CN115418217B - Organic red long afterglow material and preparation method and application thereof - Google Patents
Organic red long afterglow material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title abstract description 8
- -1 anthraquinone amine Chemical class 0.000 claims abstract description 18
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000002091 cationic group Chemical group 0.000 claims abstract description 7
- 125000005496 phosphonium group Chemical group 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- VWBVCOPVKXNMMZ-UHFFFAOYSA-N 1,5-diaminoanthracene-9,10-dione Chemical group O=C1C2=C(N)C=CC=C2C(=O)C2=C1C=CC=C2N VWBVCOPVKXNMMZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011819 refractory material Substances 0.000 claims description 6
- ZCJJIQHVZCFSGZ-UHFFFAOYSA-N 2,8-bis(diphenylphosphoryl)dibenzothiophene Chemical compound C=1C=CC=CC=1P(C=1C=C2C3=CC(=CC=C3SC2=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ZCJJIQHVZCFSGZ-UHFFFAOYSA-N 0.000 claims 1
- 230000002688 persistence Effects 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 26
- 238000004020 luminiscence type Methods 0.000 abstract description 18
- 238000000926 separation method Methods 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 12
- RVFWUIFCUQFLFQ-UHFFFAOYSA-N (8-diphenylphosphanyldibenzothiophen-2-yl)-diphenylphosphane Chemical compound C1=CC=CC=C1P(C=1C=C2C3=CC(=CC=C3SC2=CC=1)P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 RVFWUIFCUQFLFQ-UHFFFAOYSA-N 0.000 description 10
- 238000012546 transfer Methods 0.000 description 9
- KVFMUGYRGCXRMZ-UHFFFAOYSA-N CC(N)NC1=CC=CC2=C1C(=O)C3=CC=CC=C3C2=O Chemical compound CC(N)NC1=CC=CC2=C1C(=O)C3=CC=CC=C3C2=O KVFMUGYRGCXRMZ-UHFFFAOYSA-N 0.000 description 8
- 150000005838 radical anions Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 230000001443 photoexcitation Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 150000005839 radical cations Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000012984 biological imaging Methods 0.000 description 3
- 239000007850 fluorescent dye Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910003668 SrAl Inorganic materials 0.000 description 1
- 239000005084 Strontium aluminate Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005524 hole trap Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000005101 luminescent paint Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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- C09K2211/1018—Heterocyclic compounds
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- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
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Abstract
The invention relates to an organic red long afterglow material, a preparation method and application thereof, which comprises a guest molecule containing anthraquinone amine, a host molecule containing cationic quaternary phosphonium free radicals, and a melting of the guest molecule and the host molecule in a mass ratio of 1:100. The organic red long afterglow material has good flexibility and transparency, can generate macroscopic red fluorescence when irradiated under a room temperature ultraviolet lamp, and can generate macroscopic red afterglow luminescence when an excitation light source is turned off; the organic red long afterglow material realizes fluorescent emission and phosphorescent emission at room temperature, and has high concealment.
Description
Technical Field
The invention relates to the technical field of organic long-afterglow materials, in particular to an organic red long-afterglow material, and a preparation method and application thereof.
Background
The long afterglow luminescent material is called long afterglow material Long Persistent Luminescence for short, which is a photoluminescent material. The material is a material which absorbs energy and can continuously emit light after excitation is stopped, and has application prospect. Long afterglow luminescent materials, i.e. materials capable of storing the energy of external light irradiation, slowly releasing these stored energy in the form of visible light at a certain temperature (typically room temperature). The light-emitting principle belongs to photoluminescence, namely, when the light source is excited, the excitation energy is stored in an excitation state, and after the excitation is stopped, the energy is slowly released in a light form. In Matsuzawa et al 1996, a europium (Eu) and dysprosium (Dy) -doped strontium aluminate (SrAl 2O4) system was published, the afterglow decay time can be as long as 10 hours and has very high durability; the rare earth activated aluminate long afterglow material becomes the basis of luminescent paint, is favored by the industry, and is widely applied to the fields of instrument display, optoelectronic devices, night emergency indication, national defense and military and the like. However, the long afterglow materials based on inorganic systems not only need expensive rare elements, but also have high manufacturing temperature of more than 1000 ℃ and high energy consumption. In order to solve these problems, much attention has been focused on long afterglow materials based on organic systems.
At present, the organic molecules exhibit less phosphorescent behavior at room temperature, have low luminous efficiency, cause problems of low phosphorescence intensity and short phosphorescence duration, and are quenched by oxygen in air because triplet excitons are limited by spin coupling.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an organic red long afterglow material, a preparation method and application thereof, wherein the organic red long afterglow material has good flexibility and transparency, can generate macroscopic red fluorescence when irradiated under a room temperature ultraviolet lamp, and can generate macroscopic red afterglow luminescence when an excitation light source is turned off; the organic red long afterglow material realizes fluorescent emission and phosphorescent emission at room temperature, has high concealment, is convenient to use and easy to identify, thereby realizing a higher-level anti-counterfeiting function, and has good application prospects in the fields of organic photoelectric materials, anti-counterfeiting encryption and the like.
The invention is realized by the following technical scheme: an organic red long afterglow material is provided, comprising a guest molecule containing anthraquinone amine and a host molecule containing cationic quaternary phosphonium free radicals, wherein the guest molecule and the host molecule are fused in a mass ratio of 1:100.
Through the technical scheme, the invention is based on a guest molecule containing anthraquinone amine and a host molecule containing cationic quaternary phosphonium free radicals, so that organic long afterglow materials are generated through photoinduction charge transfer, charge separation and charge recombination between the host molecule and the guest molecule; the specific implementation mechanism is that for the AEAQ PPT system, when a trace AEAQ molecule is dispersed and embedded into a PPT structure, a charge separation state AEAQ ·+-(PPT)n-PPT·- is generated by photoinduction of electrons or holes, and the generated PPT ·- can generate electron transfer in a PPT crystal and finally reach a result of high-efficiency separation from AEAQ ·+, so that the charge separation state is generated. The Charge Separation (CS) state is allowed to transition from the charge separation state to AEAQ triplet state due to its energy being higher than the AEAQ triplet energy. Compared with the intersystem crossing process with the ratio of AEAQ from a singlet state to a triplet state being 23%, the charge transfer (ET) process with the ratio of 77% can effectively generate a long-life CS state, the long-life CS state can induce AEAQ triplet state under the condition of water oxygen, and the process can inhibit the exciton quenching phenomenon caused by other molecules such as oxygen of AEAQ, thereby realizing long-life afterglow phenomenon.
The invention defines that the host and guest molecules are melted in a mass ratio of 1:100, and that charge transfer states are formed between the host and guest molecules during photoexcitation. The resulting host molecule radical anion PPT ·- then separates the 1-aminoethylamino-9, 10-anthraquinone (AEAQ) radical cation AEAQ ·+ from the counter radical anion of the host molecule by charge-hopping diffusion between PPT bulk molecules and forms a stable charge-separated state AEAQ ·+-(PPT)n-PPT·-. Finally, the main molecule free radical anions and the 1-amino ethyl amino-9, 10-anthraquinone (AEAQ) free radical cations are gradually compounded, and excitation compound emission is generated, and the compound emission can still last for a long time after the light excitation is stopped; therefore, the obtained organic red long afterglow material can generate macroscopic red fluorescence under the irradiation of an ultraviolet lamp, and the excitation light source is turned off to generate macroscopic red afterglow luminescence.
The specific implementation mechanism is as follows: after ultraviolet light excitation, the guest molecule is changed from a singlet state to a triplet state, and energy is generated and falls back to emit light.
Fluorescence and phosphorescence emission from doped host-guest is primarily from the guest molecule. Guest molecules can absorb energy in the structure of the host to switch from a singlet state to a triplet state by intersystem crossing; the charge separation state energy is higher than the guest molecule triplet state energy, allowing charge transfer from the CS state to the guest triplet state, resulting in long afterglow emission of the system mainly from room temperature phosphorescence of the guest molecule and delayed fluorescence accompanying the charge separation state. The long afterglow luminescence of the doped system comprises two sources of phosphorescence emission band and weak delayed fluorescence of the guest molecule.
Further, preferably, the guest molecule is 1-aminoethylamino-9, 10-anthraquinone (AEAQ), having the specific structural formula as above;
By the above technical scheme, the invention limits that 1-amino ethylamino-9, 10-anthraquinone (AEAQ) and a host molecule are melted in a mass ratio of 1:100, and a charge transfer state is formed between the 1-amino ethylamino-9, 10-anthraquinone (AEAQ) and the host molecule during photoexcitation. Then, the generated radical anions of the host molecule are diffused by charge hopping between the host molecules, separating the 1-aminoethylamino-9, 10-anthraquinone (AEAQ) radical cation from the counter radical anions of the host molecule and forming a stable charge separated state. Finally, the main molecule free radical anions and the 1-amino ethyl amino-9, 10-anthraquinone (AEAQ) free radical cations are gradually compounded, and excitation compound emission is generated, and the compound emission can still last for a long time after the light excitation is stopped; therefore, the obtained organic red long afterglow material can generate macroscopic red fluorescence under the irradiation of an ultraviolet lamp, and the excitation light source is turned off to generate macroscopic red afterglow luminescence.
Further, preferably, the host molecule is 1, 5-diaminoanthraquinone, and the specific structural formula is as follows:
By the technical scheme, the invention limits that the mass ratio of the 1, 5-diaminoanthraquinone to the host molecule is 1:100 to be molten, and a charge transfer state is formed between the 1, 5-diaminoanthraquinone and the host molecule during photoexcitation. Then, the generated radical anions of the host molecule are diffused by charge hopping between the host molecules, separating the 1, 5-diaminoanthraquinone radical cations from the counter radical anions of the host molecule and forming a stable charge separation state. Finally, the main molecule free radical anions and the 1, 5-diaminoanthraquinone free radical cations are gradually compounded, and excitation compound emission is generated, and the main molecule free radical anions and the 1, 5-diaminoanthraquinone free radical cations still last for a long time after the light excitation is stopped; therefore, the obtained organic red long afterglow material can generate macroscopic red fluorescence under the irradiation of an ultraviolet lamp, and the excitation light source is turned off to generate macroscopic red afterglow luminescence.
Further, preferably, the host molecule is dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT), and the specific structural formula is as follows:
By the above technical scheme, the invention limits that the guest molecule and the dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT) are melted in a mass ratio of 1:100, and a charge transfer state is formed between the guest molecule and the dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT) during photoexcitation. Then, the generated dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT) radical anion is diffused by charge hopping between the dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT), and the 1-aminoethylamino-9, 10-anthraquinone (AEAQ) radical cation is separated from the counter radical anion of the dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT) and forms a stable charge separation state. Finally, the dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT) free radical anion and 1-amino ethyl amino-9, 10-anthraquinone (AEAQ) free radical cation are gradually compounded, and excitation compound emission is generated, and the emission can still be continued for a long time after light excitation is stopped; the obtained organic red long afterglow material can generate macroscopic red fluorescence under the irradiation of an ultraviolet lamp, and the excitation light source is turned off to generate macroscopic red afterglow luminescence; preferably AEAQ performs best with PPT doping, the characterization of which is determined by the duration of the red afterglow after switching off the light source.
Meanwhile, the method for preparing the organic red long afterglow material comprises the following specific steps:
s1, uniformly mixing guest molecules and host molecules according to a mass ratio of 1:100, and putting the mixture into a crucible or a tank furnace made of refractory materials to be heated and melted;
s2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the guest molecules to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
Step S4: after the film was irradiated with 365W ultraviolet light for 60 seconds, the light source was turned off, and a red afterglow of about 10 seconds was observed.
Specifically, the comparative details are as follows:
s1, uniformly mixing guest molecules and host molecules according to a mass ratio of 1:100, and putting the mixture into a crucible or a tank furnace made of refractory materials to be heated and melted;
s2, filling air into the step S1, and heating to 250 ℃ to enable the guest molecules to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
Step S4: after the film was irradiated with 365W ultraviolet light for 60 seconds, the light source was turned off, and a red afterglow of about 1 second was observed.
Through observation, the red afterglow can only be maintained for 1s when the environment is an aerobic and aerobic water environment.
S1, uniformly mixing guest molecules and host molecules according to a mass ratio of 10:100, and putting the mixture into a crucible or a tank furnace made of refractory materials for heating and melting;
s2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the guest molecules to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
Step S4: after the film was irradiated with 365W ultraviolet light for 60 seconds, the light source was turned off, and a red afterglow of about 5 seconds was observed.
S1, uniformly mixing guest molecules and host molecules according to a mass ratio of 1:1000, and putting the mixture into a crucible or a tank furnace made of refractory materials, and heating and melting;
s2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the guest molecules to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
Step S4: after the film was irradiated with 365W ultraviolet light for 60 seconds, the light source was turned off, and a red afterglow of about 2 seconds was observed.
Comparison of the above experiments shows that the effect is best only when the ratio is 1:100.
Further, in step S1, the anthraquinone amine of the guest molecule acts as an electron donor and the cationic quaternary phosphonium radical of the host molecule acts as an organic trap.
Through the technical scheme, the long-lasting luminescence is realized through an electron or hole trapping mechanism based on the existing long-afterglow luminescence mechanism, and in an electron trap, the excited electrons pass through a conduction band to reach an electron receiving trap after excitation (Ex); in the hole trap, electrons are transported through the valence band to fill holes; in both cases relaxation is prevented because either the excited electrons have migrated or holes have been filled; thermal interference can recover electrons or holes, producing afterglow emission (Em);
Similar to the long afterglow luminescence mechanism, the invention uses cationic quaternary phosphonium free radical as an organic trap and anthraquinone amine as an electron donor, firstly photo-induced charge transfer occurs between the donor and acceptor molecules, then charge separation is carried out, and before the final charge recombination, multiple charge separations can occur, thus leading to continuous luminescence of the organic long afterglow.
Based on the existing red long afterglow material, the preparation conditions are harsh, the biocompatibility is lacking, and the flexible preparation cannot be realized; the organic red long afterglow material has mild preparation condition, good flexibility and better biocompatibility.
In addition, the application of the organic red long afterglow material is provided, and the organic red long afterglow material is used as a fluorescent probe for biological imaging.
The application of the organic red long afterglow material is provided, and the organic red long afterglow material is applied to data encryption and anti-counterfeiting identification.
Through the technical scheme, the organic red long afterglow material has the advantages that the organic red long afterglow material is irradiated under a room temperature ultraviolet lamp, can generate macroscopic red fluorescence, and can generate macroscopic red afterglow luminescence after an excitation light source is turned off, so that the material can conveniently realize fluorescence emission and phosphorescence emission under room temperature conditions at the same time, and can be used as a fluorescent probe for biological imaging; the organic red-based long afterglow material also has high concealment, is convenient to use and easy to identify, thereby being capable of realizing a higher-level anti-counterfeiting function and having good application prospect in the fields of organic photoelectric materials, anti-counterfeiting marks, data encryption and the like.
The invention has the beneficial effects that: the organic red long afterglow material has the advantages that the organic red long afterglow material can generate macroscopic red fluorescence when irradiated under a room temperature ultraviolet lamp, and can generate macroscopic red afterglow luminescence when an excitation light source is turned off, so that the material can conveniently realize fluorescence emission and phosphorescence emission under room temperature conditions at the same time, and can be used as a fluorescent probe for biological imaging; the organic red-based long afterglow material also has high concealment, is convenient to use and easy to identify, thereby being capable of realizing a higher-level anti-counterfeiting function and having good application prospect in the fields of organic photoelectric materials, anti-counterfeiting marks, data encryption and the like.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated; the reagents and equipment employed in the present invention are as follows, unless otherwise specified;
Table 1 purchase of drugs and drug sources
Table 2 the instruments and model involved in the tests in the following examples:
Example 1
An organic red long afterglow material, which comprises a guest molecule containing anthraquinone amine, a host molecule containing cationic quaternary phosphonium free radicals, wherein the mass ratio of the guest molecule to the host molecule is 1:100; the method comprises the following specific steps:
S1, uniformly mixing a host molecule and a guest molecule according to a mass ratio of 1:100, and putting the mixture into a crucible or a tank furnace made of refractory materials to heat and melt;
s2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the guest molecules to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
Effect detection
The obtained organic red long afterglow material is irradiated under a room temperature ultraviolet lamp, so that macroscopic red fluorescence can be generated, and an excitation light source is turned off, so that macroscopic red afterglow luminescence can be generated.
Example 2
An organic red long afterglow material comprises a guest molecule 1-amino ethylamino-9, 10-anthraquinone (AEAQ), a host molecule dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT), and AEAQ and the PPT are melted according to a mass ratio of 1:100, and the specific steps are as follows:
s1, uniformly mixing guest molecules AEAQ and host molecules PPT in a mass ratio of 1:100, specifically weighing raw materials AEAQ (1 mg) and PPT (100 mg), and uniformly mixing the raw materials;
s2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the PPT to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
Effect detection
The obtained organic red long afterglow material is irradiated under a room temperature ultraviolet lamp, so that macroscopic red fluorescence can be generated, and an excitation light source is turned off, so that macroscopic red afterglow luminescence can be generated.
Example 3
An organic red long afterglow material comprises guest molecule 1, 5-diaminoanthraquinone and host molecule dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT), wherein the mass ratio of the 1, 5-diaminoanthraquinone to the PPT is 1:100, and the specific steps are as follows:
s1, uniformly mixing guest molecules 1, 5-diaminoanthraquinone and host molecules PPT in a mass ratio of 2:200, specifically weighing raw materials 1, 5-diaminoanthraquinone (2 mg) and PPT (200 mg), and uniformly mixing the raw materials;
s2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the PPT to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
Effect detection
The obtained organic red long afterglow material is irradiated under a room temperature ultraviolet lamp, so that macroscopic red fluorescence can be generated, and an excitation light source is turned off, so that macroscopic red afterglow luminescence can be generated.
Example 4
An organic red long afterglow material comprises a guest molecule 1-amino ethylamino-9, 10-anthraquinone (AEAQ), a host molecule dibenzothiophene derivative 2, 8-bis (diphenylphosphino) dibenzothiophene (PPT), and AEAQ and the PPT are melted according to a mass ratio of 1:100, and the specific steps are as follows:
S1, uniformly mixing guest molecules AEAQ and host molecules PPT in a mass ratio of 1:10, specifically weighing raw materials AEAQ (1 mg) and PPT (10 mg), and uniformly mixing the raw materials;
s2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the PPT to reach a molten state;
S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the transparent film-shaped organic red long afterglow material.
Effect detection
The obtained organic red long afterglow material is irradiated under a room temperature ultraviolet lamp, so that macroscopic red fluorescence can be generated, and an excitation light source is turned off, so that macroscopic red afterglow luminescence can be generated.
In summary, example 2 works better than example 2 in example 4; during photoexcitation, a charge transfer state is formed between AEAQ and PPT; then, the generated PPT free radical anions are diffused through charge jump among PPT molecules, so that AEAQ free radical cations and counter-free radical anions of the PPT are separated and form a stable charge separation state; finally, the PPT radical anion and AEAQ radical cation gradually recombine and produce excited complex emission which continues long after the photoexcitation ceases.
Finally, it should be noted that: the foregoing description is only illustrative of the preferred embodiments of the present invention, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described, or equivalents may be substituted for elements thereof, and any modifications, equivalents, improvements or changes may be made without departing from the spirit and principles of the present invention.
Claims (3)
1. An organic red long afterglow material, which is characterized by comprising a guest molecule containing anthraquinone amine, a host molecule containing cationic quaternary phosphonium free radicals, wherein the guest molecule and the host molecule are fused in a mass ratio of 1:100;
the guest molecule is 1-amino ethyl amino-9, 10-anthraquinone, and the specific structural formula is shown as follows:
；
Or the guest molecule is 1, 5-diaminoanthraquinone, and the specific structural formula is shown as follows:
；
The main molecule is dibenzothiophene derivative 2, 8-bis (diphenyl phosphinyl) dibenzothiophene, and the specific structural formula is shown as follows:
。
2. A method for preparing the organic red long afterglow material according to claim 1, characterized by comprising the following specific steps:
step S1, uniformly mixing guest molecules and host molecules according to a mass ratio of 1:100, and putting the mixture into a crucible or a tank furnace made of refractory materials for heating and melting;
Step S2, filling nitrogen into the step S1, and heating to 250 ℃ to enable the guest molecules to reach a molten state;
And S3, rapidly cooling the molten state obtained in the step S2 to room temperature to prepare the amorphous transparent film-shaped organic red long afterglow material.
3. Use of an organic red long persistence material as claimed in claim 1 for data encryption and security marking.
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