CN113816966B - Guest material of phosphorescent material, phosphorescent material and method for regulating luminescent property of phosphorescent material - Google Patents

Abstract

The invention relates to the technical field of organic optoelectronic materials, in particular to a guest material of a phosphorescent material, a phosphorescent material and a method for adjusting the luminescence performance of the phosphorescent material. The guest material of phosphorescent material, the structural formula is as follows:

R ₁ is selected from H or phenyl. A phosphorescent material includes at least one of the guest materials and a host material; the host material includes diphenyl sulfoxide and/or diphenyl sulfone. Phosphorescent materials also include water and/or protonic acids. The invention provides a new guest material of phosphorescent material, which can be doped with diphenyl sulfoxide or diphenyl sulfoxide host material to obtain phosphorescent material; meanwhile, a third component is introduced on this basis, which can form hydrogen with host molecules bond, which can effectively solidify the matrix network and further suppress the non-radiative transition of guest excitons, so that the phosphorescence quantum yield and phosphorescence lifetime are significantly improved.

Description

Guest material of phosphorescent material, phosphorescent material and method for adjusting luminescent properties of phosphorescent material method

technical field

The invention relates to the technical field of organic optoelectronic materials, in particular to a guest material of a phosphorescent material, a phosphorescent material and a method for adjusting the luminescence performance of the phosphorescent material.

Background technique

Compared with fluorescence, phosphorescence has a larger Stokes shift, which can avoid the interference of excitation light; at the same time, phosphorescence has a longer lifetime, so phosphorescence materials are widely used in anti-counterfeiting, data encryption, biological imaging and chemical sensing.

Host-guest doping strategies in phosphorescent materials, which can combine otherwise non-/weakly luminescent organics into materials with room-temperature phosphorescence properties, have attracted extensive attention. However, the phosphorescence properties and functions of most doped materials still need to be further improved.

In view of this, the present invention is proposed.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a guest material of the phosphorescent material, which can improve the performance of the phosphorescent material by doping.

The second object of the present invention is to provide a method for preparing a guest material of a phosphorescent material.

A third object of the present invention is to provide phosphorescent materials with high quantum yield and longer phosphorescent lifetime.

A fourth object of the present invention is to provide a method for adjusting the luminescence properties of phosphorescent materials.

In order to realize the above-mentioned purpose of the present invention, the following technical solutions are specially adopted:

The guest material of phosphorescent material, the structural formula is as follows:

R₁选自H或苯基。

R ₁ is selected from H or phenyl.

In a specific embodiment of the present invention, the structural formula of the guest material is

The present invention also provides a method for preparing a guest material of any of the above-mentioned phosphorescent materials, comprising the following steps:

When R ₁ is H, compound A ₁ reacts with 2-bromoacetophenone in an alcohol solvent under the catalysis of an inorganic base; then the reaction solution is refluxed under the action of ammonium acetate and acetic acid, and the post-treatment obtains the object material;

When R ₁ is a phenyl group, compound A ₂ reacts with 2-bromoacetophenone in an alcohol solvent under the catalysis of an inorganic base; then the reaction solution is refluxed under the action of ammonium acetate and acetic acid to obtain intermediate B ; Carry out Suzuki reaction with described intermediate B and phenylboronic acid, and aftertreatment obtains described guest material;

所述化合物A₂的结构式为：

所述中间体B的结构式为：

Wherein, the structural formula of the compound A ₁ is:

The structural formula of the compound A ₂ is:

The structural formula of the intermediate B is:

In a specific embodiment of the present invention, the preparation method of the compound A ₁ comprises: adding an aqueous sodium hydroxide solution to a methanol solution of acetophenone and salicylaldehyde at 0-5° C., and then reacting at room temperature, Work-up gives compound A ₁ .

In a specific embodiment of the present invention, the preparation method of the compound A ₂ comprises: adding an aqueous sodium hydroxide solution to a methanol solution of acetophenone and bromosalicylaldehyde at 0-5° C., and then at room temperature Reaction and post-treatment to obtain compound A ₂ . Wherein, the structural formula of bromosalicylaldehyde is

In a specific embodiment of the present invention, the Suzuki reaction includes: the intermediate B reacts with phenylboronic acid in an organic solvent and a protective atmosphere under the action of an inorganic base and a palladium catalyst, and the guest material is obtained by post-processing .

The present invention also provides a phosphorescent material, comprising at least one of the above-mentioned guest materials and a host material; the host material includes diphenyl sulfoxide and/or diphenyl sulfone.

In a specific embodiment of the present invention, the molar ratio of the guest material to the host material is 1:(500-1500), preferably 1:(800-1200).

In a specific embodiment of the present invention, the phosphorescence quantum yield of the two-component doped phosphorescent material is about 4.3%, and the phosphorescence lifetime is about 147ms.

In a specific embodiment of the present invention, the phosphorescent material further comprises water and/or protonic acid.

中的任一种或多种。In specific embodiments of the present invention, the protic acid includes

any one or more of.

In a specific embodiment of the present invention, when the phosphorescent material includes water, the molar ratio of the guest material, the host material and the water is 1:(500-1500):(100-500); when When the phosphorescent material includes a protonic acid, the molar ratio of the guest material, the host material and the protonic acid is 1:(500-1500):(20-80).

In a specific embodiment of the present invention, the phosphorescence quantum yield of the three-component doped phosphorescent material is 18.8%-28.5%, and the phosphorescence lifetime of the phosphorescent material is 235-308 ms.

中的任一种或多种时，所述磷光材料具有碱刺激响应功能。进一步的，所述碱为乙二胺。In a specific embodiment of the present invention, when the protonic acid is

In the case of any one or more of the above, the phosphorescent material has a function of responding to alkali stimulation. Further, the base is ethylenediamine.

The phosphorescent property of the phosphorescent material decreases under the stimulation of alkali; after heating, the phosphorescent property partially recovers.

The present invention also provides a preparation method of the above-mentioned phosphorescent material, comprising the following steps:

The guest material and the host material are mixed in proportion, heated and melted, and then cooled.

The present invention also provides another method for preparing the above phosphorescent material. The water and/or protonic acid, the guest material and the host material are mixed in proportion, heated and melted, and then cooled.

The present invention also provides a method for adjusting the luminescence properties of the phosphorescent material, comprising the following steps:

Water and/or protonic acid are introduced into the guest material and the host material.

By adding the third component of water and/or protonic acid into the doping system of the guest material and the host material, it can form hydrogen bonds with the host molecule, which can effectively solidify the matrix network and further suppress the non-radiative transition of the guest excitons, so that the phosphorus The photon quantum yield and phosphorescence lifetime are significantly improved.

Compared with the prior art, the beneficial effects of the present invention are:

(1) The present invention provides a new guest material of phosphorescent material, which can be doped with diphenyl sulfoxide and/or diphenyl sulfoxide host material to obtain a phosphorescent material; at the same time, a third component is introduced on this basis, which can The formation of hydrogen bonds with the host molecule can effectively solidify the matrix network to further suppress the non-radiative transition of guest excitons, and significantly improve the phosphorescence quantum yield and phosphorescence lifetime;

(2) The three-component doped phosphorescent material of the present invention, when the third component is acid, etc., the phosphorescent material has a reversible alkali stimulus response function, which further expands the anti-counterfeiting, optical recording and other aspects of the phosphorescent material of the present invention. Application prospects, such as being used as writing ink for multiple anti-counterfeiting, etc.

Description of drawings

In order to illustrate the specific embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the specific embodiments or the prior art. Obviously, the accompanying drawings in the following description The drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without creative efforts.

Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the guest compound of the phosphorescent material provided in Example 1 of the present invention;

Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the guest compound of the phosphorescent material provided in Example 2 of the present invention;

Fig. 3 is the luminescent color change of some phosphorescent materials provided in Example 3 of the present invention under ultraviolet light and after removing the ultraviolet light;

Fig. 4 is the luminescent color change of each phosphorescent material provided in Example 4 of the present invention under ultraviolet light and after removing the ultraviolet light;

FIG. 5 is a phosphorescence emission diagram (370 nm) of some phosphorescent materials provided in Example 3 of the present invention;

6 is a phosphorescence decay curve of some phosphorescent materials provided in Embodiment 3 of the present invention;

FIG. 7 is a phosphorescence quantum yield diagram (370 nm) of some phosphorescent materials provided in Example 3 of the present invention;

8 is a phosphorescence emission diagram (370 nm) of a three-component doped phosphorescent material provided in Example 3 of the present invention under different conditions;

FIG. 9 is a phosphorescence emission diagram (370 nm) of another three-component doped phosphorescent material provided in Example 3 of the present invention under different conditions;

10 is a luminescence image of patterns drawn by a two-component doped phosphorescent material and a three-component doped phosphorescent material provided in Example 3 of the present invention under different conditions, wherein the upper part of the pattern is a two-component Doping phosphorescent material, the middle and lower part of the pattern is a three-component doped phosphorescent material.

Detailed ways

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments, but those skilled in the art will understand that the embodiments described below are part of the embodiments of the present invention, rather than all of the embodiments, It is only used to illustrate the present invention and should not be construed as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

The guest material of phosphorescent material, the structural formula is as follows:

R₁选自H或苯基。

R ₁ is selected from H or phenyl.

In a specific embodiment of the present invention, the structural formula of the guest material is

The present invention also provides a method for preparing a guest material of any of the above-mentioned phosphorescent materials, comprising the following steps:

(a) When R ₁ is H, compound A ₁ reacts with 2-bromoacetophenone in an alcohol solvent under the catalysis of an inorganic base; then the reaction solution is subjected to reflux reaction under the action of ammonium acetate and acetic acid, and post-treatment obtaining the guest material;

(b) when R ₁ is phenyl, compound A ₂ reacts with 2-bromoacetophenone in an alcohol solvent under the catalysis of inorganic base; then the reaction solution is refluxed under the action of ammonium acetate and acetic acid to obtain Intermediate B; Suzuki reaction is performed between the intermediate B and phenylboronic acid, and the guest material is obtained by post-processing;

所述化合物A₂的结构式为：

所述中间体B的结构式为：Wherein, the structural formula of the compound A ₁ is:

The structural formula of the compound A ₂ is:

The structural formula of the intermediate B is:

In a specific embodiment of the present invention, in step (a) or step (b), the inorganic base includes potassium carbonate and/or sodium carbonate. Further, the inorganic base is potassium carbonate.

In a specific embodiment of the present invention, in step (a) or step (b), the alcohol solvent is ethanol.

In a specific embodiment of the present invention, the reaction of the compound A ₁ with the 2-bromoacetophenone is carried out with stirring at room temperature. Further, the reaction time is 8-16 h.

In a specific embodiment of the present invention, the reaction of the compound A ₂ with the 2-bromoacetophenone is carried out with stirring at room temperature. Further, the reaction time is 8-16 h.

In a specific embodiment of the present invention, in step (a), the reflux reaction time is 16-20h; in step (b), the reflux reaction time is 16-20h. In actual operation, the time of the reflux reaction can be adjusted according to the actual reaction degree.

In a specific embodiment of the present invention, in step (a), the post-treatment includes: cooling the refluxed material to room temperature, precipitating a solid crude product, collecting the solid crude product and washing to obtain the object material. Further, the washing is performed with absolute ethanol. In step (b), the post-processing method for obtaining intermediate B after the reflux reaction is the same.

In a specific embodiment of the present invention, in step (a), the molar ratio of the compound A ₁ to the 2-bromoacetophenone is 1:(1-1.5); the compound A ₁ and the inorganic The molar ratio of the base is 1:(1.5～2). In actual operation, the amount of the alcohol solvent can be adjusted according to actual needs, so as to ensure that the compound A ₁ , the 2-bromoacetophenone and the inorganic base are uniformly dissolved or dispersed.

In a specific embodiment of the present invention, in step (a), the molar ratio of the ammonium acetate to the compound A ₁ is ₁ :(7.5-8.5), such as 1:8; The dosage ratio of acetic acid is 1mmol:(0.8-1.2)mL, such as 1mmol:1mL. Wherein, the dosage ratio of compound A ₁ to acetic acid refers to: per 1 mmol of compound A ₁ , the dosage of acetic acid is 0.8-1.2 mL.

In a specific embodiment of the present invention, in step (b), the molar ratio of the compound A ₂ to the 2-bromoacetophenone is 1:(1-1.5); the compound A ₂ and the inorganic The molar ratio of the base is 1:(1.5～2).

In a specific embodiment of the present invention, in step (b), the molar ratio of the ammonium acetate to the compound A ₂ is 1:(7.5-8.5), such as 1:8 _; The dosage ratio of acetic acid is 1mmol:(0.8-1.2)mL, such as 1mmol:1mL. Wherein, the dosage ratio of compound A ₂ to acetic acid refers to: per 1 mmol of compound A ₂ , the dosage of acetic acid is 0.8-1.2 mL.

In a specific embodiment of the present invention, the Suzuki reaction includes: the intermediate B reacts with phenylboronic acid in an organic solvent and a protective atmosphere under the action of an inorganic base and a palladium catalyst, and the guest material is obtained by post-processing .

In a specific embodiment of the present invention, in the Suzuki reaction, the organic solvent is DMF; the inorganic base is sodium carbonate; and the palladium catalyst is tetrakis(triphenylphosphine)palladium.

In a specific embodiment of the present invention, the molar ratio of the intermediate B to the phenylboronic acid is 1:(1.5-3), such as 1:2.

In a specific embodiment of the present invention, the molar ratio of the inorganic base to the intermediate B is (2.5-4):1; the molar ratio of the tetrakis(triphenylphosphine)palladium to the intermediate B is: (1% to 2%): 1, preferably 1.5%: 1.

In a specific embodiment of the present invention, in step (b), the post-treatment includes: extracting the material after the Suzuki reaction with dichloromethane three times, collecting the organic phase, drying the organic phase to remove water, and then The organic solvent was removed, and the guest material was isolated by silica gel column chromatography.

In a specific embodiment of the present invention, the preparation method of the compound A ₁ comprises: adding an aqueous sodium hydroxide solution to a methanol solution of acetophenone and salicylaldehyde at 0-5° C., and then reacting at room temperature, Work-up gives compound A ₁ .

In actual operation, the mixture of acetophenone and salicylaldehyde is dissolved in methanol to obtain a methanol solution of acetophenone and salicylaldehyde; then it is cooled to 0-5°C, and drops are added to it at this temperature. Aqueous sodium hydroxide solution was added, and after the dropwise addition, the mixture was reacted at room temperature, stirred overnight, and post-treated to obtain the compound A ₁ .

In a specific embodiment of the present invention, the molar ratio of the acetophenone to the salicylaldehyde is 1:(0.8～1); the dosage ratio of the acetophenone to the methanol is 1mmol:(1～1) 2) mL, such as 1 mmol: 1.5 mL. In actual operation, the mass fraction of the sodium hydroxide aqueous solution may be 35% to 45%, such as 40%. The dosage ratio of the acetophenone and the aqueous sodium hydroxide solution is 1 mmol: (0.3-0.5) mL, such as 1 mmol: 0.4 mL. Wherein, the dosage ratio of acetophenone and sodium hydroxide aqueous solution refers to: with respect to every 1 mmol of acetophenone, the dosage of sodium hydroxide aqueous solution is 0.3-0.5 mL.

In a specific embodiment of the present invention, in the preparation of the compound A ₁ , the post-treatment includes: after removing the organic solvent in the reaction solution, adding 0.9-1.1 M hydrochloric acid to the reaction solution to carry out the reaction; after the reaction is completed, Extraction with ethyl acetate three times, collecting the organic phase, drying the organic phase to remove water, then removing the organic solvent, and separating the compound A ₁ by silica gel column chromatography.

In a specific embodiment of the present invention, the preparation method of the compound A ₂ comprises: adding an aqueous sodium hydroxide solution to a methanol solution of acetophenone and bromosalicylaldehyde at 0-5° C., and then at room temperature Reaction and post-treatment to obtain compound A ₂ . Wherein, the structural formula of bromosalicylaldehyde is

The specific preparation process of the compound A ₂ is similar to that of the compound A ₁ , the difference is that salicylaldehyde is replaced with an equimolar amount of bromosalicylaldehyde.

The protective atmosphere involved in the present invention can all be nitrogen protective atmosphere.

的合成路线可以如下：In specific embodiments of the present invention, the guest material

The synthetic route can be as follows:

。

.

的合成路线可以如下：In specific embodiments of the present invention, the guest material

The synthetic route can be as follows:

。

.

The present invention also provides a phosphorescent material, comprising at least one of the above-mentioned guest materials and a host material; the host material includes diphenyl sulfoxide and/or diphenyl sulfone.

Wherein, the structural formulas of diphenyl sulfoxide and diphenyl sulfone are respectively:

Diphenyl sulfoxide has the characteristics of oxygen atom, good crystallinity and low melting point, and is used as the host material. The oxygen atom can form hydrogen bonds with the third component, and the good crystallinity can inhibit the excitons of the guest. The non-radiative leap forward separates water and oxygen in the air, and the lower melting point is beneficial to the preparation of doped materials.

In practice, diphenyl sulfoxide and diphenyl sulfone can be purchased directly.

In a specific embodiment of the present invention, the molar ratio of the guest material to the host material is 1:(500-1500), preferably 1:(800-1200).

As in various embodiments, the molar ratio of the guest material to the host material may be 1:500, 1:600, 1:700, 1:800, 1:900, 1:1000, 1:1100, 1 : 1200, 1: 1300, 1: 1400, 1: 1500, etc.

In a specific embodiment of the present invention, the phosphorescence quantum yield of the two-component doped phosphorescent material is about 4.3%, and the phosphorescence lifetime is about 147ms.

In a specific embodiment of the present invention, the phosphorescent material further comprises water and/or protonic acid.

中的任一种或多种。In specific embodiments of the present invention, the protic acid includes

any one or more of.

In a specific embodiment of the present invention, the molar ratio of the guest material, the host material and the water is 1:(500-1500):(100-500); the guest material, the host material and the The molar ratio of the protic acid is 1:(500-1500):(20-80).

As in various embodiments, the molar ratio of the guest material to the water may be 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:200 450, 1:500, etc.; the molar ratio of the guest material to the protonic acid can be 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, 1:70, 1:75, 1:80, etc.

In a specific embodiment of the present invention, the phosphorescence quantum yield of the three-component doped phosphorescence material is 18.8%-28.5%, and the phosphorescence lifetime is 235-308ms.

In a specific embodiment of the present invention, the emission wavelength of the phosphorescent material is 500-510 nm.

中的任一种或多种时，所述磷光材料具有碱刺激响应功能。进一步的，所述碱为乙二胺。In a specific embodiment of the present invention, when the protonic acid is

In the case of any one or more of the above, the phosphorescent material has a function of responding to alkali stimulation. Further, the base is ethylenediamine.

The phosphorescent property of the phosphorescent material decreases under alkali stimulation; after heating, the phosphorescent property recovers.

The present invention also provides a preparation method of the above-mentioned phosphorescent material, comprising the following steps:

The guest material and the host material are mixed in proportion, heated and melted, and then cooled.

The present invention also provides another method for preparing the above phosphorescent material. The water and/or protonic acid, the guest material and the host material are mixed in proportion, heated and melted, and then cooled.

Specifically, when the phosphorescent material includes water, the guest material and the host material are first heated and melted, and then water is added in proportion to mix and cool to obtain the phosphorescent material; when the phosphorescent material includes a protonic acid During the process, the guest material, the host material and the protonic acid are mixed in proportion, heated and melted, and then cooled.

The present invention also provides a method for adjusting the luminescence properties of the phosphorescent material, comprising the following steps:

Water and/or protonic acid are introduced into the guest material and the host material.

By adding the third component of water and/or protonic acid into the doping system of the guest material and the host material, it can form hydrogen bonds with the host molecule, which can effectively solidify the matrix network and further suppress the non-radiative transition of the guest excitons. For two-component doped phosphorescent materials, the phosphorescence quantum yield and phosphorescence lifetime of three-component doped phosphorescent materials are significantly improved.

In a specific embodiment of the present invention, the molar amount of water added is 100-500 times that of the guest material; the molar amount of the protic acid added is 20-80 times that of the guest material.

Example 1

This embodiment provides the preparation method of the guest material PFP of the phosphorescent material, and the route is as follows:

。

.

Specifically, the preparation method includes:

(S1) The mixture of acetophenone (1.2015g) and salicylaldehyde (1.2212g) was dissolved in 15mL methanol to obtain a methanol solution of acetophenone and salicylaldehyde, cooled to 0°C, and added dropwise to the methanol solution 4 mL of a 40% aqueous sodium hydroxide solution with a mass fraction of 40%; after the dropwise addition, the reaction system was allowed to reach room temperature and stirred overnight; the organic solvent in the reaction solution was removed by evaporation, and then 20 mL of 1M hydrochloric acid was added thereto to carry out neutralization reaction; Then extract with ethyl acetate three times, collect the organic phase, and dry the organic phase with anhydrous sodium sulfate, then evaporate the organic solvent in the organic phase under reduced pressure, and separate by silica gel column chromatography to obtain a yellow solid, which is compound A ₁ .

(S2) Compound A ₁ (0.2241 g), 2-bromoacetophenone (0.1990 g) and potassium carbonate (0.2764 g) were dissolved in absolute ethanol (15 mL), and the reaction was stirred at room temperature for 12 h; after the reaction was completed, Ammonium acetate (0.6150 g) and acetic acid (1 mL) were added under reflux conditions, and after continuing the reaction for 18 h, the reaction solution was slowly cooled to room temperature overnight, the crude product was precipitated, filtered, and the solid was washed with a small amount of absolute ethanol, and separated by column chromatography. The guest compound PFP was obtained.

Among them, the 1H NMR spectrum of the guest compound PFP is shown in Figure 1.

Example 2

This embodiment provides the preparation method of the guest material PFP of the phosphorescent material, and the route is as follows:

。

.

Specifically, the preparation method includes:

(S1) The mixture of acetophenone (1.2015g) and 5-bromosalicylaldehyde (2.0101g) was dissolved in 15mL methanol to obtain a methanol solution of acetophenone and 5-bromosalicylaldehyde, cooled to 0°C, 4 mL of 40% sodium hydroxide aqueous solution was added dropwise to the methanol solution; after the dropwise addition, the reaction system was allowed to reach room temperature and stirred overnight; the organic solvent in the reaction solution was evaporated to remove, and then 20 mL of 1M hydrochloric acid was added to it , carry out the neutralization reaction; then extract with ethyl acetate three times, collect the organic phase, and dry the organic phase with anhydrous sodium sulfate, then evaporate the organic solvent in the organic phase under reduced pressure, and separate by silica gel column chromatography to obtain a yellow solid, That is compound A ₂ .

(S2) Compound A ₂ (0.3031g), 2-bromoacetophenone (0.1990g) and potassium carbonate (0.2764g) were dissolved in absolute ethanol (15mL), and the reaction was stirred at room temperature for 12h; after the reaction was completed, Ammonium acetate (0.6150 g) and acetic acid (1 mL) were added under reflux conditions, and after continuing the reaction for 18 h, the reaction solution was slowly cooled to room temperature overnight, the crude product was precipitated, filtered and the solid was washed with a small amount of absolute ethanol to obtain Intermediate B .

(S3) A mixture of Intermediate B (0.4000g), phenylboronic acid (0.2438g), sodium carbonate (0.4146g) and tetrakis(triphenylphosphine)palladium (0.0173g) was evacuated and filled with nitrogen in a container, and then added DMF (8 mL) was reacted at 120 °C for 12 h; after the reaction was completed, extracted with dichloromethane three times, the organic phase was collected, dried with anhydrous sodium sulfate, and then the organic solvent in the organic phase was evaporated under reduced pressure, A white solid was obtained by silica gel column chromatography, which was the guest compound TPFP.

Among them, the 1H NMR spectrum of the guest compound TPFP is shown in FIG. 2 .

Example 3

This embodiment provides two-component doped phosphorescent materials and three-component doped phosphorescent materials and corresponding preparation methods.

Wherein, the preparation method of the two-component doped phosphorescent material includes: weighing the host material and the guest material in proportion, mixing, heating to about 80° C., after all melting, cooling to room temperature naturally, precipitating solid two-component doping Heterophosphorescent materials.

When the third component is water, the preparation method of the three-component doped phosphorescent material includes: weighing the host material and the guest material in proportion, mixing, heating to about 80°C, and after all melting, adding water in proportion , and then naturally cooled to room temperature to precipitate a solid three-component doped phosphorescent material;

When the third component is a protonic acid, the preparation method of the three-component doped phosphorescent material includes: weighing the host material, the guest material and the protonic acid in proportion, mixing, heating to about 80°C, and after all melting, Naturally cooled to room temperature, a solid three-component doped phosphorescent material was precipitated.

Wherein, when the main material is diphenyl sulfone, the heating temperature can be raised to above the melting point of diphenyl sulfone, so that the mixed system can be melted.

Table 1 Information about different phosphorescent materials

Example 4

This embodiment provides two-component doped phosphorescent materials and three-component doped phosphorescent materials and corresponding preparation methods.

Wherein, the preparation method of the two-component doped phosphorescent material includes: weighing the host material and the guest material in proportion, mixing, heating to about 80° C., after all melting, cooling to room temperature naturally, precipitating solid two-component doping Heterophosphorescent materials.

When the third component is water, the preparation method of the three-component doped phosphorescent material includes: weighing the host material and the guest material in proportion, mixing, heating to about 80°C, and after all melting, adding water in proportion , and then naturally cooled to room temperature to precipitate a solid three-component doped phosphorescent material;

When the third component is a protonic acid, the preparation method of the three-component doped phosphorescent material includes: weighing the host material, the guest material and the protonic acid in proportion, mixing, heating to about 80°C, and after all melting, Naturally cooled to room temperature, a solid three-component doped phosphorescent material was precipitated.

Table 2 Information about different phosphorescent materials

Experimental example 1

The phosphorescence properties of each phosphorescent material provided in Example 3 were tested. After each phosphorescent material was irradiated with a 365 nm ultraviolet light, the ultraviolet light was removed to observe the phosphorescence emission. FIG. 3 is the luminescent color change of some phosphorescent materials provided in Example 3 of the present invention under ultraviolet light and after removing the ultraviolet light. Among them, "Turn on" corresponds to the luminous color under ultraviolet light, and "Turn off" corresponds to the luminous color after removing the ultraviolet light. It can be seen from FIG. 3 that the phosphorescent material emits green phosphorescence after the ultraviolet light is removed, and the phosphorescence lifetime of the three-component doped phosphorescent material is significantly longer than that of the two-component doped phosphorescent material.

The phosphorescence properties of each phosphorescent material provided in Example 4 were tested. After each phosphorescent material was irradiated with a 365 nm ultraviolet light, the ultraviolet light was removed to observe the phosphorescence emission. FIG. 4 is the luminescent color change of each phosphorescent material provided in Example 4 of the present invention under ultraviolet light and after removing the ultraviolet light. Among them, "Turn on" corresponds to the luminous color under ultraviolet light, and "Turn off" corresponds to the luminous color after removing the ultraviolet light. It can be seen from FIG. 4 that the phosphorescent material emits green phosphorescence after the ultraviolet light is removed, and the phosphorescence lifetime of the three-component doped phosphorescent material is significantly longer than that of the two-component doped phosphorescent material.

FIG. 5 is a phosphorescence emission diagram of a part of the phosphorescent material provided in Example 3 of the present invention. It can be seen from FIG. 5 that the emission wavelength of the phosphorescent material in Example 3 is about 500-510 nm.

FIG. 6 and FIG. 7 are respectively a phosphorescence decay curve and a phosphorescence quantum yield graph of a part of the phosphorescence material provided in Example 3 of the present invention. It can be seen from the figure that the phosphorescence quantum yield of the three-component doped phosphorescent material obtained after the introduction of the third component is significantly improved compared with that of the two-component doped phosphorescent material.

Experimental example 2

FIG. 8 is a phosphorescence emission diagram of the three-component doped phosphorescent material PFP-SDB-CA provided in Example 3 of the present invention under different conditions. Among them, "Original" corresponds to the initial phosphorescence emission of PFP-SDB-CA, "Fumed" corresponds to the phosphorescence emission of PFP-SDB-CA after fumigation with ethylenediamine, and "Heating" corresponds to the The corresponding phosphorescence emission map of the fumigated PFP-SDB-CA after heat treatment (place the phosphorescent material on a glass slide and heat it on a heated bottom plate at a heating temperature of 60°C). It can be seen from Figure 8 that the phosphorescent material obtained when the third component is trimesic acid has a good response function to the stimulation of alkali. After the ethylenediamine fumigation treatment, the phosphorescent property decreases and recovers after heating. .

FIG. 9 is a phosphorescence emission diagram of another three-component doped phosphorescent material PFP-SDB-H ₂ O provided in Example 3 of the present invention under different conditions. Among them, "Original" corresponds to the initial phosphorescence emission map of PFP-SDB-H ₂ O, and "Fumed" corresponds to the corresponding phosphorescence emission map of PFP-SDB-H ₂ O after fumigation with ethylenediamine. It can be seen from FIG. 9 that the phosphorescent material obtained when the third component is water is substantially unresponsive to the stimulation of alkali.

10 is the luminescence images of the patterns drawn by the two-component doped phosphorescent material PFP-SDB and the three-component doped phosphorescent material PFP-SDB-CA provided in Example 3 of the present invention under different conditions, wherein the upper part of the pattern It is a two-component doped phosphorescent material PFP-SDB, and the lower part of the pattern is a three-component doped phosphorescent material PFP-SDB-CA. Wherein, each phosphorescent material is dissolved in acetone or tetrahydrofuran, respectively, to prepare a solution with a suitable concentration (eg, 0.02 mol/L), and the pattern is drawn. It can be seen from Figure 10 that after removing the ultraviolet light, the lower part of PFP-SDB-CA has stronger phosphorescence emission than the upper part of PFP-SDB. After fumigation with ethylenediamine, the lower part of PFP-SDB The phosphorescence intensity of -CA decreased significantly, while the phosphorescence of the upper part of PFP-SDB remained basically unchanged. After heat treatment, the phosphorescence emission of the lower part of PFP-SDB-CA partially recovered, while the phosphorescence of the upper part of PFP-SDB Still basically unchanged.

It can be seen from the above experiments that the use of different three-component doped phosphorescent materials or different responsiveness of two-component doped phosphorescent materials and three-component doped phosphorescent materials can further broaden the application of the phosphorescent material of the present invention in the fields of multiple anti-counterfeiting and the like. Applications.

Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (11)

1. A phosphorescent material, characterized in that it comprises at least one of the guest materials having the following structural formula and a host material; the structural formula of the guest material is as follows:

R ₁ is selected from H or phenyl; The host material is diphenyl sulfoxide and/or diphenyl sulfone. 2. The phosphorescent material according to claim 1, wherein the structural formula of the guest material is:

3 . The phosphorescent material according to claim 1 , wherein the molar ratio of the guest material to the host material is 1:(500-1500). 4 . 4 . The phosphorescent material according to claim 3 , wherein the molar ratio of the guest material to the host material is 1:(800-1200). 5 . 5. The phosphorescent material according to claim 1, wherein the phosphorescent material further comprises water and/or protonic acid. 6. The phosphorescent material according to claim 5, wherein the protonic acid is

any one or more of. 7 . The phosphorescent material according to claim 5 , wherein when the phosphorescent material comprises water, the molar ratio of the guest material, the host material and the water is 1:(500-1500): (100～500); When the phosphorescent material includes a protonic acid, the molar ratio of the guest material, the host material and the protonic acid is 1:(500-1500):(20-80). 8 . The phosphorescent material according to claim 5 , wherein the phosphorescence quantum yield of the phosphorescent material is 18.8%-28.5%, and the phosphorescence lifetime of the phosphorescent material is 235-308 ms. 9 . 9. A method for adjusting the luminescence properties of a phosphorescent material, comprising the steps of: Introducing water and/or protonic acid into the guest material and host material; Wherein, the structural formula of the guest material is as follows:

R ₁ is selected from H or phenyl; The host material is diphenyl sulfoxide and/or diphenyl sulfone. 10 . The method for adjusting the luminescence performance of a phosphorescent material according to claim 9 , wherein the molar addition of the water is 100-500 times that of the guest material; and/or the molar addition of the protonic acid. 11 . The amount is 20 to 80 times that of the guest material. 11. The method for adjusting the luminescence performance of a phosphorescent material according to claim 9, wherein the protonic acid is

any one or more of.

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