Pure organic long-afterglow doped material and preparation method thereof

Abstract

The invention relates to the field of organic afterglow materials, and discloses a pure organic long-afterglow doped material and a preparation method thereof, the pure organic long-afterglow doped material comprises a phosphorescent element, a main powder matrix and a dichloromethane solvent; the main body powder matrix comprises diphenyl sulfone and a PMMA (Polymethyl Methacrylate) polymer; the intermediate 3, 3 '-sulfonyl bis (bromobenzene) is prepared by carrying out a reaction on dibenzothiophene and N-bromosuccinimide; the phosphorescent elements comprise 4-(3-((3-bromophenyl) sulfonyl) phenyl) dibenzo [b, d] thiophene, 3-(3-((3-bromophenyl) sulfonyl) phenyl) dibenzo [b, d] thiophene and 3-(3-((3-bromophenyl) sulfonyl) phenyl) dibenzo [b, d] thiophene, and have very good ultra-long afterglow in a polymer film and a powder matrix when being used as the phosphorescent elements. Good photostimulation responsiveness is shown under the environment condition. The pure organic long afterglow material disclosed by the invention has typical duration time, provides another new thought for information anti-counterfeiting, and can meet practical requirements in the aspects of data security and information encryption.

Description

Technical Field

[0001] The present invention relates to the technical field of organic afterglow materials, in particular to a pure organic long afterglow doping material and a preparation method thereof. Background Art

[0002] Organic afterglow materials have attracted much attention in recent years due to their applications in organic light-emitting diodes, sensors, bioimaging, information encryption, and other fields. To construct a long-lasting afterglow system, two major challenges must be overcome: the low efficiency of intersystem crossing (ISC) of organic molecules and the high non-radiative dissipation rate of triplet excitons at room temperature. To promote ISC, strategies such as donor-acceptor (DA) structures and heavy atom effects are commonly used. Methods such as crystal engineering, hydrogen bonding, and matrix doping are used to suppress non-radiative dissipation. In particular, the DA structure is a simple and effective way to significantly enhance triplet excitons because it can reduce the singlet-triplet energy gap by promoting n-π* transitions or charge transfer (CT) from donors to acceptors, thereby promoting ISC.

[0003] Most of the organic afterglow materials reported so far focus on materials such as cyanophenyl, bromophenyl, benzophenone, benzindole, naphthylamine, benzocarbazole and its isomers, and achieve afterglow by constructing a host-guest doping system. However, the work of using heavy atoms to promote benzothiophene and diphenyl sulfone to achieve long afterglow has not yet been studied. Summary of the Invention

[0004] In response to the shortcomings of the existing technology, the present invention provides a pure organic long-afterglow doping material and a preparation method thereof, and prepares three isomeric phosphorescent elements. These elements are not only easy to synthesize, conducive to promotion and application in real life, but also have many excellent and unique photophysical properties.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solutions: a pure organic long afterglow doping material, including a phosphorescent element, a main powder matrix, and a dichloromethane solvent;

[0006] The phosphorescent elements include: 4-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene, 3-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene and 3-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene;

[0007] The intermediate 3,3'-sulfonylbis(bromobenzene) is prepared by reacting dibenzothiophene and N-bromosuccinimide;

[0008] The main powder matrix includes: high-purity diphenyl sulfone and PMMA polymer.

[0009] A method for preparing a pure organic long afterglow doping material, characterized by comprising the following steps:

[0010] S1, by reacting dibenzothiophene with N-bromosuccinimide to obtain the intermediate 3,3'-sulfonylbis(bromobenzene);

[0011] S2, then reacting the obtained intermediate product with dibenzo[b,d]thiophen-4-ylboronic acid, dibenzo[b,d]thiophen-3-ylboronic acid and dibenzo[b,d]thiophen-2-ylboronic acid respectively to obtain three groups of different final products;

[0012] S3. Using three different groups of final products as guests and commercially available high-purity diphenyl sulfone as the host to construct a doping system, the weighed host and guest materials were dissolved in dichloromethane solvent, and stirred or ultrasonicated to promote uniform mixing to form a uniform solution. The solvent was evaporated at 40°C to allow the host and guest materials to co-precipitate;

[0013] S4. Dissolve the weighed single-component phosphorescent element and PMMA polymer in dichloromethane to form a uniform solution. Then mix the two solutions together and promote uniform mixing by stirring or ultrasound. Pour the mixed solution into a culture dish and evaporate the solvent at 40°C to form a thin film.

[0014] Preferably, the three groups of different final products in step S2 are single-component afterglow materials and can be used as phosphorescent elements. Such isomers maintain blue and purple fluorescence emissions under 365nm light. Once the ultraviolet light is removed, a strong yellow afterglow can be observed by the naked eye, and shorter green afterglow and yellow-brown afterglow can be captured. They have phosphorescence bands of 550nm, 419 / 606nm and 573nm respectively at room temperature without deoxygenation.

[0015] Preferably, the host-guest doping materials obtained in step S3 emit green light and blue light respectively at 365 nm, and emit a dazzling green afterglow after the ultraviolet lamp is removed, the duration of which is more than 5000 ms, and the dimming process has an obvious sequence.

[0016] Preferably, the thin film doping material obtained in step S4 is not activated for room temperature phosphorescence at 365 nm, but can be efficiently activated under excitation of a 295 nm excitation light source, with an activation time of 8-12 s. After the excitation light source is removed, the film emits a dazzling green afterglow.

[0017] The present invention provides a pure organic long-lasting glow doping material and a preparation method thereof. It has the following beneficial effects:

[0018] 1. The present invention innovatively proposes a new class of organic afterglow materials, expanding the library of organic afterglow compounds.

[0019] 2. The three isomers have very good ultra-long afterglow in polymer films and small molecule powder matrices, and show good light stimulus responsiveness at room temperature.

[0020] 3. The doping system constructed by the present invention has different afterglow times, which can realize the application of advanced anti-counterfeiting and meet the practical requirements in terms of data security and anti-counterfeiting. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 Schematic diagram of the hydrogen nuclear magnetic resonance spectrum of the isomer (a) of the present invention;

[0022] Figure 2 is a schematic diagram of the hydrogen nuclear magnetic resonance spectrum of the isomer (b) of the present invention;

[0023] Figure 3 is a schematic diagram of the hydrogen nuclear magnetic resonance spectrum of the isomer (c) of the present invention;

[0024] Figure 4 Schematic diagram of the UV-visible absorption and photoluminescence spectra of the three isomers of the present invention in solution (a);

[0025] Figure 5 Schematic diagram of UV-visible absorption and photoluminescence spectra of the solid state (b) of the three isomers of the present invention;

[0026] Figure 6 Schematic diagram of the room temperature phosphorescence lifetime of the present invention;

[0027] Figure 7 Schematic diagram of the doped photoluminescence spectrum of the PMMA film of the present invention;

[0028] Figure 8 This is a schematic diagram of the photoluminescence spectrum of diphenyl sulfone doped as a host in the present invention;

[0029] Figure 9 Schematic diagram of luminescence photographs of three isomers of the present invention;

[0030] Figure 10 This is a photographic schematic diagram of the PMMA film doped with luminescence according to the present invention;

[0031] Figure 11 This is a schematic diagram of the photo of the present invention using diphenyl sulfone as the main component for dual-component doping and luminescence;

[0032] Figure 12 Schematic diagram of the molecular structure of the organic single-molecule phosphorescent element of the present invention;

[0033] Figure 13 This is a schematic diagram of the molecular structure of the main powder matrix of the present invention;

[0034] Figure 14 Schematic diagram of the general structure of the polymer of the film material of the present invention;

[0035] Figure 15 It is a flow chart of the preparation method of the present invention. DETAILED DESCRIPTION

[0036] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the present specification. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0037] Please see the attached Figure 1 -Attached Figure 15 , an embodiment of the present invention provides a pure organic long afterglow doping material, including a phosphorescent element, a main powder matrix, and a dichloromethane solvent;

[0038] The phosphorescent elements include: 4-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene, 3-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene and 3-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene;

[0039] The intermediate 3,3'-sulfonylbis(bromobenzene) is prepared by reacting dibenzothiophene and N-bromosuccinimide;

[0040] The main powder matrix includes: high-purity diphenyl sulfone and PMMA polymer.

[0041] A method for preparing a pure organic long afterglow doping material comprises the following steps:

[0042] S1, by reacting dibenzothiophene with N-bromosuccinimide to obtain the intermediate 3,3'-sulfonylbis(bromobenzene);

[0043] S2. The obtained intermediate product is then reacted with dibenzo[b,d]thiophene-4-ylboronic acid, dibenzo[b,d]thiophene-3-ylboronic acid and dibenzo[b,d]thiophene-2-ylboronic acid respectively to obtain three different groups of final products. The three different groups of final products are single-component afterglow materials and can be used as phosphorescent elements. Such isomers maintain blue and purple fluorescence emission under 365nm light. Once the ultraviolet light is removed, a strong yellow afterglow can be observed by the naked eye, and a shorter green afterglow and yellow-brown afterglow can be captured. The phosphorescence bands are 550nm, 419 / 606nm and 573nm, respectively, at room temperature without deoxygenation.

[0044] S3. Three different groups of final products were used as guests, and commercially available high-purity diphenyl sulfone was selected as the host to construct a doping system. The weighed host and guest materials were dissolved in a dichloromethane solvent. Stirring or ultrasound was used to promote uniform mixing to form a uniform solution. The solvent was evaporated at 40°C to co-precipitate the host and guest materials. The resulting host and guest doped materials emitted green and blue light, respectively, at 365nm. After the ultraviolet light was removed, a dazzling green afterglow was emitted, which lasted for more than 5000ms, and the dimming process had a clear sequence.

[0045] S4. Dissolve the weighed single-component phosphorescent element and PMMA polymer in dichloromethane respectively to form a uniform solution, then mix the two solutions together, promote uniform mixing by stirring or ultrasound, and pour the mixed solution into a culture dish to evaporate the solvent at 40°C to form a thin film. The obtained thin film doping material is not activated for room temperature phosphorescence at 365nm, but can be efficiently activated under the excitation of a 295nm excitation light source, with an activation time of 8-12s. After the excitation light source is removed, the film emits a dazzling green afterglow.

[0046] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A pure organic long afterglow doping material, characterized in that: It includes phosphorescent element, main powder matrix and dichloromethane solvent; The phosphorescent elements include: 4-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene, 3-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene and 3-(3-((3-bromophenyl)sulfonyl)phenyl)dibenzo[b,d]thiophene; The intermediate 3,3'-sulfonylbis(bromobenzene) is prepared by reacting dibenzothiophene and N-bromosuccinimide; The main powder matrix includes: high-purity diphenyl sulfone and PMMA polymer.

2. The method for preparing a pure organic long afterglow doping material according to claim 1, characterized in that: The following steps are involved: S1. Synthesis of intermediate 3,3'-sulfonylbis(bromobenzene): intermediate 3,3'-sulfonylbis(bromobenzene) is obtained by reacting dibenzothiophene with N-bromosuccinimide; S2. Preparation of final products: then reacting the obtained intermediate product with dibenzo[b,d]thiophen-4-ylboronic acid, dibenzo[b,d]thiophen-3-ylboronic acid and dibenzo[b,d]thiophen-2-ylboronic acid, respectively, to obtain three groups of different final products; S3. Construction of the doping system: Three different groups of final products were used as guests, and commercially available high-purity diphenyl sulfone was selected as the host to construct the doping system. The weighed host and guest materials were dissolved in dichloromethane solvent. Stirring or ultrasonication were used to promote uniform mixing to form a uniform solution. The solvent was evaporated at 40°C to allow the host and guest materials to co-precipitate. S4. Thin film preparation: Dissolve the weighed single-component phosphorescent element and PMMA polymer in dichloromethane to form a uniform solution. Then mix the two solutions together and promote uniform mixing by stirring or ultrasound. Pour the mixed solution into a culture dish and evaporate the solvent at 40°C to form a thin film.

3. The method for preparing a pure organic long afterglow doping material according to claim 2, characterized in that: The three different groups of final products in step S2 are single-component afterglow materials and can be used as phosphorescent elements. These isomers maintain blue and purple fluorescence emissions under 365nm light. Once the ultraviolet light is removed, a strong yellow afterglow can be observed with the naked eye, and shorter green afterglow and yellow-brown afterglow can be captured. At room temperature without deoxygenation, they have phosphorescence bands of 550nm, 419 / 606nm, and 573nm, respectively.

4. The method for preparing a pure organic long afterglow doping material according to claim 2, characterized in that: The host-guest doping materials obtained in step S3 emit green light and blue light at 365 nm, respectively. After the ultraviolet lamp is removed, a dazzling green afterglow is emitted, which lasts for more than 5000 ms, and the dimming process has an obvious sequence.

5. The method for preparing a pure organic long afterglow doping material according to claim 2, characterized in that: The thin film doping material obtained in step S4 is not activated for room temperature phosphorescence at 365 nm, but can be efficiently activated under the excitation of a 295 nm excitation light source, with an activation time of 8-12 s. After the excitation light source is removed, the film emits a dazzling green afterglow.

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