LONG-AFTERGLOW LUMINESCENT MATERIAL

Abstract

Disclosed is a long-afterglow luminescent material, comprising A) at least one light-absorbing agent, B) at least one luminescent agent, and C) at least one photochemical cache agent. The light-absorbing agent and the luminescent agent are compounds having different structures, and the cache agent is selected from one or more compounds of formula (I), (II) and/or (III).

##STR00001##

The material has luminescent intensity reaching the level of commercialized inorganic long-afterglow powder SrAl.sub.2O.sub.4:Eu.sup.2+, Dy.sup.3+, and can emit light when the exciting light is turned off with a light emitting time up to 100 ms to 3600 s.

Claims

1. A long-afterglow luminescent material, comprising A) at least one light-absorbing agent, B) at least one luminescent agent, and C) at least one photochemical cache agent; wherein, the light-absorbing agent and the luminescent agent are compounds having different structures, and the cache agent is selected from one or more compounds of formula (I), (II) and/or (III): ##STR00089## wherein ##STR00090## part forms a divalent aromatic ring or a heteroaromatic ring having 5 to 24, preferably 6 to 14 ring carbon atoms, wherein one or more ring carbon atoms other than carbon atoms in a C═C bond connected with R.sub.x and R.sub.y may be replaced by a heteroatom selected from N, S, Se or O, and the aromatic ring or the heteroaromatic ring optionally has one or more substituents L, R.sub.x and R.sub.y are mutually independently selected from H, hydroxyl, carboxyl, amino, mercapto, ester groups, nitro, sulfo, halogen, acylamino, or alkyl having 1 to 50, preferably 1 to 24, for example 2 to 14 carbon atoms, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, aryl, aralkyl, heteroaryl with N, O, or S or heteroaryl alkyl, or a combination thereof, wherein aryl, aralkyl, heteroaryl or heteroaryl alkyl optionally has one or more substituents L; or R.sub.x and R.sub.y together form alkylene or alkenylene having 2 to 20, preferably 3 to 15 C atoms, and optionally having one or more substituents L; and L is selected from hydroxyl, carboxyl, amino, mercapto, ester groups, nitro, sulfo, halogen, acylamino, or alkyl having 1 to 50, preferably 1 to 24, for example 2 to 14 or 6 to 12 carbon atoms, alkenyl, alkynyl, alkoxy, alkylamino, or a combination thereof. ##STR00091## wherein ##STR00092## part represents phenyl substituted or unsubstituted by one or more L or represents a heterocyclic ring formed by replacing one or more ring carbon atoms other than carbon atoms connected with groups R.sub.c′ and R.sub.d′ in a five-membered or six-membered olefinic unsaturated carbocyclic ring with N, S, Se, or O, wherein the heterocyclic ring is only allowed to be condensed with at most one phenyl substituted or unsubstituted by one or more L and may be substituted by one or more groups L or one or more aryl or heteroaryl having 4 to 24, preferably 5 to 14, more preferably 6 to 10 ring carbon atoms, R.sub.c′ and R.sub.d′ each independently has a definition given for R.sub.x and R.sub.y in formula (I), but not together form a divalent group, and at least one of R.sub.c′ and R.sub.d′ is aryl or heteroaryl; and L is as defined in formula (I); a premise is that when the ##STR00093## part is phenyl substituted or unsubstituted by one or more L, then the groups R.sub.c′ and R.sub.d′ together form a divalent group —C(═O)—NH—NH—C(═O)—, optionally substituted by L.
Ar—CR.sub.a═CR.sub.bR.sub.c   (III) wherein Ar represents aryl or heteroaryl having 5 to 24, preferably 6 to 14 ring carbon atoms, wherein one or more ring carbon atoms may be replaced by heteroatoms selected from N, S, Se or O, preferably phenyl, and aryl or heteroaryl optionally has one or more substituents L; R.sub.a, R.sub.b and R.sub.c each independently have the definition given for R.sub.x and R.sub.y in formula (I), provided that at most one of R.sub.a, R.sub.b and R.sub.c is H; and L is as defined in formula (I).

2. The long-afterglow luminescent material according to claim 1, wherein in formula (I): ##STR00094## part is an acridine ring or an anthracene ring substituted or unsubstituted by the group L; R.sub.x and R.sub.y are mutually independently selected from alkyl having 1 to 18, preferably 2 to 12 carbon atoms, alkoxy, alkylthio (alkyl-S—), alkylamino or aryl, or preferably together form alkylene having 2 to 20, preferably 3 to 15 C atoms, and optionally having one or more substituents L, or a combination thereof; and more preferably, the groups R.sub.x and R.sub.y are mutually independently selected from alkyl having 1 to 8 carbon atoms, alkoxy, alkylthio, sulfo alkoxy, sulfo alkylthio, phenyl or alkylene having 3 to 12 C atoms, such as adamantylene; L is selected from hydroxyl, sulfo, linear or branched alkyl having 1 to 12, more preferably 1 to 6 carbon atoms, alkoxy, alkylamino, amino, or a combination thereof; and aryl is preferably phenyl, biphenyl or naphthyl substituted or unsubstituted by L, and more preferably phenyl or naphthyl.

3. The long-afterglow luminescent material according to claim 1, wherein in formula (II): ##STR00095## part is a thiophene ring, a phenylthiophene ring, a benzene ring, a naphthalene ring, ##STR00096## substituted or unsubstituted by one or more groups L, or a combination thereof; R.sub.c′ and R.sub.d′ are each independently selected from alkyl having 1 to 18, preferably 1 to 12 carbon atoms, alkoxy, alkylamino or aryl, or a combination thereof, wherein aryl may be substituted by one or more groups L and preferably is phenyl or naphthyl substituted or unsubstituted by L; or R.sub.c′ and R.sub.d′ together form —CO—NH—NH—CO— groups; and/or L is selected from hydroxyl, sulfo, halogen, nitro, linear or branched alkyl having 1 to 12, more preferably 1 to 6 carbon atoms, alkoxy, alkylamino, amino, or a combination thereof.

4. The long-afterglow luminescent material according to claim 1, wherein in formula (III): R.sub.a, R.sub.b and R.sub.c are each independently and preferably selected from H, hydroxyl, linear or branched alkyl having 1 to 18, preferably 1 to 12 carbon atoms, alkoxy, alkylamino or aryl such as phenyl, or a combination thereof; preferably, R.sub.b and R.sub.c together form alkylene having 2 to 20, preferably 3 to 15 C atoms, such as adamantylene; L is selected from hydroxyl, sulfo, C1-C6 alkyl ester vinyl (C.sub.1-6alkyl-O—C(═O)—C═C—), linear or branched alkyl having 1 to 12, more preferably 1 to 6 carbon atoms, alkoxy, alkylamino, or a combination thereof; and/or aryl is preferably phenyl or naphthyl substituted or unsubstituted by L.

5. The long-afterglow luminescent material according to claim 1, wherein the photochemical cache agent is selected from one or more of phenylthiophene compounds of the following formula (IV), a compound of the following formula (V), acridine compounds of the following formula (VI), a compound of the following formula (VII), a compound of the following formula (VIII), luminol compounds of the following formula (IX), phenylimidazole compounds of the following formula (X), and derivatives of these compounds: ##STR00097## wherein G and T are a single bond, C or heteroatoms selected from O, S, Se and N, provided that G and T are not single bond or C at the same time; groups R.sub.1-11 represent H, hydroxyl, carboxyl, amino, mercapto, ester, nitro, sulfo, halogen, acylamino, or alkyl having 1 to 50, preferably 1 to 24, for example 2 to 14 carbon atoms, alkenyl, alkynyl, alkoxy, alkylthio, alkylamino, aryl, aralkyl, heteroaryl with N, O, or S or heteroaryl alkyl, or a combination thereof, wherein aryl, aralkyl, heteroaryl or heteroaryl alkyl optionally have one or more substituents L; and L is selected from hydroxyl, carboxyl, amino, mercapto, ester, nitro, sulfo, halogen, acylamino, or alkyl having 1 to 50, preferably 1 to 24, for example 2 to 14 or 6 to 12 carbon atoms, alkenyl, alkynyl, alkoxy and alkylamino.

6. The long-afterglow luminescent material according to claim 1, wherein the photochemical cache agent is a non-polymeric compound, and its molecular weight is preferably less than 2000, more preferably less than 1000.

7. The long-afterglow luminescent material according to claim 1, wherein a molar ratio of the light-absorbing agent to the luminescent agent is within a range of 1:1.1 to 1:10000, preferably 1:10 to 1:8000 or 1:50 to 1:6000, more preferably 1:100 to 1:4000 or 1:200 to 1:2000.

8. The long-afterglow luminescent material according to claim 1, wherein the light-absorbing agent and the luminescent agent are respectively at least one compound of different types selected from the following list: polymethine cyanine dyes, porphyrin and phthalocyanine dyes and complexes thereof, methylene blue compounds, phycoerythrin, hypocrellin, benzophenone compounds, metal-organic frameworks (MOFs), quantum dots (QDs), graphene, carbon nanotubes, titanium dioxide semiconductors, iridium complexes, rare-earth complexes, polyfluorene compounds, coumarin compounds, naphthalimide compounds, triacene and higher acene compounds, rhodamine compounds, fluorescein compounds, dipyrromethene boron difluoride compounds (BODIPY), resorufin compounds, pyrazoline compounds, triphenylamine compounds, carbazole compounds, green fluorescent protein, Bimane compounds, perovskite compounds, TADF compounds, and derivatives and copolymers of these compounds.

9. The long-afterglow luminescent material according to claim 1, wherein the light-absorbing agent is selected from polymethine cyanine dyes, porphyrin and phthalocyanine dyes and complexes thereof, methylene blue compounds, phycoerythrin, hypocrellin, benzophenone compounds, metal-organic frameworks (MOFs), quantum dots (QDs), graphene, carbon nanotubes, titanium dioxide semiconductors, and derivatives and copolymers of these compounds.

10. The long-afterglow luminescent material according to claim 1, wherein the light-absorbing agent is selected from: iridium complexes, rare-earth complexes, polyfluorene compounds, coumarin compounds, naphthalimide compounds, triacene or higher acene compounds, rhodamine compounds, fluorescein compounds, dipyrromethene boron difluoride compounds (BODIPY), resorufin compounds, pyrazoline compounds, triphenylamine compounds, carbazole compounds, green fluorescent protein, Bimane compounds, perovskite compounds, TADF compounds, and derivatives and copolymers of these compounds.

11. The long-afterglow luminescent material according to claim 1, wherein the photochemical cache agent is selected from one or more of the following: ##STR00098## ##STR00099## ##STR00100##

12. The long-afterglow luminescent material according to claim 1, wherein the long-afterglow material further comprises a photochemical storage agent component D), selected from fullerene as shown in the following formula (XI) or surface-modified fullerene compounds, polyene oligomers, compounds shown in following formulae (XII-1) to (XII-8) and derivatives of the compounds: ##STR00101## ##STR00102## In above structures, each substituent R, for example, R′ and R.sub.1-11, represents H, hydroxyl, carboxyl, amino, mercapto, ester, an aldehyde group, nitro, sulfo, halogen, or alkyl having 1 to 50 carbon atoms, alkenyl, alkynyl, aryl, alkoxy, alkylamino. Preferably, the R groups are selected from alkane, olefin, alkyne, aryl, methoxy, ethoxy, dimethylamino, diethylamino, methyl, ethyl, propyl, butyl, tert-butyl, phenyl, or a combination thereof. z represents an integer greater than 1.

13. The long-afterglow luminescent material according to claim 11, wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C) and optionally D), is 0.1% to 80%, preferably 0.3% to 60%, more preferably 0.5% to 40%, most preferably 1% to 20%.

14. The long-afterglow luminescent material according to claim 1, wherein the long-afterglow material further comprises a carrier medium component E) for dissolving, dispersing or adsorbing the components A) to C), preferably selected from an organic solvent, an aqueous phase solvent, a polymeric dispersion medium, a protein, phospholipid liposomes, and adsorptive particles.

15. The long-afterglow luminescent material according to claim 1, existing in states or forms of crystal, nanoparticle, powder, film, block, metal-organic framework, composite, organic solvent system, ionic liquid, aqueous solution, aerosol dust, and gel sol.

16. The long-afterglow luminescent material according to claim 1, comprising, by weight based on a material mixture, no more than 0.1%, preferably no more than 0.01%, more preferably no more than 0.001% or 0.0001% of rare-earth-doped inorganic luminescent nanoparticles, and most preferably not comprising the rare-earth-doped inorganic luminescent nanoparticles.

17. A method of using the long-afterglow luminescent material according to claim 1, as a light source, luminescent technology and fluorescence control platform, being used for up-conversion luminescence, biological imaging, surgical navigation, homogeneous detection, lateral chromatography, catalytic synthesis, photochemical reaction, plant research, single particle tracing, luminescent probes, indication, display, anti-counterfeiting, information encryption, information storage, quantum teleportation, ultra-micro ranging and photochemical invisibility, etc., wherein the mixture is prepared into states or forms of crystal, nanoparticle, powder, film, block, metal-organic framework, composite, organic solvent system, ionic liquid, aqueous solution, aerosol dust, and gel sol.

18. A method for preparing the long-afterglow material according to claim 1, comprising: (1) providing components A) to C) and an optional D), and (2) mixing the components A) to C) and the optional D) or mixing them with the carrier medium component E) for dissolving, dispersing or adsorbing the components A) to C) to obtain a mixture.

19. The method according to claim 18, wherein the mixture is prepared into states or forms of crystal, nanoparticle, powder, film, block, metal-organic framework, composite, organic solvent system, ionic liquid, aqueous solution, aerosol dust, and gel sol.

Description

DESCRIPTION OF THE DRAWINGS

[0152] FIG. 1 is a schematic diagram of a photochemical long-afterglow luminescent material according to the present invention.

[0153] FIG. 2 is a luminescent picture of a long-afterglow material, which is taken in the dark after excitation light is turned off. The left side is a material of Example 1 of the present invention, and the right side is a commercialized inorganic long-afterglow powder SrAl.sub.2O.sub.4 :Eu.sup.2+, Dy.sup.3+ material.

[0154] FIG. 3 is a luminescent decay curve of a long-afterglow material of Example 1.

[0155] FIG. 4 is a transmission electron microscope of a long-afterglow luminescent nanomaterial of Example 15.

[0156] FIG. 5 is a luminescent spectrogram of a long-afterglow material of Example 16.

EXAMPLE

[0157] 1. Performance Test Method

[0158] In a long-afterglow luminescent test of the present invention, professional instruments and equipment in the field were used. A wavelength tunable laser (Opolette 355) from Opotek, Inc., USA was used as excitation light source, and the power density of excitation light was maintained at 100 mW cm.sup.−2. Excitation light of a specific wavelength was used to irradiate a sample for charging, and the irradiating and charging time was 3 s. After charging, the laser was turned off, and the luminescent performance test was initiated. A fluorescence spectrometer (Edinburgh FLS-920) from Edinburgh Instruments was used to test the long-afterglow luminescent intensity, and the temperature was kept at a room temperature of 25 degrees Celsius. A long-afterglow test system (OPT-2003) of Beijing Aobodi Photoelectricity Technology Co., Ltd. was used to test the long-afterglow luminescent time.

[0159] The phrase “visible to the naked eye” used in the invention is a professional term in the field of long-afterglow luminescent materials, which means that the luminescent brightness of the material is greater than or equal to 0.32 mcd m.sup.−2 (the unit mcd refers to millicandela), and visible light is usually visible to the naked eye when being at the radiation level of this brightness or above. The phrase “luminescent time” used in the invention is a professional term in the field of the long-afterglow luminescent materials, which means the time elapsed before the luminescent brightness of the material decays to a level visible to the naked eye. The phrase “blue long-afterglow luminescence” used in the invention is the expression of the long-afterglow luminescent color of the material, which means that there is obvious long-afterglow luminescence generated in a blue wavelength interval; and similarly, the description is also accordingly applicable to other colors used in the invention. In actual situations, due to differences in observation methods or influence from individual differences, there may be errors in observation results such as luminescent color or luminescent time.

[0160] 2. List of Raw Materials Used

TABLE-US-00001 Component Compound name or number Source or structure A PdPc [00057] A PtTPBP [00058] A Hemin [00059] A PdOEP [00060] A Methylene blue (MB-1) [00061] A PbS quantum dots (PbS) Suzhou Xingshuo Nanotech Co., Ltd. A Graphene Quantum Dots Jiangsu XFNano Material Tech. Co., Ltd. (GQDs) B Iridium complex (Ir-1) [00062] B Terbium complex (Tb-1) [00063] B Europium complex (Eu-1) [00064] B Iridium complex (Ir-2) [00065] B BDP-1 [00066] B BDP-2 [00067] B BDP-3 [00068] B Rhodamine B (RhB) [00069] B Perylene [00070] B Silicon Rhodamine (Rh-1) [00071] C Acridin-1 [00072] C Acridin-2 [00073] C Luminol compound (Luminol- 1) [00074] C Luminol compound (Luminol- 2) [00075] C EA-1 [00076] C EA-2 [00077] C OA-1 [00078] C OA-2 [00079] C BT-1 [00080] C BT-2 [00081] C CA-1 [00082] C CA-2 [00083] C CA-3 [00084] C CA-4 [00085] C PN-1 [00086] C MEHPPV used in W02019/027370A1 [00087] D PyD-1 [00088]

[0161] 3. Preparation of Long-Afterglow Material Compositions

Example 1

[0162] All components of the photochemical long-afterglow material were mixed in a toluene solvent according to the ratio shown in Table 1, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 3 mmol L.sup.−1, and a concentration of a luminescent agent was 1 mmol L.sup.−1. First, 100 mW cm.sup.−2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 1.

Examples 2-4

[0163] The operation of Example 1 was repeated, and the only difference was that all the components and their contents listed in Table 1 below were used.

Comparative Examples 1-6

[0164] The operation of Example 1 was repeated, and the only difference was that all the components and their contents listed in Table 1 below were used.

Comparative Example 7

[0165] All components of the photochemical long-afterglow material were mixed in a toluene solvent according to the ratio as shown in Table 2, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 0 mmol L.sup.−1, and a concentration of a luminescent agent was 1 mmol L.sup.−1. First, 100 mW cm.sup.−2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 2.

Example 5-10

[0166] The operation of Comparative Example 7 was repeated, and the only difference was that all the components and their contents listed in Table 2 below were used.

Comparative Examples 8

[0167] The operation of Comparative Example 7 was repeated, and the only difference was that all the components and their contents listed in Table 2 below were used.

Example 11

[0168] All components of the photochemical long-afterglow material were mixed in a dichloromethane solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.−1, and a concentration of a luminescent agent was 1 mmol L.sup.−1. First, 100 mW cm.sup.−2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain blue long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 12

[0169] The operation of Example 11 was repeated, and the only difference was that all the components and their contents listed in Table 3 below were used.

Example 13

[0170] All components of the photochemical long-afterglow material were mixed in a dichloromethane solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.−1, and a concentration of a luminescent agent was 1 mmol L.sup.−1. Then, dichloromethane therein was removed to obtain long-afterglow powder without a solvent medium. First, 100 mW cm.sup.−2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 14

[0171] All components of the photochemical long-afterglow material were mixed in a toluene solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.−1, and a concentration of a luminescent agent was 1 mmol L.sup.−1. Then, methylene bis(4-cyclohexyl isocyanate) and polyester polyol were added according to a mass ratio of 1:2, and the total volume of the two substances added was equal to the volume of the above toluene solution. A mixed liquor was stirred uniformly, toluene and dissolved bubbles therein were removed, then the mixed liquor was placed in an oven at 60 degrees Celsius to be dried and cured in the dark, and then a colorless and transparent polyurethane film was formed. First, 100 mW cm.sup.−2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 15

[0172] All components of the photochemical long-afterglow material were mixed in a liquid paraffin solvent according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol L.sup.−1, and a concentration of a luminescent agent was 1 mmol L.sup.−1. Subsequently, a ten-fold volume of an aqueous solution containing bovine serum albumin (BSA) was added, wherein the concentration of BSA was 10 mg mL.sup.−1. A mixture was pre-emulsified by using ultrasonic waves (Sonics VC750, Sonics & Materials, Inc) at room temperature for 10 minutes, and then a high-pressure nano homogenizer (FB-110Q, LiTu Mechanical equipment Engineering Co., Ltd) was immediately used to continue emulsification for 20 minutes. An emulsion was heated at 90 degrees Celsius for 1 hour. After the emulsion was cooled to the room temperature, gradient centrifugation and filtration were performed to obtain long-afterglow nanoparticles uniformly dispersed in water. First, 100 mW cm.sup.−2 635 mu light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain blue long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 16-18

[0173] The operation of Example 15 was repeated, and the only difference was that the experimental conditions such as all the components and their contents listed in Table 3 below were used.

Example 19

[0174] The long-afterglow nanoparticles uniformly dispersed in water were prepared according to Example 15. Subsequently, sodium silicate was added to the above aqueous solution, standing was performed for one day under the condition of pH 8.0, and a silicone hydrogel was prepared by hydrolysis of sodium silicate to obtain long-afterglow hydrogel. First, 100 mW cm.sup.−2 730 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 20

[0175] All components of the photochemical long-afterglow material were mixed in deionized water according to the ratio in Table 3, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 1 mmol L.sup.−1, and a concentration of a luminescent agent was 1 mmol L.sup.−1. Then, dichloromethane therein was removed to obtain long-afterglow powder without a solvent medium. First, 100 mW cm.sup.−2 635 rim light was used for irradiating for 3 s to charge. After charging was completed , the laser was turned off to obtain yellow long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 3.

Example 21

[0176] All components of the photochemical long-afterglow material were mixed in a toluene according to the ratio in Table 4, ultrasonic waves were used to assist the dissolution of all the components, and finally a uniform and transparent solution was formed. In the solution, a molar concentration of a photochemical cache agent was 2 mmol and a concentration of a luminescent agent was 2 mmol L.sup.−1. First, 100 mW cm 635 nm light was used for irradiating for 3 s to charge. After charging was completed, the laser was turned off to obtain green long-afterglow luminescence visible to the naked eye. Then, a fluorescence spectrometer and a long-afterglow test system were respectively used to measure the long-afterglow luminescent intensity and luminescent time of the obtained product. The test results were as shown in Table 4.

Examples 22-28

[0177] The operation of Example 21 was repeated, and the only difference was that the experimental conditions such as all the components and their contents listed in Table 4 below were used.

TABLE-US-00002 TABLE 1 Component Ex 1 Ex 2 Ex 3 Ex 4 C1 C2 C3 C4 C5 C6 A PdPc PdPc PdPc PdPc PdPc PdPc PdPc Ir-1 PdPc RhB B Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 MB-1 Perylene C CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 MEHPPV CA-1 CA-1 CA-1 D None None None None None None None None None None E Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene A/B molar ratio 1:500 1:1500 1:5000 1:8000 2:1 1:15000 1:500 — 1:500 1:500 Excitation   730    730    730    730   730 730 730  365   730  532 wavelength (nm) Performance Test Luminescent 305870   98370   29080   17530   130 670 220 3410   330 1260 intensity (a.u.) Luminescent   20.1   15.3   10.5   8.2 n.m. n.m. n.m.   1.6 n.m. n.m. time (s) n.m.: not measurable due to too-low brightness

TABLE-US-00003 TABLE 2 Component C7 Ex 5 Ex 6 Ex 7 Ex 8 Ex 9 C8 Ex 10 A PdPc PdPc PdPc PdPc PdPc PdPc PdPc PdPc B Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 Ir-1 C None CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 CA-1 Molar concentration 0   0.5    1      3      5     10    20      3    of C (mmol L.sup.−1) D None None None None None None None PyD-1 Content of D (%) 0   0      0      0      0     0     0      0.01 E Toluene Toluene Toluene Toluene Toluene Toluene Toluene Toluene A/B molar ratio 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 Performance Test Luminescent intensity 0 57170   121520   306230   237690   92460   5530   273580    (a.u.) Luminescent time (s) n.m.   13.0   15.9   20.1   18.3   14.9   2.9   23.6  n.m.: not measurable due to too-low brightness

TABLE-US-00004 TABLE 3 Component Ex 11 Ex 12 Ex 13 Ex 14 Ex 15 Ex 16 Ex 17 Ex 18 Ex 19 Ex 20 A PdPc PdPc PtTPBP PbS PdPc GQDs PdPc PdPc PdPc MB-1 B BDP-1 RhB Ir-1 Tb-1 Perylene Tb-1 BDP-2 Ir-1 Ir-1 RhB C EA-1 Luminol-1 BT-1 CA-1 Acridin-1 CA-1 OA-1 CA-1 CA-1 CA-2 E Dichloro Ethanol Dichloro Polyurethane Nano Nano Nano Nano Hydrogel water methane methane film protein protein protein protein A/B molar ratio 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 1:500 Excitation  730    730    635     808    730    532    730    730    730    635   wavelength (nm) Performance Test Luminescent Blue Yellow Green Green Blue Green red Blue Green Yellow color Luminescent 12500   9560   21690   102680   37570   73160   6580   56520   43270   3790   intensity (a.u.) Luminescent  186.5   5.9   68.7   15.2   11.1   14.9  260.2   12.8   11.7   2.1 time (s)

TABLE-US-00005 TABLE 4 Component Ex 21 Ex 22 Ex 23 Ex 24 Ex 25 Ex 26 Ex 27 Ex 28 A PdOEP Hemin PtTPBP PtTPBP PtTPBP PtTPBP PtTPBP PtTPBP B BDP-3 Eu-1 Ir-2 Rh-1 Eu-1 Eu-1 Eu-1 Eu-1 C EA-2 Luminol-2 BT-2 CA-3 Acridin-2 CA-4 OA-2 PN-1 E Toluene Ethanol Dichloro- Dichloro- Dichloro- Dichloro- Dichloro- Dichloro- methane methane methane methane methane methane A/B molar ratio 1:400 1:400 1:400 1:400 1:400 1:400 1:400 1:400 Excitation  532    532    635     635     635     635    635     635   wavelength (nm) Performance Test Luminescent Green Red Blue Red Red Red Red Red color Luminescent 13690   52130   32950   218270   273640   480650   7150   102890   intensity (a.u.) Luminescent  320.1   31.6   81.1   18.4   14.5   21.6  351.9   38.4 time (s)