CN100357271C - Hole transport materials with 9-phenyl carbazole as core and process for making same - Google Patents
Hole transport materials with 9-phenyl carbazole as core and process for making same Download PDFInfo
- Publication number
- CN100357271C CN100357271C CNB2005100169097A CN200510016909A CN100357271C CN 100357271 C CN100357271 C CN 100357271C CN B2005100169097 A CNB2005100169097 A CN B2005100169097A CN 200510016909 A CN200510016909 A CN 200510016909A CN 100357271 C CN100357271 C CN 100357271C
- Authority
- CN
- China
- Prior art keywords
- carbazole
- molar part
- phenyl
- methylphenyl
- hole transmission
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The present invention belongs to a hole transmission material with 9-phenylimidazole as a core and the technical field of preparation thereof. The hole transmission material containing hole transmission elements is prepared in a such manner that carbazole is used as a basic raw material which reacts with paradibromobenzene or p-Iodotoluene to obtain the core of 9-phenylimidazole; after an iodination reaction is carried out, the 9-phenylimidazole carries out an Ullmann reaction with diarylamine or carbazole. The result of the cyclic voltammetry of molecules indicates that the molecules have favorable oxidation reduction reversibility between 0 and 1.6 V, and the compounds have high glass transition temperature, high thermal decomposition temperature and high thermal stability due to the introduction of a rigid carbazole base groups. Thereby, the compounds used as the hole transmission layers of an organic electroluminescent device have favorable hole transmission performance mainly due to the synergistic effect of the core and the peripheral hole transmission elements, so that the hole transmission performance of the whole molecule is improved.
Description
Technical field: the invention belongs to photoelectron material and technical field, being specifically related to the 9-phenyl carbazole is hole mobile material of nuclear and preparation method thereof.
Background technology: the electroluminescent of organic compound is to find the 1950's.The structure of simple organic LED adds one deck organic luminous layer exactly between anode and negative electrode, and the hole is injected from anode, and electronics injects from negative electrode, and both meet at luminescent layer and form exciton and luminous.The performance that will obtain in such device just requires luminescent material not only to help the injection of electronics and transmission but also helps the injection and the transmission in hole.Yet its electron energy state is difficult to mate with two electrodes simultaneously for luminescent material, and one high and one low often to two kinds of mobility of charge carrier rates.So just need between anode and luminescent layer, introduce hole transmission layer, between negative electrode and luminescent layer, introduce electron transfer layer, inject with the equilibrium that reaches positive negative carrier, effectively transmission and effectively compound, thus improve luminous efficiency.The people such as C.W.Tang of Kodak in 1987 (Appl.Phys.Lett., 1987,51,913) are at luminescent layer Alq
3And add hole transmission layer N between the anode, and N '-two (3-aminomethyl phenyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4,4 '-diamines (TPD) obtains having low-work voltage, high brightness, high-efficiency LED device.This is the historical breakthrough of organic electroluminescent, up to the present Alq
3Be still the luminous and electronic transmission performance excellent material of tool.Therefore the selection of hole mobile material just seems particularly important, most widely used hole mobile material is TPD, N at present, N '-two (1-naphthyl)-N, N '-phenylbenzene-1,1 '-phenylbenzene-4, some tri-arylamine group compounds of 4 '-diamines (NPD) etc. are (referring to United States Patent (USP): 5763110,5972247,6099996,6475648).They have better suited hole transport character, and its hole mobility is 10
-5-10
-2Cm
2v
-1s
-1Between.They can form uniform amorphous membrance under the condition of vacuum evaporation.For organic molecule, if it has stable amorphous phase being higher than under the condition of room temperature, so this molecule is called as molecular glass or amorphous molecular material.That is to say whether molecule has glass transition temperature (T in eigenstate
g), and whether this glassy transition can stable existence be an important factor of this molecular glass attitude stability of decision.For hole mobile material TPD (T commonly used
g: 65 ℃), NPD (T
g: 100 ℃), all belong to this amorphous molecular material, but TPD just produces metamorphosis under mild conditions, crystallization occurs; And NPD (T
g: 100 ℃) the vitreous state less stable.The poor stability of hole mobile material affects the life-span of organic electroluminescence device widely, therefore increases the stability and the raising T of the amorphous state of hole mobile material
gCan significantly increase the life-span of device.
Summary of the invention:
Based on the limitation that traditional hole mobile material exists, we propose with the 9-phenyl carbazole is nuclear, and the peripheral hole transport primitive of introducing by the nuclear and the synergy of hole transport primitive on every side, improves the stability and the hole transport performance of whole molecule.
The purpose of this invention is to provide a kind of is the hole mobile material of nuclear with the 9-phenyl carbazole.
It is the preparation method of the hole mobile material of nuclear with the 9-phenyl carbazole that another object of the present invention provides a kind of.
With the 9-phenyl carbazole is that the hole mobile material of nuclear has following structure:
The preparation method of hole mobile material provided by the invention comprises the steps:
A.9-the preparation of phenyl carbazole nuclear: with the carbazole is basic raw material, utilizes Liv Ullmann (Ullmann) reaction, examines with paradibromobenzene or to toluene iodide prepared in reaction 9-phenyl carbazole:
9-is to the preparation of bromophenyl carbazole: under the nitrogen protection; with 1 molar part paradibromobenzene; 0.5 molar part carbazole; 1-3 molar part Anhydrous potassium carbonate; 0.03-0.05 molar part cuprous iodide; 0.01-0.03 molar part 18-hat-6 and 0.4-1.0 molar part 1; 3-dimethyl-3; 4; 5; 6-tetrahydrochysene-2-pyrimidone (DMPU) mixes; be heated to 160-180 ℃; reacted 12-16 hour; use in the dilute hydrochloric acid then and remaining salt of wormwood, use dichloromethane extraction, with ammoniacal liquor flush away cupric ion; be washed to neutrality with saturated common salt; use the anhydrous sodium sulphate drying, after the decompression rotary evaporation fell solvent, sherwood oil was a leacheate; silica gel column chromatography separates, and obtains white crystal 9-to the bromophenyl carbazole.
9-p-methylphenyl carbazole: under the nitrogen protection; with 1 molar part carbazole; 1 molar part is to toluene iodide; 1-3 molar part Anhydrous potassium carbonate; 0.03-0.05 molar part cuprous iodide; 0.01-0.03 molar part 18-hat-6 and 0.4-1.0 molar part DMPU mix; be heated to 160-180 ℃; reacted 20-26 hour; use in the dilute hydrochloric acid then and remaining salt of wormwood; use dichloromethane extraction; with ammoniacal liquor flush away cupric ion; be washed to neutrality with saturated common salt; use the anhydrous sodium sulphate drying; after the decompression rotary evaporation fell solvent, the chloroform/ethanol recrystallization got white solid 9-p-methylphenyl carbazole.
1; 4-two carbazyl benzene: under the nitrogen protection; with 1 molar part carbazole; 0.5 molar part paradibromobenzene; 1-3 molar part Anhydrous potassium carbonate; 0.03-0.05 molar part cuprous iodide; 0.01-0.03 molar part 18-hat-6 and 0.4-1.0 molar part DMPU mix; at 150-200 ℃ of following stirring reaction 8-12 hour; use in the dilute hydrochloric acid then and remaining salt of wormwood; use dichloromethane extraction; with ammoniacal liquor flush away cupric ion; be washed to neutrality with saturated common salt; use the anhydrous sodium sulphate drying, the decompression rotary evaporation falls solvent, the chloroform/ethanol recrystallization; get white solid 1,4-two carbazyl benzene.
B. He iodide reaction:
With 1 molar part 9-to bromophenyl carbazole or 1 molar part 1,4-two carbazyl benzene or 1 molar part 9-p-methylphenyl carbazole and 1.0-3.5 molar part potassiumiodide and 1.0-4.0 molar part Potassium Iodate are dissolved in the Glacial acetic acid, 80-100 ℃ backflow 4-6 hour, product is toppled in the entry, leach solid, wash with saturated common salt with saturated sodium bicarbonate and to be washed to neutrality, the chloroform/ethanol recrystallization, the iodo product.
C. the preparation of hole mobile material:
With 1 molar part iodo product, the pentanoic of 1-4 molar part or carbazole or (p-methylphenyl) aniline or (p-methoxyphenyl) aniline or (aminomethyl phenyl) aniline or two (p-methylphenyl) amine or (p-methylphenyl) (to carbazole-9-base phenyl) amine or (to carbazole-9-base phenyl) aniline or (to carbazole-9-base phenyl) (p-methylphenyl) amine or (to carbazole-9-base phenyl) (p-methoxyphenyl) amine or (to carbazole-9-base phenyl) (aminomethyl phenyl) amine and 1.0-3.0 molar part Anhydrous potassium carbonate, 0.03-0.4 molar part cuprous iodide, 0.01-0.1 molar part 18-hat-6 and 0.5-2 molar part DMPU mix, at 150-200 ℃ of following stirring reaction 10-30 hour, use in the dilute hydrochloric acid then and remaining salt of wormwood, use dichloromethane extraction, with ammoniacal liquor flush away cupric ion, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying, the decompression rotary evaporation falls solvent, column chromatography is separated, and gets solid hole mobile material product.
Material provided by the invention can be used as hole transmission layer in organic electroluminescence device.
Embodiment:
Embodiment 1:9-is synthetic to the bromophenyl carbazole.
Under the nitrogen protection, with carbazole 10g (0.06mol), paradibromobenzene 28.4g (0.12mol); salt of wormwood 16.6g (0.12mol); cuprous iodide 800mg (0.004mol), 18-hat-6528mg (0.002mol) and 1,3-dimethyl-3; 4; 5, the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 2mL ℃ was reacted 14.5 hours; in the dilute hydrochloric acid and remaining salt of wormwood; dichloromethane extraction, ammoniacal liquor flush away cupric ion, saturated common salt is washed to neutrality; the anhydrous sodium sulphate drying; after the decompression rotary evaporation fell solvent, sherwood oil was a leacheate, and silica gel column chromatography separates; obtain 9-to bromophenyl carbazole white crystal 15g, productive rate 77.6%.
Embodiment 2:3,6-two iodos-9-is synthetic to the bromophenyl carbazole.
With 9-to bromophenyl carbazole 1g (3mmol), potassiumiodide 1g (6mmol), Potassium Iodate 1.4g (7mmol), 80 ℃ of the mixture heating up of Glacial acetic acid 60mL, reacted 4 hours, topple in the entry, leach solid, saturated sodium bicarbonate is washed, saturated common salt is washed to neutrality, the chloroform/ethanol recrystallization gets white solid 1.70g, productive rate: 95.5%.
Embodiment 3:3, the synthetic and sign of 6-two (hexichol amido)-9-(to the hexichol amido) phenyl carbazole.
Under the nitrogen protection; with 3; 6-two iodos-9-is to bromophenyl carbazole 3g (0.005mol), pentanoic 7g (0.04mol), salt of wormwood 11g (0.08mol); cuprous iodide 427mg (0.0023mol); 18-is preced with-6 264mg (0.001mol) and 1,3-dimethyl-3,4; 5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 1mL ℃ was reacted 18 hours, in the dilute hydrochloric acid and remaining salt of wormwood; dichloromethane extraction; ammoniacal liquor flush away cupric ion, saturated common salt is washed to neutrality, the anhydrous sodium sulphate drying; after the decompression rotary evaporation falls solvent; the excessive pentanoic of hot ethanol flush away, sherwood oil/methylene dichloride=4: 1 are leacheate, and silica gel column chromatography separates; get white solid 2.56g, productive rate 65.8%%.
Product property is as follows: second-order transition temperature is 129 ℃; Heat decomposition temperature is 307 ℃; First oxidizing potential is 0.67V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 3.6V; Luminosity is 10813cd/m
2Luminous efficiency is 2.20Lm/w.
Embodiment 4:3, the synthetic and sign of 6-two carbazyls-9-(to carbazyl) phenyl carbazole.
Under the nitrogen protection, with 3,6-two iodos-9-is to bromophenyl carbazole 3g (0.005mol); carbazole 6.68g (0.04mol), salt of wormwood 11g (0.08mol), cuprous iodide 427mg (0.0023mol); 18-is preced with-6 264mg (0.001mol) and 1; 3-dimethyl-3,4,5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 1mL ℃; reacted 18 hours, in the dilute hydrochloric acid and remaining salt of wormwood, dichloromethane extraction; ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality, and the anhydrous sodium sulphate drying is after the decompression rotary evaporation falls solvent; the excessive carbazole of hot ethanol flush away; petrol ether/ethyl acetate=100: 1 is a leacheate, and silica gel column chromatography separates, productive rate 87%.
Product property is as follows: second-order transition temperature is 190.1 ℃; Heat decomposition temperature is 438.7 ℃; First oxidizing potential is 0.96V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 6.1V; Luminosity is 12705cd/m
2Luminous efficiency is 1.61Lm/w.
Embodiment 5:3, the synthetic and sign of 6-two ((p-methylphenyl) phenyl amido)-9-(4-((p-methylphenyl) phenyl) amido) phenyl carbazole.
Under the nitrogen protection; with 3; 6-two iodos-9-is to bromophenyl carbazole 3g (0.005mol), p-methylphenyl phenyl amine 7.2g (0.04mol), salt of wormwood 11g (0.08mol); cuprous iodide 427mg (0.0023mol); 18-is preced with-6 264mg (0.001mol) and 1,3-dimethyl-3,4; 5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 1mL ℃ was reacted 18 hours, in the dilute hydrochloric acid and remaining salt of wormwood; dichloromethane extraction; ammoniacal liquor flush away cupric ion, saturated common salt is washed to neutrality, the anhydrous sodium sulphate drying; after the decompression rotary evaporation falls solvent; the excessive p-methylphenyl phenyl amine of hot ethanol flush away, petrol ether/ethyl acetate=150: 1 are leacheate, and silica gel column chromatography separates; get white solid, productive rate 63%
Product property is as follows: second-order transition temperature is 111.8 ℃; Heat decomposition temperature is 490.6 ℃; First oxidizing potential is 0.62V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 2.9V; Luminosity is 16251cd/m
2Luminous efficiency is 2.27Lm/w.
Embodiment 6:3,6-two ((p-methoxyphenyl) phenyl amido)-9-(4-((p-methoxyphenyl) phenyl) amido) phenyl carbazole synthetic.
With (p-methoxyphenyl) phenyl amine and 3,6-two iodos-9-is a raw material to the bromophenyl carbazole, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 3.Product is a white solid, productive rate: 60%
Embodiment 7:3,6-two ((aminomethyl phenyl) phenyl amido)-9-(4-((aminomethyl phenyl) phenyl) amido) phenyl carbazole synthetic.
With (aminomethyl phenyl) phenyl amine and 3,6-two iodos-9-is a raw material to the bromophenyl carbazole, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 3.Product is a white solid, productive rate: 65%
Embodiment 8:3,6-two (two (p-methylphenyl) amido)-9-(the synthetic and sign of 4-(two (p-methylphenyl) amido) phenyl carbazole.
With two (p-methylphenyl) amine and 3,6-two iodos-9-is a raw material to the bromophenyl carbazole, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 3.Product is a white solid, productive rate: 80%
Product property is as follows: second-order transition temperature is 111.8 ℃; Heat decomposition temperature is 490.6 ℃; First oxidizing potential is 0.62V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 2.9V; Luminosity is 16251cd/m
2Luminous efficiency is 2.27Lm/w.
Embodiment 9:3, the synthetic and sign of 6-two ((to the carbazyl phenyl) p-methylphenyl amido)-9-((to the carbazyl phenyl) p-methylphenyl amido) phenyl carbazole.
With (to the carbazyl phenyl) p-methylphenyl amine and 3,6-two iodos-9-is a raw material to the bromophenyl carbazole, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 3.Product is a white solid, productive rate: 32%
Product property is as follows: second-order transition temperature is 202 ℃; Heat decomposition temperature is 534 ℃; First oxidizing potential is 0.67V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 2.7V; Luminosity is 12971cd/m
2Luminous efficiency is 2.50Lm/w.
Embodiment 10:3,6-two (hexichol amido)-9-is synthetic to the bromophenyl carbazole.
Under the nitrogen protection, with 3,6-two iodos-9-is to bromophenyl carbazole 3g (0.005mol); pentanoic 3.4g (0.02mol); potassium hydroxide 4.5g (0.08mol), cuprous chloride 40mg (0.4mmol), 1; 10-phenanthroline 60mg (0.4mmol) mixes; add toluene 50mL, water-and-oil separator is installed, 135 ℃ were refluxed 40 hours; steam and remove toluene; the hydrochloric acid neutralization, chloroform extraction, ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality; anhydrous sodium sulphate drying, decompression be after rotary evaporation falls solvent, and sherwood oil/methylene dichloride=15: 1 is the separation of leacheate silica gel column chromatography; get pale solid, productive rate 75%.
Embodiment 11:3-hexichol amido-6-iodo-9-is synthetic to the bromophenyl carbazole.
Under the nitrogen protection, with 3,6-two iodos-9-is to bromophenyl carbazole 3g (0.005mol); pentanoic 0.845g (0.005mol); potassium hydroxide 1.1g (0.02mol), cuprous chloride 20mg (0.2mmol), 1; 10 phenanthroline 30mg (0.2mmol) mix; add toluene 50mL, water-and-oil separator is installed, 135 ℃ were refluxed 40 hours; steam and remove toluene; the hydrochloric acid neutralization, chloroform extraction, ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality; the anhydrous sodium sulphate drying, after the decompression rotary evaporation fell solvent, sherwood oil separated for the leacheate silica gel column chromatography; get pale solid, productive rate 60%.
Embodiment 12:3-hexichol amido-6-carbazyl-9-is synthetic to the carbazyl phenyl carbazole.
Under the nitrogen protection; with 3-hexichol amido-6-iodo-9-to bromophenyl carbazole 200mg (0.325mmol); carbazole 217mg (1.3mmol); salt of wormwood 358mg (2.6mmol); cuprous iodide 100mg (0.5mmol), 18-is preced with-6 50mg (0.001mol) and 1,3-dimethyl-3; 4; 5, the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 0.5mL ℃ was reacted 24 hours; dilute hydrochloric acid reacts away remaining salt of wormwood; dichloromethane extraction, ammoniacal liquor flush away cupric ion, saturated common salt is washed to neutrality; the anhydrous sodium sulphate drying; decompression is after rotary evaporation falls solvent, and the excessive pentanoic of hot ethanol flush away, sherwood oil/methylene dichloride=4: 1 are the separation of leacheate silica gel column chromatography; get white solid, productive rate 82%.
Embodiment 13:3,6-two (hexichol amido)-9-is to the synthetic and sign of carbazyl phenyl carbazole.
Under the nitrogen protection; with 3; 6-two (hexichol amido)-9-is to bromophenyl carbazole 1g (1.5mmol), carbazole 375mg (2.25mmol), salt of wormwood 828mg (6mmol); cuprous iodide 100mg (0.5mmol); 18-is preced with-6 50mg (0.001mol) and 1,3-dimethyl-3,4; 5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 0.5mL ℃ was reacted 24 hours, in the dilute hydrochloric acid and remaining salt of wormwood; dichloromethane extraction; ammoniacal liquor flush away cupric ion, saturated common salt is washed to neutrality, the anhydrous sodium sulphate drying; after the decompression rotary evaporation falls solvent; the excessive pentanoic of hot ethanol flush away, petrol ether/ethyl acetate=4: 1 are leacheate, and silica gel column chromatography separates; get white solid, productive rate 85%.
Product property is as follows: second-order transition temperature is 152.9 ℃; Heat decomposition temperature is 426.1 ℃; First oxidizing potential is 0.675V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 5.4V; Luminosity is 10109cd/m
2Luminous efficiency is 1.48Lm/w.
Embodiment 14:1,4-two carbazyl benzene synthetic.
Under the nitrogen protection; the carbazole of paradibromobenzene and 2 times of molar weights is preced with 1 of-6 and 0.5 times of molar weights at the 18-of the cuprous iodide of the Anhydrous potassium carbonate of 2-6 times of molar weight, 0.06 times of molar weight, 0.01 times of molar weight; 3-dimethyl-3; 4; 5; 6-tetrahydrochysene-2-pyrimidone (DMPU) exists down; 150-200 ℃ of following stirring reaction 10 hours, in the dilute hydrochloric acid and remaining salt of wormwood, dichloromethane extraction; ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality, the anhydrous sodium sulphate drying, and the decompression rotary evaporation falls solvent; the chloroform/ethanol recrystallization gets white solid.Productive rate: 86%.
Embodiment 15:3-hexichol amido-9-is to the synthetic and sign of carbazyl phenyl carbazole.
With 1,4-two carbazyl benzene 1g (3.2mmol), potassiumiodide 182mg (1.1mmol), Potassium Iodate 256.8mg (1.2mmol), 80 ℃ of the mixture heating up of Glacial acetic acid 60mL, reacted 4 hours, pour in the water, leach solid, saturated sodium bicarbonate is washed, saturated common salt is washed to neutrality, the chloroform/ethanol recrystallization.Under the nitrogen protection with iodo product 3-iodo-9-to carbazyl phenyl carbazole 1g (1.7mmol); pentanoic 574mg (3.4mmol); salt of wormwood 828mg (6mmol); cuprous iodide 100mg (0.5mmol); 18-is preced with-6 50mg (0.001mol) and 1,3-dimethyl-3,4; 5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 0.5mL ℃ was reacted 24 hours, in the dilute hydrochloric acid and remaining salt of wormwood; dichloromethane extraction; ammoniacal liquor flush away cupric ion, saturated common salt is washed to neutrality, the anhydrous sodium sulphate drying; after the decompression rotary evaporation falls solvent; the excessive pentanoic of hot ethanol flush away, sherwood oil/methylene dichloride=10: 1 are leacheate, and silica gel column chromatography separates; get the light green solid, overall yield 60%.
Product property is as follows: second-order transition temperature is 110.3 ℃; Heat decomposition temperature is 377.1 ℃; First oxidizing potential is 0.79V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 4.2V; Luminosity is 4867cd/m
2At 18.1V; Luminous efficiency is 0.57Lm/w.
Embodiment 16:3-hexichol amido-9-(3-hexichol amido-to carbazyl) phenyl carbazole synthetic with characterize.
With 1,4-two carbazyl benzene are raw material, and with diphenylamine reaction, reaction conditions and treatment step are with embodiment 15 behind two iodos.Product is the light green solid, overall yield: 65%
Product property is as follows: second-order transition temperature is 141.1 ℃; Heat decomposition temperature is 424.2 ℃; First oxidizing potential is 0.78V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 7.3V; Luminosity is 7778cd/m
2At 20.6V; Luminous efficiency is 1.36Lm/w.
Embodiment 17:3 6-two (hexichol amido)-9-(3-hexichol amido-to carbazyl) phenyl carbazole synthetic with characterize.
With 1,4-two carbazyl benzene are raw material, and with diphenylamine reaction, reaction conditions and treatment step are with embodiment 15 behind three iodos.Product is that light green is solid, overall yield: 75%
Product property is as follows: second-order transition temperature is 136.7 ℃; Heat decomposition temperature is 435.8 ℃; First oxidizing potential is 0.72V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 6.5V; Luminosity is 9839cd/m
2At 21.4V; Luminous efficiency is 1.91Lm/w.
Synthesizing of embodiment 18:9-p-methylphenyl carbazole.
Under the nitrogen protection; with carbazole 2g (0.012mol); to toluene iodide 3.12g (0.015mol), salt of wormwood 4.14g (0.03mol), cuprous iodide 427mg (0.0023mol); 18-hat-6264mg (0.001mol) and 1; 3-dimethyl-3,4,5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 1mL ℃; reacted 24 hours, in the dilute hydrochloric acid and remaining salt of wormwood, dichloromethane extraction; ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality, and the anhydrous sodium sulphate drying is after the decompression rotary evaporation falls solvent; the chloroform/ethanol recrystallization gets white solid, productive rate 96%
Embodiment 19:3,6-two iodos-9-p-methylphenyl carbazole synthetic.
With 9-p-methylphenyl carbazole is raw material, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 2.Product is the light gray solid, chloroform/ethanol recrystallization, productive rate: 98%
Embodiment 20:3, the synthetic and sign of 6-two (hexichol amido)-9-p-methylphenyl carbazole.
With pentanoic and 3,6-two iodos-9-p-methylphenyl carbazole is a raw material, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 3.Sherwood oil/methylene dichloride=5: 1 is a leacheate, and silica gel column chromatography separates, and product is the light green solid, productive rate: 88%
Product property is as follows: second-order transition temperature is 80.6 ℃; Heat decomposition temperature is 335.3 ℃; First oxidizing potential is 0.65V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 6.2V; Luminosity is 7139cd/m
2Luminous efficiency is 1.27Lm/w.
Embodiment 21:3, the synthetic and sign of 6-two (two carbazyls)-9-p-methylphenyl carbazole.
Under the nitrogen protection; with 3; 6-two iodos-9-p-methylphenyl carbazole 1g (2mmol); carbazole 1.36g (8mmol), salt of wormwood 2.2g (16mmol), cuprous iodide 300mg (1.6mmol); 18-is preced with-6 200mg (0.001mol) and 1; 3-dimethyl-3,4,5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 1mL ℃; reacted 15 hours, dilute hydrochloric acid reacts away remaining salt of wormwood, dichloromethane extraction; ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality, and the anhydrous sodium sulphate drying is after the decompression rotary evaporation falls solvent; the excessive pentanoic of hot ethanol flush away; petrol ether/ethyl acetate=10: 1 is a leacheate, and silica gel column chromatography separates, pale yellow colored solid productive rate 70%.
Product property is as follows: second-order transition temperature is 129.5 ℃; Heat decomposition temperature is 490.6 ℃; First oxidizing potential is 0.85V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 9V; Luminosity is 4957cd/m
2Luminous efficiency is 1.05Lm/w.
Embodiment 22:3, the synthetic and sign of 6-two ((to the carbazyl phenyl) phenyl amido)-9-p-methylphenyl carbazole.
Under the nitrogen protection; with 3; 6-two iodos-9-p-methylphenyl carbazole 778mg (1.5mmol); 4-carbazyl phenyl amine 1g (3mmol), salt of wormwood 828mg (6mmol), cuprous iodide 100mg (0.5mmol); 18-is preced with-6 50mg (0.001mol) and 1; 3-dimethyl-3,4,5; the mixture heating up to 170 of 6-tetrahydrochysene-2-pyrimidone (DMPU) 0.5mL ℃; reacted 24 hours, in the dilute hydrochloric acid and remaining salt of wormwood, dichloromethane extraction; ammoniacal liquor flush away cupric ion; saturated common salt is washed to neutrality, and the anhydrous sodium sulphate drying is after the decompression rotary evaporation falls solvent; the excessive pentanoic of hot ethanol flush away; petrol ether/ethyl acetate=15: 1 is a leacheate, and silica gel column chromatography separates, pale yellow colored solid productive rate 71%.
Product property is as follows: second-order transition temperature is 176.8 ℃; Heat decomposition temperature is 522.8 ℃; First oxidizing potential is 0.68V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 4.7V; Luminosity is 11833cd/m
2Luminous efficiency is 1.36Lm/w.
Embodiment 23:3,6-two ((to the carbazyl phenyl) p-methylphenyl amido)-9-p-methylphenyl carbazole synthetic.
With (to the carbazyl phenyl) p-methylphenyl amine and 3,6-two iodos-9-p-methylphenyl carbazole is a raw material, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 21.Product is a faint yellow solid, productive rate: 75%
Product property is as follows: second-order transition temperature is 186.1 ℃; Heat decomposition temperature is 538.2 ℃; First oxidizing potential is 0.655V, is hole transmission layer with this compound, Alq
3Be luminescent layer, ITO is an anode, and Al/LiF is that the device performance that makes of negative electrode is as follows: trigger voltage is 5.4V; Luminosity is 11139cd/m
2Luminous efficiency is 1.95Lm/w.
Embodiment 24:3,6-two ((to the carbazyl phenyl) p-methoxyphenyl amido)-9-p-methylphenyl carbazole synthetic.
With (to the carbazyl phenyl) p-methoxyphenyl amine and 3,6-two iodos-9-p-methylphenyl carbazole is a raw material, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 21.Product is a faint yellow solid, productive rate: 60%
Embodiment 25:3,6-two (aminomethyl phenyl amido between (to the carbazyl phenyl))-9-p-methylphenyl carbazole synthetic.
With tolyl amine and 3 between (to the carbazyl phenyl), 6-two iodos-9-p-methylphenyl carbazole is a raw material, and feed intake the when reaction conditions and treatment step of raw material are with embodiment 21.Product is a faint yellow solid, productive rate: 75%
Claims (3)
1. one kind is the hole mobile material of nuclear with the 9-phenyl carbazole, it is characterized in that this material has following structure:
Or
2. according to claim 1 a kind of be the hole mobile material of nuclear with the 9-phenyl carbazole, its preparation method comprises the steps:
A.9-the preparation of phenyl carbazole nuclear: with the carbazole is basic raw material, utilizes Liv Ullmann (Ullmann) reaction, examines with paradibromobenzene or to toluene iodide prepared in reaction 9-phenyl carbazole:
9-is to the preparation of bromophenyl carbazole: under the nitrogen protection, with 1 molar part paradibromobenzene, 0.5 molar part carbazole, 1-3 molar part Anhydrous potassium carbonate, 0.03-0.05 molar part cuprous iodide, 0.01-0.03 molar part 18-hat-6 and 0.4-1.0 molar part 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone (DMPU) mixes, be heated to 160-180 ℃, reacted 12-16 hour, use in the dilute hydrochloric acid then and remaining salt of wormwood, use dichloromethane extraction, with ammoniacal liquor flush away cupric ion, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying, after the decompression rotary evaporation fell solvent, sherwood oil was a leacheate, silica gel column chromatography separates, and obtains white crystal 9-to the bromophenyl carbazole;
9-p-methylphenyl carbazole: under the nitrogen protection, with 1 molar part carbazole, 1 molar part is to toluene iodide, 1-3 molar part Anhydrous potassium carbonate, 0.03-0.05 molar part cuprous iodide, 0.01-0.03 molar part 18-hat-6 and 0.4-1.0 molar part DMPU mix, be heated to 160-180 ℃, reacted 20-26 hour, use in the dilute hydrochloric acid then and remaining salt of wormwood, use dichloromethane extraction, with ammoniacal liquor flush away cupric ion, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying, after the decompression rotary evaporation fell solvent, the chloroform/ethanol recrystallization got white solid 9-p-methylphenyl carbazole;
1,4-two carbazyl benzene: under the nitrogen protection, with 1 molar part carbazole, 0.5 molar part paradibromobenzene, 1-3 molar part Anhydrous potassium carbonate, 0.03-0.05 molar part cuprous iodide, 0.01-0.03 molar part 18-hat-6 and 0.4-1.0 molar part DMPU mix, at 150-200 ℃ of following stirring reaction 8-12 hour, use in the dilute hydrochloric acid then and remaining salt of wormwood, use dichloromethane extraction, with ammoniacal liquor flush away cupric ion, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying, the decompression rotary evaporation falls solvent, the chloroform/ethanol recrystallization, get white solid 1,4-two carbazyl benzene;
B. He iodide reaction:
With 1 molar part 9-to bromophenyl carbazole or 1 molar part 1,4-two carbazyl benzene or 1 molar part 9-p-methylphenyl carbazole and 1.0-3.5 molar part potassiumiodide and 1.0-4.0 molar part Potassium Iodate are dissolved in the Glacial acetic acid, 80-100 ℃ backflow 4-6 hour, product is toppled in the entry, leach solid, wash with saturated common salt with saturated sodium bicarbonate and to be washed to neutrality, the chloroform/ethanol recrystallization, the iodo product;
C. the preparation of hole mobile material:
With 1 molar part iodo product, the pentanoic of 1-4 molar part or carbazole or (p-methylphenyl) aniline or (p-methoxyphenyl) aniline or (aminomethyl phenyl) aniline or two (p-methylphenyl) amine or (p-methylphenyl) (to carbazole-9-base phenyl) amine or (to carbazole-9-base phenyl) aniline or (to carbazole-9-base phenyl) (p-methylphenyl) amine or (to carbazole-9-base phenyl) (p-methoxyphenyl) amine or (to carbazole-9-base phenyl) (aminomethyl phenyl) amine and 1.0-3.0 molar part Anhydrous potassium carbonate, 0.03-0.4 molar part cuprous iodide, 0.01-0.1 molar part 18-hat-6 and 0.5-2 molar part DMPU mix, at 150-200 ℃ of following stirring reaction 10-30 hour, use in the dilute hydrochloric acid then and remaining salt of wormwood, use dichloromethane extraction, with ammoniacal liquor flush away cupric ion, be washed to neutrality with saturated common salt, use the anhydrous sodium sulphate drying, the decompression rotary evaporation falls solvent, column chromatography is separated, and gets solid hole mobile material product.
3. according to claim 1 a kind of be the hole mobile material of nuclear with the 9-phenyl carbazole, it is characterized in that this class material can be used as hole transmission layer in organic electroluminescence device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100169097A CN100357271C (en) | 2005-06-22 | 2005-06-22 | Hole transport materials with 9-phenyl carbazole as core and process for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100169097A CN100357271C (en) | 2005-06-22 | 2005-06-22 | Hole transport materials with 9-phenyl carbazole as core and process for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1702066A CN1702066A (en) | 2005-11-30 |
| CN100357271C true CN100357271C (en) | 2007-12-26 |
Family
ID=35632050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100169097A Active CN100357271C (en) | 2005-06-22 | 2005-06-22 | Hole transport materials with 9-phenyl carbazole as core and process for making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100357271C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003927A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Organic electroluminescence phosphorescence host material, preparation method thereof and organic electroluminescence device |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008127290A (en) * | 2006-11-16 | 2008-06-05 | Bando Chem Ind Ltd | New carbazole derivative and utilization thereof |
| CN101250405B (en) * | 2008-02-26 | 2011-01-19 | 南京大学 | Novel mercapto fluorescence probe and uses thereof |
| CN101270342B (en) * | 2008-03-28 | 2011-07-20 | 南京大学 | Tumour targeting fluorescent probe and application in tumour NO test |
| TWI549942B (en) | 2010-08-26 | 2016-09-21 | 首威公司 | N-phenyl triscarbazole |
| EP2433928A1 (en) * | 2010-08-26 | 2012-03-28 | Solvay SA | N-phenyl triscarbazole |
| KR101960977B1 (en) * | 2010-10-11 | 2019-03-21 | 닛산 가가쿠 가부시키가이샤 | N-cycloalkylalkyl triscarbazoles |
| DE102011054855B4 (en) * | 2010-10-28 | 2019-07-11 | Lg Display Co., Ltd. | Phosphorescent compound and organic electroluminescent device using the same |
| JP6051864B2 (en) * | 2011-03-14 | 2016-12-27 | 東レ株式会社 | Light emitting device material and light emitting device |
| CN103570620B (en) * | 2011-12-29 | 2016-06-15 | 昆山维信诺显示技术有限公司 | The luxuriant and rich with fragrance compounds of a kind of 1,12-imino group benzo [c], intermediate and preparation method and application |
| CN103183638B (en) * | 2011-12-31 | 2015-09-02 | 昆山维信诺显示技术有限公司 | One compounds, its method for making and the organic electroluminescence device containing it |
| CN103855309A (en) * | 2012-11-30 | 2014-06-11 | 海洋王照明科技股份有限公司 | Organic electroluminescence device and preparation method thereof |
| US9455412B2 (en) * | 2013-12-23 | 2016-09-27 | Universal Display Corporation | Organic electroluminescent materials and devices |
| CN105566199B (en) * | 2014-10-14 | 2018-06-26 | 北京化工大学 | One kind conjugation sweet-smelling alkynyl carbazole compound |
| DE102015108002A1 (en) * | 2015-01-20 | 2016-07-21 | Cynora Gmbh | Composition for use in optoelectronic devices |
| CN106631985A (en) * | 2016-09-30 | 2017-05-10 | 齐鲁工业大学 | Crystal structure for 3,6-diiodo-N-(4-bromophenyl)carbazole and application thereof |
| CN108409636A (en) * | 2018-03-27 | 2018-08-17 | 南京工业大学 | A kind of structure, synthesis and its application of carbazoles small molecule hole transport material |
| CN111233910B (en) * | 2020-03-11 | 2022-04-22 | 上海交通大学 | Preparation method of T-shaped nitrogen boron nitrogen hetero diphenyl phenalene derivative |
| CN113512177A (en) * | 2021-03-30 | 2021-10-19 | 广州万物物联科技有限公司 | Red light polymer and preparation method thereof |
| CN113201120A (en) * | 2021-03-30 | 2021-08-03 | 广州万物物联科技有限公司 | Red light polymer electroluminescent material and preparation method thereof |
| CN113150251A (en) * | 2021-03-30 | 2021-07-23 | 广州万物物联科技有限公司 | Red light polymer electroluminescent material and preparation method thereof |
| CN113278135A (en) * | 2021-03-30 | 2021-08-20 | 广州万物物联科技有限公司 | Green light polymer electroluminescent material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07150138A (en) * | 1993-11-30 | 1995-06-13 | Sanyo Electric Co Ltd | Organic electroluminescent device |
| JPH10316658A (en) * | 1997-05-21 | 1998-12-02 | Mitsubishi Chem Corp | 4,4'-bis(n-carbazolyl) diphenylamine derivative and organic electroluminescent element produced by using the derivative |
| JPH11329737A (en) * | 1998-03-13 | 1999-11-30 | Taiho Ind Co Ltd | Organic multilayer type electroluminescent element and synthesizing method of structure body for organic multilayer type electroluminescent element |
| JP3164596B2 (en) * | 1991-04-12 | 2001-05-08 | 出光興産株式会社 | Hydroxyarylamine compound, method for producing the same, and electrophotographic photoreceptor using the same |
| CN1365381A (en) * | 2000-03-27 | 2002-08-21 | 出光兴产株式会社 | Organic electroluminescent element |
| US20030205696A1 (en) * | 2002-04-25 | 2003-11-06 | Canon Kabushiki Kaisha | Carbazole-based materials for guest-host electroluminescent systems |
| JP2004217557A (en) * | 2003-01-14 | 2004-08-05 | Mitsubishi Chemicals Corp | Carbazole-based compound, charge transport material, and organic electroluminescent device |
| WO2005051046A1 (en) * | 2003-11-21 | 2005-06-02 | Canon Kabushiki Kaisha | Light-emitting device, organic compound and display |
| CN1702065A (en) * | 2004-04-02 | 2005-11-30 | 三星Sdi株式会社 | Fluorene-based compound and organic electroluminescent display device using the same |
-
2005
- 2005-06-22 CN CNB2005100169097A patent/CN100357271C/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3164596B2 (en) * | 1991-04-12 | 2001-05-08 | 出光興産株式会社 | Hydroxyarylamine compound, method for producing the same, and electrophotographic photoreceptor using the same |
| JPH07150138A (en) * | 1993-11-30 | 1995-06-13 | Sanyo Electric Co Ltd | Organic electroluminescent device |
| JPH10316658A (en) * | 1997-05-21 | 1998-12-02 | Mitsubishi Chem Corp | 4,4'-bis(n-carbazolyl) diphenylamine derivative and organic electroluminescent element produced by using the derivative |
| JPH11329737A (en) * | 1998-03-13 | 1999-11-30 | Taiho Ind Co Ltd | Organic multilayer type electroluminescent element and synthesizing method of structure body for organic multilayer type electroluminescent element |
| CN1365381A (en) * | 2000-03-27 | 2002-08-21 | 出光兴产株式会社 | Organic electroluminescent element |
| US20030205696A1 (en) * | 2002-04-25 | 2003-11-06 | Canon Kabushiki Kaisha | Carbazole-based materials for guest-host electroluminescent systems |
| JP2004217557A (en) * | 2003-01-14 | 2004-08-05 | Mitsubishi Chemicals Corp | Carbazole-based compound, charge transport material, and organic electroluminescent device |
| WO2005051046A1 (en) * | 2003-11-21 | 2005-06-02 | Canon Kabushiki Kaisha | Light-emitting device, organic compound and display |
| CN1702065A (en) * | 2004-04-02 | 2005-11-30 | 三星Sdi株式会社 | Fluorene-based compound and organic electroluminescent display device using the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003927A (en) * | 2013-02-21 | 2014-08-27 | 海洋王照明科技股份有限公司 | Organic electroluminescence phosphorescence host material, preparation method thereof and organic electroluminescence device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1702066A (en) | 2005-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100357271C (en) | Hole transport materials with 9-phenyl carbazole as core and process for making same | |
| EP1926795B1 (en) | New compound and organic light emitting device using the same(1) | |
| KR101506999B1 (en) | Compound for organic photoelectric device and organic photoelectric device including the same | |
| CN101747256B (en) | Blue color emitting compound and organic light emitting diode comprising the same | |
| WO2006041263A1 (en) | Chromophore compounds and organic electroluminescenc display device comprising the same | |
| KR101791022B1 (en) | spiro compounds and organic light-emitting diode including the same | |
| CN107017349B (en) | Organic light-emitting display device | |
| CN102190627A (en) | 9,10-phenanthroimidazole derivatives and use thereof as electroluminescent materials | |
| CN104529870A (en) | Adamantane derivatives and application thereof as organic electrophosphorescence main body material | |
| EP1808912B1 (en) | Electron transport compound and organic light emitting device comprising the same | |
| CN105111230A (en) | Di-aza-carbazole derivatives and application thereof | |
| CN113248532B (en) | Organic compound, organic photoelectric element containing organic compound and application | |
| CN104650040B (en) | A kind of organic electroluminescent compounds of azophenlyene analog derivative | |
| CN102272262A (en) | Novel compounds for an organic photoelectric device, and organic photoelectric device comprising same | |
| CN107056798A (en) | A kind of thiophene or furan derivatives and the organic luminescent device using the derivative | |
| CN106898709A (en) | A kind of red phosphorescent organic electroluminescence device | |
| CN102898469B (en) | The two phosphine oxygen of difunctionalization replaces fluorenyl photoelectric functional material and its preparation method and application | |
| KR20050095613A (en) | Light-emitting device, condensed polycyclic compound used therein and method for producing same | |
| CN107325036A (en) | A kind of electroluminescent organic material and its organic luminescent device | |
| CN114773317B (en) | Acceptor type organic blue light material, preparation method and application thereof, and electroluminescent device | |
| CN110790796A (en) | Novel organic metal iridium complex, preparation method thereof and organic electroluminescent device containing metal iridium complex | |
| CN114262328B (en) | Organic electroluminescent compound, preparation method thereof and organic electroluminescent device | |
| CN107266436A (en) | A kind of organic photoelectrical material and its preparation method and application | |
| US20240032419A1 (en) | Electron transport material and fabricating method thereof, and organic light-emitting diode | |
| CN112409314A (en) | Organic electroluminescent compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |