Organic long afterglow material with circular polarization characteristics and preparation method and application thereof

Abstract

The present invention discloses an organic long afterglow material with circular polarization characteristics and a preparation method and application thereof. The preparation method of the organic long afterglow material comprises: uniformly mixing a main material and a guest material to obtain a solid powder, heating and melting the solid powder, naturally cooling to room temperature, and precipitating white crystals as the organic long afterglow material. The organic long afterglow material of the present invention has an afterglow time of 5 seconds under water, oxygen and room temperature conditions, and after being enhanced by a polymer, the afterglow time can reach 10 seconds. The improvement of time and mild and non-harsh conditions will be very beneficial to the application of organic crystalline LPL materials in various scenarios. When the organic long afterglow material is used for information encryption and anti-counterfeiting, the encryption and anti-counterfeiting of afterglow, circularly polarized light and temperature response in multiple dimensions greatly improves the level of information security.

Description

Technical Field

[0001] The invention belongs to the technical field of organic long afterglow materials, and in particular relates to an organic long afterglow material with circular polarization characteristics and a preparation method and application thereof. Background Art

[0002] Organic long-persistent luminescence (LPL) materials are increasingly being researched and developed due to their "green" preparation process, easy-to-control luminescence, and environmental friendliness. Compared with inorganic long-persistent luminescence materials, this organic material has convenient and gradually adjustable emission lifetime and wavelength and stimulus-responsive emission characteristics, and has unique advantages in application fields such as information encryption, anti-counterfeiting, biosensing, and bioimaging.

[0003] In general, the persistent phosphorescence effect of pure organic compounds or complexes can be induced by precisely controlling the inter-system crossing (ISC) constant and non-radiative decay. Methods to enhance phosphorescence performance, such as crystallization induction, supramolecular assembly, H-aggregation, host-guest doping, and polymerization, can effectively stabilize ternary excitons under ambient conditions and achieve high-performance persistent phosphorescence effects. In particular, by utilizing intermolecular interactions, such as the photoinduced transfer of charge or energy between the host and the guest to suppress non-radiative decay, small molecule organic materials doped with phosphorescent guests in the host matrix can release prominent persistent RTP emission. However, since triplet excitons are easily quenched by oxygen or other non-radiative deactivation pathways, the luminescence performance of pure organic phosphorescent materials still needs to be improved. In addition, crystalline materials usually have poor reproducibility and processability, which greatly limits the widespread application of organic room temperature phosphorescent materials. Introducing a rigid polymer matrix into the doped material is another widely explored method that can effectively suppress molecular vibrations and thus efficiently obtain long afterglow emission.

[0004] In addition, circularly polarized luminescence (CPL) has attracted much attention due to its excellent optical sensitivity, spatial resolution and chiral properties. Its luminescence mechanism is mainly based on fluorescence or thermally activated delayed fluorescence rather than persistent room temperature phosphorescence (RTP) properties. At present, inorganic long afterglow materials cannot achieve CPL characteristics. Therefore, achieving organic long afterglow emission with CPL characteristics is considered to be an emerging type of luminescence, which will effectively expand the application scenarios of such organic long afterglow materials. However, due to the lack of a clear luminescence mechanism, the research on organic long afterglow emission strategies with CPL characteristics is still very rare. With the development of several organic host-guest doping systems or polymer systems with room temperature circularly polarized long-persistent luminescence (CPLPL), it is necessary to find a more efficient luminescence mechanism to achieve this CPLPL emission. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing a host-guest induced organic long afterglow material with circular polarization characteristics. The guest material of the preparation method is based on axially chiral biaryl rings and their derivatives. 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.

[0006] Another object of the present invention is to provide an organic long afterglow material having circular polarization characteristics obtained by the above preparation method.

[0007] Another object of the present invention is to provide a method for preparing a thin film, which enhances the luminescence performance of an organic long afterglow material by introducing a rigid polymer and heating the polymer to above the glass transition temperature.

[0008] Another object of the present invention is to provide the use of the above-mentioned organic long afterglow material in expressing Morse code.

[0009] The purpose of the present invention is achieved through the following technical solutions.

[0010] A method for preparing an organic long afterglow material with circular polarization characteristics, comprising: uniformly mixing a host material and a guest material to obtain a solid powder, heating and melting the solid powder, and naturally cooling it to room temperature to precipitate white crystals as the organic long afterglow material, wherein, in terms of the amount of the substance, the ratio of the guest material to the host material is (3-5): (100-1000), and the guest material is Ring a and ring b, together with the two ring-forming carbon atoms to which they are bonded, form a ring structure having three or more atoms, wherein the atoms of ring a and ring b are carbon atoms, nitrogen atoms, silicon atoms, oxygen atoms and / or sulfur atoms, R1=NH2, OH, CN, P-Ph2, -OCH2-CH=CH2 or CH=CH(C6H5); R2=NH2, OH, CN, P-Ph2, OCH3 or CH=CH(C6H5);

[0011] The main material is Wherein, X1=H, NH2, OH, -CH3 or -COOH.

[0012] In the above technical solution, the guest material is of R configuration or S configuration.

[0013] In the above technical solution, the heating and melting temperature is 50-100° C., and the heating and melting time is 3-5 minutes.

[0014] In the above technical solution, the structures of R1 and R2 are the same.

[0015] A method for preparing a thin film comprises: mixing an organic long afterglow material, a polymer and dichloromethane, stirring at room temperature for at least 5 minutes to obtain a slurry, coating the slurry on a substrate, heating at T°C for 3 to 5 minutes, and naturally cooling to room temperature to obtain a thin film on the substrate, wherein T is greater than or equal to the glass transition temperature of the polymer, T=100 to 200, the polymer is PVP, PMMA, PVA, PAM, polylactic acid, poly-L-lactic acid, poly-D-lactic acid, poly-L-lysine or poly-D-lysine, and the ratio of the organic long afterglow material to the polymer is 1:(2 to 10) by mass.

[0016] In the above technical solution, the coating method is screen printing or drip coating.

[0017] In the above technical solution, the substrate is a glass sheet or paper.

[0018] In the above technical solution, in terms of mass fraction, the ratio of the mass fraction of the organic long afterglow material to the volume fraction of the dichloromethane is 1:(20-100), the unit of the mass fraction is g, and the unit of the volume fraction is mL.

[0019] The application of the above organic long afterglow material in expressing Morse code.

[0020] In the above technical solution, the method of expressing Morse code using organic long afterglow materials includes:

[0021] The meaning to be expressed is converted into Morse code, and the dot (.) and dash (-) in the Morse code are respectively assigned the meanings of the R configuration and the S configuration, thereby obtaining a specific arrangement order of the R configuration and the S configuration of the meaning to be expressed;

[0022] A thin film is prepared using an organic long afterglow material, and a thin film using an R-configuration guest material and a thin film using an S-configuration guest material are arranged in a specific arrangement order;

[0023] When translating Morse code, the specific arrangement order of the R configuration and the S configuration is determined by testing the circularly polarized luminescence spectrum of the film, thereby obtaining the order of the dot (.) and the dash (-).

[0024] The beneficial effects of the present invention are as follows:

[0025] 1. The organic long afterglow material of the present invention has good afterglow luminescence performance in a water and oxygen environment at room temperature, and its long afterglow performance is better than that of organic long afterglow materials. The afterglow time of most existing organic long afterglow materials is less than 2s, and must be in anhydrous and oxygen-free conditions. The afterglow time of the organic long afterglow material of the present invention can reach 5s under water and oxygen and room temperature conditions, and after being enhanced by polymers, the afterglow time can reach 10s. The improvement of time and mild and non-harsh conditions will be very beneficial to the application of organic crystalline LPL materials in various scenarios.

[0026] 2. When organic long afterglow materials are used for information encryption and anti-counterfeiting, the multi-dimensional encryption and anti-counterfeiting of afterglow, circularly polarized light and temperature response greatly improves the level of information security. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 (a) Optical microscope of the organic long afterglow material obtained in Example 1-R (from left to right: when excited, 2 seconds after turning off the UV lamp, and 5 seconds after turning off the UV lamp), (b) Macroscopic LPL image of the film prepared from the organic long afterglow material in Example 1-R at room temperature (from left to right: when excited, 4 seconds after turning off the UV lamp, and 10 seconds after turning off the UV lamp);

[0028] Figure 2 (a) XRD of the organic long afterglow material obtained in Example 1-R, (b) XRD of a thin film prepared from the organic long afterglow material in Example 1-R;

[0029] Figure 3 (a) Afterglow performance attenuation spectrum of the organic long afterglow material obtained in Example 1-R, (b) Afterglow performance attenuation spectrum of the film prepared from the organic long afterglow material in Example 1-R;

[0030] Figure 4(a) UV absorption and (b) circular dichroism (CD) spectra of the guest materials of R configuration (R-NA) and S configuration (S-NA) in Example 1;

[0031] Figure 5 (a) UV absorption and (b) circular dichroism spectra of films prepared from the organic long afterglow materials of Example 1-R (R-vP) and Example 1-S (S-vP) in Example 1;

[0032] Figure 6 (a) fluorescence and phosphorescence spectra of a film prepared from the organic long afterglow material of Example 1-R and (b) circularly polarized luminescence spectra (CPL) of films prepared from the organic long afterglow materials of Example 1-R (R-vPVP) and Example 1-S (S-vPVP) in Example 1;

[0033] Figure 7 (a) the afterglow performance attenuation spectrum of the organic long afterglow material of Example 2-R in Example 2 and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material of Example 2-R in Example 2;

[0034] Figure 8 Circular dichroism spectra (CD) of films prepared from the organic long afterglow materials of Example 2-R (R-vP) and Example 2-S (S-vP) in Example 2;

[0035] Fig. 9 Circularly polarized luminescence spectra (CPL) of films prepared from the organic long afterglow materials of Example 2-R (R-vP) and Example 2-S (S-vP) in Example 2;

[0036] Fig.10 (a) the afterglow performance attenuation spectrum of Example 3-R organic long afterglow material in Example 3 and (b) the afterglow performance attenuation spectrum of a film prepared from Example 3-R organic long afterglow material in Example 3;

[0037] Fig.11 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 4-R of Example 4 and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 4-R of Example 4;

[0038] Fig.12 (a) Optical microscope of the organic long afterglow material obtained in Example 5-R (from left to right: when excited, 1 second after turning off the UV lamp, and 5 seconds after turning off the UV lamp) and (b) Macroscopic LPL images of the film prepared from the organic long afterglow material in Example 5-R under room temperature conditions (from left to right: when excited, 4 seconds after turning off the UV lamp, and 10 seconds after turning off the UV lamp);

[0039] Fig.13 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 5-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 5-R;

[0040] Fig.14 Circular dichroism spectra (CD) of films prepared from the organic long afterglow materials of Example 5-R (R-vP) and Example 5-S (S-vP) in Example 5;

[0041] Fig.15 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 6-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 6-R;

[0042] Fig.16 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 7-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 7-R;

[0043] Fig.17 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 8-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 8-R;

[0044] Fig.18 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 9-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 9-R;

[0045] Fig.19 Circular dichroism spectra of films prepared from the organic long afterglow materials of Example 9-R (R-vP) and Example 9-S (S-vP) in Example 9;

[0046] Fig. 20 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 10-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 10-R;

[0047] Fig.21 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 11-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 11-R;

[0048] Fig. 22 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 12-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 12-R;

[0049] Fig.23(a) an optical microscope of the organic long afterglow material obtained in Example 13-R (from left to right: when excited, 1 second after the UV lamp is turned off, and 5 seconds after the UV lamp is turned off) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 13-R under room temperature conditions (from left to right: when excited, 2 seconds after the UV lamp is turned off, and 10 seconds after the UV lamp is turned off);

[0050] Fig.24 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 13-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 13-R;

[0051] Fig.25 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 14-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 14-R;

[0052] Fig.26 (a) an optical microscope of the organic long afterglow material obtained in Example 15-R (from left to right: when excited, 1 second after the UV lamp is turned off, and 4 seconds after the UV lamp is turned off) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 15-R under room temperature conditions (from left to right: when excited, 2 seconds after the UV lamp is turned off, and 10 seconds after the UV lamp is turned off);

[0053] Fig. 27 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 16-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 16-R;

[0054] Fig.28 Circular dichroism spectra of films prepared from the organic long afterglow materials of Example 17-R (R-vP) and Example 17-S (S-vP) in Example 17;

[0055] Fig.29 Circular dichroism spectra of films prepared from the organic long afterglow materials of Example 18-R (R-vP) and Example 18-S (S-vP) in Example 18;

[0056] Fig.30 (a) an optical microscope of the organic long afterglow material obtained in Example 19-R (from left to right: when excited, 2 seconds after turning off the UV lamp, and 5 seconds after turning off the UV lamp) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 19-R under room temperature conditions (from left to right: when excited, 3 seconds after turning off the UV lamp, and 10 seconds after turning off the UV lamp);

[0057] Fig.31(a) XRD of the organic long afterglow material obtained in Example 19-R and (b) XRD of a film prepared from the organic long afterglow material in Example 19-R;

[0058] Fig.32 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 19-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 19-R;

[0059] Fig.33 (a) UV absorption and (b) circular dichroism spectra of the guest materials in Example 19-R (R-) and Example 19-S (S-) in Example 19;

[0060] Fig.34 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 20-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 20-R;

[0061] Fig.35 Circular dichroism spectra of films prepared from the organic long afterglow materials of Example 20-R (R-vP) and Example 20-S (S-vP) in Example 20;

[0062] Fig.36 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 21-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 21-R;

[0063] Fig.37 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 22-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 22-R;

[0064] Fig.38 (a) an optical microscope of the organic long afterglow material obtained in Example 23-R (from left to right: upon excitation, 1 second after turning off the UV lamp, and 4 seconds after turning off the UV lamp) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 23-R under room temperature conditions (from left to right: upon excitation, 4 seconds after turning off the UV lamp, and 9 seconds after turning off the UV lamp);

[0065] Fig.39 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 23-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 23-R;

[0066] Fig.40is the circular dichroism spectra of the films prepared from the organic long afterglow materials of Example 23-(R-vP)R and Example 23-S(S-vP) in Example 23;

[0067] Fig.41 (a) an optical microscope of the organic long afterglow material obtained in Example 24-R (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 2 seconds after the UV lamp is turned off) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 24-R under room temperature conditions (from left to right: upon excitation, 4 seconds after the UV lamp is turned off, and 8 seconds after the UV lamp is turned off);

[0068] Fig.42 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 25-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 25-R;

[0069] Fig.43 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 26-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 26-R;

[0070] Fig.44 (a) an optical microscope of the organic long afterglow material obtained in Example 27-R (from left to right: when excited, 1 second after the UV lamp is turned off, and 3 seconds after the UV lamp is turned off) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 27-R under room temperature conditions (from left to right: when excited, 2 seconds after the UV lamp is turned off, and 9 seconds after the UV lamp is turned off);

[0071] Fig.45 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 28-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 28-R;

[0072] Fig.46 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 29-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 29-R;

[0073] Fig.47 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 30-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 30-R;

[0074] Fig.48(a) an optical microscope of the organic long afterglow material obtained in Example 31-R (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 4 seconds after the UV lamp is turned off) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 31-R under room temperature conditions (from left to right: upon excitation, 4 seconds after the UV lamp is turned off, and 10 seconds after the UV lamp is turned off);

[0075] Fig.49 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 32-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 32-R;

[0076] Fig.50 (a) an optical microscope of the organic long afterglow material obtained in Example 33-R (from left to right: upon excitation, 1 second after the UV lamp is turned off, and 3 seconds after the UV lamp is turned off) and (b) a macroscopic LPL image of a film prepared from the organic long afterglow material in Example 33-R under room temperature conditions (from left to right: upon excitation, 2 seconds after the UV lamp is turned off, and 8 seconds after the UV lamp is turned off);

[0077] Fig.51 (a) the afterglow performance attenuation spectrum of the organic long afterglow material in Example 34-R and (b) the afterglow performance attenuation spectrum of a film prepared from the organic long afterglow material in Example 34-R;

[0078] Fig.52 is the circular dichroism spectra of the films prepared from the organic long afterglow materials of Example 35-R (R-) and Example 35-S (S-) in Example 35;

[0079] Fig.53 This is a rendering of information encryption of the three letters "TJU" by the slurry prepared from the organic long afterglow materials in Example 1-R and Example 1-S through a screen printing coating method;

[0080] Fig.54 Circularly polarized luminescence spectra (CPL) of thin films prepared by screen printing coating method using slurries prepared from organic long afterglow materials in Example 1-R (R-) and Example 1-S (S-) in Example 1;

[0081] Fig.55 This is an anti-counterfeiting effect diagram of the "Phoenix" pattern using a screen printing coating method using the slurry prepared from the organic long afterglow materials in Example 1-R and Example 1-S in Example 1. DETAILED DESCRIPTION

[0082] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0083] The sources of the drugs involved in the following embodiments are as follows:

[0084] The object material was purchased from Tianjin Xiens Biochemical Technology Co., Ltd. (purity: 98%);

[0085] The main material was purchased from Tianjin Xiens Biochemical Technology Co., Ltd. (purity: 98%);

[0086] The polymer was purchased from Tianjin Xiens Biochemical Technology Co., Ltd. (purity: 98%);

[0087]

[0088]

[0089] The instruments and models involved in the following embodiments are as follows:

[0090] Leica DM2700M functional optical microscope;

[0091] Ocean Optics multi-band spectrometer;

[0092] Circular polarization spectrometer (JASCO CPL-300);

[0093] Circular dichroism spectrometer (JASCO J-810).

[0094] Room temperature: 20~25℃.

[0095] Screen printing: The screen used is 200 mesh. The thickness of the film formed after screen printing is 0.3mm.

[0096] Examples 1 to 18

[0097] A method for preparing an organic long afterglow material with circular polarization characteristics, comprising: uniformly mixing a host material and a guest material to obtain a solid powder, placing the solid powder on a heating plate and heating it at 100° C. for 3 minutes to melt it, naturally cooling it to room temperature, and precipitating white crystals as the organic long afterglow material, wherein the ratio of the guest material to the host material is 5:1000 in terms of the amount of the substance, wherein the guest material is an R configuration or an S configuration, as shown in Table 1 for details.

[0098] A method for preparing a thin film, comprising: mixing an organic long afterglow material, a polymer and dichloromethane, stirring for 5 minutes at room temperature to obtain a slurry, preparing glass as a substrate, dripping the slurry on the glass substrate by a drop coating method, heating at T℃ for 5 minutes, and naturally cooling to room temperature to obtain a thin film on the substrate, wherein the ratio of the organic long afterglow material to the polymer is 1:2 by mass, the ratio of the mass fraction of the organic long afterglow material to the volume fraction of dichloromethane is 1:20, the unit of mass fraction is g, and the unit of volume fraction is mL. The polymer is PVP, PMMA, PVA, PAM, poly-L-lactic acid, poly-D-lactic acid, poly-L-lysine or poly-D-lysine, and the polymer, guest material, host material and T are shown in Table 1.

[0099] Table 1

[0100]

[0101]

[0102]

[0103] The composition of the organic long afterglow material obtained by the present invention is that the main material forms regular flaky crystals, and the guest material is uniformly and freely dispersed in the flaky crystals of the main material. After the rigid polymer is introduced, a film with relatively uniform luminescence and circular polarization characteristics can be obtained.

[0104] Depend on Figure 1 It can be seen from a that regular rectangular crystals can be clearly seen under an optical microscope, and the size is relatively uniform. The crystals are square flakes and the size of a single crystal is about 20 μm, proving that the organic long afterglow material obtained in Example 1 is indeed a crystalline structure. The white crystals are excited with a 365nm ultraviolet lamp, and the ultraviolet lamp is turned off after irradiation for 3 seconds, and the crystals can still maintain afterglow for 5 seconds; Figure 1 Figure b is a macroscopic LPL picture of a film made of the organic long afterglow material obtained in Example 1 at room temperature. The film is excited by a 365nm ultraviolet lamp, and the ultraviolet lamp is turned off after irradiation for 3 seconds. The film can maintain the afterglow for 10 seconds. It can be seen that the obtained film emits light more evenly, indicating that the organic long afterglow material introduced into the polymer in the present invention enhances the luminescence performance of the long afterglow material. Among them, the performance of the organic long afterglow materials and films obtained in Example 1-R and Example 1-S are completely consistent.

[0105] Figure 2 a is the XRD of the organic long afterglow material with circular polarization characteristics obtained in Example 1. It can be seen from the figure that the organic long afterglow material has obvious and sharp peaks, indicating that it has good crystallization properties. Figure 2It can be seen from b that after the rigid polymer is introduced into the film, the crystallinity decreases, and the performance of the organic long afterglow material and film obtained in Example 1-R and Example 1-S is completely consistent.

[0106] Depend on Figure 3 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Figure 3 It can be seen from b that -2s to 0s is the time when the film prepared by the organic long afterglow material in Example 1 is irradiated with a 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; 0s to 10s is the time when the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s, which is similar to the afterglow time observed by the naked eye. Among them, the performance of the organic long afterglow materials and films obtained in Example 1-R and Example 1-S are completely consistent.

[0107] Figure 4 The (a) UV absorption and (b) circular dichroism spectra of the R-configuration and S-configuration guest materials in Example 1 are shown in FIG. Figure 4 From a, we can see that both guest materials have UV absorption at 249, 280, and 345 nm. Figure 4 From b, it can be seen that at the three ultraviolet absorption locations, the two configurations of the guest materials have circular dichroism signals, indicating that the two guest materials selected in Example 1 are chiral enantiomers in the ground state.

[0108] Depend on Figure 5 It can be seen from a that the film prepared by the organic long afterglow material in Example 1 has ultraviolet absorption at 247, 274, and 352 nm. Figure 5 From b, we can see that at the three UV absorption locations, circular dichroism signals appear in both films of the two configurations.

[0109] Depend on Figure 6 From a, it can be seen that the fluorescence emission wavelength of the film is 404nm, and the phosphorescence emission wavelength of the film is 516nm and 538nm (the fluorescence and phosphorescence spectra of the films obtained in Example 1-R and Example 1-S are completely consistent). Figure 6 From b, we can see that at the maximum wavelength of phosphorescence emission, a symmetrical circularly polarized phosphorescence mirror signal can be seen, indicating that after 365nm excitation, the excited state still has chirality.

[0110] Depend on Figure 7From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Figure 7 From b, it can be seen that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 2-R and Example 2-S is completely consistent.

[0111] Depend on Figure 8 The symmetrical mirror CD signals of the two configurations of Example 2-R and Example 2-S indicate that the R-configuration and S-configuration guest materials selected in Example 2 are chiral enantiomers in the ground state.

[0112] Fig. 9 This is the circular polarization spectrum of the film under excitation at a wavelength of 365nm. The symmetrical CPL mirror signal indicates that after 365nm excitation, the excited state still has chirality.

[0113] Depend on Fig.10 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.10 From b, it can be seen that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 3-R and Example 3-S is completely consistent.

[0114] Depend on Fig.11 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 6s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 6s, which is similar to the afterglow time observed by the naked eye. Fig.10 From b, it can be seen that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 4-R and Example 4-S is completely consistent.

[0115] from Fig.12The regular square crystals can be clearly seen in the optical microscope of a, and the size is relatively uniform, which proves that the organic long afterglow material obtained in Example 5 is indeed a crystalline structure. The crystals are square flakes and the size of a single crystal is about 20μm. The white crystals are excited by a 365nm ultraviolet lamp. After irradiation for 3 seconds, the excitation light source is turned off, and the crystals can still maintain afterglow for 5s; Fig.12 As can be seen from b, when the film is excited by a 365nm ultraviolet lamp for 3 seconds and then the excitation light source is turned off, the film can maintain afterglow for 10 seconds, indicating that the introduction of the rigid polymer enhances the luminescence performance of the organic long afterglow material, and the film emits light more uniformly. The performance of the organic long afterglow material and the film obtained in Example 5-R and Example 5-S are completely consistent.

[0116] Depend on Fig.13 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.13 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s, which is similar to the afterglow time observed by the naked eye. The performance of the organic long afterglow materials and films obtained in Example 5-R and Example 5-S are completely consistent.

[0117] Depend on Fig.14 The symmetrical mirror CD signals of the two configurations of Example 5-R and Example 5-S indicate that the two configurations of the guest materials of Example 5-R and Example 5-S selected in Example 5 are chiral enantiomers in the ground state.

[0118] Depend on Fig.15 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.15 From b, it can be seen that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 6-R and Example 6-S is completely consistent.

[0119] Depend on Fig.16From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.15 From b, it can be seen that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 7-R and Example 7-S is completely consistent.

[0120] Depend on Fig.17 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.16 From b, it can be seen that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 8-R and Example 8-S is completely consistent.

[0121] Depend on Fig.18 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.17 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 9-R and Example 9-S are completely consistent.

[0122] Depend on Fig.19 The symmetrical mirror CD signals indicate that the two guest materials selected in Example 9 are chiral enantiomers in the ground state.

[0123] Depend on Fig. 20 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig. 20 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 10-R and Example 10-S are completely consistent.

[0124] Depend on Fig.21 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 6s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 6s, which is similar to the afterglow time observed by the naked eye. Fig.21 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 11-R and Example 11-S is completely consistent.

[0125] Depend on Fig. 22 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig. 22 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 8s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 8s. The performance of the organic long afterglow material and film obtained in Example 12-R and Example 12-S are completely consistent.

[0126] Depend on Fig.23 From a, it can be seen that regular rectangular crystals can be clearly seen from an optical microscope, and the size is relatively uniform, proving that the organic long afterglow material obtained in Example 13 is indeed a crystal structure, the crystal is in a square plate shape, and the size of a single crystal is about 15 μm. The white crystal is excited by a 365nm ultraviolet lamp. After irradiation for 3 seconds, the excitation light source is turned off, and the crystal can still maintain afterglow for 5 seconds; Fig.23 It can be seen from b that when the film is excited by a 365nm ultraviolet lamp, the film emits light more evenly. After irradiation for 3 seconds, the ultraviolet lamp is turned off and the film can maintain the afterglow for 10 seconds, indicating that the introduction of the polymer enhances the luminescence performance of the organic long afterglow material. The performance of the organic long afterglow material and film obtained in Example 13-R and Example 13-S are completely consistent.

[0127] Depend on Fig.24From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 6s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 6s, which is similar to the afterglow time observed by the naked eye. Fig.24 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 13-R and Example 13-S are completely consistent.

[0128] Depend on Fig.25 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 6s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 6s, which is similar to the afterglow time observed by the naked eye. Fig.25 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 14-R and Example 14-S are completely consistent.

[0129] Depend on Fig.26 From a, it can be seen that regular rectangular crystals can be clearly seen from an optical microscope, and the size is relatively uniform, proving that the organic long afterglow material obtained in Example 15 is indeed a crystalline structure. The crystals are square flakes and the size of a single crystal is about 20 μm. The white crystals are excited by a 365nm ultraviolet lamp for 3 seconds, and then the excitation light source is turned off, and the crystals can still maintain afterglow for 4 seconds. Fig.23 As can be seen from b, the film is excited by a 365nm ultraviolet lamp, and it can be seen that the obtained film emits light more evenly. After irradiation for 3 seconds, the ultraviolet lamp is turned off, and the film can maintain afterglow for 10 seconds, indicating that the introduction of rigid polymer enhances the luminescence performance of the organic long afterglow material, and the performance of the organic long afterglow material and film obtained in Example 15-R and Example 15-S is completely consistent.

[0130] Depend on Fig. 27 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig. 27It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. The performance of the organic long afterglow material and film obtained in Example 16-R and Example 16-S is completely consistent.

[0131] Depend on Fig.28 The symmetrical mirror CD signals indicate that the two configurations of films obtained in Example 17 are chiral enantiomeric films.

[0132] Depend on Fig.29 The symmetrical mirror CD signals indicate that the two configurations of films obtained in Example 18 are chiral enantiomeric films.

[0133] Embodiments 19 to 35

[0134] A method for preparing an organic long afterglow material with circular polarization characteristics, comprising: uniformly mixing a host material and a guest material to obtain a solid powder, placing the solid powder on a heating plate and heating it at 100° C. for 3 minutes to melt it, naturally cooling it to room temperature, and precipitating white crystals as the organic long afterglow material, wherein the ratio of the guest material to the host material is 3:1000 in terms of the amount of the substance, wherein the guest material is of R configuration or S configuration, as shown in Table 2 for details.

[0135] A method for preparing a thin film, comprising: mixing an organic long afterglow material, a polymer and dichloromethane, stirring for 5 minutes at room temperature to obtain a slurry, preparing a glass substrate, coating the slurry on the substrate by a drop coating method, heating at T℃ for 5 minutes, and naturally cooling to room temperature to obtain a thin film on the substrate, wherein the ratio of the organic long afterglow material to the polymer is 1:2 by mass, the ratio of the mass fraction of the organic long afterglow material to the volume fraction of dichloromethane is 1:20, the unit of mass fraction is g, and the unit of volume fraction is mL. The polymer is PVP, PMMA, PVA or PAM, and the polymer, guest material, host material and T are detailed in Table 2.

[0136] Table 2

[0137]

[0138]

[0139]

[0140]

[0141] Depend on Fig.30From a, we can see that the square crystals can be clearly seen from the optical microscope, and the size is relatively uniform, which proves that the organic long afterglow material obtained in Example 19 is indeed a crystalline structure. The crystals are square or flaky, and the size of a single crystal is about 20μm. The white crystals are excited by a 365nm ultraviolet lamp. After irradiation for 3 seconds, the ultraviolet lamp is turned off, and the crystals can still maintain afterglow for 5s. Fig.30 It can be seen from b that when the film is excited by a 365nm ultraviolet lamp, the film emits light more evenly. After irradiation for 3 seconds, the excitation light source is turned off and the film can maintain afterglow for 10 seconds, indicating that the introduction of rigid polymer enhances the RTP performance of the long afterglow material. Among them, the performance of the organic long afterglow material and film obtained in Example 19-R and Example 19-S is completely consistent.

[0142] Fig.31 a is the XRD of the organic long afterglow material obtained in Example 19. As can be seen from the figure, the organic long afterglow material has obvious and sharp peaks, indicating that it has good crystallization properties. Fig.31 It can be seen from b that after the introduction of the rigid polymer, the XRD crystallinity of the film decreases, among which, the performance of the organic long afterglow material and film obtained in Example 19-R and Example 19-S is completely consistent.

[0143] Depend on Fig.32 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.32 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s, which is similar to the afterglow time observed by the naked eye. Among them, the performance of the organic long afterglow materials and films obtained in Example 19-R and Example 19-S are completely consistent.

[0144] Depend on Fig.33 It can be seen from a that the guest materials of Example 19-R and Example 19-S have ultraviolet absorption at 245, 275, and 352 nm. Fig.33 From b, it can be seen that at the three ultraviolet absorption locations, the two configurations of the guest materials have circular dichroism signals, indicating that the two guest materials selected in Example 19 are chiral enantiomers in the ground state.

[0145] Depend on Fig.34From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 4s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 4s, which is similar to the afterglow time observed by the naked eye. Fig.34 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 9s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 9s. Among them, the performance of the organic long afterglow material and film obtained in Example 20-R and Example 20-S is completely consistent.

[0146] Depend on Fig.35 It can be seen that the films prepared from the two configurations of guest materials both show circular dichroism signals, indicating that the films still have chirality.

[0147] Depend on Fig.36 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 2s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye. Fig.36 It can be seen from b that from -2s to 0s, the film is irradiated with 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 9s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 9s. Among them, the performance of the organic long afterglow material and film obtained in Example 21-R and Example 21-S is completely consistent.

[0148] Depend on Fig.37 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 2s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye. Fig.37 It can be seen from b that from -2s to 0s, the film is irradiated with 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 7s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 7s. Among them, the performance of the organic long afterglow material and film obtained in Example 22-R and Example 22-S is completely consistent.

[0149] from Fig.38 It can be seen from a that after 3 seconds of irradiation with a 365nm ultraviolet lamp to excite the white crystal, the excitation light source is turned off, and the crystal can still maintain afterglow for 4 seconds. The organic long afterglow material obtained in Example 23 emits light more uniformly. Fig.38It can be seen from b that when the film is excited by a 365nm ultraviolet lamp, the film can emit relatively uniform light. After irradiation for 3 seconds, the excitation light source is turned off and the polymer film can maintain afterglow for 9s, indicating that the introduction of rigid polymers enhances the luminescence performance of the long afterglow material. Among them, the performance of the organic long afterglow materials and films obtained in Example 23-R and Example 23-S are completely consistent.

[0150] Depend on Fig.39 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 4s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 4s, which is similar to the afterglow time observed by the naked eye. Fig.39 From b, we can see that from -2s to 0s, the film was irradiated by 365nm ultraviolet light, and the film exhibited photoluminescence characteristics; from 0s to 9s, the film exhibited green long afterglow light after the ultraviolet light was removed, and the afterglow time was about 9s, which is similar to the afterglow time observed by the naked eye.

[0151] Depend on Fig.40 It can be seen that the films prepared from the two configurations of guest materials in Example 23-R and Example 23-S both have circular dichroism signals, indicating that the doped films still have chirality. Among them, the performance of the organic long afterglow materials and films obtained in Example 23-R and Example 23-S are completely consistent.

[0152] Depend on Fig.41 From a, we can see that when a 365nm ultraviolet lamp is used to excite a white crystal for 3 seconds, the excitation light source is turned off, and the crystal can still maintain an afterglow for 2 seconds. The organic long afterglow material emits light more evenly. Fig.41 As shown in b, the film can maintain afterglow for 8s after 365nm ultraviolet light excites the film for 3 seconds and then the excitation light source is turned off, indicating that the introduction of the rigid polymer enhances the luminescence performance of the organic long afterglow material. It can be seen that the obtained film emits light more uniformly, and the performance of the organic long afterglow material and film obtained in Example 24-R and Example 24-S is completely consistent.

[0153] Depend on Fig.42 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 3s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 3s, which is similar to the afterglow time observed by the naked eye. Fig.42It can be seen from b that from -2s to 0s, the film is irradiated with 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 9s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 9s. Among them, the performance of the organic long afterglow material and film obtained in Example 25-R and Example 25-S is completely consistent.

[0154] Depend on Fig.43 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 2s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye. Fig.43 It can be seen from b that from -2s to 0s, the film is irradiated with 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 9s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 9s. Among them, the performance of the organic long afterglow material and film obtained in Example 26-R and Example 26-S is completely consistent.

[0155] Depend on Fig.44 From a, it can be seen that the square crystals can be clearly seen from the optical microscope, and the size is relatively uniform, proving that the organic long afterglow material obtained in Example 25 is indeed a crystalline structure. The crystals are square or flaky, and the size of a single crystal is about 20 μm. The white crystals are excited by a 365nm ultraviolet lamp for 3 seconds, and then the excitation light source is turned off, and the crystals can still maintain afterglow for 3 seconds. Fig.44 It can be seen from b that when the film is excited by a 365nm ultraviolet lamp for 3 seconds and then the excitation light source is turned off, the film can maintain afterglow for 9s, indicating that the introduction of the rigid polymer enhances the luminescence performance of the organic long afterglow material and the film emits light more uniformly. Among them, the performance of the organic long afterglow material and the film obtained in Example 27-R and Example 27-S are completely consistent.

[0156] Depend on Fig.45 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 1s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 1s, which is similar to the afterglow time observed by the naked eye. Fig.45 It can be seen from b that from -2s to 0s, the film is irradiated with 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 6s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 6s. Among them, the performance of the organic long afterglow material and film obtained in Example 28-R and Example 28-S is completely consistent.

[0157] Depend on Fig.46From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 6s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 6s, which is similar to the afterglow time observed by the naked eye. Fig.46 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 10s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 10s. Among them, the performance of the organic long afterglow material and film obtained in Example 29-R and Example 29-S is completely consistent.

[0158] Depend on Fig.47 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 5s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 5s, which is similar to the afterglow time observed by the naked eye. Fig.47 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 8s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 8s. Among them, the performance of the organic long afterglow material and film obtained in Example 30-R and Example 30-S is completely consistent.

[0159] Depend on Fig.48 From a, we can see that when a 365nm ultraviolet lamp is used to excite a white crystal for 3 seconds, the excitation light source is turned off and the crystal can still maintain an afterglow for 4 seconds. The organic long afterglow material emits light more evenly. Fig.48 From b, it can be seen that when the film is excited by a 365nm ultraviolet lamp for 3 seconds and then the excitation light source is turned off, the polymer film can maintain afterglow for 10 seconds, indicating that the introduction of the rigid polymer enhances the luminescence performance of the organic long afterglow material, and the film emits light more uniformly. Among them, the performance of the organic long afterglow materials and films obtained in Example 31-R and Example 31-S are completely consistent.

[0160] Depend on Fig.49 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 2s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye. Fig.49It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 9s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 9s. Among them, the performance of the organic long afterglow material and film obtained in Example 32-R and Example 32-S is completely consistent.

[0161] Depend on Fig.50 From a, we can see that the square crystals can be clearly seen from the optical microscope, and the size is relatively uniform, which proves that the organic long afterglow material obtained in Example 33 is indeed a crystalline structure. The crystals are square or flaky, and the size of a single crystal is about 15μm. The white crystals are excited by a 365nm ultraviolet lamp for 3 seconds, and then the excitation light source is turned off, and the crystals can still maintain afterglow for 3s. Fig.50 As shown in b, the film can maintain afterglow for 8s after 365nm ultraviolet light excites the film for 3 seconds and then the excitation light source is turned off, indicating that the introduction of the rigid polymer enhances the luminescence performance of the organic long afterglow material. The film emits light more evenly, and the performance of the organic long afterglow material and film obtained in Example 33-R and Example 33-S is completely consistent.

[0162] Depend on Fig.51 From a, we can know that -2s to 0s is when the 365nm UV lamp irradiates the organic long afterglow material, and the organic long afterglow material exhibits photoluminescence characteristics; 0s to 2s is when the UV lamp is removed and the organic long afterglow material exhibits green long afterglow light, and the afterglow time is about 2s, which is similar to the afterglow time observed by the naked eye. Fig.51 It can be seen from b that from -2s to 0s, the film is irradiated by 365nm ultraviolet lamp, and the film exhibits photoluminescence characteristics; from 0s to 9s, the film exhibits green long afterglow light after the ultraviolet lamp is removed, and the afterglow time is about 9s. The performance of the organic long afterglow material and film obtained in Example 34-R and Example 34-S are completely consistent.

[0163] Depend on Fig.52 The symmetrical mirror CD signals indicate that the two configurations of films obtained in Example 35 are chiral enantiomeric films.

[0164] The method of expressing Morse code using organic long afterglow materials comprises the following steps:

[0165] The meaning to be expressed is converted into Morse code, and the dot (.) and dash (-) in the Morse code are respectively assigned the meanings of the R configuration and the S configuration, thereby obtaining a specific arrangement order of the R configuration and the S configuration of the meaning to be expressed;

[0166] A thin film is prepared using an organic long afterglow material, and a thin film using an R-configuration guest material and a thin film using an S-configuration guest material are arranged in a specific arrangement order;

[0167] When translating Morse code, the circularly polarized luminescence spectrum of the film is tested to determine the specific arrangement order of the R configuration and the S configuration, thereby obtaining the order of the dot (.) and dash (-), and then determining the Morse code.

[0168] The following further describes the technical solution for preparing an organic long afterglow material with circular polarization characteristics for use in information encryption and anti-counterfeiting.

[0169] If the meaning to be expressed is "TJU", such as Fig.53 As shown, in Morse code, "_" represents the letter "T", "." "_" "_" "_" represents the letter "J", and "." "." "_" represents the letter "U". "." is given the meaning of "S configuration", and "_" is given the meaning of "R configuration", that is, "TJU" adopts the specific arrangement order of "R configuration, S configuration, R configuration, R configuration, R configuration, S configuration, S configuration, R configuration";

[0170] According to the method in Example 1, the organic long afterglow material in Example 1 is used to print a film with the pattern of "18952022". The guest materials of the film used for the eight numbers "18952022" are R configuration, S configuration, R configuration, R configuration, R configuration, S configuration, S configuration, R configuration. The pattern shows strong blue fluorescence emission under the excitation of 365nm ultraviolet lamp. When the ultraviolet lamp excitation light source is removed, it can be seen that all digital patterns show similar emission colors and afterglow time of up to 10s. Anti-counterfeiting can be achieved through afterglow time.

[0171] From the surface, only excited state luminescence and afterglow after excitation can be seen in the film of the "18952022" pattern. By testing the circularly polarized luminescence spectrum of the "18952022" pattern, the CPL signal of each number in the "18952022" pattern can be determined, and then the specific arrangement order of the film of the R-configured guest material and the film of the S-configured guest material can be determined, thereby determining the order of the dots (.) and dashes (-). That is, the Morse code is hidden by the mirror CPL signals of different numbers, thereby realizing the information encryption of the letters "TJU". The mirror CPL signals of the R-configuration and S-configuration of the guest material in Example 1 are as follows: Fig.54 shown.

[0172] According to the method in Example 1, the organic long afterglow material in Example 1 (the guest material is R configuration or S configuration), the polymer in Example 1 and dichloromethane are mixed and stirred at room temperature for 5 minutes to obtain a slurry. Paper is prepared as a substrate, and the slurry is dripped on the substrate by drop coating to obtain a phoenix pattern. The photo of the pattern is shown in FIG. Fig.55As shown in a, under the excitation of 365nm ultraviolet light, the pattern shows strong blue fluorescence emission. When the ultraviolet excitation light source is removed, it can be seen that the Phoenix patterns of both configurations show similar emission colors and an afterglow time of up to 5s. After the pattern is heated at 110℃ for 5min and cooled naturally to room temperature, under the excitation of 365nm ultraviolet light, the pattern shows strong blue fluorescence emission. When the ultraviolet excitation light source is removed, as shown in a Fig.55 As shown in b, it can be seen that both configurations of Phoenix patterns show similar emission colors and afterglow times of up to 10s. The significant difference in afterglow time before and after heating, and the difference in mirror CPL signals produced by different doping, give the pattern a CPL and LPL anti-counterfeiting dimension that is difficult to replicate. Therefore, there is reason to believe that these organic long afterglow materials with circular polarization characteristics will show great advantages in the fields of information encryption and anti-counterfeiting.

[0173] The present invention is described above by way of example. It should be noted that, without departing from the core of the present invention, any simple deformation, modification or other equivalent replacement that can be made by those skilled in the art without inventive effort falls within the protection scope of the present invention.

Claims

1. A method for preparing an organic long afterglow material with circular polarization characteristics, characterized in that: include: The host material and the guest material are uniformly mixed to obtain a solid powder, the solid powder is heated and melted, and naturally cooled to room temperature, and white crystals are precipitated as an organic long afterglow material, wherein the ratio of the guest material to the host material is (3-5): (100-1000) in terms of the amount of the substance, and the guest material is The main material is Among them, X1=H.

2. The preparation method according to claim 1, characterized in that: The guest material is in R configuration or S configuration.

3. The preparation method according to claim 1, characterized in that: The heating and melting temperature is 100°C.

4. The preparation method according to claim 1, characterized in that: The heating and melting time is 3 to 5 minutes.

5. A method for preparing a thin film, characterized in that: include: The organic long afterglow material, polymer and dichloromethane described in claim 1 are mixed, stirred at room temperature for at least 5 minutes to obtain a slurry, the slurry is coated on a substrate, heated at T℃ for 3 to 5 minutes, and naturally cooled to room temperature to obtain a thin film on the substrate, wherein T is greater than or equal to the glass transition temperature of the polymer, T=100 to 200, the polymer is PVP, PMMA, PVA, PAM, polylactic acid, poly-L-lactic acid, poly-D-lactic acid, poly-L-lysine or poly-D-lysine, and the ratio of the organic long afterglow material to the polymer is 1:(2 to 10) by mass.

6. The method according to claim 5, characterized in that The coating method is screen printing or drop coating.

7. The method according to claim 5, characterized in that The substrate is a glass sheet or paper.

8. The method according to claim 5, characterized in that Calculated by mass fraction, the ratio of the mass fraction of the organic long afterglow material to the volume fraction of the dichloromethane is 1:(20-100), the unit of the mass fraction is g, and the unit of the volume fraction is mL.

9. Use of the organic long afterglow material as claimed in claim 1 in expressing Morse code.

10. The use according to claim 9, characterized in that: Methods for expressing Morse code using organic long afterglow materials include: The meaning to be expressed is converted into Morse code, and the dot and dash in the Morse code are respectively assigned the meanings of the R configuration and the S configuration, thereby obtaining a specific arrangement order of the R configuration and the S configuration of the meaning to be expressed; A thin film is prepared using an organic long afterglow material, and a thin film of an R-configuration guest material and a thin film of an S-configuration guest material are arranged in a specific order; When translating Morse code, the order of dots and dashes is obtained by testing the circularly polarized luminescence spectrum of the film and determining the specific arrangement order of the R configuration and the S configuration.

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