A tetraphenylstyryl-imidazopyrazine derivative with aie property and use thereof

Abstract

The application discloses a tetraphenylstyryl-imidazole pyrazine derivative with AIE properties and application, and has the following structure: 4-(1,2,2-triphenylvinyl) benzaldehyde, 5,6-diaminopyrazine-2,3-dicyan, sodium bisulfite are placed in N,N-dimethylformamide, and are reacted at 150 DEG C for 12h; after reaction, the functional organic material C-1 is obtained through separation and purification. The obtained product C-1, methyl iodide and N,N-diisopropylethylamine are placed in N,N-dimethylformamide, and are reacted at 90 DEG C for 1-2h; after reaction, a tetraphenylstyryl-imidazole pyrazine derivative with AIE properties is obtained. The functional organic material disclosed by the application has the advantages of low preparation cost, simple operation, simple method, and the material shows significant AIE characteristics, and can be applied to technical fields of luminescent materials and inkless writing.

Description

Technical Field

[0001] This invention belongs to the field of organic synthesis, specifically relating to the preparation of a tetraphenylethylene-imidazolium pyrazine derivative with AIE properties. Background Technology

[0002] Since the phenomenon of aggregation-induced emission (AIE) was formally proposed as a technical term by Professor Tang Benzhong's research team in 2001, it has attracted widespread attention and has made significant progress in recent years. AIE is mainly attributed to the restricted intramolecular motion; when the solution concentration increases or the material is in a solid state, molecular aggregation leads to a substantial enhancement of luminescence. AIE materials overcome the quenching of luminescence in the solid or aggregated state of traditional dye molecules, emitting intense light even in the solid state. As a novel and advanced material with excellent performance, AIE materials have great application potential in various fields.

[0003] Tetraphenylene (TPE) is a typical AIE organic fluorescent dye. Its structure contains a benzene ring that can rotate freely around the carbon-carbon double bond. In the aggregated state, this prevents π-π stacking and restricts intramolecular rotation and vibration, thus giving it good solid-state luminescence properties. By modifying the structure of TPE, its fluorescence properties can also be changed, such as giving it good fluorescence emission in solvents and a redshift.

[0004] This invention combines tetraphenylethylene and imidazopyrazine, modifying the imidazopyrazine skeleton to synthesize a novel method for tetraphenylethylene-imidazopyrazine derivatives. The reaction uses highly conjugated reactants 4-(1,2,2-triphenylvinyl)benzaldehyde and 5,6-diaminopyrazine-2,3-dicarboxynitrile as substrates, sodium bisulfite as a catalyst, and N,N-dimethylformamide as a solvent. This reaction utilizes readily available and inexpensive raw materials and is simple to operate. In the second step, the obtained C-1 product is further derivatized and reacted with RX using N,N-diisopropylethylamine as a catalyst and N,N-dimethylformamide as a solvent. This further yields the target product. This reaction utilizes readily available and inexpensive raw materials, is simple to operate, and operates under mild reaction conditions. Summary of the Invention

[0005] The purpose of this invention is to provide a novel functional organic material that is easy to synthesize, and the compound exhibits significant AIE properties.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] Tetraphenylene-imidazolium pyrazine derivatives exhibiting AIE properties, wherein the molecular structure of the material includes any one of the following:

[0008]

[0009] Includes the following steps:

[0010] Synthesis of C-1 functional organic material: 4-(1,2,2-triphenylvinyl)benzaldehyde, 5,6-diaminopyrazine-2,3-dicarboxynitrile, and sodium bisulfite were placed in N,N-dimethylformamide and reacted at 150℃ for 12 h. After the reaction was completed, the functional organic material C-1 was obtained by extraction and column chromatography separation and purification.

[0011] Synthesis of C-2 to C-7 functional organic materials: The obtained products C-1, RX, and N,N-diisopropylethylamine were placed in N,N-dimethylformamide and reacted at 90°C. After the reaction was completed, the functional organic materials C-2 to C-7 were obtained by extraction and column chromatography separation and purification.

[0012] The specific synthesis route is as follows:

[0013]

[0014] The functional organic materials synthesized in this invention have a large conjugated system, and the material molecules all have significant AIE characteristics. The preparation method described in this invention is simple, easy to operate, and low in cost, and can be applied to the fields of luminescent materials, inkless writing, and anti-counterfeiting. Attached Figure Description

[0015] Figure 1 This is the hydrogen NMR spectrum of C-1.

[0016] Figure 2 This is the carbon NMR spectrum of C-1.

[0017] Figure 3 This is the hydrogen NMR spectrum of C-2.

[0018] Figure 4 This is the carbon NMR spectrum of C-2.

[0019] Figure 5 This is the hydrogen NMR spectrum of C-6.

[0020] Figure 6 This is the carbon NMR spectrum of C-6.

[0021] Figure 7 The fluorescence spectra of C-1 in mixed solutions of water and tetrahydrofuran in different proportions are shown.

[0022] Figure 8 This is an image of C-1 under a 365°C UV lamp.

[0023] Figure 9The fluorescence spectra of C-2 in mixed solutions of water and tetrahydrofuran in different proportions are shown.

[0024] Figure 10 This is an image of C-2 under a 365°C UV lamp.

[0025] Figure 11 Fluorescence spectra of C-3 in mixed solutions of water and tetrahydrofuran in different proportions.

[0026] Figure 12 This is an image of C-3 under a 365°C UV lamp.

[0027] Figure 13 Fluorescence spectra of C-6 in mixed solutions of water and tetrahydrofuran in different proportions.

[0028] Figure 14 This is an image of C-6 under a 365°C UV lamp.

[0029] Figure 15 Images for ACQ and AIE.

[0030] Figure 16 These are the normalized fluorescence spectra of solid-state compounds C-1 to C-7.

[0031] Figure 17 Images of compounds C-1 to C-7 under a 365°C UV lamp. Detailed Implementation

[0032] The present invention will be further illustrated below with reference to the embodiments, but the scope of protection of the present invention is not limited to the scope described in the embodiments.

[0033] Example 1: Synthesis of C-1 material molecules

[0034] 4-(1,2,2-triphenylvinyl)benzaldehyde (360.8 mg, 1 mmol), 5,6-diaminopyrazine-2,3-dicarboxynitrile (160.1 mg, 1 mmol), sodium bisulfite (52.2 mg, 0.5 mmol), and 8 mL of N,N-dimethylformamide were added sequentially to a 25 mL reaction flask. After reacting at 150 °C for 12 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 2:1) to obtain the yellow material molecule C-1, with a mass of 125.6 mg and a yield of 50.2%.

[0035] The structural formula is as follows:

[0036]

[0037] Example 2: Synthesis of C-2 material molecules

[0038] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, iodomethane (141.9 mg, 0.5 mmol), cesium carbonate (97.7 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 2 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 2:1) to obtain the red-orange material molecule, with a mass of 15.0 mg and a yield of 29.2%.

[0039] The structure is as follows:

[0040]

[0041] Example 3: Synthesis of C-2 material molecules

[0042] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, iodomethane (141.9 mg, 0.5 mmol), N,N-diisopropylethylamine (38.8 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 1 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 2:1) to obtain the red-orange material molecule, with a mass of 25.6 mg and a yield of 49.8%.

[0043] The structure is as follows:

[0044]

[0045] Examples 2 and 3 show that when N,N-diisopropylethylamine is used as a catalyst, not only can the reaction time be shortened, but the reaction yield can also be increased.

[0046] Example 4: Synthesis of C-2 material molecules

[0047] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, methyl iodide (141.9 mg, 0.5 mmol), cesium carbonate (97.7 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 5 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 2:1) to obtain the red-orange material molecule, with a mass of 15.6 mg and a yield of 30.3%. The structural formula is as follows:

[0048]

[0049] Examples 3 and 4 demonstrate that using N,N-diisopropylethylamine as a catalyst not only shortens the reaction time but also increases the reaction yield. Therefore, the conditions in Example 3 are the optimal conditions.

[0050] Example 5: Synthesis of C-3 material molecules

[0051] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, 1-bromoethane (54.5 mg, 0.5 mmol), N,N-diisopropylethylamine (38.8 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 1 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 3:1) to obtain the yellow-orange material molecule, with a mass of 30.2 mg and a yield of 57.1%.

[0052] Example 6: Synthesis of C-4 Material Molecules

[0053] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, n-butane (68.5 mg, 0.5 mmol), N,N-diisopropylethylamine (38.8 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 1 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 2:1) to obtain the red material molecule, with a mass of 35.8 mg and a yield of 64.3%.

[0054] The structure is as follows:

[0055]

[0056] Example 7: Synthesis of C-5 material molecules

[0057] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, 1-bromohexane (82.5 mg, 0.5 mmol), N,N-diisopropylethylamine (38.8 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 1 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 2:1) to obtain the red-orange material molecule, with a mass of 29.6 mg and a yield of 50.6%.

[0058] The structure is as follows:

[0059]

[0060] Example 8: Synthesis of C-6 material molecules

[0061] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, benzyl bromide (136.8 mg, 0.5 mmol), N,N-diisopropylethylamine (38.8 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 1 h, the mixture was extracted with ethyl acetate. The extract was then subjected to column chromatography (PE:EA = 2:1) to obtain the red-orange material molecule, with a mass of 38.4 mg and a yield of 65.1%.

[0062]

[0063] Example 9: Synthesis of C-7 material molecules

[0064] The C-1 (50.0 mg, 0.1 mmol) obtained in Example 1, (bromomethyl)cyclohexane (88.5 mg, 0.5 mmol), N,N-diisopropylethylamine (38.8 mg, 0.3 mmol), and 2 mL of N,N-dimethylformamide were added sequentially to a 10 mL reaction flask. After reacting at 90 °C for 1 h, the mixture was extracted with ethyl acetate and subjected to column chromatography (PE:EA = 2:1) to obtain the red-orange material molecule, with a mass of 39.2 mg and a yield of 65.7%.

[0065] The structure is as follows:

[0066]

[0067] The proton NMR spectrum of C-1 is as follows: Figure 1 As shown, the carbon NMR spectrum is as follows: Figure 2 As shown.

[0068] The proton NMR spectrum of C-2 is as follows: Figure 3 As shown, the carbon NMR spectrum is as follows: Figure 4 As shown.

[0069] The proton NMR spectrum of C-6 is as follows: Figure 5 As shown, the carbon NMR spectrum is as follows: Figure 6 As shown.

[0070] Example 10

[0071] Weigh a certain amount of the prepared C-1 to C-7, dissolve them with THF to prepare a 1 mM stock solution, seal it and store it in the refrigerator.

[0072] Preparation of AIE system solutions: Using a pipette, pipette 0, 0.3, 0.6, 0.9, 1.2, 1.5, 1.8, 2.1, 2.4, 2.7, and 2.85 mL of aqueous solution, respectively. Then pipette 3, 2.7, 2.4, 2.1, 1.8, 1.5, 1.2, 0.9, 0.6, 0.3, and 0.15 mL of tetrahydrofuran solution, mixing them to a total volume of 3 mL. This prepares tetrahydrofuran-water mixed solutions with water volume fractions of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, and 95%. Add 30 μL of the stock solution to the 3 mL of the solution and test the AIE properties of the dye molecules at a concentration of 10 μM.

[0073] The AIE properties of C-1 to C-7 dye molecules were studied. The dye molecule concentration was 10 μM. In mixed solutions of water and tetrahydrofuran (water content 0%-95%) with different water volume ratios, THF was a good solvent for dye molecules C-1 to C-7, while water was a poor solvent. When water was added to the good solvent THF, the molecules aggregated after the concentration reached a certain level, accompanied by obvious enhanced luminescence (AIE phenomenon).

[0074] To study the AIE properties of C-1, fluorescence spectra were measured, such as... Figure 7 As shown, pure tetrahydrofuran exhibits almost no fluorescence, with an emission wavelength around 450 nm. With increasing water content (0-60%), neither the fluorescence intensity nor the emission wavelength changes significantly. When the water content increases to 70%-80%, the fluorescence intensity remains unchanged, but the emission wavelength shows a significant red shift, indicating that the dye molecules possess an ICT effect. When the water content is 90% or higher, dye molecule C-1 emits strong orange fluorescence. This is because at low concentrations (0%-80%), the four benzene rings of tetraphenylethylene can rotate, releasing energy through non-radiative transitions, thus the molecule does not emit light. However, when the water content is 90% or higher, dye molecule C-1 aggregates, inhibiting the rotation of the four benzene rings of tetraphenylethylene, hindering non-radiative transitions, and thus enhancing luminescence, exhibiting significant AIE properties.

[0075] The AIE properties of C-2 were studied using a dye concentration of 10 μM. The fluorescence spectrum is shown below. Figure 9As shown, pure tetrahydrofuran exhibits almost no fluorescence, with an emission wavelength around 450 nm. With increasing water content (0-60%), neither the fluorescence intensity nor the emission wavelength changes significantly. When the water content increases to 70%-80%, the fluorescence intensity remains unchanged, but the emission wavelength shows a significant red shift, indicating that the dye molecules possess an ICT effect. When the water content is 90% or higher, dye molecule C-1 emits strong orange-red fluorescence. This is because at low concentrations (0%-80%), the four benzene rings of tetraphenylethylene can rotate, releasing energy through non-radiative transitions, thus the molecule does not emit light. However, when the water content is 90% or higher, dye molecule C-2 aggregates, inhibiting the rotation of the four benzene rings of tetraphenylethylene, hindering non-radiative transitions, and thus enhancing luminescence, exhibiting significant AIE properties.

[0076] The AIE properties of C-3 were tested at a dye concentration of 10 μM, and the fluorescence spectrum was measured as follows: Figure 11 As shown, the dye exhibits almost no fluorescence in pure tetrahydrofuran solvent, with an emission wavelength around 450 nm. With increasing water content (from 0 to 60%), neither the fluorescence intensity nor the emission wavelength changes significantly. When the water content increases to 70%-80%, the fluorescence intensity remains unchanged, but the emission wavelength shows a significant red shift, indicating that the dye molecule possesses an ICT effect. When the water content is 90% or higher, dye molecule C-3 emits strong yellow fluorescence. This is because at low concentrations (0%-80%), the four benzene rings of tetraphenylethylene can rotate, releasing energy through non-radiative transitions, thus the molecule does not emit light. However, when the water content is 90% or higher, dye molecule C-1 aggregates, inhibiting the rotation of the four benzene rings of tetraphenylethylene, hindering non-radiative transitions, and thus enhancing luminescence, exhibiting significant AIE properties.

[0077] The AIE properties of C-6, dye test concentration of 10 μM, fluorescence spectrum, as shown below. Figure 13 As shown, the dye exhibits almost no fluorescence in pure tetrahydrofuran solvent, with an emission wavelength around 450 nm. With increasing water content (0-60%), neither the fluorescence intensity nor the emission wavelength changes significantly. When the water content increases to 70%-80%, the fluorescence intensity remains unchanged, but the emission wavelength shows a significant red shift, indicating that the dye molecule possesses an ICT effect. When the water content is 90% or higher, dye molecule C-6 emits strong orange fluorescence. This is because at low concentrations (0%-80%), the four benzene rings of tetraphenylethylene can rotate, releasing energy through non-radiative transitions, thus the molecule does not emit light. However, when the water content is 90% or higher, dye molecule C-1 aggregates, inhibiting the rotation of the four benzene rings of tetraphenylethylene, hindering non-radiative transitions, and thus enhancing luminescence, exhibiting significant AIE properties.

[0078] Prior to this, literature reported on traditional dye molecules, namely molecules with ACQ properties, such as... Figure 15 As shown, it exhibits properties opposite to AIE. It emits strong light in pure organic solvents, but as the water content increases, the dye molecules emit very little light or even no light at all. Tetraphenylene is a relatively typical AIE fluorescent luminescent group. Based on this, we designed this reaction and studied the AIE properties of the product.

[0079] Example 11

[0080] Using C-1 as the parent compound, six derivatives C-2 to C-7 were obtained, with the aim of regulating fluorescence properties by increasing the carbon chain length. To this end, solid-state fluorescence was tested, and the normalized solid-state fluorescence spectrum is shown below. Figure 16 , 17 As shown. By Figure 16 , 17 It can be seen that the emission wavelengths of derivatives C-2 to C-7 all exhibit a significant redshift, with a maximum redshift of 110 nm (from C-1 to C-7). This demonstrates that such a design is quite effective and reasonable.

[0081] Methylation can lengthen carbon chains and affect the π-π stacking pattern of compounds, which is why there are significant differences in fluorescence spectra.

Claims

1. A tetraphenylethylene-imidazolium pyrazine derivative with AIE properties, characterized in that, The structural formula of the derivative is selected from any one of the following formulas: 。 2. The method for preparing the tetraphenylethylene-imidazolium pyrazine derivative with AIE properties according to claim 1, characterized in that, Includes the following steps: (1) 4-(1,2,2-triphenylvinyl)benzaldehyde, 5,6-diaminopyrazine-2,3-dicarboxynitrile and sodium bisulfite were placed in N,N-dimethylformamide and reacted at 120-150℃ for 12 h. After the reaction was completed, the functional organic material C-1 was obtained by separation and purification. (2) The obtained product C-1, haloalkanes RX, and N,N-diisopropylethylamine were placed in N,N-dimethylformamide and reacted at 80-90℃ for 1-2 h. After the reaction was completed, the tetraphenylethylene-imidazolium derivative with AIE properties was obtained by separation and purification. The synthesis process is as follows: ， The structural formula of the haloalkane RX is selected from any of the following: 。 3. The method for preparing the tetraphenylethylene-imidazolium pyrazine derivative with AIE properties according to claim 2, characterized in that, In step (1), the reaction is carried out at 150°C for 12 hours; In step (2), the reaction is carried out at 90°C for 2 hours.

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