Organic long afterglow material and preparation method thereof
By dissolving 9,9-dimethylsilicone and tripaniline in a solvent under mild conditions and heating treatment, the formation of organic long afterglow materials was successfully induced, which solved the difficulty in inducing silicone under mild conditions in the prior art. The problem of long afterglow emission of molecules has achieved the preparation of materials with good afterglow luminescence properties.
Patent Information
- Application Number
- CN202411475680.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-22
- Publication Date
- 2025-02-18
AI Technical Summary
The prior art is difficult to induce long afterglow emission of small silicon fluorene molecules under mild conditions, resulting in limited application under environmental conditions.
The formation of organic long afterglow material was induced by dissolving 9,9-dimethylsilicone and tripaniline in a solvent and evaporating at a heating temperature of 30-50°C.
The preparation of organic long afterglow materials with good afterglow luminescence properties in a room temperature water and aerobic environment is realized, and the preparation method is simple, the raw materials are cheap and easy to obtain, the conditions are mild, and there is no need for harsh conditions such as high temperature and high pressure.
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Figure CN119463854A_ABST
Abstract
Description
Technical Field
[0001] The present application belongs to the field of material technology, and in particular relates to an organic long afterglow material and a preparation method thereof. Background Art
[0002] Organic long-persistent luminescence (LPL) materials have unique application trends in the fields of information encryption and anti-counterfeiting, bioimaging and sensing due to their long emission lifetime, processability, and easy control of luminescence properties.
[0003] Generally speaking, organic long afterglow is caused by ultra-long-lived RTP. However, it is very difficult to achieve RTP under ambient conditions because the spin prohibition of triplet exciton transitions can be easily quenched by oxygen and other non-radiative processes. To overcome these problems, researchers have proposed two main methods to achieve RTP, namely, promoting intersystem crossing (ISC) to enhance the abundance of triplet excitons under the action of introducing carbon, heteroatoms, and halogens, and suppressing non-radiative transitions by imposing a more stringent environment through crystallization engineering, H aggregation, phosphorus doping, and supramolecular assembly. Among them, silicene small molecules are widely used in the field of organic optoelectronic materials due to their high thermal stability and easy molecular modification. However, how to induce the RTP performance of silicene molecules has not been systematically reported due to the luminescence limitation of the molecules themselves. Therefore, the development of RTP performance based on silicene is very important. Summary of the invention
[0004] The purpose of the embodiments of the present application is to provide a method for preparing an organic long afterglow material. The preparation method is simple, the raw materials are cheap and easily available, the conditions are mild and do not require harsh conditions such as high temperature and high pressure, and can induce the technical problem of long afterglow emission of the organic small molecule 9,9-dimethylsilylene.
[0005] The embodiment of the present application is implemented as follows: a method for preparing an organic long afterglow material comprises: Dissolving 9,9-dimethylsilylfluorene and triphenylamine in a solvent to obtain a mixed solution; The mixed solution is placed under a heating temperature condition of 30-50° C. for volatilization treatment to obtain an organic long afterglow material.
[0006] The embodiment of the present application further provides an organic long afterglow material, which is prepared by the above-mentioned method for preparing the organic long afterglow material.
[0007] The embodiment of the present application provides a method for preparing an organic long afterglow material, by dissolving 9,9-dimethylsilylene and triphenylamine in a solvent, and then subjecting the obtained mixed solution to a volatilization treatment under a heating temperature condition of 30-50°C, the long afterglow emission of the organic small molecule 9,9-dimethylsilylene is induced, and the obtained long afterglow material has good afterglow luminescence performance in a water and oxygen environment at room temperature; in addition, the preparation method of the present application is simple, the raw materials are cheap and easily available, the conditions are mild and do not require harsh conditions such as high temperature and high pressure, which is very beneficial to the application of organic LPL materials. BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Figure 1 Optical microscope pictures of the organic long afterglow material provided in Example 1 of the present application (from left to right: when excited, 1 s, 2 s and 4 s after turning off the UV lamp); Figure 2 Macroscopic LPL images of the organic long afterglow material provided in Example 1 of the present application under room temperature conditions (from left to right: when excited, 1 s, 2 s, and 4 s after turning off the UV lamp); Figure 3 This is an afterglow time decay curve diagram of the organic long afterglow material provided in Example 1 of the present application; Figure 4 This is a graph of the afterglow time attenuation curve of the organic long afterglow material provided in Example 1 of the present application after being placed in a water-oxygen environment at room temperature for one month; Figure 5 Macroscopic LPL images of the organic long afterglow material provided in Example 2 of the present application under room temperature conditions (from left to right: when excited, 1 s, 2 s, and 3 s after turning off the UV lamp); Figure 6 This is a macroscopic LPL image of the organic long afterglow material provided in Example 3 of the present application under room temperature conditions (from left to right: when excited, 1 s, 2 s, and 3 s after turning off the UV lamp); Figure 7 This is a macroscopic LPL image of the organic long afterglow material provided in Example 4 of the present application under room temperature conditions (from left to right: when excited, 1 s, 2 s, and 3 s after turning off the UV lamp); Figure 8 This is a macroscopic LPL image of the organic long afterglow material provided in Example 5 of the present application under room temperature conditions (from left to right: during excitation, 1 s, 2 s and 3 s after turning off the UV lamp). DETAILED DESCRIPTION
[0009] In order to make the purpose, technical solution and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
[0010] The present application provides a method for preparing an organic long afterglow material, comprising the following steps: Dissolving 9,9-dimethylsilylfluorene and triphenylamine in a solvent to obtain a mixed solution; The mixed solution is placed under a heating temperature condition of 30-50° C. for volatilization treatment to obtain an organic long afterglow material.
[0011] Among them, 9,9-dimethylsilylfluorene is a luminescent body, and its structural formula is ; Triphenylamine is the main material, and its structural formula is triphenylamine In the previous study, this application also used diphenylamine , 4,4'-dimethylbenzophenone As a host material, it cannot induce the long afterglow emission of 9,9-dimethylsilylfluorene.
[0012] The mass ratio of 9,9-dimethylsilylfluorene to triphenylamine is 1:(100-1000), preferably 1:(100-200).
[0013] The role of the solvent is to dissolve 9,9-dimethylsilylfluorene and triphenylamine, and dichloromethane is preferred. The ratio of the mass fraction of the luminophore to the volume fraction of the dichloromethane is 1:1000, the unit of the mass fraction is g, and the unit of the volume fraction is mL.
[0014] If the heating temperature of the mixed solution is too high / low, the volatilization rate of the solvent will be too fast / slow, thus affecting the crystallization effect. Therefore, the heating temperature is preferably 40° C. and the heating time is 3 h.
[0015] Optionally, the host material, the luminophore and the solvent are mixed in a glass bottle. After the host material and the luminophore are completely dissolved in the solvent, the mixed solution is heated at a specific temperature. After the solvent evaporates, the precipitated white crystals are the organic long afterglow material.
[0016] Examples of certain embodiments of the present application are given below, which are not intended to limit the scope of the present application.
[0017] In addition, it should be noted that the numerical values given in the following examples are as accurate as possible, but those skilled in the art understand that due to unavoidable measurement errors and experimental operation problems, each number should be understood as an approximate number rather than an absolutely accurate value. For example, due to the error of the weighing instrument, the weight value of each raw material in the organic long afterglow material in each example should be understood to have an error of ±2% or ±1%.
[0018] The sources of the drugs involved in the following examples are as follows: 9,9-Dimethylsilylfluorene was purchased from Tianjin Xiensi Biochemical Technology Co., Ltd. (purity: 98%); Triphenylamine was purchased from Tianjin Xiensi Biochemical Technology Co., Ltd. (purity: 98%); Dichloromethane was purchased from Tianjin Jiangtian Chemical Technology Co., Ltd. (purity: 98%).
[0019] The instruments and models involved in the following embodiments are as follows: Leica DM2700M functional optical microscope; Ocean Optics multi-band spectrometer.
[0020] Example 1 9,9-dimethylsilylene, triphenylamine and dichloromethane were mixed in a glass bottle. After 9,9-dimethylsilylene and triphenylamine were completely dissolved in dichloromethane, the mixed solution was heated at 40°C for 3 hours. After the solvent evaporated, the precipitated white crystals were organic long afterglow materials. The ratio of 9,9-dimethylsilylene to triphenylamine was 1:100 by mass fraction, and the ratio of the mass fraction (g) of 9,9-dimethylsilylene to the volume fraction (mL) of dichloromethane was 1:1000.
[0021] Depend on Figure 1 It can be seen that the optical microscope can clearly see regular rectangular crystals with uniform size, square flakes and a single crystal size of about 50 μm, proving that the organic long afterglow material obtained in Example 1 is indeed a crystalline structure. The white crystals were excited with a 365 nm ultraviolet lamp, and the ultraviolet lamp was turned off after irradiation for 3 seconds, and the crystals could still maintain afterglow for 4 seconds.
[0022] Figure 2 This is a macroscopic LPL picture of the organic long afterglow material obtained in Example 1 at room temperature. The material is excited by a 365 nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off and the afterglow can be maintained for 4 seconds. It can be seen that the obtained afterglow material emits light more evenly.
[0023] Depend on Figure 3It can be seen that from -2 s to 0 s, the organic long afterglow material is irradiated with 365 nm ultraviolet light, and the organic long afterglow material exhibits photoluminescence characteristics; from 0 s to 4 s, after the ultraviolet light is removed, the organic long afterglow material exhibits yellow-green long afterglow light, and the afterglow time is about 4 s, which is similar to the afterglow time observed by the naked eye.
[0024] Figure 4 This is the afterglow time decay curve of the organic long afterglow material obtained in Example 1 after being placed in a water and oxygen environment at room temperature for one month. It can be seen from the figure that -2 s to 0 s is when the organic long afterglow material is irradiated by a 365 nm ultraviolet lamp, and the organic long afterglow material exhibits photoluminescence characteristics; 0 s to 4 s is when the organic long afterglow material exhibits yellow-green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 4 s. This afterglow time shows that the organic long afterglow material obtained in Example 1 has relatively excellent water and oxygen stability.
[0025] Example 2 9,9-dimethylsilylene, triphenylamine and dichloromethane were mixed in a glass bottle. After 9,9-dimethylsilylene and triphenylamine were completely dissolved in dichloromethane, the mixed solution was heated at 40°C for 3 hours. After the solvent evaporated, the precipitated white crystals were organic long afterglow materials. The ratio of 9,9-dimethylsilylene to triphenylamine was 1:200 by mass fraction, and the ratio of the mass fraction (g) of 9,9-dimethylsilylene to the volume fraction (mL) of dichloromethane was 1:1000.
[0026] Figure 5 This is a macroscopic LPL picture of the organic long afterglow material obtained in Example 2 at room temperature. The material is excited by a 365 nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off and the afterglow can be maintained for 3 seconds. It can be seen that the obtained afterglow material emits light more evenly.
[0027] Example 3 9,9-dimethylsilylene, triphenylamine and dichloromethane were mixed in a glass bottle. After 9,9-dimethylsilylene and triphenylamine were completely dissolved in dichloromethane, the mixed solution was heated at 40°C for 3 hours. After the solvent evaporated, the precipitated white crystals were organic long afterglow materials. The ratio of 9,9-dimethylsilylene to triphenylamine was 1:500 by mass fraction, and the ratio of the mass fraction (g) of 9,9-dimethylsilylene to the volume fraction (mL) of dichloromethane was 1:1000.
[0028] Figure 6 This is a macroscopic LPL picture of the organic long afterglow material obtained in Example 3 at room temperature. The material is excited by a 365 nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off and the afterglow can be maintained for 3 seconds. It can be seen that the obtained afterglow material emits light more evenly.
[0029] Example 4 9,9-dimethylsilylene, triphenylamine and dichloromethane were mixed in a glass bottle. After 9,9-dimethylsilylene and triphenylamine were completely dissolved in dichloromethane, the mixed solution was heated at 40°C for 3 hours. After the solvent evaporated, the precipitated white crystals were organic long afterglow materials. The ratio of 9,9-dimethylsilylene to triphenylamine was 1:700 by mass fraction, and the ratio of the mass fraction (g) of 9,9-dimethylsilylene to the volume fraction (mL) of dichloromethane was 1:1000.
[0030] Figure 7 This is a macroscopic LPL picture of the organic long afterglow material obtained in Example 4 at room temperature. The material is excited by a 365 nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off and the afterglow can be maintained for 3 seconds. It can be seen that the obtained afterglow material emits light more evenly.
[0031] Example 5 9,9-dimethylsilylene, triphenylamine and dichloromethane were mixed in a glass bottle. After 9,9-dimethylsilylene and triphenylamine were completely dissolved in dichloromethane, the mixed solution was heated at 40°C for 3 hours. After the solvent evaporated, the precipitated white crystals were organic long afterglow materials. The ratio of 9,9-dimethylsilylene to triphenylamine was 1:1000 by mass fraction, and the ratio of the mass fraction (g) of 9,9-dimethylsilylene to the volume fraction (mL) of dichloromethane was 1:1000.
[0032] Figure 8 This is a macroscopic LPL picture of the organic long afterglow material obtained in Example 5 at room temperature. The material is excited by a 365 nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off and the afterglow can be maintained for 3 seconds. It can be seen that the obtained afterglow material emits light more evenly.
[0033] Comparative Example 1 9,9-dimethylsilylene, diphenylamine and dichloromethane were mixed in a glass bottle. After 9,9-dimethylsilylene and diphenylamine were completely dissolved in dichloromethane, the mixed solution was heated at 40°C for 3 h. After the solvent evaporated, the obtained material was excited with a 365 nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp was turned off, and the afterglow time was 0. Among them, the ratio of the 9,9-dimethylsilylene to diphenylamine was 1:100 by mass fraction; the ratio of the mass fraction (g) of 9,9-dimethylsilylene to the volume fraction (mL) of dichloromethane was 1:1000.
[0034] Comparative Example 2 9,9-dimethylsilicon dioxide, 4,4'-dimethylbenzophenone and dichloromethane were mixed in a glass bottle. After 9,9-dimethylsilicon dioxide and 4,4'-dimethylbenzophenone were completely dissolved in dichloromethane, the mixed solution was heated at 40°C for 3 h. After the solvent evaporated, the obtained material was excited with a 365 nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp was turned off, and the afterglow time was 0. In which, the ratio of the 9,9-dimethylsilicon dioxide to 4,4'-dimethylbenzophenone was 1:100 by mass fraction; the ratio of the mass fraction (g) of 9,9-dimethylsilicon dioxide to the volume fraction (mL) of dichloromethane was 1:1000.
[0035] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the present application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached claims.
[0036] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims
1. A method for preparing an organic long afterglow material, characterized in that: include: Dissolving 9,9-dimethylsilylfluorene and triphenylamine in a solvent to obtain a mixed solution; The mixed solution is placed under a heating temperature condition of 30-50° C. for volatilization treatment to obtain an organic long afterglow material.
2. The method for preparing an organic long afterglow material according to claim 1, characterized in that: The mass ratio of the 9,9-dimethylsilylfluorene to triphenylamine is 1:(100-1000).
3. The method for preparing an organic long afterglow material according to claim 1, characterized in that: The mass ratio of the 9,9-dimethylsilylene to the main material is 1:(100-200).
4. The method for preparing an organic long afterglow material according to claim 1, characterized in that: The heating temperature is 40° C. and the heating time is 3 h.
5. The method for preparing an organic long afterglow material according to claim 1, characterized in that: The solvent is dichloromethane.
6. The method for preparing an organic long afterglow material according to claim 1 or 5, characterized in that: The mass volume ratio of the 9,9-dimethylsilylfluorene to the solvent is 1:1000.
7. An organic long afterglow material, characterized in that: The organic long afterglow material is prepared by the method for preparing the organic long afterglow material according to any one of claims 1-6.