CN111574562A - Organic long-afterglow material with light activation characteristic and preparation method and application thereof - Google Patents
Organic long-afterglow material with light activation characteristic and preparation method and application thereof Download PDFInfo
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- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000001424 substituent group Chemical group 0.000 claims abstract description 4
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007832 Na2SO4 Substances 0.000 claims description 9
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- SXXLKZCNJHJYFL-UHFFFAOYSA-N 4,5,6,7-tetrahydro-[1,2]oxazolo[4,5-c]pyridin-5-ium-3-olate Chemical compound C1CNCC2=C1ONC2=O SXXLKZCNJHJYFL-UHFFFAOYSA-N 0.000 description 23
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- AITNMTXHTIIIBB-UHFFFAOYSA-N 1-bromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C=C1 AITNMTXHTIIIBB-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
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Abstract
The invention discloses an organic long afterglow material with light activation characteristic, a preparation method and application thereof, wherein the chemical structure of the material has a general formula:
wherein R is H, F, OCH3(ii) a The series of compounds are prepared by taking the triphenylphosphine oxide derivative as a research object and connecting different substituent groups at the para positions of three benzene rings of the triphenylphosphine oxide. By controlling the ultraviolet irradiation time, the phosphorescence service life and the phosphorescence intensity of the series of materials are obviously improved. And combining different dynamic adjustability, thereby realizing multiple information encryption application.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to an organic long afterglow material with a light activation characteristic and application thereof in the field of information encryption.
Background
The long afterglow material is a photoluminescence material with long service life excited state property, can absorb the energy of exciting light, can still continuously emit light for more than 0.1 second after the excitation is stopped, and can well distinguish the light emission by naked eyes. In recent years, long afterglow materials are widely used in the fields of display, emergency signal lamps, data encryption, biological imaging and the like because of their abundant excited states and long luminescence life. At present, inorganic materials with long-life excited state properties have been developed sufficiently, but the processing conditions are severe, the material sources are scarce, the heavy metal biotoxicity and other defects limit the wide application of the inorganic materials. Compared with inorganic long afterglow materials, the organic long afterglow material has the advantages of flexibility, easy synthesis, easy modification, good biocompatibility and the like, and is a long afterglow luminescent system mainly constructed by strategies of crystal induction, host and object doping, heavy atom introduction and the like.
So far, a series of organic long afterglow materials have been developed, which can observe ultra-long luminescence immediately after the light source is turned off after the excitation light is irradiated, and the afterglow life is regulated by different irradiation time periods of the excitation light, that is, only a few examples of organic long afterglow materials with light activation characteristics are provided, for example, a series of dynamic ultra-long organic phosphorus molecules are designed and synthesized by the huangweiji team in 2018, the molecules are gradually activated under the stimulation of ultraviolet light, and the lifetime is gradually increased from 1.8 milliseconds to 1.33 seconds, but there is still a great room for improvement in terms of the preparation cost of the materials and the excitation life of the materials themselves.
Disclosure of Invention
The invention aims to provide an organic long-afterglow material with a light activation characteristic, a preparation method thereof and application of the material in the field of information encryption, which not only can provide an organic long-afterglow material with lower cost and simple preparation process, but also can improve the practical application effect of the material in the field of information encryption.
The organic long afterglow material with light activation characteristic has triphenyl phosphine oxide derivative as component, and through altering the para substituent of three benzene rings of triphenyl phosphine oxide and controlling the ultraviolet irradiation time, the material has obviously raised phosphorescence life and strength in crystal state and different dynamic adjustability, and may be used in enciphering multiple information.
The triphenylphosphine oxide derivative has the following structural general formula:
wherein R is H, F, OCH3。
The specific synthetic route of the preparation of the triphenylphosphine oxide derivative is as follows: :
wherein R is F, OCH3。
The preparation method of TRP comprises the following steps: dissolving Br-R in super-dry tetrahydrofuran under nitrogen atmosphere, placing the solution into a Dewar flask at the temperature of-78 ℃, adding n-butyllithium according to the ratio of 1:1-1:1.5 after 10min, stirring the solution for 1 to 2 hours, adding phosphine trichloride with the equivalent of less than or equal to one third, and then stirring the solution for 8 to 12 hours at room temperature; the post-treatment is to add water to quench butyl lithium, and then carry out reduced pressure distillation to remove tetrahydrofuran; then using water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4Dewatering, drying, and distilling under reduced pressure to remove solvent; and finally, purifying by column chromatography to obtain the TRP.
Wherein R is H, F, OCH3。
Synthesis of TRPO: application of TRP to CH2Cl2Dissolving, placing in ice-water bath at 0 ℃, and slowly dripping 3-10mLH2O2And then stirred at room temperature for 2-4 hours. With water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4And (3) removing water, drying, then distilling under reduced pressure, and removing the solvent to obtain the TRPO.
The invention relates to an organic long afterglow material with light activation property, which takes triphenylphosphine oxide derivatives as research objects. The series of materials under the crystal can obviously improve the phosphorescence life and the intensity through the extension of the ultraviolet irradiation time, and the luminescence life can be quickly recovered to the initial value under the heating. By changing different substituent groups, the maximum light activation amplitude can realize the adjustment of the light-emitting life from 95.4 microseconds to 1.5 seconds. And by combining different dynamic adjustability, the application of multiple information encryption is realized, which is the further development of the organic long afterglow material.
Has the advantages that:
1. the synthesis raw materials of the triphenylphosphine oxide derivative are cheap and easily available, the steps are greatly simplified compared with other materials, the whole preparation process only needs two steps, and most of the operation processes are carried out at room temperature, so that the preparation conditions are mild;
2. three light-activated pure organic long afterglow materials which need to be irradiated for different time lengths are obtained by changing three benzene ring para-substituents of triphenylphosphine oxide;
3. by controlling the irradiation duration of the ultraviolet light, the dynamic adjustment of the luminous intensity and the service life of the organic long-afterglow material is realized, the adjustment of the luminous service life from 95.4 microseconds to 1.5 seconds can be realized with the largest light activation amplitude, and the luminous service life is improved by about sixteen thousand and thousands times;
4. three compound crystals with different light activation performances are placed into a specific shape, after the crystal is irradiated by a 300nm ultraviolet lamp and is turned off, compound afterglow sequentially appears according to the length of time required by activation, different encrypted information can be observed, and multiple information encryption application is realized.
Drawings
FIG. 1: nuclear magnetic representation hydrogen spectrogram of the material THPO;
FIG. 2: nuclear magnetic characterization carbon spectrogram of the material THPO;
FIG. 3: nuclear magnetic representation phosphorus spectrogram of the material THPO;
FIG. 4: nuclear magnetic representation hydrogen spectrogram of the material TFPO;
FIG. 5: nuclear magnetic representation carbon spectrogram of material TFPO;
FIG. 6: nuclear magnetic representation carbon spectrogram of material TFPO;
FIG. 7: nuclear magnetic representation hydrogen spectrum of material TOCH3 PO;
FIG. 8: nuclear magnetic characterization carbon spectrum of material TOCH3 PO;
FIG. 9: nuclear magnetic representation phosphorus spectrogram of the material TOCH3 PO;
FIG. 10: the emission spectra of the three materials THPO, TFP and TOCH3P crystal and the phosphorescence spectra before and after light activation, wherein the left side is the luminous picture of the compound under the ultraviolet lamp, the middle picture is the luminous picture after the ultraviolet lamp is turned off, and the right side is the ultra-long luminous picture after the ultraviolet lamp is turned off after light activation;
FIG. 11: the phosphorescence spectrum of THPO every 1 minute within 20 minutes and the phosphorescence intensity change curve chart of THPO after long-time ultraviolet irradiation activation;
FIG. 12: the phosphorescence spectrum of the TFPO every 20 minutes and the phosphorescence intensity change curve chart of the TFPO after the TFPO is activated by the long-time irradiation of ultraviolet light within 5 hours;
FIG. 13: phosphorescence spectrum of TOCH3PO every 1 minute within 20 minutes, and phosphorescence intensity change curve of TOCH3PO after long-term irradiation activation of ultraviolet light;
FIG. 14: lifetime plots of crystals before and after THPO photoactivation;
FIG. 15: life time diagram of crystal before and after TFPO light activation;
FIG. 16: lifetime map of crystal before and after TOCH3PO photoactivation;
FIG. 17: the three materials of THPO, TFP and TOCH3P crystal are arranged into a pattern of a Chinese character 'go';
FIG. 18: the three materials THPO, TFP, TOCH3P are applied to the multiple information encryption process schematic diagram.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following describes the technical solution of the present invention with reference to fig. 1 to 18 and the embodiments.
An organic long afterglow material with light activation characteristics has the following structural general formula:
wherein R is H, F, OCH3。
Example 1: preparation method of THPO
The chemical structure of THPO is as follows:
synthesis of THPO: triphenylphosphine (5g) was taken with CH2Cl2Dissolving and placing in ice-water bath at 0 ℃, and slowly dripping H2O2(5mL) and then stirred at room temperature for 2-4 hours. With water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4Drying under reduced pressure to remove water, and distilling to remove solvent to obtain THPO as white powder. Structural characterization of compound THPO:1H NMR(400MHz, DMSO,):7.66–7.52(m,15H).13C NMR(101MHz,DMSO,):133.25,132.23,132.04,132.02, 131.53,131.43,128.82,128.70.31P NMR(DMSO,):25.53.
the specific synthetic route is as follows:
example 2: preparation method of TFPO
The chemical structural formula of TFPO is as follows:
synthesis of TFPO: in N2Under protection, 1-fluoro-4-bromobenzene (5g) is dissolved in 40mL of super-dry tetrahydrofuran and is placed into a Dewar flask at-78 ℃; after 10min, adding n-BuLi (17.9mL) and stirring for 1h, then adding phosphine trichloride (0.82mL), heating to room temperature, and stirring for 8-12 h; water (20mL) was added to quench the butyllithium, then the tetrahydrofuran was removed by distillation under reduced pressure; then using water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4Dewatering, drying, and distilling under reduced pressure to remove solvent; finally purifying by column chromatography to obtain white powder; mixing the white powder with CH2Cl2Dissolving and placing in ice-water bath at 0 ℃, and slowly dripping H2O2(5mL) and then stirred at room temperature for 2-4 hours. With water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4Drying under reduced pressure, and removing solvent to obtain TFPO as white powder. Structural characterization of compound TFPO:1HNMR(400MHz,DMSO,):7.75–7.63(m,6H),7.47–7.36(m,6H).13C NMR(101MHz,DMSO,):165.71,165.68,163.21,163.18,134.51,134.42,134.39,134.30,129.25,129.22,128.19,116.37, 116.24,116.15,116.02.31P NMR(DMSO,):41.36.
the specific synthetic route is as follows:
example 3: TOCH3Method for preparing PO
TOCH3PO has the following chemical structure:
TOCH3synthesis of PO: in N2Under protection, 4-bromoanisole (5g) is dissolved in 40mL of ultra-dry tetrahydrofuran and is put into a Dewar flask at-78 ℃; after 10min, adding n-BuLi (16.7mL) and stirring for 1h, then adding phosphine trichloride (0.77mL), heating to room temperature, and stirring for 8-12 h; water (20mL) was added to quench the butyllithium, then the tetrahydrofuran was removed by distillation under reduced pressure; then using water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4Dewatering, drying, and distilling under reduced pressure to remove solvent; finally, purifying by column chromatography to obtain white powder; mixing the white powder with CH2Cl2Dissolving and placing in ice-water bath at 0 ℃, and slowly dripping H2O2(5mL), followed by stirring at room temperature for 2-4 hours. With water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4Drying under reduced pressure to remove solvent to obtain TOCH3PO, white powder. Compound TOCH3Structural characterization of PO:1H NMR(400MHz,DMSO,):7.67–7.61(m,12H).13C NMR(101MHz,DMSO,): 137.65,137.62,133.49,133.39,131.33,130.29,129.19,129.06.31P NMR(DMSO,):41.71.
the specific synthetic route is as follows:
test example: three characterization and photophysical property tests of organic long afterglow materials with light activation characteristics:
dissolving the above three compounds (5-10mg) in 0.5mL of deuterated reagent, and characterizing the structure of the compound by 400Hz NMR instrument, and the NMR chart of THPO, as shown in figures 1-3 (wherein figure 1 is hydrogen spectrum, figure 2 is carbon spectrum, and figure 3 is phosphorus spectrum); nuclear magnetic characterization of TFPO, as shown in fig. 4-6 (where fig. 4 is a hydrogen spectrum, fig. 5 is a carbon spectrum, and fig. 6 is a phosphorus spectrum); TOCH3Nuclear magnetic characterization of PO, as shown in fig. 7-9 (where fig. 7 is a hydrogen spectrum, fig. 8 is a carbon spectrum, and fig. 9 is a phosphorus spectrum).
The emission spectrum of the compound crystal and the phosphorescence spectrum before and after light activation were measured, as shown in fig. 10, where the left inset is a picture of the emission of the compound under the ultraviolet lamp, the middle inset is a picture of the emission after the ultraviolet lamp was turned off, and the right inset is a picture of the ultra-long emission after the ultraviolet lamp was turned off after light activation.
The afterglow life of the three materials can be regulated and controlled by the irradiation duration of exciting light under the crystal state, and the phosphorescence life and the phosphorescence intensity are obviously improved along with the extension of the ultraviolet irradiation time. The specific operation is that three kinds of crystals are respectively irradiated by using a ZF-7 type portable ultraviolet lamp with the power of 8W and the wavelength of 300nm, the irradiation time required for the three materials to be activated to the maximum service life is different, the THPO needs 10-15 minutes, the TFPO needs 3-3.2 hours, and the TOCH needs3PO took 15-20 minutes.
FIG. 11 is a graph showing the phosphorescence spectrum of THPO every 1 minute and the change of phosphorescence intensity of THPO after long-term ultraviolet light irradiation activation in 20 minutes, FIG. 12 is a graph showing the phosphorescence spectrum of TFPO every 20 minutes and the change of phosphorescence intensity of TFPO after long-term ultraviolet light irradiation activation in 5 hours, FIG. 13 is a graph showing the change of TOCH in 20 minutes3Phosphorescence spectrum of PO at intervals of 1 minute, and TOCH3Graph of change of phosphorescence intensity of PO after long-time irradiation activation of ultraviolet light.
Shown in FIGS. 14-16 as THPO, TFPO and TOCH, respectively3The life diagram of the crystal before and after PO photoactivation, the order of the life variation amplitude from large to small before and after the photoactivation is as follows: TOCH3PO, TFPO, THPO, the specific life ranges before and after photoactivation of the three materials are as follows:
| before activation | After activation | |
| THPO | 99.0ms | 189.7ms |
| TFPO | 59.7ms | 828.1ms |
| TOCH3PO | 95.4μs | 1.5s |
The fully activated crystal can be quickly inactivated by heating and restored to the initial state, or slowly restored to the initial state at normal temperature, and the dynamic reversible regulation of the pure organic long afterglow is realized.
Application example: multiple information encryption application
Placing compound crystal TRPO with different light activation durations into a word of "go", as shown in FIG. 17, wherein THPO is placed at A, TFPO is placed at B, and TOCH is placed at C3And PO. The afterglow life of the material in a crystal state can be regulated and controlled by the irradiation duration of exciting light, the activation rates are different, and the afterglow sequence observable by naked eyes is as follows: THPO, TFPO, TOCH3PO；
After the 300nm ultraviolet lamp is irradiated and turned off, compound afterglow appears in sequence according to the length of time required by activation, and different encrypted information can be observed. No pattern can be seen after the ultraviolet lamp is irradiated and immediately turned off, and a second pattern can be seen at the moment when the ultraviolet lamp is turned off after being irradiated for 10 seconds; "soil" which can be seen at the moment when the ultraviolet lamp is turned off after 1 minute of irradiation; the "go" was seen at the instant the UV lamp was turned off after 5 minutes of irradiation, as shown in FIG. 18.
Claims (9)
1. The organic long afterglow material with light activation characteristic is characterized in that the main component of the material is triphenyl phosphine oxide derivative.
2. The organic long-afterglow material with the light-activated characteristic as claimed in claim 1, wherein the triphenylphosphine oxide derivative is a pure organic material with the light-activated characteristic formed by changing substituents at para positions of three benzene rings of the triphenylphosphine oxide, and the photophysical properties of the material, such as light-emitting lifetime, light-activated rate, light-activated amplitude, and the like, can be regulated and controlled.
3. The organic long-afterglow material with light-activated characteristics as claimed in claim 1, wherein the triphenylphosphine oxide derivative can control the photophysical properties such as luminous intensity, luminous lifetime, etc. by controlling the UV irradiation time.
4. The organic long afterglow material having light activated characteristics as claimed in claim 1, wherein the structural formula thereof is as follows:
wherein R is H, F, OCH3。
5. The organic long afterglow material of claim 4 having a light activated property, wherein the material is one of the following structures:
6. the method for preparing the organic long afterglow material with light activation property of claim 4, wherein the method comprises the following steps:
wherein X is Br, R is F, OCH3；
Preparation of TRP: dissolving Br-R in super-dry tetrahydrofuran under nitrogen atmosphere, placing the solution into a Dewar flask at the temperature of-78 ℃, adding n-butyllithium according to the ratio of 1:1-1:1.5 after 10min, stirring the solution for 1 to 2 hours, adding phosphine trichloride with the equivalent of less than or equal to one third, and then stirring the solution for 8 to 12 hours at room temperature; the post-treatment is to add water to quench butyl lithium, and then carry out reduced pressure distillation to remove tetrahydrofuran; then using water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4Dewatering, drying, and distilling under reduced pressure to remove solvent; finally, purifying by column chromatography to obtain TRP;
wherein R is H, F, OCH3；
Preparation of TRPO: application of TRP to CH2Cl2Dissolving and placing in ice-water bath at 0 ℃, slowly dropping 3-10mL of H2O2Then stirring at room temperature overnight; with water and CH2Cl2Extracting for three times, collecting organic phase and using anhydrous Na2SO4And (3) removing water, drying, then distilling under reduced pressure, and removing the solvent to obtain the TRPO.
7. The use of the organic long afterglow material with light activation property as claimed in any one of claims 1 to 5 in information encryption, wherein three different pure organic material crystals with light activation property are selected and placed into a specific shape, after the ultraviolet lamp is irradiated and turned off, compound afterglow appears in sequence according to the time length required for activation, so that different encrypted information can be observed, and multiple information encryption application is realized.
8. The application of the organic long afterglow material with light activation property in information encryption according to claim 5, wherein three compound crystals with different light activation properties are arranged into a specific shape, after the ultraviolet lamp is irradiated and turned off, the compound afterglow sequentially appears according to the time length required by activation, so that different encrypted information can be observed, and multiple information encryption application is realized.
9. Use of an organic long persistent material with light activated properties for information encryption according to claim 8, said uv lamp being in particular a ZF-7 type hand-held uv lamp with a power of 8W and a wavelength of 300 nm.
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| CN113121409A (en) * | 2021-03-03 | 2021-07-16 | 太原理工大学 | Organic fluorescent material with information deep hiding function, preparation and application |
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