Application of a two-component organic long afterglow luminescent material

Abstract

An application of a two-component organic long afterglow luminescent material, which belongs to the technical field of organic luminescent materials. This type of molecule exhibits strong fluorescence and high fluorescence quantum yield in solutions of different polarities, and the fluorescence lifetime in the solution reaches nanosecond level; solid molecules also exhibit strong fluorescence and high quantum yield; the material prepared by two-component doping exhibits the characteristics of long afterglow luminescence, the doped material has both TADF and room temperature phosphorescence, and the afterglow duration reaches more than 6 seconds, and the prepared organic long afterglow luminescent material is applied to bio-optical imaging, security anti-counterfeiting or information encryption.

Description

Technical Field

[0001] The invention relates to the field of organic luminescent materials, and in particular to the application of a two-component organic long afterglow luminescent material. Background Art

[0002] Long afterglow luminescence refers to the phenomenon that a material can continue to emit light for a period of time after the excitation light source is turned off. In recent years, optoelectronic functional materials with long-life excited state properties have important applications in basic scientific research, display, data encryption, anti-counterfeiting, and bio-imaging. However, long afterglow materials are still limited to inorganic materials. Due to the harsh processing conditions of inorganic long afterglow materials, the scarcity of material sources, and the biological toxicity of rare earth ions and heavy metals, their further application is limited. Therefore, it is very necessary to develop easily available, high-performance organic long afterglow materials.

[0003] The long-life luminescence of organic long afterglow materials reported so far mainly comes from room temperature phosphorescence, and some comes from thermally activated delayed fluorescence (TADF), or both. Phosphorescence is the luminescence of triplet excitons returning to the ground state through radiative transition, and its luminescence lifetime is above milliseconds; TADF is the conversion of triplet excitons into singlet excitons through reverse intersystem crossing, and then returning to the ground state through radiative transition, and its luminescence lifetime is at microseconds. No matter which type of luminescence, triplet excitons must be used, but in organic molecular systems, due to the existence of spin prohibition, triplet excitons are not easy to form and are easily deactivated by non-radiative transitions. People have developed some effective strategies to stabilize triplet excitons, such as crystal induction, heavy atom effect, hydrogen bonding, self-assembly, host-guest doping, etc.

[0004] Host-guest doping is a common and easy method for preparing two-component afterglow materials, in which the guest molecule emits light, the host molecule is a rigid matrix, there is no covalent bond between the host and the guest, the guest molecule has no afterglow in the single-component molecular solution and solid state, and exhibits afterglow properties after being mixed with the host molecule in a suitable manner. At present, in the host-guest afterglow system, the afterglow mechanism is described as: the rigid matrix inhibits the non-radiative deactivation of the triplet excited state of the guest molecule, causing the triplet excited state of the molecule to return to the ground state and emit phosphorescence. Since the phosphorescence emission rate constant of the pure molecular system is low, the phosphorescence lifetime is inversely proportional to the phosphorescence emission rate constant and can reach the second level. However, there is no rational systematic method for selecting host and guest molecules. The discovery of new and efficient room-temperature afterglow systems is mainly based on continuous attempts and extensive screening, which is the current status of this research field. Summary of the invention

[0005] In order to obtain a two-component organic long afterglow luminescent material with better performance, the present invention first provides a type of multi-resonance small molecule luminescent material, and then selects phenyl benzoate with better crystallization effect as the main material.

[0006] The technology of the present invention is achieved through the following technical solutions:

[0007] Application of a two-component organic long afterglow luminescent material, wherein the luminescent material is applied in bio-optical imaging, security and anti-counterfeiting or information encryption;

[0008] The luminescent material comprises a host and a guest, and the mass content of the guest is 0.01 to 1 wt%;

[0009] The structure of the guest is shown in formula (I):

[0010] ;

[0011] Formula (I);

[0012] Wherein, R1-R4 are each independently one of hydrogen, an alkyl group having 1 to 10 carbon atoms, a cyano group, a C5-C25 phenyl group having at least one substituent or no substituent, or a heteroaryl group;

[0013] The substituent is selected from an alkyl group having 1 to 10 carbon atoms;

[0014] The structure of the main body is shown in formula (II):

[0015] ;

[0016] Formula (II).

[0017] In some specific materials, R1-R4 are independently one of hydrogen, an alkyl group having 1 to 10 carbon atoms, a cyano group, a C5-C15 phenyl group having at least one substituent or having no substituent, or a heteroaryl group;

[0018] The substituent is selected from an alkyl group having 1 to 10 carbon atoms;

[0019] The heteroatom on the heteroaryl group is selected from at least one of O, N, and S.

[0020] In some specific materials, the structure of the guest is selected from:

[0021] .

[0022] A method for preparing an organic long afterglow luminescent material: mixing a compound of formula I, a compound of formula II and an organic solvent, and drying to obtain the organic long afterglow luminescent material.

[0023] Another method for preparing an organic long afterglow luminescent material: dissolving the compound of formula I and the compound of formula II in organic solvents respectively, then mixing them evenly and drying them to obtain the organic long afterglow luminescent material.

[0024] The two-component afterglow material, the compound of formula I and the compound of formula II are completely dissolved in dichloromethane, and the two-component doped solid afterglow material is obtained after natural volatilization.

[0025] The dual-component organic long afterglow multi-resonance small molecule luminescent material having both phosphorescence and delayed fluorescence of the present invention has the following characteristics:

[0026] 1. The molecular system is novel, has a large expansion space and a narrow half-peak width of the spectrum.

[0027] 2. The organic multi-resonance small molecule luminescent material provided by the present invention exhibits strong fluorescence both in solution and in the solid state, has a large quantum yield and can exist stably.

[0028] 3. The organic long afterglow luminescent material provided by the present invention exhibits continuous luminescence for more than several seconds after being irradiated by a 365nm ultraviolet lamp.

[0029] 4. The organic long afterglow luminescent material provided by the present invention has two long-life properties of luminescence: TADF and room temperature phosphorescence.

[0030] 5. The preparation method of the organic afterglow luminescent material provided by the present invention is simple, and the prepared material can be used for anti-counterfeiting and information encryption. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 It is the photophysical property spectrum of afterglow materials prepared by organic multi-resonance small molecule luminescent material pDCz-BP and phenyl benzoate in different doping ratios.

[0032] Among them, (a) is the room temperature steady-state fluorescence spectrum of materials doped with pDCz-BP and phenyl benzoate in different ratios, and (b) is the room temperature transient fluorescence spectrum of materials doped with pDCz-BP and phenyl benzoate in different ratios.

[0033] Figure 2 It is the photophysical property spectrum of afterglow materials prepared by organic multi-resonance small molecule luminescent material pSCz-BP and phenyl benzoate in different doping ratios.

[0034] Among them, (a) is the room temperature steady-state fluorescence spectrum of materials doped with pSCz-BP and phenyl benzoate in different ratios, and (b) is the room temperature transient fluorescence spectrum of materials doped with pSCz-BP and phenyl benzoate in different ratios.

[0035] Figure 3 It is the room temperature transient fluorescence spectrum of the afterglow material prepared by the organic multi-resonance small molecule luminescent material pDCz-BP and phenyl benzoate in different doping ratios.

[0036] Among them, (a) is the room temperature transient fluorescence spectrum of the afterglow material prepared by pDCz-BP and phenyl benzoate at different doping ratios at 415nm, and (b) is the room temperature transient fluorescence spectrum of the afterglow material prepared by pDCz-BP and phenyl benzoate at different doping ratios at 480nm.

[0037] Figure 4 It is the room temperature transient fluorescence spectrum of the afterglow material prepared by the organic multi-resonance small molecule luminescent material pSCz-BP and phenyl benzoate in different doping ratios.

[0038] Among them, (a) is the room temperature transient fluorescence spectrum of the afterglow material prepared by pSCz-BP and phenyl benzoate at different doping ratios at 415nm, and (b) is the room temperature transient fluorescence spectrum of the afterglow material prepared by pSCz-BP and phenyl benzoate at different doping ratios at 480nm.

[0039] Figure 5 It is the temperature-dependent lifetime curve and temperature-dependent phosphorescence spectrum of the organic multi-resonance small molecule luminescent material pDCz-BP and phenyl benzoate at a doping concentration of 0.1% at 80K-280K.

[0040] Among them, (a) is the variable temperature fluorescence lifetime spectrum of the afterglow material prepared when the doping concentration of pDCz-BP and phenyl benzoate is 0.1% at 445nm, and (b) is the variable temperature phosphorescence spectrum of the afterglow material prepared when the doping concentration of pDCz-BP and phenyl benzoate is 0.1% at 80K-280K.

[0041] Figure 6 It is the temperature-dependent lifetime curve and temperature-dependent phosphorescence spectrum of the organic multi-resonance small molecule luminescent material pSCz-BP and phenyl benzoate at a doping concentration of 0.1% at 80K-280K.

[0042] Among them, (a) is the variable temperature fluorescence lifetime spectrum of the afterglow material prepared when the doping concentration of pSCz-BP and phenyl benzoate is 0.1% at 445nm, and (b) is the variable temperature phosphorescence spectrum of the afterglow material prepared when the doping concentration of pSCz-BP and phenyl benzoate is 0.1% at 80K-280K.

[0043] Figure 7 This is the phosphorescence lifetime curve of the organic multi-resonance small molecule luminescent material pDCz-BP and phenyl benzoate at 77K when the doping concentration is 0.1%.

[0044] Among them, (a) is the phosphorescence lifetime spectrum of the afterglow material prepared when the doping concentration of pDCz-BP and phenyl benzoate is 0.1% at 496nm at 77K, and (b) is the variable temperature phosphorescence spectrum of the afterglow material prepared when the doping concentration of pDCz-BP and phenyl benzoate is 0.1% at 528nm at 77K.

[0045] Figure 8 This is the phosphorescence lifetime curve of the organic multi-resonance small molecule luminescent material pSCz-BP and phenyl benzoate at 77K when the doping concentration is 0.1%.

[0046] Among them, (a) is the phosphorescence lifetime spectrum of the afterglow material prepared when the doping concentration of pSCz-BP and phenyl benzoate is 0.1% at 496nm at 77K, and (b) is the variable temperature phosphorescence spectrum of the afterglow material prepared when the doping concentration of pSCz-BP and phenyl benzoate is 0.1% at 530nm at 77K.

[0047] Fig. 9 Afterglow pattern made of the organic multi-resonance small molecule luminescent material pDCz-BP and the doping material with phenyl benzoate at a doping concentration of 0.1%.

[0048] Fig.10 The organic multi-resonance small molecule luminescent material pDCz-BP and phenyl benzoate doping concentration of 0.1% are used for encryption applications.

[0049] Fig.11 The structural formula of the fluorescent molecule 9-phenyl-3,3'-bicarbazole. DETAILED DESCRIPTION

[0050] The present invention will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention.

[0051]

[0052] Example 1: The synthesis steps of the two-component organic long afterglow multi-resonance small molecule luminescent material compound pDCz-BP having both phosphorescence and delayed fluorescence are as follows:

[0053] Step 1: Add raw material 1-1 (5.17 g, 16.18 mmol), 1,4-dibromo-2,3-difluorobenzene (2 g, 7.36 mmol), cesium carbonate (10.55 g, 32.37 mmol) to a 250 ml three-necked flask, add 40 ml N, N-dimethylformamide (DMF), evacuate and replace nitrogen three times, and then stir and react for 12 h at 75 ° C in a nitrogen atmosphere. After cooling, add a large amount of water, filter the product after precipitation, and recrystallize with dichloromethane and methanol to obtain 3.81 g of a white powdery crude product of 2-1 with a yield of 73%.

[0054] Step 2: Add the dried compound 2-1 (3.0 g, 3.45 mmol), palladium acetate (0.26 g, 1.17 mmol), triphenylphosphine (2.62 g, 9.99 mmol), potassium carbonate (4.76 g, 34.46 mmol), benzyltriethylammonium chloride (1.57 g, 6.89 mmol) to a 250 ml three-necked flask, add 50 ml of dimethylacetamide (DMAc), evacuate and replace nitrogen three times, and then stir and react under reflux conditions in a nitrogen atmosphere for 12 hours. After cooling, add a large amount of water to precipitate a dark green solid, then wash with a large amount of ethanol, and then use column chromatography to separate and purify, and then dry to obtain a light yellow powder pDCz-BP, which weighs 1.67 g and has a yield of 68.5%. After recrystallization, a light yellow powder pDCz-BP pure product 1.06 g is obtained, and the yield is 63.5%.

[0055] The NMR spectrum of the compound pDCz-BP is: 1H MMR (400MHz, Chloroform-d) δ8.39 (d, 3H), 8.33 (s, 1H), 8.29 (s, 1H), 8.22 (s, 1H), 8.09 (d, 1H), 7.95 (d, 1H), 7.80 (d, 1H), 7.74-7.62 (m, 11H), 7.50-7.39 (m, 10H), 7.34-7.25 (m, 4H). 13C NMR (400MHz, Chloroform-d) rm-d) δ 145.87, 144.25, 142.44, 139.25, 139.09, 136.82, 132.56, 131.90, 130.22, 130.17, 130.12, 129.71128.77, 128.38, 128.05, 127.91, 127.57, 127.08, 125.26, 123.11, 121.20, 120.90, 120.26, 120.02, 119.41, 114.42, 113.77, MALDI-TOF: found by 710.2717.

[0056] Example 2: The synthesis steps of the dual-component organic long afterglow multi-resonance small molecule luminescent material compound pSCz-BP having both phosphorescence and delayed fluorescence are as follows:

[0057] Step 1: Add raw material 1-2 (4.52g, 16.18mmol), 1,4-dibromo-2,3-difluorobenzene (2g, 7.36mmol), cesium carbonate (10.55g, 32.37mmol) to a 250ml three-necked flask, add 40ml N, N-dimethylformamide (DMF), evacuate and replace nitrogen three times, and then stir and react for 12h at 75°C in a nitrogen atmosphere. After cooling, add a large amount of water, filter after the product is precipitated, and recrystallize with dichloromethane and methanol to obtain 4.55g of a white powdery crude product of 2-2 with a yield of 78.3%.

[0058] Step 2: Add the dried compound 2-2 (3.0 g, 3.79 mmol), palladium acetate (0.29 g, 1.29 mmol), triphenylphosphine (2.89 g, 11.00 mmol), potassium carbonate (5.24 g, 37.94 mmol), benzyltriethylammonium chloride (1.73 g, 7.59 mmol) to a 250 ml three-necked flask, add 50 ml of dimethylacetamide (DMAc), evacuate and replace nitrogen three times, and then stir and react under reflux conditions in a nitrogen atmosphere for 12 h. After cooling, add a large amount of water to precipitate a dark green solid, then wash with a large amount of ethanol, and then use column chromatography to separate and purify, and then dry to obtain a light yellow powder pSCz-BP, which weighs 1.52 g and has a yield of 63.5%. After recrystallization, a light yellow powder pSCz-BP pure product 0.93 was obtained, and the yield was 61.5%.

[0059] The NMR spectrum of the compound pSCz-BP is: 1H MMR (400MHz, Chloroform-d) δ8.22 (s, 1H), 8.17 (s, 2H), 8.12 (s, 2H), 8.07 (s, 1H), 8.02 (d, 1H), 7.84 (d, 1H), 7.64-7.57 (m, 2H), 7.43 (d, 2H), 7.34 (s, 2H), 1.48 (s, 9H), 1.42 (d, 27). 13C NMR (151 MHz, Chloroform-d) δ 147.31, 145.39, 143.85, 142.89, 140.13, 137.88, 137.20, 131.78, 131.45, 130.24, 125.48, 124.46, 123.78, 123.27, 121.85, 120.02, 118.58, 117.62, 117.44, 117.05, 116.39, 112.92, 111.74, 109.33, 366.02, 34.97, 34.78, 32.64, 31.92, 31.76, MALDI-TOF: found by 630.3937.

[0060] Example 3: The synthesis steps of the dual-component organic long afterglow multi-resonance small molecule luminescent material compound 3-3a having both phosphorescence and delayed fluorescence are as follows:

[0061] Step 1: Add raw material 3-1 (6.15g, 16.18mmol), 1,4-dibromo-2,3-difluorobenzene (2g, 7.36mmol), cesium carbonate (10.55g, 32.37mmol) to a 250ml three-necked flask, add 40ml N, N-dimethylformamide (DMF), evacuate and replace nitrogen three times, and then stir and react for 12h at 75°C in a nitrogen atmosphere. After cooling, add a large amount of water, filter the product after precipitation, and recrystallize with dichloromethane and methanol to obtain 5.50g of a white powdery crude product of 3-2 with a yield of 75.5%.

[0062] Step 2: Add the dried compound 3-2 (3.0 g, 3.03 mmol), palladium acetate (0.23 g, 1.13 mmol), triphenylphosphine (2.30 g, 8.78 mmol), potassium carbonate (4.18 g, 30.28 mmol), benzyltriethylammonium chloride (1.38 g, 6.06 mmol) to a 250 ml three-necked flask, add 50 ml of dimethylacetamide (DMAc), evacuate and replace nitrogen three times, and then stir and react under reflux conditions in a nitrogen atmosphere for 12 h. After cooling, add a large amount of water to precipitate a dark green solid, then wash with a large amount of ethanol, and then use column chromatography to separate and purify, and then dry to obtain a light yellow powder 3-3a, which weighs 1.55 g and has a yield of 61.8%.

[0063] Example 4: The synthesis steps of the dual-component organic long afterglow multi-resonance small molecule luminescent material compound 4-3b having both phosphorescence and delayed fluorescence are as follows:

[0064] Step 1: Add raw material 4-1 (6.66g, 16.18mmol), 1,4-dibromo-2,3-difluorobenzene (2g, 7.36mmol), cesium carbonate (10.55g, 32.37mmol) to a 250ml three-necked flask, add 40mlN, N-dimethylformamide (DMF), evacuate and replace nitrogen three times, and then stir and react for 12h at 75°C in a nitrogen atmosphere. After cooling, add a large amount of water, filter the product after precipitation, and recrystallize with dichloromethane and methanol to obtain 4.81g of a white powdery crude product of 4-2 with a yield of 62.0%.

[0065] Step 2: Add the dried compound 4-2 (3.0 g, 2.84 mmol), palladium acetate (0.22 g, 0.97 mmol), triphenylphosphine (2.16 g, 8.25 mmol), potassium carbonate (3.93 g, 28.44 mmol), benzyltriethylammonium chloride (1.29 g, 5.69 mmol) to a 250 ml three-necked flask, add 50 ml of dimethylacetamide (DMAc), evacuate and replace nitrogen three times, and then stir and react under reflux conditions in a nitrogen atmosphere for 12 h. After cooling, add a large amount of water to precipitate a dark green solid, then wash with a large amount of ethanol, and then use column chromatography to separate and purify, and then dry to obtain a light yellow powder 4-3b, which weighs 1.50 g and has a yield of 58.8%.

[0066] Example 5: The synthesis steps of the dual-component organic long afterglow multi-resonance small molecule luminescent material compound 5-3c having both phosphorescence and delayed fluorescence are as follows:

[0067] Step 1: Add the raw material 5-1 (5.20g, 16.18mmol), 1,4-dibromo-2,3-difluorobenzene (2g, 7.36mmol), cesium carbonate (10.55g, 32.37mmol) to a 250ml three-necked flask, add 40mlN, N-dimethylformamide (DMF), evacuate and replace nitrogen three times, and then stir and react for 12h at 75°C in a nitrogen atmosphere. After cooling, add a large amount of water, filter the product after precipitation, and recrystallize with dichloromethane and methanol to obtain 5.08g of a white powdery crude product of 5-2, with a yield of 79.0%.

[0068] Step 2: Add the dried compound 5-2 (3.0 g, 3.43 mmol), palladium acetate (0.22 g, 0.97 mmol), triphenylphosphine (2.61 g, 9.95 mmol), potassium carbonate (4.74 g, 34.30 mmol), benzyltriethylammonium chloride (1.56 g, 6.86 mmol) to a 250 ml three-necked flask, add 50 ml of dimethylacetamide (DMAc), evacuate and replace nitrogen three times, and then stir and react under reflux conditions in a nitrogen atmosphere for 12 h. After cooling, add a large amount of water to precipitate a dark green solid, then wash with a large amount of ethanol, and then use column chromatography to separate and purify, and then dry to obtain a light yellow powder 5-3c, which weighs 1.22 g and has a yield of 49.7%.

[0069] Example 6: The synthesis steps of the dual-component organic long afterglow multi-resonance small molecule luminescent material compound 6-3d having both phosphorescence and delayed fluorescence are as follows:

[0070] Step 1: Add the raw material 6-1 (8.05g, 16.18mmol), 1,4-dibromo-2,3-difluorobenzene (2g, 7.36mmol), cesium carbonate (10.55g, 32.37mmol) to a 250ml three-necked flask, then add 40mlN, N-dimethylformamide (DMF), evacuate and replace nitrogen three times, then stir and react for 12h at 75°C in a nitrogen atmosphere. After cooling, add a large amount of water, filter the product after precipitation, and recrystallize with dichloromethane and methanol to obtain 5.22g of a white powdery crude product of 6-2 with a yield of 57.8%.

[0071] Step 2: Add the dried compound 6-2 (3.0 g, 2.44 mmol), palladium acetate (0.19 g, 0.83 mmol), triphenylphosphine (1.86 g, 7.09 mmol), potassium carbonate (3.38 g, 24.45 mmol), benzyltriethylammonium chloride (1.11 g, 4.89 mmol) to a 250 ml three-necked flask, add 50 ml of dimethylacetamide (DMAc), evacuate and replace nitrogen three times, and then stir and react under reflux conditions in a nitrogen atmosphere for 12 h. After cooling, add a large amount of water to precipitate a dark green solid, then wash with a large amount of ethanol, then use column chromatography to separate and purify, and then dry to obtain a light yellow powder 6-3d, which weighs 1.72 g and has a yield of 65.8%.

[0072] Example 7: Performance testing test:

[0073] 1. Photophysical property test of afterglow material prepared from multi-resonance small molecule material pDCz-BP and phenyl benzoate:

[0074] Prepare a 10mg / mL dichloromethane solution of phenyl benzoate, prepare a 100mg / mL dichloromethane solution of pDCz-BP, take appropriate amounts of the two solutions, mix the two solutions, evaporate naturally, and after the dichloromethane evaporates to dryness, obtain the pDCz-BP two-component long afterglow luminescent material, and prepare two-component long afterglow luminescent materials with pDCz-BP mass contents of 0.01, 0.1, and 1wt% respectively: pDCz-BP-PhB-0.01%, pDCz-BP-PhB-0.1%, and pDCz-BP-PhB-1%. At room temperature, under 365nm ultraviolet light, the material emits blue light, and the afterglow color is blue, such as Figure 1 The fluorescence peak shown in (a) is 443nm. Figure 1 The peak of the afterglow luminescence shown in (b) is 480nm, and its luminescence lifetime is 166ms, 307ms, and 149ms respectively. Through the temperature change test, the results are as follows Figure 5 As shown, the two-component afterglow material has both thermally activated delayed fluorescence and room temperature phosphorescence luminescence properties.

[0075] 2. Photophysical property test of afterglow material prepared from multi-resonance small molecule material pSCz-BP and phenyl benzoate:

[0076] Prepare a 10 mg / mL dichloromethane solution of phenyl benzoate, prepare a 100 mg / mL dichloromethane solution of pSCz-BP, take an appropriate amount of the two solutions, mix the two solutions, evaporate naturally, and after the dichloromethane evaporates to dryness, obtain the pSCz-BP two-component long afterglow luminescent material, and prepare two-component long afterglow luminescent materials with pSCz-BP mass contents of 0.01, 0.1, and 1 wt% respectively: pSCz-BP-PhB-0.01%, pSCz-BP-PhB-0.1%, and pSCz-BP-PhB-1%. At room temperature, under 365nm ultraviolet light, the material emits blue light, and the afterglow color is blue, such as Figure 2 The fluorescence peak shown in (a) is 443nm. Figure 2 The peak value of the afterglow luminescence shown in (b) is 530nm, and the luminescence lifetimes are 264ms, 255ms, and 155ms respectively. The results of the temperature change test are as follows Figure 6 As shown, the two-component afterglow material has both thermally activated delayed fluorescence and room temperature phosphorescence luminescence properties.

[0077] 3. The room temperature transient fluorescence spectra of the afterglow materials with pDCz-BP and phenyl benzoate doping ratios of 0.01%, 0.1% and 1% at 415nm and 480nm were tested. Figure 3 As shown in (a) and (b), the lifetime of the afterglow material with a doping ratio of 0.01% at 415nm is 58ms, the lifetime of the afterglow material with a doping ratio of 0.1% at 415nm is 42ms, and the lifetime of the afterglow material with a doping ratio of 1% at 415nm is 25ms. The lifetime of the afterglow material with a doping ratio of 0.01% at 480nm is 264ms, the lifetime of the afterglow material with a doping ratio of 0.1% at 480nm is 255ms, and the lifetime of the afterglow material with a doping ratio of 1% at 480nm is 155ms.

[0078] 4. The room temperature transient fluorescence spectra of the afterglow materials with pSCz-BP and phenyl benzoate doping ratios of 0.01%, 0.1% and 1% at 415nm and 480nm were tested. Figure 4As shown in (a) and (b), the lifetime of the afterglow material with a doping ratio of 0.01% at 415nm is 45ms, the lifetime of the afterglow material with a doping ratio of 0.1% at 415nm is 35ms, and the lifetime of the afterglow material with a doping ratio of 1% at 415nm is 37ms. The lifetime of the afterglow material with a doping ratio of 0.01% at 480nm is 264ms, the lifetime of the afterglow material with a doping ratio of 0.1% at 480nm is 255ms, and the lifetime of the afterglow material with a doping ratio of 1% at 480nm is 155ms.

[0079] 5. The phosphorescence lifetime of the multi-resonance small molecule material pDCz-BP and phenyl benzoate doping concentration of 0.1wt% at 77K was tested. Figure 7 As shown, the phosphorescence lifetime at 496nm is as long as 2.49s, and the phosphorescence lifetime at 528nm is as long as 2.93s.

[0080] 6. The phosphorescence lifetime of the multi-resonance small molecule material pSCz-BP and phenyl benzoate doping concentration of 0.1wt% at 77K was tested. Figure 8 As shown, the phosphorescence lifetime at 496nm is as long as 2.48s, and the phosphorescence lifetime at 528nm is as long as 2.66s.

[0081] 7. Since the melting point of the organic matrix PhB is relatively low (60°C), the doped material can be easily processed into the desired shape of the afterglow object by melting and casting. The organic multi-resonance small molecule luminescent material pDCz-BP and phenyl benzoate are made into a mixed material with a doping concentration of 0.1%, and then the mixed material is heated and melted. The obtained afterglow melt is sandwiched between quartz plates and cooled to room temperature to form an afterglow film. Through the pre-designed mask for 365nm ultraviolet excitation, a specific afterglow pattern can be obtained and the afterglow duration can reach more than 6 seconds, such as Fig. 9 As shown, it shows potential application in the field of anti-counterfeiting.

[0082] 8. Considering that the organic multi-resonance small molecule luminescent material pDCz-BP and the doping material of phenyl benzoate with a doping concentration of 0.1% have ultra-long-life phosphorescence emission, it can be used for information encryption. The organic multi-resonance small molecule luminescent material pDCz-BP and phenyl benzoate are made into a mixed material with a doping concentration of 0.1%, and then the mixed material is heated and melted, and drop-coated to form a "2024" pattern. Through simple screening, we selected 9-phenyl-3,3'-bicarbazole molecules as auxiliary fluorescent bodies. The structure of 9-phenyl-3,3'-bicarbazole is as follows Fig.11 As shown, the 9-phenyl-3,3'-bicarbazole molecules are heated and melted and then dripped onto the remaining part of the pattern "8888". Fig.10As shown in the figure, the pattern "8888" is the encrypted information. When irradiated with 365 nm ultraviolet light, the pattern appears as "8888" with no difference in blue light, successfully achieving information encryption. When the ultraviolet light source is removed in a dark environment, the pattern appears as "2024" with blue light, successfully achieving information decryption.

[0083] Although the present invention is disclosed as above, the protection scope of the present invention is not limited thereto. Those skilled in the art may make various changes and modifications without departing from the spirit and scope of the present invention, and these changes and modifications will fall within the protection scope of the present invention.

Claims

1. An application of a two-component organic long afterglow luminescent material, characterized in that: The luminescent material is used in bio-optical imaging, security and anti-counterfeiting, or information encryption for purposes other than disease diagnosis and treatment; The luminescent material is composed of a host and a guest, and the mass percentage of the guest is 0.01% to 1%; The structure of the guest is shown in formula (I): ； Formula (I); Wherein, R1-R4 are each independently one of hydrogen, an alkyl group having 1 to 10 carbon atoms, a cyano group, and a phenyl group having at least one substituent or having no substituent; The substituent is selected from an alkyl group having 1 to 10 carbon atoms; The structure of the main body is shown in formula (II): ； Formula (II).

2. The use of a two-component organic long afterglow luminescent material according to claim 1, characterized in that: The structure of the object is selected from: 。

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