CN104672244B - Compound based on carbazole derivative - Google Patents

Compound based on carbazole derivative Download PDF

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CN104672244B
CN104672244B CN201510080323.0A CN201510080323A CN104672244B CN 104672244 B CN104672244 B CN 104672244B CN 201510080323 A CN201510080323 A CN 201510080323A CN 104672244 B CN104672244 B CN 104672244B
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electroluminescence device
organic electroluminescence
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CN104672244A (en
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黄锦海
苏建华
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Shanghai Taoe Chemical Technology Co Ltd
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Abstract

The invention discloses a compound based on a carbazole derivative. The compound has a structural formula I shown in the specification. The compound based on the carbazole derivative can be used for manufacturing an organic electroluminescence device and has the characteristic of high stability.

Description

A kind of compound based on carbazole derivates
Technical field
The present invention relates to field of organic electroluminescent materials, more particularly to a kind of chemical combination based on carbazole derivates Thing.
Technical background
Organic electroluminescence device (OLEDs) is by spin coating or vacuum evaporation deposition one between two metal electrodes The device that layer organic material is prepared from, a classical three layer organic electroluminescence device include hole transmission layer, luminescent layer And electron transfer layer.By anode produce hole Jing hole transmission layers combined with the electronics Jing electron transfer layers produced by negative electrode Luminescent layer forms exciton, then lights.Organic electroluminescence device can be adjusted as desired by the material of change luminescent layer The light of the various needs of section transmitting.
Organic electroluminescence device as a kind of new Display Technique, with self-luminous, wide viewing angle, low energy consumption, efficiency High, thin, rich color, fast response time, Applicable temperature scope are wide, low driving voltage, can make flexible with it is transparent The particular advantages such as display floater and environmental friendliness, can apply on flat faced display and a new generation's illumination, it is also possible to as The backlight of LCD.
Since invention at the bottom of the eighties in 20th century, organic electroluminescence device has industrially been applied, such as Used as screens such as camera and mobile phones, but current OLED is low due to efficiency, and it is wider that the factor such as service life is short restricts which General application, particularly large screen display, it is therefore desirable to improve the efficiency of device.And just restrict one of key factor It is the performance of the electroluminescent organic material in organic electroluminescence device.Run in applied voltage additionally, due to OLED When, Joule heat can be produced so that organic material is susceptible to crystallization, have impact on life-span and the efficiency of device, therefore, it is also desirable to The electroluminescent organic material of exploitation stability and high efficiency.
Organic electrophosphorescenpolymer phenomenon, breaches theoretical restriction of the organic electroluminescent quantum efficiency less than 25%, and lifting is arrived 100% (Baldo M.A., Forrest S.R.Et al, Nature, 1998,395,151-154), its application are also greatly carried The high efficiency of organic electroluminescence device.Usually, electroluminescent phosphorescence is needed using host-guest system technology, conventional as phosphorus The CBP (4,4'-bis (9-carbazolyl)-biphenyl) of light material of main part with efficient and high triplet energy level, when its work For material of main part when, triplet energy state effectively can be transferred to object phosphorescent light-emitting materials from light emitting host material.But by In the characteristic of the hole of the CBP easily transmission difficult flowing of electronics so that the charge unbalance of luminescent layer, the effect of device is as a result reduced Rate.
The content of the invention
Present invention firstly provides a kind of compound based on carbazole derivates, which is the compound with following structure Formulas I：
Wherein L be sky, singly-bound, the substituted or unsubstituted alkyl of C1-C8, the substituted or unsubstituted aryl of C6-C30, The replacement of C3-C30 or unsubstituted heteroaryl；
Wherein X1And X2CH or N is expressed as independently；
Wherein Ar1Substituted or unsubstituted alkyl, the replacement of C6-C60 or unsubstituted aryl selected from C1-C12, The replacement of C3-C60 or unsubstituted heteroaryl, the replacement of C2-C8 or unsubstituted thiazolinyl, the replacement of C2-C8 or not Substituted alkynyl；
Wherein Ar2Selected from for following structural：
Wherein A, B, C, D, E and F are independently selected from O, S, NAr3Or CAr4Ar5；
Wherein, Ar3、Ar4And Ar5Substituted or unsubstituted alkyl separately selected from C1-C8, the alcoxyl of C1-C8 Base, the replacement of C6-C30 or unsubstituted aryl, the replacement of C3-C30 or unsubstituted heteroaryl, the replacement of C2-C8 or The unsubstituted thiazolinyl of person, the replacement of C2-C8 or unsubstituted alkynyl；
Wherein preferably mode is：
L is selected from phenyl, by the alkyl-substituted phenyl of C1-C4, naphthyl, by the alkyl-substituted naphthyls of C1-C4, xenyl or quilt The alkyl-substituted xenyls of C1-C4；
Ar1、Ar3、Ar4And Ar5Alkyl separately selected from C1-C8, the alkoxyl of C1-C8, phenyl, naphthyl, anthracene Base, phenanthryl, pyrenyl, perylenyl, fluoranthene base, (9,9- dialkyl group) fluorenyl, (bis- replacements of 9,9- or unsubstituted aryl) fluorenyl, 9, 9- is Spirofluorene-based, dibenzothiophenes base, dibenzofuran group, pyridine radicals, pyrimidine radicals, thiadiazolyl group, triazol radical, three nitrogen piperazine bases, Quinolyl, triaromatic amine base, carbazyl；
Wherein above-mentioned phenyl, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluoranthene base, (9,9- dialkyl group) fluorenyl, (9,9- Two replacements or unsubstituted aryl) fluorenyl, 9,9- Spirofluorene-based, dibenzothiophenes base, dibenzofuran group, pyridine radicals, pyrimidine Base, thiadiazolyl group, triazol radical, three nitrogen piperazine bases, quinolyl further can be taken by the aryl of the alkyl or C6-C30 of C1-C4 Generation；
Wherein described alkyl can be straight chain, side chain or be cycloalkyl；
Further preferred mode is：
L is selected from phenyl, naphthyl, xenyl；
Wherein Ar1、Ar3、Ar4And Ar5Selected from methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, n-hexyl, quilt The substituted or unsubstituted following aryl of C1-C4 alkyl and heteroaryl：
It is further preferred that compound of the compound based on carbazole derivates of the present invention for following structural 1-30：
The compound based on carbazole derivates of the present invention can pass through Suzuki coupling reactions and Buchwald- Hartwig reactions are prepared.
The compound based on carbazole derivates of the present invention can be applied in organic electroluminescence device, organic solar electricity Pond, OTFT or organophotoreceptorswith field.
Present invention also offers a kind of organic electroluminescence device, the device includes anode, negative electrode and organic layer, organic layer Comprising a layer in luminescent layer, hole injection layer, hole transmission layer, hole blocking layer, electron injecting layer or electron transfer layer or More than one layer, wherein at least one layer chemical combination based on carbazole derivates contained as described in structural formula (I) in the organic layer Thing：
Wherein X1、X2、Ar1、Ar2And L is defined as described above.
Wherein organic layer is luminescent layer；
Or organic layer is luminescent layer and electron transfer layer；
Or organic layer is luminescent layer, electron transfer layer and electron injecting layer；
Or organic layer is hole transmission layer and luminescent layer；
Or organic layer is hole injection layer, hole transmission layer and luminescent layer；
Or organic layer is hole transmission layer, luminescent layer and electron transfer layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer and electron transfer layer；
Or organic layer is hole injection layer, hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer；
Or organic layer is hole injection layer, hole transmission layer, barrier layer, luminescent layer, electron transfer layer and electron injection Layer；
Or organic layer is hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and hole blocking layer；
Or organic layer is hole transmission layer, luminescent layer, electron injecting layer and hole blocking layer；
The layer that the compound based on carbazole derivates wherein as described in structure formula (I) is located is luminescent layer；
Compound of the compound based on carbazole derivates wherein described in structure formula (I) for structural formula 1-30；
When the compound based on carbazole derivates as described in structure Formulas I is used for luminescent device preparation, can be used alone, Can also be used in mixed way with other compounds；Can be used alone based on the compound of carbazole derivates as described in structure Formulas I A kind of compound therein, it is also possible to while using two or more the compound in structure Formulas I.
The organic electroluminescence device of the present invention, further preferred mode are that the organic electroluminescence device includes sun Contain in pole, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, wherein luminescent layer The compound of one or more structure formula (I)；It is further preferred that the knot containing one or more in luminescent layer The compound of structure formula 1-30.
The luminescent layer of organic electroluminescence device contains phosphorescence light emitting guest material and the compound with structure formula (I) is made For material of main part, used as material of main part, its concentration is the 20-99.9% of entirely luminous layer weight to wherein structure formula (I) compound, It is preferred that 80-99%, more preferably 90-99%.
The gross thickness of the organic electroluminescence device organic layer of the present invention is 1-1000nm, preferred 50-500nm.
The organic electroluminescence device of the present invention when having the compound of structure Formulas I using the present invention, it is possible to use takes With other materials, such as hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and barrier layer etc., and Obtain blue and green light, gold-tinted, HONGGUANG or white light.
The hole transmission layer and hole injection layer of organic electroluminescence device of the present invention, material requested have good hole Transmission performance, effectively can be transferred to hole on luminescent layer from anode.Can include that other small molecules and macromolecule are organic Compound, including but not limited to carbazole compound, triaromatic amine compound, benzidine compound, compound of fluorene class, phthalocyanine Class compound, six cyano group, six miscellaneous triphen (hexanitrilehexaazatriphenylene), tetra- fluoro- 7,7' of 2,3,5,6-, 8, Tetra- cyanogen dimethyl-parabenzoquinones (F4-TCNQ) of 8'-, Polyvinyl carbazole, polythiophene, polyethylene or polyphenyl sulfonic acid.
The luminescent layer of the organic electroluminescence device of the present invention, with the good characteristics of luminescence, can be adjusted as needed The scope of visible ray.Except the present invention with Compounds of structural formula I as phosphorescent light body material in addition to, other phosphorescence of can also arranging in pairs or groups Material of main part, phosphorescence light emitting guest material can include at least one metal in ruthenium, copper, rhodium, silver, iridium, platinum, gold and osmium Metal-organic complex.
The Organic Electron Transport Material of organic electroluminescence device of the present invention is required with good electronic transmission performance, energy It is enough effectively electronics from cathode transport to luminescent layer in, with very big electron mobility.Following compound can be selected, but This is not limited to, oxa- oxazole, thiazole compound, triazole compound, three nitrogen piperazine class compounds, triazine class chemical combination Thing, quinoline class compound, phenodiazine anthracene compound, siliceous heterocycle compound, quinolines, ferrosin class compound, Metallo-chelate (such as Alq3), fluorine substituted benzene compound, benzimidazoles compound.
The electron injecting layer of organic electroluminescence device of the present invention, effectively can be injected into organic layer from negative electrode electronics In, alkali metal or alkali-metal compound are mainly selected from, or selected from alkaline-earth metal or the compound or alkali of alkaline-earth metal Metal complex, can select following compound, but not limited to this, it is alkali metal, alkaline-earth metal, rare earth metal, alkali-metal Oxide or halogenide, the oxide of alkaline-earth metal or halogenide, the oxide of rare earth metal or halogenide, alkali metal Or the organic complex of alkaline-earth metal；Preferably lithium, lithium fluoride, lithium oxide, lithium nitride, 8-hydroxyquinoline lithium, caesium, carbonic acid Caesium, 8-hydroxyquinoline caesium, calcium, calcium fluoride, calcium oxide, magnesium, Afluon (Asta), magnesium carbonate, magnesium oxide, these compounds individually can make With can also mixture use, it is also possible to use cooperatively with other electroluminescent organic materials.
Each layer of organic layer in the organic electroluminescence device of the present invention, can be steamed by vacuum vapour deposition, molecular beam It is prepared by the modes such as plating method, the dip coating for being dissolved in solvent, spin-coating method, stick coating method or inkjet printing.For metal motor can make It is prepared with vapour deposition method or sputtering method.
Device experimental shows, compound based on carbazole derivates of the present invention as described in structure formula (I), with preferable heat Stability, high-luminous-efficiency, high luminance purity.The organic electroluminescence made using the compound based on carbazole derivates Part has the advantages that electroluminescent efficiency is good and excitation is excellent and life-span length.
Description of the drawings
Hydrogen nuclear magnetic spectrograms of the Fig. 1 for compound 18.
Hydrogen nuclear magnetic spectrograms of the Fig. 2 for compound 19.
Fig. 3 is a kind of organic electroluminescence device structural representation of the present invention
Wherein, 110 glass substrate is represented as, 120 are represented as anode, and 130 are represented as hole injection layer, and 140 are represented as sky Cave transport layer, 150 are represented as luminescent layer, and 160 are represented as electron transfer layer, and 170 are represented as electron injecting layer, and 180 are represented as the moon Pole.
Specific embodiment
In order to describe the present invention in more detail, especially exemplified by example below, but not limited to this.
The synthesis of 1 compound 18 of embodiment
The synthesis of intermediate 18-1
3-bromobenzaldehyde (5.5g), phenanthrenequione (6g), aniline (4.5g), ammonium acetate (8g) and acetic acid are added in there-necked flask (100ml), it is heated to reflux 12 hours under nitrogen protection, cools down, add water, extracted with dichloromethane, anhydrous sodium sulfate drying is dense Contracting, crude product ethanol and recrystallize with dichloromethane, obtain product 8.5g, yield 65%.1H NMR(400MHz,CDCl3):δ 8.46-8.86 (d, J=7.6Hz, 1H), 8.76-8.78 (d, J=8.4Hz, 1H), 8.70-8.72 (d, J=8.4Hz, 1H), 7.83(s,1H),7.10‐7.77(m,13H).
The synthesis of intermediate 18-2
In single-necked flask, add compound 18-1 (4.49g, 10mmol), connection boric acid frequency to receive alcohol ester (3.0g, 12mmol), Potassium acetate (3.0g), two triphenylphosphine palladiums of dichloro (50mg), dioxane (60mL) are heated to 100 DEG C of reaction 12h, while hot mistake Silica gel, washs filter cake with dichloromethane, revolves solvent evaporated, and crude product column chromatography is purified, and obtains product 3.2g, yield 64.5%.1H NMR(400MHz,CDCl3):δ 8.88-8.90 (d, J=7.6Hz, 1H), 8.77-8.79 (d, J=8.4Hz, 1H), 8.71-8.72 (d, J=8.4Hz, 1H), 8.14 (s, 1H), 7.21-7.76 (m, 13H), 1.33 (s, 12H).
The synthesis of intermediate 18-3
Bromo- 9, the 9- dimethyl fluorenes (140g, 0.5mol) of 2-, o-chloraniline (95g, 0.75mol), uncle are added toward reaction bulb Butanol potassium (90g, 0.8mol), palladium (3.3g, 15mmol), tri-butyl phosphine tetrafluoroborate (8.7g, 30mmol) and first Benzene (1.5L), is heated to reflux 24 hours under nitrogen protection, cools down, and washing is dried, and removes toluene, and crude product is crossed column purification and obtained 90g products, yield 57%.
The synthesis of intermediate 18-4
In flask, intermediate 18-3 (40g, 0,125mol), sodium carbonate (40g, 0.38mol), palladium are added (0.5g, 2.2mmol), tricyclohexyl phosphine tetrafluoroborate (1.6g, 4.4mmol) and dimethyl acetylamide (0.5L), heat back Stream 5 hours, cooling, subtracts and partial solvent is evaporated off, and cools down, is added to the water, is extracted with ethyl acetate, and is dried, and crosses column purification and obtains 15g products, yield 43%.1H NMR(400MHz,CDCl3):δ8.38(s,1H),8.05‐8.14(m,2H),7.82‐7.84(d, J=7.6Hz, 1H), 7.23-7.45 (m, 7H), 1.55 (s, 6H).
The synthesis of intermediate 18-5
Intermediate 18-4 (10g, 35.3mmol) is added toward reaction bulb, to bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide (7.9g, 70.6mmol), palladium (0.3g, 1.3mmol), tri-butyl phosphine tetrafluoroborate (0.8g, 2.7mmol) and toluene (150mL), it is heated to reflux 24 hours under nitrogen protection, cools down, remove toluene, adds dichloromethane, washing to be dried, crude product Post is crossed, 10g products, yield 57% is obtained.
The synthesis of compound 18
In single-necked flask, intermediate 18-5 (0.6g, 1.4mmol), intermediate 18-2 (0.7g, 1.4mmol), carbon are added Sour potassium (1.38g, 10mmol), tetra-triphenylphosphine palladium (10mg), tetrahydrofuran (9mL), water (4mL) are heated to 80 DEG C of reaction 8h, Cooling, is extracted with dichloromethane, with anhydrous sodium sulfate drying, is concentrated to give crude product, obtains 0.31g products in Jing column chromatography for separation Product, yield 30%.1H NMR(400MHz,CDCl3):δ 8.91-8.93 (d, J=8.0Hz, 1H), 8.79-8.81 (d, J= 8.4Hz, 1H), 8.72-8.74 (d, J=8.4Hz, 1H), 8.46 (s, 1H), 8.20-8.22 (d, J=7.6Hz, 1H), 7.97 (s, 1H), 7.86-7.88 (d, J=7.2Hz, 1H), 7.23-7.79 (m, 24H), 1.54 (s, 6H). the proton magnetic of compound 18 Spectrogram is shown in Fig. 1.
The synthesis of 2 compound 19 of embodiment
The synthesis of intermediate 19-1
Intermediate 18-4 (10g, 35.3mmol), a bromo-iodobenzene (12g, 42mmol), potassium tert-butoxide are added toward reaction bulb (7.9g, 70.6mmol), palladium (0.3g, 1.3mmol), tri-butyl phosphine tetrafluoroborate (0.8g, 2.7mmol) and toluene (150mL), it is heated to reflux 24 hours under nitrogen protection, cools down, remove toluene, adds dichloromethane, washing to be dried, crude product Post is crossed, 11g products, yield 71% is obtained.1H NMR(400MHz,CDCl3):δ 8.43 (s, 1H), 8.18-8.20 (d, J= 7.6Hz, 1H), 7.85-7.87 (d, J=7.6Hz, 1H), 7.83-7.88 (m, 1H), 7.64-7.66 (m, 1H), 7.28-7.59 (m,9H),1.52(s,6H).
The synthesis of compound 19
Intermediate 19-1 (2.1g, 4.8mmol), intermediate 18-2 (2.4g, 4.8mmol), carbon are added in single-necked flask Sour potassium (3g), tetra-triphenylphosphine palladium (30mg), tetrahydrofuran (20mL), water (11mL) are heated to 80 DEG C of reaction 24h, and cooling is used Dichloromethane is extracted, and with anhydrous sodium sulfate drying, is concentrated to give crude product, is obtained product 1.64g, yield in Jing column chromatography for separation 47%.1H NMR(400MHz,CDCl3):δ 8.86-8.88 (d, J=7.6Hz, 1H), 8.74-8.76 (d, J=8.0Hz, 1H), 8.69-8.71 (d, J=8.4Hz, 1H), 8.51 (s, 1H), 8.26-8.28 (d, J=8.4Hz, 1H), 7.89-7.90 (d, J= 7.2Hz, 1H), 7.81-7.83 (d, J=7.6Hz, 1H), 7.01-7.76 (m, 24H). the hydrogen nuclear magnetic spectrogram of compound 19 is shown in figure 2。
Embodiment 3
The preparation of organic electroluminescence device
OLED is prepared using the compound 19 of embodiment 2
First, by electrically conducting transparent ito glass substrate 110 (above with anode 120) (the limited public affairs of South China glass group share Department) Jing successively：Deionized water, ethanol, acetone and deionized water are cleaned, then with oxygen plasma treatment 30 seconds.
Then, it is hole injection layer 130 to be deposited with the thick HAT-CN of 5nm on ITO
Then, TAPC is deposited with, forms the thick hole transmission layers 140 of 65nm.
Then, steam on hole transmission layer and cross the thick luminescent layers 150 of 10nm, wherein, compound 19 is main body luminescent material, And using Ir (ppy) 2acac of 7% weight ratio as phosphorescence doping guest materials.
Then, the thick TmPyPB of 50nm are deposited with as electron transfer layer 160 on luminescent layer.
Finally, evaporation 1nm LiF are electron injecting layer 170 and 100nm Al as device cathodes 180.
Prepared device (structural representation is shown in Fig. 3) is measured in 100mA/ with Photo Research PR650 spectrogrphs cm2Driving current under power efficiency be 21lm/W, be green spectral.
Comparative example 1
First, by electrically conducting transparent ito glass substrate 110 (above with anode 120) (the limited public affairs of South China glass group share Department) Jing successively：Deionized water, ethanol, acetone and deionized water are cleaned, then with oxygen plasma treatment 30 seconds.
Then, it is hole injection layer 130 to be deposited with the thick HAT-CN of 5nm on ITO
Then, TAPC is deposited with, forms the thick hole transmission layers 140 of 65nm.
Then, steam on hole transmission layer and cross 10nm thickness luminescent layers 150, wherein, compound CBP is main body luminescent material, And with the Ir (ppy) of 7% weight ratio2Acac is used as phosphorescence doping guest materials.
Then, the thick TmPyPB of 50nm are deposited with as electron transfer layer 160 on luminescent layer.
Finally, evaporation 1nm LiF are electron injecting layer 170 and 100nm Al as device cathodes 180.
Prepared device (structural representation is shown in Fig. 3) is measured in 100mA/ with Photo Research PR650 spectrogrphs cm2Driving current under power efficiency be 16lm/W, be green spectral.
Under identical drive-current condition, using the present invention carbazole derivates phosphorescent light body material prepare it is organic The power efficiency of electroluminescent device is higher than comparative example, as described above, the compound of the present invention has high stability, preparation Organic electroluminescence device has high efficiency and optical purity.
The structural formula of compound described in device is as follows：

Claims (4)

1. a kind of compound based on carbazole derivates, it is characterised in which is the compound with following structure Formulas I：
Wherein L is selected from xenyl or by the alkyl-substituted xenyls of C1-C4；
Wherein X1And X2CH or N is expressed as independently；
Wherein Ar1Selected from by the substituted or unsubstituted following aryl of C1-C4 alkyl：
Wherein Ar2Selected from following structural：
Wherein A, B, C, D, E and F are independently selected from O, S, NAr3Or CAr4Ar5；
Wherein, Ar3Selected from methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, n-hexyl, replaced or not by C1-C4 alkyl The following aryl for replacing：
Ar4And Ar5Methyl, ethyl, propyl group, isopropyl, the tert-butyl group, normal-butyl, n-hexyl are selected from separately.
2. the compound based on carbazole derivates according to claim 1, it is characterised in that wherein
L is selected from xenyl.
3. the compound based on carbazole derivates according to claim 1, which is the compound of following structural：
4. application of the compound described in any one of claim 1-3 based on carbazole derivates in organic electroluminescence device.
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