CN103194217B - Preparation method of dual-core cadmium complex with blue light performance - Google Patents
Preparation method of dual-core cadmium complex with blue light performance Download PDFInfo
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- CN103194217B CN103194217B CN201310144785.5A CN201310144785A CN103194217B CN 103194217 B CN103194217 B CN 103194217B CN 201310144785 A CN201310144785 A CN 201310144785A CN 103194217 B CN103194217 B CN 103194217B
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- luminescent material
- blue light
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Abstract
The invention relates to a dual-core organic luminescent material and a preparation method of the luminescent material and discloses a blue light organic luminescent material and a preparation of the luminescent material. According to the invention, the problems of low brightness and luminous efficiency of the blue light organic luminescent material in the prior art are solved. The molecular formula of the product disclosed by the invention is C20H24CdN6O5S. The preparation method of the blue light organic luminescent material disclosed by the invention comprises the following steps of: 1) preparation of 4-[(8-hydroxyl-5-quinoline)azo] phenylsulfonic acid; and 2) preparation of a coordination polymer: respectively dissolving a ligand and cadmium chloride into a solvent and mixing, then adding organic alkali and stirring at the room temperature for 1 hour to acquire red blocked crystals. The product prepared through the method disclosed by the invention is single crystal in a complete crystal form; and through a luminous performance test, the blue light organic luminescent material prepared through the method disclosed by the invention shows blue fluorescence and has high heat stability and favorable film forming characteristic. The yield of the product prepared through the method disclosed by the invention is higher than 40%.
Description
Technical field
The present invention relates to luminous organic material and preparation method thereof, be specifically related to a kind of 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid Dinuclear cadmium complex and preparation method thereof.
Background technology
Owing to there being the concern of good performance and potential application prospect and extremely people in sensor technology, photochemistry and electroluminescent material etc. containing the emitting complexes of azo ligands, become the focus of research.Researchist has synthesized a large amount of d
10the title complex particularly containing cadmium containing azo ligands metal complexes of race, and have studied their luminescent properties, research finds that the size of the pi-conjugated system of part and the electronic effect of ligand substituting base are the important factors regulating title complex luminescent properties; As the people such as X. Feng in 2010 report a series of azo title complex 3,3'-azodibenzoate (3,3'-ADB) and 4,4'-azodibenzoate (4,4'-ADB) part has been used for having synthesized [Cd (3,3'-ADB)
2(H
2nMe
2) (NH
4)]
n{ Tb
2(4,4'-ADB)
3[(CH
3)
2sO]
416 [(CH
3)
2sO] }
n, above-mentioned title complex has good fluorescence property.People were investigated the ligand polymer of a lot of azo in recent years, but can form the rarely found of multinuclear coordination, and obtained ligand polymer is mostly the luminous organic material of purple light, and had almost not having of blue light.Although people have done large quantity research to emitting complexes, the brightness of existing blue light organic luminescent material and luminous efficiency are still on the low side.
Summary of the invention
The object of the invention is the problem that brightness and luminous efficiency in order to solve existing blue light organic luminescent material is on the low side; And a kind of blue light organic luminescent material and preparation method thereof is provided.
Blue light organic luminescent material { { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF} in the present invention
nmolecular formula be C
20h
24cdN
6o
5s, its structural formula is
。
{ { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF}
nthe step of preparation method is as follows: one, the preparation of 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid: Sulphanilic Acid (1.221g, 7.06mol) is dissolved in 20mL H
2in O, add HCl solution (37%, 1.47mL), temperature 0-5 DEG C.Dropwise add the NaNO of 5%
2solution (7.06 mmol, 10mL), diazonium effect is completed after stirring 60min at 0-5 DEG C, and by oxine (1.025g, 7.06 mmol) in 0.5M NaOH solution (16mL), cooling and stirring is extremely thick, dropwise add in 60min, and at room temperature stir a night, adjust pH to the 7.5-8.0(sodium acetate soln of dilution) filtering-depositing.Thick product is (50mL) recrystallization twice in water, then at vacuum drying oven inner drying (productive rate 40%).
Two, at N, in the solvent of N '-dimethyl methane amide (DMF, 2 mL) and ethanol (10 mL), Cadmium chloride fine powder (CdCl is added
22.5H
2o (30mg, 0.13mmol)) with 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid (5mg, 0.015mmol), quadrol (ethylenediamine (0.025mL)) is added after stirring, at ambient temperature, after magnetic agitation reacts 1 hour, gained solution is transferred in the reactor with polytetrafluoroethyllining lining (25 mL), temperature programming 100 ° of C, 100h, obtain red bulk crystals, after being filtered by product, seasoning, productive rate is 46.8 % (calculating with Cd).
In step one, sodium acetate soln adjust ph is used in above-mentioned reaction.
The present invention selects water as the recrystallization reagent of part, and than the N used in bibliographical information, N '-dimethyl methane amide improves 10% ~ 20% for productive rate in the synthesis of part, reach more than 40%, and the synthesis of water on later stage ligand polymer does not affect.The inventive method preparing product is the monocrystalline that crystal formation is intact; The present invention obtains blue light organic luminescent material and tests through luminescent properties, all presents blue-fluorescence, and its brightness and luminous efficiency are enhanced, but also there is high efficiency fluorescence and good film forming characteristics, and stability is strong, and the productive rate that the present invention obtains product is high, reaches more than 40%.
Accompanying drawing explanation
Fig. 1 is the crystalline structure figure that embodiment one method obtains product.Fig. 2 is the infrared spectrogram that embodiment one method obtains product.Fig. 3 is the fluorescence spectrum figure that part 4-of the present invention [(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid and embodiment one method obtain product; In figure-and (a, a ')-represent part 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid fluorescence spectrum ,-(b, b ')-embodiment one method obtains product fluorescence spectrum.
Embodiment
Embodiment one: blue light organic luminescent material { { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (the quadrol) } DMF} in present embodiment
nmolecular formula be C
20h
24cdN
6o
5s, its structural formula is
。
{ { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF}
nthe step of preparation method is as follows: one, the preparation of 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid: Sulphanilic Acid (1.221g, 7.06mol) is dissolved in 20mL H
2in O, add HCl solution (37%, 1.47mL), temperature 0-5 DEG C.Dropwise add the NaNO of 5%
2solution (7.06 mmol, 10mL), diazonium effect is completed after stirring 60min at 0-5 DEG C, and by oxine (1.025g, 7.06 mmol) in 0.5M NaOH solution (16mL), cooling and stirring is extremely thick, dropwise add in 60min, and at room temperature stir a night, adjust pH to the 7.5-8.0(sodium acetate soln of dilution) filtering-depositing.Thick product is (50mL) recrystallization twice in water, then at vacuum drying oven inner drying (productive rate 40%).
Two, at N, in the solvent of N '-dimethyl methane amide (DMF, 2 mL) and ethanol (10 mL), Cadmium chloride fine powder (CdCl is added
22.5H
2o (30mg, 0.13mmol)) with 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid (5mg, 0.015mmol), quadrol (ethylenediamine (0.025mL)) is added after stirring, at ambient temperature, after magnetic agitation reacts 1 hour, gained solution is transferred in the reactor with polytetrafluoroethyllining lining (25 mL), temperature programming 100 ° of C, 100h, obtain red bulk crystals, after being filtered by product, seasoning, productive rate is 46.8 % (calculating with Cd).
Present embodiment uses sodium acetate soln adjust ph in step one.
The productive rate of present embodiment is 46.8%, { { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF}
nthe monocrystalline crystal that red crystal formation is intact, present blue-fluorescence, maximum emission peak wavelength is respectively
λ max=421 nm.The present invention obtains blue light organic luminescent material brightness and luminous efficiency is enhanced (the obvious enhancing of the luminous strength ratio part of present embodiment product as seen from Figure 3, namely brightness increases thus luminous efficiency is improved), and have high efficiency fluorescence and good film forming characteristics, and stability is strong.
The reaction equation of present embodiment is as follows:
The preparation of step one, 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid:
Step 2, { { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF}
npreparation:
Embodiment two: blue light organic luminescent material { { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF} in present embodiment
nthe step of preparation method is as follows: one, the preparation of 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid: Sulphanilic Acid (1.221g, 7.06mol) is dissolved in 20mL H
2in O, add HCl solution (37%, 1.47mL), temperature 0-5 DEG C.Dropwise add the NaNO of 5%
2solution (7.06 mmol, 10mL), diazonium effect is completed after stirring 60min at 0-5 DEG C, and by oxine (1.025g, 7.06 mmol) in 0.5M NaOH solution (16mL), cooling and stirring is extremely thick, dropwise add in 60min, and at room temperature stir a night, adjust pH to the 7.5-8.0(sodium acetate soln of dilution) filtering-depositing.Thick product is (50mL) recrystallization twice in water, then at vacuum drying oven inner drying (productive rate 40%).
Two, at N, in the solvent of N '-dimethyl methane amide (DMF, 2 mL) and ethanol (10 mL), Cadmium chloride fine powder (CdCl is added
22.5H
2o (30mg, 0.13mmol)) with 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid (5mg, 0.015mmol), quadrol (ethylenediamine (0.025mL)) is added after stirring, at ambient temperature, after magnetic agitation reacts 1 hour, gained solution is transferred in the reactor with polytetrafluoroethyllining lining (25 mL), temperature programming 100 ° of C, 100h, obtain red bulk crystals, after being filtered by product, seasoning, productive rate is 46.8 % (calculating with Cd).
Claims (2)
1. blue light organic luminescent material, is characterized in that blue light organic luminescent material { { Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF}
nmolecular formula be C
20h
24cdN
6o
5s, its structural formula is
2. prepare the method for blue light organic luminescent material described in claim 1, it is characterized in that preparation method's step of blue light organic luminescent material is as follows: one, the preparation of 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid: 1.221g Sulphanilic Acid is dissolved in 20mL water, add 37% hydrochloric acid soln 1.47mL, temperature of reaction is 0 ~ 5 DEG C, then 5% sodium nitrite solution 10mL is dropwise added, stir under 0 ~ 5 DEG C of condition after 60 minutes and complete diazotization, and it is extremely thick 1.025g oxine to be dissolved in cooling and stirring in 16mL0.5M sodium hydroxide solution, dropwise added in 60 minutes, and at room temperature stir a night, pH to 7.5 ~ 8.0 are adjusted with the sodium acetate soln of dilution, filtering-depositing, thick product twice, recrystallization in 50mL water, then at vacuum drying oven inner drying, productive rate is 40%, two, at 2mL N, 0.03g Cadmium chloride fine powder and 0.005g 4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid is added in the solvent of N '-dimethyl methane amide and 10 mL ethanol, 0.025mL quadrol is added after stirring, at ambient temperature, after magnetic agitation reacts 1 hour, gained solution is transferred to 25mL with in teflon-lined reactor, temperature programming 100 DEG C, 100h, obtain red bulk crystals, after product is filtered, seasoning, productive rate is 46.8%, calculates with Cd.
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| CN104693220A (en) * | 2015-03-27 | 2015-06-10 | 吉林化工学院 | Preparing method for azobenzene-4, 4'-dicarboxylic acid copper complex with blue light performance |
| CN104789211A (en) * | 2015-03-30 | 2015-07-22 | 吉林化工学院 | Preparation method for azobenzene-4,4'-dicarboxylic acid cadmium complex with blue light performance |
| CN104761586A (en) * | 2015-03-30 | 2015-07-08 | 吉林化工学院 | Preparation method of manganese 4-[(8-hydroxy-5-quinolyl)azo]-benzenesulfonate complex with blue-light performance |
| CN104744515A (en) * | 2015-03-31 | 2015-07-01 | 吉林化工学院 | Preparation method of manganese azobenzene-4,4'-dicarboxylate complex with blue-light performance |
| CN106916176A (en) * | 2017-03-08 | 2017-07-04 | 天津师范大学 | A kind of soluble chloride bridging dinuclear cadmium complex and preparation method and applications |
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| CN103045234A (en) * | 2013-01-24 | 2013-04-17 | 吉林化工学院 | Preparation method of 4-[(8-hydroxyl-5-quinoline) azo] zinc benzene sulfonate complex with purple light property |
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| CN103045234A (en) * | 2013-01-24 | 2013-04-17 | 吉林化工学院 | Preparation method of 4-[(8-hydroxyl-5-quinoline) azo] zinc benzene sulfonate complex with purple light property |
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| Title |
|---|
| Preparation of coordination polymers with 8-hydroxyquinoline azo benzensulfonic acid as a planar multidentate ligand and the study of their photochemical and photo-stability properties;Hong-Xia Chen等;《Dalton Trans.》;20121218;第42卷;4831–4839 * |
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