阅读说明：本技术 一种组装调控荧光增强聚集诱导发光材料、微纳米球及制备方法与应用 (Assembly and regulation fluorescence-enhanced aggregation-induced emission material, micro-nanosphere and preparation method and application ) 是由 苗新蕊 蔡正楷 李金星 于 2020-12-28 设计创作，主要内容包括：本发明公开了一种组装调控荧光增强聚集诱导发光材料、微纳米球及制备方法与应用。所述发光材料分子式为式I。本发明的材料结构稳定,具有聚集诱导发光及力致变色性能,发光性能良好,粉末状态荧光量子产率可达45.5％,研磨后粉末荧光量子产率可达65.6％；采用蒸发溶剂和不良溶剂中聚集法,可将发光材料通过自组装制备成不同尺寸的微纳米球,纳米尺度的球状组装体荧光量子产率可达85.3％；本发明的聚集诱导发光材料合成制备方法操作简单,反应条件温和,产率高；本发明的聚集诱导发光材料及组装微纳米球不溶于水和大多数有机溶剂,荧光效率高,并具有力致变色性能,可用于防伪、实时监测压力变化,生物荧光探针以及生物成像等领域。(The invention discloses an assembly and regulation fluorescence-enhanced aggregation-induced emission material, a micro-nanosphere, a preparation method and application. The molecular formula of the luminescent material is shown as formula I. The material has a stable structure, has aggregation-induced luminescence and force-induced discoloration properties, and has good luminescence performance, the fluorescence quantum yield of the powder state can reach 45.5%, and the fluorescence quantum yield of the powder after grinding can reach 65.6%; by adopting an evaporation solvent and poor solvent in-situ aggregation method, the luminescent material can be prepared into micro-nanospheres with different sizes through self-assembly, and the fluorescence quantum yield of the spherical assembly with the nanoscale can reach 85.3 percent; the synthesis and preparation method of the aggregation-induced emission material is simple to operate and has a reaction stripThe method is mild and high in yield; the aggregation-induced emission material and the assembled micro-nano sphere are insoluble in water and most organic solvents, have high fluorescence efficiency and force-induced color change performance, and can be used in the fields of anti-counterfeiting, real-time monitoring of pressure change, biological fluorescent probes, biological imaging and the like.)

1. The assembly-regulated fluorescence-enhanced aggregation-induced emission material is characterized in that the assembly-regulated fluorescence-enhanced aggregation-induced emission material is a 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative, and the structural formula (I) of the assembly-regulated fluorescence-enhanced aggregation-induced emission material is as follows:

2. the method for preparing an assembly-controlled fluorescence-enhanced aggregation-induced emission material as claimed in claim 1, wherein the synthetic route is,

the method comprises the following steps:

(1) bis (4-bromophenyl) methanone a and bis-glutaryl diboron are used as raw materials, and [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl₂) Under the catalytic condition of (2), obtaining an intermediate product bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b;

(2) mixing intermediate bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-ylphenyl) methanone b and iodobenzene derivative in tetrakis (triphenylphosphine) palladium (Pd [ P (Ph))₃]₄) Under the catalytic condition of (2) to obtain an intermediate product di ([1,1' -biphenyl)]-4-yl) methanone derivative c;

(3) and (3) reacting the intermediate product di ([1,1 '-biphenyl ] -4-yl) methanone derivative c with titanium tetrachloride and zinc powder to obtain the 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative (I).

3. The method for preparing an assembly-regulated fluorescence-enhanced aggregation-induced emission material according to claim 2, wherein in the step (1), the intermediate bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b is prepared by the following steps: 5 parts of bis (4-bromophenyl) methanone a, 5-15 parts of potassium acetate, 12-14 parts of bis (glutaryl diboron) and 0.1-0.3 part of Pd (dppf) Cl in terms of molar parts under the protection of nitrogen₂Dissolving in 300 portions of 100, 4-dioxane, stirring at 70-90 ℃ for 16-24 hours, separating and purifying to obtain the bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b.

4. The method for preparing an assembly-regulated fluorescence-enhanced aggregation-induced emission material according to claim 3, wherein the purification step adopts column chromatography for separation and purification.

5. The method for preparing an assembly-regulated fluorescence-enhanced aggregation-induced emission material according to any one of claims 2 to 4,

in the step (2), the intermediate product bis ([1,1 '-biphenyl ] -4-yl) methanone derivative c is specifically prepared by dissolving 1 to 3 parts by mole of bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b, 2.2 to 2.4 parts by mole of an iodobenzene derivative and 0.03 to 0.09 part by mole of tetrakis (triphenylphosphine) palladium obtained in the step (I) in 20 to 60 parts by mole of toluene, reacting at 85 to 100 ℃ for 18 to 26 hours, and then separating and purifying to obtain bis ([1,1' -biphenyl ] -4-yl) methanone derivative c;

in the step (3), the 1,1,2, 2-tetra- ([1,1' -biphenyl)]The specific preparation steps of the (4-yl) ethylene derivative (I) comprise the following steps of obtaining 1-3 parts of bis ([1,1' -biphenyl) by mole parts under the protection of nitrogen]Adding the (4-yl) ketone derivative c and 8-24 parts of zinc powder into 50-150 parts of dry tetrahydrofuran solvent, and dropwise adding 4-12 parts of TiCl at-70 to-80 DEG C₄Reacting for 30-50 minutes, taking out and naturally recovering to room temperature, then reacting for 15-24 hours at 85-95 ℃, and then separating and purifying to obtain 1,1,2, 2-tetra- ([1,1' -biphenyl)]-4-yl) ethylene derivatives.

6. The method for preparing an assembly-regulated fluorescence-enhanced aggregation-induced emission material according to claim 5, wherein the purification step in the step (2) is performed by separation and purification through column chromatography; and (3) the purification step adopts column chromatography for separation and purification or recrystallization by tetrahydrofuran.

7. A micro-nanosphere for assembling a fluorescence-enhanced aggregation-induced emission material, wherein the micro-nanosphere is formed by self-assembling the fluorescence-enhanced aggregation-induced emission material according to claim 1 through intermolecular halogen bonds.

8. The method for preparing the micro-nanospheres for assembling and controlling the fluorescence-enhanced aggregation-induced emission material as claimed in claim 7, comprising the steps of:

(1) preparing the assembled and regulated fluorescence-enhanced aggregation-induced emission material microspheres: the assembly-regulated fluorescence-enhanced aggregation-induced emission material according to claim 1, which is dissolved in tetrahydrofuran and is provided at a concentration of 10^-4～10^-5mol.L^-1Taking 1 part of the solution, adding 5-9 parts of distilled water while shaking, centrifuging to obtain a precipitate, cleaning the precipitate, and drying to obtain the micron-sized aggregation-induced emission fluorescent microspheres;

(2) preparing a nano ball of the assembly, regulation and control fluorescence-enhanced aggregation-induced luminescent material: the assembly-regulated fluorescence-enhanced aggregation-induced emission material according to claim 1, which is dissolved in tetrahydrofuran and is provided at a concentration of 10^-4～10^-5mol.L^-1The solution is dripped into ice blocks by a syringe drop by drop, the ice blocks are melted after the solution is completely permeated into the ice blocks, and the nano-scale aggregation-induced emission assembly ball is prepared after freezing, freezing and drying.

9. The use of the assembly-regulated fluorescence-enhanced aggregation-induced emission material of claim 1, wherein the assembly-regulated fluorescence-enhanced aggregation-induced emission material has a mechanochromic property, and is used in the fields of anti-counterfeiting, real-time monitoring of pressure change, nondestructive detection of pressure, structural damage detection, display, and illumination.

10. The use of the assembled fluorescent-enhanced aggregation-induced emission material assembly nanospheres of claim 7, wherein the assembled fluorescent-enhanced aggregation-induced emission nanospheres have applications in the fields of chemical sensing, optoelectronics, bioluminescent probes, and biological imaging.

Technical Field

The invention belongs to the technical field of organic photoelectricity, and particularly relates to an assembly and regulation fluorescence-enhanced aggregation-induced emission material, a micro-nanosphere, a preparation method and an application.

Background

Fluorescent materials have shown a very important position in the fields of organic light emitting diodes, organic solid lasers, biological living cell markers, anti-counterfeiting, fluorescent sensors and the like. However, most of the fluorescent materials have a problem: the luminescent property of the fluorescent material in a solution is good, but the fluorescence efficiency is sharply reduced in an aggregation state, namely fluorescence quenching occurs. In many practical applications, a solid or thin film phosphor is required, which limits the practical applications of such phosphors. The aggregation-induced emission material opens up a new approach for the application of fluorescent substances.

It is known that the introduction of halogen heavy atoms into molecules can cause the fluorescence quenching of the molecules, but at the same time, the heavy atom effect can promote the intersystem crossing of dipoles from a ground state to a triplet excited state, thereby enhancing phosphorescence. At present, the work for preparing room temperature phosphorescent materials based on heavy atom effect is more, and the introduction of halogen heavy atoms into aggregation-induced emission elements to enhance the fluorescence property of molecules is rarely reported. To date, Wang and Chen et al report the introduction of bromine into enaminone derivatives and squaraine dyes, respectively, and found that the crystal or powder fluorescence quantum yield of the two materials is improved due to the heavy atom effect, but not more than 50% (adv. optical mater.2019,7,1801719; chem. eur.j.2019,25,469), the application of such materials is directly limited by the low fluorescence quantum yield. Therefore, it is urgently needed to develop a new material and a preparation method thereof, wherein the heavy atom effect can significantly improve the aggregation-induced emission efficiency, so that the high-sensitivity online sensing detection is easier.

Disclosure of Invention

The invention aims to provide an assembly and regulation fluorescence-enhanced aggregation-induced emission material, a micro-nanosphere and a preparation method. The material of the invention has stable structure, good luminescence performance in crystalline state/microcrystalline state and assembly, and high fluorescence quantum efficiency. The luminescent material of the invention has simple synthesis process, mild reaction condition, high yield and easy cultivation to obtain single crystal. In addition, the materials of the present invention have a force to enhance the luminescent and color change properties.

It is another object of the present invention to provide the above-mentioned use with assembly-induced luminescent materials. The luminescent material with the assembly induced luminescence property is applied to the fields of chemical sensing, biological fluorescent probes, photoelectricity and biological imaging. The luminescent material with the aggregation-induced emission property can also be applied to the fields of nondestructive pressure detection, real-time pressure change detection, structural damage detection, display, illumination, anti-counterfeiting and the like. The 'assembly induced luminescence' material has the advantages of low preparation cost, strong light stability, good long-acting tracking effect and the like.

The purpose of the invention is realized by the following scheme:

an assembly-regulated fluorescence-enhanced aggregation-induced emission material, which is a 1,1,2, 2-tetrakis- ([1,1' -biphenyl ] -4-yl) ethylene derivative having a molecular formula of formula I:

preferably, the assembly-controlled fluorescence-enhanced aggregation-induced emission material is in a crystalline state or a microcrystalline state, and the assembly body is a micro-nano sphere.

Preferably, the assembly-controlled fluorescence-enhanced aggregation-induced emission material has a photoluminescence range of 400-650nm, and the assembly microsphere has a photoluminescence range of 400-720 nm.

Preferably, the compound of formula I has a crystal space group P

The preparation method of the assembly regulation fluorescence-enhanced aggregation-induced emission material comprises the following steps:

the compound of the formula I is prepared by adopting the following synthetic route:

the method comprises the following steps:

(1) bis (4-bromophenyl) methanone a and bis-glutaryl diboron are used as raw materials, and [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (Pd (dppf) Cl₂) Under the catalytic condition of (2), obtaining an intermediate product bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b;

(2) mixing intermediate bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-ylphenyl) methanone b and iodobenzene derivative in tetrakis (triphenylphosphine) palladium (Pd [ P (Ph))₃]₄) Under the catalytic condition of (2) to obtain an intermediate product di ([1,1' -biphenyl)]-4-yl) methanone derivative c;

(3) and (3) reacting the intermediate product di ([1,1 '-biphenyl ] -4-yl) methanone derivative c with titanium tetrachloride and zinc powder to obtain the 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative (I).

Preferably, the preparation of the intermediate product bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b in the step (1): 5 parts of bis (4-bromophenyl) methanone a, 5-15 parts of potassium acetate, 12-14 parts of bis (glutaryl diboron) and 0.1-0.3 part of dichloro [1,1' -bis (diphenylphosphino) ferrocene in terms of molar parts under the protection of nitrogen]Palladium (Pd (dppf) Cl₂) Dissolving in 300 portions of 100, 4-dioxane, stirring at 70-90 ℃ for 16-24 hours, separating and purifying to obtain the bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b. Wherein Pd (dppf) Cl₂The name of Chinese is [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride.

Further preferably, the purification step adopts column chromatography for separation and purification.

Preferably, the intermediate bis ([1,1 '-biphenyl ] -4-yl) methanone derivative c in the step (2) is prepared by dissolving 1 to 3 parts by mole of bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone b, 2.2 to 2.4 parts by mole of the iodobenzene derivative obtained in the step (I) and 0.03 to 0.09 part by mole of tetrakis (triphenylphosphine) palladium in 20 to 60 parts by mole of toluene, reacting at 85 to 100 ℃ for 18 to 26 hours, and then separating and purifying to obtain the bis ([1,1' -biphenyl ] -4-yl) methanone derivative c.

Further preferably, the purification step adopts column chromatography for separation and purification.

Preferably, the preparation of the 1,1,2, 2-tetrakis- ([1,1' -biphenyl ] -4-yl) ethylene derivative (I) of step (3): based on the parts by mole, the weight of the catalyst is calculated, under the protection of nitrogen, 1 to 3 parts of di ([1,1' -biphenyl ] -4-yl) ketone derivative c obtained in the step II and 8 to 24 parts of zinc powder are put into 50 to 150 parts of dry tetrahydrofuran solvent, dropwise adding 4-12 parts of titanium tetrachloride at-70 to-80 ℃ for reacting for 30-50 minutes, taking out and naturally returning to room temperature, then reacting for 15-24 hours at 85-95 ℃, and then separating and purifying to obtain the 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative.

Further preferably, the purification step in step (3) is separation and purification by column chromatography or recrystallization with tetrahydrofuran.

The micro-nano sphere for assembling and regulating the fluorescence-enhanced aggregation-induced emission material is formed by self-assembling the fluorescence-enhanced aggregation-induced emission material through intermolecular halogen bonds.

The preparation method of the micro-nanosphere for assembling and regulating the fluorescence-enhanced aggregation-induced luminescent material comprises the following steps:

(1) preparing the assembled and regulated fluorescence-enhanced aggregation-induced emission material microspheres: dissolving the assembly regulation fluorescence-enhanced aggregation-induced emission material in tetrahydrofuran to obtain a solution with a concentration of 10^-4～10^-5mol.L^-1Taking 1 part of the solution, adding 5-9 parts of distilled water while shaking, centrifuging to obtain a precipitate, cleaning the precipitate, and drying to obtain the micron-sized aggregation-induced emission fluorescent microspheres;

(2) assembling regulation and controlPreparing a fluorescence-enhanced aggregation-induced luminescent material nanosphere: dissolving the assembly regulation fluorescence-enhanced aggregation-induced emission material in tetrahydrofuran to obtain a solution with a concentration of 10^-4～10^-5mol.L^-1The solution is dripped into the ice blocks by a needle tube drop by drop, the ice blocks are melted after the solution is completely permeated into the ice crystal gaps of the ice blocks, and the aggregation-induced luminescence nanospheres are prepared after freeze drying.

The assembly regulation and control fluorescence-enhanced aggregation-induced emission material has the photochromic property and is applied to the fields of anti-counterfeiting, real-time monitoring of pressure change, nondestructive detection of pressure, structural damage detection, display and illumination.

The application of the micro-nanosphere assembled and regulated with the fluorescence-enhanced aggregation-induced emission material is the application of the micro-nanosphere with the aggregation-induced emission property in the fields of chemical sensing, photoelectricity, biological fluorescent probes and biological imaging.

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

(1) the meta-bromine substituted 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative prepared by the invention has simple production process, and can be produced under the nitrogen atmosphere and normal pressure only by a simple heating device; the requirement on experimental equipment is low, and only a common heating device and a reflux device are needed, so that the mass production is facilitated;

(2) the meta-bromine substituted 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative prepared by the invention is synthesized by Suzuki reaction and Memmerle reaction, and has high yield; the light color adjustment is realized by connecting different electron-donating groups and electron-withdrawing groups;

(3) the meta-bromine substituted 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative luminescent material prepared by the invention has aggregation-induced luminescence property, the crystalline fluorescence quantum efficiency can reach 45.5%, and the fluorescence quantum efficiency of the self-assembled microsphere constructed by intermolecular halogen bond induction can reach at least 85.3%;

(4) the meta-bromine substituted 1,1,2, 2-tetra- ([1,1' -biphenyl ] -4-yl) ethylene derivative luminescent material prepared by the invention is a mechanoluminescence aggregation-induced luminescent material, and the mechanoluminescence emission peak is positioned at 520 nm; the powder and crystal respond to mechanical forces such as friction, pressure, impact force, etc.

Drawings

FIG. 1 shows the concentration of 2.0X 10 in toluene, tetrahydrofuran and acetonitrile solutions of the fluorescence-enhanced aggregation-induced emission material prepared in example 4^-4Absorption spectrum at mol/L;

FIG. 2a is a photograph of aggregation-induced emission of the fluorescence-enhanced aggregation-induced emission material of example 4 in a tetrahydrofuran/water mixture (under a 365nm UV lamp, the suspension emits green light);

FIG. 2b is the emission spectrum of the fluorescence-enhanced aggregation-induced emission material of example 4 in the mixed solution of tetrahydrofuran/water at different ratios;

FIG. 3a is a SEM image of assembling fluorescent enhanced aggregation-inducing luminescent material-assembled microspheres of example 4;

FIG. 3b is a graph of the luminescence spectrum of the microsphere thin film material of example 4;

FIG. 4a is a force-induced color change and reversible recovery picture of the assembled regulated fluorescence-enhanced aggregation-induced emission material of example 7 (under a 365nm ultraviolet lamp, the original powder emitting blue light emits green light after being ground, and the blue light is recovered after annealing or solvent fumigation);

FIG. 4b is the mechanoluminescence spectrum of the original powder and the milled powder of the fluorescence-enhanced aggregation-induced emission material of example 7;

fig. 5a is a picture of a paper money for practicing the assembly, regulation and control of fluorescence-enhanced aggregation-induced emission material of example 8 under natural light (a 100 yuan character cannot be displayed);

fig. 5b is a light-emitting anti-counterfeit picture (100-element-like green light emission) of the kungfu money made of the fluorescence-enhanced aggregation-induced emission material regulated and controlled by spraying, assembly and control in example 8 under an ultraviolet lamp.

Detailed Description

The present invention is further illustrated below with reference to specific examples, which are intended to be illustrative only and not to limit the scope of the invention. The materials referred to in the following examples are commercially available.

Example 1

Synthetic route for intermediate compound b:

synthesis of intermediate Compound b

In a three-necked flask equipped with a magnetic stirrer were added 2 parts of bis (4-bromophenyl) methanone a, 5 parts of potassium acetate, 2.5 parts of diboron diglutaryl and 0.1 part of Pd (dppf) Cl₂Dissolving in 100 parts of 1, 4-dioxane, stirring at 80 ℃ for 16-24 hours, extracting with dichloromethane, washing with saturated saline water for 4 times, drying with anhydrous magnesium sulfate, filtering, distilling to remove the solvent, and purifying the product by column chromatography with petroleum ether/ethyl acetate (10:1) as an eluent to obtain bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone. The yield was 86.5%. Nuclear magnetic data¹H NMR(500MHz,CDCl₃): δ 7.91(d, J ═ 8.2Hz,4H),7.76(d, J ═ 8.3Hz,4H),1.37(s,24H) indicated that the resulting compound was the target product.

Example 2

Synthetic route for intermediate compound c:

synthesis of intermediate Compound c

Adding 1 part of bis (4- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) methanone (b), 2.2 parts of m-bromoiodobenzene and 0.03 part of tetrakis (triphenylphosphine) palladium into a three-neck flask with a magnetic stirrer, dissolving in 60 parts of toluene, reacting at 85-100 ℃ for 18-26 hours, extracting with dichloromethane, washing with saturated saline solution for 4 times, drying with anhydrous magnesium sulfate, filtering, distilling to remove the solvent, and purifying the product by using petroleum ether/ethyl acetate (8:1) as eluent column chromatography to obtain bis (3 '-bromo- [1,1' -biphenyl)]-4-yl) methanone. The yield was 87.2%. Nuclear magnetic data¹H NMR(400Hz,CDCl₃) δ 7.95 to 7.89(m,4H),7.80(t, J ═ 1.9Hz,2H),7.72 to 7.67(m,4H),7.56(dddd, J ═ 14.9,8.0,1.9,1.0Hz,4H),7.36(t, J ═ 7.8Hz,2H) indicated that the resulting compound was the target product.

Example 3

Synthetic route to the target compound I:

synthesis of target Compound I

In a three-necked flask equipped with a magnetic stirrer, bis (3 '-bromo- [1,1' -biphenyl) obtained in example 2 was placed]3 parts of-4-yl) ketone and 24 parts of zinc powder are put into 150 parts of dry tetrahydrofuran solvent, 12 parts of titanium tetrachloride is added dropwise at the temperature of-78 ℃ for reaction for 30 minutes, the mixture is taken out and naturally returned to the room temperature, after 30 minutes, the mixture is reacted for 15 to 24 hours at the temperature of 85 to 95 ℃, then the solvent is removed, and the 1,1,2, 2-tetra (3 '-bromo [1,1' -biphenyl ] is obtained by column separation and purification]-4-yl) ethylene. Nuclear magnetic data¹H NMR(500Hz,CDCl₃): δ 7.71(t, J ═ 1.8Hz,4H),7.49(ddd, J ═ 7.8,1.7,1.0Hz,4H),7.43(ddd, J ═ 7.9,2.0,1.0Hz,4H),7.40 to 7.33(m,8H),7.26(s,4H),7.17(d, J ═ 8.0Hz,8H) indicated that the obtained compound was the target product.

Example 4

Preparing self-assembled microspheres:

the target molecule prepared in example 3 was dissolved in a solution of toluene, tetrahydrofuran and acetonitrile to obtain a solution of aggregation-induced emission material, the concentration of which was 2.0X 10^-4mol/L. The absorption spectrum of the solution is shown in FIG. 1, and the increase in the polarity of the solvent results in a blue shift of the maximum absorption peak of the solution.

And (2) respectively dripping 9-1 part of target molecules dissolved in tetrahydrofuran solution into 1-9 parts of distilled water, and oscillating while adding, so that the aggregation-induced emission performance of the target molecules is gradually enhanced, as shown in figure 2. Fig. 2a is a picture of aggregation-induced emission of the aggregation-induced emission material in a tetrahydrofuran/water mixed solution, wherein target molecules emit green light after aggregation in mixed solutions with different ratios. FIG. 2b shows the luminescence spectrum with a maximum emission peak wavelength of 520 nm.

When the volume ratio of the tetrahydrofuran to the water is 2:3, the fluorescence intensity of the aggregation-induced luminescent material is maximum, so that the microspheres are prepared according to the ratio. Dripping 2 parts of the solution into 3 parts of distilled water while shaking; then centrifuging to take the precipitate, cleaning the precipitate, and drying to obtain the micron-sized aggregation-induced emission fluorescent microspheres. The SEM topography of the microspheres is shown in FIG. 3a, and the diameters of the self-assembled spheres are 0.4-2.0 μm.

The target molecule dissolved in the tetrahydrofuran solution is directly dropped on the glass substrate to prepare the green light-emitting film, the fluorescence spectrum of which is shown in figure 3b, and the wavelength of the maximum emission peak is 504 nm.

Example 5

The target molecule prepared in example 3 was dissolved in tetrahydrofuran to obtain a tetrahydrofuran solution of an aggregation-induced emission material, and the concentration of the solution was set to 1.0X 10^-5mol/L. The solution is directly dripped on paper materials (such as filter paper) to obtain the nano-scale microspheres, and the yield of fluorescence quantum is up to more than 80%.

Example 6

The target molecule prepared in example 3 was dissolved in tetrahydrofuran to obtain a tetrahydrofuran solution of an aggregation-induced emission material, and the concentration of the tetrahydrofuran solution was set to 6.0 × 10^-5mol/L. The solution is directly injected into ice blocks by a syringe, and the solution is gathered in interstitial pores of the ice crystals to form nanospheres. And melting the ice, and freeze-drying to obtain the nanoscale aggregation-induced emission fluorescent sphere.

Example 7

The crystallites of the target molecules prepared in example 3 were tested for their mechanoluminescence properties. The white aggregation-induced emission material microcrystal emits blue light under an ultraviolet lamp; the powder turns yellow after grinding, and emits green light under an ultraviolet lamp; the powder was returned to the original state by heating and fumigating with tetrahydrofuran solvent as shown in fig. 4 a. FIG. 4b is a fluorescence spectrum of the original powder of the aggregation-induced emission material after grinding.

Example 8

The target molecule prepared in example 3 was dissolved in tetrahydrofuran to obtain tetrahydrofuran as an aggregation-induced emission materialSolution with a concentration of 2.0X 10^-4mol/L, the solution is colorless. The marking template is placed on the paper material, the solution is sprayed on the template by adopting a spraying mode, no mark is left on the paper material after drying, but strong green light is emitted under the irradiation of an ultraviolet lamp, as shown in figures 5a and 5 b. Fig. 5a is a light-emitting picture of the light-gathering and inducing luminescent material on the paper money for doing exercises under natural light, and the surface of the paper money for doing exercises has no mark. Fig. 5b is a luminescent anti-counterfeiting picture of the aggregation-induced luminescent material on the kungfu money under the ultraviolet lamp, and a 100-element character formed by spraying the solution emits strong green light.

The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Those skilled in the art should also realize that such changes, modifications, substitutions, combinations and simplifications are equivalent substitutions and are intended to be included within the scope of the present disclosure without departing from the spirit and scope of the disclosure.