2 of 5.5g, red solid.

3rd step:The preparation of compound CJH-5

The K of the CJH-2 and 2.0g of 2.2g2PtCl4In being dispersed in the ethylene glycol ethyl ether of 60ml and 20ml water, in nitrogen protection Under, it is warming up to 80 DEG C of stirring reactions 24 hours, room temperature is cooled to, filter, filter cake is washed with water, is vacuum dried, and obtains the chemical combination of 1.8g Thing CJH-5, brown solid.

4th step:The preparation of compound DPYPT-AC-015

The acetylacetone,2,4-pentanedione of CJH-5 and 225mg and the natrium carbonicum calcinatum of 470mg for taking 1.0g is dispersed in the ethylene glycol of 40ml In ether, under nitrogen protection, 100 DEG C of intensification stirring reaction 24 hours is cooled to room temperature, filters, and filter cake is washed with water, then is used DCM dissolves, and filters, and filtrate is dried, and filters, and filtrate reduced in volume is done, and obtains the compound DPYPT-AC-015 of 850mg, and redness is solid Body.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.31-8.36(m,3H),8.15-8.18(m,2H),7.82-7.86(m, 2H),7.51-7.56(m,2H),5.00(s,1H),1.68(s,6H)。

(1)Vitrification point(DSC):279.18℃;

(2)UV maximum absorption wavelengths(DCM):250nm,285nm,295nm;

(3)Phosphorescent emissions wavelength(DCM):612nm.

The preparation of the compound DPYIR-DPY-001 of embodiment 3

The second step of DPYIR-AC-001 and 480mg embodiments 1 of 768mg prepares gained compound CJH-2, sweet with 20ml Oily dispersed with stirring, under nitrogen protection, is warming up to 180 DEG C, and stirring reaction 8 hours is cooled to room temperature, and reactant liquor is poured into In the 1N watery hydrochloric acid of 100ml, suction filtration, filter cake wash with water, will obtain solid silica gel column separating purification, obtain 460mg's DPYIR-DPY-001, brown solid.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.27-8.34(m,4H),8.14-8.16(d,2H),7.87-7.90(m, 2H),7.53-7.56(m,4H),7.22-7.26(m,4H),7.06-7.10(m,2H)。

(1)Vitrification point(DSC):286.35℃;

(2)UV maximum absorption wavelengths(DCM):250nm,280nm,295nm;

(3)Phosphorescent emissions wavelength(DCM):616nm.

The preparation of the compound DPYIR-PY-001 of embodiment 4

By the 2- pyridine carboxylic acids of the step of 1.4g embodiments 1 the 3rd preparation gained CJH-5 and 707mg, the Anhydrous potassium carbonate of 324mg And Isosorbide-5-Nitrae-the dioxane of 50ml, temperature rising reflux stirring reaction 8 hours, reduced pressure concentration do, residue over silica gel post separation is pure Change, obtain the compound DPYIR-PY-001 of 1.1g, the solid of brown.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.25-8.38(m,6H),8.13-8.17(m,3H),7.81-7.89(m, 3H),7.50-7.57(m,4H),7.21-7.24(m,4H),6.92-6.95(m,2H)。

(1)Vitrification point(DSC):>300℃;

(2)UV maximum absorption wavelengths(DCM):250nm,285nm,315nm;

(3)Phosphorescent emissions wavelength(DCM):618nm.

The preparation of the compound DPYIR-AC-015 of embodiment 5

The first step:The preparation of compound CJH-5

With reference to the step of embodiment 1 the 3rd, 2- (1- (4- fluorophenyls) -1H- pyrazoles -5- bases) pyridine is replaced with into 2- (1- (pyrroles Pyridine -4- bases) -1H- pyrazoles -5- bases) pyridine, it is prepared into CJH-5, brown solid.

Second step:The preparation of compound DPYIR-AC-015

With reference to the step of embodiment 1 the 4th, CJH-5 reacts with the sodium carbonate of acetylacetone,2,4-pentanedione and excess, pure with silica gel post separation Change, obtain compound DPYIR-AC-015, the solid of brown.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.33-8.42(m,6H),8.15-8.22(m,4H),7.82-7.87(m, 4H),7.52-7.57(m,4H),5.01(s,1H),1.66(s,6H)。

(1)Vitrification point(DSC):>300℃;

(2)UV maximum absorption wavelengths(DCM):255nm,305nm,325nm;

(3)Phosphorescent emissions wavelength(DCM):610nm.

The preparation of the compound DPYIR-AC-008 of embodiment 6

With reference to embodiment 2,4- chloropyridine hydrochloric acid salts used by the first step are replaced with into 2- bromonaphthalenes and is prepared into 2- diazanyl naphthalenes, then joined According to the second to four step, synthesis obtains compound DPYIR-AC-008, the solid of brown.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.26-8.35(m,4H),8.10-8.21(m,8H),7.85-7.91(m, 4H),7.70-7.76(m,4H),7.28-7.36(m,4H),5.01(s,1H),1.64(s,6H)。

(1)Vitrification point(DSC):>300℃;

(2)UV maximum absorption wavelengths(DCM):305nm,315nm,325nm;

(3)Phosphorescent emissions wavelength(DCM):594nm.

The preparation of the compound DPYIR-PY-007 of embodiment 7

With reference to step prepare compound CJH-2 of embodiment 2 the first to two(2- (1- (naphthalene -1- bases) -1H- pyrazoles -5- bases) pyrrole Pyridine), CJH-5 is obtained with reference to the 3rd step prepare compound of embodiment 1, refer again to the synthesis of embodiment 4 and obtain compound DPYIR-PY- 007, red solid.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.31-8.39(m,6H),8.14-8.25(m,9H),7.74-7.90(m, 5H),7.74-7.85(m,4H),7.36-7.38(d,4H)。

(1)Vitrification point(DSC):>300℃;

(2)UV maximum absorption wavelengths(DCM):255nm,305nm,325nm;

(3)Phosphorescent emissions wavelength(DCM):610nm.

The preparation of the compound DPYIR-PY-008 of embodiment 8

Compound DPYIR-PY-008, red solid are obtained with reference to the synthesis of embodiment 7.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.25-8.37(m,6H),8.14-8.25(m,9H),7.79-7.89(m, 5H),7.74-7.83(m,4H),7.29-7.36(m,4H)。

(1)Vitrification point(DSC):>300℃;

(2)UV maximum absorption wavelengths(DCM):255nm,305nm,325nm;

(3)Phosphorescent emissions wavelength(DCM):612nm.

The preparation of the compound DPYIR-PY-012 of embodiment 9

Compound DPYIR-PY-012, red solid are obtained with reference to the synthesis of embodiment 7.

Experimental data:

1H NMR(CDCl3,300MHz):δ=8.34-8.47(m,5H),8.33-8.45(m,6H),8.17-8.29(m, 9H),7.75-7.83(m,4H),7.26-7.34(m,2H)。

(1)Vitrification point(DSC):>300℃;

(2)UV maximum absorption wavelengths(DCM):205nm,255nm,305nm;

(3)Phosphorescent emissions wavelength(DCM):606nm.

The preparation of the compound DPYIR-PY-015 of embodiment 10

Compound DPYIR-PY-015, red solid are obtained with reference to the synthesis of embodiment 7.

Experimental data:

1H NMR(CDCl3300MHz):δ=8.33-8.42(m7H)8.13-8.21(m5H)7.84-7.90(m 4H), 7.54-7.62(m,4H),6.95-7.14(m,3H)

(1)Vitrification point(DSC):>300℃;

(2)UV maximum absorption wavelengths(DCM):255nm,305nm,325nm;

(3)Phosphorescent emissions wavelength(DCM):610nm.

Embodiment 11 prepares device OLED-1, OLED-2, OLED-3

1)The glass substrate of ITO conductive layer will be coated with ultrasonically treated 30 minutes in cleaning agent, rushed in deionized water Wash, ultrasound 30 minutes, are baked to are completely dried under a clean environment in acetone/ethanol mixed solvent, use ultraviolet rays cleaning Machine irradiates 10 minutes, and with low energy cation beam bombarded surface.

2)The above-mentioned ito glass substrate handled well is placed in vacuum chamber, 1 × 10 is evacuated to-5~9 × 10-3Pa, Continue to be deposited with respectively compound TDATA on above-mentioned anode tunic as hole injection layer, evaporation rate is 0.1nm/s, evaporation film Thickness is 40nm;

Wherein, the structural formula of TDATA is as follows:

3)It is hole transmission layer to continue to be deposited with NPB on above-mentioned hole injection layer, and evaporation rate is 0.1nm/s, evaporation film Thickness is 10nm;

Wherein, the structural formula of NPB is as follows:

4)Continue to be deposited with compound DPYIR-AC-001 and CBP shown in a laminar I on hole transmission layer as device Organic luminous layer, the evaporation rate ratio of compound DPYIR-AC-001 and CBP is 1:100, the use of compound DPYIR-AC-001 Measure as the 5% of CBP mass, evaporation rate is 0.1nm/s, the thickness of evaporation gained organic luminous layer is 50nm;

5)Continue to be deposited with one layer of Alq3 material on organic luminous layer as the electron transfer layer of device, evaporation rate is 0.1nm/s, evaporation thickness is 20nm;

Wherein, the structural formula of Alq3 is as follows:

6)Magnesium/ag alloy layer is deposited with successively on electron transfer layer as the cathode layer of device, wherein magnesium/ag alloy layer Evaporation rate be 2.0~3.0nm/s, evaporation thickness be 100nm, magnesium and silver mass ratio be 1:9, present invention offer is provided Device OLED-1.

According to upper identical step, only by step 4)DPYIR-AC-001 used replaces with DPYIR-AC-008, obtains The OLED-2 that the present invention is provided;

According to upper identical step, only by step 4)DPYIR-AC-001 used replaces with DPYIR-AC-015, obtains The OLED-3 that the present invention is provided.

The performance test results of obtained device OLED-1 to OLED-3 are as shown in table 1.

The performance test results of table 1, OLED-1 to OLED-3

From the foregoing, it will be observed that the organic luminescent device shown in 5% Formulas I of doping obtained by compound, current density is higher, power efficiency More it is up to be close to 10cd/A, and it is photochromic for darkorange or peony.

Embodiment 12 prepares device OLED-4~OLED-8

Prepared by the method according to embodiment 11, DPYIR-AC-001 is only replaced with successively DPYIR-PY-001, DPYIR- PY-007, DPYIR-PY-008, DPYIR-PY-012, DPYIR-PY-015, obtain device OLED-4~OLED-8.

The performance of device refers to table 2:

The performance test results of table 2, OLED-4 to OLED-8

From the foregoing, it will be observed that the organic luminescent device shown in 5% Formulas I of doping obtained by compound, current density is higher, power efficiency More it is up to be close to 10cd/A, and photochromic is purer redness.

Although describing the present invention with reference to preferred embodiment, above-described embodiment is the invention is not limited in, should Work as understanding, under the guiding of present inventive concept, those skilled in the art can carry out various modifications and improvements, and claims are general The scope of the present invention is included.

Claims (18)

1. any one in following compound:
2. any one in following compound:
3. containing the luminescent material of the arbitrary compound of claim 1-2.
4. luminescent material according to claim 3, it is characterised in that:The luminescent material is the luminous material of organic electrophosphorescenpolymer Material;
The emission wavelength of the luminescent material is 460-620nm.
5. application of the arbitrary compound of claim 1-2 in luminescent material is prepared.
6. application according to claim 5, it is characterised in that:The luminescent material is organic electroluminescent phosphorescence luminescent material;
The emission wavelength of the luminescent material is 460-620nm.
7. application of the arbitrary compound of claim 1-2 as luminescent layer in organic electroluminescence device is prepared.
8. application according to claim 7, it is characterised in that:The organic electroluminescence device is sent out for organic electrophosphorescenpolymer Optical device.
9. application according to claim 8, it is characterised in that:The organic electroluminescence device is from the bottom to top successively by saturating Bright substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer composition;
Wherein, the material for constituting the transparent substrate is glass or flexible substrate;
The material for constituting the anode layer is inorganic material or organic conductive polymer;Wherein, the inorganic material is indium oxide Tin, zinc oxide, zinc tin oxide, gold, silver or copper;The organic conductive polymer selected from polythiophene, polyvinylbenzenesulfonic acid sodium and At least one in polyaniline;
The material for constituting the hole injection layer is TDATA;
The structural formula of the TDATA is as follows:
The material for constituting the hole transmission layer is NPB;
The structural formula of the NPB is as follows:
The material for constituting the organic luminous layer is the arbitrary compound of claim 1-2 and material of main part;
Wherein, the material of main part be mCP, CBP, NATZ or
Wherein, the structural formula of mCP, CBP and NATZ is as follows:
The quality of the arbitrary Compound Compound of claim 1-2 is the 1-10% of main body quality of materials;
The material for constituting the electron transfer layer is Alq3, Gaq3 or BPhen;
Wherein, the structural formula of Alq3, Gaq3, BPhen is as follows successively:
Constitute alloys or following units of any one or any two kinds of compositions of the material of the cathode layer in following elements The fluoride of element:Lithium, magnesium, calcium, strontium, aluminium, indium, copper, Jin Heyin.
10. application according to claim 9, it is characterised in that:Based on the quality of the arbitrary compound of claim 1-2 The 5% of body quality of materials.
11. applications according to claim 9, it is characterised in that:
The thickness of the hole injection layer is 30-50nm;
The thickness of the hole transmission layer is 5-15nm;
The thickness of the organic luminous layer is 10-100nm;
The thickness of the electron transfer layer is 10-30nm;
The thickness of the cathode layer is 90-110nm.
12. applications according to claim 11, it is characterised in that:The thickness of the hole injection layer is 40nm;
The thickness of the hole transmission layer is 10nm;
The thickness of the organic luminous layer is 50nm;
The thickness of the electron transfer layer is 20nm;
The thickness of the cathode layer is 100nm.
13. containing the arbitrary compound of claim 1-2 as luminescent layer organic electroluminescence device.
14. devices according to claim 13, it is characterised in that:The organic electroluminescence device is organic electrophosphorescenpolymer Luminescent device.
15. devices according to claim 14, it is characterised in that:The organic electroluminescence device from the bottom to top successively by Transparent substrate, anode, hole injection layer, hole transmission layer, organic luminous layer, electron transfer layer and cathode layer composition;
Wherein, the material for constituting the transparent substrate is glass or flexible substrate;
The material for constituting the anode layer is inorganic material or organic conductive polymer;Wherein, the inorganic material is indium oxide Tin, zinc oxide, zinc tin oxide, gold, silver or copper;The organic conductive polymer selected from polythiophene, polyvinylbenzenesulfonic acid sodium and At least one in polyaniline;
The material for constituting the hole injection layer is TDATA;
The structural formula of the TDATA is as follows:
The material for constituting the hole transmission layer is NPB;
The structural formula of the NPB is as follows:
The material for constituting the organic luminous layer is the arbitrary compound of claim 1-2 and material of main part;
Wherein, the material of main part be mCP, CBP, NATZ or
Wherein, the structural formula of mCP, CBP and NATZ is as follows:
The quality of the arbitrary compound of claim 1-2 is the 1-10% of main body quality of materials;
The material for constituting the electron transfer layer is Alq3, Gaq3 or BPhen;
Wherein, the structural formula of Alq3, Gaq3, BPhen is as follows successively:
Constitute alloys or following units of any one or any two kinds of compositions of the material of the cathode layer in following elements The fluoride of element:Lithium, magnesium, calcium, strontium, aluminium, indium, copper, Jin Heyin.
16. devices according to claim 15, it is characterised in that:The quality of the arbitrary compound of claim 1-2 is The 5% of material of main part quality.
17. devices according to claim 15, it is characterised in that:
The thickness of the hole injection layer is 30-50nm;
The thickness of the hole transmission layer is 5-15nm;
The thickness of the organic luminous layer is 10-100nm;
The thickness of the electron transfer layer is 10-30nm;
The thickness of the cathode layer is 90-110nm.
18. devices according to claim 17, it is characterised in that:The thickness of the hole injection layer is 40nm;
The thickness of the hole transmission layer is 10nm;
The thickness of the organic luminous layer is 50nm;
The thickness of the electron transfer layer is 20nm;
The thickness of the cathode layer is 100nm.
CN201310682801.6A 2013-12-12 2013-12-12 Compound containing pyrazole structural unit CN103936792B (en)

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CN1517427A (en) * 2002-12-28 2004-08-04 三星Sdi株式会社 Compound with red light and organic electroluminescence device using the compound
CN1705730A (en) * 2001-11-07 2005-12-07 E·I·内穆尔杜邦公司 Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds
US20060263635A1 (en) * 2005-05-06 2006-11-23 Fuji Photo Film Co., Ltd. Organic electroluminescent device

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5742581B2 (en) * 2011-08-16 2015-07-01 コニカミノルタ株式会社 Organic electroluminescence element, display device, lighting device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1449640A (en) * 2000-06-30 2003-10-15 纳幕尔杜邦公司 Electroluminescent iridium compounds with fluorinated phenylpyridines, phenylpyrimidines, and phenylquinolines and devices made with such
CN1705730A (en) * 2001-11-07 2005-12-07 E·I·内穆尔杜邦公司 Electroluminescent iridium compounds having red-orange or red emission and devices made with such compounds
CN1517427A (en) * 2002-12-28 2004-08-04 三星Sdi株式会社 Compound with red light and organic electroluminescence device using the compound
US20060263635A1 (en) * 2005-05-06 2006-11-23 Fuji Photo Film Co., Ltd. Organic electroluminescent device

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