CN103232844A - Preparation method of trinuclear zinc complex having pulp light performance - Google Patents

Abstract

The invention relates to a pulp light organic luminescent material and a preparation method of the luminescent material, in particular relates to a trinuclear organic luminescent material and a preparation method of the luminescent material, solving the problems that the brightness and the luminescent efficiency of an existing pulp light organic luminescent material are low. The molecular formula of the product provided by the invention is C3OH3OZn3N6O16S2. The preparation method of the pulp light organic luminescent material provided by the invention comprises the following steps: 1, the preparation of 4-[(8-hydroxy-5-quinolyl)azo]benzenesulfonic acid; and 2, the preparation of a coordination polymer: dissolving a ligand and zinc chloride in a solvent respectively, mixing the obtained two solutions, adding an organic base into the mixed solution, stirring the obtained solution at room temperature for one hour, adding the stirred product into a reaction kettle with a polytetrafluoroethylene lining, and raising the temperature to 100 DEG C for 100 hours by a program to obtain a red block crystal. The product prepared by the method disclosed by the invention is a single crystal in a complete crystal form and is high in yield which reaches more than 40%; and through a luminescent performance test, the pulp light organic luminescent materials prepared by the method disclosed by the invention all present pulp fluorescence and also have pretty high thermal stability and excellent film forming characteristic.

Description

A kind of preparation method with purple light performance three nuclear Zn complexes

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 three nuclear Zn complexes 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 zinc, 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 [Zn (and 3,3'-ADB) (CH ₃CH ₂OH)] and [Zn (and 4,4'-ADB) (Py) ₂] _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.Though people have done big quantity research to the luminescent ligand compound, brightness and the luminous efficiency of existing purple light luminous organic 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 purple light luminous organic material; And provide a kind of purple light luminous organic material and preparation method thereof.

Purple light luminous organic material { { Zn among the present invention ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}Molecular formula be C ₃₀H ₃₀Zn ₃N ₆O ₁₆S ₂, its structural formula is

。

{ { Zn ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}Preparation 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 H ₂O(2 mL) and in the solvent of ethanol (10 mL) add zinc chloride (ZnCl ₂(30mg, 0.22mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.01mL)) 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 41.3 % (calculating with Zn).

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 the purple light luminous organic material and tests through luminescent properties, all presents purple 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: purple light the luminous organic material { { Zn in the present embodiment ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}Molecular formula be C ₃₀H ₃₀Zn ₃N ₆O ₁₆S ₂, its structural formula is

{ { Zn ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}Preparation 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 H ₂O(2 mL) and in the solvent of ethanol (10 mL) add zinc chloride (ZnCl ₂(30mg, 0.22mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.01mL)) 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 41.3 % (calculating with Zn).

Present embodiment is regulated the pH value with sodium acetate soln in step 1.

The productive rate of present embodiment is 41.3%, { { Zn ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}The intact monocrystalline crystal of red crystal formation presents purple fluorescence, and the maximum emission peak wavelength is respectively λ _Max=392 nm.The present invention makes the brightness of purple light luminous organic material 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, { { Zn ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}Preparation:

Embodiment two: purple light luminous organic material { { Zn in the present embodiment ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}Preparation 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 H ₂O(2 mL) and in the solvent of ethanol (10 mL) add zinc chloride (ZnCl ₂(30mg, 0.22mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.01mL)) 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 41.3 % (calculating with Zn).

Claims (3)

1. the purple light luminous organic material is characterized in that purple light luminous organic material { { Zn ₃4-[(8-hydroxyl-5-quinoline) and azo] Phenylsulfonic acid } ₂(OH) ₂(H ₂O) _{6 n}Molecular formula be C ₃₀H ₃₀Zn ₃N ₆O ₁₆S ₂, its structural formula is

。

2. the method for preparing the described purple light luminous organic material of claim 1, the preparation method's step that it is characterized in that the purple light luminous organic 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 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 H ₂O(2 mL) and in the solvent of ethanol (10 mL) add zinc chloride (ZnCl ₂(30mg, 0.22mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] (5mg 0.015mmol), stirs the back and adds quadrol (ethylenediamine (0.01mL)) 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 41.3 % (calculating with Zn).

3. the preparation method of purple light luminous organic 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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