CN1173004C - Method for preparing organic phosporescence material - Google Patents
Method for preparing organic phosporescence material Download PDFInfo
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- CN1173004C CN1173004C CNB021460523A CN02146052A CN1173004C CN 1173004 C CN1173004 C CN 1173004C CN B021460523 A CNB021460523 A CN B021460523A CN 02146052 A CN02146052 A CN 02146052A CN 1173004 C CN1173004 C CN 1173004C
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Abstract
The present invention relates to a preparation method of an organic phosphorescent material and the application of the organic phosphorescent material in organic electroluminescence. 10 to 50 mmol of substituted 2-methoxy benzoyl hydrazine is dissolved in superfluous phosphorus oxychloride under the protection of nitrogen, and is heated to reflux to react overnight. Then, the reaction liquid is slowly poured into ice water; deposition obtained by filtration is recrystallized by ethanol to prepare substituted 2-methoxy-1, 3, 4-oxadiazole; 5 to 40 mmol of the substituted 2-methoxy-1, 3, 4-oxadiazole is taken to be dissolved into a methylene chloride solvent; the methylene chloride solution of boron tribromide is dropwise added; deposition is collected by filtration; a white needle-shaped 2-(2-hydroxyphenyl)-1, 3, 4-oxadiazole crystal is obtained after recrystallization by ethanol for two times. The preparation technology of the present invention does not contain metallic ions, and the yield is more than 50%. The prepared organic material transmits strong blue or green phosphorescence at room temperature, and belongs to intrinsic luminescence.
Description
Technical field
The present invention relates to a kind of preparation of organic phosphorescent material.
Background technology
Since C.W.Tang in 1987 utilizes oxine aluminium (Alq
3) for luminescent layer, arylamine molecule are that hole transmission layer has prepared double-deck organic electroluminescence device, realized that people have carried out research extensively and profoundly to luminous organic material and electroluminescent device thereof, and have obtained the achievement that attracts people's attention since the organic electroluminescent.The mechanism of organic electroluminescent is under the extra electric field effect, and electronics and hole are injected the back from positive and negative polarities respectively and produced luminous in organic materials migration, compound and decay.In electroluminescent, the generation and the photoluminescence of exciton are different, it is by injecting electronics and hole at different electrodes place, and a certain appropriate position in device takes place compound and forms through electronics and hole transmission layer respectively.In this case, the formation of triplet state just by the intersystem crossing process of singlet state, can also not disposed by the difference of spin and realize in the system.Promptly in the electroluminescent system generation of exciton not only singlet state but also triplet state, both ratios should be 1: 3 by the statistics principle.Therefore for the electroluminescent device of routine, because its triplet state is luminous invalid, its electricity/luminous energy efficiency of conversion can not surpass 25%.Over nearly three, four years, the luminous very big interest that causes scientist of the phosphorescence of heavy metal organic coordination compound, luminous because its singlet state and triplet state can produce, theoretical electroluminescent efficiency can reach 100%, breaks through the only effective 25% luminous limit of singlet state.The heavy metal ion of reporting in the document mainly comprises: Cu (I), Au (I), Os (III), Ir (III), Pt (II) etc.As people such as Forrest three (2-phenylpyridine) iridium Ir (Ppy)
3Be doped to that prepared electroluminescent device has very high efficient among the BCP, power efficiency reaches 31lm/W (Appl.Phys.Lett., 1999,75,4).The title complex current efficiency of the Cyclometalated platinum of three teeth of people such as C.M.Che report is 4.2cd/A (Chem.Commun., 2002,206).The title complex device external quantum efficiency of the osmium of people such as Malliaras report reaches 1% (Adv.Mater., 2002,14,433).Common part mainly comprises: porphyrin, phthalocyanine, two (hexichol phosphorus) methane, 1, two (the hexichol phosphorus) 3 of 8-, 6-dioxy octane 2-phenylpyridine.Yet, do not contain present strong phosphorescent emissions under organic phosphorescent material, the especially room temperature condition of heavy metal ion pure organic materials but seldom.
Summary of the invention:
The preparation method who the purpose of this invention is to provide an organophosphorus luminescent material;
Another object of the present invention provides this application of organophosphorus luminescent material in organic electroluminescent.
Enol form isomer is for to stablize conformation under the ground state, and it forms the singlet excited of enol form under the condition of being excited.Exist the tautomerism of keto-acid and enol form under the excited state, so the singlet excited of enol form generates the singlet state of keto-acid via the intramolecularly prototropy.The singlet state of keto-acid forms the triplet state of keto-acid by scurrying between being to jump again.Exist the tautomerism of keto-acid triplet state and enol form triplet state simultaneously, the triplet state attenuation returns ground state, and it is luminous that phosphorescence promptly takes place.This quasi-molecule Bao Kuo oxadiazole, three classes such as triazole and phenolic group quinoline have the organic materials system of intramolecular hydrogen bond.Other molecular system with intramolecular hydrogen bond all has above-mentioned character.With the electroluminescent device of this kind material, under common light, all observe bright blue look or green emitting as luminescent layer.Trigger voltage is 4-6V; Luminosity is 600-1200cd/m
2Current efficiency is 0.3-0.8cd/A; Power efficiency is 0.18-0.65lm/W.
Excited state molecule inner proton transfevent phosphorescence light emitting molecule system provided by the invention has following formula:
R wherein
1Be H or OH; R
1During=H, be the sub-transferred material of simple substance; R
1=OH is the diproton transferred material;
Ar
1Be phenyl, Ar
2Be following group:
Preparation process is as follows:
Under the nitrogen protection 2-methoxybenzoyl hydrazine 10-50mmol that replaces is dissolved in the excessive phosphorus oxychloride, is heated to backflow, reaction is spent the night; Reaction solution is slowly poured in the frozen water then, filters the precipitation obtain and makes the 2-methoxyl group-1,3 of replacement, 4-oxadiazole with ethyl alcohol recrystallization; The 2-methoxyl group-1,3 of replacement, 4-oxadiazole 5-40mmol is dissolved in the dichloromethane solvent ,-60 ℃--78 ℃ of dichloromethane solution 20-80mmol that drip boron tribromide down; Slowly rise to room temperature after dropwising, react and pour in the frozen water after 18-36 hour, filter collecting precipitation, the 2-that ethyl alcohol recrystallization must replace for twice (2-hydroxy phenyl)-1,3,4-oxadiazole white needle-like crystals.
Preparation technology of the present invention does not contain metal ion, and productive rate is all more than 50%.Have the emission of very strong indigo plant or green phosphorescent under the organic materials room temperature that makes, it is luminous to belong to intrinsic.
Embodiment
Embodiment 1:2-(2-hydroxy phenyl)-5-phenyl-1,3,4-oxadiazole synthetic
A). Synthetic 2-(2-p-methoxy-phenyl)-5-phenyl-1,3,4-oxadiazole
Under nitrogen protection, N '-benzoyl-2-methoxybenzoyl hydrazine 10.3g (38.1mmol) is dissolved in the 120mL phosphorus oxychloride, is heated to backflow, and reaction is spent the night; Reaction solution is slowly poured in the 250mL frozen water.The precipitation that filtration obtains obtains product 8.1g (84%) with ethyl alcohol recrystallization.
B). Synthetic 2-(2-hydroxy phenyl)-5-phenyl-1,3,4-oxadiazole
2-(2-p-methoxy-phenyl)-5-phenyl-1,3,4-oxadiazole 8.5 g (33.7mmol) are dissolved in the 40mL methylene dichloride;-78 ℃ drip boron tribromide 38mL (80mmol) down, dropwised in 30 minutes; Reaction solution slowly rises to room temperature, carefully pours in the frozen water after 18 hours; Filter collecting precipitation, ethyl alcohol recrystallization gets white needle-like crystals 7.3g (91%) twice.
Embodiment 2:2-hydroxy phenyl-5-(2-naphthyl)-1,3,4-oxadiazole synthetic
A). Synthetic 2-p-methoxy-phenyl-5-(2-naphthyl)-1,3,4-oxadiazole
Under nitrogen protection, with the N-O-methoxy benzoyl-N of 16g (50mmol) '-2-naphthoyl hydrazides joins in the 400mL phosphorus oxychloride, is heated to 80 ℃, coreaction 15 hours; Steam excessive phosphorus oxychloride.Pour into after the cooling in the 300mL water, filter, get the pale solid; Water is given a baby a bath on the third day after its birth and use ethyl alcohol recrystallization behind time solid, must the 7.8g product, and productive rate 51.7%.
B). Synthetic 2-hydroxy phenyl-5-(2-naphthyl)-1,3,4-oxadiazole
With 2-o-methoxyphenyl-5-(2-naphthyl)-1,3 of 12g (40mmol), the 4-oxadiazole is dissolved in the 20mL methylene dichloride under nitrogen protection, is cooled to-60 ℃ with liquid nitrogen-Virahol then; Drip the 15mL dichloromethane solution of 80mmol boron tribromide, engender solid in the reaction solution, rose to the room temperature coreaction naturally 24 hours; Reactant to going in the frozen water, is filtered, get white solid; Water is given a baby a bath on the third day after its birth and use ethyl alcohol recrystallization behind time solid, must the 6.34g product, and productive rate 55.1%.
Embodiment 3:2-hydroxy phenyl-5-xenyl-1,3, the 4-oxadiazole
A). Synthetic 2-p-methoxy-phenyl-5-xenyl-1,3,4-oxadiazole
Under nitrogen protection, with the N-O-methoxy benzoyl-N of 17.4g (50mmol) '-2-dibenzoyl base hydrazides joins in the 300mL phosphorus oxychloride, is heated to 80 ℃, coreaction 15 hours; Steam excessive phosphorus oxychloride.Pour into after the cooling in the 500mL water, filter, get the pale solid; Water is given a baby a bath on the third day after its birth and use ethyl alcohol recrystallization behind time solid, must the 8.3g product, and productive rate 67%.
B). Synthetic 2-hydroxy phenyl-5-(2-naphthyl)-1,3,4-oxadiazole
With 2-p-methoxy-phenyl-5-xenyl-1,3 of 7g (35mmol), the 4-oxadiazole is dissolved in the 20mL methylene dichloride under nitrogen protection, is cooled to-70 ℃ with liquid nitrogen-Virahol then; Drip the 25mL dichloromethane solution of 70mmol boron tribromide, engender solid in the reaction solution, rose to the room temperature coreaction naturally 24 hours; Reactant to going in the frozen water, is filtered, get white solid; Water is given a baby a bath on the third day after its birth and use ethyl alcohol recrystallization behind time solid, must the 5.34g product, and productive rate 82%.
Embodiment 4:2-hydroxy phenyl-5-(4-diphenylamino) phenyl-1,3, the 4-oxadiazole
A). Synthetic 2-p-methoxy-phenyl-5-(4-diphenylamino) phenyl-1,3,4-oxadiazole
Under nitrogen protection, with the N-O-methoxy benzoyl-N of 16g (50mmol) '-triphen amido hydrazides joins in the 1000mL phosphorus oxychloride, is heated to 80 ℃, coreaction 15 hours; Steam excessive phosphorus oxychloride.Pour into after the cooling in the 300mL water, filter, get the pale solid; Water is given a baby a bath on the third day after its birth and use ethyl alcohol recrystallization behind time solid, must the 9.2g solid, and productive rate 73%, Mp134-136 ℃.
B). Synthetic 2-hydroxy phenyl-5-(4-diphenylamino) phenyl-1,3,4-oxadiazole
Under nitrogen protection, with 9.2g (22mmol) 2-o-methoxyphenyl-5-(4-diphenylamino) phenyl-1,3, the 4-oxadiazole is dissolved in the 40mL methylene dichloride, then with liquid nitrogen-Virahol cooling, drips the dichloromethane solution of boron tribromide (33mmol); Drip off the relief reactant and rise to room temperature gradually, continue reaction 24 hours; Reactant is poured in the water, chloroform extraction, solvent is steamed in dry back; With 4: 1 sherwood oils and ethyl acetate carry out silicagel column separate the 8.2g solid, use ethyl alcohol recrystallization then, productive rate 88%, Mp150-152 ℃.
Embodiment 5:2,5-two (2-hydroxy phenyl)-1,3,4-oxadiazole synthetic
A). under nitrogen protection, 2 '-methoxyl group N '-benzoyl-2-methoxybenzoyl hydrazine 10.3g (32mmol) is dissolved in the 120mL phosphorus oxychloride, is heated to backflow, and reaction is spent the night; Reaction solution is slowly poured in the 250mL frozen water.The precipitation that filtration obtains obtains product 7.6g (78%) with ethyl alcohol recrystallization.
B). under nitrogen protection, with 2.82g (10mmol) 2,5-two o-methoxyphenyls-1,3,4-oxadiazole are dissolved in the 40mL methylene dichloride, then with liquid nitrogen-Virahol cooling, drip the dichloromethane solution of boron tribromide (30mmol).Drip off afterreaction liquid and rise to room temperature gradually, continue reaction 24 hours.Reactant is poured in the water, filtered the solid ethyl alcohol recrystallization that obtains and get the 2.3g solid, productive rate 92%.Mp158-160℃。
Embodiment 6: the preparation of electroluminescent device
The structure that device adopts usually: ITO/NPB/ luminescent layer/CBP/Alq
3/ Mg:Ag.The molecule of each layer is all used the method film forming of vacuum evaporation; Luminescent layer is 2-(2-hydroxy phenyl)-5-phenyl-1,3, the 4-oxadiazole is introduced (N between luminescent layer and ITO, N-two-naphthyl-N,-4,4 the N-phenylbenzene)-(1,1 '-biphenyl) '-diamines (NPB) is as hole transmission layer, 4,4 '-(N, N-two carbazyls) biphenyl (BCP) stops hole in the luminescent layer, oxine aluminium (Alq as hole blocking layer
3) as electron transfer layer; Obtained device is that bright blue look luminous, and luminous maximum peak is positioned at 451nm, also has two acromions to be positioned at 480nm and 516nm; High-high brightness 600-800cd/m
2, current efficiency 0.44cd/A, power efficiency 0.14lm/W.
Claims (2)
1. the preparation method of an organic phosphorescent material is characterized in that material choice excited state molecule inner proton transfevent phosphorescence light emitting molecule system, and formula is:
R wherein
1Be H or OH; R
1During=H, be the sub-transferred material of simple substance; R
1=OH is the diproton transferred material;
Ar
1Be phenyl, Ar
2Be following group:
Preparation process is as follows:
Under the nitrogen protection 2-methoxybenzoyl hydrazine 10-50mmol that replaces is dissolved in the excessive phosphorus oxychloride, is heated to backflow, reaction is spent the night; Reaction solution is slowly poured in the frozen water then, the precipitation that filtration obtains makes the 2-methoxyl group-1 of replacement with ethyl alcohol recrystallization, 3,4-oxadiazole 5-40mmol is dissolved in the dichloromethane solvent ,-60 ℃--78 ℃ of dichloromethane solution 20-80mmol that drip boron tribromide down; Slowly rise to room temperature after dropwising, react and pour in the frozen water after 18-36 hour, filter collecting precipitation, the 2-that ethyl alcohol recrystallization must replace for twice (2-hydroxy phenyl)-1,3,4-oxadiazole white needle-like crystals;
The 2-methoxybenzoyl hydrazine of described replacement be N '-benzoyl-2-methoxybenzoyl hydrazine, N-O-methoxy benzoyl-N '-2-naphthoyl hydrazides, N-O-methoxy benzoyl-N '-2-dibenzoyl base hydrazides, N-O-methoxy benzoyl-N '-triphen amido hydrazides or 2 '-methoxyl group N '-benzoyl-2-methoxybenzoyl hydrazine;
The 2-methoxyl group-1,3 of described replacement, 4-oxadiazole are 2-(2-p-methoxy-phenyl)-5-phenyl-1,3,4-oxadiazole, 2-p-methoxy-phenyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-p-methoxy-phenyl-5-xenyl-1,3,4-oxadiazole, 2-o-methoxyphenyl-5-(4-diphenylamino) phenyl-1,3,4-oxadiazole or 2,5-two (2-p-methoxy-phenyl)-1,3, the 4-oxadiazole;
The 2-of described replacement (2-hydroxy phenyl)-1,3,4-oxadiazole are 2-(2-hydroxy phenyl)-5-phenyl-1,3,4-oxadiazole, 2-hydroxy phenyl-5-(2-naphthyl)-1,3,4-oxadiazole, 2-hydroxy phenyl-5-xenyl-1,3,4-oxadiazole, 2-hydroxy phenyl-5-(4-diphenylamino) phenyl-1,3,4-oxadiazole or 2,5-two (2-hydroxy phenyl)-1,3, the 4-oxadiazole.
2. the organic phosphorescent material of method preparation is according to claim 1 used in organic electroluminescent.
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