CN115521776A - Quasi-solid-state ionic up-conversion luminescent material with electrically-controlled luminescence response, preparation and application thereof - Google Patents
Quasi-solid-state ionic up-conversion luminescent material with electrically-controlled luminescence response, preparation and application thereof Download PDFInfo
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- CN115521776A CN115521776A CN202210967557.7A CN202210967557A CN115521776A CN 115521776 A CN115521776 A CN 115521776A CN 202210967557 A CN202210967557 A CN 202210967557A CN 115521776 A CN115521776 A CN 115521776A
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- ionic
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- luminescent material
- solid
- conversion luminescent
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- 238000004020 luminiscence type Methods 0.000 title claims abstract description 72
- 230000004044 response Effects 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 50
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
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- FCNCGHJSNVOIKE-UHFFFAOYSA-N 9,10-diphenylanthracene Chemical class C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 FCNCGHJSNVOIKE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims abstract description 5
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 44
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- VFMUXPQZKOKPOF-UHFFFAOYSA-N 2,3,7,8,12,13,17,18-octaethyl-21,23-dihydroporphyrin platinum Chemical group [Pt].CCc1c(CC)c2cc3[nH]c(cc4nc(cc5[nH]c(cc1n2)c(CC)c5CC)c(CC)c4CC)c(CC)c3CC VFMUXPQZKOKPOF-UHFFFAOYSA-N 0.000 claims description 6
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- 125000000217 alkyl group Chemical group 0.000 claims description 5
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- HCIIFBHDBOCSAF-UHFFFAOYSA-N octaethylporphyrin Chemical compound N1C(C=C2C(=C(CC)C(C=C3C(=C(CC)C(=C4)N3)CC)=N2)CC)=C(CC)C(CC)=C1C=C1C(CC)=C(CC)C4=N1 HCIIFBHDBOCSAF-UHFFFAOYSA-N 0.000 claims description 4
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 4
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- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
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- 230000014759 maintenance of location Effects 0.000 claims description 2
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- AVPXPBPKCXAWMJ-UHFFFAOYSA-N 9,10-bis[4-(chloromethyl)phenyl]anthracene Chemical compound C1=CC(CCl)=CC=C1C(C1=CC=CC=C11)=C(C=CC=C2)C2=C1C1=CC=C(CCl)C=C1 AVPXPBPKCXAWMJ-UHFFFAOYSA-N 0.000 description 1
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
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- 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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- 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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- 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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- 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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- 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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Abstract
The invention discloses a quasi-solid-state ionic up-conversion luminescent material with electrically-controlled luminescence response, and preparation and 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 diphenylanthracene, an ionic derivative of anthracene, an ionic derivative of pyrene, or an ionic derivative of perylene; the quasi-solid matrix is a gel matrix consisting of silicon dioxide and a viscous solvent. Under the action of the quasi-solid matrix, the high-efficiency oxygen removal and isolation effect is achieved, the limit condition of an oxygen-free environment is eliminated, the sensitivity of the up-conversion luminescent material to oxygen is reduced, an ion motion channel is provided for the ion annihilation agent, and the up-conversion luminescent material is convenient to regulate and control and respond to an electric field.
Description
Technical Field
The invention relates to the field of photon up-conversion materials. More particularly, relates to a quasi-solid ionic up-conversion luminescent material with electrically-controlled luminescence response, preparation and application thereof.
Background
Solar energy is a clean and resource-rich energy source and is considered to be one of the most promising renewable energy sources. In order to make more efficient use of solar energy, it is desirable to extract as much energy as possible from sunlight, particularly using low energy photons that do not meet the band gap of conventional light harvesting materials. Photon up-conversion is a process of converting low-energy photons into high-energy photons, and up-conversion based on triplet-triplet annihilation (TTA-UC) can convert light with long wavelength into light with higher available energy and short wavelength by using low-power excitation light, and has important application value in the aspects of photocatalysis, biological imaging and the like.
The TTA-UC system consists of two chromophores (photosensitizer and annihilator). First, the donor (photosensitizer) absorbs a photon to its first excited singlet state 1 S, followed by intersystem crossing (ISC) to the first excited triplet state 1 T, the photosensitizer transfers energy to the acceptor through triplet-triplet energy transfer (TTET), allowing the acceptor to reach its first excited triplet state 1 T, two triplet receptors interact, triplet-triplet annihilation (TTA) occurs, and one acceptor molecule reaches the first excited singlet state 1 S, the other acceptor molecule is inactivated to ground state S 0 . Finally, the acceptor molecule reaching the first excited state decays in the form of an anti-stokes shift radiative transition. Both TTET and TTA involve a Dexter-type electron exchange mechanism, which needs to be completed by collision, but at present, TTA up-conversion is mostly completed in a low-viscosity and oxygen-removed organic solvent, and the use of the organic solvent has the limitations of easy volatilization, difficult encapsulation, limited dissolving capacity of an up-conversion dye and the like, so that the TTET and the TTA are hindered in practical application.
In addition, although up-conversion can also be used for biosensing and chemosensing by stimulus response, i.e., TTA-UC switching is achieved in response to external stimuli such as temperature, chemicals, oxygen, light, electric fields, and mechanical forces. However, there are still few TTA systems with stimulus response, so the aggregate TTA-UC system with fast smart response is still to be further developed or innovated.
Therefore, it is important to develop an upconversion luminescent material with low sensitivity to oxygen and a stimulus response to solve the above problems.
Disclosure of Invention
The first purpose of the invention is to provide a quasi-solid ionic up-conversion luminescent material with electrically-controlled luminescence response. The quasi-solid ionic up-conversion luminescent material can realize regulation response to an electric field by introducing an ionic annihilating agent, realize 'writing' and 'erasing' of information, and reduce sensitivity to oxygen under the wrapping of a quasi-solid substrate, so that the up-conversion luminescent material can realize up-conversion luminescence in the air.
It is a second object of the present invention to provide a method for preparing an up-converting luminescent material as described above.
The third purpose of the invention is to provide an application of the up-conversion luminescent material in manufacturing anti-counterfeiting products.
It is a fourth object of the present invention to provide an information recording device comprising the upconversion luminescent material as described above.
In order to achieve the first purpose, the invention adopts the following technical scheme:
the invention discloses a quasi-solid ionic up-conversion luminescent material with electrically-controlled luminescence response, which comprises a photosensitizer, an ionic annihilator and a quasi-solid substrate;
wherein the ionic annihilator is selected from one or more of an ionic derivative of diphenylanthracene, an ionic derivative of anthracene, an ionic derivative of pyrene, or an ionic derivative of perylene;
the quasi-solid matrix is a gel matrix consisting of silicon dioxide and a viscous solvent.
On one hand, the quasi-solid ionic 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 an ionic annihilating agent, so that the strength and weakness of the conversion luminescent intensity on a voltage action area and a non-voltage action area are compared, the information is written, and the information is quickly erased in a voltage reversal mode; 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, reduces adverse effects of the gel matrix on an up-conversion system, reduces the sensitivity of the up-conversion luminescent material to the oxygen, gets rid of the limitation condition of an oxygen-free environment, and further expands the application range of the up-conversion system.
In one embodiment, the general structures of two ionic derivatives of diphenylanthracene are provided in the present invention, but the structure of ionization of annihilating agents (e.g. anthracene, pyrene, perylene, etc.) which are commonly used in the art and have similar structures can be modified by the same structure design, so long as the energy level of the photosensitizer can be matched to achieve the effects of up-conversion luminescence and electrical modulation response, and the general structures of the ionic derivatives of anthracene, pyrene or perylene are not listed in the present invention.
The two ionic derivatives of diphenylanthracene mentioned above have the structural formula shown in formula I or formula II:
wherein, R is 1 、R 2 Each independently represents substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Any one of cycloalkyl groups of (a); the R is 1 、R 2 May be the same or different;
the A is selected from one or more of halogen, acetic acid, hexafluorophosphoric acid, tetraphenylboronic acid and tetrakis (pentafluorophenyl) boronic acid; preferably, when A is selected from hexafluorophosphoric acid, tetrakis (pentafluorophenyl) borate or tetraphenylboronic acid, the interaction between the anions and cations is relatively weak, and the electric response is more easily realized by the electric field.
Further, for R 1 、R 2 Selection of groups, illustratively, canIs 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, or the like; when said R is 1 、R 2 When a substituent is present, the substituent is selected from C 6 -C 14 Aryl or alkyl substituted C 6 -C 14 The aryl group of (a) may be, for example, a phenyl group, a naphthyl group, a phenanthryl group, and the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, or an n-nonyl group.
Further, photosensitizers conventional in the art are selected for use in the present invention, for example: porphyrin-based photosensitizers or metal-complexed pyridine-based photosensitizers; preferably, the photosensitizer is selected from octaethylporphyrin platinum or octaethylporphyrin palladium, wherein the structural formulas of the octaethylporphyrin platinum (PtOEP) and the octaethylporphyrin palladium (PdOEP) are as follows:
further, the molar ratio of the photosensitizer to the ionic annihilator is 1-5000; in an exemplary manner, the first and second electrodes are, the molar ratio of the photosensitizer to the ionic annihilator can also be 1-5,1: 1000,1, 10-2000, 1-20-30, 1.
Furthermore, the quasi-solid matrix provided by the invention has the functions of removing oxygen and providing an ion movement channel, and particularly, the selected viscous solvent such as DMSO can react with oxygen to remove part of oxygen in the system, so that the formed gel matrix can block oxygen in the air, further the oxygen separation effect is realized, and the gel matrix also provides a movement channel for ions, so that the ion annihilation agent can rapidly move in the gel matrix, and conditions are provided for responding to electric regulation. The mass fraction of 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 has better effects of removing oxygen and oxygen, and the formed quasi-solid matrix can be more favorable for ion movement; preferably, the viscous solvent is selected from DMSO.
Further, the up-conversion luminescent material realizes the conversion of green light into blue light through excitation in air.
In order 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 photosensitizer, ionic annihilator, silicon dioxide and viscous solvent, and stirring in air for 2-5 min to obtain the final product.
Preferably, the concentration of the photosensitizer in the viscous solvent is 1.0 × 10 -6 -2.0×10 -4 mol/L。
In order to achieve the third objective, the invention discloses an application of the quasi-solid ionic up-conversion luminescent material in manufacturing anti-counterfeiting products.
To achieve the fourth object, the present invention discloses an information recording device comprising the quasi-solid ionic up-conversion luminescent material; the information recording device comprises a writing tool and a conductive layer coated with the quasi-solid ionic up-conversion luminescent material; the conducting 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, voltage and exciting light are applied to the up-conversion luminescent material on the conducting layer in the air environment, and a writing tool moves on the conducting layer to realize trace retention; when the voltage is reversed, erasure of the traces is achieved.
In a specific embodiment, the level 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, the larger the applied voltage is, the faster the erasing speed is after reversing the voltage, wherein the applied voltage is 2-20V; the wavelength of the exciting light is 532nm.
The invention has the following beneficial effects:
the invention discloses a quasi-solid-state ionic up-conversion luminescent material with electrically-controlled luminescent response, and preparation and application thereof. The up-conversion luminescent material comprises a photosensitizer, an ionic annihilator 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 adjusted through simple voltage, the quasi-solid-state ionic up-conversion luminescence material has the difference of up-conversion luminescence intensity under the stimulation action of an electric signal, the characteristic of quick response is realized, and the application range of the up-conversion luminescence material is further expanded.
(2) The quasi-solid-state ionic up-conversion luminescent material with electrically-controlled luminescence response provided by the invention does not need to be operated in a glove box, and the whole preparation process and the regulation and control process are realized by operating in the air, so that the material has great practical application significance to the up-conversion luminescent material sensitive to oxygen.
(3) The annihilator in the quasi-solid-state ionic up-conversion luminescent material with the electrically regulated luminescence response is simple to synthesize, does not need a particularly complex separation and purification process, and has cheap and easily-obtained raw materials.
(4) The quasi-solid-state ionic up-conversion luminescent material with the electrically regulated luminescence response can be used as a writable information recording device, has a reversible writing function, can realize the functions of writing and erasing, and is very critical to the information recording device.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 shows a physical diagram of an up-converting luminescent material of example 11.
FIG. 2 shows the emission spectrum of the upconversion luminescent material of example 11 under 532nm laser.
Fig. 3 shows a luminescence response diagram of the upconversion luminescent material of example 11 under electrical control.
Fig. 4 is a graph showing comparison of luminescence responses under electrical control of the samples of the experimental group and the two control groups of test example 1.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and figures. It will be understood by those skilled in the art that the following detailed description is intended to be illustrative and not restrictive, and should not be taken to limit the scope of the invention, which is defined by any of the ranges set forth herein including the endpoints and any number between the endpoints and any sub-range defined by the endpoints or any number between the endpoints.
In the present invention, the preparation method is a conventional method unless otherwise specified. The starting materials used are, unless otherwise specified, available from published commercial sources, and the percentages are, unless otherwise specified, percentages by mass.
Example 1
1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) chloride (DPA) 2 Cl), comprising the steps of:
1) Synthesis of (Anthracene-9, 10-diylbis (4, 1-phenylene)) dimethanol (DPA 2 CH) 2 OH):
8.23g (4.0 eq) of potassium carbonate was weighed, 40mL of deionized water was added and dissolved, 5g (1.0 eq) of 9, 10-dibromoanthracene and 9g (4.0 eq) of 4-hydroxymethylphenylboronic acid were weighed in a 500mL Schlenk bottle, an aqueous solution of potassium carbonate was added, 100mL of 1, 4-dioxane was added, nitrogen gas was introduced three times under vacuum, 172mg (0.01 eq) of tetratriphenylphosphine palladium was added under nitrogen atmosphere, and then nitrogen gas was introduced 3 times under vacuum. Heating to 110 ℃ under the condition of introducing nitrogen, refluxing, then closing the nitrogen, generating a white solid after the reaction is finished, adding deionized water, and carrying out suction filtration to obtain a solid, and recrystallizing with THF.
1 H 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 C 28 H 22 O 2 ＝390.1620,found 390.1621.
2) Synthesis of 9, 10-bis (4- (chloromethyl) phenyl) anthracene (DPA 2 CH) 2 Cl):
100mg (1.0 eq) of DPA2CH 2 OH was added to a 250mL round bottom flask, 50mL of anhydrous dichloromethane was added, stirring was carried out at room temperature, and 10uL (0.5 eq) of DMF was added. 0.1uL (2.0 eq) of thionyl chloride was added slowly under ice-cooling. During the reaction process, the reactant is gradually dissolved, the organic solvent is removed by rotation under reduced pressure, and column chromatography is carried out by taking dichloromethane as an eluent to obtain a milky white solid with the yield of 94.3%.
1 H 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 C 28 H 20 Cl 2 ＝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 was weighed 2 Cl was added to 100mL of DMF, and 3.6mL (10.0 eq) of trimethylamine was added to the reaction system. After 24h, ethanol/n-hexane recrystallised 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 C 34 H 38 N 2 ＝237.1512,found 237.1513.
Example 2
1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) hexafluorophosphate (DPA 2 PF) 6 ) The preparation method comprises the following steps:
50mg (1.0 eq) of DPA2Cl was dissolved in 2mL of water per 1.5mL of ethanol, 154mg (10.0 eq) of sodium hexafluorophosphate was dissolved in 2mL of water, the former was dropped into the latter, a white precipitate was immediately precipitated, and the mixture was washed with water and sonicated three times.
1 H 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). 13 C 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 C 34 H 38 N 2 ＝237.1512,found 237.1513；[M] - calculated for F6P＝144.9647,found 144.9648.
Example 3
1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) acetate (DPA 2 CH) 3 COO), the process comprising the steps of:
50mg (1.0 eq) of DPA2Cl was dissolved in 2mL of water per 1.5mL of ethanol, 75mg (10.0 eq) of sodium acetate was dissolved in 2mL of water, the former was added dropwise to the latter, a white precipitate was immediately precipitated, and the mixture was washed with water and sonicated three times.
Example 4
1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) The preparation method comprises the following steps:
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 added dropwise to the latter, a white precipitate immediately precipitated, and the mixture was washed with ethanol/water and sonicated three times. Acetone/acetonitrile recrystallization.
1 H 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 C 34 H 38 N 2 ＝237.1512,found 237.1512；[M] - calculated for C 24 H 20 B＝319.1633,found 319.1666.
Example 5
1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2F) 5 BPH 4 ) The preparation method comprises the following steps:
potassium pentafluorotetraphenylborate was weighed and dissolved in 5mL of ethanol. DPA2Cl was dissolved in 6.5mL of ethanol as a pale yellow solution. Mixing the two, and adding deionized water to obtain a milky white solid.
Example 6
A process for the preparation of N, N-trimethyl-1- (4- (10-phenylanthran-9-yl) phenyl) methylammonium 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 it, 1g (1.25 eq) of 9-bromo-10-phenylanthracene and 365mg (1.0 eq) of 4-hydroxymethylphenylboronic acid were weighed in a 50mL Schlenk bottle, an aqueous solution of potassium carbonate was added, 12mL of 1, 4-dioxane was added, nitrogen gas was introduced three times under vacuum, 14mg (0.005 eq) of tetratriphenylphosphine palladium was added under nitrogen gas, and then nitrogen gas was introduced three times under vacuum. Heating to 105 deg.C under nitrogen, refluxing, and closing nitrogen. At 100 ℃, the reaction mass is completely dissolved, and after 12 hours of reaction, the mixture is extracted with dichloromethane/water for three times and dried by anhydrous magnesium sulfate. Column chromatography was performed with dichloromethane as eluent to give 650mg of off-white solid in 75% yield.
1 H 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) of DPACH 2 OH was added to a round bottom flask, 5uL (0.2 eq) of DMF,5mL of anhydrous dichloromethane were added, and 40uL (2.0 eq) of thionyl chloride was added slowly under ice bath. In the form of a pale yellow solution. After 24h, with dichloromethane: and (3) separating and purifying by using an eluent column chromatography of petroleum ether = 1.
1 H 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-phenylanthracen-9-yl) phenyl) methylammonium chloride (DPACL):
350mg (1.0 eq) of DPACH 2 Cl and 18mL DMF were added to a 100mL round bottom flask, stirred at room temperature, and 0.7mL (4.0 eq) trimethylamine was added and the solution was clear to light yellow. After one and a half hours, 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 precipitated out, which was then filtered off and recrystallized to give a milky white solid.
1 H 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
N, N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methylamine hexafluorophosphate (DPAPF) 6 ) The preparation method comprises the following steps:
100mg of DPACL is dissolved in 5mL of ethanol, 192mg of sodium hexafluorophosphate is dissolved in 2mL of water, the former is dripped into the latter, white precipitate is generated immediately, the mixture is centrifuged at 8000r/min for 5min, and the mixture is washed with water and treated with ultrasound three times.
Example 8
N, N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) acetic acid methylamine (DPACH) 3 COO), comprising the steps of:
50mg (1.0 eq) of DPACl was dissolved in 2mL of water per 1.5mL of ethanol, 75mg (10.0 eq) of sodium acetate was dissolved in 2mL of water, the former was added dropwise to the latter, a white precipitate immediately precipitated, and the mixture was washed with water and sonicated three times.
Example 9
N, N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methylamine tetraphenylborate (DPABPH) 4 ) The preparation method comprises the following steps:
200mg of DPACl is dissolved in 10mL of ethanol, sodium tetraphenylborate is dissolved in 20mL of ethanol, the former is dripped into the latter, white precipitate is generated immediately, the mixture is centrifuged at 8000r/min-5min, and the mixture is washed with ethanol and ultrasonically treated for three times.
1 H 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
N, N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methylamine tetrakis (perfluorophenyl) borate (DPAB) 5 FPH 4 ) The preparation method comprises the following steps:
potassium pentafluorotetraphenylborate was weighed and dissolved in 5mL of ethanol. DPACl was dissolved in 6.5mL ethanol as a pale yellow solution. Mixing the two, and adding deionized water to obtain a milky white solid.
Example 11
The utility model provides a quasi solid-state ionic up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
under the air atmosphere, a photosensitizer platinum octaethylporphyrin (PtOEP) and an ionic annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Adding into chromatographic pure dimethyl sulfoxide DMSO, mixing, and adding silicon dioxideAnd stirring uniformly to obtain the up-conversion luminescent material shown in figure 1.
Wherein the concentration of photosensitizer in DMSO solution is 1.0 × 10 -5 mol/L, the molar ratio of the photosensitizer to the annihilating agent is 1.
Up-conversion test performance: under the conditions of air and room temperature, the spectrum of the up-conversion luminescence of a quasi-solid system is shown in figure 2, under the condition that the wavelength of exciting light is 532nm, the system obtains anti-Stokes shift blue luminescence, 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 the conductive layer Indium Tin Oxide (ITO), and then a platinum wire is used as a pen to write on the up-conversion luminescent material. The platinum wire and the ITO are respectively connected to the cathode and the anode, after voltage is applied, the intensity difference of the up-conversion luminous intensity along with the movement of the pen on the up-conversion luminous material can be generated, so that the pen can write on the up-conversion luminous material, and after the voltage is reversed, the handwriting can be erased, which is shown in detail 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, which in turn causes a change in the chromophore concentration, which appears as a change in the intensity of the up-converted luminescence under excitation by the 532nm laser.
Example 12
The utility model provides a quasi solid-state ionic up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the photosensitizer concentration is changed to 1.0X 10 -6 mol/L。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 13
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation method is the same as that of example 11, except that the molar ratio of the photosensitizer to the annihilating agent is changed to 1.
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 14
The utility model provides a quasi solid-state ionic up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is the same as in example 11 except that the mass fraction of silica is changed to 5%.
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 15
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is the same as in example 11 except that the mass fraction of silica is changed to 10%.
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 16
The utility model provides a quasi solid-state ionic up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is the same as in example 11 except that the mass fraction of silica is changed to 13.8%.
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 17
The utility model provides a quasi solid-state ionic up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is the same as that of example 11, except that the photosensitizer platinum octaethylporphyrin (PtOEP) is replaced by palladium octaethylporphyrin (PdOEP).
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 18
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation method is the same as that of example 11, except that the annihilating agent 1,1' - (anthracene-9, 10-diyl bis (4, 1-phenylene)) bis is used(N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement was made with 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N-trimethylmethylamine) chloride (DPA 2 Cl).
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 19
The utility model provides a quasi solid-state ionic up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by 1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) hexafluorophosphate (DPA 2 PF) 6 )。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 20
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the annihilating agent 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by 1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) acetate (DPA 2 CH) 3 COO)。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 21
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by 1,1' - (Anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2F) 5 BPH 4 )。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 22
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by N, N-trimethyl-1- (4- (10-phenylanthren-9-yl) phenyl) methylammonium chloride (DPACl).
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 23
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by N, N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methylamine hexafluorophosphate (DPAPF) 6 )。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 24
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by N, N, N-trimethyl-1- (4- (10-phenylanthren-9-yl) phenyl) acetic acid methylamine (DPACH) 3 COO)。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 25
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation method is the same as that of example 11, except that the annihilator 1,1' - (anthracene-9, 10-di)Bis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by N, N, N-trimethyl-1- (4- (10-phenylanthren-9-yl) phenyl) methylamine tetraphenylborate (DPPABPH) 4 )。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Example 26
The utility model provides a quasi solid-state ion type up-conversion luminescent material of electrically-controlled luminescence response, which comprises the following steps:
the preparation process is identical to that of example 11, except that the annihilator 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) 4 ) Replacement by N, N, N-trimethyl-1- (4- (10-phenylanthracen-9-yl) phenyl) methylamine tetrakis (perfluorophenyl) borate (DPAB) 5 FPH 4 )。
The results of up-conversion luminescence and electrically-controlled luminescence response properties were the same as those of example 11.
Test example 1
In order to show that the quasi-solid-state ionic up-conversion luminescent material with electrically-controlled luminescent response has the functions of anti-counterfeiting and character encryption/decryption, the example provides two control groups and carries out analysis and comparison on the electrically-controlled luminescent response and the experimental group;
1) The experimental group is the quasi-solid ionic up-conversion luminescent material prepared in example 11;
2) Control 1 is a quasi-solid ionic up-conversion luminescent material containing only ionic annihilator, and is prepared in the same way as in example 11, except that no photosensitizer platinum octaethylporphyrin (PtOEP) is added.
3) Control 2, a quasi-solid ionic up-conversion phosphor containing only a photosensitizer, was prepared as in example 11 except that 1,1' - (anthracene-9, 10-diylbis (4, 1-phenylene)) bis (N, N, N-trimethylmethylamine) tetraphenylborate (DPA 2 BPH) was used without the addition of an ionic annihilator 4 )。
The research result is as follows: as can be seen from fig. 4, only the quasi-solid ionic upconversion luminescent material with both photosensitizer and ionic annihilator has clear writing under 532nm laser and 365nm ultraviolet lamp, the cationic chromophore moves with the movement of the cathode in the electric field, which brings the change of the chromophore concentration, and the change shows the change of the upconversion luminescence intensity under the excitation of 532nm laser and the change of the fluorescence intensity under 365nm ultraviolet lamp; only the quasi-solid ionic up-conversion luminescent material of the ionic annihilation agent has no photosensitizer under 532nm laser, so that no up-conversion luminescence is realized, and obvious writing can be seen under an ultraviolet lamp; only the quasi-solid ionic up-conversion luminescent material of the photosensitizer does not emit up-conversion luminescence at all under 532nm laser due to the lack of ionic annihilation agents, and red phosphorescence of the photosensitizer can be observed only under a 365nm ultraviolet lamp, but written writing cannot be seen. The method shows that the quasi-solid ionic 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 above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A quasi-solid ionic up-conversion luminescent material with electrically-controlled luminescence response is characterized in that 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 diphenylanthracene, an ionic derivative of anthracene, an ionic derivative of pyrene, or an ionic derivative of perylene;
the quasi-solid matrix is a gel matrix consisting of silicon dioxide and a viscous solvent.
2. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein the ionic annihilator is selected from ionic derivatives of diphenylanthracene, represented by the following formula I or formula II:
wherein, R is 1 、R 2 Each independently represents substituted or unsubstituted C 1 -C 10 Alkyl, substituted or unsubstituted C 3 -C 10 Any one of cycloalkyl groups of (a); the R is 1 、R 2 May be the same or different;
a is selected from one or more of halogen, acetic acid, hexafluorophosphoric acid, tetraphenylboronic acid and tetrakis (pentafluorophenyl) boronic acid;
preferably, a is selected from one or more of hexafluorophosphoric acid, tetraphenylboronic acid or tetrakis (pentafluorophenyl) boronic acid.
3. The quasi-solid ionic up-conversion luminescent material as claimed in claim 2, wherein R is selected from the group consisting of 1 、R 2 Is selected from C 6 -C 14 Aryl or alkyl substituted C 6 -C 14 Aryl group of (1).
4. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein the photosensitizer is selected from porphyrin-based photosensitizers or metal-complexed pyridine-based photosensitizers;
preferably, the photosensitizer is selected from platinum octaethylporphyrin or palladium octaethylporphyrin.
5. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein the molar ratio of the photosensitizer to the ionic annihilator is 1;
preferably, the mass fraction of the silicon dioxide in the quasi-solid matrix is 1-20%;
preferably, the mass fraction of the silicon dioxide in the quasi-solid matrix is 5-15%;
preferably, the viscous solvent is selected from DMSO.
6. The quasi-solid ionic up-conversion luminescent material according to claim 1, wherein the up-conversion luminescent material achieves conversion of green light into blue light by excitation in air.
7. A method for preparing a quasi-solid state ionic up-conversion luminescent material according to any one of claims 1 to 6, comprising the steps of:
mixing a photosensitizer, an ionic annihilation agent, silicon dioxide and a viscous solvent, and stirring in the air for 2-5 min to obtain the composite material;
preferably, the concentration of the photosensitizer in the viscous solvent is 1.0 × 10 -6 -2.0×10 -4 mol/L。
8. Use of the quasi-solid ionic up-conversion luminescent material according to any one of claims 1 to 6 in the manufacture of anti-counterfeiting products.
9. An information recording device comprising a writing instrument and a conductive layer coated with a quasi-solid ionic upconverting luminescent material according to any one of claims 1 to 6; the conducting layer is made of indium tin oxide; the writing tool is made of one of a platinum wire, a silver wire or a copper wire; the writing tool and the conductive layer are connected to the cathode and the anode, respectively.
10. The information recording apparatus according to claim 9, wherein the trace retention is achieved by applying a voltage and an excitation light to the conductive layer in an air atmosphere and moving an up-conversion luminescent material on the conductive layer with a writing tool; when the voltage is reversed, the erasure of the trace is realized;
preferably, the applied voltage is 2-20V; the wavelength of the exciting light is 532nm.
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