Manganese-based organic-inorganic hybrid photoluminescent material and preparation method thereof
A manganese-based hybrid luminescent material emitting red fluorescence is developed, addressing toxicity and stability issues of lead-based materials and expanding applications through a simple synthesis method, enhancing its use in diverse fields.
Patent Information
- Application Number
- CN202510277856.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-10
- Publication Date
- 2025-06-10
AI Technical Summary
Traditional lead-based luminescent materials are toxic and unstable, limiting their applications, while existing manganese-based materials primarily emit green fluorescence, restricting their color diversity and applicability.
A manganese-based organic-inorganic hybrid luminescent material is synthesized using manganese chloride and optically active 3-hydroxy-piperidine salt, forming enantiomeric crystals that emit strong red fluorescence under UV light.
The new material enriches the color palette of manganese-based luminescent materials, offering broad applications in solar cells, spacecraft coatings, LED lighting, communication, sensing, and stealth technology, with a simple, low-cost, and environmentally friendly synthesis process.
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Abstract
Description
Technical Field
[0001] The present invention relates to a photoluminescent material, and particularly to a manganese-based photoluminescent material and a preparation method thereof. Background Art
[0002] After absorbing light of a specific wavelength, a photoluminescent material can re-emit light of a different wavelength. Due to its unique optical properties, it is widely used in fields such as Led lighting, electronic screens, light-emitting diodes, and fluorescent probes.
[0003] Traditional lead-based luminescent materials have attracted much attention from researchers due to their high luminescence efficiency and excellent electrical properties. However, the toxicity and instability of lead severely limit its applications. Traditional lead-based photoluminescent materials are highly toxic and have poor stability. Therefore, it is urgent to find new lead-free luminescent materials. Divalent manganese ions with a 3d 5 electronic configuration have become candidates for a new generation of luminescent materials due to their excellent luminescence performance, good stability, low toxicity, and low cost. Compared with pure metal materials, organic-inorganic hybrid materials not only retain the thermal and mechanical stability of inorganic components but also have the processability of organic components.
[0004] Therefore, exploring manganese-based organic-inorganic hybrid luminescent materials has very important scientific value and practical significance.
[0005] In existing manganese-based organic-inorganic hybrid luminescent materials, most manganese ions are 4-coordinated and emit green fluorescence. For example, the [C 6 H 14 NO]2MnCl4 manganese-based halide synthesized by Chen et al. has a stable green light emission at 545 nm (New J. Chem., 2022, 46, 1054). Manganese-based luminescent materials with other color fluorescences are relatively few, which to a certain extent limits their applications. The material prepared in the present invention emits strong red fluorescence under the irradiation of an ultraviolet lamp, enriching the types of manganese-based luminescent materials. Summary of the Invention
[0006] Aiming at the deficiencies of the existing technology, the present invention provides a manganese-based organic-inorganic hybrid photoluminescent material, which improves the deficiencies of current traditional photoluminescent materials, enriches the types of manganese-based luminescent materials, and broadens their application scope.
[0007] The present invention also discloses a preparation method of the manganese-based organic-inorganic hybrid photoluminescent material. The material is synthesized by reacting non-lead metal manganese chloride with a chiral organic amine to prepare a pair of enantiomeric photoluminescent crystal materials.
[0008] The technical solution adopted by the present invention is as follows: A manganese-based organic-inorganic hybrid photoluminescent material is obtained by using manganese chloride as a metal raw material and (R / S)-3-hydroxypiperidine hydrochloride as an organic amine ligand for a synthesis reaction. The molecular formula of this luminescent material is: C 5 H 12 Cl 3 MnNO.
[0009] For the preparation method of the manganese-based organic-inorganic hybrid photoluminescent material as described above, take the corresponding molar equivalents of manganese chloride and ( R )-3-hydroxypiperidine hydrochloride and dissolve them separately in an organic solvent. Then mix the two solutions and continuously stir until the solution is clear and transparent. Slowly evaporate the solvent to precipitate crystals to obtain: ( R )-C 5 H 12 Cl 3 MnNO.
[0010] For the preparation method of the manganese-based organic-inorganic hybrid photoluminescent material as described above, take the corresponding molar equivalents of manganese chloride and ( S )-3-hydroxypiperidine hydrochloride and dissolve them separately in an organic solvent. Then mix the two solutions and continuously stir until the solution is clear and transparent. Slowly evaporate the solvent to precipitate crystals to obtain: ( S )-C 5 H 12 Cl 3 MnNO.
[0011] In the preparation method of the manganese-based organic-inorganic hybrid photoluminescent material, manganese chloride and (R / S)-3-hydroxypiperidine hydrochloride react in a molar ratio of 1:1. The organic solvent used is methanol, ethanol or acetonitrile.
[0012] Advantages of the invention: 1. The present invention proposes a chiral organic-inorganic hybrid photoluminescent crystal material, which enriches the family of photoluminescent materials. By reacting manganese chloride with chiral 3-hydroxypiperidine hydrochloride, the deficiencies of current traditional photoluminescent materials are improved. This material emits strong red light under the irradiation of an ultraviolet lamp and has broad application potential in fields such as solar cells (photovoltaics), spacecraft coatings, Led lighting, communication, sensing (fluorescent probes), optical storage, and stealth coatings.
[0013] 2. The preparation method of the chiral organic-inorganic hybrid photoluminescent crystal material of the present invention only involves simple operations such as stirring and dissolving, filtration, etc. The preparation process is simple, with strong operability and low energy consumption, achieving the purpose of reducing costs and being environmentally friendly. By assembling manganese chloride metal with chiral (R / S)-3-hydroxypiperidine hydrochloride, the reaction solution is crystallized by the evaporation solvent method to prepare a pair of enantiomeric manganese-based organic-inorganic hybrid luminescent materials. This synthesis method has the characteristics of simple process, high yield, high purity, and environmental friendliness.
[0014] 3. Compared with the existing preparation technologies of photoluminescent materials that mostly use highly toxic metal lead as raw materials, the preparation method of the manganese-based organic-inorganic hybrid photoluminescent material of the present invention uses less toxic manganese chloride as raw material and has better biocompatibility. BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Figure 1 The crystal structure of the manganese-based organic-inorganic hybrid luminescent material ([[]] R R )-C 5 H 12 Cl 3 MnNO at 300 K is shown; Figure 2 The schematic fluorescence spectrum of the manganese-based organic-inorganic hybrid luminescent material ([[]] R R )-C 5 H 12 Cl 3 MnNO is shown; Figure 3 The pxrd pattern of the manganese-based organic-inorganic hybrid luminescent material ([[]] R R )-C 5 H 12 Cl 3 MnNO is shown; Figure 4 The crystal structure of the manganese-based organic-inorganic hybrid luminescent material ([[]] S S )-C 5 H 12 Cl 3 MnNO at 300 K is shown; Figure 5 The schematic fluorescence spectrum of the manganese-based organic-inorganic hybrid luminescent material ([[]] S S )-C 5 H 12 Cl 3 MnNO is shown; Figure 6 The pxrd pattern of the manganese-based organic-inorganic hybrid luminescent material ([[]] S S )-C 5 H 12 Cl 3PXRD pattern of MnNO. Detailed implementation mode
[0016] To make the technical concept and advantages of the present invention for realizing its invention purpose clearer and more understandable, the technical solution of the present invention will be further described in detail below with reference to the accompanying drawings. It should be understood that the following embodiments are only for explaining and illustrating the preferred implementation modes of the present invention, and should not be regarded as and do not constitute a limitation on the scope of patent protection required by the present invention.
[0017] Example 1 Take 5 mmol of manganese chloride and 5 mmol of ( R )-3-hydroxypiperidine hydrochloride and dissolve them separately in 20 mL of methanol in a small beaker, and mix them together. Stir at a temperature of 300 K for 15 min until the solution is clear, filter it with filter paper into another beaker, and place it in a fume hood at a temperature of 283 - 298 K to volatilize the solvent. After two days, red needle-like crystals precipitate to obtain: ( R )-C 5 H 12 Cl 3 MnNO.
[0018] The product yield reaches 91% and the purity is high.
[0019] As Figure 1 shown, the crystal structure of the ( R )-C 5 H 12 Cl 3 MnNO crystal prepared in this example at 300 K crystallizes in the P 2 1 2 1 2 1 space group (point group 222, orthorhombic system).
[0020] As Figure 2 shown, the ( R )-C 5 H 12 Cl 3 MnNO crystal prepared in this example emits red light at 636 nm under ultraviolet light irradiation at 365 nm.
[0021] As Figure 3 shown, the experimental PXRD data of the ( R )-C 5 H 12 Cl 3 MnNO crystal prepared in this example at room temperature is basically consistent with the simulated data, indicating that the purity of the crystal sample is very high.
[0022] Example 2 Take 5 mmol of manganese chloride and 5 mmol of ( R )-3-hydroxypiperidine hydrochloride and dissolve them separately in 20 mL of methanol in a small beaker. Mix them together and stir at 300 K for 15 min until the solution becomes clear. Filter it through filter paper into another beaker and place it in a fume hood at 283 - 298 K to volatilize the solvent. After two days, red needle-like crystals precipitate to obtain: ( S )-C 5 H 12 Cl 3 MnNO.
[0023] The product yield reaches 93% and the purity is high.
[0024] As Figure 4 shown, the crystal structure of ( S )-C 5 H 12 Cl 3 MnNO crystal prepared in this example at 300 K crystallizes in P 2 1 2 1 2 1 space group (point group 222, orthorhombic system).
[0025] As Figure 5 shown, the ( S )-C 5 H 12 Cl 3 MnNO crystal prepared in this example emits red light at 636 nm under ultraviolet light irradiation at 365 nm.
[0026] As Figure 6 shown, the experimental PXRD data of the ( S )-C 5 H 12 Cl 3 MnNO crystal prepared in this example at room temperature is basically consistent with the simulated data, indicating that the purity of the crystal sample is very high.
[0027] The manganese-based organic-inorganic hybrid photoluminescent material proposed by the present invention emits strong red fluorescence under ultraviolet lamp irradiation, enriching the types and application ranges of manganese-based luminescent materials. The preparation method of the manganese-based organic-inorganic hybrid luminescent material of the present invention uses manganese chloride metal to assemble with chiral (R / S)-3-hydroxypiperidine hydrochloride, and the reaction solution is crystallized by the evaporation solvent method. The preparation process is simple, highly operable, low in energy consumption, environmentally friendly, and has high yield, high purity and low production cost.
Claims
1. A manganese-based organic-inorganic hybrid photoluminescent material, characterized in that: The luminescent material is obtained by a synthetic reaction using manganese chloride as a metal raw material and (R / S)-3-hydroxypiperidine hydrochloride as an organic amine ligand. The molecular formula of the luminescent material is: C5H 12 Cl3MnNO。 2. The method for preparing the manganese-based organic-inorganic hybrid photoluminescent material according to claim 1, characterized in that: Take the corresponding molar equivalent of manganese chloride and ( R )-3-Hydroxypiperidine hydrochloride is dissolved in an organic solvent respectively, and then the two solutions are mixed and stirred continuously until the solution is clear and transparent, and the solvent is slowly evaporated to precipitate crystals to obtain: ( R )-C5H 12 Cl3MnNO。 3. The method for preparing a manganese-based organic-inorganic hybrid photoluminescent material according to claim 1, characterized in that: Take the corresponding molar equivalent of manganese chloride and ( S )-3-Hydroxypiperidine hydrochloride is dissolved in an organic solvent respectively, and then the two solutions are mixed and stirred continuously until the solution is clear and transparent, and the solvent is slowly evaporated to precipitate crystals to obtain: ( S )-C5H 12 Cl3MnNO。 4. The method for preparing a manganese-based organic-inorganic hybrid photoluminescent material according to claim 2 or 3, characterized in that: Manganese chloride and (R / S)-3-hydroxypiperidine hydrochloride are reacted in a molar ratio of 1:
1.
5. The method for preparing a manganese-based organic-inorganic hybrid photoluminescent material according to claim 2 or 3, characterized in that: The organic solvent used is methanol, ethanol or acetonitrile.