CN103740361B - Dye/metal-organic framework composite material for white light emission and preparation method thereof - Google Patents

Abstract

The composition and mole percentage of the dye/metal organic framework composite material for white light emission disclosed by the present invention are: metal organic framework containing indium 70-90%, pyridine semicyanine dye 5-15%, acridine dye 5% -15%. The preparation method is as follows: first, the indium-containing metal-organic framework is synthesized by solvothermal reaction using benzene polycarboxylic acid organic ligand and indium salt, and then the pyridine hemicyanine dye and acridine are introduced into the indium-containing metal-organic framework by ion exchange method. dyes to obtain dye/metal organic framework composites. The synthesis method has simple process, mild conditions, easy-to-obtain raw materials, and high yield. The prepared dye/metal organic framework composite material has high thermochemical stability, and the color coordinates of the luminous color are very close to those of ideal white light. The index is higher than 80, and the luminous quantum efficiency is greater than 20%. It is expected to be used as a new type of white light emitting material in the fields of display and light emitting devices.

Description

A dye/metal organic framework composite material for white light emission and its preparation method

technical field

The invention relates to a dye/metal organic framework composite material for white light emission and a preparation method thereof.

Background technique

The application of luminescent materials in many fields such as fluorescent lamps, plasma flat panel displays, optical switches, and light-emitting diodes has made it a research hotspot in the international forefront in the past ten years. Designing and developing luminescent materials with long life, low energy consumption and high efficiency is the goal pursued by many physicists and chemists. The advantages of small size, low heat generation, low power consumption, and long life make white LEDs a new generation of energy-saving light sources. The traditional LED white light phosphor is a combination of phosphors of various colors, and there is no single phosphor. Moreover, traditional phosphors have disadvantages such as low color rendering index, low color temperature, and low luminous efficiency, which need further improvement. The use of dye/metal organic framework composite materials can prepare a single phosphor, and under the excitation of ultraviolet light, it can emit white light with high color rendering index, color temperature value that meets the requirements, and luminous efficiency. Therefore, the design and preparation of its materials are of great significance. of.

Metal-organic frameworks are a new type of porous crystalline material formed by the coordination of metal ions or metal clusters and organic bridging ligands. Similar to traditional porous materials such as zeolite molecular sieves, metal-organic framework materials also have special topology, regularity of internal arrangement, and pores of specific size and shape, but the framework materials show greater structural variability, tunable characteristics and Richer physicochemical properties. Metal-organic framework materials not only have the luminescent properties of traditional materials, but also derive new optical behaviors from the characteristics of the materials themselves. Compared with other luminescent materials, metal organic framework materials have the characteristics of designable and tailorable in synthesis. In addition, the luminescent properties of framework materials are related to the chemical environment, coordination configuration, crystal structure and their interaction with guest molecules in the channel. The functions are also closely related, which makes the luminescent metal-organic framework materials not only cover the luminescent properties of traditional complexes, but also have the potential to produce new luminescent properties and luminescent behaviors, so they have great applications in the field of luminescent materials. value.

In dye/MOF composites, not only inorganic metal ions and organic ligands can provide unique luminescent properties, but also dye guest molecules assembled in the pores of the framework materials can also generate luminescence. The luminescence mechanism of organic ligands and dye guest molecules is the same as their luminescence mechanism in solution, both originate from the transition of organic ligands and guest molecules from the lowest singlet excited state to the ground state, but due to the interaction between metal ions and ligands in the framework material The coordination increases the rigidity of the ligand, and the separation and assembly of the dye guest molecule by the framework channel greatly reduces the probability of non-radiative transition, thereby greatly enhancing the luminous intensity and luminous quantum efficiency of the organic ligand and the dye guest molecule. In addition, The assembly of dye molecules by the pores of the metal organic framework can further improve the thermochemical stability of the dye molecules, which provides a new way for the practical application of organic dye molecules in luminescent materials. Therefore, this new type of composite material can further improve the white light emission performance, and promote the progress of luminescent materials in many fields such as fluorescent lamps, plasma flat panel displays, optical switches, and light-emitting diodes.

Contents of the invention

The purpose of the present invention is to provide a dye/metal organic framework composite material for white light emission and its preparation method to solve the problem of low luminous efficiency and low thermochemical stability of organic fluorescent dye molecules in solid state due to concentration quenching. problem.

The composition and mole percentage of the dye/metal organic framework composite material for white light emission of the present invention are: 70-90% of indium-containing metal organic framework, 5-15% of pyridine semicyanine dye, and 5-15% of acridine dye .

A method for preparing a dye/metal organic framework composite material for white light emission, comprising the following steps:

(1) Preparation of metal-organic frameworks containing indium:

Dissolve 0.1-1mmol benzene polycarboxylic acid ligand and 1-2mmol indium salt in a mixed solvent of 10-100mL organic solvent and 1-50mL water, add 0.1-0.5μL hydrochloric acid with a mass concentration of 36.5% dropwise and stir Put it into a closed reaction kettle after uniformity, and react at a constant temperature of 60-150°C for 1-7 days to obtain a metal-organic framework containing indium;

(2) Ion-exchange reactions of pyridine hemicyanine dyes and acridine dyes with metal-organic frameworks:

Dissolve 1-10 mg of pyridine hemicyanine dye in 100-200 mL of N,N dimethylformamide solvent, and then add 0.1-1 g of indium-containing metal organic framework prepared in step (1) to carry out ion exchange reaction 1 -24h, take out the reacted metal-organic framework by filtration, then add it into N,N dimethylformamide solution containing 0.1-10mg of acridine dye for ion exchange reaction for 1-24h, filter and wash with ethanol solvent to obtain the dye / Metal Organic Framework Composites.

In step (1) of the above preparation method, the benzene polycarboxylic acid ligand is [1,1′:4″,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid, p-phenylene Dicarboxylic acid, 4,4'-biphenyldicarboxylic acid or 1,3,5-tris(4-carboxyphenyl)benzene. Said indium salt is indium chloride, indium nitrate or indium acetate. The organic solvent is N,N dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, methanol, ethanol or acetone.

The pyridine hemicyanine dye mentioned in the step (2) is 4-(4-dimethylaminostyrene)-1-methylpyridinium iodide, 4-(4-dimethylaminostyrene)-1-methylpyridine Sulfonate, 4-(4-(dianilinostyrene)-1-picoline iodide salt or 4-(4-(N-alkyl)aminostyrene) pyridinium iodide salt. The acridine dye It is acridine-9-aminoiodonium salt, 3,6-diamino-10-methyl-10-acridine chlorate or N-methylacridine iodide salt.

The beneficial effects of the present invention are:

1. The metal organic framework of the present invention is an anionic framework structure, which can undergo ion exchange reaction with cationic dyes, the exchange substitution concentration of dyes is high, and the interaction between dye molecules and metal organic frameworks is strong. Metal-organic frameworks have a high degree of crystallization, large crystal size, good stability, and have the advantages of simple synthesis process and high yield;

2. The channels of the metal-organic framework of the present invention can separate and protect the dye molecules, reduce the non-radiative transition probability of the dye molecules, thereby greatly enhancing the luminous intensity and luminous quantum efficiency of the dye molecules, and improving the dye molecules. The thermochemical stability of the molecule.

3. The metal-organic framework of the present invention has strong designability, and the adjustment and control of the luminescent performance can be realized by changing different organic ligands. In addition, the content of pyridine semicyanine dye and acridine dye can also be changed. , to realize the adjustment and optimization of performance parameters such as color rendering index and luminous efficiency.

Detailed ways

Example 1:

(1) Preparation of metal-organic frameworks containing indium:

Weigh 0.1mmol [1,1′:4″,1″-terphenyl]-3,3″,5,5″-tetracarboxylic acid ligand and 1mmol indium chloride and dissolve in 60mL N,N-dimethylformaldehyde A mixed solvent of amide and 10 mL of water was added dropwise to 0.1 μL of 36.5% hydrochloric acid, stirred evenly, then placed in a closed reaction kettle, and reacted at a constant temperature of 70 °C for 1 day to obtain a metal-organic framework containing indium.

(2) Ion-exchange reactions of pyridine hemicyanine dyes and acridine dyes with metal-organic frameworks:

Get 1 mg of pyridine hemicyanine dye 4-(4-dimethylaminostyrene)-1-picoline iodide and dissolve it in 100 mL of N,N dimethylformamide solvent, then add 0.8 g of step (1 ) prepared indium-containing metal-organic framework for ion-exchange reaction for 3 hours, filtered to take out the reacted metal-organic framework, and then added to N,N dimethyl formazan containing 0.3 mg of acridine dye N-methylacridium iodide The ion exchange reaction was carried out in the amide solution for 5 h, and after filtration, the dye/metal organic framework composite material was obtained by washing with ethanol for 3 times.

The luminous quantum efficiency of the pyridine hemicyanine dye 4-(4-dimethylaminostyrene)-1-methylpyridinium iodide in the composite material is higher than 40%, compared with about 1% of the dye in dilute solution state. Luminescence quantum efficiency has been significantly improved. The luminous efficiency of the acridine dye N-methylacridine iodide is also greatly improved. The prepared dye/metal organic framework composite produces good white light emission under the excitation of a 365nm ultraviolet lamp, and the color coordinate value of the luminescent color is (0.309, 0.323), which is very close to the color coordinate of ideal white light. In addition, the color temperature is 6738K , the color rendering index is 85, the total luminous quantum efficiency is 23%, the thermal stability of the dye/metal organic framework composite material is good, and the thermal decomposition temperature is higher than 260 ° C. It is expected to be used as an excellent white light emitting material in display and lighting applications in other fields.

Example 2:

(1) Preparation of metal-organic frameworks containing indium:

Weigh 0.3mmol of 1,3,5-tris(4-carboxybenzene)benzoic acid and 2mmol of indium chloride dissolved in a mixed solvent of 100mL of ethanol and 20mL of water, add 0.3μL of hydrochloric acid with a mass concentration of 36.5% dropwise and stir After uniformity, put it into a closed reaction kettle, and react at a constant temperature of 80° C. for 2 days to obtain a metal-organic framework containing indium.

(2) Ion-exchange reactions of pyridine hemicyanine dyes and acridine dyes with metal-organic frameworks:

Get 3mg of pyridine hemicyanine dye 4-(4-(dianilinostyrene)-1-picoline iodide salt and dissolve it in 150mL of N,N dimethylformamide solvent, then add 0.1g step ( 1) After the prepared metal-organic framework containing indium was subjected to ion exchange reaction for 10 hours, the reacted metal-organic framework was taken out by filtration, and then added to N,N dimethyl The ion exchange reaction was carried out in the formamide solution for 1 h, and after filtration, it was washed with ethanol for 3 times to obtain the dye/metal organic framework composite material.

The luminescence quantum efficiency of the pyridine hemicyanine dye 4-(4-(dianilinostyrene)-1-methylpyridinium iodide salt in the composite material is higher than 50%, compared with 1% of the dye in dilute solution state The luminous quantum efficiency has been significantly improved. The luminous efficiency of acridine dye N-methylacridine iodide is also corresponding. The prepared dye/metal organic framework composite material produces good white light emission under the excitation of the ultraviolet lamp of 365nm, and the luminous color The color coordinate value is (0.335, 0.313), which is very close to the color coordinate of ideal white light. In addition, the color temperature is 5358K, the color rendering index is 86, and the total luminous quantum efficiency is 27%. It is expected to be used as an excellent white light emitting material in the world. Applied in fields such as display and lighting.

Example 3:

(1) Preparation of metal-organic frameworks containing indium:

Weigh 0.7mmol of terephthalic acid and 2mmol of indium acetate dissolved in a mixed solvent of 100mL of tetrahydrofuran and 50mL of water, add 0.5μL of hydrochloric acid with a mass concentration of 36.5% dropwise and stir evenly, then put it into a closed reaction kettle, ℃ constant temperature reaction for 7 days to obtain a metal organic framework containing indium.

(2) Ion-exchange reactions of pyridine hemicyanine dyes and acridine dyes with metal-organic frameworks:

Take 5 mg of pyridine hemicyanine dye 4-(4-dimethylaminostyrene)-1-methylpyridine sulfonate and dissolve it in 200 mL of DMF solvent, then add 1 g of indium-containing metal prepared in step (1) After the organic framework undergoes ion exchange reaction for 1 hour, the reacted metal-organic framework is taken out by filtration, and then added to N,N dimethylformamide solution containing 10 mg of acridine dye acridine-9-aminoiodonium salt for ion exchange reaction for 10 hours , washed three times with ethanol after filtration to obtain the dye/metal organic framework composite.

The luminescence quantum efficiency of the pyridine hemicyanine dye 4-(4-(dianilinostyrene)-1-methylpyridinium iodide in the composite material ranges from 30% to 50%, compared to the dye in dilute solution state The luminous quantum efficiency of 2% has been significantly improved. The luminous efficiency of acridine dye acridine-9-aminoiodonium salt is also greatly improved. In addition, the prepared dye/metal organic framework composite material can also produce Good white light emission with color coordinates between (0.31,0.33) and (0.33,0.33).

Example 4:

(1) Preparation of metal-organic frameworks containing indium:

Weigh 1mmol of 4,4′-biphenyldicarboxylic acid and 2mmol of indium nitrate dissolved in a mixed solvent of 10mL N,N-dimethylacetamide and 1mL of water, add 0.5μL of 36.5% hydrochloric acid dropwise and stir After uniformity, put it into a closed reaction kettle, and react at a constant temperature of 150° C. for 5 days to obtain a metal organic framework containing indium.

(2) Ion-exchange reactions of pyridine hemicyanine dyes and acridine dyes with metal-organic frameworks:

Take 10 mg of pyridine hemicyanine dye 4-(4-(N-alkyl)aminostyrene) pyridinium iodide and dissolve it in 200 mL of N,N dimethylformamide, and then add 1 g of the After the metal organic framework containing indium undergoes ion exchange reaction for 24 hours, the well reacted metal organic framework is taken out by filtration, and then added to the The ion-exchange reaction was carried out in N,N dimethylformamide solution for 24 hours, filtered and washed twice with ethanol to obtain the dye/metal organic framework composite.

The luminescence quantum efficiency of the pyridine hemicyanine dye 4-(4-(N-alkyl)aminostyrene)pyridinium iodide in the composite material ranges from 30% to 50%, compared to 2% of the dye in dilute solution state The luminous quantum efficiency has been significantly improved. The luminous efficiency of the acridine dye 3,6-diamino-10-methyl-10-acridine chlorate is also greatly improved. In addition, the prepared dye/metal organic framework composite can also produce good white light emission under the excitation of 365nm ultraviolet lamp, and the color coordinates are between (0.31, 0.33) and (0.33, 0.33).

Claims (7)

1., for dyestuff/metal organic frame matrix material of white light emission, it is characterized in that its composition and mole percent level are: containing the metal organic frame 70-90% of indium, pyridine hemicyanine dye 5-15%, acridine dye 5-15%.

2. prepare the method for the dyestuff for white light emission according to claim 1/metal organic frame matrix material, it is characterized in that comprising the following steps:

(1) containing the preparation of the metal organic frame of indium:

Benzene polycarboxylic acid's part of 0.1-1 mmol and 1-2 mmol indium salt are dissolved in the mixed solvent of 10-100 mL organic solvent and 1-50 mL water, the mass concentration dropwise adding 0.1-0.5 μ L be 36.5% hydrochloric acid stir after put into airtight reactor, at 60-150 ^oc isothermal reaction 1-7 days, obtains the metal organic frame containing indium;

(2) ion exchange reaction of pyridine hemicyanine dye and acridine dye and metal organic frame:

The pyridine hemicyanine dye getting 1-10 mg is dissolved in the N of 100-200 mL, in N-dimethylformamide solvent, inwardly add the metal organic frame containing indium prepared by 0.1-1 g step (1) again and carry out ion exchange reaction 1-24 h, filter and take out completely reacted metal organic frame, join the N containing 0.1-10 mg acridine dye again, carry out ion exchange reaction 1-24 h in N-dimethylformamide solution, with alcohol solvent cleaning after filtration, obtain dyestuff/metal organic frame matrix material.

3. the method for the dyestuff for white light emission according to claim 2/metal organic frame matrix material, it is characterized in that in step (1), said benzene polycarboxylic acid's part is [1,1 ': 4 ' ', 1 ' '-terphenyl]-3,3 ' ', 5,5 ' '-tetracarboxylic acid, terephthalic acid, 4,4'-biphenyl dicarboxylic acid or 1,3,5-tri-(4-carboxyl benzene) benzene.

4. the method for the dyestuff for white light emission according to claim 2/metal organic frame matrix material, is characterized in that in step (1), said indium salt is indium chloride, indium nitrate or indium acetate.

5. the method for the dyestuff for white light emission according to claim 2/metal organic frame matrix material, it is characterized in that in step (1), said organic solvent is N, N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran (THF), methyl alcohol, ethanol or acetone.

6. the method for the dyestuff for white light emission according to claim 2/metal organic frame matrix material, is characterized in that in step (2), said pyridine hemicyanine dye is 4-(4-dimethylamino vinylbenzene)-1-picoline salt compounded of iodine, 4-(4-dimethylamino vinylbenzene)-1-picoline sulfonate, 4-(4-(hexichol amido vinylbenzene)-1-picoline salt compounded of iodine or 4-(4-(N-alkyl) aminostyryl) pyridinium iodide.

7. the method for the dyestuff for white light emission according to claim 2/metal organic frame matrix material, it is characterized in that in step (2), said acridine dye is acridine-9-amino salt compounded of iodine, 3,6-diaminostilbene 0-methyl isophthalic acid 0-Acrizane hydrochlorate or N-methylacridine salt compounded of iodine.