CN1263822C - Luminous material of metal complex type containing hole transmission group and preparation process thereof - Google Patents
Luminous material of metal complex type containing hole transmission group and preparation process thereof Download PDFInfo
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- CN1263822C CN1263822C CN 200410012446 CN200410012446A CN1263822C CN 1263822 C CN1263822 C CN 1263822C CN 200410012446 CN200410012446 CN 200410012446 CN 200410012446 A CN200410012446 A CN 200410012446A CN 1263822 C CN1263822 C CN 1263822C
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- carbazole
- oxine
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Abstract
The present invention relates to a metal complex type luminous material containing hole transmission base groups, which is a 5-(N-methylene carbazole)-8-hydroxyquinoline aluminium complex. The preparing method of a metal complex comprises the following steps that (1) 8-hydroxyquinoline acts with formaldehyde under the action of hydrochloric acid gas and is added with hydrochloric acid to make 5-chloromethyl-8-hydroxy quinoline hydrochloride under room temperature; (2) carbazole uses dimethyl sulfoxide as solvent and is ground with sodium hydride under the room temperature to generate carbazole sodium salt; (3) 5-chloromethyl-8-hydroxy quinoline hydrochloride and carbazole sodium salt make a reaction under the room temperature with the existence of potassium hydroxide to generate 5-(N-methylene carbazole)-8-hydroxyquinoline; (4) 5-(N-methylene carbazole)-8-hydroxyquinoline and aluminium trichloride are complex to a metal complex. The luminous material has high quantum yield and electron mobility and a device combined by the luminous material as a main body material can regulate electron injection and hole transmission to a balance. The preparation method of the metal complex has the advantages of simple operation and high resultant purity.
Description
Technical field
The present invention relates to a kind of luminescent material, specifically belong to a kind of metal complex type luminescent material that contains cavity transmission group and preparation method thereof.
Background technology
Organic electroluminescent (Organic electroluminescence) is to utilize some organic materials compound molecules can luminous performance remove to make luminescent device under galvanic action, and is used for the technology in the light demonstration field of information.1987, people such as the Tang of Kodak (W.C.Tang, D.D.C.Bradley; Appl.Phys.Lett.1987,51 (12): 913-915) adopt bilayer structure first, be hole mobile material with the aromatic diamines analog derivative promptly, oxine aluminium is the luminescent layer material, prepares the organic electroluminescence device of high-luminous-efficiency, high brightness and low driving voltage.After this breakthrough development, people have given very big concern to the design of material and the optimization of device.From molecular structure, oxine aluminium belongs to " inner complex salt ", and between organism and inorganics, structure is highly stable.Adopt the classical electroluminescent device of oxine aluminium as electric transmission and luminescent material, glow color is green, with the material of main part that it is constructed as luminescent device, can realize high efficiency green glow, gold-tinted and red emission by mixing.Yet, because the fluorescence quantum yield lower (in DMF, having only 11%) of oxine aluminium itself and electronic mobility also lower (have only hole mobile material 1/100), when forming device by it in addition, be difficult to balance is adjusted in electronics injection and hole transport, this has just restricted the further raising of device performance.Therefore, on the basis of oxine structure, introduce the quantum yield height, hole transport that transmission efficiency is high (carbazyl) or electronics inject (oxadiazole base) group, oxine constructed of aluminium unit that luminescent properties is good and hole transport or electronics inject group and include a molecule in, and designing novel luminous organic material compound molecule is the aim of this series property invention.
Summary of the invention
The object of the present invention is to provide a kind of quantum yield and high metal complex type luminescent material of electronic mobility that contains cavity transmission group, by its device that is combined into for material of main part, electronics injection and hole transport can be adjusted to balance, and the preparation method of metal complex is simple to operate, product purity is high.
A kind of metal complex type luminescent material that contains cavity transmission group provided by the invention, it is 5-(N-methylene radical carbazole)-oxine aluminium complex, its structural formula is:
The present invention contains the preparation method of the metal complex type luminescent material of cavity transmission group, comprises the steps:
(1) by oxine under the hydrogen chloride gas effect with the formaldehyde effect, and add hydrochloric acid, under the room temperature, make 5-chloromethyl-oxine hydrochloride (II);
(2) carbazole is solvent with the dimethyl sulfoxide (DMSO), at room temperature grinds with sodium hydride, generates carbazole sodium salt (III);
(3) use 5-chloromethyl-oxine hydrochloride and carbazole sodium salt in the presence of potassium hydroxide, room temperature reaction generates 5-(N-methylene radical carbazole)-oxine (IV);
(4) complexing in the dichloromethane solvent that refluxes of 5-(N-methylene radical carbazole)-oxine and aluminum chloride generates metal complex (I).
Reactant consumption mol ratio is in described (1) step: oxine: formaldehyde: hydrochloric acid=l: l～2: 1.5～2;
Reactant consumption mol ratio is in described (2) step: carbazole: sodium hydride=1: 1.2～1.7;
Reactant consumption mol ratio is in described (3) step: potassium hydroxide: 5-chloromethyl-oxine hydrochloride=1: 1～1.5;
Reactant consumption mol ratio is in described (4) step: 5-(N-methylene radical carbazole)-oxine: aluminum chloride=3: 1.
Compared with prior art the present invention has following characteristics, and preparing of success included typical cavity transmission group carbazyl and luminophore oxine aluminium in the same molecule luminescent metal complexes; By its device that is combined into for material of main part, electronics injection and hole transport can be adjusted to balance, thereby for the combination that realizes the luminescent device that quantum yield and electronic mobility are high provides material, and the metal complex of preparation, the purity height, the yield height, equipment is simple, easy to operate, help enlarging production and reducing production costs.
EXAMPLE l
In the there-necked flask of the 100ml that magnetic stirring apparatus, airway are housed, add the 3.7g oxine, the formaldehyde solution of 8ml 37%, the 10ml concentrated hydrochloric acid will make by the vitriol oil and sodium-chlor reaction then.Feed down continuously through Calcium Chloride Powder Anhydrous exsiccant hydrogen chloride gas, stirring reaction 90min obtains a large amount of yellow mercury oxides, and the suction filtration drying gets yellow solid II4.5g productive rate 77.5%, m.p.285 ℃.In the there-necked flask of 100ml, add the pure carbazole of 3.3g, the 50ml anhydrous dimethyl sulphoxide, stirring and dissolving, drop into the sodium hydride of equimolar amount then, stirring reaction is emitted up to no bubble, filters, filtrate pouring into is equipped with in the there-necked flask of 100ml of magnetic stirring apparatus, thermometer and reflux condensing tube, add 1.1g potassium hydroxide,, drop into reaction flask in three batches the Compound I I4.5g of previous step gained, under the room temperature behind the stirring reaction 6h, stop to stir, suction filtration is used the dissolve with ethanol heat filtering, get faint yellow solid IV3.3g, productive rate 51.8%.In the 50ml there-necked flask, add the ligand compound IV (1.333g) and the methylene dichloride (30ml) that have made.3ml is contained AlCl
3Methanol solution (0.32g) is diluted to 10ml with methylene dichloride, under reflux state, drips, and the color flavescence green gradually of reaction solution, and be attended by a large amount of precipitations and separate out, be cooled to room temperature, with the sedimentation and filtration of separating out, filter cake washed with dichloromethane, drying, obtain complex compound 1.32g, productive rate 81%
1H-NMR (d
6DMSO, ppm)
δ: 8.88 (ortho position of N is hydrocarbon in the oxine for s, 3H), 8.22 (contraposition of N is hydrocarbon in the oxine for s, 3H), 7.52-6.87 (m, 33H, all the other benzene ring hydrogens), 5.95 (s, 6H ,-CH
2-); FTIR (KBr, cm
-1): 3050,1660,1590,1575,1530,1170,795.
Embodiment 2
Method according to example 1 prepares 5-chloromethyl-oxine hydrochloride (II).
In mortar, add 10ml dimethyl sulfoxide (DMSO), the pure carbazole of 3.3g, stirring and dissolving, the sodium hydride that in batches adds equimolar amount, constantly stir till no bubble produces simultaneously, solution becomes incarnadine, add 4.3g compound 5-chloromethyl-oxine hydrochloride (II) and potassium hydroxide 1.1g then in batches, constantly grind 2h.Above-mentioned solution is poured in the beaker that 300ml distilled water is housed, and with the neutralization of 10% hydrochloric acid, suction filtration is dissolved in the ethanol of heat with the solid of gained, and filtered while hot concentrates filtrate, rotation remove desolvate solid IV3.63g, productive rate 57%.In the 50ml there-necked flask, add the ligand compound IV (1.333g) and the methylene dichloride (30ml) that have made.3ml is contained AlCl
3Methanol solution (0.32g) is diluted to 10ml with methylene dichloride, under reflux state, drip, the color flavescence green gradually of reaction solution, and be attended by a large amount of precipitations and separate out, be cooled to room temperature, with the sedimentation and filtration of separating out, the filter cake washed with dichloromethane, drying obtains complex compound III1.32g, productive rate 81%
1H-NMR (d
6DMSO, ppm)
δ: 8.88 (ortho position of N is hydrocarbon in the oxine for s, 3H), 8.22 (contraposition of N is hydrocarbon in the oxine for s, 3H), 7.52-6.87 (m, 33H, all the other benzene ring hydrogens), 5.95 (s, 6H ,-CH
2-); FTIR (KBr, cm
-1): 3050,1660,1590,1575,1530,1170,795.
Embodiment 3
Method according to example 1 prepares 5-chloromethyl-oxine hydrochloride (II).
In mortar, add 10ml dimethyl sulfoxide (DMSO), the pure carbazole of 3.3g, grind dissolving, sodium hydride with 1.2 times of molar weights adds under constantly grinding in batches, till no bubble produces, solution becomes incarnadine, the potassium hydroxide that in batches adds 4.3g compound 5-chloromethyl-oxine hydrochloride (II) and 1.5 times of molar weights then continues to grind 2h.Above-mentioned solution is equipped with in the beaker of pouring 300ml distilled water into, and with the neutralization of 10% hydrochloric acid, suction filtration is dissolved in the ethanol of heat with the solid of gained, and filtered while hot concentrates filtrate, rotation remove desolvate solid III3.9g, productive rate 61.2%.
In the 50ml there-necked flask, add the ligand compound IV (1.333g) and the methylene dichloride (30ml) that have made.3ml is contained AlCl
3Methanol solution (0.32g) is diluted to 10ml with methylene dichloride, under reflux state, drip, the color flavescence green gradually of reaction solution, and be attended by a large amount of precipitations and separate out, be cooled to room temperature, with the sedimentation and filtration of separating out, the filter cake washed with dichloromethane, drying obtains complex compound IV1.32g, productive rate 81%
1H-NMR (d
6DMSO, ppm) δ: 8.88 (ortho position of N is hydrocarbon in the oxine for s, 3H), 8.22 (contraposition of N is hydrocarbon in the oxine for s, 3H), 7.52-6.87 (m, 33H, all the other benzene ring hydrogens), 5.95 (s, 6H ,-CH
2-); FTIR (KBr, cm
-1): 3050,1660,1590,1575,1530,1170,795.
Claims (3)
1, a kind of metal complex type luminescent material that contains cavity transmission group is characterized in that, it is 5-(N-methylene radical carbazole)-oxine aluminium complex, and its structural formula is:
2, according to the described preparation method who contains the metal complex type luminescent material of cavity transmission group of claim 1, it is characterized in that comprising the steps:
(1) by oxine under the hydrogen chloride gas effect with the formaldehyde effect, and add hydrochloric acid, under the room temperature, make 5-chloromethyl-oxine hydrochloride;
(2) carbazole is solvent with the dimethyl sulfoxide (DMSO), at room temperature grinds with sodium hydride, generates the carbazole sodium salt;
(3) use 5-chloromethyl-oxine hydrochloride and carbazole sodium salt in the presence of potassium hydroxide, room temperature reaction generates 5-(N-methylene radical carbazole)-oxine;
(4) complexing in the dichloromethane solvent that refluxes of 5-(N-methylene radical carbazole)-oxine and aluminum chloride generates metal complex.
3, according to the described preparation method who contains the metal complex type luminescent material of cavity transmission group of claim 2, it is characterized in that:
Reactant consumption mol ratio is in described (1) step: oxine: formaldehyde: hydrochloric acid=1: 1～2: 1.5～2;
Reactant consumption mol ratio is in described (2) step: carbazole: sodium hydride=1: 1.2～1.7;
Reactant consumption mol ratio is in described (3) step: potassium hydroxide: 5-chloromethyl-oxine hydrochloride=1: 1～1.5;
Reactant consumption mol ratio is in described (4) step: 5-(N-methylene radical carbazole)-oxine: aluminum chloride=3: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410012446 CN1263822C (en) | 2004-07-26 | 2004-07-26 | Luminous material of metal complex type containing hole transmission group and preparation process thereof |
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| CN 200410012446 CN1263822C (en) | 2004-07-26 | 2004-07-26 | Luminous material of metal complex type containing hole transmission group and preparation process thereof |
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| CN1597838A CN1597838A (en) | 2005-03-23 |
| CN1263822C true CN1263822C (en) | 2006-07-12 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101058616B (en) * | 2007-04-30 | 2010-05-19 | 中国科学院广州化学研究所 | Crosslinking polymer containing cavity transmission unit of 8-hydroxyquinoline metal complex and preparation method |
| CN112961097A (en) * | 2019-12-13 | 2021-06-15 | 中国科学院大连化学物理研究所 | Preparation method and application of organic metal compound |
| CN113072687B (en) * | 2021-03-10 | 2022-12-13 | 东南大学 | Carbazole porous polymer containing 8-hydroxyquinoline group, and preparation method and application thereof |
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