CN114656364B - Mn-based organic-inorganic hybrid metal halide luminescent material and preparation method thereof - Google Patents

Abstract

The invention discloses a Mn-based hybrid metal halide luminescent material and a preparation method thereof, belonging to the field of photoelectric materials. The photoelectric materials comprise four types, and the chemical formulas are (C) ₁₃ H ₂₆ N) ₃ MnBr ₅ ，(C ₁₃ H ₂₆ N) ₂ MnCl ₄ ，(C ₇ H ₁₈ N) ₂ MnBr ₄ ，(C ₇ H ₁₈ N) ₂ MnCl ₄ . The invention uses N-methyl dicyclohexylamine and butyl trimethyl ammonium chloride as luminescent materials of organic ligands, the excitation wavelength ranges of the four compounds are 200-480nm, the optimal excitation is blue light excitation of about 450nm, the emission peak is located near 520nm, the optimal narrow-band green light emission is presented, the luminous efficiency is high, and the thermal quenching resistance is good. The preparation process is simple, has extremely low cost and is extremely easy to popularize in large-scale technology. The luminescent material can be used for manufacturing a luminescent device, and is used in the fields of display, illumination and the like.

Description

A kind of Mn-based organic-inorganic hybrid metal halide luminescent material and its preparation method

technical field

The invention relates to the technical field of solid-state lighting and liquid crystal display backlight, in particular to organic-inorganic hybrid metal halides based on N-methyldicyclohexylamine and butyltrimethylammonium chloride ligands and their preparation methods and applications in optoelectronics applications in the field.

Background technique

Organic–inorganic metal halides have attracted considerable attention in the fields of solid-state lighting and display backlighting due to their tunable emission. In particular, low-dimensional metal halides have become a hotspot in the research of white light-emitting diodes due to their bright and stable emission properties.

Through the appropriate combination of organic cations and metal halides, the half-width of organic-inorganic metal halides can be controlled as well as their size from high-dimensional to low-dimensional. The narrow half-peak width can ensure that the fluorescent material has high color purity, and thus can exhibit a high color gamut for application in the field of display backlight. The inorganic part in zero-dimensional organic-inorganic metal halides is isolated by large organic cations, which has a unique electronic structure and isolated anionic metal halide polyhedral structural units, so it can exhibit the photophysical properties of a single metal halide, with High photoluminescence quantum efficiency and long decay lifetime. However, most zero-dimensional metal halides exhibit fluorescence emission based on self-trapped excitons with large Stokes shifts, which makes them difficult to be used in white LED devices excited by blue light. Compared with blue light chips, the cost of near ultraviolet light chips is much higher than that of blue light chips, and the luminous efficiency is lower. Therefore, the most ideal excitation light source for white LED devices is the blue chip, not the ultraviolet chip. Based on this, exploring luminescent materials excited by blue light is the focus of future research.

Compared with traditional organic-inorganic hybrid metal halides, zero-dimensional Mn-based metal halides make it possible to obtain efficient emission under ideal blue light excitation due to their unique dd transitions. In addition, Mn-based metal halides have many advantages, such as simple preparation process, high efficiency, low toxicity, and low price. This has led to the extensive investigation of organic-inorganic hybrid metal halide materials with Mn2 ⁺ as the metal cation.

Contents of the invention

In order to achieve the above object, the present invention introduces two different organic cations, N-methyldicyclohexylamine cation, and butyltrimethylammonium chloride is an organic ligand, so that the preparation has good heat quenching resistance and high luminous intensity. The manganese-based hybrid metal halide narrow-band green luminescent material has an emission peak around 520nm and an optimal excitation wavelength of 450nm.

Another object of the present invention is to provide cheap, easy to prepare and high luminous intensity narrow-band green fluorescent materials, manganese-based organic compounds with N-methyldicyclohexylamine cation and butyltrimethylammonium chloride as ligands. -The preparation process of the inorganic hybrid metal halide luminescent material is simple, the cost is extremely low, and it is easy to promote large-scale technology.

A manganese-based organic-inorganic hybrid metal halide luminescent material, characterized in that the luminescent material includes four materials, the chemical formulas are (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ , wherein: C ₁₃ H ₂₆ N ⁺ is N-methyldicyclohexylamine cation, C ₇ H ₁₈ N ⁺ is Butyltrimethylammonium chloride cation.

Further, in the luminescent material, (C ₁₃ H ₂₆ N) ₃ MnBr ₅ belongs to the orthorhombic crystal system, the space group is Pbca, and (C ₁₃ H ₂₆ N) ₂ MnCl ₄ belongs to the monoclinic crystal system, and the space group is P21c , (C ₇ H ₁₈ N) ₂ MnBr ₄ belongs to the orthorhombic crystal system, the space group is P21c, (C ₇ H ₁₈ N) ₂ MnCl ₄ belongs to the monoclinic crystal system, and the space group is C2/c.

Further, the luminescent material is excited by 250-480nm light, and there is green fluorescence emission, wherein the best excitation is 450nm blue light excitation; the emission peak is located at 520nm, showing an ideal narrow-band green light emission; half of the four compounds The peak widths are 43nm, 48nm, 51nm and 60nm, respectively.

Further, the luminescent material has good thermal quenching resistance at high temperature; (C ₁₃ H ₂₆ N) ₃ MnBr ₅ can still maintain 82.7% of the emission intensity at room temperature at 420K, (C ₁₃ H ₂₆ N) ₂ MnCl ₄ can still maintain 64.4% of the emission intensity at room temperature at 420K, (C ₇ H ₁₈ N) ₂ MnBr ₄ can still maintain 74.8% of the emission intensity at room temperature at 380K, (C ₇ H ₁₈ N) ₂ MnCl ₄ can still maintain 53.0% of the emission intensity at room temperature at 380K.

The preparation method of manganese-based organic-inorganic hybrid metal halide luminescent material as described above, the luminescent material is prepared by cooling crystallization method or solid phase grinding method, comprising the following steps:

Solid phase grinding method:

1)-Weighing materials: Weigh the required raw materials C ₁₃ H ₂₅ N, C ₇ H ₁₈ NCl, manganese-containing compounds and a small amount of acid (HCl or HBr), and add the raw materials into the mortar;

2) Grinding and mixing: fully grind and mix the raw materials to obtain (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ powder. Cooling crystallization method:

3) Weighing materials: weighing the required raw materials C ₁₃ H ₂₅ N, C ₇ H ₁₈ NCl, and manganese-containing compounds in sequence, and adding the raw materials into the reaction vessel;

4) Stirring and dissolving: Add some organic solvent and acid as a solvent into the reaction vessel, heat to 50-90°C and stir to obtain a clear solution;

5) Crystallization: put the solution obtained in step 2) into an oven, the initial temperature of the oven is the temperature at which step 2) is stirred until it is completely dissolved, the oven program is set to slowly cool down, and the temperature is lowered for 1-10 days to obtain (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ crystals, the obtained reaction liquid and crystals Filtration and drying are performed in sequence to obtain dry N-methyldicyclohexylamine cation and organic-inorganic hybrid metal halide crystals of butyltrimethylammonium chloride cation ligand.

Further, the organic solvent in step (2) in the cooling crystallization method is N,N-dimethylformamide, and the HX acid in step (3) is hydrochloric acid, hydrobromic acid or other acids.

Further, the temperature of the reaction of stirring and heating the solution in step (2) in the temperature-lowering crystallization method is 50-90°C.

Further, the organic-inorganic hybrid metal halide crystal of the N-methyldicyclohexylamine cation and the butyltrimethylammonium chloride cation ligand is applied to the fields of illumination, display backlight and laser.

The technical key point of the present invention is:

Compared with the prior art, the present invention has the following advantages and beneficial effects:

(1) Excellent thermal quenching resistance and high luminous efficiency;

(2) There is a narrow half-peak width, which is comparable to the commercial narrow-band green phosphor β-Sialon:Eu ²⁺ ;

(3) The price of the luminescent material is extremely low;

(4) Stable physical and chemical properties;

(5) The preparation method of the present invention is simple and easy to be popularized on a large scale. The luminescent material can be used in the manufacture of luminescent devices, and in the fields of illumination, liquid crystal display backlight and the like.

Description of drawings

Fig. 1 is the comparison between the powder X-ray diffraction (XRD) pattern and the single crystal XRD pattern of the sample prepared in Example 1 of the present invention.

Fig. 2 is the comparison between the powder X-ray diffraction (XRD) pattern and the single crystal XRD pattern of the sample prepared in Example 2 of the present invention.

Fig. 3 is the comparison between the powder X-ray diffraction (XRD) pattern and the single crystal XRD pattern of the sample prepared in Example 3 of the present invention.

Fig. 4 is a comparison between the powder X-ray diffraction (XRD) pattern and the single crystal XRD pattern of the sample prepared in Example 4 of the present invention.

FIG. 5 is an excitation emission spectrum diagram of the sample prepared in Example 1 of the present invention.

Fig. 6 is an excitation emission spectrum diagram of the sample prepared in Example 2 of the present invention.

FIG. 7 is an excitation emission spectrum diagram of the sample prepared in Example 3 of the present invention.

FIG. 8 is an excitation emission spectrum diagram of the sample prepared in Example 4 of the present invention.

Fig. 9 is a temperature-varying spectrogram of the sample prepared in Example 1 of the present invention.

Fig. 10 is a temperature-varying spectrogram of the sample prepared in Example 2 of the present invention.

Fig. 11 is a temperature-varying spectrogram of the sample prepared in Example 3 of the present invention.

Fig. 12 is a temperature-varying spectrogram of the sample prepared in Example 4 of the present invention.

Detailed ways

In order to better describe the present invention, the present invention will be further described in detail in conjunction with the following examples. The following content is illustrative but not restrictive, and the implementation of the present invention is not limited thereto.

Example 1

The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material with the chemical composition formula of (C ₁₃ H ₂₆ N) ₃ MnBr ₅ in this example is as follows:

Dosing according to the stoichiometric ratio, weighing high-purity MnBr ₂ compound powder raw material, measuring organic N-methyldicyclohexylamine (C ₁₃ H ₂₅ N) solution, and measuring HBr acid. Mix the measured organic matter N-methyldicyclohexylamine (C ₁₃ H ₂₅ N) solution with the powder raw material of the _MnBr compound and dissolve it in a container, and mix a certain amount of N, N-dimethylformamide solution Add to the container where the above organic methyl dicyclohexylamine (C ₁₃ H ₂₅ N) solution and MnBr ₂ powder raw materials are located, and then add the measured amount of HBr acid. Then heat the obtained mixed solution to a temperature of 50-90°C and continue to stir until the mixture inside is completely dissolved to obtain a clear solution. Put the obtained clear solution into an oven at 50-90°C and set the program to cool down for 2 -4 days, the required (C ₁₃ H ₂₆ N) ₃ MnBr ₅ crystals and residual solution were obtained, and the obtained reaction solution and crystals were filtered and dried in sequence to obtain the ( C ₁₃ H ₂₆ N) ₃ MnBr ₅ crystal.

The powder X-ray diffraction (XRD) spectrum of the organic-inorganic hybrid metal halide luminescent material prepared in this embodiment is shown in Figure 1, and the excitation spectrum and emission spectrum are shown in Figure 5. The optimal excitation wavelength is 450 nm, the emission peak is at 515 nm, and the half-maximum width is 43 nm. It shows that this organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.

Example 2

The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material with the chemical composition formula of (C ₁₃ H ₂₆ N) ₂ MnCl ₄ in this example is as follows:

Dosing according to the stoichiometric ratio, weighing high-purity MnCl ₂ compound powder raw material, measuring organic N-methyldicyclohexylamine (C ₁₃ H ₂₅ N) solution, and measuring HCl acid. Mix the measured organic matter N-methyldicyclohexylamine (C ₁₃ H ₂₅ N) solution with the powder raw material of the MnCl ₂ compound and dissolve it in a container, and mix a certain amount of N,N-dimethylformamide solution Add to the container where the above organic matter N-methyldicyclohexylamine (C ₁₃ H ₂₅ N) solution and MnCl ₂ powder raw materials are located, and then add the measured amount of HCl acid. Then heat the obtained mixed solution to a temperature of 90-95°C and continue to stir until the mixture inside is completely dissolved to obtain a clear solution. Put the obtained clear solution into an oven at 90-95°C and set the program to cool down for 2 -4 days, the required (C ₁₃ H ₂₆ N) ₂ MnCl ₄ crystals and residual solution were obtained, and the obtained reaction liquid and crystals were filtered and dried in sequence to obtain the ( C ₁₃ H ₂₆ N) ₂ MnCl ₄ crystals.

The powder X-ray diffraction (XRD) spectrum of the organic-inorganic hybrid metal halide luminescent material prepared in this example is shown in FIG. 2 , and the excitation spectrum and emission spectrum are shown in FIG. 6 . The optimum excitation wavelength is 450 nm, the emission peak is at 515 nm, and the half-maximum width is 48 nm. It shows that this organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.

Example 3

The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material with the chemical composition formula of (C ₇ H ₁₈ N) ₂ MnBr ₄ in this example is as follows:

The stoichiometric ratio is used for batching, and the high-purity MnBr ₂ compound powder raw material, the organic butyltrimethylammonium chloride (C ₇ H ₁₈ NCl) powder, and the HBr acid are weighed respectively. The weighed organic matter butyltrimethylammonium chloride is mixed with the powder raw material of the _MnBr compound and dissolved in a container, and then the measured amount of HBr acid is added. Then heat the obtained mixed solution to a temperature of 60-90°C and continue to stir until the mixture inside is completely dissolved to obtain a clear solution. Put the obtained clear solution into an oven at 60-90°C and set the program to cool down for 2 -3 days, the required (C ₇ H ₁₈ N) ₂ MnBr ₄ crystals and residual solution were obtained, and the obtained reaction liquid and crystals were filtered and dried in sequence to obtain (C ₇ H ₁₈ N) ₂ MnBr ₄ crystals.

The powder X-ray diffraction (XRD) pattern of the organic-inorganic hybrid metal halide luminescent material prepared in this embodiment is shown in Figure 3, and the excitation spectrum and emission spectrum are shown in Figure 7. The optimal excitation wavelength is 450 nm, the emission peak is at 521 nm, and the half-maximum width is 51 nm. It shows that this organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.

Example 4

The preparation method of the manganese-based organic-inorganic hybrid metal halide luminescent material with the chemical composition formula of (C ₇ H ₁₈ N) ₂ MnCl ₄ in this example is as follows:

The stoichiometric ratio is used for batching, and the high-purity MnCl ₂ compound powder raw material, the organic butyltrimethylammonium chloride (C ₇ H ₁₈ NCl) powder, and the HCl acid are weighed respectively. The weighed organic matter butyltrimethylammonium chloride is mixed with the powder raw material of the _MnCl2 compound and dissolved in the container, and then the measured HCl acid is added. Then heat the obtained mixed solution to a temperature of 60-90°C and continue to stir until the mixture inside is completely dissolved to obtain a clear solution. Put the obtained clear solution into an oven at 60-90°C and set the program to cool down for 2 -3 days, the required (C ₇ H ₁₈ N) ₂ MnCl ₄ crystals and residual solution were obtained, and the obtained reaction solution and crystals were filtered and dried in sequence to obtain (C ₇ H ₁₈ N) ₂ MnCl ₄ crystals.

The powder X-ray diffraction (XRD) spectrum of the organic-inorganic hybrid metal halide luminescent material prepared in this example is shown in FIG. 4 , and the excitation spectrum and emission spectrum are shown in FIG. 8 . The optimal excitation wavelength is 450 nm, the emission peak is at 525 nm, and the half-maximum width is 60 nm. It shows that this organic-inorganic hybrid metal halide luminescent material can realize narrow-band green light emission.

The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the embodiment, and any other changes, modifications, substitutions and combinations made without departing from the spirit and principle of the present invention , simplification, all should be equivalent replacement methods, and are all included in the protection scope of the present invention.

Examples 5-8 Taking the preparation of four manganese-based organic-inorganic hybrid perovskite materials by the cooling crystallization method as an example, the organic-inorganic hybrid materials (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N ) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ half peak width and luminous efficiency to measure the application of organic-inorganic hybrid perovskite materials in the field of luminescence.

Table 1

Example chemical composition half width quantum efficiency 5 (C ₁₃ H ₂₆ N) ₃ MnBr ₅ 43nm 77.8% 6 (C ₁₃ H ₂₆ N) ₂ MnCl ₄ 48nm 79.3% 7 (C ₇ H ₁₈ N) ₂ MnBr ₄ 51nm 33.4% 8 (C ₇ H ₁₈ N) ₂ MnCl ₄ 60nm 76.5%

Examples 9-12 Taking the preparation of four manganese-based organic-inorganic hybrid perovskite materials by the cooling crystallization method as an example, the organic-inorganic hybrid materials (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N ) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ luminescence intensities at different temperatures to measure the thermal quenching resistance of organic-inorganic hybrid perovskite materials performance.

Table 2

Example chemical composition measure temperature Percentage (relative to room temperature strength) 9 (C ₁₃ H ₂₆ N) ₃ MnBr ₅ 420K 82.7% 10 (C ₁₃ H ₂₆ N) ₂ MnCl ₄ 420K 64.4% 11 (C ₇ H ₁₈ N) ₂ MnBr ₄ 380K 74.8% 12 (C ₇ H ₁₈ N) ₂ MnCl ₄ 380K 53.0%

Examples 13-16 Taking the preparation of four manganese-based organic-inorganic hybrid perovskite materials by the cooling crystallization method as an example, the organic-inorganic hybrid materials (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N ) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ are packaged with K ₂ SiF ₆ :Mn ⁴⁺ red phosphor and InGaN blue light chip respectively to form an LED backlight panel, to Measure the application of organic-inorganic hybrid perovskite materials in liquid crystal backlight display.

table 3

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Claims (7)

1. A manganese-based organic-inorganic hybrid metal halide luminescent material, characterized in that the luminescent material is the following four materials, chemical formulas are respectively (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N ) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ , wherein: C ₁₃ H ₂₆ N ⁺ is N-methyldicyclohexylamine cation, C ₇ H ₁₈ N ⁺ is butyltrimethylammonium chloride cation; Among the luminescent materials, (C ₁₃ H ₂₆ N) ₃ MnBr ₅ belongs to the orthorhombic crystal system, the space group is Pbca, (C ₁₃ H ₂₆ N) ₂ MnCl ₄ belongs to the monoclinic crystal system, the space group is P21c, (C ₇ H ₁₈ N) ₂ MnBr ₄ belongs to orthorhombic crystal system with space group P21c, and (C ₇ H ₁₈ N) ₂ MnCl ₄ belongs to monoclinic crystal system with space group C2/c. 2. The manganese-based organic-inorganic hybrid metal halide luminescent material as claimed in claim 1, characterized in that the luminescent material is excited by 250-480nm light, and there is green fluorescence emission, wherein the best excitation is 450nm blue light Excitation; the emission peak is located at 520nm, showing a narrow-band green emission; the half-peak widths of the four compounds are 43nm, 48nm, 51nm and 60nm, respectively. 3. The manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 1, characterized in that the luminescent material has thermal quenching resistance at high temperature; (C ₁₃ H ₂₆ N) ₃ MnBr ₅ At 420K, it is 82.7% of the emission intensity at normal temperature, (C ₁₃ H ₂₆ N) ₂ MnCl ₄ is 64.4% of the emission intensity at normal temperature at 420K, and (C ₇ H ₁₈ N) ₂ MnBr ₄ is at 380K at normal temperature. 74.8% of the emission intensity, (C ₇ H ₁₈ N) ₂ MnCl ₄ at 380K is 53.0% of the emission intensity at room temperature. 4. A method for preparing a manganese-based organic-inorganic hybrid metal halide luminescent material as claimed in any one of claims 1-3, wherein the luminescent material is prepared by a cooling crystallization method and a solid-phase grinding method, Include the following steps: Solid phase grinding method: 1) Weighing materials: Weigh the required raw materials C ₁₃ H ₂₅ N, C ₇ H ₁₈ NCl, manganese-containing compounds and a small amount of acid, the acids are HCl and HBr, and add the raw materials into the mortar; 2) Grinding and mixing: fully grind and mix the raw materials to obtain (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ powder; Cooling crystallization method: 1) Weighing materials: Weigh the required raw materials C ₁₃ H ₂₅ N, C ₇ H ₁₈ NCl, manganese-containing compounds in sequence, Add raw materials to the reaction vessel; 2) Stirring and dissolving: Add some organic solvent and acid as a solvent into the reaction vessel, heat to 50-90°C and stir to obtain a clear solution; 3) Crystallization: Put the solution obtained in step 2) into an oven. The initial temperature of the oven is the temperature at which step 2) is stirred until it is completely dissolved. The oven program is set to slowly cool down, and the temperature is lowered for 1-10 days to obtain (C ₁₃ H ₂₆ N) ₃ MnBr ₅ , (C ₁₃ H ₂₆ N) ₂ MnCl ₄ , (C ₇ H ₁₈ N) ₂ MnBr ₄ , (C ₇ H ₁₈ N) ₂ MnCl ₄ crystals, the resulting reaction solution and crystals are filtered and dried in sequence to obtain dry N-methyldicyclohexylamine cations, butyltrimethylammonium chloride cation ligands Organic-inorganic hybrid metal halide crystals. 5. The preparation method of manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 4, characterized in that the organic solvent described in step (2) in the cooling crystallization method is N,N-dimethyl formaldehyde Amide, the acid described in step (2) is hydrochloric acid or hydrobromic acid. 6. The preparation method of manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 4, characterized in that the temperature of the solution stirring and heating reaction in step (2) in the cooling crystallization method is 50-90°C. 7. The manganese-based organic-inorganic hybrid metal halide luminescent material according to claim 1, characterized in that the N-methyldicyclohexylamine cation, the organic compound of the butyltrimethylammonium chloride cation ligand -Inorganic hybrid metal halide crystals are used in lighting, display backlight, and laser fields.

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