CN115521776B - Quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, preparation and application - Google Patents
Quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, preparation and application Download PDFInfo
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- CN115521776B CN115521776B CN202210967557.7A CN202210967557A CN115521776B CN 115521776 B CN115521776 B CN 115521776B CN 202210967557 A CN202210967557 A CN 202210967557A CN 115521776 B CN115521776 B CN 115521776B
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- quasi
- luminescent material
- ionic
- conversion luminescent
- solid
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a quasi-solid ion type up-conversion luminescent material with an electrically controlled luminescence response, a preparation method and an application thereof. The up-conversion luminescent material comprises a photosensitizer, an ionic annihilator and a quasi-solid matrix; wherein the ionic annihilator is selected from one or more of an ionic derivative of diphenyl anthracene, an ionic derivative of pyrene or an ionic derivative of perylene; the quasi-solid matrix is a gel matrix composed of silicon dioxide and a viscous solvent. Under the action of the quasi-solid matrix, the method not only achieves better deoxidization and oxygen isolation effects, gets rid of the limiting condition of an anaerobic environment, reduces the sensitivity of the up-conversion luminescent material to oxygen, but also provides an ion motion channel for the ionic annihilator, and is convenient for the up-conversion luminescent material to regulate and control the response to an electric field.
Description
Technical Field
The present invention relates to the field of photon up-conversion materials. More particularly, to a quasi-solid ion up-conversion luminescent material with electrically controlled luminescence response, preparation and application.
Background
Solar energy is a clean and resource-rich energy source, and is considered as one of renewable energy sources with the most application prospect. In order to more efficiently utilize solar energy, it is desirable to extract as much energy as possible from sunlight, particularly with low energy photons that do not meet the bandgap of conventional light harvesting materials. Photon up-conversion is a process of converting low-energy photons into high-energy photons, and up-conversion (TTA-UC) based on triplet-triplet annihilation can convert light with long wavelength into light with short wavelength and high available energy by using low-power excitation light, so that the photon up-conversion has important application value in photocatalysis, biological imaging and other aspects.
The TTA-UC system consists of two chromophores (photosensitizer and annihilator). First, a donor (photosensitizer) absorbs a photon to its first excited singlet state 1 S, then intersystem crossing (ISC) to first excited triplet state 1 T occurs, the photosensitizer transfers energy to the acceptor by triplet-triplet energy transfer (TTET), causing the acceptor to reach its first excited triplet state 1 T, the two triplet acceptors interact, triplet-triplet annihilation (TTA) occurs, one acceptor molecule reaches the first excited singlet state 1 S, and the other acceptor molecule is deactivated to the ground state S 0. Finally, the acceptor molecule reaching the first excited state decays in the form of an anti-stokes shift radiation transition. The TTET and TTA processes both involve a Dexter type electron exchange mechanism, and the TTA up-conversion is finished through collision, but at present, the TTA up-conversion is mostly finished in a low-viscosity and deoxidized organic solvent, and the organic solvent has the limitations of easy volatilization, difficult encapsulation, limited up-conversion dye dissolution capacity and the like, so that the up-conversion dye is hindered in practical application.
In addition, although up-conversion may also be used for biosensing and chemical sensing by stimulus response, i.e. by responding to external stimuli such as temperature, chemicals, oxygen, light, electric fields and mechanical forces, the TTA-UC switching is achieved. However, the TTA system with the stimulus response is still less, so the aggregated TTA-UC system with the rapid intelligent response is still to be further developed or innovated.
Therefore, it is important to develop an up-conversion luminescent material that has low sensitivity to oxygen and can have stimulus response.
Disclosure of Invention
A first object of the present invention is to provide a quasi-solid ionic up-conversion luminescent material with electrically controlled luminescence response. The quasi-solid ion up-conversion luminescent material can realize regulation and control response to an electric field through the introduction of the ion annihilator, realize writing and erasing of information, reduce sensitivity to oxygen under the wrapping of a quasi-solid matrix, and enable the up-conversion luminescent material to realize up-conversion luminescence in air.
A second object of the present invention is to provide a method for preparing an up-conversion luminescent material as described above.
A third object of the present invention is to provide a use of an up-conversion luminescent material as described above for the manufacture of a security product.
A fourth object of the present invention is to provide an information recording apparatus comprising the up-conversion luminescent material as described above.
In order to achieve the first object, the present invention adopts the following technical scheme:
The invention discloses a quasi-solid ion up-conversion luminescent material with an electrically controlled luminescence response, wherein the up-conversion luminescent material comprises a photosensitizer, an ion annihilator and a quasi-solid matrix;
wherein the ionic annihilator is selected from one or more of an ionic derivative of diphenyl anthracene, an ionic derivative of pyrene or an ionic derivative of perylene;
the quasi-solid matrix is a gel matrix composed of silicon dioxide and a viscous solvent.
On one hand, the quasi-solid ion type up-conversion luminescent material provided by the invention can respond to the regulation and control of voltage and control the movement of ions under the introduction of the ion annihilation agent, so that the intensity contrast of up-conversion luminescence intensity in a voltage action area and a non-voltage action area is achieved, the writing of information is realized, and the erasure of information is realized rapidly by reversing the voltage; on the other hand, the gel matrix composed of the silicon dioxide and the viscous solvent is beneficial to eliminating and isolating oxygen in the air, reducing the adverse effect on an up-conversion system, reducing the sensitivity of the up-conversion luminescent material to oxygen, getting rid of the limiting condition of an anaerobic environment, and further expanding the application range of the up-conversion system.
In a specific embodiment, the invention provides the general structures of the ionic derivatives of two diphenylanthracene, but the general structures of the ionic derivatives of anthracene, the ionic derivatives of pyrene or the ionic derivatives of perylene can be not listed any more as long as the effects of up-conversion luminescence and electrical regulation response can be realized by matching the energy level of a photosensitizer by adopting the same structural design to carry out ionization structural modification of annihilation agents (such as anthracene, pyrene, perylene and the like) which are commonly used in the field and have similar structures.
The structural formula of the ionic derivatives of the two diphenylanthracene are shown in the following formula I or formula II:
Wherein each of the R 1、R2 independently represents any one of a substituted or unsubstituted C 1-C10 alkyl group, a substituted or unsubstituted C 3-C10 cycloalkyl group; the R 1、R2 may be the same or different;
The A is selected from one or more of halogen, acetic acid, hexafluorophosphoric acid, tetraphenyl boric acid and tetra (pentafluorophenyl) boric acid; preferably, when A is selected from hexafluorophosphoric acid, tetrakis (pentafluorophenyl) boric acid or tetraphenyl boric acid, the interaction between the anions and cations is relatively weak, and is more susceptible to the action of an electric field, thus achieving an electric response.
Further, for the selection of the R 1、R2 group, there may be exemplified methylene, ethylene, propylene, isopropylene, n-butylene, sec-butylene, isobutylene, tert-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, n-nonylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene and the like; when a substituent is present on the R 1、R2, the substituent is selected from aryl of C 6-C14 or aryl of C 6-C14 substituted with an alkyl group, which may be, for example, phenyl, naphthyl, phenanthryl, and which may be methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, or n-nonyl.
Further, the present invention employs photosensitizers conventional in the art, such as: porphyrin-based photosensitizers or metal-complexed pyridine-based photosensitizers; preferably, the photosensitizer is selected from platinum octaethylporphyrin or palladium octaethylporphyrin, wherein the structural formula of platinum octaethylporphyrin (PtOEP) and palladium octaethylporphyrin (PdOEP) is as follows:
Further, the molar ratio of the photosensitizer to the ionic annihilator is 1:1-5000; illustratively, the molar ratio of the photosensitizer to the ionic annihilator can also be 1:1-5,1:1-10,1:1-20,1:1-30,1:1-40,1:1-50,1:1-60,1:1-70,1:1-80,1:1-90,1:1-100,1:1-200,1:1-500,1:1-1000,1:1-2000,1:5-10,1:5-20,1:5-30,1:5-40,1:5-50,1:5-60,1:5-70,1:5-80,1:5-90,1:5-100,1:5-200,1:5-500,1:5-1000,1:5-2000,1:5-5000,1:10-20,1:10-30,1:10-40,1:10-50,1:10-60,1:10-70,1:10-80,1:10-90,1:10-100,1:10-200,1:10-500,1:10-1000,1:10-2000,1:10-5000,1:20-30,1:20-40,1:20-50,1:20-60,1:20-70,1:20-80,1:20-90,1:20-100,1:20-200,1:20-500,1:20-1000,1:20-2000,1:20-5000,1:50-60,1:50-70,1:50-80,1:50-90,1:50-100,1:50-200,1:50-500,1:50-1000,1:50-2000,1:50-5000,1:100-200,1:100-500,1:100-1000,1:100-2000,1:100-5000,1:200-500,1:200-1000,1:200-2000,1:200-5000,1:500-1000,1:500-2000,1:500-5000,1:1000-2000,1:1000-5000,1:2000-5000, or the like.
Furthermore, the quasi-solid matrix provided by the invention has the functions of deoxidizing and isolating oxygen and providing ion movement channels, specifically, the selected viscous solvent such as DMSO can react with oxygen to remove part of the oxygen in the system, the formed gel matrix can isolate the oxygen in the air and further realize the oxygen isolation effect, and the gel matrix also provides a movement channel for ions, so that the ionic annihilator can rapidly move in the gel matrix and provides conditions for responding to electric regulation. The mass fraction of the silicon dioxide in the quasi-solid matrix is 1% -20%; preferably, when the mass fraction of the silicon dioxide is between 5 and 15 percent, the formed quasi-solid matrix structure and the deoxidization and oxygen isolation effect are better, and the formed quasi-solid matrix can be more beneficial to ion movement; preferably, the viscous solvent is selected from DMSO.
Further, the up-conversion luminescent material realizes conversion from green light to blue light by excitation in air.
To achieve the second object, the present invention discloses a method for preparing the quasi-solid ionic up-conversion luminescent material, which comprises the following steps:
Mixing the photosensitizer, the ionic annihilation agent and the silicon dioxide with the viscous solvent, and stirring in air for 2-5 min to obtain the fluorescent dye.
Preferably, the photosensitizer is present in the viscous solvent at a concentration of 1.0X10 -6-2.0×10-4 mol/L.
To achieve the third objective, the present invention discloses an application of the above-mentioned quasi-solid ion type up-conversion luminescent material in the preparation of anti-counterfeiting products.
To achieve the fourth object, the present invention discloses an information recording apparatus comprising the quasi-solid ion type up-conversion luminescent material as described above; the information recording apparatus includes a writing instrument, and a conductive layer coated with the quasi-solid ion type up-conversion luminescent material as described above; the conductive layer is made of indium tin oxide; the writing tool is made of one of platinum wires, silver wires or copper wires; the writing tool and the conductive layer are respectively connected to the cathode and the anode.
Further, applying voltage and excitation light to the up-conversion luminescent material on the conductive layer in an air environment, and moving the writing tool on the conductive layer to realize trace retention; after reversing the voltage, erasure of the trace is achieved.
In a specific embodiment, the height of the applied voltage only affects the response speed of forming marks during writing, the larger the applied voltage is, the faster the response speed is, and similarly, when the voltage is reversed, the larger the applied voltage is, the faster the erasing speed is, wherein the applied voltage is 2-20V; the wavelength of the excitation light is 532nm.
The beneficial effects of the invention are as follows:
The invention discloses a quasi-solid ion up-conversion luminescent material with an electrically controlled luminescence response, a preparation method and an application thereof. The up-conversion luminescent material comprises a photosensitizer, an ionic annihilation agent and a quasi-solid matrix, and has the following advantages compared with the prior art:
(1) The invention firstly proposes that the up-conversion luminescence is regulated by simple voltage, and the quasi-solid ion type up-conversion luminescence material has the difference of up-conversion luminescence intensity under the stimulation action of an electric signal, has the characteristic of quick response, and further expands the application range of the up-conversion luminescence material.
(2) The quasi-solid ion type up-conversion luminescent material with the electrically controlled luminescent response does not need to be operated in a glove box, and the whole preparation process and the control process are realized by being operated in air, so that the quasi-solid ion type up-conversion luminescent material has great practical application significance on the up-conversion luminescent material sensitive to oxygen.
(3) The annihilator in the quasi-solid ion type up-conversion luminescent material with the electrically-controlled luminescence response is simple to synthesize, does not need a particularly complex separation and purification process, and has low-cost and easily-obtained raw materials.
(4) The quasi-solid ion type up-conversion luminescent material with the electrically controlled luminescence response can be used as a writable information recording device, has the function of reversible writing, can realize the function of writing and erasing, and is very critical to the information recording device.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 shows a physical diagram of an up-conversion luminescent material of example 11.
Fig. 2 shows the luminescence spectrum of the upconversion luminescent material of example 11 under 532nm laser light.
Fig. 3 shows the luminescence response of the up-conversion luminescent material of example 11 under electrical control.
Fig. 4 shows a graph of the luminescence response of samples of experimental group and two control groups of experimental example 1 under electrical control.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and drawings. It should be understood by those skilled in the art that the following detailed description is intended to be illustrative and not limiting, and that any ranges recited herein include the endpoints and any numerical values between the endpoints and any sub-ranges between the endpoints.
In the invention, the preparation methods are all conventional methods unless otherwise specified. All materials used, unless otherwise indicated, are commercially available from the public disclosure and all percentages, such as by mass, are percentages unless otherwise indicated.
Example 1
A process for the preparation of 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) chloride (DPA 2 Cl), comprising the steps of:
1) Synthesis of (anthracene-9, 10-diylbis (4, 1-phenylene)) dimethanol (DPA 2CH 2 OH):
8.23g (4.0 eq) of potassium carbonate was weighed, 40mL of deionized water was added to dissolve the potassium carbonate, 5g (1.0 eq) of 9, 10-dibromoanthracene and 9g (4.0 eq) of 4-hydroxymethylphenylboric acid were weighed into a 500mL Schlenk bottle, a potassium carbonate aqueous solution was added, 100mL of 1, 4-dioxane was added, vacuum was applied to the bottle three times, and 172mg (0.01 eq) of tetraphenylphosphine palladium was added under a nitrogen atmosphere, followed by vacuum application to the bottle 3 times. Under the condition of introducing nitrogen, heating to 110 ℃, refluxing, closing the nitrogen, generating white solid after the reaction is finished, adding deionized water, and recrystallizing the solid obtained by suction filtration by using THF.
1H NMR(400MHz,DMSO)δ7.61(d,J＝6.8Hz,8H),7.43(s,8H),5.36(s,2H),4.71(s,4H).HRMS(m/z):calculated for C28H22O2＝390.1620,found 390.1621.
2) Synthesis of 9, 10-bis (4- (chloromethyl) phenyl) anthracene (DPA 2CH 2 Cl):
100mg (1.0 eq) of DPA2CH 2 OH was added to a 250mL round bottom flask, 50mL of anhydrous dichloromethane was added, and stirred at room temperature, 10uL (0.5 eq) of DMF was added. 0.1uL (2.0 eq) of thionyl chloride was slowly added under ice bath. In the reaction process, the reactant is gradually dissolved, the organic solvent is removed by screwing under reduced pressure, and column chromatography is carried out by taking methylene dichloride as an eluent, so that milky solid is obtained, and the yield is 94.3%.
1H NMR(400MHz,DMSO)δ7.73(d,J＝7.1Hz,4H),7.61–7.54(m,4H),7.54–7.38(m,8H),4.98(s,4H).HRMS(m/z):calculated for C28H20Cl2＝426.0942,found 426.0943.
3) Synthesis of 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) chloride (DPA 2 Cl):
1g (1.0 eq) of DPA2CH 2 Cl was weighed into 100mL of DMF and 3.6mL (10.0 eq) of trimethylamine was added to the reaction system. After 24h, ethanol/n-hexane was recrystallized to give a milky white solid.
1H NMR(400MHz,DMSO)δ7.83(t,J＝8.2Hz,4H),7.62(d,J＝6.1Hz,8H),7.46(d,J＝7.0Hz,4H),4.74(s,4H),3.19(s,18H).13C NMR(150MHz,DMSO-d6)δ140.58,136.51,133.61,131.92,129.53,128.49,126.93,126.27,67.89,52.34.
HRMS(m/z):[M]2+calculated for C34H38N2＝237.1512,found 237.1513.
Example 2
A process for preparing 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) hexafluorophosphate (DPA 2PF 6), the process comprising the steps of:
50mg (1.0 eq) of DPA2Cl was dissolved in 2mL of water/1.5 mL of ethanol, 154mg (10.0 eq) of sodium hexafluorophosphate was dissolved in 2mL of water, the former was dropped into the latter, white precipitate immediately precipitated, and the water was washed with ultrasound three times.
1H NMR(400MHz,DMSO)δ7.81(d,J＝7.4Hz,4H),7.62(d,J＝7.0Hz,8H),7.46(d,J＝6.9Hz,4H),4.71(s,4H),3.18(s,18H).13C NMR(150MHz,DMSO-d6)δ140.28,136.08,133.13,131.56,129.13,127.91,126.51,125.85,67.75,51.99.
HRMS(m/z):[M]2+calculated for C34H38N2＝237.1512,found 237.1513;[M]-calculated for F6P＝144.9647,found 144.9648.
Example 3
A process for the preparation of 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) acetate (DPA 2CH 3 COO), comprising the steps of:
50mg (1.0 eq) of DPA2Cl was dissolved in 2mL of water/1.5 mL of ethanol, 75mg (10.0 eq) of sodium acetate was dissolved in 2mL of water, the former was dropped into the latter, white precipitate immediately precipitated, and the water was washed with ultrasound three times.
Example 4
A process for preparing 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4), the process comprising the steps of:
50mg (1.0 eq) of DPA2Cl was dissolved in 2mL of water/1.5 mL of ethanol, 322mg (10.0 eq) of sodium tetraphenylborate was dissolved in 3mL of water/2.5 mL of ethanol, the former was dropped into the latter, white precipitate immediately precipitated, and ethanol/water washing was performed three times. Acetone/acetonitrile recrystallization.
1H NMR(400MHz,DMSO)δ7.81(d,J＝7.3Hz,4H),7.62(d,J＝6.6Hz,8H),7.49–7.41(m,4H),7.18(s,16H),6.92(t,J＝7.1Hz,16H),6.78(t,J＝7.0Hz,8H),4.70(s,4H),3.17(s,18H).13C NMR(150MHz,DMSO-d6)δ163.39(q,J＝49.5Hz),140.25,136.03,135.57,133.10,131.53,129.10,127.85,126.46,125.78,125.35,121.55,67.69,39.52.
HRMS(m/z):[M]2+calculated for C34H38N2＝237.1512,found 237.1512;[M]-calculated for C24H20B＝319.1633,found 319.1666.
Example 5
A process for the preparation of 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2F 5BPH4), comprising the steps of:
The potassium pentafluoroetetraphenyl borate was weighed and dissolved by adding 5mL of ethanol. DPA2Cl was dissolved in 6.5mL ethanol as a pale yellow solution. Mixing the two, and adding deionized water to obtain milky solid.
Example 6
A process for the preparation of N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methyl ammonium chloride (DPACl), comprising the steps of:
1) Synthesis of (4- (10-phenylanthracen-9-yl) phenyl) methanol (DPACH 2 OH):
415mg (1.25 eq) of potassium carbonate was weighed, 1mL of deionized water was added to dissolve the potassium carbonate, 1g (1.25 eq) of 9-bromo-10-phenylanthracene and 365mg (1.0 eq) of 4-hydroxymethylphenylboronic acid were weighed into a 50mL Schlenk flask, an aqueous potassium carbonate solution was added, 12mL of 1, 4-dioxane was added, the vacuum was applied to the flask three times, and under the nitrogen atmosphere, 14mg (0.005 eq) of palladium tetraphenylphosphine was added, followed by three times of vacuum application. Under nitrogen, heating to 105 ℃, and turning off the nitrogen after refluxing. At 100 ℃, the reactants are completely dissolved, after 12h of reaction, the mixture is extracted three times with dichloromethane/water and dried over anhydrous magnesium sulfate. Column chromatography was performed with dichloromethane as eluent to give 650mg of milky white solid in 75% yield.
1H NMR(400MHz,DMSO)δ7.63(dt,J＝17.5,9.3Hz,10H),7.44(dd,J＝19.7,7.5Hz,7H),4.70(s,2H).
2) Synthesis of 9- (4- (chloromethyl) phenyl) -10-phenylanthracene (DPACH 2 Cl):
100mg (1.0 eq) DPACH 2 OH was added to the round bottom flask, 5uL (0.2 eq) DMF,5mL anhydrous dichloromethane, and 40uL (2.0 eq) thionyl chloride was slowly added under ice bath. In the form of a pale yellow solution. After 24h, dichloromethane: petroleum ether=1:1, and purifying by column chromatography.
1H NMR(400MHz,DMSO)δ7.58(dddd,J＝31.7,22.8,17.1,7.5Hz,17H),4.98(s,2H).
3) Synthesis of N, N, N-trimethyl-1- (4- (10-phenylanthracene-9-yl) phenyl) methyl ammonium chloride (DPACl):
350mg (1.0 eq) DPACH 2 Cl and 18mL DMF are added to a 100mL round bottom flask, stirred at room temperature, 0.7mL (4.0 eq) trimethylamine is added and the solution is clear to light yellow. After one half hour, the reaction solution became cloudy and milky. After the reaction, about 80mL of diethyl ether was added dropwise to the stirred reaction solution, and a white solid was precipitated, filtered off with suction and recrystallized to give a milky solid.
1H NMR(400MHz,DMSO)δ7.82(d,J＝7.2Hz,2H),7.74–7.56(m,9H),7.45(dd,J＝12.1,6.3Hz,6H),4.74(s,2H),3.20(s,9H).
Example 7
A process for the preparation of N, N-trimethyl-1- (4- (10-phenylanthracene-9-yl) phenyl) hexafluorophosphate methylamine (DPAPF 6), comprising the steps of:
100mg DPACl mL of ethanol was dissolved, 192mg of sodium hexafluorophosphate was dissolved in 2mL of water, the former was dropped into the latter, a white precipitate was immediately produced, and the mixture was centrifuged at 8000r/min for 5min, washed with water and sonicated three times.
Example 8
A process for the preparation of methylamine N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) acetate (DPACH 3 COO), comprising the steps of:
50mg (1.0 eq) DPACl of sodium acetate was dissolved in 2mL of water/1.5 mL of ethanol, 75mg (10.0 eq) of sodium acetate was dissolved in 2mL of water, the former was dropped into the latter, white precipitate immediately precipitated, and the water was washed with ultrasound three times.
Example 9
A process for the preparation of N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methanamine tetraphenylborate (DPABPH 4), comprising the steps of:
200mg DPACl mL of ethanol and 20mL of ethanol are dissolved in the solution, the former is dripped into the latter, white precipitation is generated immediately, the centrifugation is carried out for 8000r/min-5min, and the ethanol is used for washing and ultrasonic treatment is carried out for three times.
1H NMR(400MHz,DMSO)δ7.81(d,J＝7.2Hz,2H),7.77–7.56(m,9H),7.45(dd,J＝12.9,6.6Hz,6H),7.18(s,8H),6.92(t,J＝7.1Hz,8H),6.79(t,J＝7.0Hz,4H),4.71(s,2H),3.18(s,9H).
Example 10
A process for the preparation of N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methanamine tetrakis (perfluorophenyl) borate (DPAB 5FPH4), comprising the steps of:
The potassium pentafluoroetetraphenyl borate was weighed and dissolved by adding 5mL of ethanol. DPACl was dissolved in 6.5mL of ethanol as a pale yellow solution. Mixing the two, and adding deionized water to obtain milky solid.
Example 11
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
under the air atmosphere, a photosensitizer of octaethylporphyrin platinum (PtOEP) and an ionic annihilation agent of 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) are added into chromatographic pure dimethyl sulfoxide DMSO, uniformly mixed, added with silicon dioxide and uniformly stirred, so that the up-conversion luminescent material shown in figure 1 can be obtained.
Wherein the concentration of the photosensitizer in the DMSO solution is 1.0X10 -5 mol/L, the mol ratio of the photosensitizer to the annihilator is 1:24, and the mass fraction of the silicon dioxide is 7.4%.
Up-conversion test performance: under the conditions of air and room temperature, the up-conversion luminescence spectrum of the quasi-solid system is shown as figure 2, and under the condition that the excitation light wavelength is 532nm, the system obtains blue luminescence with anti-Stokes displacement, and the strongest emission peak of the up-conversion luminescence is 440nm.
Electrically-controlled luminescence response performance: the up-conversion luminescent material is coated on a conductive layer of Indium Tin Oxide (ITO) and then written on by using a platinum wire as a pen. The platinum wire and the ITO are respectively connected on the cathode and the anode, after voltage is applied, the up-conversion luminous intensity can generate strength difference along with the movement of the pen on the up-conversion luminous material, so that the pen can write on the up-conversion luminous material, and after the voltage is reversed, handwriting can be erased, as shown in figure 3. The applied voltage was 10V.
This is because the cationic chromophore moves with the movement of the cathode in the electric field, and thus changes in chromophore concentration, which is manifested as a change in intensity of up-converted luminescence under excitation by 532nm laser.
Example 12
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was the same as in example 11, except that the photosensitizer concentration was changed to 1.0X10 -6 mol/L.
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 13
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
the preparation was identical to example 11 except that the molar ratio of photosensitizer to annihilator was changed to 1:12.
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 14
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
the preparation method was the same as in example 11 except that the mass fraction of silica was changed to 5%.
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 15
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation method is the same as in example 11, except that the mass fraction of silica is changed to 10%.
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 16
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
the preparation method was the same as in example 11 except that the mass fraction of silica was changed to 13.8%.
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 17
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
the preparation process is identical to example 11, except that the photosensitizer platinum octaethylporphyrin (PtOEP) is replaced by palladium octaethylporphyrin (PdOEP).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 18
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
the preparation was identical to example 11 except that the annihilator 1,1'- (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) chloride (DPA 2 Cl).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 19
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1'- (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) hexafluorophosphate (DPA 2PF 6).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 20
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1'- (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) acetate (DPA 2CH 3 COO).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 21
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1'- (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2F 5BPH4).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 22
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with N, N-trimethyl-1- (4- (10-phenylanthracene-9-yl) phenyl) methyl ammonium chloride (DPACl).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 23
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with N, N-trimethyl-1- (4- (10-phenylanthracene-9-yl) phenyl) hexafluoro methylamine phosphate (DPAPF 6).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 24
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with methylamine N, N, N-trimethyl-1- (4- (10-phenylanthracene-9-yl) phenyl) acetate (DPACH 3 COO).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 25
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with N, N-trimethyl-1- (4- (10-phenylanthracene-9-yl) phenyl) methylamine tetraphenylborate (DPABPH 4).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Example 26
Providing a quasi-solid ion type up-conversion luminescent material with electrically controlled luminescence response, which comprises the following specific steps:
The preparation was identical to example 11 except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) was replaced with N N, N-trimethyl-1- (4- (10-phenylanthracene-9-yl) phenyl) methylamine tetrakis (perfluorophenyl) borate (DPAB 5FPH4).
The up-conversion luminescence and the electrically controlled luminescence response performance results were the same as in example 11.
Test example 1
In order to illustrate that the quasi-solid ion type up-conversion luminescent material with the electric regulation luminescence response has the functions of anti-counterfeiting and text encryption/decryption, two control groups are provided and are analyzed and compared with the electric regulation luminescence response of an experimental group;
1) The experimental group is the quasi-solid ion type up-conversion luminescent material prepared in the example 11;
2) Control 1 is a quasi-solid ionic upconversion luminescent material containing only ionic annihilator, and the preparation method is the same as that of example 11, except that the photosensitizer platinum octaethylporphyrin (PtOEP) is not added.
3) Control group 2 is a quasi-solid ionic upconversion luminescent material containing only photosensitizer, and the preparation method is the same as that of example 11, except that no ionic annihilation agent 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2BPH 4) is added.
Study results: as can be seen from fig. 4, only the quasi-solid ion type up-conversion luminescent material in which both the photosensitizer and the ionic annihilator exist has clear writing under both 532nm laser light and 365nm ultraviolet light, and the cationic chromophore moves along with the movement of the cathode in an electric field, so that the change of chromophore concentration is brought, the change of up-conversion luminescence intensity is shown under the excitation of 532nm laser light, and the change of fluorescence intensity is shown under the excitation of 365nm ultraviolet light; only the quasi-solid ion up-conversion luminescent material of the ion annihilator has no up-conversion luminescence under 532nm laser because no photosensitizer exists, and obvious handwriting can be seen under an ultraviolet lamp; only the quasi-solid ion type up-conversion luminescent material of the photosensitizer lacks the ionic annihilation agent under 532nm laser, so that up-conversion luminescence is completely absent, and red phosphorescence of the photosensitizer can be observed only under 365nm ultraviolet lamp, but written handwriting cannot be seen. The method shows that the quasi-solid ion type up-conversion luminescent material can realize encryption and decryption of characters in the air, and has an anti-counterfeiting effect.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (12)
1. A quasi-solid ionic up-conversion luminescent material with electrically controlled luminescence response, characterized in that the up-conversion luminescent material comprises a photosensitizer, an ionic annihilator and a quasi-solid matrix;
the ionic annihilator is selected from ionic derivatives of diphenyl anthracene, and the structural formula of the ionic annihilator is shown in the following formula I or formula II:
I；/>II；
Wherein each of the R 1、R2 independently represents any one of a substituted or unsubstituted C 1-C10 alkyl group, a substituted or unsubstituted C 3-C10 cycloalkyl group; the R 1、R2 may be the same or different;
the A is selected from one or more of halogen, acetic acid, hexafluorophosphoric acid, tetraphenyl boric acid and tetra (pentafluorophenyl) boric acid;
the substituent of R 1、R2 is selected from aryl of C 6-C14 or aryl of C 6-C14 substituted by alkyl;
the photosensitizer is selected from platinum octaethylporphyrin or palladium octaethylporphyrin;
the quasi-solid matrix is a gel matrix composed of silicon dioxide and a viscous solvent; the viscous solvent is selected from DMSO.
2. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein a is one or more selected from hexafluorophosphoric acid, tetraphenylboronic acid or tetrakis (pentafluorophenyl) boronic acid.
3. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein a molar ratio of the photosensitizer to the ionic annihilator is 1:1-5000.
4. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein the mass fraction of silica in the quasi-solid matrix is 1% -20%.
5. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein the mass fraction of silica in the quasi-solid matrix is 5% -15%.
6. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein the up-conversion luminescent material is excited in air to realize conversion of green light into blue light.
7. A method for preparing a quasi-solid ionic up-conversion luminescent material according to any one of claims 1 to 6, comprising the steps of:
Mixing the photosensitizer, the ionic annihilation agent and the silicon dioxide with a viscous solvent, and stirring in air for 2-5 min to obtain the fluorescent dye.
8. The method according to claim 7, wherein the concentration of the photosensitizer in the viscous solvent is 1.0X10 -6-2.0×10-4 mol/L.
9. Use of a quasi-solid ionic up-conversion luminescent material according to any one of claims 1-6 for the manufacture of anti-counterfeit products.
10. An information recording apparatus, characterized in that the information recording apparatus comprises a writing instrument, and a conductive layer coated with the quasi-solid ionic up-conversion luminescent material according to any one of claims 1 to 6; the conductive layer is made of indium tin oxide; the writing tool is made of one of platinum wires, silver wires or copper wires; the writing tool and the conductive layer are respectively connected to the cathode and the anode.
11. The information recording apparatus according to claim 10, wherein the trace retention is achieved by applying a voltage and excitation light to the conductive layer in an air environment, and by up-converting movement of the luminescent material on the conductive layer with the writing instrument; after reversing the voltage, erasure of the trace is achieved.
12. The information recording apparatus according to claim 11, wherein the applied voltage is 2 to 20V; the wavelength of the excitation light is 532 nm.
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