Long-afterglow luminescent material
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). The material has luminescent intensity reaching the level of commercialized inorganic long-afterglow powder SrAl 2 O 4 :Eu 2+ , Dy 3+ , and can emit light when the exciting light is turned off with a light emitting time up to 100 ms to 3600 s.
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,
the light-absorbing agent is at least one compound selected from polymethine cyanine dyes, porphyrin and phthalocyanine dyes and complexes thereof, phycoerythrin, hypocrellin, benzophenone compounds, metal-organic frameworks (MOFs), quantum dots (QDs), and derivatives of these compounds, the luminescent agent is at least one compound selected from iridium complexes, rare-earth complexes, polyfluorene compounds, coumarin compounds, naphthalimide compounds, triacene and higher acene compounds, dipyrromethene boron difluoride compounds (BODIPY), pyrazoline compounds, triphenylamine compounds, carbazole compounds, green fluorescent protein, perovskite luminescent nanomaterials, thermally activated delayed fluorescence (TADF) compounds, and derivatives of these compounds, and the light absorbing agent has a relatively large molar coefficient, the luminescent agent has a relatively high luminescent quantum efficiency, and an absorption peak of the light absorbing agent overlaps an emission peak of the luminescent agent as little as possible;
wherein the cache agent is selected from one or more compounds of formula (II), phenylthiophene compounds of the following formula (IV), luminol compounds of the following formula (IX), phenylimidazole compounds of the following formula (X), and derivatives of these compounds:
wherein
part is a
substituted or unsubstituted by one or more groups L, or a combination thereof;
R c′ and R d′ are each independently aryl, wherein aryl may be substituted by one or more groups L; and
L is selected from hydroxyl, nitro, sulfo, halogen, alkyl having 1 to 50 carbon atoms, alkoxy, alkylamino, or a combination thereof;
wherein
groups R 1-8 represent H, amino, halogen, alkyl having 1 to 50 carbon atoms, alkoxy, alkylamino, aryl, or a combination thereof, wherein aryl optionally has one or more substituents L′; and
L′ is selected from alkyl having 1 to 50 carbon atoms or alkoxy; and
wherein a molar ratio of the light-absorbing agent to the luminescent agent is within a range of 1:1.1 to 1:10000, and
wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C), is 0.1% to 80%.
2. The long-afterglow luminescent material according to claim 1 , wherein the photochemical cache agent is a non-polymeric compound.
3. The long-afterglow luminescent material according to claim 2 , wherein the photochemical cache agent has a molecular weight of less than 2000.
4. The long-afterglow luminescent material according to claim 2 , wherein the photochemical cache agent has a molecular weight of less than 1000.
5. 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 1:10 to 1:8000.
6. The long-afterglow luminescent material according to claim 1 , wherein the photochemical cache agent is selected from one or more of the following:
7. 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), surface-modified fullerene compounds, polyene oligomers, compounds shown in following formulae (XII-1) to (XII-8) and derivatives of the compounds:
wherein in the above structures, each substituent R′ and R 1-11 , represents H, hydroxyl, carboxyl, amino, mercapto, ester, an aldehyde group, nitro, sulfo, halogen, alkyl having 1 to 50 carbon atoms, alkenyl, alkynyl, aryl, alkoxy, or alkylamino, and
wherein z represents an integer greater than 1;
wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C) and D), is 0.1% to 80%.
8. The long-afterglow luminescent material according to claim 7 , wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C) and D), is 0.3% to 60%.
9. The long-afterglow luminescent material according to claim 7 , wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C) and D), is 0.5% to 40%.
10. The long-afterglow luminescent material according to claim 1 , wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C), is 0.3% to 60%.
11. 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).
12. The long-afterglow luminescent material according to claim 11 , 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.
13. The long-afterglow luminescent material according to claim 11 , wherein the carrier medium component E) is selected from an organic solvent, an aqueous phase solvent, a polymeric dispersion medium, a protein, phospholipid liposomes, or adsorptive particles.
14. The long-afterglow luminescent material according to claim 1 , comprising, by weight based on a material mixture, no more than 0.1% of rare-earth-doped inorganic luminescent nanoparticles.
15. The long-afterglow luminescent material according to claim 14 , comprising, by weight based on a material mixture, no more than 0.01% of the rare-earth-doped inorganic luminescent nanoparticles.
16. The long-afterglow luminescent material according to claim 14 , comprising, by weight based on a material mixture, no more than 0.001% of the rare-earth-doped inorganic luminescent nanoparticles.
17. The long-afterglow luminescent material according to claim 14 , comprising no rare-earth-doped inorganic luminescent nanoparticles.
18. The long-afterglow luminescent material according to claim 1 , wherein L in formula (II) is selected from hydroxyl, sulfo, halogen, nitro, linear or branched alkyl having 1 to 12 carbon atoms, alkoxy, alkylamino, or a combination thereof.
19. The long-afterglow luminescent material according to claim 1 , wherein in formula (II)
part is
R c′ and R d′ are each independently selected from phenyl or naphthyl, wherein phenyl or naphthyl may be substituted by one or more groups L; and
L is selected from hydroxyl, sulfo, alkyl having 1 to 12 carbon atoms, alkoxy, alkylamino, or a combination thereof.
20. The long-afterglow luminescent material according to claim 1 , wherein in formula (IV)
R 1 , R 2 , R 4 and R 5 are independently H;
R 3 is alkoxy having 1 to 18 carbon atoms;
R 6 and R 7 are independently alkyl having 1 to 18 carbon atoms; and
R 8 is H or alkyl having 1 to 18 carbon atoms.
21. The long-afterglow luminescent material according to claim 1 , wherein in formula (IX)
R 1 represents H, amino, or alkylamino having 1 to 18 carbon atoms;
R 2 , R 5 and R 6 represent H;
R 3 represents H or alkyl having 1 to 18 carbon atoms; and
R 4 represents H or amino.
22. The long-afterglow luminescent material according to claim 1 , wherein in formula (X)
R 1 represents H;
R 2 represents phenyl;
R 3 represents alkyl having 1 to 18 carbon atoms, alkoxy having 1 to 18 carbon atoms, or alkylamino;
R 4 represents H or amino;
R 5 represents H or alkoxy; and
R 6 , R 7 and R 8 independently represent H or alkyl having 1 to 18 carbon atoms.
23. The long-afterglow luminescent material according to claim 1 , wherein a content of the photochemical cache agent, by total mass of the three components of the components A) to C), is 0.5% to 40%.
24. 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 1:50 to 1:6000.
25. 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 1:100 to 1:4000.
26. A long-afterglow luminescent material, comprising:
at least one light-absorbing agent selected from polymethine cyanine dyes, porphyrin and phthalocyanine dyes and complexes thereof, phycoerythrin, hypocrellin, benzophenone compounds, metal-organic frameworks (MOFs), quantum dots (QDs), and derivatives of these compounds;
at least one luminescent agent selected iridium complexes, rare-earth complexes, polyfluorene compounds, coumarin compounds, naphthalimide compounds, triacene and higher acene compounds, dipyrromethene boron difluoride compounds (BODIPY), pyrazoline compounds, triphenylamine compounds, carbazole compounds, green fluorescent protein, perovskite luminescent nanomaterials, thermally activated delayed fluorescence (TADF) compounds, and derivatives of these compounds; and
at least one photochemical cache agent selected from one of the following compounds:
wherein the light absorbing agent has a relatively large molar coefficient, the luminescent agent has a relatively high luminescent quantum efficiency, and an absorption peak of the light absorbing agent overlaps an emission peak of the luminescent agent as little as possible.
27. The long-afterglow luminescent material of claim 26 , wherein: the light-absorbing agent is selected from one or more of the following compounds:
graphene quantum dots; carbon quantum dots; CdSe quantum dots; and PbS quantum dots; and
the luminescent agent is selected from one of the following compounds: