CN116768887A - Preparation method of iridescent and dual-band fluorescent emission material - Google Patents
Preparation method of iridescent and dual-band fluorescent emission material Download PDFInfo
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- CN116768887A CN116768887A CN202310456247.3A CN202310456247A CN116768887A CN 116768887 A CN116768887 A CN 116768887A CN 202310456247 A CN202310456247 A CN 202310456247A CN 116768887 A CN116768887 A CN 116768887A
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- carbazolyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000463 material Substances 0.000 title claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000013078 crystal Substances 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 27
- -1 carbazolyl bromoimidazopyridine Chemical compound 0.000 claims abstract description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003208 petroleum Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- CEBAHYWORUOILU-UHFFFAOYSA-N (4-cyanophenyl)boronic acid Chemical compound OB(O)C1=CC=C(C#N)C=C1 CEBAHYWORUOILU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000009792 diffusion process Methods 0.000 claims abstract description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 5
- 235000011399 aloe vera Nutrition 0.000 claims abstract description 4
- 239000003086 colorant Substances 0.000 claims abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 241001116389 Aloe Species 0.000 claims abstract 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims abstract 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000012043 crude product Substances 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 235000002961 Aloe barbadensis Nutrition 0.000 claims description 2
- 244000186892 Aloe vera Species 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 239000012046 mixed solvent Substances 0.000 claims 2
- 230000000638 stimulation Effects 0.000 claims 2
- 238000012258 culturing Methods 0.000 claims 1
- 239000003480 eluent Substances 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 235000019439 ethyl acetate Nutrition 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 235000019219 chocolate Nutrition 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
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- 230000009977 dual effect Effects 0.000 description 2
- 210000004709 eyebrow Anatomy 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000002348 vinylic group Chemical group 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical group N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- JQOAQUXIUNVRQW-UHFFFAOYSA-N hexane Chemical compound CCCCCC.CCCCCC JQOAQUXIUNVRQW-UHFFFAOYSA-N 0.000 description 1
- 150000005232 imidazopyridines Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- 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
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
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- C—CHEMISTRY; METALLURGY
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- 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
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
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- Theoretical Computer Science (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a preparation method of an iridescent and dual-band fluorescent emission material, which comprises the following steps: adding carbazolyl bromoimidazopyridine and p-cyanobenzeneboronic acid, tetra (triphenylphosphine) palladium and potassium carbonate as catalysts, tetrahydrofuran and water as solvents into a reaction bottle, and adding the mixture into a reaction bottle, wherein the mixture is prepared by mixing at least one of the components of the mixture with water, the catalyst and the catalyst o C~80 o And C, heating and refluxing under stirring, and separating and purifying the crude reaction product to obtain a novel carbazolyl imidazopyridine compound. The crystal with five different colors is obtained by using methylene dichloride-petroleum ether, tetrahydrofuran-petroleum ether, acetone-petroleum ether and ethyl acetate-petroleum ether as solvents through a solvent diffusion method. The invention develops the polycrystalline state and the solvent inclusion compound crystalline state material, realizes iridescence and dual-band fluorescence emission of one compound, and displays the performance of force-induced color change, and can be used for preparing the compoundThe crystal is dispersed in aloe gel to form high-level anti-fake material, and the novel material has wide application foreground in anti-fake pattern.
Description
Technical Field
The invention belongs to the field of organic functional materials, and particularly relates to a preparation method of an iridescent and dual-band fluorescent emission material.
Background
In solvent-mediated crystallization, solvent molecules are contained in the crystal lattice by intermolecular interactions between the solvent and the solute or filling channels/voids within the crystal lattice, which is known as solvent inclusion. Solvent inclusion offers the possibility of adjusting the product properties (mechanical, solubility, stability, bioavailability) without changing the chemical structure of the molecule. More importantly, the solvent inclusion compound can be used for separating and purifying medicines, capturing volatile harmful solvents and chemically sensing. However, solvent clathrates have not been reported to exhibit iridescence and dual band fluorescence emissions.
The phenomenon of crystallization into two or more crystals under different thermodynamic conditions (temperature, pressure, pH, etc.) is called as polycrystals, such as pure carbon (diamond and graphite), calcium carbonate (stone powder and yak oyster powder), basic copper chloride (α and β), eight different crystal forms of copper phthalocyanine, etc. Based on different physical and chemical properties such as melting point, hardness, stability, color or dissolution rate, the polymorphism is used for enriching the color of pigment, improving the bioavailability of the medicine, reducing toxicity, improving the treatment effect, and stabilizing chocolate on V-type for a long time, so that the chocolate is not easy to "frosting". In addition, polymorphism facilitates polymorphic emission (fluorescence, phosphorescence, and thermally activated delayed fluorescence) and explores the intrinsic mechanism of mechanochromatism. However, to our knowledge, there are few reports of a crystal form exhibiting two fluorescence emission bands and having high contrast with force-induced color change properties.
Disclosure of Invention
The invention aims to deeply discuss and excavate new optical properties of solvent inclusion compound and polycrystal, and provides a new construction method for realizing rainbow color and dual-band fluorescence emission and anti-counterfeiting patterns by using a single compound.
The invention adopts the following ideas: adding carbazolyl bromoimidazopyridine and p-cyanobenzeneboronic acid, tetra (triphenylphosphine) palladium and potassium carbonate as catalysts, tetrahydrofuran and water as solvents into a reaction bottle, and adding the mixture into a reaction bottle, wherein the mixture is prepared by mixing at least one of the components of the mixture with water, the catalyst and the catalyst o C-80 o And C, heating and refluxing under stirring, and separating and purifying a reaction crude product to obtain the carbazolyl imidazopyridine compound. The method comprises the steps of obtaining crystals with different colors by using dichloromethane-petroleum ether, tetrahydrofuran-petroleum ether, acetone-petroleum ether and ethyl acetate-petroleum ether as solvents through a solvent diffusion method, dispersing aloe vera gel, designing and drawing patterns, and constructing an advanced anti-counterfeiting pattern by means of different external force stimulus responses.
The aim of the invention is achieved by the following technical scheme.
A synthetic method of iridescent and dual-band fluorescent emission materials comprises the following preparation processes:
adding carbazolyl bromoimidazopyridine, p-cyanobenzeneboronic acid, a catalyst, alkali and a solvent into a reaction vessel under the protection of argon, and carrying out reaction at 60 DEG C o C-80 o And C, heating and refluxing for 12-24 hours under stirring, and separating and purifying the crude product by column chromatography to obtain the carbazolyl imidazopyridine compound.
Further, the preparation equation of the carbazolyl imidazopyridine compound is shown as follows:
in the preparation method, the molar ratio of the bromo-imidazopyridine compound to the p-cyanobenzeneboronic acid, the potassium carbonate and the tetra (triphenylphosphine) palladium is 1:1.2-1:2-1:0.01.
In the preparation method, the organic solvent is tetrahydrofuran and water, and the volume ratio is 10:1.
the principle of the invention is as follows: the cyano benzene substituted imidazopyridine is used as an electron withdrawing group, the carbazole is used as an electron donating group, a distorted donor (D) -pi-acceptor (A) molecular configuration is constructed through a benzene bridge, and the molecular conformation and stacking mode are regulated through different solvent polarities. The distorted molecular conformation aids in the formation of a relaxed molecular stack, thereby favoring the formation of solvent clathrates. Meanwhile, the heteroatom on the imidazopyridine can form various weak interactions with solvent molecules to further influence the molecular conformation and stacking mode, so that various fluorescence emissions are obtained, and iridescence and dual-band fluorescence emissions of a single compound are realized.
Compared with the prior art, the invention has the following advantages:
(1) The invention realizes iridescence and dual-band fluorescence emission of a single compound, and at present, the single compound has a multi-crystal state report and a solvent inclusion compound report, until no single compound has a report of dual-band emission and large-span fluorescence emission wavelength;
(2) The five crystals with different fluorescence emissions cultured by the invention can realize coverage from blue light, yellow light and red light, and present different force color change performances, and the five crystal forms of a single compound are used for constructing the anti-counterfeiting pattern, and the binding force color change can realize high-level encryption of the anti-counterfeiting pattern.
Drawings
FIGS. 1, 2 and 3 are the hydrogen spectrum, carbon spectrum and mass spectrum of the target product obtained in example 1;
FIG. 4 is a photograph showing fluorescence of five crystals of the objective product obtained in example 1 after grinding under 365 and nm ultraviolet light;
FIG. 5 is fluorescence emission spectra of five crystals of the objective product obtained in example 1;
FIG. 6 is a schematic diagram showing an anti-counterfeiting pattern constructed by five crystals of the target product obtained in example 1.
Detailed Description
The invention is further described by way of specific examples, but the scope and embodiments of the invention are not limited thereto.
Example 1
In a two-necked flask, carbazolyl bromoimidazopyridine (1.52 g,5.3 mmol), 4-cyanobenzeneboronic acid (0.77 g,3.5 mmol), THF (20.0 mL) and aqueous potassium carbonate (12.5 mL, 2.0M) were charged. At N 2 Pd (PPh) was added to the mixture 3 ) 4 (280.4 mg,0.4 mmol). The bright yellow solution was then slowly heated to 80 ℃ under nitrogen and held for 24 hours, after which the reaction was extracted with DCM and water. Combining the organic phases in anhydrous Na 2 SO 4 And (3) drying, filtering and concentrating under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (silica gel as stationary phase, petroleum ether/ethyl acetate=2:1, v/v) to give a yellowish green solid 1.56, g, 52% yield. Melting point 202-203 ℃.
Five different crystals were successfully grown by slow diffusion of saturated solutions of CzIPCN in Dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EtOAc), acetone (ACE) into n-Hexane (n-Hexane), named BC, YC, BT, RE and RA, respectively, according to different colors and solvents, by solvent diffusion. Blue BC and yellow YC appear in the same mixed solution (n-hexane/dichloromethane), while blue BT, red RE and RA come from n-hexane/tetrahydrofuran, n-hexane/ethyl acetate and n-hexane/acetone solutions in sequence. These crystals remain very stable after a few months of standing. In addition, their fluorescence emission spectra showed BC (469 nm) and BT (459 nm) exhibited single emission peaks, but YC (467 nm and 535 nm), RE (442 nm and 575 nm), and RA (450 nm and 575 nm) exhibited dual band emissions.
We outline a vinylic bear with five crystals. The eyebrows of the bear used crystals RE and RA with pink fluorescence emission, eyes were crystals YC with yellow fluorescence emission, nose and mouth were crystals BC and BT with similar blue fluorescence emission, and the facial outline was traced out blue fluorescence with the powder after grinding of the crystals. After gentle crushing of small Xiong Mei, the eyebrows turned blue fluorescent emission due to the sensitivity of crystals RE and RA to weak forces (light pressure). And after the eyes are crushed, the original yellow color is changed into yellow-green color. Further applies force to eyes of the little bear, and changes the color from yellow green to warm white. Finally, the eyes were reground and YC changed to blue fluorescence emission. Finally, a vinylic bear with blue fluorescence on the whole face is displayed. This provides a method for preparing a dynamic security pattern.
The hydrogen spectrum, the carbon spectrum and the mass spectrum of the obtained target product are shown in fig. 1, 2 and 3, and the structural characterization data are shown as follows:
1 H-NMR (500 MHz, CDCl 3 ) δ/ppm= 8.25~8.16 (m, 5H), 7.99 (s, 1H), 7.93 (s, 1H), 7.78 (dd, J = 20Hz, 4H), 7.67 (d, J = 10Hz, 2H), 7.50~7.42 (m, 4H), 7.31 (t, J = 15Hz, 2H), 7.09 (d, J = 5Hz, 1H) ; 13 C-NMR (100 MHz, CDCl 3 ) δ/ppm= 141.57, 141.00, 138.23, 136.01, 132.91, 131.00, 128.21, 127.63, 122.80, 122.59, 121.28, 118.74, 115.62, 115.33, 113.87, 110.45, 107.25, 107.19, 105.11, 103.81. HRMS (MALDI-TOF): m/z 483.1593 [[M +Na] + calculated value 483.1586].
The structure of the target compound was deduced from the above characterization data as follows:
Claims (9)
1. the preparation method of the iridescent and dual-band fluorescent emission material is characterized by comprising the following specific steps:
adding carbazolyl bromoimidazopyridine and p-cyanobenzeneboronic acid, tetra (triphenylphosphine) palladium and potassium carbonate as catalysts, tetrahydrofuran and water as solvents into a reaction bottle, and adding the mixture into a reaction bottle, wherein the mixture is prepared by mixing at least one of the components of the mixture with water, the catalyst and the catalyst o C-80 o Stirring, heating and refluxing, and separating and purifying a reaction crude product to obtain a carbazolyl imidazopyridine compound; the method comprises the steps of obtaining five crystals with different colors by using methylene dichloride-petroleum ether, tetrahydrofuran-petroleum ether, acetone-petroleum ether and ethyl acetate-petroleum ether as solvents through a solvent diffusion method; dispersing the crystal in aloe gel, and changing fluorescence emission of the crystal by different external force stimulation to construct high-level anti-counterfeiting pattern; the structural formula of the carbazolyl imidazopyridine compound is。
2. The method for synthesizing carbazolyl imidazopyridine compounds according to claim 1, wherein the molar ratio of the palladium catalyst to the p-cyanobenzeneboronic acid is 1:100.
3. The method for synthesizing the carbazolyl imidazopyridine compound according to claim 1, wherein the feeding molar ratio of carbazolyl bromoimidazopyridine to p-cyanobenzeneboronic acid is 1:1.2.
4. The method for synthesizing the carbazolyl imidazopyridine compound according to claim 1, wherein the solvent is a mixed solvent of tetrahydrofuran and water, and the volume ratio of the mixed solvent is 10:1.
5. The method for synthesizing the carbazolyl imidazopyridine compound according to claim 1, wherein the feeding molar ratio of the base to the carbazolyl bromoimidazopyridine is 2:1.
6. The method for synthesizing the carbazolyl imidazopyridine compound according to claim 1, wherein the reaction time of the preparation method is 12-24 hours.
7. The method for synthesizing carbazolyl imidazopyridines according to claim 1, wherein the separation method of the crude product is column chromatography with ethyl acetate and petroleum ether as eluent.
8. The method for culturing different crystals of carbazolyl imidazopyridine compound according to claim 1, wherein the crystals are cultured in the form of dichloromethane-petroleum ether (two crystal forms), tetrahydrofuran-petroleum ether, acetone-petroleum ether and ethyl acetate-petroleum ether, respectively.
9. The method for constructing an anti-counterfeiting pattern by using different crystals of the carbazolyl imidazopyridine compound according to claim 1, wherein the crystal-dispersed medium is aloe vera gel, and the external force stimulation mode is light pressure, heavy pressure and grinding.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310456247.3A CN116768887A (en) | 2023-04-25 | 2023-04-25 | Preparation method of iridescent and dual-band fluorescent emission material |
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