阅读说明：本技术 一种含氮两亲性有机离子锰卤化物发光材料及其制备方法与应用 (Nitrogen-containing amphiphilic organic ion manganese halide luminescent material and preparation method and application thereof ) 是由 叶柿 张帅 赵逸飞 张勤远 于 2020-11-25 设计创作，主要内容包括：本发明公开了一种含氮两亲性有机离子锰卤化物发光材料及其制备方法与应用。其结构通式为[L-C-nH-(2n+1)]-2MnX-4,其中n代表疏水烷基链的长度,L选自甲基咪唑,吡啶、三甲基铵等含氮离子性亲水基团,X选自卤素、拟卤素或者其任意比例的组合,收获的产物在紫外或者蓝光照射下展示出良好的绿色或黄色荧光效果,且不易吸湿分解,在460nm激发下荧光效果很强,是性能优异的光学材料,用此发光材料和红色发光材料结合蓝光LED芯片产生白光,持续工作1200min,发光效率没有明显改变。(The invention discloses a nitrogen-containing amphiphilic organic ion manganese halide luminescent material and a preparation method and application thereof. The structural general formula is [ L-C ] n H 2n+1 ] 2 MnX 4 Wherein n represents borealisThe length of a water alkyl chain, L is selected from nitrogen-containing ionic hydrophilic groups such as methylimidazole, pyridine, trimethylammonium and the like, X is selected from halogen, pseudohalogen or a combination of halogen and pseudohalogen in any proportion, the obtained product shows a good green or yellow fluorescent effect under ultraviolet or blue light irradiation, is not easy to absorb moisture and decompose, has a strong fluorescent effect under 460nm excitation, is an optical material with excellent performance, and is combined with a blue light LED chip to generate white light by using the luminescent material and a red luminescent material, and the white light LED chip can work for 1200min continuously without obvious change of the luminescent efficiency.)

1. The nitrogen-containing amphiphilic organic ion manganese halide luminescent material is characterized by having a structural general formula as follows:

wherein n represents the number of carbon atoms at the tail of the alkyl group, and the value of n is more than or equal to 6; the alkyl tail is used as a substituent of a nitrogen atom in the hydrophilic head group L, and the L is selected from various nitrogen-ion-containing hydrophilic head groups; each X is independently selected from a halide ion or a pseudohalide ion.

2. The nitrogen-containing amphiphilic organic ion manganese halide luminescent material as claimed in claim 1, wherein the halide is F^-、Cl^-、Br^-、I^-One or more than one of the pseudohalogen ions is CN^-、SCN^-、NCS^-、CP^-、NC^-、OCN^-、OSCN^-、SeCN^-、BF₄ ^-、PF₆ ^-And COO^-One or more of them.

3. The nitrogen-containing amphiphilic organic ion manganese halide light-emitting material of claim 1, wherein the nitrogen-containing ionic hydrophilic head group is methylimidazole, imidazole, pyridine, trimethylammonium, triethylammonium, pyrrole, or piperidine.

4. The nitrogen-containing amphiphilic organic ion manganese halide luminescent material as claimed in claim 1, wherein the halide luminescent material is in a crystal form belonging to triclinic system, P-1 space group, and has a unit cell parameter ab isc isAlpha is 99.90-100.00 degrees, beta is 91.49-91.50 degrees, and gamma is 92.82-92.83 degrees.

5. The preparation method of the nitrogen-containing amphiphilic organic ion manganese halide luminescent material according to any one of claims 1 to 4, characterized by comprising the following steps:

(1) adding halogen salt containing nitrogen ion amphiphilic organic ions into the solvent 1, and dissolving uniformly to obtain a solution 1; adding manganese halide or a hydrate thereof into a solvent 2, and uniformly dissolving to obtain a solution 2;

(2) and uniformly mixing the solution 1 and the solution 2, filtering to obtain filtrate, and crystallizing to obtain the nitrogen-containing amphiphilic organic ion manganese halide luminescent material.

6. The method for preparing nitrogen-containing amphiphilic organic ion manganese halide luminescent material according to claim 5, wherein the halogen salt of nitrogen-containing amphiphilic organic ion in step (1) is halogen salt of N-hexadecylpyridine, and the anion of the halogen salt is selected from F^-、Cl^-、Br^-、I^-Or a pseudohalide ion; the anions in the manganese halide are independently selected from F^-、Cl^-、Br^-、I^-Or a pseudohalide ion; the solvent 1 and the solvent 2 are alcohol, deionized water, pseudohalogen hydride or halogen acid.

7. The method for preparing the nitrogen-containing amphiphilic organic ion manganese halide luminescent material according to claim 5, wherein in the solution 1 in the step (1), the concentration of the halogen salt of the nitrogen-containing amphiphilic organic ion is 0.1-2 mmol/mL; in the solution 2 in the step (1), the concentration of the manganese halide is 0.1-4 mmol/mL.

8. The method for preparing the nitrogen-containing amphiphilic organic ion manganese halide luminescent material according to claim 5, wherein the volume ratio of the solution 1 to the solution 2 in the step (2) is 8:1-1: 2; the temperature of the crystallization treatment in the step (2) is 20 ℃ to 120 ℃, and the time of the crystallization treatment is 24 hours to 180 hours.

9. The method for preparing the nitrogen-containing amphiphilic organic ion manganese halide luminescent material according to claim 6, wherein the alcohol is a monohydric alcohol with 1-5 carbon atoms; the hydrohalic acid is hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, and the pseudohalogen hydride is hydrogen thiocyanate and tetrafluoroboric acid.

10. Use of the nitrogen-containing amphiphilic organic ion manganese halide luminescent material according to any one of claims 1 to 4 in the preparation of white light LEDs.

Technical Field

The invention belongs to the field of functional materials, and particularly relates to a nitrogen-containing amphiphilic organic ion manganese halide luminescent material, and a preparation method and application thereof.

Background

Luminescent materials are a class of substances that absorb photons (or electromagnetic waves) and then re-emit the photons. From quantum mechanics theory, the luminescence process can be described as a process in which a substance absorbs photons, transits to an excited state of a higher energy level, returns to a low energy state, and emits photons. Photoluminescence is the most common light-emitting mode in light-emitting materials, and can be applied to the fields of energy, sensing, display and the like. Photoluminescent materials are commonly used in cathode ray, plasma and liquid crystal displays, fluorescent lamps, sensors and white LEDs, and their powders are ideal materials for producing luminescent coatings, anti-counterfeiting coatings, luminescent plastics, etc.

Among illumination light sources, white LEDs have been widely used in real life due to their high efficiency, long life, low power consumption, and environmental friendliness. Commercially available white LEDs are typically composed of a single blue gallium nitride (GaN) chip combined with a yellow Yttrium Aluminum Garnet (YAG) phosphor, but have a low color rendering index (CRI < 75).

In recent years, organic-inorganic hybrid metal halides have gained wide attention in the field of LED applications. In which lead (Pb) is hybridized²⁺) The most prominent halide properties are (Lingling Mao, Constantinos C.Stoumpos, and Mercury G.Kanatzidis Journal of the American Chemical Society 2019141 (3), 1171-. However, due to the serious biological toxicity of Pb, the search for lead-free compounds is always a key problem for exploring green and environment-friendly high-efficiency luminescent materials. Divalent tin (Sn)²⁺) With monovalent copper (Cu)¹⁺) The highly efficient luminescent compounds of (a) provide a solution to some extent, but due to the easily oxidizable nature of these two ions, there is still a great distance from practical application. Divalent manganese (Mn)²⁺) The compound has the obvious advantages of high-efficiency luminescence, high thermal stability, cheap raw materials, simple preparation, low toxicity and the like, has the most practical application potential in the hybrid materials, and is concerned greatly (Viktoriia Morad, Ihor Cherniukh, Lena)Yevhen Shynkarenko,Sergii Yakunin,and Maksym V.Kovalenko Chemistry of Materials 2019 31(24),10161-10169)。Mn²⁺Having 3d as transition metal ion⁵The electronic configuration, the electronic population of which is strongly influenced by the ligand. Mn under weak field ligand²⁺It has a high spin distribution, i.e. 5 d electrons occupy 5 d orbitals, respectively. The energy absorption and fluorescence emission of Mn are both d-d transitions of the steric forbidden region and spin forbidden transitions under high spin (⁴D,⁴G→⁶S). The energy level spacing between each atomic spectral term of the compound can change along with the coordination number and the ligand environment, the rule can be approximately given by a Tanabe-Sugano diagram, and Mn can increase along with the crystal strength²⁺And (4) red shift of luminescence. Mn in tetrahedral coordination sites²⁺The luminescence is usually in the green band (emission peak around 520 nm), and can be further adjusted between cyan (500nm) and yellow (550nm) by adjusting the complex ion. Has strong research significance and application prospect. With conventional Mn²⁺Compared with the doped electrodeless luminescent material (patent number CN107384387B), the organic-inorganic hybrid material has the characteristics of simple synthesis conditions, simple components, no need of doping and high quantum efficiency. However, these materials are highly hygroscopic and have insufficient thermal stability (patent No. CN 108192605A).

Disclosure of Invention

In order to overcome the defects in the prior art, the hydrophobic groups in the amphiphilic organic ions have a protective effect on the luminescent material, so that the thermal stability and the moisture absorption stability of the luminescent material are greatly improved.

The invention aims to provide a zero-dimensional organic-inorganic hybrid manganese metal halide with fluorescence property, wherein an organic part L consists of a hydrophobic alkane tail part and a nitrogen-containing hydrophilic group head part, and the tail part is combined with the head part in the form of a nitrogen substituent. Abbreviated as [ L-C ]_nH_2n+1]₂[MnX₄]L is one of nitrogen-containing ionic organic hydrophilic groups such as methylimidazole, imidazole, pyridine, trimethylammonium group, triethylammonium, pyrrole, piperidine and the like; x is selected from halide or pseudohalide. Preferably, X is Br. The material shows good green or yellow fluorescence effect under the irradiation of ultraviolet or blue light, particularly has extremely strong 365nm fluorescence effect, and is an optical material with excellent performance.

The invention also discloses a method for preparing the material, which has the advantages of high yield, cost saving, easy operation and contribution to industrial production.

The invention further aims to provide the nitrogen-containing amphiphilic organic ion manganese halide luminescent material with the fluorescent property, which is obtained by the preparation method and is applied to the fields of white light LEDs and the like.

The purpose of the invention is realized by at least one of the following technical solutions.

The invention provides a nitrogen-containing amphiphilic organic ion manganese halide luminescent material (zero-dimensional manganese metal halide), which is an ionic compound of halide salt of tetrahalogenated manganese and nitrogen-containing amphiphilic organic ion, and the structural formula is [ L-C ]_nH_2n+1N]₂ ⁺[MnX₄]^2-L is a nitrogen-containing organic hydrophilic group such as methylimidazole and pyridine, and X is independently selected from halogen or pseudohalogen.

The nitrogen-containing amphiphilic organic ion manganese halide luminescent material (zero-dimensional manganese metal halide) provided by the invention has a structural general formula shown as the following (formula I):

wherein n represents the number of carbon atoms at the tail of the alkyl group, and the value of n is more than or equal to 6; the alkyl tail is used as a substituent of a nitrogen atom in the hydrophilic head group L, and the L can be selected from various nitrogen ion-containing hydrophilic groups; each X is independently selected from a halide ion or a pseudohalide ion.

Further, the halogen ion is F^-、Cl^-、Br^-、I^-One or more than one of the pseudohalogen ions is CN^-、SCN^-、NCS^-、CP^-、NC^-、OCN^-、OSCN^-、SeCN^-、BF₄ ^-、PF₆ ^-And COO^-One or more of them.

Preferably, X is selected from F^-、Cl^-、Br^-、I^-、CN^-And SCN^-One or more of them.

Further preferably, X is selected from Cl^-、Br^-、I^-One or more of them.

Further, the nitrogen ion-containing hydrophilic head group is a group selected from methylimidazole, imidazole, pyridine, trimethylammonium group, triethylammonium, pyrrole, piperidine and the like, and the tail of the alkyl group having a carbon number of n is a nitrogen substituent of the selected group.

Preferably, the nitrogen-containing ionic hydrophilic head group is selected from the group consisting of methylimidazole, pyridine, pyrrole, trimethylammonium, and triethylamine.

Further preferably, the nitrogen-ion containing hydrophilic head group is selected from the group consisting of methylimidazole, pyridine and trimethylammonium.

Further, the halide luminescent material is in a crystal form belonging to a triclinic system, P-1 space group, and a isb isAlpha is 99.90-100.00 degrees, beta is 91.49-91.50 degrees, and gamma is 92.82-92.83 degrees.

The invention provides a method for preparing the nitrogen-containing amphiphilic organic ion manganese metal halide luminescent material, which comprises the following steps:

(1) adding halogen salt containing nitrogen amphiphilic organic ions into the solvent 1, and dissolving uniformly to obtain a solution 1; adding manganese halide or a hydrate thereof into a solvent 2, and uniformly dissolving to obtain a solution 2;

(2) and uniformly mixing the solution 1 and the solution 2 in a container, filtering to obtain filtrate, and performing crystallization treatment to obtain the nitrogen-containing amphiphilic organic ion manganese halide luminescent material.

Further, the halogen salt of the nitrogen ion-containing amphiphilic organic ion in the step (1) is the halogen salt of N-hexadecyl pyridine, wherein the anion of the halogen salt is selected from F^-、Cl^-、Br^-、I^-Or a pseudohalide ion; the manganese halide is a non-hydrate, wherein the anion is independently selected from F^-、Cl^-、Br^-、I^-Or a pseudohalide ion; the solvent 1 and the solvent 2 are alcohol, deionized water, halogen acid or pseudohalogen hydride.

Preferably, the halogen salt of the nitrogen-containing amphiphilic organic ion in the step (1) is N-hexadecyl pyridine bromide; the alcohol is monohydric alcohol with the carbon atom number of 1-5; the manganese halide is manganese dibromide; the hydrohalic acid is hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, and the pseudohalogen hydride is hydrogen thiocyanate and tetrafluoroboric acid. Further preferably, the alcohol is ethanol or isopropanol.

Further, in the solution 1 in the step (1), the concentration of the N-hexadecyl pyridine bromide is 0.1-2 mmol/mL; in the solution 2 in the step (1), the concentration of the manganese halide is 0.1-4 mmol/mL.

Further, the volume ratio of the solution 1 to the solution 2 in the step (2) is 8:1-1: 2;

further, the temperature of the crystallization treatment in the step (2) is 20-120 ℃, and the time of the crystallization treatment is 24-180 hours.

The invention provides application of a nitrogen-containing amphiphilic organic ion manganese halide luminescent material in preparation of a white light LED.

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

the zero-dimensional nitrogen-containing amphiphilic organic ion manganese halide with the fluorescence property shows a good green or yellow fluorescence effect under the irradiation of ultraviolet light or blue light, is less prone to moisture absorption and deliquescence, has a strong fluorescence effect under the excitation of 460nm, and is an optical material with excellent performance; the luminescent material and the red luminescent material are combined with a blue LED chip to generate white light, the luminous efficiency is not obviously changed when the white light is continuously measured at room temperature for 1200min under the condition of electrifying, and the material has long-term stability and does not obviously absorb moisture or decompose when being used as fluorescent powder as shown in figure 5.

Drawings

FIG. 1 is a comparison graph of fitting XRD and single crystal data of nitrogen-containing amphiphilic organic ionic manganese metal halide luminescent material prepared in example 1;

FIG. 2 is an infrared spectrum of a N-cetylpyridinium manganese metal bromide luminescent material prepared in example 1;

FIG. 3 is a graph of the excitation and emission fluorescence spectra of the N-cetylpyridinium manganese metal bromide luminescent material prepared in example 1;

FIG. 4 is a graph showing the fluorescence lifetime of the N-cetylpyridinium manganese metal bromide luminescent material prepared in example 1;

FIG. 5 is a graph of luminous efficiency as a function of time for a device made of the N-cetylpyridinium manganese metal bromide light-emitting material prepared in example 1;

FIG. 6 is an XRD of the manganese N-cetylpyridinium metal chloride luminescent material prepared in example 2;

FIG. 7 is a fluorescence spectrum and organic ion structure of the N-cetylpyridinium manganese metal chloride luminescent material prepared in example 2;

FIG. 8 is an XRD of the N-hexadecyl manganese pyridine metal iodide luminescent material prepared in example 3;

FIG. 9 is a fluorescence spectrum and an organic ion structural formula of the N-cetylpyridinium manganese metal iodide luminescent material prepared in example 3;

FIG. 10 is an XRD of the N-dodecylmanganese pyridine metal chloride phosphor prepared in example 4;

FIG. 11 is a fluorescence spectrum and an organic ion formula of the N-dodecylmanganese pyridinato metal chloride light-emitting material prepared in example 4;

FIG. 12 is an XRD of 1-methyl-3-hexadecylimidazolium manganese metal bromide luminescent material prepared in example 6;

FIG. 13 is a fluorescence spectrum and an organic ion formula of a 1-methyl-3-hexadecylimidazolomanganesium bromide light-emitting material prepared in example 6;

FIG. 14 is an XRD of 1-methyl-3-tetradecylimidazolium manganese metal bromide luminescent material prepared in example 7;

FIG. 15 is a fluorescence spectrum and organic ionic structure of 1-methyl-3-tetradecyl imidazolium manganese metal bromide luminescent material prepared in example 7;

FIG. 16 is an XRD of 1-methyl-3-tetradecylimidazole manganese metal bromoiodide luminescent material prepared in example 8;

FIG. 17 is a fluorescence spectrum and an organic ion formula of a 1-methyl-3-tetradecyl imidazole manganese metal bromoiodide luminescent material prepared in example 8;

FIG. 18 is an XRD of a hexadecyltrimethylammonium manganese metal bromide luminescent material prepared in example 9;

FIG. 19 is a fluorescence spectrum and an organic ion structural formula of a hexadecyl trimethyl ammonium manganese metal bromide light-emitting material prepared in example 9.

FIG. 20 is an XRD of octyltrimethylammonium manganese metal bromide luminescent material prepared in example 10;

FIG. 21 is a fluorescence spectrum and an organic ion structural formula of the octyltrimethylammonium manganese metal bromide light-emitting material prepared in example 10.

FIG. 22 is an XRD of dodecyltrimethylammonium manganese metal bromide luminescent material prepared in example 12;

fig. 23 is a fluorescence spectrum and an organic ion structural formula of a dodecyltrimethylammonium manganese metal bromide luminescent material prepared in example 12.

Detailed Description

The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.

Example 1

The preparation method of the N-hexadecyl pyridine manganese metal bromide luminescent material comprises the following steps:

(1) 2mmol of N-hexadecyl pyridine bromide is put into a container, and 4ml of ethanol is added to be fully dissolved;

(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;

(3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, filtering the obtained solution by using a needle head type filter, and taking filtrate; the filtrate was placed in a vessel and slowly evaporated in a 30 ℃ oven, after 180 hours crystals (N-cetylpyridinium manganese metal bromide luminescent material) formed at the bottom of the vessel.

And carrying out related detection on the obtained green transparent crystal, wherein the specific data are as follows:

crystal structure: at 150K, Cu Ka radiation monochromatized by a graphite monochromator is used as a light source on a Bruker X-ray single crystal diffractometerDiffraction data were collected over a range of angles (0-90) in a beta-omega scan at room temperature. All data reduction is carried out by using CrysAlisPro software and analysis is carried out by using Olex2 software, coordinates and anisotropic thermal parameters of all non-hydrogen atoms are refined by a full matrix least square method, and all hydrogen atoms are theoretically hydrogenated. The tetrabromo-manganese N-hexadecyl pyridine ion compound luminescent material belongs to a triclinic system, a P-1 space group, and 8N-hexadecyl pyridine cations [ C ] are contained in an asymmetric unit₁₆H₃₃N-C₅H₅N]⁺And 4 tetrabromomanganese [ MnX ]₄]^2-. Structure of crystalSee fig. 1, and crystallographic data, see table 1.

Powder X-ray diffraction: powder X-ray diffraction of tetrabromomanganese N-hexadecylpyridine ionic compound (i.e. nitrogen-containing amphiphilic organic ion manganese halide luminescent material)The spectra were tested at room temperature using a model PANalytical produced by Pasnacaceae, the Netherlands.

The measurement conditions were tube pressure: 40kV, pipe flow: 20mA, Cu k alpha radiation scanning speed of 1 degree/min^-1Step interval: 0.02 °, scan range (2 θ): 5-90 deg. and the scanning mode is continuous scanning, see figure 1. As can be seen from FIG. 1, the XRD peak observed in the experiment is well matched with the XRD pattern with the closure of crystal structure data, which shows that the tetrabromo manganese N-hexadecyl pyridine ionic compound is successfully synthesized and has better crystallinity and purity.

Infrared (fig. 2): v (pyridine ring C-C ═ N): 3061cm^-1，2920cm^-1(ii) a V (methylene C-H)2917cm^-1，2849cm^-1(ii) a ν (aromatic C ═ C): 1471cm^-1；

Fluorescence spectrum analysis: the fluorescence spectrum of the manganese tetrabromide N-hexadecyl pyridine ion compound was measured by using an F-4600 spectrophotometer manufactured by Hitachi corporation. When excited by ultraviolet light of 322nm and blue light of 460nm, the tetrabromo manganese N-hexadecyl pyridine ionic compound has a strong peak at 532nm, and the details are shown in figure 3.

And (3) fluorescence lifetime test: the fluorescence lifetime test of the tetrabromo-manganese N-hexadecyl pyridine ion compound luminescent material was carried out by using FLS-920 produced by Edinburgh corporation. When excited by blue light at 460nm, the fluorescence attenuation signal of the strongest emission peak at 532nm is detected, the curve is compounded with a single exponential attenuation equation, and the fitting life of the curve is 0.183 ms. See figure 4 for details.

And (3) testing the luminous stability: the luminescent material and the red luminescent material are combined with a blue LED chip to generate white light, the white light is continuously measured for 1200min under the condition of electrifying, the luminous efficiency is not obviously changed, and the luminescent material is not obviously absorbed or decomposed, which is shown in the attached figure 5.

TABLE 1 crystallography data for tetrabromomanganic N-hexadecylpyridinium Ionic Compounds

Example 2

The preparation method of the N-hexadecyl pyridine manganese chloride luminescent material comprises the following steps:

(1) 2mmol of N-hexadecyl pyridine chloride is taken out of a container, and 8ml of isopropanol is added to be fully dissolved;

(2) 1mmol of manganese chloride tetrahydrate is put into a container, and 4ml of isopropanol is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, filtering the mixture by using a needle filter, placing the filtrate into a container, slowly evaporating the filtrate in an oven at the temperature of 30 ℃, and generating crystals after 150 hours. The XRD pattern of the N-hexadecyl manganese pyridinium chloride luminescent material prepared in example 2 is shown in fig. 6, which shows that there are many diffraction peaks at low angles, corresponding to the formation of crystal planes with large spacing in the lattice arrangement of organic ions. The fluorescence spectrum of the N-cetylpyridinium manganese chloride luminescent material prepared in example 2 is shown in FIG. 7, and the inset is the structural formula of the N-cetylpyridinium cation. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 530 nm.

Example 3

The preparation method of the N-hexadecyl manganese pyridine metal iodide luminescent material comprises the following steps:

(1) 2mmol of N-hexadecyl pyridine iodide is put into a container, and 4ml of 45 percent hydriodic acid is added to be fully dissolved;

(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 percent hydriodic acid is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 3:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 40 ℃ for evaporation, and generating crystals after 150 hours. The XRD pattern of the N-hexadecyl manganese pyridine iodide luminescent material prepared in example 3 is shown in fig. 8, which shows that there are many diffraction peaks at low angles, and it corresponds to that organic ions form crystal planes with large spacing in lattice arrangement. The fluorescence spectrum of the N-cetylpyridinium manganese metal iodide luminescent material prepared in example 3 is shown in fig. 9, and the inset is the structural formula of the N-cetylpyridinium cation. The material has strong yellow fluorescence broad peak emission under 450nm excitation, and the emission peak position is about 540 nm.

Example 4

The preparation method of the N-dodecyl manganese pyridine metal chloride luminescent material comprises the following steps:

(1) 2mmol of N-dodecyl pyridine chloride is put into a container, and 4ml of hydrochloric acid with the concentration of 37 wt% is added to be fully dissolved;

(2) 1mmol of manganese chloride is put into a container, and 2ml of hydrochloric acid with the concentration of 37 wt% is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 60 hours. The XRD pattern of the N-dodecylmanganese pyridinium chloride luminescent material prepared in example 4 is shown in fig. 10, which shows that there are many diffraction peaks at low angles, corresponding to the formation of crystal planes with large spacing in the lattice arrangement of organic ions. The fluorescence spectrum of the N-dodecylmanganese pyridine metal chloride luminescent material prepared in example 4 is shown in FIG. 11, wherein the inset is the structural formula of the N-dodecylpyridine cation. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 525 nm.

Example 5

The preparation method of the N-dodecyl manganese pyridine metal chlorine iodide luminescent material comprises the following steps:

(1) 1.5mmol of N-dodecyl pyridine chloride and 0.5mmol of N-dodecyl pyridine iodide are put into a container, and 3ml of deionized water is added to be fully dissolved;

(2) 1mmol of manganese iodide monohydrate is put into a container, and 3ml of ethanol is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, slowly evaporating the filtrate in an oven at the temperature of 30 ℃, and generating crystals after 100 hours. The material has strong yellow-green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 532 nm.

Example 6

The preparation method of the 1-methyl-3-hexadecyl imidazole manganese metal bromide luminescent material comprises the following steps:

(1) 2mmol of 1-methyl-3-hexadecyl imidazole bromide is put into a container, and 4ml of hydrobromic acid with the concentration of 40 percent is added to be fully dissolved;

(2) 1mmol of manganese bromide-tetrahydrate is put into a container, and 4ml of hydrobromic acid with the concentration of 40 percent is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.

An XRD pattern of the 1-methyl-3-hexadecylimidazolemanganesium bromide luminescent material prepared in example 6 is shown in fig. 12. The fluorescence spectrum of the 1-methyl-3-hexadecyl imidazole manganese metal bromide luminescent material prepared in example 6 is shown in FIG. 13, wherein the inset is the structural formula of 1-methyl-3-hexadecyl imidazole cation. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 530 nm.

Example 7

The preparation method of the 1-methyl-3-tetradecyl imidazole manganese metal bromide luminescent material comprises the following steps:

(1) placing 2mmol 1-methyl-3-tetradecyl imidazole bromide into a container, and adding 4ml n-propanol for full dissolution;

(2) putting 1mmol of manganese bromide into a container, and adding 2ml of n-propanol to fully dissolve;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 30 ℃ for evaporation, and generating crystals after 90 hours.

The XRD pattern of the 1-methyl-3-tetradecyl imidazole manganese metal bromide luminescent material prepared in the example 7 is shown in figure 14, the low-angle diffraction peak is strong, and the large-distance organic crystal face has strong oriented growth in the growth process. The fluorescence spectrum of the 1-methyl-3-tetradecyl imidazole manganese metal bromide luminescent material prepared in example 7 is shown in FIG. 15, and the inset is the structural formula of 1-methyl-3-tetradecyl imidazole cation. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 525 nm.

Example 8

The preparation method of the 1-methyl-3-tetradecyl imidazole manganese metal chlorobromide luminescent material comprises the following steps:

(1) 2mmol of 1-methyl-3-tetradecyl imidazole bromide is put into a container, and 4ml of methanol is added to be fully dissolved;

(2) putting 1mmol of manganese chloride into a container, and adding 2ml of methanol to fully dissolve;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 30 ℃ for evaporation, and generating crystals after 120 hours.

An XRD pattern of the 1-methyl-3-tetradecyl imidazolium manganese metal chlorobromide luminescent material prepared in example 7 is shown in FIG. 16. The fluorescence spectrum of the 1-methyl-3-tetradecyl imidazolium manganese metal chlorobromide luminescent material prepared in example 7 is shown in FIG. 17, and the inset is the structural diagram of the-methyl-3-tetradecyl imidazolium cation. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 525 nm.

Example 9

The preparation method of the hexadecyl trimethyl ammonium manganese metal bromide luminescent material comprises the following steps:

(1) 1mmol of hexadecyl trimethyl ammonium bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;

(2) putting 1mmol of manganese bromide hexahydrate into a container, and adding 2ml of hydrobromic acid with the concentration of 8mol/L to fully dissolve the manganese bromide hexahydrate;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.

The XRD pattern of the hexadecyl trimethyl ammonium manganese metal bromide luminescent material prepared in the example 8 is shown in figure 18, the diffraction peaks of the luminous material are mainly distributed at low angles and have large intensity, and the fact that organic crystal planes with large intervals have strong oriented growth is also shown in the growth process. The fluorescence spectrum of the cetyltrimethylammonium manganese metal bromide luminescent material prepared in example 8 is shown in fig. 19, and the inset is the structural formula of cetyltrimethylammonium cation. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 530 nm.

Example 10

The preparation method of the octyl trimethyl ammonium manganese metal bromide luminescent material comprises the following steps:

(1) 2mmol of octyl trimethyl ammonium bromide is put into a container and added into 4ml of n-butyl alcohol to be fully dissolved;

(2) putting 1mmol of manganese bromide into a container, and adding 4ml of n-butanol to dissolve the manganese bromide fully;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 120 hours.

The XRD pattern of the octyltrimethylammonium manganese metal bromide luminescent material prepared in example 9 is shown in FIG. 20. The fluorescence spectrum of the octyltrimethylammonium manganese metal bromide luminescent material prepared in example 9 is shown in fig. 21, and the inset is the structural formula of the octyltrimethylammonium cation. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 535 nm.

Example 11

The preparation method of the octyl trimethyl ammonium manganese metal chloride luminescent material comprises the following steps:

(1) 1mmol of octyl trimethyl ammonium chloride is put into a container, and 2ml of deionized water is added to fully dissolve the octyl trimethyl ammonium chloride;

(2) putting 1mmol of manganese chloride tetrahydrate into a container, and adding 2ml of deionized water to fully dissolve the manganese chloride tetrahydrate;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 60 ℃ for evaporation, and generating crystals after 150 hours. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 530 nm.

Example 12

The preparation method of the dodecyl trimethyl ammonium manganese metal bromide luminescent material comprises the following steps:

(1) 1mmol of dodecyl trimethyl ammonium bromide is put into a container, 2ml of ethanol is added to fully dissolve

(2) 1mmol of manganese bromide tetrahydrate is put into a container, and 2ml of ethanol is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 30 ℃ for evaporation, and generating crystals after 90 hours.

The XRD pattern of the dodecyl trimethyl ammonium manganese metal bromide luminescent material prepared in example 11 is shown in FIG. 22. The fluorescence spectrum of the dodecyltrimethylammonium manganese metal bromide luminescent material prepared in example 11 is shown in fig. 23, and the inset is the structural formula of octyltrimethylammonium cation. The material has strong yellow-green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 540 nm.

Example 13

The preparation method of the dodecyl trimethyl ammonium manganese metal iodide luminescent material comprises the following steps:

(1) 2mmol of dodecyl trimethyl ammonium iodide was placed in a vessel, and 4ml of 45 wt% hydriodic acid was added to dissolve it sufficiently;

(2) 1mmol of manganese iodide is put into a container, and 2ml of 45 wt% hydriodic acid is added to fully dissolve the manganese iodide;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 150 hours. The material has strong yellow fluorescence broad peak emission under 450nm excitation, and the emission peak position is about 552 nm.

Example 14

The preparation method of the dodecyl trimethyl ammonium manganese metal bromide iodide luminescent material comprises the following steps:

(1) 1mmol of dodecyl trimethyl ammonium bromide is put into a container, and 2ml of hydriodic acid with the concentration of 45 wt% is added to be fully dissolved;

(2) 1mmol of manganese bromide was charged into a vessel, and 2ml of 45 wt% hydroiodic acid was added to dissolve it sufficiently. (ii) a

(3) And (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 60 ℃ for evaporation, and generating crystals after 90 hours. The material has strong yellow-green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 545 nm.

Example 15

The preparation method of the N-hexadecyl pyridine manganese metal chlorine iodide luminescent material comprises the following steps:

(1) 1mmol of N-hexadecylpyridinium chloride is put into a container, and 4ml of 49 wt% hydriodic acid is added to be fully dissolved;

(2) putting 1mmol of manganese chloride into a container, and adding 2ml of deionized water to fully dissolve the manganese chloride;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 4:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 60 ℃ for evaporation, and generating crystals after 120 hours. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 532 nm.

Example 16

The preparation method of the N-dodecyl manganese pyridine metal fluorine chloride luminescent material comprises the following steps:

(1) 1mmol of N-dodecyl pyridine chloride is put into a container, and 1ml of hydrofluoric acid with the concentration of 49 wt% is added to be fully dissolved;

(2) putting 1mmol of manganese fluoride into a container, and adding 2ml of ethanol to fully dissolve;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 40 ℃ for evaporation, and generating crystals after 90 hours. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 520 nm.

Example 17

The preparation method of the N-dodecyl manganese pyridine metal bromide luminescent material comprises the following steps:

(1) 1mmol of N-dodecyl pyridine bromide is put into a container, and 1ml of deionized water is added to be fully dissolved;

(2) 1mmol of manganese bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 150 hours. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 525 nm.

Example 18

The preparation method of the 1-methyl-3-decyl imidazole manganese metal bromide luminescent material comprises the following steps:

(1) putting 1mmol of 1-methyl-3-decyl imidazole bromide into a container, and adding 2ml of n-butanol to dissolve completely;

(2) putting 1mmol of manganese bromide into a container, and adding 2ml of isopropanol to fully dissolve;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 30 ℃ for evaporation, and generating crystals after 1200 hours. The material has strong green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 520 nm.

Example 19

The preparation method of the 1-methyl-3-tetradecyl imidazole manganese metal fluorobromide luminescent material comprises the following steps:

(1) putting 1mmol 1-methyl-3-tetradecyl imidazole chloride into a container, and adding 4ml 49 wt% hydrofluoric acid for fully dissolving;

(2) 1mmol of manganese fluoride is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 4:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 60 ℃ for evaporation, and generating crystals after 90 hours. The material has strong yellow-green fluorescence broad peak emission under the excitation of 450nm, and the emission peak position is about 530 nm.

Example 20

The preparation method of the 1-methyl-3-tetradecyl imidazole manganese metal iodide luminescent material comprises the following steps:

(1) 1mmol 1-methyl-3-tetradecyl imidazole iodide is put into a container, and 1ml 45 wt% hydriodic acid is added to fully dissolve the mixture;

(2) putting 1mmol of manganese iodide into a container, and adding 2ml of deionized water to fully dissolve;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at the temperature of 60 ℃ for evaporation, and generating crystals after 90 hours.

Example 21

The preparation method of the hexadecyl trimethyl ammonium manganese metal fluorobromide luminescent material comprises the following steps:

(1) 2mmol of hexadecyl trimethyl ammonium bromide is put into a container, and 2ml of hydrobromic acid with the concentration of 8mol/L is added to be fully dissolved;

(2) putting 1mmol of manganese fluoride into a container, and adding 2ml of 49 wt% hydrofluoric acid for fully dissolving;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 1:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle head type filter, putting the filtrate into an oven at the temperature of 30 ℃ for evaporation, and generating crystals after 180 hours.

Example 22

The preparation method of the decyl trimethyl ammonium manganese metal bromide luminescent material comprises the following steps:

(1) 1mmol of decyltrimethylammonium bromide is put into a container, and 6ml of n-pentanol is added to be fully dissolved;

(2) putting 1mmol of manganese bromide into a container, and adding 2ml of isopropanol to fully dissolve;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 6:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 60 ℃ for evaporation, and generating crystals after 120 hours.

Example 23

The preparation method of the dodecyl trimethyl ammonium manganese metal chloride luminescent material comprises the following steps:

(1) 1mmol of dodecyl trimethyl ammonium chloride is put into a container, and 2ml of deionized water is added to fully dissolve the dodecyl trimethyl ammonium chloride;

(2) putting 1mmol of manganese chloride tetrahydrate into a container, and adding 2ml of deionized water to fully dissolve the manganese chloride tetrahydrate;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 2:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 60 ℃ for evaporation, and generating crystals after 150 hours.

Example 24

The preparation method of the dodecyl trimethyl ammonium manganese metal oxyfluoride luminescent material comprises the following steps:

(1) 1mmol of dodecyl trimethyl ammonium iodide is put into a container, and 4ml of deionized water is added to be fully dissolved;

(2) putting 1mmol of manganese fluoride tetrahydrate into a container, and adding 0.5ml of 49% wt hydrofluoric acid for fully dissolving;

(3) and (3) taking the solution in the step (1) and the solution in the step (2) in the volume ratio of 4:1, uniformly mixing the solution and the solution, putting the obtained solution into a container, filtering the solution by using a needle filter, putting the filtrate into an oven at 50 ℃ for evaporation, and generating crystals after 150 hours.

The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.