CN103194217A - 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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- CN103194217A CN103194217A CN2013101447855A CN201310144785A CN103194217A CN 103194217 A CN103194217 A CN 103194217A CN 2013101447855 A CN2013101447855 A CN 2013101447855A CN 201310144785 A CN201310144785 A CN 201310144785A CN 103194217 A CN103194217 A CN 103194217A
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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 double-core cadmium complex and preparation method thereof.
Background technology
The people's attention extremely because the luminescent ligand compound that contains azo ligands has good performance and potential application prospect at aspects such as sensor technology, photochemistry and electroluminescent materials becomes the focus of research.The researchist has synthesized a large amount of d
10Family contains the title complex that the azo ligands metal complexes particularly contains cadmium, and has studied their luminescent properties, discovers that the size of the pi-conjugated system of part and the substituent electronic effect of part are the important factors of regulating the title complex luminescent properties; Reported a series of azo title complex 3 as people such as X. Feng in 2010,3'-azodibenzoate (3,3'-ADB) and 4,4'-azodibenzoate (4,4'-ADB) part be used for having synthesized [Cd (and 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 fluorescence property preferably.People had also studied the ligand polymer of a lot of azo classes in recent years, but can form the rarely found of multinuclear coordination, and prepared ligand polymer mostly is the luminous organic material of purple light, and had almost not having of blue light.Though people have done big quantity research to the luminescent ligand compound, brightness and the luminous efficiency of existing blue light organic luminescent material are still on the low side.
Summary of the invention
The objective of the invention is in order to solve brightness and the luminous efficiency problem on the low side of existing blue light organic luminescent material; And provide a kind of blue light organic luminescent material and preparation method thereof.
Blue light organic luminescent material among the present invention Cd{4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } (quadrol) } DMF}
nMolecular formula be C
20H
24CdN
6O
5S, its structural formula is
Cd{4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } (quadrol) } DMF}
nPreparation method's step is as follows: azo one, 4-[(8-hydroxyl-5-quinoline)] preparation of Phenylsulfonic acid: (1.221g 7.06mol) is dissolved in 20mL H to Sulphanilic Acid
2Among the O, and adding HCl solution (37%, 1.47mL), temperature 0-5 ℃.Dropwise add 5% NaNO
2Solution (7.06 mmol, 10mL), behind 0-5 ℃ of stirring 60min, finish the diazonium effect, and with oxine (1.025g, 7.06 mmol) cooling and stirring is extremely thick in 0.5M NaOH solution (16mL), in 60min, dropwise add, and at room temperature stir a night, transfer pH to the 7.5-8.0(sodium acetate soln of dilution) filtering-depositing.Thick product (50mL) recrystallization twice in water is then at vacuum drying oven inner drying (productive rate 40%).
Two, at N, add Cadmium chloride fine powder (CdCl in the solvent of N '-dimethyl formamide (DMF, 2 mL) and ethanol (10 mL)
22.5H
2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.025mL)) Phenylsulfonic acid, at ambient temperature, the magnetic agitation reaction was transferred to gained solution in the reactor that has polytetrafluoroethyllining lining (25 mL) 100 ° of C of temperature programming, 100h after 1 hour, obtain red bulk crystals, after the product filtration, seasoning, productive rate is 46.8 % (calculating with Cd).
In step 1, regulate the pH value with sodium acetate soln in the above-mentioned reaction.
The present invention selects for use water as the recrystallization reagent of part, and than employed N in the bibliographical information, N '-dimethyl formamide improves 10% ~ 20% for the synthetic productive rate of going up of part, reached more than 40%, and water is to the synthetic not influence of later stage ligand polymer.The inventive method preparing product is the intact monocrystalline of crystal formation; The present invention makes blue light organic luminescent material and tests through luminescent properties, all presents blue-fluorescence, and its brightness and luminous efficiency are enhanced, but also have high efficiency fluorescence and film forming characteristics preferably, and stability is strong, and the present invention makes the productive rate height of product, reaches more than 40%.
Description of drawings
Fig. 1 is the crystalline structure figure that embodiment one method makes product.Fig. 2 is the infrared spectrogram that embodiment one method makes product.Fig. 3 is part 4-[(8-hydroxyl of the present invention-5-quinoline) azo] Phenylsulfonic acid and embodiment one method make the fluorescence spectrum figure of product; Among the figure-and (a, a ')-expression part 4-[(8-hydroxyl-5-quinoline) azo] the Phenylsulfonic acid fluorescence spectrum ,-(b, b ')-embodiment one method makes the product fluorescence spectrum.
Embodiment
Embodiment one: the blue light organic luminescent material in the present embodiment Cd{4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } (quadrol) } DMF}
nMolecular formula be C
20H
24CdN
6O
5S, its structural formula is
Cd{4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } (quadrol) } DMF}
nPreparation method's step is as follows: azo one, 4-[(8-hydroxyl-5-quinoline)] preparation of Phenylsulfonic acid: (1.221g 7.06mol) is dissolved in 20mL H to Sulphanilic Acid
2Among the O, and adding HCl solution (37%, 1.47mL), temperature 0-5 ℃.Dropwise add 5% NaNO
2Solution (7.06 mmol, 10mL), behind 0-5 ℃ of stirring 60min, finish the diazonium effect, and with oxine (1.025g, 7.06 mmol) cooling and stirring is extremely thick in 0.5M NaOH solution (16mL), in 60min, dropwise add, and at room temperature stir a night, transfer pH to the 7.5-8.0(sodium acetate soln of dilution) filtering-depositing.Thick product (50mL) recrystallization twice in water is then at vacuum drying oven inner drying (productive rate 40%).
Two, at N, add Cadmium chloride fine powder (CdCl in the solvent of N '-dimethyl formamide (DMF, 2 mL) and ethanol (10 mL)
22.5H
2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.025mL)) Phenylsulfonic acid, at ambient temperature, the magnetic agitation reaction was transferred to gained solution in the reactor that has polytetrafluoroethyllining lining (25 mL) 100 ° of C of temperature programming, 100h after 1 hour, obtain red bulk crystals, after the product filtration, seasoning, productive rate is 46.8 % (calculating with Cd).
Present embodiment is regulated the pH value with sodium acetate soln in step 1.
The productive rate of present embodiment is 46.8%, Cd{4-[(8-hydroxyl-5-quinoline) azo] Phenylsulfonic acid } (quadrol) } DMF}
nThe intact monocrystalline crystal of red crystal formation presents blue-fluorescence, and the maximum emission peak wavelength is respectively
λ Max=421 nm.The present invention makes 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, thereby be that the brightness increase is improved luminous efficiency), and have high efficiency fluorescence and good film forming characteristics, and stability is strong.
The reaction equation of present embodiment is as follows:
Step 1,4-[(8-hydroxyl-5-quinoline) azo] preparation of Phenylsulfonic acid:
Step 2, Cd{4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } (quadrol) } DMF}
nPreparation:
Embodiment two: blue light organic luminescent material in the present embodiment Cd{4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } (quadrol) } DMF}
nPreparation method's step is as follows: azo one, 4-[(8-hydroxyl-5-quinoline)] preparation of Phenylsulfonic acid: (1.221g 7.06mol) is dissolved in 20mL H to Sulphanilic Acid
2Among the O, and adding HCl solution (37%, 1.47mL), temperature 0-5 ℃.Dropwise add 5% NaNO
2Solution (7.06 mmol, 10mL), behind 0-5 ℃ of stirring 60min, finish the diazonium effect, and with oxine (1.025g, 7.06 mmol) cooling and stirring is extremely thick in 0.5M NaOH solution (16mL), in 60min, dropwise add, and at room temperature stir a night, transfer pH to the 7.5-8.0(sodium acetate soln of dilution) filtering-depositing.Thick product (50mL) recrystallization twice in water is then at vacuum drying oven inner drying (productive rate 40%).
Two, at N, add Cadmium chloride fine powder (CdCl in the solvent of N '-dimethyl formamide (DMF, 2 mL) and ethanol (10 mL)
22.5H
2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.025mL)) Phenylsulfonic acid, at ambient temperature, the magnetic agitation reaction was transferred to gained solution in the reactor that has polytetrafluoroethyllining lining (25 mL) 100 ° of C of temperature programming, 100h after 1 hour, obtain red bulk crystals, after the product filtration, seasoning, productive rate is 46.8 % (calculating with Cd).
Claims (3)
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. the method for preparing the described blue light organic luminescent material of claim 1, the preparation method's step that it is characterized in that blue light organic luminescent material is as follows: azo one, 4-[(8-hydroxyl-5-quinoline)] preparation of Phenylsulfonic acid: (1.221g 7.06mol) is dissolved in 20mL H to Sulphanilic Acid
2Among the O, add HCl solution (37%, 1.47mL), temperature 0-5 ℃, dropwise add 5% NaNO
2Solution (7.06 mmol, 10mL), behind 0-5 ℃ of stirring 60min, finish the diazonium effect, and oxine (1.025g, 7.06 mmol) cooling and stirring in 0.5M NaOH solution (16mL) is extremely thick, in 60min, dropwise add, and at room temperature stir a night, transfer pH to 7.5-8.0(with the sodium acetate soln of dilution) filtering-depositing, thick product twice in (50mL) recrystallization in water, then at vacuum drying oven inner drying (productive rate 40%)
Two, at N, add Cadmium chloride fine powder (CdCl in the solvent of N '-dimethyl formamide (DMF, 2 mL) and ethanol (10 mL)
22.5H
2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.025mL)) Phenylsulfonic acid, at ambient temperature, the magnetic agitation reaction was transferred to gained solution in the reactor that has polytetrafluoroethyllining lining (25 mL) 100 ° of C of temperature programming, 100h after 1 hour, obtain red bulk crystals, after the product filtration, seasoning, productive rate is 46.8 % (calculating with Cd).
3. the preparation method of blue light organic luminescent material according to claim 2 is characterized in that regulating the pH value with sodium acetate soln in the step 1.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
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 |
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 |
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 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007302807A (en) * | 2006-05-12 | 2007-11-22 | Mitsubishi Chemicals Corp | Azo dye for anisotropic dye film, composition containing the azo dye, anisotropic dye film and polarizing element |
US20080257206A1 (en) * | 2007-04-23 | 2008-10-23 | Sukanya Rengaswamy | Dye-based black ink formulations and ink-jet ink sets |
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 |
-
2013
- 2013-04-24 CN CN201310144785.5A patent/CN103194217B/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007302807A (en) * | 2006-05-12 | 2007-11-22 | Mitsubishi Chemicals Corp | Azo dye for anisotropic dye film, composition containing the azo dye, anisotropic dye film and polarizing element |
US20080257206A1 (en) * | 2007-04-23 | 2008-10-23 | Sukanya Rengaswamy | Dye-based black ink formulations and ink-jet ink sets |
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 |
Non-Patent Citations (1)
Title |
---|
HONG-XIA CHEN等: "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", 《DALTON TRANS.》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
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 |
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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