Red and green luminescence tunable manganese-based polymer metal halide material and preparation thereof

Abstract

The invention discloses a red-green luminescence tunable manganese-based polymer metal halide and a preparation method thereof, and the preparation method comprises the following steps: evaporating a solvent from an aqueous solution containing polymer cations and manganese bromide at a high temperature to obtain the red-green luminescence tunable manganese-based polymer metal halide; the polymer cation is selected from at least one of polyquaternary ammonium salt, polyquaternary phosphonium salt and polytertiary sulfonium salt; the red-green luminescence tunable manganese-based polymer metal halide can show continuous adjustable conversion from green light emission to red light emission under an ultraviolet lamp along with the increase of the manganese content in the material. The method is a universal manganese-based polymer metal halide material preparation method and is used for preparing a manganese-based metal halide luminescent material. The method is simple to operate, large in preparation amount and wide in application range of polymer cations, and the amorphous polymer metal halide luminescent material can be prepared.

Description

Technical Field

[0001] The invention relates to the field of preparation of metal halide luminescent materials, and in particular to an amorphous manganese-based polymer metal halide material with adjustable red and green light emission, which is prepared by using polymer cations and manganese bromide as raw materials. Background Art

[0002] Manganese-based metal halide materials exhibit excellent luminescence properties and have great application potential in many fields such as LED display, lighting, X-ray detection imaging and temperature sensing. Therefore, the preparation methods of manganese-based metal halide materials have attracted much attention. At present, many methods have been developed, including cooling crystallization method, hydrothermal method, anti-solvent diffusion method, etc. These methods are used to prepare all-inorganic manganese-based metal halide materials and organic-inorganic hybrid manganese-based metal halide materials. The prepared all-inorganic and organic-inorganic hybrid manganese-based metal halide materials are single crystals or nanocrystals. Due to the lattice restriction of the crystal, these materials can only show a single fluorescence emission of green or red light. The development of fluorescent materials with multiple luminescent colors has become one of the hot research directions of manganese-based metal halide materials.

[0003] Polymer materials are of various types, complex and changeable structures, rich and varied properties, and excellent performance. Therefore, they are widely used in various fields such as aerospace, petrochemicals, production and life. As a type of polymer material, polymer cations play an important role in sewage treatment, papermaking, antibacterial sterilization, and biomedicine because of the rich positive charge in their structure. If polymer cations are used to replace inorganic cations or organic cations and react with manganese halides to prepare manganese-based polymer metal halides, then the material will introduce excellent processability unique to polymers while having the red or green light emission characteristic of manganese-based metal halide materials. In addition, the amorphous polymer structure can allow the existence of multiple manganese-based metal halide luminescence centers, thereby achieving the tunability of red and green light emission. Based on this, the present invention proposes a new universal preparation method for manganese-based polymer metal halide materials, which can achieve efficient preparation of manganese-based polymer metal halides, and the luminescent color of the prepared material is adjustable, and the material itself has excellent processability that conventional manganese-based metal halide crystal materials do not have. Summary of the invention

[0004] According to one aspect of the present application, a method for preparing a universal manganese-based polymer metal halide material with adjustable red and green light emission is provided, which is used to prepare a manganese-based polymer metal halide material including a variety of polymer cations, overcoming the problems of the current manganese-based metal halide crystal material having a single and unadjustable luminescent color and the lack of processability of the brittle crystals. The method is simple to operate, can be prepared on a large scale, has a wide range of applicability to the types of polymer cations, and the prepared material has the red and green light emission characteristic of the manganese-based halide material and is adjustable, and the material itself has excellent processability.

[0005] The method for preparing the manganese-based polymer metal halide material with adjustable red and green light emission is characterized by comprising the following steps:

[0006] In a solution, a reaction system containing polymer cations and manganese bromide is volatilized at a high temperature to obtain a manganese-based polymer metal halide.

[0007] The polymer cation is selected from at least one of a polyquaternary ammonium salt, a polyquaternary phosphonium salt, and a polytertiary sulfonium salt;

[0008] Optionally, the cationic molecular weight M w >1000Da.

[0009] Optionally, the solvent used in the solution is selected from at least one of water, methanol and ethanol.

[0010] Optionally, the molar ratio of the cation contained in the polymer cation to manganese bromide in the solution is 1:0.01 to 1:2.

[0011] Optionally, the concentration of the cation and manganese bromide in the polymer cation is 0.01 mol / L to 10 mol / L in terms of manganese bromide.

[0012] Optionally, the volatilization temperature of the solvent in the solution is 80-250°C.

[0013] Definitions and explanations of terms

[0014] Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by those skilled in the art to which the subject matter of the claims pertains. Unless otherwise indicated, all patents, patent applications, and publications cited herein are incorporated herein by reference in their entirety. If there are multiple definitions of a term herein, the definition in this chapter shall prevail.

[0015] It should be understood that definitions of standard chemical terms can be found in the reference literature. Unless specific definitions are set forth, the terms used herein in the relevant descriptions of analytical chemistry, organic chemistry, and polymer chemistry are those known in the art.

[0016] The term polyquaternium is understood to mean polymers containing a quaternary ammonium structure in the polymer repeating unit, wherein the quaternary ammonium structure refers to a tetrasubstituted nitrogen cation.

[0017] The term polyquaternary phosphonium salt is understood to mean a polymer containing a quaternary phosphonium salt structure in the polymer repeating unit, wherein the quaternary phosphonium salt structure refers to a tetrasubstituted phosphonium cation.

[0018] The term poly-tert-sulfonium salt is understood to mean a polymer containing a tert-sulfonium salt structure in the polymer repeating unit, wherein the tert-sulfonium salt structure refers to a tri-substituted sulfonium cation.

[0019] The beneficial effects of this application include:

[0020] 1) The method for preparing the manganese-based polymer metal halide material provided in the present application has wide applicability to polymer cations, and different structures and different molecular weights can be used to prepare the manganese-based polymer metal halide luminescent material.

[0021] 2) The preparation method of the manganese-based polymer metal halide material provided in the present application is different from the traditional manganese-based metal halide luminescent material. The feed ratio of cation and manganese bromide can be adjusted at will and is not limited by the stoichiometric ratio.

[0022] 3) The preparation method of the manganese-based polymer metal halide material provided in the present application is different from the traditional manganese-based metal halide luminescent material that can only exhibit a single fluorescent color. By changing the feed ratio, a continuous change of luminescence from green light to red light can be achieved.

[0023] 4) The preparation method of the manganese-based polymer metal halide material provided in the present application can obtain an amorphous manganese-based metal halide material, wherein the introduction of polymer cations provides the material with processability that conventional manganese-based metal halide crystal materials do not have.

[0024] 5) The preparation method of the manganese-based polymer metal halide material provided in the present application is simple to operate and can realize the mass preparation of the material, which greatly expands the types of manganese-based halide materials and provides new development ideas for manganese-based halide materials.

[0025] The red-green luminescent tunable manganese-based polymer metal halide can show a continuous and adjustable transition from green light emission to red light emission under ultraviolet light as the manganese content in the material increases. The method is a universal method for preparing manganese-based polymer metal halide materials, which is used to prepare manganese-based metal halide luminescent materials. The method is simple to operate, has a large preparation amount, is widely applicable to polymer cations, and can prepare amorphous polymer metal halide luminescent materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1is the infrared spectrum of the product of Example 1 of the present invention;

[0027] Figure 2 is the X-ray photoelectron spectrum of the product of Example 1 of the present invention;

[0028] Figure 3 is the excitation and emission spectra of the product of Example 1 of the present invention;

[0029] Figure 4 is the infrared spectrum of the product of Example 2 of the present invention;

[0030] Figure 5 is the X-ray photoelectron spectrum of the product of Example 2 of the present invention;

[0031] Figure 6 is the excitation and emission spectra of the product of Example 2 of the present invention;

[0032] Figure 7 is the excitation and emission spectra of the product of Example 3 of the present invention;

[0033] Figure 8 is the excitation and emission spectra of the product of Example 4 of the present invention;

[0034] Fig. 9 The present invention is a fluorescent photograph showing that the red-green luminescence tunable manganese-based polymer metal halide shows a continuous and adjustable transition from green light emission to red light emission under ultraviolet light as the manganese content in the material increases; DETAILED DESCRIPTION

[0035] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0036] Unless otherwise specified, the raw materials and solvents in the examples of the present application were purchased from commercial sources, among which polydimethyldiallylammonium chloride (M w <100000Da) and manganese bromide were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., and other chemical reagents were purchased from Sinopharm Chemical Reagent Co., Ltd.

[0037] The preparation method of polydimethyldiallylammonium bromide is as follows: dialyze a solution of polydimethyldiallylammonium chloride (50%) in a saturated potassium bromide aqueous solution to exchange halogen ions until all chloride ions are replaced by bromide ions, and then freeze-dry the sample to obtain a solid.

[0038] The analysis method in the examples of this application is as follows:

[0039] The prepared materials were analyzed by infrared spectroscopy using a Nicolet iS50 infrared spectrometer. The test sample was solid powder and the test mode was ATR mode.

[0040] The prepared materials were analyzed and tested using Thermo Scientific X-ray photoelectron spectroscopy, and the test samples were solid powders.

[0041] The excitation and emission spectra of the prepared materials were tested using an Edinburgh FLS1000 steady-state fluorescence spectrometer, and the test samples were solid powders.

[0042] Embodiment 1:

[0043] This embodiment provides a method for preparing a green light emitting manganese-based polymer metal halide by volatilizing a solvent from polydimethyldiallylammonium bromide and manganese bromide in an aqueous solution, comprising the following steps:

[0044] (1) Preparation of manganese-based polymer metal halide precursor solution

[0045] Add a magnetic particle, polydimethyldiallylammonium bromide (412 mg, 2 mmol (based on the cation in the polymer cation)), manganese bromide (43 mg, 0.2 mmol) and 2 mL of water into a sample bottle, stir to fully dissolve the polymer cation and manganese bromide, and filter with a filter membrane with a pore size of 0.22 μm to obtain a clear and transparent solution.

[0046] (2) Preparation of manganese-based polymer metal halides

[0047] The precursor solution obtained in step (1) is placed in an environment of 140° C. (a heating plate, oven or other heating equipment that can provide the required temperature can be used, and the present invention uses an oven) to evaporate the solvent, thereby obtaining a manganese-based polymer metal halide luminescent material under corresponding conditions.

[0048] Embodiment 2:

[0049] This embodiment provides a method for preparing a yellow light emitting manganese-based polymer metal halide by volatilizing a solvent from polydimethyldiallylammonium bromide and manganese bromide in an aqueous solution, comprising the following steps:

[0050] (1) Preparation of manganese-based polymer metal halide precursor solution

[0051] Add a magnet, polydimethyldiallylammonium bromide (412 mg, 2 mmol (based on the cation in the polymer cation)), manganese bromide (171.8 mg, 0.8 mmol) and 4 mL of water into a sample bottle, stir to fully dissolve the polymer cation and manganese bromide, and filter with a filter membrane with a pore size of 0.22 μm to obtain a clear and transparent solution.

[0052] (2) Preparation of manganese-based polymer metal halides

[0053] The precursor solution obtained in step (1) is placed in an environment of 150° C. (a heating plate, oven or other heating equipment that can provide the required temperature can be used, and the present invention uses an oven) to evaporate the solvent, thereby obtaining a manganese-based polymer metal halide luminescent material under corresponding conditions.

[0054] Embodiment 3:

[0055] This embodiment provides a method for preparing a red light emitting manganese-based polymer metal halide by volatilizing a solvent from polydimethyldiallylammonium bromide and manganese bromide in an aqueous solution, comprising the following steps:

[0056] (1) Preparation of manganese-based polymer metal halide precursor solution

[0057] Add a magnet, polydimethyldiallylammonium bromide (412 mg, 2 mmol (based on the cation in the polymer cation)), manganese bromide (343.6 mg, 1.6 mmol) and 6 mL of water into a sample bottle, stir to fully dissolve the polymer cation and manganese bromide, and filter with a filter membrane with a pore size of 0.22 μm to obtain a clear and transparent solution.

[0058] (2) Preparation of manganese-based polymer metal halides

[0059] The precursor solution obtained in step (1) is placed in an environment of 160° C. (a heating plate, oven or other heating device that can provide the required temperature can be used, and the present invention uses an oven) to evaporate the solvent, thereby obtaining a manganese-based polymer metal halide luminescent material under corresponding conditions.

[0060] Embodiment 4:

[0061] This embodiment provides a method for preparing a yellow-green light emitting manganese-based polymer metal halide by volatilizing a solvent from polydimethyldiallylammonium bromide and manganese bromide in an aqueous solution, comprising the following steps:

[0062] (1) Preparation of manganese-based polymer metal halide precursor solution

[0063] Add a magnet, polydimethyldiallylammonium bromide (412 mg, 2 mmol (based on the cation in the polymer cation)), manganese bromide (128.9 mg, 0.6 mmol), 4 mL of water and 1 mL of ethanol into a sample bottle, and stir to fully dissolve the polymer cation and manganese bromide to obtain a clear and transparent solution.

[0064] (2) Preparation of manganese-based polymer metal halides

[0065] The precursor solution obtained in step (1) is placed in an environment of 130° C. (a heating plate, oven or other heating equipment that can provide the required temperature can be used, and the present invention uses an oven) to evaporate the solvent, thereby obtaining a manganese-based polymer metal halide luminescent material under corresponding conditions.

[0066] Comparative Example 1:

[0067] A magnetic particle, polydimethyldiallylammonium bromide (412 mg, 2 mmol (based on the cation in the polymer cation)), manganese bromide (10.7 mg, 0.05 mmol), 4 mL of water and 1 mL of ethanol were added to a sample bottle, and the polymer cation and manganese bromide were fully dissolved by stirring to obtain a clear and transparent solution. The solution was placed in an environment of 120° C. (a heating plate, an oven or other heating device that can provide the required temperature can be used, and a heating plate is used in the present invention) to evaporate the solvent. Since the ratio of manganese bromide to polymer cation in the obtained product is not within the range of the present invention, the enantiomorphic product cannot show the characteristic luminescence of manganese-based polymer metal halide.

[0068] The infrared spectrum of the product of Example 1 is shown in the attached Figure 1 As shown in the figure, the peak position is consistent with the corresponding polymer cation, indicating that the polymer part of the obtained product has the expected structure; the X-ray photoelectron spectrum of the product of Example 1 is shown in the attached figure. Figure 2 As shown in Figure 1, the peaks of elements (C, N, Mn, Br, etc.) are consistent with the expected peaks, and the measured manganese ions are divalent, indicating that the material contains the expected manganese-based halide structure; the excitation and emission spectra of the product of Example 1 are shown in Figure 1. Figure 3 As shown, they are all characteristic excitation and emission spectra of manganese-based metal halides, which are pure green light emission. The infrared spectrum of the product of Example 2 is shown in the attached Figure 4 As shown in the figure, the peak position is consistent with the corresponding polymer cation, indicating that the polymer part of the obtained product has the expected structure; the X-ray photoelectron spectrum of the product of Example 2 is shown in the attached figure. Figure 5 As shown in Figure 2, the peaks of elements (C, N, Mn, Br, etc.) are consistent with the expected peaks, and the measured manganese ions are divalent, indicating that the material contains the expected manganese-based halide structure; the excitation and emission spectra of the product of Example 2 are shown in Figure 2. Figure 6 As shown in the figure, the excitation and emission spectra of the characteristic manganese-based metal halide are yellow light emission with green light and red light superimposed. The excitation and emission spectra of the product of Example 3 are shown in the figure. Figure 7 As shown, they are all characteristic excitation and emission spectra of manganese-based metal halides, with characteristic red light emission. The excitation and emission spectra of the product of Example 4 are shown in the attached Figure 8 As shown in the figure, the excitation and emission spectra of the characteristic manganese-based metal halide are yellow-green emission with green and red light superimposed. Fig. 9The following are photos of the prepared materials under natural light and 365nm ultraviolet light at different manganese contents. Since the luminous color of the material can be continuously adjusted at different manganese contents, it is expected that this type of material can be used in full-spectrum lighting and other fields.

[0069] The present invention uses polymer cations and manganese bromide as raw materials, and prepares manganese-based polymer metal halide materials by solvent volatilization. The operation is simple, batch preparation of materials can be achieved, and the feeding is not restricted by the stoichiometric ratio. The obtained material has red and green luminescence tunability, and continuous tuning of the luminescence spectrum is achieved, which provides great advantages for the method. The present invention successfully combines polymer cations in polymer chemistry with metal halide materials in inorganic chemistry to prepare a new manganese-based polymer metal halide luminescent material, expands the types and luminescent properties of current manganese-based metal halide luminescent materials, and provides great help for the development of this field.

[0070] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing a manganese-based polymer metal halide with tunable red and green luminescence, characterized in that: The following steps are involved: A solution containing polymer cations and manganese bromide, and volatilizing the solvent to obtain a manganese-based polymer metal halide material; The polymer cation is selected from at least one or more of polyquaternary ammonium salts, polyquaternary phosphonium salts and polytertiary sulfonium salts.

2. The method for preparing a manganese-based polymer metal halide with tunable red and green light emission according to claim 1, characterized in that: The polymer cation is at least one of a polyquaternary ammonium salt (a polymer having a repeating unit of -R1R2NXR3R4-, wherein R1-4 are alkyl groups and X is a halogen), a polyquaternary phosphonium salt (a polymer having a repeating unit of -R1R2PXR3R4-, wherein R is an alkyl group and X is a halogen), and a polytertiary sulfonium salt (a polymer having a repeating unit of -R1R2SXR3-, wherein R is an alkyl group and X is a halogen); Among them, the molecular weight of the polymeric cation is 1000 Da < M<1000000>0 Da, preferably, 10000 Da < M w <1000000> Da.​ 3. The method for preparing a manganese-based polymer metal halide with tunable red and green light emission according to claim 1, characterized in that: The solution of the polymer cation and manganese bromide, the solvent is optional; Optionally, the solvent is selected from at least one or more of water, methanol, and ethanol, wherein the selected solvent must dissolve both the polymer cation and the manganese bromide; Preferably, the solvent is at least one or both of water and methanol.

4. The method for preparing a manganese-based polymer metal halide with tunable red and green light emission according to claim 1, characterized in that: The ratio of polymer cations to manganese bromide in the solution of polymer cations and manganese bromide is adjustable; Optionally, the molar ratio of the cation to manganese bromide in the polymer cation is 1:0.01 to 1:2; Preferably, the molar ratio of cation to manganese bromide in the polymer cation is 1:0.05 to 1:

1.

5. The method for preparing a manganese-based polymer metal halide with tunable red and green light emission according to claim 1, 3 or 4, characterized in that: The concentrations of the solution of polymer cation and manganese bromide are adjustable; Optionally, the concentration of the cation and manganese bromide in the polymer cation is 0.01 mol / L to 10 mol / L in terms of manganese bromide; Preferably, the concentration of the cation and manganese bromide in the polymer cation is 0.1 mol / L to 2 mol / L in terms of manganese bromide.

6. The method for preparing a manganese-based polymer metal halide with tunable red and green light emission according to claim 1, characterized in that: The solvent evaporates at high temperature, and the temperature is adjustable; Optionally, the volatilization temperature of the solvent is 80 to 250°C; Preferably, the volatilization temperature of the solvent is 100-180°C.

7. A manganese-based polymer metal halide with tunable red and green luminescence obtained by the preparation method according to any one of claims 1 to 6.

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