CN118005639A - Tetraphenyl ethylene-imidazole pyrazine derivative with AIE property and application thereof - Google Patents
Tetraphenyl ethylene-imidazole pyrazine derivative with AIE property and application thereof Download PDFInfo
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims abstract description 18
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011368 organic material Substances 0.000 claims abstract description 9
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000746 purification Methods 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 5
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000001350 alkyl halides Chemical class 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 24
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- UPTYCYWTFGTCCG-UHFFFAOYSA-N 5-(1-piperazinylsulfonyl)isoquinoline Chemical compound C=1C=CC2=CN=CC=C2C=1S(=O)(=O)N1CCNCC1 UPTYCYWTFGTCCG-UHFFFAOYSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000000975 dye Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 11
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 238000004020 luminiscence type Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- ZKAMEFMDQNTDFK-UHFFFAOYSA-N 1h-imidazo[4,5-b]pyrazine Chemical compound C1=CN=C2NC=NC2=N1 ZKAMEFMDQNTDFK-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- UUWSLBWDFJMSFP-UHFFFAOYSA-N bromomethylcyclohexane Chemical compound BrCC1CCCCC1 UUWSLBWDFJMSFP-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a tetraphenyl ethylene-imidazole pyrazine derivative with AIE property and application thereof, wherein the structure is as follows: 4- (1, 2-triphenylvinyl) benzaldehyde, 5, 6-diaminopyrazine-2, 3-dimethyl nitrile and sodium bisulphite are placed in N, N-dimethylformamide to react for 12 hours at 150 ℃, and after the reaction is finished, the functional organic material C-1 is obtained through separation and purification. The obtained products C-1, methyl iodide and N, N-diisopropylethylamine are placed in N, N-dimethylformamide to react for 1 to 2 hours at the temperature of 90 ℃, and the tetraphenyl ethylene-imidazole pyrazine derivative with AIE property is obtained after the reaction is finished. The functional organic material has the advantages of low preparation cost, simple and convenient operation and simple method, and the material has obvious AIE characteristics and can be applied to the technical fields of luminescent materials, inkless writing and the like.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to preparation of a tetraphenyl ethylene-imidazole pyrazine derivative with AIE properties.
Background
The phenomenon of "aggregation-induced emission (AIE)" has received extensive attention since being proposed by Tang Benzhong professor research team in 2001 as a term, and has made a long progress in recent years. The AIE phenomenon is mainly due to limited intramolecular movement, and when the concentration of the solution is increased or the solution is in a solid state, the aggregation of molecules can greatly enhance the luminescence. The AIE material overcomes the defect of luminescence quenching of the traditional dye molecules in a solid state or an aggregation state, can emit strong light in the solid state, and has great application potential in various fields as a novel advanced material with excellent performance.
Tetraphenyl ethylene (TPE) is a typical AIE organic fluorescent dye having a benzene ring freely rotatable around a carbon-carbon double bond in its structure, and having a superior solid state light emitting property by preventing pi-pi accumulation in an aggregated state and restricting rotation and vibration in a molecule. By structurally modifying the TPE, the fluorescent properties of the TPE can also be changed, such as good fluorescence emission in a solvent, wavelength red shift and the like.
The invention combines the two (tetraphenyl ethylene and the imidazopyrazine) to modify the imidazopyrazine skeleton, and invents a new method for synthesizing the tetraphenyl ethylene-imidazopyrazine derivative, which takes reactants of 4- (1, 2-triphenylvinyl) benzaldehyde with a highly conjugated structure and 5, 6-diaminopyrazine-2, 3-dimethylnitrile as reaction substrates, sodium bisulphite as a catalyst and N, N-dimethylformamide as a solvent for reaction, and the reaction raw materials are easy to obtain, low in price, simple to operate and the like. And the second step of reaction is to continuously carry out derivatization on the obtained C-1 product, continuously react with R-X, continuously carry out the reaction with N, N-diisopropylethylamine as a catalyst and N, N-dimethylformamide as a solvent to obtain the target product, wherein the reaction raw materials are easy to obtain, the price is low, the operation is simple, and the reaction condition is mild.
Disclosure of Invention
The object of the present invention is to provide a novel functional organic material which is easy to synthesize and which has remarkable AIE characteristics.
The aim of the invention is achieved by the following technical scheme:
The structural formula of the material molecule comprises any one of the following components:
The method comprises the following steps:
Synthesis of C-1 functional organic material: 4- (1, 2-triphenylvinyl) benzaldehyde, 5, 6-diaminopyrazine-2, 3-dimethyl nitrile and sodium bisulphite are placed in N, N-dimethylformamide to react for 12 hours at 150 ℃, and after the reaction is finished, the functional organic material C-1 is obtained through extraction and column chromatography separation and purification.
Synthesizing a C-2 to C-7 functional organic material: the obtained products C-1, R-X, N, N-diisopropylethylamine are placed in N, N-dimethylformamide to react at 90 ℃, and after the reaction is finished, the functional organic materials C-2 to C-7 are obtained through extraction and column chromatography separation and purification.
The specific synthetic route is as follows:
the functional organic material synthesized by the invention has a larger conjugated system, and the molecules of the material have obvious AIE characteristics.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of C-1.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of C-1.
FIG. 3 shows a hydrogen nuclear magnetic resonance spectrum of C-2.
FIG. 4 is a nuclear magnetic resonance carbon spectrum of C-2.
FIG. 5 shows a hydrogen nuclear magnetic resonance spectrum of C-6.
FIG. 6 is a nuclear magnetic resonance carbon spectrum of C-6.
FIG. 7 shows fluorescence spectra of C-1 in different proportions of water and tetrahydrofuran mixed solutions.
FIG. 8 is a corresponding picture of C-1 under a 365 UV lamp.
FIG. 9 is a fluorescence spectrum of C-2 in different proportions of water and tetrahydrofuran mixed solution.
FIG. 10 is a corresponding picture of C-2 under a 365 UV lamp.
FIG. 11 is a fluorescence spectrum of C-3 in different proportions of water and tetrahydrofuran mixed solution.
FIG. 12 is a corresponding picture of C-3 under 365 UV light.
FIG. 13 is a fluorescence spectrum of C-6 in different proportions of water and tetrahydrofuran mixed solution.
FIG. 14 is a corresponding picture of C-6 under a 365 UV lamp.
Fig. 15 is ACQ and AIE pictures.
FIG. 16 shows normalized fluorescence spectra of compounds C-1 to C-7.
FIG. 17 is a photograph of compounds C-1 to C-7 under 365 UV light.
Detailed Description
The present invention will be further illustrated by the following examples, but the scope of the invention is not limited to the examples.
Example 1: synthesis of C-1 material molecules
4- (1, 2-Triphenylvinyl) benzaldehyde (360.8 mg,1 mmol), 5, 6-diaminopyrazine-2, 3-carbonitrile (160.1 mg,1 mmol), sodium bisulphite (52.2 mg,0.5 mmol) and 8mL of N, N-dimethylformamide were sequentially added to a 25mL reaction flask, reacted at a heating temperature of 150℃for 12 hours, extracted with ethyl acetate, and subjected to column chromatography (PE: EA=2:1) to give the yellow material molecule C-1, 125.6mg in mass and 50.2% in yield.
The structural formula is as follows:
example 2: synthesis of C-2 material molecules
C-1 (50.0 mg,0.1 mmol), methyl iodide (141.9 mg,0.5 mmol), cesium carbonate (97.7 mg,0.3 mmol), 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 2 hours, extracted with ethyl acetate, and the red-orange material molecule was obtained by column chromatography (PE: EA=2:1) in a mass of 15.0mg and a yield of 29.2%.
The structural formula is as follows:
example 3: synthesis of C-2 material molecules
C-1 (50.0 mg,0.1 mmol), methyl iodide (141.9 mg,0.5 mmol), N-diisopropylethylamine (38.8 mg,0.3 mmol) and 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 1 hour, extracted with ethyl acetate, and the red-orange material was obtained by column chromatography (PE: EA=2:1) in a mass of 25.6mg and a yield of 49.8%.
The structural formula is as follows:
It was found from examples 2 and 3 that when N, N-diisopropylethylamine was used as a catalyst, not only the reaction time was shortened but also the reaction yield was improved.
Example 4: synthesis of C-2 material molecules
C-1 (50.0 mg,0.1 mmol), methyl iodide (141.9 mg,0.5 mmol), cesium carbonate (97.7 mg,0.3 mmol) and 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 5 hours, extracted with ethyl acetate, and subjected to column chromatography (PE: EA=2:1) to obtain the molecules of the reddish orange material with a mass of 15.6mg and a yield of 30.3%. The structural formula is as follows:
it was found from examples 3 and 4 that when N, N-diisopropylethylamine was used as a catalyst, not only the reaction time was shortened but also the reaction yield was improved. The conditions of example 3 are therefore optimal.
Example 5: synthesis of C-3 material molecules
C-1 (50.0 mg,0.1 mmol), 1-bromoethane (54.5, 0.5 mmol), N-diisopropylethylamine (38.8 mg,0.3 mmol), 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 1 hour, extracted with ethyl acetate, and subjected to column chromatography (PE: EA=3:1) to obtain the yellowish orange material molecule with a mass of 30.2mg and a yield of 57.1%.
Example 6: synthesis of C-4 material molecules
C-1 (50.0 mg,0.1 mmol), N-bromobutane (68.5 mg,0.5 mmol), N-diisopropylethylamine (38.8 mg,0.3 mmol), 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 1 hour, extracted with ethyl acetate, and the red material molecule was obtained by column chromatography (PE: EA=2:1) in a mass of 35.8mg and a yield of 64.3%.
The structural formula is as follows:
Example 7: synthesis of C-5 material molecules
C-1 (50.0 mg,0.1 mmol), 1-bromohexane (82.5 mg,0.5 mmol), N-diisopropylethylamine (38.8 mg,0.3 mmol), 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 1 hour, extracted with ethyl acetate, and subjected to column chromatography (PE: EA=2:1) to obtain the molecules of the reddish orange material, 29.6mg in mass, and 50.6% in yield.
The structural formula is as follows:
example 8: synthesis of C-6 material molecules
C-1 (50.0 mg,0.1 mmol), benzyl bromide (136.8 mg,0.5 mmol), N-diisopropylethylamine (38.8 mg,0.3 mmol), 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 1 hour, extracted with ethyl acetate, and the red-orange material molecule was obtained by column chromatography (PE: EA=2:1) with a mass of 38.4mg and a yield of 65.1%.
Example 9: synthesis of C-7 material molecules
C-1 (50.0 mg,0.1 mmol), (bromomethyl) cyclohexane (88.5 mg,0.5 mmol), N-diisopropylethylamine (38.8 mg,0.3 mmol) and 2mL of N, N-dimethylformamide obtained in example 1 were sequentially added to a 10mL reaction flask, reacted at a heating temperature of 90℃for 1 hour, extracted with ethyl acetate, and subjected to column chromatography (PE: EA=2:1) to obtain the molecules of the reddish orange material, 39.2mg in mass, 65.7% in yield.
The structural formula is as follows:
The nuclear magnetic resonance hydrogen spectrum of C-1 is shown in figure 1, and the nuclear magnetic resonance carbon spectrum is shown in figure 2.
The nuclear magnetic resonance hydrogen spectrum of C-2 is shown in FIG. 3, and the nuclear magnetic resonance carbon spectrum is shown in FIG. 4.
The nuclear magnetic resonance hydrogen spectrum of C-6 is shown in FIG. 5, and the nuclear magnetic resonance carbon spectrum is shown in FIG. 6.
Example 10
A certain amount of prepared C-1 to C-7 is weighed, dissolved by THF, prepared into mother solution with concentration of 1mM, sealed and stored in a refrigerating manner.
Preparing AIE system solution: pipette 0, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8, 2.1, 2.4, 2.7, 2.85mL of aqueous solution was pipetted, and 3, 2.7, 2.4, 2.1, 1.8, 1.5, 1.2, 0.9, 0.6, 0.3, 0.15mL of tetrahydrofuran solution was pipetted to mix them into a total volume of 3mL of solution to prepare tetrahydrofuran-water mixed solutions with water volume fractions of 0, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, respectively. mu.L of the mother liquor was added to 3mL of the solution, and the dye molecule having a concentration of 10. Mu.M was tested for AIE properties.
In examining the AIE properties of C-1 to C-7, dye molecules were tested at a concentration of 10. Mu.M, THF was a benign solvent for dye molecules C-1 to C-7 in a mixed solution of water and tetrahydrofuran (water content 0% -95%) in various water volume ratios, water was a poor solvent, and when water was added to the benign solvent THF, the molecules aggregated to some extent, with a significant luminescence enhancement (AIE phenomenon).
The AIE property of C-1 was studied, and the fluorescence spectrum was tested, as shown in FIG. 7, in which there was almost no fluorescence in pure tetrahydrofuran, the emission wavelength was located around 450nm, the fluorescence intensity and emission wavelength did not change significantly with increasing water content (0-60%), the fluorescence intensity did not change significantly when the water content was increased to 70% -80%, the emission wavelength had a significant red shift, indicating that the dye molecule had ICT effect, and when the water content was 90% or more, the dye molecule C-1 emitted strong orange fluorescence. The dye molecule is in low concentration (0% -80%), four benzene rings of tetraphenyl ethylene can rotate, energy is released through non-radiative transition, so that the molecule does not emit light, and when the moisture content is 90% or more, dye molecule C-1 gathers, rotation of four benzene rings of tetraphenyl ethylene is inhibited, non-radiative transition is blocked, and therefore the luminescence of the molecule is enhanced, and the molecule shows remarkable AIE property.
As shown in FIG. 9, the AIE property of C-2 is studied, the dye test concentration is 10 mu M, the fluorescence spectrum is shown in FIG. 9, the fluorescence is almost zero, the emission wavelength is near 450nm, the fluorescence intensity and the emission wavelength do not change obviously with the increase of the water content (0-60%), the fluorescence intensity does not change obviously when the water content is increased to 70% -80%, the emission wavelength is shifted in red obviously, the dye molecule has ICT effect, and the dye molecule C-1 emits strong orange-red fluorescence when the water content is 90% or above. The dye molecule is in low concentration (0% -80%), four benzene rings of tetraphenyl ethylene can rotate, energy is released through non-radiative transition, so that the molecule does not emit light, and when the moisture content is 90% or more, dye molecule C-2 gathers, rotation of four benzene rings of tetraphenyl ethylene is inhibited, non-radiative transition is blocked, and therefore the luminescence of the molecule is enhanced, and the molecule shows remarkable AIE property.
The AIE property of C-3, dye test concentration is 10. Mu.M, test fluorescence spectrum, as shown in FIG. 11, there is almost no fluorescence in pure tetrahydrofuran solvent, emission wavelength is near 450nm, with increasing water content (increasing from 0 to 60%), there is no obvious change in fluorescence intensity and emission wavelength, when water content increases to 70% -80%, there is no obvious change in fluorescence intensity, emission wavelength is obviously red shifted, indicating dye molecule has ICT effect, when water content is 90% and above, dye molecule C-3 emits strong yellow fluorescence. The dye molecule is in low concentration (0% -80%), four benzene rings of tetraphenyl ethylene can rotate, energy is released through non-radiative transition, so that the molecule does not emit light, and when the moisture content is 90% or more, dye molecule C-1 gathers, rotation of four benzene rings of tetraphenyl ethylene is inhibited, non-radiative transition is blocked, and therefore the luminescence of the molecule is enhanced, and the molecule shows remarkable AIE property.
The AIE property of C-6, the dye test concentration is 10 mu M, the fluorescence spectrum chart shows that the dye has almost no fluorescence in pure tetrahydrofuran solvent, the emission wavelength is near 450nm, the fluorescence intensity and the emission wavelength do not change obviously with the increase of the water content (0-60%), the fluorescence intensity does not change obviously when the water content is increased to 70% -80%, the emission wavelength has obvious red shift, the dye molecule has ICT effect, and the dye molecule C-6 emits strong orange fluorescence when the water content is 90% or above. The dye molecule is in low concentration (0% -80%), four benzene rings of tetraphenyl ethylene can rotate, energy is released through non-radiative transition, so that the molecule does not emit light, and when the moisture content is 90% or more, dye molecule C-1 gathers, rotation of four benzene rings of tetraphenyl ethylene is inhibited, non-radiative transition is blocked, and therefore the luminescence of the molecule is enhanced, and the molecule shows remarkable AIE property.
Heretofore, the literature reported that conventional dye molecules, i.e., molecules having ACQ properties, as shown in fig. 15, exhibit properties opposite to those of AIE, emit light strongly in pure organic solvents, dye molecules emit light weakly or even not with increasing water content, tetraphenyl ethylene is a more typical AIE fluorescent chromophore, based on which we devised this reaction and studied the AIE properties of the product.
Example 11
The C-1 is used as a parent body for derivatization to obtain 6 derivatives C-2-C-7, wherein the fluorescent property is hoped to be regulated and controlled by lengthening a carbon chain. For this purpose, the invention performs solid fluorescence test, and solid normalized fluorescence spectra are shown in fig. 16 and 17. As can be seen from FIGS. 16 and 17, the derivatives were carried out with a relatively pronounced red shift in the emission wavelength of C-2 to C-7, with a red shift of 110nm to the greatest extent, and the (C-1 to C-7) designs were found to be relatively effective and reasonable.
By methylation of the carbon chain, it is possible to influence the pi-pi stacking mode of the compounds, so that the fluorescence spectra are significantly different.
Claims (5)
1. A tetraphenyl ethylene-imidazole pyrazine derivative having AIE properties, wherein the structural formula of the derivative comprises any one of the following formulas:
2. The method for producing a tetraphenyl ethylene-imidazopyrazine derivative with AIE properties according to claim 1, characterized by comprising the steps of:
(1) 4- (1, 2-triphenylvinyl) benzaldehyde, 5, 6-diaminopyrazine-2, 3-dimethyl nitrile and sodium bisulphite are placed in N, N-dimethylformamide to react for 12 hours at 120-150 ℃, and after the reaction is finished, the functional organic material C-1 is obtained through separation and purification;
(2) The obtained product C-1 and halogenated alkane R-X, N, N-diisopropylethylamine are placed in N, N-dimethylformamide to react for 1 to 2 hours at the temperature of 80 to 90 ℃, and after the reaction is finished, the tetraphenyl ethylene-imidazole pyrazine derivative with AIE properties is obtained by separation and purification;
The synthesis process is as follows:
3. the method for producing a tetraphenyl ethylene-imidazopyrazine derivative of the nature of AIE according to claim 2 wherein the structural formula of the haloalkane R-X includes any one of the following:
4. The method for producing a tetraphenyl ethylene-imidazopyrazine derivative having AIE properties according to claim 2 wherein in step (1) the reaction is carried out at 150 ℃ for 12 hours;
In the step (2), the reaction is carried out for 2 hours at the temperature of 90 ℃.
5. The method for producing a tetraphenyl ethylene-imidazopyrazine derivative having AIE properties of claim 2 wherein said reaction solvent is N, N-dimethylformamide.
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