CN103848822A - 1,8-carbazole derivative, preparation method and application thereof in luminescent device - Google Patents

1,8-carbazole derivative, preparation method and application thereof in luminescent device Download PDF

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CN103848822A
CN103848822A CN201410085106.6A CN201410085106A CN103848822A CN 103848822 A CN103848822 A CN 103848822A CN 201410085106 A CN201410085106 A CN 201410085106A CN 103848822 A CN103848822 A CN 103848822A
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carbazole
carbazole derivative
butyl
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王磊
穆广园
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WUHAN SHANGSAI PHOTOELECTRIC TECHNOLOGY Co Ltd
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Abstract

The invention discloses a novel 1,8-carbazole derivative, a preparation method and an optical device of using the carbazole derivative, wherein the 1,8-carbazole derivative has the following general formula structure as shown in the secification. Eectrondrawing groups are formed at the 1st and 8th bits of the carbazole derivative, and alkyls are formed at the 3, 6 and 9 bits. Thus, synthesis of 1,8-dibasic carbazole is achieved. The generating probability of an excitor can be effectively increased by the carbazole derivative, the luminous efficiency of the device is effectively improved, and the 1,8-carbazole derivative can be widely applied to the field of organic electroluminescence.

Description

1,8-position carbazole derivative, its preparation method and the application in luminescent device thereof
Technical field
The present invention relates to organic materials and the application in organic electroluminescence device thereof, be specifically related to a kind of 1,8-position carbazole derivative, its preparation method and the application in luminescent device thereof
Background technology
The discovery of organic electrophosphorescenpolymer phenomenon, for solid basis has been established in the real industrialization of OLED illumination, large quantities of main body phosphor materials are also developed thereupon, particularly carbazoles phosphorescence main body has been brought into play irreplaceable effect (Applied Physics Letters.2008,93 (6): 063303-063305).Carbazole has higher triplet energy level and high hole mobility is widely used in blue emitting phosphor material of main part, be CBP(Chemistry of Materials.2009 for the carbazoles derivative of phosphorescent light body material the earliest, 21 (13): 2565-2567), it is applied to green glow phosphorescence luminescent layer, and maximum efficiency has reached 89cd/A.
According to electronic configuration rule, the general the position of substitution of carbazole group is two of 3,6-, its 1, two replacements of 8-are corresponding more difficult, therefore developing the carbazoles derivative that 1,8-two positions replaces provides more feasible path for the many deficiencies that make up carbazoles host compound; Because carbazole group has higher hole mobility, its electronic mobility is relatively low, for further injection and the transmission in balance electronic and hole, the group that need to introduce some electron types makes it form better bipolar phosphor material, improves phosphorescence device efficiency; In addition, the rigid structure of carbazole, in general common solvent, as methylene dichloride, normal hexane solubleness is relatively little, and because spin coating device is more cost-saving, thereby the solubleness that therefore strengthens carbazole compound is more amenable for use with solution processing device.Generally, take carbazole as core, above modify the groups of rigidity two of 3,6-, thereby improve better the thermostability of compound, as the tertiary butyl, 9-substituted fluorene class etc.; Carbazole 1, the group on two of 8-, because the existence of 9 nitrogen-atoms has certain crowding, can strengthen the rigidity of compound, improves the thermodynamic stability of compound; In addition, by carbazole 1,8-position is connected can reduce conjugation effectively, strengthen the triplet state of compound, be applied to better in blue emitting phosphor device, 9-position nitrogen-atoms connects the alkane chain of certain length, strengthens the solubleness of carbazoles derivative, the film-forming properties that improves material of main part, is applied in phosphorescence device better.
Summary of the invention
For the problems referred to above, the invention provides a kind of photoelectric property good 1,8-position carbazole derivative, its preparation method and the application in luminescent device thereof.
For achieving the above object, carbazole derivative of the present invention, has the structure shown in formula I:
Figure BDA0000474813090000021
Wherein, Ar 1and Ar 2be electron-withdrawing group independently; R 1, R 2and R 3be hydrogen or alkyl independently respectively.
Further, described electron-withdrawing group Ar 1and Ar 2there is rigid structure, R 1, R 2and R 3for the alkyl chain of hydrogen or 1-20 carbon.
Further, described Ar 1and Ar 2identical or different.
Further, described Ar 1with described Ar 2be (1a) one to (22c) group independently respectively, described (1a) is as follows to (22c) group:
Figure BDA0000474813090000031
Figure BDA0000474813090000041
Figure BDA0000474813090000051
Further, this carbazole derivative comprises
Figure 20141008510661000021
Further, described carbazole derivative is as the hole transmission layer of LED device or the material of main part of luminescent layer.
For achieving the above object, the preparation method of carbazole derivative of the present invention comprises
Compound 3, the preparation of 6-di-t-butyl carbazole:
In the dry there-necked flask of 1000ml, under nitrogen protection condition, by carbazole, ZnCl 2be dissolved in Nitromethane 99Min., in whipping process, dropwise add tert-butyl chloride, after dropwising, reaction solution continues to stir at ambient temperature 4 hours, the cancellation that adds water reaction, dichloromethane extraction 3 times, separatory, organic phase anhydrous magnesium sulfate drying, filter, the solvent that evaporate to dryness is all, obtains yellow solid methylene dichloride and methanol crystallization, finally obtain white crystal 3,6-di-t-butyl carbazole;
Compound 1,8-bis-is bromo-3, the preparation of 6-di-t-butyl carbazole:
3,6-di-t-butyl carbazole is dissolved in the glacial acetic acid solution of 90 ℃, bromine is dissolved in acetic acid and dropwise adds, under nitrogen protection, isothermal reaction 3.5 hours, when solution is cooled to room temperature, reaction solution is concentrated, and filter, obtain crude product, use normal hexane recrystallization, filter to obtain white solid powder 1,8-bis-is bromo-3,6-di-t-butyl carbazole;
Compound 9-alkyl-1,8-bis-is bromo-3, the preparation of 6-di-t-butyl carbazole:
With 9-methyl isophthalic acid, 8-bis-is bromo-3, and 6-di-t-butyl carbazole is example, in the dry flask of 250ml; add successively 1,8-bis-bromo-3,6-di-t-butyl carbazole; NaH is dissolved in DMF, and after stirring at room temperature 30min, methyl iodide adds wherein; under nitrogen protection, continue reaction 18 hours, the cancellation of reaction water, reaction solution dichloromethane extraction; merge organic phase, use anhydrous magnesium sulfate drying simultaneously, filter; evaporate to dryness organic solvent, reacting coarse product is purified with quick silicagel column, finally obtains white crystal.
The present invention uses the luminescent device of carbazole derivative, comprises pair of electrodes and is arranged on the organic medium in described electrode, and described organic medium is carbazole derivative, and described carbazole derivative is the arbitrary described carbazole derivative of claim 1 to 5.
Accompanying drawing explanation
Fig. 1 is the blue-light device blue-light device energy level schematic diagram of compound 5 as material of main part doped F Irpic, and unit is eV;
Fig. 2 is the blue-light device brightness-current density-voltage response of compound 5 as material of main part doped F Irpic;
Fig. 3 compound 5 is as the blue-light device electroluminescent spectrum of material of main part doped F Irpic;
Fig. 4 is that compound 8 is as material of main part doping Ir (ppy) 3green device structure iron, shown in unit be eV;
Fig. 5 is that compound 8 is as material of main part doping Ir (ppy) 3green device brightness-current density-voltage response;
Fig. 6 is that compound 8 is as material of main part doping Ir (ppy) 3green device electroluminescent spectrum.
Embodiment
Below in conjunction with Figure of description, the present invention will be further described.
Carbazole derivative of the present invention, has the structure shown in formula I:
Wherein, Ar 1and Ar 2be electron-withdrawing group independently; R 1, R 2and R 3be hydrogen or alkyl independently respectively.
Further, described electron-withdrawing group Ar 1and Ar 2there is rigid structure, R 1, R 2and R 3for the alkyl chain of hydrogen or 1-20 carbon.
Further, described Ar 1and Ar 2identical or different.
Further, described Ar 1with described Ar 2be (1a) one to (22c) group independently respectively, described (1a) is as follows to (22c) group:
Figure BDA0000474813090000091
Figure 20141008510661000023
Figure BDA0000474813090000111
Further, this carbazole derivative comprises
Figure 20141008510661000022
Further, described carbazole derivative is as the hole transmission layer of LED device, luminescent layer, or the material of main part of luminescent layer.
The preparation method of carbazole derivative of the present invention, described method comprises
Compound 3, the preparation of 6-di-t-butyl carbazole:
In the dry there-necked flask of 1000ml, under nitrogen protection condition, by carbazole, ZnCl2 is dissolved in nitre methane, dropwise adds tert-butyl chloride, after dropwising in whipping process, reaction solution continues to stir at ambient temperature 4 hours, the cancellation that adds water reaction, dichloromethane extraction 3 times, separatory, organic phase anhydrous magnesium sulfate drying, filters, the solvent that evaporate to dryness is all, obtain yellow solid methylene dichloride and methanol crystallization, finally obtain white crystal 3,6-di-t-butyl carbazole;
Compound 1,8-bis-is bromo-3, the preparation of 6-di-t-butyl carbazole:
3,6-di-t-butyl carbazole is dissolved in the glacial acetic acid solution of 90 ℃, bromine is dissolved in acetic acid and dropwise adds, under nitrogen protection, isothermal reaction 3.5 hours, when solution is cooled to room temperature, reaction solution is concentrated, and filter, obtain crude product, use normal hexane recrystallization, filter to obtain white solid powder 1,8-bis-is bromo-3,6-di-t-butyl carbazole;
Compound 9-alkyl-1,8-bis-is bromo-3, the preparation of 6-di-t-butyl carbazole:
With 9-methyl isophthalic acid, 8-bis-is bromo-3, and 6-di-t-butyl carbazole is example, in the dry flask of 250ml; add successively 1,8-bis-bromo-3,6-di-t-butyl carbazole; NaH is dissolved in DMF, and after stirring at room temperature 30min, methyl iodide adds wherein; under nitrogen protection, continue reaction 18 hours, the cancellation of reaction water, reaction solution dichloromethane extraction; merge organic phase, use anhydrous magnesium sulfate drying simultaneously, filter; evaporate to dryness organic solvent, reacting coarse product is purified with quick silicagel column, finally obtains white crystal.
The present invention uses the luminescent device of carbazole derivative, comprises pair of electrodes and is arranged on the organic medium in described electrode, and described organic medium is carbazole derivative, and described carbazole derivative is the arbitrary described carbazole derivative of claim 1 to 5.
Embodiment 1
9-methyl isophthalic acid, 8-bis-is bromo-3,6-di-t-butyl carbazole (4) synthetic
Figure BDA0000474813090000141
I) tert-butyl chloride, zinc chloride, Nitromethane 99Min., room temperature, 4 hours; Ii) glacial acetic acid, bromine, 90 ℃; Iii) methyl iodide, sodium hydride, DMF
1. compound 3,6-di-t-butyl carbazole (2) synthetic
In the dry there-necked flask of 1000ml, under nitrogen protection condition, by carbazole (20.0g, 120mmol), ZnCl 2(50.0g, 360mmol) be dissolved in Nitromethane 99Min. (400ml), in whipping process, dropwise add tert-butyl chloride (40.0ml, 360mmol), after dropwising, reaction solution continues to stir at ambient temperature 4 hours, the cancellation that adds water reaction, methylene dichloride (200ml) extraction 3 times, separatory, organic phase anhydrous magnesium sulfate drying, filters the solvent that evaporate to dryness is all, obtain yellow solid methylene dichloride and methanol crystallization, finally obtain white crystal 3,6-di-t-butyl carbazole (2) 30.5g, productive rate: 91%. 1H-NMR(CDCl 3,400MHz):δ(ppm)8.08(s,2H),7.86(s,1H),7.48～7.45(m,2H),7.35～7.33(d,J=8.4Hz,2H),1.45(s,18H)。
2. compound 1,8-bis-is bromo-3,6-di-t-butyl carbazole (3) synthetic
3,6-di-t-butyl carbazole (2) (0.81g, 2.9mmol) is dissolved in glacial acetic acid (100ml) solution of 90 ℃; bromine (0.92g, 5.8mmol) is dissolved in acetic acid (10ml) and dropwise adds, under nitrogen protection; isothermal reaction 3.5 hours; when solution is cooled to room temperature, reaction solution is concentrated, and filters; obtain crude product; use normal hexane recrystallization, filter to obtain white solid powder 1.1g, productive rate: 85%. 1H-NMR(CDCl 3,400MHz):δ(ppm)8.13(s,1H),7.97(s,2H),7.63(s,2H),1.44(s,18H)。
3. compound 9-methyl isophthalic acid, 8-bis-is bromo-3,6-di-t-butyl carbazole (4) synthetic
In the dry flask of 250ml; add successively 1; 8-bis-is bromo-3,6-di-t-butyl carbazole (3) (1.3g, 3.0mmol); NaH (0.11g; 4.6mmol) be dissolved in DMF (100ml), after stirring at room temperature 30min, methyl iodide (0.64g; 4.5mmol) add wherein; under nitrogen protection, continue reaction 18 hours, the cancellation of reaction water, reaction solution dichloromethane extraction; merge organic phase; use anhydrous magnesium sulfate drying simultaneously, filter evaporate to dryness organic solvent; reacting coarse product is purified with quick silicagel column, finally obtains white crystal 1.30g.Productive rate: 96%. 1H-NMR(CDCl 3,400MHz):δ(ppm)7.94(s,2H),7.64(s,2H),4.42(s,3H),1.45(s,18H)。
Embodiment 2
Synthesizing of compound 5
Figure BDA0000474813090000151
In dry single port flask, add successively compound 9-methyl isophthalic acid, 8-bis-bromo-3; 6-di-t-butyl carbazole, phenylo boric acid pinacol ester group benzoglyoxaline between 1-phenyl-N-, four (triphenyl phosphorus) palladium; wet chemical (2M), toluene, ethanolic soln; after the ultrasonic 30min of gained solution, under nitrogen protection, lucifuge heating reflux reaction 24 hours; question response liquid is cooled to room temperature, and the cancellation that adds water reaction, with dichloromethane extraction; merge organic phase
Use anhydrous magnesium sulfate drying simultaneously, filter, evaporate to dryness organic solvent, gained crude product is purified with fast silica gel chromatogram post, finally all obtains white solid product.Productive rate: 74%.MS(APCI):calcd?for?C 59H 51N 5:829.4,found,830.5(M)+。
Synthesizing of compound 6
Figure BDA0000474813090000152
In dry single port flask, add successively compound 9-methyl isophthalic acid, 8-bis-bromo-3, 6-di-t-butyl carbazole, 3-(3-phenylo boric acid pinacol ester group) pyridine, four (triphenyl phosphorus) palladium, wet chemical (2M), toluene, ethanolic soln, after the ultrasonic 30min of gained solution, under nitrogen protection, lucifuge heating reflux reaction 24 hours, question response liquid is cooled to room temperature, the cancellation that adds water reaction, with dichloromethane extraction, merge organic phase, use anhydrous magnesium sulfate drying simultaneously, filter, evaporate to dryness organic solvent, gained crude product is purified with fast silica gel chromatogram post, finally all obtain white solid product.Productive rate: 79%.MS(APCI):calcd?for?C 43H 41N 3:599.3,found,600.2(M+1)+。
Synthesizing of compound 7
Figure BDA0000474813090000161
In dry single port flask, add successively compound 9-methyl isophthalic acid, 8-bis-bromo-3, 6-di-t-butyl carbazole, 8-(3-phenylo boric acid pinacol ester group) quinoline, four (triphenyl phosphorus) palladium, wet chemical (2M), toluene, ethanolic soln, after the ultrasonic 30min of gained solution, under nitrogen protection, lucifuge heating reflux reaction 24 hours, question response liquid is cooled to room temperature, the cancellation that adds water reaction, with dichloromethane extraction, merge organic phase, use anhydrous magnesium sulfate drying simultaneously, filter, evaporate to dryness organic solvent, gained crude product is purified with fast silica gel chromatogram post, finally all obtain white solid product.Productive rate: 77%.MS(APCI):calcd?for?C 51H 45N 3:699.9,found,700.6(M+1)+。
Synthesizing of compound 8
Figure BDA0000474813090000162
In dry single port flask, add successively compound 9-methyl isophthalic acid, 8-bis-bromo-3, 6-di-t-butyl carbazole, 2-(3-phenylo boric acid pinacol ester group)-1, 3, 5-triazine, four (triphenyl phosphorus) palladium, wet chemical (2M), toluene, ethanolic soln, after the ultrasonic 30min of gained solution, under nitrogen protection, lucifuge heating reflux reaction 24 hours, question response liquid is cooled to room temperature, the cancellation that adds water reaction, with dichloromethane extraction, merge organic phase, use anhydrous magnesium sulfate drying simultaneously, filter, evaporate to dryness organic solvent, gained crude product is purified with fast silica gel chromatogram post, finally all obtain white solid product.Productive rate: 77%.MS(APCI):calcd?for?C 39H 37N 7:603.7,found,604.5(M+1)+。
Embodiment 3
Device preparation and application using compound 5 as blue phosphorescent material of main part
ITO in succession in clean-out system and deionized water with ultrasonic cleaning 30 minutes.Then vacuum-drying 2 hours (105 ℃), then ito glass is put into the O that plasma reactor carries out 1 minute 2plasma treatment, is sent to and in vacuum chamber, prepares organic membrane and metal electrode.Method by vacuum evaporation is prepared into device using 5 as material of main part.This experiment apparatus structure is: ITO/MoO 3(10nm)/NPB (40nm)/mCP (5nm)/Host:6wt%FIrpic (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm), as Fig. 2
Embodiment 4
Device performance checking using compound 5 as blue phosphorescent material of main part
This experiment apparatus structure is: ITO/MoO 3(10nm)/NPB (40nm)/mCP (5nm)/Host5:6wt%FIrpic (20nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm).
Aluminium is as the negative electrode of device, and ITO is as anode.Galvanic positive pole is added on to ITO layer, negative pole is added on to metal level, can obtain the bright uniform blue light sending from ITO layer, CIE coordinate is (0.15,0.31), cut-in voltage is 3.0V, and high-high brightness is 9565cd/m2, maximum current efficiency is 27.6cd/A, maximum lumen efficiency is 27.0lm/W, and maximum external quantum efficiency is 11.6%, as Fig. 1,2,3.
Embodiment 5
Device performance checking using compound 8 as green phosphorescent material of main part
This experiment apparatus structure is: ITO/MoO 3(10nm)/NPB (40nm)/mCP (5nm)/Host8:8wt%Ir (ppy) 3(20nm)/TmPyPB (40nm)/LiF (1nm)/Al (100nm).
Aluminium is as the negative electrode of device, and ITO is as anode.Galvanic positive pole is added on to ITO layer, negative pole is added on to metal level, can obtain the bright uniform blue light that sends from ITO layer, CIE coordinate is (0.31,0.62), cut-in voltage is 2.8V, and high-high brightness is 36570cd/m2, and maximum current efficiency is 115.12cd/A, as Fig. 4,5,6.
Finally it should be noted that: above embodiment is only for illustrating technical scheme of the present invention, not for limitation of the present invention, although the present invention is had been described in detail with reference to above-described embodiment, it will be understood by those skilled in the art that: still can modify or be equal to replacement the specific embodiment of the present invention, and do not depart from any modification of spirit and scope of the invention or be equal to replacement, it all should be encompassed within the scope of claim of the present invention.

Claims (8)

1. one kind 1,8-position carbazole derivative, is characterized in that: have the structure shown in formula I:
Figure FDA0000474813080000011
Wherein, Ar 1and Ar 2be electron-withdrawing group independently; R 2, R 2, R 3be hydrogen or alkyl independently respectively.
2. according to claim 11,8-position carbazole derivative, is characterized in that: described electron-withdrawing group Ar 1and Ar 2there is rigid structure, R 1, R 2and R 3for the alkyl chain of hydrogen or 1-20 carbon.
3. according to claim 11,8-position carbazole derivative, is characterized in that: described Ar 1and Ar 2identical or different.
4. according to claim 11,8-position carbazole derivative, is characterized in that: described Ar 1with described Ar 2be (1a) one to (22c) group independently respectively, described (1a) is as follows to (22c) group:
Figure FDA0000474813080000012
Figure FDA0000474813080000031
Figure FDA0000474813080000041
5. according to claim 11,8-position carbazole derivative, is characterized in that: wherein this carbazole derivative comprises
Figure FDA0000474813080000051
6. according to claim 11,8-position carbazole derivative, is characterized in that: described carbazole derivative is as hole transmission layer or the luminescent layer of LED device; Or described carbazole derivative is as the material of main part of luminescent layer.
7. one kind 1, the preparation method of 8-position carbazole derivative, is characterized in that: described method comprises
Compound 3, the preparation of 6-di-t-butyl carbazole:
In the dry there-necked flask of 1000ml, under nitrogen protection condition, by carbazole, ZnCl 2be dissolved in nitro
In methane, in whipping process, dropwise add tert-butyl chloride, after dropwising, reaction solution continues to stir at ambient temperature 4 hours, the cancellation that adds water reaction, dichloromethane extraction 3 times, separatory, organic phase anhydrous magnesium sulfate drying, filter, the solvent that evaporate to dryness is all, obtains yellow solid methylene dichloride and methanol crystallization, finally obtain white crystal 3,6-di-t-butyl carbazole;
Compound 1,8-bis-is bromo-3, the preparation of 6-di-t-butyl carbazole:
3,6-di-t-butyl carbazole is dissolved in the glacial acetic acid solution of 90 ℃, bromine is dissolved in acetic acid and dropwise adds, under nitrogen protection, isothermal reaction 3.5 hours, when solution is cooled to room temperature, reaction solution is concentrated, and filter, obtain crude product, use normal hexane recrystallization, filter to obtain white solid powder 1,8-bis-is bromo-3,6-di-t-butyl carbazole;
Compound 9-alkyl-1,8-bis-is bromo-3, the preparation of 6-di-t-butyl carbazole:
With 9-methyl isophthalic acid, 8-bis-is bromo-3, and 6-di-t-butyl carbazole is example, in the dry flask of 250ml; add successively 1,8-bis-bromo-3,6-di-t-butyl carbazole; NaH is dissolved in DMF, and after stirring at room temperature 30min, methyl iodide adds wherein; under nitrogen protection, continue reaction 18 hours, the cancellation of reaction water, reaction solution dichloromethane extraction; merge organic phase, use anhydrous magnesium sulfate drying simultaneously, filter; evaporate to dryness organic solvent, reacting coarse product is purified with quick silicagel column, finally obtains white crystal.
8. one kind uses 1, the luminescent device of 8-position carbazole derivative, is characterized in that: comprise pair of electrodes and be arranged on the organic medium in described electrode, described organic medium is carbazole derivative, described carbazole derivative is that claim 1 to 6 is arbitrary described 1,8-position carbazole derivative.
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