阅读说明：本技术 掺杂发光材料及其制备方法和应用 (Doped luminescent material and preparation method and application thereof ) 是由 黄小波 王丹 雷云祥 吴华悦 刘妙昌 于 2021-01-21 设计创作，主要内容包括：本发明涉及有机光电材料技术领域,尤其是涉及一种掺杂发光材料及其制备方法和应用。掺杂发光材料,包括化合物Ⅰ和化合物Ⅱ；所述化合物Ⅰ和所述化合物Ⅱ的结构式如下：其中,R-1选自苯基、取代苯基、咔唑基和取代咔唑基中的任一种；R-2选自H、卤素原子和烷氧基中的任一种；R-3选自苯基、取代苯基、苄基和取代苄基中的任一种。本发明的掺杂发光材料,表现出荧光和室温磷光的双发射。并且通过调控这种双发射可以结合成几乎纯的白色发射,极大的拓宽了掺杂发光材料在实际生产生活中的应用。(The invention relates to the technical field of organic photoelectric materials, in particular to a doped luminescent material and a preparation method and application thereof. The doped luminescent material comprises a compound I and a compound II; the structural formulas of the compound I and the compound II are as follows: wherein R is 1 Any one selected from phenyl, substituted phenyl, carbazolyl and substituted carbazolyl; r 2 Selected from any one of H, halogen atom and alkoxy group；R 3 Selected from any one of phenyl, substituted phenyl, benzyl and substituted benzyl. The doped luminescent material of the invention shows dual emission of fluorescence and room temperature phosphorescence. And the double-emission can be combined into almost pure white emission by regulating and controlling the double-emission, so that the application of the doped luminescent material in actual production and life is greatly widened.)

1. The doped luminescent material is characterized by comprising a compound I and a compound II;

the structural formulas of the compound I and the compound II are as follows:

wherein R is₁Any one selected from phenyl, substituted phenyl, carbazolyl and substituted carbazolyl;

R₂any one selected from the group consisting of H, a halogen atom, and an alkoxy group;

R₃selected from any one of phenyl, substituted phenyl, benzyl and substituted benzyl.

2. The doped luminescent material of claim 1, wherein the substituent of the substituted phenyl group comprises any one of a halogen atom, an alkoxy group, an aldehyde group, a cyano group, a carbazolyl group, and an amine group;

preferably, R₁Any one of the following structures:

3. the doped luminescent material of claim 1, wherein R is₂Any one selected from H, F and methoxy;

R₃any one of the following structures:

4. the doped luminescent material of claim 1, wherein the compound i is selected from at least one of the following structures:

5. the doped luminescent material of claim 1, wherein the compound ii is selected from at least one of the following structures:

6. the doped luminescent material according to any one of claims 1 to 5, wherein the doping molar ratio of the compound I to the compound II is 1: 1 (50 to 50000);

preferably, the doping molar ratio of the compound I to the compound II is 1: 1000-2000.

7. The method of preparing a doped luminescent material according to any one of claims 1 to 6, comprising the steps of:

heating and melting a mixture of the compound I and the compound II, and cooling for crystallization;

alternatively, the first and second electrodes may be,

and respectively heating and melting the compound I and the compound II, uniformly mixing, and cooling and crystallizing.

8. Ink and/or ink, characterized in that it comprises a doped luminescent material according to any one of claims 1 to 6.

9. Use of a doped luminescent material according to any one of claims 1 to 6 in the preparation of a white light emitting material.

10. A white light emitting material comprising the doped luminescent material of any one of claims 1 to 6;

preferably, the CIE x coordinate of the doped luminescent material is 0.30-0.40, and the CIE y coordinate is 0.30-0.40;

more preferably, the CIE x coordinate of the doped luminescent material is 0.31-0.38, and the CIE y coordinate is 0.30-0.36;

preferably, the doped luminescent material is excited at a wavelength of 330-380 nm;

preferably, the compound I comprises a compound I₂Compound I₃And I₄At least one of the compounds II, the compound II comprises a compound II₁。

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a doped luminescent material and a preparation method and application thereof.

Background

Phosphorescent materials have good development prospects in anti-counterfeiting, photoelectric devices and biological applications, and have attracted wide attention of many scientists in recent years. As more single molecule room temperature phosphorescent materials were originally discovered, multi-component doped phosphorescent materials gradually attracted more people's eyeballs. However, there is a lack of systematic studies on multicomponent doped phosphorescent materials.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

It is a first object of the present invention to provide a doped luminescent material.

The second purpose of the invention is to provide a preparation method of the doped luminescent material.

A third object of the invention is to provide the use of doped luminescent materials.

In order to achieve the above purpose of the present invention, the following technical solutions are adopted:

the doped luminescent material comprises a compound I and a compound II;

the structural formulas of the compound I and the compound II are as follows:

wherein R is₁Any one selected from phenyl, substituted phenyl, carbazolyl and substituted carbazolyl;

R₂any one selected from the group consisting of H, a halogen atom, and an alkoxy group;

R₃selected from phenyl, substituted phenyl, benzyl and substitutedAny one of benzyl groups.

The doped luminescent material of the invention shows dual emission of fluorescence and room temperature phosphorescence. And the double emission can be combined into almost pure white emission through regulation and control, so that the application of the doped luminescent material in actual production and life is greatly widened.

In a specific embodiment of the present invention, the substituent of the substituted phenyl group includes any one of a halogen atom, an alkoxy group, an aldehyde group, a cyano group, a carbazolyl group, and an amine group.

In a particular embodiment of the invention, R₁Any one of the following structures:

in a particular embodiment of the invention, R₂Any one selected from H, F and methoxy.

In a particular embodiment of the invention, R₃Any one of the following structures:

in a particular embodiment of the invention, the compound i is selected from at least one of the following structures:

in a particular embodiment of the invention, said compound ii is selected from at least one of the following structures:

in a specific embodiment of the invention, the doping molar ratio of the compound I to the compound II is 1: 50 to 50000, preferably 1: 1000 to 2000.

In a particular embodiment of the invention, the process for the preparation of said compound i comprises:

carrying out Suzuki coupling reaction on the compound E and the compound F to obtain a compound I;

wherein the structural formulas of the compound E and the compound F are as follows:

in a specific embodiment of the invention, the conditions of the Suzuki coupling reaction include: and reacting the compound E and the compound F for 10-24 h at 70-85 ℃ in a nitrogen atmosphere by using a mixture of DMF and water as a solvent under the action of bis (triphenylphosphine) palladium dichloride and potassium carbonate.

In a specific embodiment of the present invention, the synthetic route of the compound E is as follows:

the specific method comprises the following steps:

(a) carrying out reflux reaction on 2, 6-dimethyl pyrone and cyanoacetic acid in acetic anhydride to obtain a compound B;

(b) stirring the compound B and piperidine in acetonitrile for reaction for 3-5 h at 85-95 ℃ to obtain a compound C;

(c) reacting the compound C with potassium carbonate in acetonitrile at 45-55 ℃ for 1.5-2.5 h, mixing with methyl iodide, and reacting at 75-85 ℃ for 4-6 h to obtain a compound D;

(d) and carrying out bromination reaction on the compound D and a brominating agent NBS to obtain a compound E.

Wherein, in the step (a), the temperature of the reflux reaction is 135-145 ℃, and the time of the reflux reaction is 4-6 h.

The invention also provides a preparation method of the doped luminescent material, which comprises the following steps:

heating and melting a mixture of the compound I and the compound II, and cooling for crystallization;

or respectively heating and melting the compound I and the compound II, uniformly mixing, and cooling for crystallization.

In actual operation, the heating and melting temperature can be adjusted according to actual conditions, and the mixture of the compounds is ensured to be molten.

In a specific embodiment of the present invention, the method further comprises: and grinding the material obtained after cooling and crystallization.

The invention also provides application of the doped luminescent material in preparation of ink and/or ink.

Further, the ink and/or ink is anti-counterfeiting printing ink and/or ink, or writing and drawing ink and/or ink.

The invention also provides the application of the doped luminescent material in preparing a white light emitting material.

In a specific embodiment of the present invention, the white light emitting material includes any one of the doped luminescent materials described above.

In a specific embodiment of the invention, the doped luminescent material has a CIE x coordinate of 0.30 to 0.40 and a CIE y coordinate of 0.30 to 0.40. Preferably, the CIE x coordinate of the doped luminescent material is 0.31-0.38, and the CIE y coordinate is 0.30-0.36.

In the specific embodiment of the invention, the doped luminescent material is excited at a wavelength of 330-380 nm.

In a particular embodiment of the invention, said compound I comprises compound I₂Compound I₃And I₄At least one of the compounds II, the compound II comprises a compound II₁。

In a specific embodiment of the invention, in the doped luminescent material, the doping molar ratio of the compound I to the compound II is 1: 1000-2000.

Compared with the prior art, the invention has the beneficial effects that:

(1) the doped luminescent material of the invention shows dual-emission of fluorescence and room temperature phosphorescence, and has adjustable color; emitting fluorescence at about 440-460 nm under the irradiation of a 365nm excitation light source, and emitting yellow and orange phosphorescence after the excitation light source is closed;

(2) according to the invention, the white luminescent doped luminescent material is obtained by regulating and controlling different excitation light sources, so that the application of the doped luminescent material in actual production and life is greatly widened.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 shows a compound I provided in an example of the present invention₁The nuclear magnetic resonance hydrogen spectrum of (a);

FIG. 2 shows compound I provided in an example of the present invention₁Nuclear magnetic resonance carbon spectrum of (a);

FIG. 3 shows compound I provided in an example of the present invention₂The nuclear magnetic resonance hydrogen spectrum of (a);

FIG. 4 shows compound I provided in an example of the present invention₂Nuclear magnetic resonance carbon spectrum of (a);

FIG. 5 shows Compound I provided in an example of the present invention₃The nuclear magnetic resonance hydrogen spectrum of (a);

FIG. 6 shows Compound I provided in an example of the present invention₃Nuclear magnetic resonance carbon spectrum of (a);

FIG. 7 shows Compound I provided in an example of the present invention₄The nuclear magnetic resonance hydrogen spectrum of (a);

FIG. 8 shows Compound I provided in an example of the present invention₄Nuclear magnetic resonance carbon spectrum of (a);

FIG. 9 shows an embodiment of the present inventionProviding a doped luminescent material L₁₁、L₂₁、L₃₁And L₄₁A photograph showing the change in the color of light emitted before and after the irradiation of ultraviolet light;

FIG. 10 shows a doped luminescent material L according to an embodiment of the present invention₁₁’、L₁₂、L₁₃、L₁₄And L₁₅A photograph showing the change in the color of light emitted before and after the irradiation of ultraviolet light;

FIG. 11 shows a doped luminescent material L according to an embodiment of the present invention₅₁、L₆₁、L₇₁、L₈₁And L₉₁A photograph showing the change in the color of light emitted before and after the irradiation of ultraviolet light;

FIG. 12 shows a doped luminescent material L according to an embodiment of the present invention₁₁、L₂₁、L₃₁And L₄₁Phosphorescence emission pattern of (a);

FIG. 13 shows a doped luminescent material L according to an embodiment of the present invention₁₁、L₁₂、L₁₃、L₁₄And L₁₅Phosphorescence emission pattern of (a);

FIG. 14 shows a doped luminescent material L according to an embodiment of the present invention₆₁、L₇₁、L₈₁And L₉₁Phosphorescence emission pattern of (a);

FIG. 15 shows a doped luminescent material L according to an embodiment of the present invention₁₁、L₂₁、L₃₁And L₄₁The time delay decay curve of (d);

FIG. 16 shows a guest compound I according to an embodiment of the present invention₂And a host compound II₁Transient spectra of the doped luminescent material obtained under different doping concentrations;

FIG. 17 shows Compound I provided in an example of the present invention₂And compounds II₁Obtaining CIE coordinates of the doped luminescent material under different doping concentrations;

FIG. 18 shows a guest compound I provided in an embodiment of the present invention₂And a host compound II₁Obtaining fluorescent phosphorescence pictures of the doped luminescent materials under different doping concentrations;

FIG. 19 shows a doped luminescent material L according to an embodiment of the present invention₃₁CIE coordinates in different excited states;

fig. 20 is a photograph of patterns formed by doping luminescent materials according to an embodiment of the present invention emitting light at different uv excitation wavelengths.

Detailed Description

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

References to "a" in the structural formulae of the present invention indicate the attachment of the group of the structural formula containing "a" to the rest of the compound via the position of the "a".

The doped luminescent material comprises a compound I and a compound II;

the structural formulas of the compound I and the compound II are as follows:

wherein R is₁Any one selected from phenyl, substituted phenyl, carbazolyl and substituted carbazolyl;

R₂any one selected from the group consisting of H, a halogen atom, and an alkoxy group;

R₃selected from any one of phenyl, substituted phenyl, benzyl and substituted benzyl.

The doped luminescent material of the invention shows dual emission of fluorescence and room temperature phosphorescence. And the double emission can be combined into almost pure white emission through regulation and control, so that the application of the doped luminescent material in actual production and life is greatly widened.

As in the different embodiments, the halogen atom is any of F, Cl, Br, I; alkoxy groups include methoxy, ethoxy, and the like.

In a specific embodiment of the present invention, the substituent of the substituted phenyl group includes any one of a halogen atom, an alkoxy group, an aldehyde group, a cyano group, a carbazolyl group, and an amine group.

In a particular embodiment of the invention, R₁Any one of the following structures:

in a particular embodiment of the invention, R₂Any one selected from H, F and methoxy.

In a particular embodiment of the invention, R₃Any one of the following structures:

in a particular embodiment of the invention, compound i is selected from at least one of the following structures:

in a particular embodiment of the invention, compound ii is selected from at least one of the following structures:

in a specific embodiment of the invention, the doping molar ratio of the compound I to the compound II is 1: 50 to 50000, preferably 1: 1000 to 2000.

In various embodiments, the molar ratio of doping for compound i and compound ii can be 1: 50, 1: 100, 1: 200, 1: 500, 1: 1000, 1: 2000, 1: 5000, 1: 10000, 1: 15000, 1: 20000, 1: 25000, 1: 30000, 1: 35000, 1: 40000, 1: 45000, and 1: 50000.

In a particular embodiment of the invention, the process for the preparation of said compound i comprises:

carrying out Suzuki coupling reaction on the compound E and the compound F to obtain a compound I;

wherein the structural formulas of the compound E and the compound F are as follows:

in a specific embodiment of the invention, the conditions of the Suzuki coupling reaction include: and reacting the compound E and the compound F for 10-24 h at 70-85 ℃ in a nitrogen atmosphere by using a mixture of DMF and water as a solvent under the action of bis (triphenylphosphine) palladium dichloride and potassium carbonate. The reaction temperature can be 80 ℃ and the reaction time can be 12 h.

As in the different embodiments, the volume ratio of DMF to water may be 3: 1. The amount of the bis (triphenylphosphine) palladium dichloride is the amount of a conventional catalyst, and can be 2 mol% to 10 mol%, such as 5 mol%, of the compound E; the potassium carbonate may be added in an amount of 5 mol% to 15 mol%, such as 5 mol%, of the compound E. The molar ratio of compound E to compound F can be 1: 1 to 1.5, for example 1: 1.2.

In a specific embodiment of the present invention, the synthetic route of the compound E is as follows:

the specific method comprises the following steps:

(a) carrying out reflux reaction on 2, 6-dimethyl pyrone (compound A) and cyanoacetic acid in acetic anhydride to obtain a compound B;

(b) stirring the compound B and piperidine in acetonitrile for reaction for 3-5 h at 85-95 ℃ to obtain a compound C;

(c) reacting the compound C with potassium carbonate in acetonitrile at 45-55 ℃ for 1.5-2.5 h, mixing with methyl iodide, and reacting at 75-85 ℃ for 4-6 h to obtain a compound D;

(d) and carrying out bromination reaction on the compound D and a brominating agent NBS to obtain a compound E.

Wherein, in the step (a), the temperature of the reflux reaction is 135-145 ℃, and the time of the reflux reaction is 4-6 h.

As in various embodiments, the bromination reaction conditions include: carbon tetrachloride is used as solvent, and benzoyl peroxide is used as initiator.

The invention also provides a preparation method of the doped luminescent material, which comprises the following steps:

heating and melting a mixture of the compound I and the compound II, and cooling for crystallization;

or respectively heating and melting the compound I and the compound II, uniformly mixing, and cooling for crystallization.

In a specific embodiment of the present invention, the method further comprises: and grinding the material obtained after cooling and crystallization.

The invention also provides application of the doped luminescent material in preparation of ink and/or ink.

Further, the ink and/or ink is anti-counterfeiting printing ink and/or ink, or writing and drawing ink and/or ink.

Further, the ink and/or ink includes a solvent. A solvent is used to dissolve the doped luminescent material, such as dichloromethane.

The invention also provides the application of the doped luminescent material in preparing a white light emitting material.

In a specific embodiment of the present invention, the white light emitting material includes any one of the doped luminescent materials described above.

In a specific embodiment of the invention, the doped luminescent material has a CIE x coordinate of 0.30 to 0.40 and a CIE y coordinate of 0.30 to 0.40. Preferably, the CIE x coordinate of the doped luminescent material is 0.31-0.38, and the CIE y coordinate is 0.30-0.36.

In the specific embodiment of the invention, the doped luminescent material is excited at a wavelength of 330-3800 nm.

In a particular embodiment of the invention, said compound I comprises compound I₂Compound I₃And I₄At least one of the compounds II, the compound II comprises a compound II₁。

In a specific embodiment of the invention, in the doped luminescent material, the doping molar ratio of the compound I to the compound II is 1: 1000-2000.

Example 1

This example provides a preparation of compound i, the synthetic route is as follows:

the specific procedure for the preparation of compound E from compound a is as follows:

(a) compound A was dissolved in 50mL of acetic anhydride at a molar ratio of 1: 2 and refluxed at 140 ℃ for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, then poured into 500mL of water, stirred for 30min, extracted three times with dichloromethane, the organic phase was dried with anhydrous sodium sulfate, and then the organic solvent was evaporated under reduced pressure, and compound B was obtained as a yellow solid by silica gel column chromatography.

(b) Compound B3 g and piperidine 2mL were mixed in 10mL acetonitrile, stirred at 90 ℃ for 4h, after completion of the reaction, cooled to room temperature, the organic solvent was evaporated under reduced pressure and the residue was chromatographed on silica gel column to give compound C as a white solid.

(c) Dissolving the compound C and potassium carbonate in acetonitrile at a molar ratio of 1: 2, reacting at 50 ℃ for 2h, adding methyl iodide (the molar ratio of the amount of methyl iodide to the amount of the compound C is 1: 5), heating to 80 ℃, continuing to react for 5h, and cooling the obtained material to room temperature or separating out a white solid at low temperature, namely the compound D.

(d) Adding a trace amount of pyridine 100 μ L into compound D, N-bromosuccinimide and benzoyl peroxide at a molar ratio of 1: 1.1: 1 in carbon tetrachloride as solvent, and reacting for 22h to obtain compound E.

Mixing compound E with a different boronic acid compound F in a ratio of 1: 1.2 Suzuki coupling reaction to obtain the corresponding compound I. Wherein, the Suzuki coupling reaction conditions comprise:

reacting the compound E with the compound F for 12 hours under the action of bis (triphenylphosphine) palladium dichloride and potassium carbonate and a mixture of DMF and water as a solvent in a nitrogen atmosphere; the molar ratio of compound E to compound F was 1: 1.2, the reaction temperature was 80 ℃, bis (triphenylphosphine) palladium dichloride in an amount of 5 mol% based on compound E, potassium carbonate in an amount of 5 mol% based on compound E, and the volume ratio of DMF to water was 3: 1.

Specific structural information, etc. are shown in Table 1 (wherein the yield refers to the yield of the step of preparing the corresponding compound I from compound E).

TABLE 1 numbering and structural information of different compounds I

The structures of the prepared compounds I are characterized by nuclear magnetic hydrogen spectrums and nuclear magnetic carbon spectrums, and the compounds with corresponding structures are confirmed to be prepared. With a compound I₁、Ⅰ₂、Ⅰ₃、Ⅰ₄By way of exampleIn the description, FIGS. 1 to 8 show the compounds I obtained₁、Ⅰ₂、Ⅰ₃、Ⅰ₄The nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum of (1).

Example 2

This example provides doped luminescent materials and their preparation methods, and the numbers, raw materials and raw material ratios of the doped luminescent materials are shown in table 2.

A method of preparing a doped luminescent material comprising: and weighing the compound I and the compound II in proportion, mixing, heating to about 48 ℃ (the temperature can be properly adjusted to enable the compounds to be mixed and melted) to enable the compounds to be completely melted, and cooling to separate out crystals to obtain the doped luminescent material.

The doped luminescent material is further ground into powder in a grinding dish.

TABLE 2 different doped luminescent materials and raw materials information

Experimental example 1

In order to verify the light emitting performance of the doped light emitting material prepared in the present invention, the properties of the doped light emitting material prepared in the examples were tested.

FIG. 9 shows a doped luminescent material L according to an embodiment of the present invention₁₁、L₂₁、L₃₁And L₄₁A photograph showing the change in the color of light emitted before and after the irradiation of ultraviolet light; FIG. 10 shows a doped luminescent material L according to an embodiment of the present invention₁₁’、L₁₂、L₁₃、L₁₄And L₁₅A photograph showing the change in the color of light emitted before and after the irradiation of ultraviolet light; FIG. 11 shows a doped luminescent material L according to an embodiment of the present invention₅₁、L₆₁、L₇₁、L₈₁And L₉₁A photograph showing the change in the color of light emitted before and after the irradiation of ultraviolet light; the wavelength of ultraviolet light is 365nm (Turn on pairs)Corresponding to the emission color of the uv light, and Turn off corresponding to the emission color with the uv light removed). As can be seen from the figure, the doped luminescent material has certain fluorescence under 365nm ultraviolet illumination; after the ultraviolet light is removed, phosphorescence such as yellow and orange is emitted, and the phosphorescence life is longer.

FIG. 12 shows a doped luminescent material L according to an embodiment of the present invention₁₁、L₂₁、L₃₁And L₄₁Phosphorescence emission pattern of (a); FIG. 13 provides guest compound I for an embodiment of the present invention₁And a host compound II₁、Ⅱ₅、Ⅱ₃、Ⅱ₄、Ⅱ₂Doped luminescent material L of₁₁’、L₁₂、L₁₃、L₁₄And L₁₅Phosphorescence emission pattern of (a); FIG. 14 shows a doped luminescent material L according to an embodiment of the present invention₆₁、L₇₁、L₈₁And L₉₁Phosphorescence emission diagram of (a).

FIG. 15 shows a doped luminescent material L according to an embodiment of the present invention₁₁、L₂₁、L₃₁And L₄₁Time delay decay curve of (1).

Experimental example 2

FIG. 16 shows Compound I provided in an example of the present invention₂And compounds II₁Transient spectra of the doped luminescent material obtained under different doping concentrations; FIG. 17 shows Compound I provided in an example of the present invention₂And compounds II₁The CIE coordinates of the doped luminescent material obtained under different doping concentrations have an excitation wavelength of 380 nm; FIG. 18 shows Compound I provided in an example of the present invention₂And compounds II₁And obtaining fluorescent phosphorescence pictures of the doped luminescent materials under different doping concentrations. Wherein the doping concentrations labeled 1: 50, 1: 200, 1: 1000, 1: 2000, 1: 5000, 1: 10000, 1: 20000 and 1: 50000 correspond to the doped luminescent materials L prepared in the examples₂₁-50、L₂₁-200、L₂₁、L₂₁-2000、L₂₁-5000、L₂₁-10000、L₂₁-20000 and L₂₁-50000. Doped luminescent material L₂₁、L₂₁2000 at 380nm excitationThe CIE coordinates were (0.33, 0.35) and (0.31, 0.30), respectively.

Doped luminescent material L₃₁Under the ultraviolet illumination of different excitation wavelengths, the luminous color and the luminous intensity are different, and the same phosphorescence is emitted after the ultraviolet light is removed. FIG. 19 shows a doped luminescent material L according to an embodiment of the present invention₃₁CIE coordinates in different excited states. By adjusting the different excitation wavelengths, the relative intensity of the fluorescent-phosphorescent emission, as well as the color, can be adjusted. Doped luminescent material L₃₁CIE coordinates at 330nm, 360nm, 370nm, 390nm excitation are (0.38, 0.36), (0.34, 0.33), (0.32 ) and (0.21, 0.23), respectively.

Experimental example 3

Doped luminescent materials L respectively prepared by adopting the embodiments of the invention₁₁And L₂₁Drawing patterns on the rice paper, and respectively taking luminous pictures of the patterns under the illumination conditions of 400nm, 370nm and 330nm and taking out the luminous pictures after light is removed. Specifically, as shown in fig. 20, the method for drawing a pattern includes: mixing L with₁₁And L₂₁Respectively dissolved in dichloromethane solution, and a Chinese art brush pen and rice paper are used for creating a paper containing L dissolved therein₁₁And a flower drawn with a methylene chloride solution ink of₂₁The dichloromethane solution ink of (1).

Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.