Electron-rich material co-constructed organic long-afterglow crystal material, preparation method and application thereof

Abstract

The application belongs to the technical field of organic afterglow crystal materials, and particularly relates to an electron-rich material co-constructed organic long afterglow crystal material and a preparation method and application thereof. The electron-rich diphenylamine material which is easy to crystallize and cheap and easy to obtain is selected as a host material, and the electron-rich halogenated benzene derivative which is cheap and easy to obtain is introduced as a guest material, so that a series of crystal materials with regular structure are constructed, and a long afterglow luminescent new material with long afterglow time and adjustable color is obtained. The experiment proves that the electron-rich material co-constructed organic long afterglow crystal material provided by the application can be excited by ultraviolet light, has the characteristics of environmental stability, the afterglow time is more than 2s, and the crystal morphology can be regular, the afterglow color can also be adjusted, which shows the application potential in the information encryption and anti-counterfeiting fields, and can provide a theoretical basis and material basis for data encryption, anti-counterfeiting and other practical applications.

Description

Technical Field

[0001] This invention belongs to the field of organic afterglow crystal material technology, specifically relating to an organic long afterglow crystal material co-constructed with electron-rich materials, its preparation method, and its application. Background Technology

[0002] Long-afterglow luminescent materials, also known as phosphorescent materials or "night-shining pearls," are photoluminescent materials. When excited by a light source, they emit visible light and store some of the light energy. After excitation ceases, they slowly release the energy in the form of light. Long-afterglow luminescent materials mainly include organic and inorganic types. Currently, inorganic long-afterglow luminescent materials are the most widely used, finding applications in transportation, national defense, fire safety, medical diagnosis, and daily life. However, the synthesis conditions for inorganic materials are demanding, raw materials are scarce, and the control over their photoelectric properties is limited, severely restricting their application in daily life and industrial production.

[0003] With the development of flexible electronics, high-efficiency, multi-color, and intelligent organic long-afterglow materials have seen rapid advancements in just a few years. In particular, color-tunable long-afterglow luminescent materials have found widespread application in many cutting-edge fields such as organic electronics, bioelectronics, and high-end anti-counterfeiting due to their unique luminescent properties. Furthermore, compared to inorganic long-afterglow materials, organic long-afterglow materials exhibit better biocompatibility and conductivity, and possess advantages such as low cost and easy structural modification, thus attracting increasing attention in recent years.

[0004] However, due to the inherent weak spin-orbit coupling (SOC) and forbidden intersystem crossing (ISC) of rapid nonradiative transitions of triplet excitons in organic materials, highly efficient and durable long-afterglow materials based on pure organic materials are relatively rare, which greatly limits the application of organic long-afterglow materials. Currently, a series of afterglow materials prepared through host-guest or donor-acceptor doping have been reported. Due to the interaction between the host and guest materials, SOC is effectively enhanced, nonradiative transitions are suppressed, and ISC is improved, resulting in a significant increase in afterglow time and performance. However, most of the reported host and guest materials require complex structures, and energy level matching between the host and guest materials is necessary. Furthermore, the materials are often limited in variety, have few sources, and are expensive, which further restricts the market application of organic long-afterglow materials.

[0005] To better compensate for the weak ISC effect and the susceptibility of phosphorescence lifetime to water and oxygen quenching caused by nonradiative transitions in organic materials, some researchers have attempted to improve material properties by constructing crystal structures. Constructing suitable crystal structures can not only provide a rigid environment to suppress nonradiative transitions of guest molecules, but also... Resonant energy transfer (FRET) involves the synergistic interaction between host and guest molecules in photophysics processes, thereby significantly enhancing the phosphorescence lifetime and extending the afterglow time of crystalline materials.

[0006] However, the key to obtaining high-efficiency afterglow materials lies in how to prepare crystalline materials using simple methods. Furthermore, how to combine the advantages of host-guest material preparation with the host-guest method to prepare crystalline materials to better improve their afterglow performance and duration remains a long-standing technical bottleneck in this field. Summary of the Invention

[0007] In view of this, one of the objectives of the present invention is to provide an organic long afterglow crystal material co-constructed with electron-rich materials, the raw materials for which are inexpensive and readily available, and the material has good afterglow luminescence performance with an afterglow time exceeding 2 seconds.

[0008] The second objective of this invention is to provide a method for preparing organic long afterglow crystal materials co-constructed with the aforementioned electron-rich materials. This method utilizes simple, inexpensive, and readily available electron-rich materials as both host and guest materials to prepare the crystal material. The preparation method is simple, the conditions are mild, and it does not require harsh conditions such as high temperature and high pressure. Furthermore, the prepared material exhibits excellent afterglow luminescence properties.

[0009] The third objective of this invention is to provide applications of the organic long afterglow crystal material co-constructed with the aforementioned electron-rich materials.

[0010] One of the objectives of this invention is achieved through the following technical solution:

[0011] An organic long afterglow crystal material co-constructed with electron-rich materials is prepared by evaporation and crystallization of a host material and a guest material; in the organic long afterglow crystal material co-constructed with electron-rich materials, the host material forms regular crystals, and the guest material is freely dispersed in the crystals of the host material;

[0012] The structural formula of the main material is:

[0013]

[0014] R0 is selected from one or two of H, CH3, OCH3, CN, CHO, and NO2;

[0015] The structural formula of the object material is: One of them.

[0016] More preferably, the structural formula of the main material is:

[0017] More preferably, in the preparation of the organic long afterglow crystal material co-constructed with the electron-rich material, the mass ratio of the host material to the guest material is (80-120):1. More preferably, the mass ratio of the host material to the guest material is 100:1.

[0018] More preferably, the excitation wavelength of the organic long afterglow crystal material co-constructed by the electron-rich material is 365 nm.

[0019] The second objective of this invention is achieved by the following technical solution:

[0020] A method for preparing an organic long afterglow crystal material co-constructed with electron-rich materials as described above includes the following steps: mixing the host material and the guest material uniformly to obtain a solid powder, then stirring and dissolving the solid powder in a solvent, and then allowing it to evaporate at room temperature to precipitate crystals, thereby obtaining the organic long afterglow crystal material co-constructed with electron-rich materials.

[0021] More preferably, the solvent includes dichloromethane and ethanol.

[0022] More preferably, the solid powder is dissolved in a solvent by stirring, specifically by first adding dichloromethane to the solid powder to dissolve it, and then adding ethanol and stirring until completely dissolved.

[0023] More preferably, the volume ratio of dichloromethane to ethanol is 1:80 to 120, and more preferably 1:100.

[0024] More preferably, the concentration of the solid powder in the solvent is 15–25 mg / mL, more preferably 20 mg / mL.

[0025] More preferably, the stirring speed for dissolving is 500-1000 rpm, and the time is 3-10 min.

[0026] More preferably, after crystal precipitation, the process further includes centrifuging the solution after crystal precipitation, washing the crystals after centrifugation, and drying at room temperature (20-25°C) for 2-5 hours.

[0027] The third objective of this invention is achieved by the following technical solution:

[0028] The application of organic long afterglow crystal materials co-constructed with electron-rich materials, as described above, is specifically as a luminescent material used in data encryption and anti-counterfeiting.

[0029] The overall beneficial effects of this invention are as follows:

[0030] 1. The organic long afterglow crystal material co-constructed by electron-rich materials provided by the present invention cleverly selects electron-rich materials (diphenylamine materials) that are easy to crystallize and are inexpensive and readily available as the main material, and introduces electron-rich halobenzene derivatives as guest materials to construct a series of structurally regular crystal materials, thereby obtaining a new long afterglow luminescent material with a long afterglow time.

[0031] Experiments have confirmed that the organic long-afterglow crystal material co-constructed with electron-rich materials provided in this invention can be excited by ultraviolet light and exhibits excellent afterglow luminescence performance, with afterglow times exceeding 2 seconds, superior to conventional crystalline afterglow materials. Furthermore, it can form regular crystal morphologies, and the afterglow color is adjustable. The improved afterglow time, adjustable color, and mild, undemanding preparation conditions will greatly benefit the application of organic crystalline long-afterglow materials in various scenarios.

[0032] 2. Currently, the host and guest materials of organic crystal afterglow materials are generally complex and expensive, while the host and guest materials used in this invention are inexpensive, readily available, and simple in structure, with a cost that is only a fraction of that of most current afterglow materials. This provides more possibilities for their practical commercial application.

[0033] 3. In the preparation of organic long-afterglow crystalline materials, this invention constructs a crystal structure through host-guest blending via evaporation crystallization. In this process, selecting easily crystallizable host-guest materials for mixing is crucial for constructing the crystalline material. The crystal structure not only provides a rigid environment, suppressing non-radiative transitions of guest molecules, but also... Resonant energy transfer (FRET) enables host and guest molecules to interact synergistically in photophysics processes, thereby enhancing the afterglow time of crystalline materials. Specifically, this invention, in its technical improvements, focuses on enhancing the afterglow time and color of organic long-afterglow crystalline materials. A small amount of structurally similar electronic guest material is doped into the host material through evaporation-crystallization mixing, successfully constructing a novel host-guest crystalline material that can be excited by ultraviolet light and effectively enhances the afterglow time, brightness, and color of the crystalline material. This improvement in afterglow time, brightness, and color effectively supports the efficient long-afterglow luminescence applications of organic crystalline long-afterglow materials.

[0034] 4. The application of the organic long afterglow material provided by this invention is that, by simply mixing and crystallizing host and guest materials with the simplest similar structures, afterglow materials that can exhibit different luminescence times and colors can be successfully prepared, demonstrating its application potential in the fields of information encryption and anti-counterfeiting.

[0035] Therefore, this invention not only provides new ideas for the design and synthesis of novel host-guest crystal long afterglow materials with tunable luminescence colors, but more importantly, these novel organic host-guest systems have advantages such as low cost, simple structure, easy preparation, and excellent performance, which can provide theoretical basis and material foundation for practical applications such as data encryption and anti-counterfeiting. Attached Figure Description

[0036] Figure 1 Optical images of the organic long afterglow crystal material co-constructed with electron-rich materials obtained in Example 1 of the present invention before (a) and after (be) 365nm ultraviolet light illumination.

[0037] Figure 2 Optical images of the organic long afterglow crystal material co-constructed with electron-rich materials obtained in Example 2 of the present invention before (a) and after (bh) 365nm ultraviolet light illumination.

[0038] Figure 3 This is a graph showing the afterglow performance decay curve of the organic long afterglow crystal material co-constructed with electron-rich materials obtained in Example 2 of the present invention.

[0039] Figure 4 Optical images of the organic long afterglow crystal material co-constructed with electron-rich materials obtained in Example 3 of the present invention before (a) and after (bh) 365nm ultraviolet light illumination.

[0040] Figure 5 This is a graph showing the afterglow performance decay curve of the organic long afterglow crystal material co-constructed with electron-rich materials obtained in Example 3 of the present invention.

[0041] Figure 6 Optical images showing the afterglow of the organic crystal material obtained in Comparative Example 1 before (a) and after (b) 365 nm ultraviolet light illumination. Detailed Implementation

[0042] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments and test examples. However, those skilled in the art should understand that the embodiments are only used to illustrate the technical solution of the present invention and should not be regarded as limiting the scope of protection of the present invention. Based on the following embodiments, all other implementation schemes obtained by those skilled in the art without creative effort, such as implementation schemes obtained by modification, variation or simple substitution, should fall within the scope of protection of the present invention.

[0043] In the following embodiments, both the main body materials and the object materials used were purchased from the manufacturer, primarily Beijing Innocare Technology Co., Ltd.

[0044] Example 1

[0045] This embodiment provides an organic long afterglow crystal material co-constructed with electron-rich materials, which is prepared by an evaporation crystallization method using a host material and a guest material. In the organic long afterglow crystal material co-constructed with electron-rich materials, the host material forms regular crystals, and the guest material is freely dispersed within the crystals of the host material. The structural formula of the host material is: (MODPA); The structural formula of the object material is: (4-Bromobenzaldehyde).

[0046] The preparation method of the above-mentioned organic long afterglow crystal material co-constructed with electron-rich materials includes the following steps: 0.0010 g of guest material 4-bromobenzaldehyde and 0.1000 g of host material MODPA are accurately weighed and mixed according to a host material to guest material mass ratio of 100:1 to obtain a solid powder. 0.05 mL of dichloromethane is added to the solid powder and dissolved for 1 min. Then, 5 mL of ethanol is added and stirred at 600 rpm for 5 min at room temperature (20-25°C) until completely dissolved. The solution is then placed in an atmospheric environment at room temperature (20-25°C) to slowly evaporate until crystals precipitate. After crystal precipitation, the solution containing crystals is centrifuged. After centrifugation, the crystals are washed with ethanol and dried at room temperature (20-25°C) for 3 h to obtain the organic long afterglow crystal material co-constructed with electron-rich materials of Example 1, which is used for subsequent structural analysis and performance testing.

[0047] Example 2

[0048] This embodiment provides an organic long afterglow crystal material co-constructed with electron-rich materials, prepared by an evaporation crystallization method using a host material and a guest material. The preparation process of the material in Example 2 is basically the same as that in Example 1, the only difference being the structure of the guest material used. In this embodiment, the guest material used is...

[0049] Example 3

[0050] This embodiment provides an organic long afterglow crystal material co-constructed with electron-rich materials, prepared by an evaporation crystallization method using a host material and a guest material. The preparation process of the material in Example 3 is basically the same as that in Example 1, the only difference being the structure of the guest material used. In this embodiment, the guest material used is...

[0051] Comparative Example 1

[0052] This comparative example provides an organic crystalline material prepared by an evaporation crystallization method using a host material and a guest material. The preparation process of this organic crystalline material is basically the same as that of Example 1, the only difference being the structure of the guest material used. The guest material used in this comparative example is... (4,7-Dibromo-2,1,3-benzothiadiazole).

[0053] Experimental Example 1: Material Structure Characterization and Performance Testing

[0054] (1) Test results of organic long afterglow material in Example 1

[0055] Under aerobic conditions at room temperature, the organic long-afterglow crystal material co-constructed from the electron-rich material of Example 1 was excited using a 365nm ultraviolet lamp. The excitation source was then turned off, and the change in afterglow brightness of the crystal material was recorded. The results are as follows: Figure 1 As shown.

[0056] Depend on Figure 1 It can be seen that the crystal material of Example 1 is excited by a 365nm ultraviolet lamp ( Figure 1 After a), the excitation source is turned off. After the source is removed, the crystal material emits a green afterglow. Figure 1 b), in the first 1 second, Figure 1 c represents the 1st second after the light source is removed. Figure 1 d represents the 1.5s mark, during which the afterglow of the compound is relatively strong. From the 1.5s mark onwards, the afterglow gradually weakens, reaching its peak at the 2.0s mark. Figure 1 e) There is still afterglow, which shows that the afterglow time of the crystal material in Example 1 is as high as 2s, and the afterglow performance is excellent.

[0057] (2) Test results of organic long afterglow material in Example 2

[0058] First, the structure of the organic long afterglow crystal material co-constructed with electron-rich materials in Example 2 of this invention was characterized using a polarizing microscope. The polarizing microscope results showed that the material of Example 2 was a regular cuboid crystal with relatively uniform size, indicating that the organic long afterglow material obtained in Example 2 did indeed have a crystalline structure. Furthermore, the crystals were square or rectangular plate-like crystals.

[0059] Under aerobic conditions at room temperature, the organic long-afterglow crystal material co-constructed from the electron-rich material of Example 2 was excited using a 365nm ultraviolet lamp. The excitation source was then turned off, and the change in afterglow brightness of the crystal material was recorded. The results are as follows: Figure 2 As shown. By Figure 2 It can be seen that the crystal material of Example 2 was excited by a 365nm ultraviolet lamp ( Figure 2 After a), the excitation source is turned off. After the source is removed, the crystal material emits a yellowish-green afterglow. Figure 2 b), in the first 1 second, Figure 2 c represents 0.5 seconds after the light source is removed. Figure 2 d represents the 1st second, 2e and 2f represent 1.5 and 2 seconds respectively, during which the afterglow of the compound is relatively strong, starting from the 1.5th second (e.g., ...). Figure 2 After the afterglow (as shown in e) gradually weakens, at 2.5s ( Figure 2The afterglow lingered after g), and in the 3rd second ( Figure 2 h) The afterglow is not obvious, which shows that the afterglow time of the crystal material in Example 2 is as high as 3s, and the afterglow performance is excellent.

[0060] The afterglow performance degradation of the organic long afterglow crystal material co-constructed with electron-rich materials in Example 2 was tested using a marine optical multi-band spectrometer. The results are as follows: Figure 3 As shown. Figure 3 In the text, -2s to 0s represents the organic long-afterglow crystal material co-constructed with electron-rich materials in Example 2 under 365nm ultraviolet light irradiation, exhibiting photoluminescence characteristics; 0s to 8s represents the organic long-afterglow crystal material co-constructed with electron-rich materials in Example 2 after the ultraviolet light is removed, exhibiting yellow-green long-afterglow light emission with an afterglow time of about 3s, similar to the afterglow time observed by the naked eye.

[0061] (3) Test results of organic long afterglow material in Example 3

[0062] Under aerobic conditions at room temperature, the organic long-afterglow crystal material co-constructed from the electron-rich material of Example 3 was excited using a 365nm ultraviolet lamp. The excitation source was then turned off, and the change in afterglow brightness of the crystal material was recorded. The results are as follows: Figure 4 As shown.

[0063] Depend on Figure 4 It can be seen that the crystal material of Example 3 was excited by a 365nm ultraviolet lamp ( Figure 4 After a), the excitation source is turned off. After the source is removed, the crystal material emits a green afterglow. Figure 4 b) In the first 3 seconds, Figure 4 c represents the 1.5s after the light source is removed. Figure 4 f represents the 3rd second, during which the afterglow of the compound is relatively strong, starting from the 3.5th second (e.g., Figure 4 Afterglow gradually weakens after g (as shown), at 4.3s ( Figure 4 There was still afterglow after h), at 4.3s ( Figure 4 h) The afterglow was not obvious, which shows that the afterglow time of the crystal material in Example 3 is as high as 4.3s, and the afterglow performance is excellent.

[0064] The afterglow performance degradation of the organic long afterglow crystal material co-constructed with electron-rich materials in Example 3 was tested using a marine optical multi-band spectrometer. The results are as follows: Figure 5 As shown. Figure 5In the diagram, -2s to 0s represents the organic long-afterglow crystal material co-constructed from the electron-rich material in Example 3 under 365nm ultraviolet light irradiation, exhibiting photoluminescence characteristics; 0s to 8s represents the organic long-afterglow crystal material co-constructed from the electron-rich material in Example 3 after the ultraviolet light is removed, exhibiting green long-afterglow light emission with an afterglow time of approximately 4.3s, similar to the afterglow time observed by the naked eye.

[0065] (4) Test results of the afterglow material of the pilot in Comparative Example 1

[0066] Under aerobic conditions at room temperature, the organic crystal material of Comparative Example 1 was excited with a 365nm ultraviolet lamp, and then the excitation source was turned off. The change in afterglow brightness of the crystal material after the light source was removed was recorded. The results are as follows: Figure 6 As shown. By Figure 6 It can be seen that the crystal material of Comparative Example 1 is excited by a 365nm ultraviolet lamp ( Figure 6 After a), turn off the excitation source. The crystal material does not emit light after the source is removed. Figure 6 b). This indicates that the preparation of host-guest type afterglow materials requires energy level matching of the materials.

[0067] Table 1 below shows the comparison results of afterglow color and afterglow time of the materials in Examples 1-3 and Comparative Example 1.

[0068] Table 1

[0069]

[0070] As shown in Table 1, the organic long-afterglow materials provided in Examples 1-3 of this invention all exhibit afterglow times exceeding 2 seconds under aerobic conditions at room temperature, with a maximum of 4.3 seconds, significantly superior to the afterglow performance of the material in Comparative Example 1. Furthermore, the afterglow color of the organic long-afterglow crystalline material of this invention is adjustable from yellow to yellowish-green. The improved afterglow time, adjustable color, and mild, undemanding preparation conditions are highly beneficial for the application of organic crystalline long-afterglow materials in various scenarios.

[0071] In summary, the organic long afterglow crystal material co-constructed with electron-rich materials provided by this invention not only offers new ideas for the design and synthesis of novel host-guest crystal long afterglow materials with tunable luminescence colors, but more importantly, these novel organic host-guest systems have advantages such as low cost, simple structure, easy preparation, and excellent performance, which can provide theoretical basis and material foundation for practical applications such as data encryption and anti-counterfeiting.

Claims

1. An organic long afterglow crystal material co-constructed with electron-rich materials, characterized in that, The organic long afterglow crystal material co-constructed with electron-rich materials is prepared by evaporation and crystallization of host material and guest material; in the organic long afterglow crystal material co-constructed with electron-rich materials, the host material forms regular crystals, and the guest material is freely dispersed in the crystals of the host material; The structural formula of the main material is: ; The structural formula of the object material is: , , One of them.

2. The organic long afterglow crystal material co-constructed with electron-rich materials according to claim 1, characterized in that, When preparing the organic long afterglow crystal material co-constructed with the electron-rich material, the mass ratio of the host material to the guest material is 80~120:

1.

3. A method for preparing an organic long afterglow crystal material co-constructed with electron-rich materials as described in claim 1, characterized in that, The process includes the following steps: mixing the host material and the guest material evenly to obtain a solid powder, then stirring and dissolving the solid powder in a solvent, allowing it to evaporate at room temperature, and precipitating crystals to obtain the organic long afterglow crystal material co-constructed by the electron-rich material.

4. The method for preparing the organic long afterglow crystal material co-constructed with electron-rich materials according to claim 3, characterized in that, The solvent includes dichloromethane and ethanol; the solid powder is dissolved in the solvent by stirring, specifically by first adding dichloromethane to the solid powder to dissolve it, and then adding ethanol and stirring until completely dissolved.

5. The method for preparing the organic long afterglow crystal material co-constructed with electron-rich materials according to claim 4, characterized in that, The volume ratio of dichloromethane to ethanol is 1:80~120.

6. The method for preparing the organic long afterglow crystal material co-constructed with electron-rich materials according to claim 3, characterized in that, The concentration of the solid powder in the solvent is 15~25 mg / mL.

7. The method for preparing the organic long afterglow crystal material co-constructed with electron-rich materials according to claim 3, characterized in that, The stirring speed for dissolving is 500~1000 rpm, and the time is 3~10 min.

8. The method for preparing the organic long afterglow crystal material co-constructed with electron-rich materials according to any one of claims 3 to 7, characterized in that, After crystals precipitate, the process also includes centrifuging the solution after crystal precipitation, washing the crystals after centrifugation, and drying at room temperature (20-25°C) for 2-5 hours.

9. An application of an organic long afterglow crystal material co-constructed with electron-rich materials as described in claim 1 or 2, characterized in that, Applications of luminescent materials in data encryption and anti-counterfeiting.

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