CN103059836A - Method for preparing 4-[(8-hydroxy-5-quinolinyl)azo] cadmium benzoate complex with purple light performance - Google Patents

Abstract

The invention discloses an organic purple light emitting material and a preparation method thereof, relating to organic light emitting materials and preparation methods thereof. The organic purple light emitting material is used for solving the problems of low brightness and light emitting efficiency of the existing organic purple light emitting materials. The molecular formula of the organic purple light emitting material is C16H13N3CdO5. The preparation method of the organic purple light emitting material comprises the following steps of: (1) preparing 4-[(8-hydroxy-5-quinolinyl)azo] benzoic acid; and (2) preparing coordination polymers: respectively dissolving ligand and cadmium chloride into a solvent, mixing and adding 1,4-dioxane of 1 mL, adjusting the pH to be 3 by using NaOH/HCl, stirring for 30 minutes at room temperature, putting a mixture in a reaction kettle with a polytetrafluoroethylene inner liner, and carrying out temperature programming to 100 DEG C for 100 hours, thereby obtaining red rhomboidal crystals. The products prepared by the preparation method disclosed by the invention are single crystals with intact crystal forms; and shown by light emitting performance tests, organic purple light emitting materials prepared by the preparation method are all of purple fluorescence and have higher thermal stability and good film forming characteristics. The yield of the products prepared by the preparation method is high and is over 40%.

Description

A kind ofly have purple light performance 4-[(8-hydroxyl-5-quinoline) azo] preparation method of phenylformic acid cadmium complex

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] the phenylformic acid cadmium complex and preparation method thereof.

Background technology

Good performance and potential application prospect are arranged and extremely people's concern at aspects such as sensor technology, photochemistry and electroluminescent materials owing to containing the luminescent ligand compound of azo ligands, become 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, and research finds that the size of the pi-conjugated system of part and the electronic effect of ligand substituting base are the important factors of regulating the title complex luminescent properties; Reported a series of azo title complex 3 such as the 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 preferably fluorescence property.People had also studied the ligand polymer of a lot of azos in recent years, but carried out the rarely found of coordination with cadmium.Although people have done large 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 among the present invention Cd{4-[(8-hydroxyl-5-quinoline) and azo] phenylformic acid } (H ₂O) } H ₂O} _nMolecular formula be C ₁₆H ₁₃N ₃CdO ₅, its structural formula is

。

Cd{4-[(8-hydroxyl-5-quinoline) and azo] phenylformic acid } (H ₂O) } H ₂O} _nPreparation method's step is as follows: one, 4-[(8-hydroxyl-5-quinoline) azo] benzoic preparation: para-amino benzoic acid (0.935g, 7.06mol) is dissolved in 20mL H 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 18%).

Two, at N, N '-dimethyl formamide (DMF, 3 mL) and in the solvent of water (12 mL) add Cadmium chloride fine powder (CdCl22.5H2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] phenylformic acid (5mg, 0.015mmol), add Isosorbide-5-Nitrae-dioxane (Isosorbide-5-Nitrae-dioxane (1mL)) after stirring, regulate pH=3 with NaOH/HCl, gained solution is transferred in the teflon-lined stainless steel cauldron of 25mL 100 ° of C of temperature programming, 100h after continuing to stir 30min, obtain red rhomboid crystal, after the product filtration, seasoning, productive rate is 43.2 % (calculating with Cd).

In step 1, regulate the pH value with sodium acetate soln in the above-mentioned reaction.

The present invention selects water as the recrystallization reagent of part, and than employed N in the bibliographical information, N '-dimethyl formamide improves about 5% for the synthetic upper productive rate of part, and water is on the synthetic not impact 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 productive rate that the present invention makes product is high, 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] phenylformic 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 phenylformic acid fluorescence spectrum ,-(b, b ')-embodiment one method makes the product fluorescence spectrum.

Embodiment

Embodiment one: the purple light luminous organic material in the present embodiment Cd{4-[(8-hydroxyl-5-quinoline) and azo] phenylformic acid } (H ₂O) } H ₂O} _nMolecular formula be C ₁₆H ₁₃N ₃CdO ₅, its structural formula is

。

Cd{4-[(8-hydroxyl-5-quinoline) and azo] phenylformic acid } (H ₂O) } H ₂O} _nPreparation method's step is as follows: one, 4-[(8-hydroxyl-5-quinoline) azo] benzoic preparation: para-amino benzoic acid (0.935g, 7.06mol) is dissolved in 20mL H 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 18%).

Two, at N, N '-dimethyl formamide (DMF, 3 mL) and in the solvent of water (12 mL) add Cadmium chloride fine powder (CdCl22.5H2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] phenylformic acid (5mg, 0.015mmol), add Isosorbide-5-Nitrae-dioxane (Isosorbide-5-Nitrae-dioxane (1mL)) after stirring, regulate pH=3 with NaOH/HCl, gained solution is transferred in the teflon-lined stainless steel cauldron of 25mL 100 ° of C of temperature programming, 100h after continuing to stir 30min, obtain red rhomboid crystal, after the product filtration, seasoning, productive rate is 43.2 % (calculating with Cd).

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

The productive rate of present embodiment is 43.2%, Cd{4-[(8-hydroxyl-5-quinoline) azo] phenylformic acid } (H ₂O) } H ₂O} _nThe intact monocrystalline crystal of red crystal formation presents purple fluorescence, and the maximum emission peak wavelength is respectively λ _Max=394 nm.The present invention makes the brightness of purple light luminous organic material and luminous efficiency is enhanced (the as seen from Figure 3 obvious enhancing of the luminous strength ratio part of present embodiment product, 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] benzoic preparation:

Step 2, Cd{4-[(8-hydroxyl-5-quinoline) and azo] phenylformic acid } (H ₂O) } H ₂O} _nPreparation:

Embodiment two: purple light luminous organic material in the present embodiment Cd{4-[(8-hydroxyl-5-quinoline) and azo] phenylformic acid } (H ₂O) } H ₂O} _nPreparation method's step is as follows: one, 4-[(8-hydroxyl-5-quinoline) azo] benzoic preparation: para-amino benzoic acid (0.935g, 7.06mol) is dissolved in 20mL H 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 18%).Two, at N, N '-dimethyl formamide (DMF, 3 mL) and in the solvent of water (12 mL) add Cadmium chloride fine powder (CdCl22.5H2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] phenylformic acid (5mg, 0.015mmol), add Isosorbide-5-Nitrae-dioxane (Isosorbide-5-Nitrae-dioxane (1mL)) after stirring, regulate pH=3 with NaOH/HCl, gained solution is transferred in the teflon-lined stainless steel cauldron of 25mL 100 ° of C of temperature programming, 100h after continuing to stir 30min, obtain red rhomboid crystal, after the product filtration, seasoning, productive rate is 43.2 % (calculating with Cd).

Claims (3)

1. purple light luminous organic material is characterized in that purple light luminous organic material { { Cd{4-[(8-hydroxyl-5-quinoline) azo] phenylformic acid } (H ₂O) } H ₂O} _nMolecular formula be C ₁₆H ₁₃N ₃CdO ₅, 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: one, 4-[(8-hydroxyl-5-quinoline) azo] benzoic preparation: para-amino benzoic acid (0.935g, 7.06mol) is dissolved in 20mL H 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 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 18%)

；

Two, at N, N '-dimethyl formamide (DMF, 3 mL) and in the solvent of water (12 mL) add Cadmium chloride fine powder (CdCl22.5H2O (30mg, 0.13mmol)) and 4-[(8-hydroxyl-5-quinoline) azo] phenylformic acid (5mg, 0.015mmol), add Isosorbide-5-Nitrae-dioxane (Isosorbide-5-Nitrae-dioxane (1mL)) after stirring, regulate pH=3 with NaOH/HCl, gained solution is transferred in the teflon-lined stainless steel cauldron of 25mL 100 ° of C of temperature programming, 100h after continuing to stir 30min, obtain red rhomboid crystal, after the product filtration, seasoning, productive rate is 43.2 % (calculating with Cd).

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.

Images