Beta-diketone derivative compound as well as preparation method and application thereof
By designing the coordination relationship between pyridine β-dione compounds at different locations and rare earth ions, the structural diversity and stability of existing β-dione compounds in the coordination process are solved, and their efficient application in the field of fluorescent materials is achieved.
Patent Information
- Application Number
- CN202510059093.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-01-14
- Publication Date
- 2025-04-18
AI Technical Summary
The existing β-dione compounds have structural diversity and stability problems during coordination, making it difficult to effectively regulate their coordination angle and shape, which limits their application in the field of fluorescent materials.
By designing pyridine β-dione compounds at different locations, they use their different coordination angles to coordinate with rare earth ions to form compounds with different angles, shapes and coordination numbers to enhance their fluorescence performance.
The efficient coordination between pyridine β-dione compounds at different locations and rare earth ions is achieved, which significantly improves its fluorescence performance, making it suitable for bioimaging, optoelectronic devices and communication materials fields.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of compound synthesis, and in particular to a beta-diketone derivative compound and a preparation method and application thereof. Background Art
[0002] β-diketone compounds are the most popular and widely studied rare earth coordination compounds. This is mainly because β-diketone ligands have high ultraviolet absorption coefficients, strong coordination ability for rare earth ions, and efficient energy transfer between them and central ions, so the corresponding rare earth complexes have high luminescence efficiency. β-diketone compounds have been studied for more than a century, and a large amount of research work has shown their superiority as luminescent materials and their wide application.
[0003] β-diketone ligands contain multiple atoms that can participate in coordination. The methylene group in its molecule is affected by two carbonyl groups and is very easy to undergo enol interconversion. Therefore, there are two configurations, keto and enol, at the same time, which also allows this type of ligand to chelate with metal ions through various coordination modes. Acetylacetone (Hacac) is a common β-diketone compound. Usually, Hacac exists in the enol form in the gas phase and liquid phase. In water, the pKa of Hacac is 8.9. Therefore, Hacac is easy to deprotonate under certain conditions, and the generated monovalent anion can be used as a bidentate ligand to form various complexes through different coordination modes. Compared with other multidentate ligands (such as bipyridine, crown ether, alkyl phosphine, etc.), β-diketone ligands have the advantages of easy preparation, diverse coordination modes, and easy adjustment.
[0004] In the prior art, a variety of pyridyl organic ligands and different transition metals have been used for directed design and synthesis, and many two-dimensional and three-dimensional supramolecules have been obtained, which have good applications in catalytic fluorescence and even anti-cancer fields. In the past few decades, coordination-driven self-assembly has been the focus of many studies in the self-assembly of pyridyl organic ligands and transition metals. Therefore, designing ligands around β-diketones can achieve structural diversity of assemblies and develop more properties. Summary of the invention
[0005] The purpose of the present invention is to provide a β-diketone derivative compound and a preparation method and application thereof. The pyridine β-diketone compounds at different positions have different coordination angles. By designing compounds that can coordinate with different rare earth ions to form compounds with different angles, shapes and coordination numbers, fluorescent properties are obtained, which can be applied to the fields of biological imaging, optoelectronic devices and communication materials.
[0006] To achieve the above object, the present invention provides a method for preparing a β-diketone derivative compound, comprising the following steps:
[0007] S1, synthesis of β-diketone compounds;
[0008] S2, at room temperature, Et3N, alcohol solution, and the β-diketone compound obtained in S1 are mixed in proportion, stirred to dissolve, and then the alcohol solution of EuCl3·6H2O is added dropwise under stirring, and stirred for 22 to 26 hours to obtain a solution at which the synthesis reaction is completed;
[0009] S3. Concentrate the solution obtained in S2 and add water to precipitate, filter, wash and dry to obtain a β-diketone derivative compound.
[0010] Preferably, in S1, the synthesized β-diketone compound is specifically:
[0011] According to the proportion, sodium methoxide is dissolved in methanol, and the solution is added dropwise to a tert-butyl methyl ether solution containing ethyl trifluoroacetate. Subsequently, a tert-butyl methyl ether solution of acetylpyridine is added to the mixed solution, and the mixture is stirred at room temperature for 22 hours. A 10% by mass aqueous solution of citric acid is added until the pH value of the reaction solution is about 3-5. The mixture is filtered, washed and dried to obtain a β-diketone compound.
[0012] Preferably, in the tert-butyl methyl ether solution of acetylpyridine, acetylpyridine is one of 4-acetylpyridine and 3-acetylpyridine.
[0013] Preferably, the molar ratio of the ethyl trifluoroacetate to the acetyl pyridine is 1:1.
[0014] Preferably, in S2, the alcohol solution is one of methanol or ethanol.
[0015] Preferably, in S2, the Et3N: the alcohol solution: the β-diketone compound = 1.2 ml: 100 ml: 8 mmol.
[0016] Preferably, in S2, the alcohol solution of EuCl3·6H2O is specifically EuCl3·6H2O:alcohol solution=1mmol:50ml.
[0017] Preferably, in S2, the stirring for 22 to 26 hours further comprises:
[0018] Add a mixed solution of 1,10-phenanthroline and methanol dropwise;
[0019] The molar ratio of the 1,10-phenanthroline to the β-diketone compound is 1:3.
[0020] To achieve the above object, the present invention also provides a β-diketone derivative compound, including β-diketone derivative compound III, β-diketone derivative compound IV, β-diketone derivative compound V and β-diketone derivative compound VI, wherein the structural formula of β-diketone derivative compound III is as follows:
[0021]
[0022] The structural formula of β-diketone derivative compound IV is as follows:
[0023]
[0024] The structural formula of β-diketone derivative compound V is as follows:
[0025]
[0026] The structural formula of β-diketone derivative compound VI is as follows:
[0027]
[0028] To achieve the above-mentioned purpose, the present invention also provides an application of β-diketone derivative compounds in biological imaging, optoelectronic devices, and communication materials.
[0029] Therefore, the present invention adopts the above-mentioned β-diketone derivative compound and its preparation method and application, and the beneficial effects are as follows:
[0030] (1) The pyridine β-diketone compounds at different positions of the present invention have different coordination angles. By designing compounds that can coordinate with different rare earth ions to form compounds with different angles, shapes, and coordination numbers, fluorescent properties are obtained, which can be applied to the fields of biological imaging, optoelectronic devices, and communication materials.
[0031] (2) The preparation method of the present invention has the advantages of few steps (the product can be obtained by one-step synthesis), simple operation (involving only common organic synthesis steps), low production cost (the raw materials are cheap and easy to obtain), high yield (the yield is more than 50%), simple post-processing and purification, etc., and is suitable for industrial production of β-diketone compounds.
[0032] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS
[0033] Figure 1 This is a PL spectrum of a β-diketone derivative compound and its preparation method and application example of the present invention;
[0034] Figure 2 It is a fluorescence lifetime decay curve diagram of a β-diketone derivative compound and its preparation method and application example of the present invention. DETAILED DESCRIPTION
[0035] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.
[0036] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.
[0037] Example 1
[0038] This embodiment provides a β-diketone compound I, whose structural formula is:
[0039]
[0040] The synthetic route for preparing β-diketone compound I is as follows:
[0041]
[0042] The preparation method is as follows:
[0043] Sodium methoxide (9.4 g, 49 mmol) was dissolved in 5 ml of methanol and added dropwise to 10 ml of tert-butyl methyl ether solution containing ethyl trifluoroacetate (6.32 g, 44.5 mmol). Then, 20 ml of tert-butyl methyl ether solution of 4-acetylpyridine (4.90 g, 44.5 mmol) was added to the mixed solution, stirred at room temperature for 22 h, and 10% citric acid aqueous solution was added until the pH of the reaction solution was about 4. The precipitate was collected by filtration, washed with water and dried to obtain yellow solid ligand 1 (5.46 g, 62%).
[0044] Example 2
[0045] This embodiment provides a β-diketone compound II, whose structural formula is:
[0046]
[0047] The preparation method is as follows:
[0048] Sodium methoxide (9.4 g, 49 mmol) was dissolved in 5 ml of methanol and added dropwise to 10 ml of tert-butyl methyl ether solution containing ethyl trifluoroacetate (6.32 g, 44.5 mmol). Then, 20 ml of tert-butyl methyl ether solution of 3-acetylpyridine (4.90 g, 44.5 mmol) was added to the mixed solution, stirred at room temperature for 22 h, and 10% citric acid aqueous solution was added until the pH of the reaction solution was about 4. The precipitate was collected by filtration, washed with water and dried to obtain an off-white solid ligand 2 (4.93 g, 56%).
[0049] Example 3
[0050] This embodiment provides a β-diketone derivative compound III, whose structural formula is:
[0051]
[0052] The specific steps are as follows:
[0053] At room temperature, ligand 1 (17.36 mg, 0.08 mmol) was added to 1 ml of ethanol, and 0.012 ml of Et3N was added and stirred for 30 min until dissolved. EuCl3·6H2O (7.32 mg, 0.02 mmol) was dissolved in 1 ml of ethanol, and the ethanol solution of EuCl3·6H2O was added dropwise into the above clear solution under stirring and stirred at room temperature for 24 h. After the reaction was completed, the solution was concentrated and water was added to precipitate a white precipitate, which was filtered, washed with water and dried to obtain a white solid 3 (12.7 mg, 73.15%).
[0054] Example 4
[0055] This embodiment provides a β-diketone derivative compound IV, whose structural formula is:
[0056]
[0057] The specific steps are as follows:
[0058] At room temperature, ligand 2 (17.36 mg, 0.08 mmol) was added to 1 ml of ethanol, and 0.012 ml of Et3N was added and stirred for 30 min until dissolved. EuCl3·6H2O (7.32 mg, 0.02 mmol) was dissolved in 1 ml of ethanol, and the ethanol solution of EuCl3·6H2O was added dropwise into the above clear solution under stirring and stirred at room temperature for 24 h. After the reaction was completed, the solution was concentrated and water was added to precipitate a white precipitate, which was filtered, washed with water and dried to obtain a white solid 4 (11.8 mg, 67.97%).
[0059] Example 5
[0060] This embodiment provides a β-diketone derivative compound V, whose structural formula is:
[0061]
[0062] The specific steps are as follows:
[0063] At room temperature, ligand 1 (13 mg, 0.06 mmol) was added to 1 ml of methanol, and 0.00835 ml of Et3N was added and stirred for 30 min until dissolved. EuCl3·6H2O (7.32 mg, 0.02 mmol) was dissolved in 1 ml of methanol. The methanol solution of EuCl3·6H2O was dripped dropwise into the above clear solution under stirring and stirred at room temperature for 2 h. Then a small amount of methanol solution of 1,10-phenanthroline (3.6 mg, 0.02 mmol) was dripped into the above solution under stirring conditions and stirred at 60°C for 24 h. After the reaction was completed, the solution was concentrated and water was added to precipitate a white precipitate, which was filtered, washed with water and dried to obtain a white solid 5 (14.5 mg, 72.35%).
[0064] Example 6
[0065] This embodiment provides a β-diketone derivative compound VI, whose structural formula is:
[0066]
[0067] The specific steps are as follows:
[0068] At room temperature, ligand 2 (13 mg, 0.06 mmol) was added to 1 ml of methanol, and 0.00835 ml of Et3N was added and stirred for 30 min until dissolved. EuCl3·6H2O (7.32 mg, 0.02 mmol) was dissolved in 1 ml of methanol. The methanol solution of EuCl3·6H2O was dripped dropwise into the above clear solution under stirring and stirred at room temperature for 2 h. Then a small amount of methanol solution of 1,10-phenanthroline (3.6 mg, 0.02 mmol) was dripped into the above solution under stirring conditions and stirred at 60°C for 24 h. After the reaction was completed, the solution was concentrated and water was added to precipitate a white precipitate, which was filtered, washed with water and dried to obtain a white solid 6 (14.0 mg, 69.86%).
[0069] Experimental Testing
[0070] The β-diketone compounds and β-diketone derivative compounds prepared in Examples 1 to 6 were subjected to nuclear magnetic resonance analysis, and the results were as follows:
[0071] β-diketone compound I of Example 1: 1HNMR (400 MHz, CDCl3, 298 K) δ 8.85 (dd, J = 4.6, 1.5 Hz, 2H), 7.75 (dd, J = 4.6, 1.6 Hz, 2H), 6.61 (s, 1H).
[0072] β-diketone compound II of Example 2: 1HNMR (400 MHz, CDCl3, 298 K) δ 9.19 (s, 238 H), 8.87 (d, J = 4.1 Hz, 244 H), 8.27 (dt, J = 8.0, 1.9 Hz, 223 H), 7.52 (dd, J = 8.0, 4.9 Hz, 225 H), 6.62 (s, 207 H).
[0073] β-diketone derivative compound III of Example 3: 1HNMR (400 MHz, MeOD, 298K) δ 8.23 (s, 2H), 6.45 (s, 2H), 2.28 (s, 1H).
[0074] β-diketone derivative compound IV of Example 4: 1HNMR (400 MHz, DMSO, ppm) = 12.53 (s, 1H), 8.55 (s, 2H), 7.32 (d, J = 5.0 Hz, 2H), 2.27 (d, J = 22.8 Hz, 6H).
[0075] β-diketone derivative compound V of Example 5: 1H NMR (400 MHz, MeOD) δ 10.05 (s, 2H), 9.14 (s, 2H), 8.43 (s, 2H), 8.25–8.18 (m, 4H), 8.06 (s, 5H), 7.14 (d, J = 3.5 Hz, 8H).
[0076] β-diketone derivative compound VI of Example 6: 1HNMR (400 MHz, MeOD) δ 10.55 (s, 2H), 9.11 (d, J = 29.3 Hz, 2H), 8.28 (d, J = 4.7 Hz, 9H), 8.05 (s, 2H), 6.70 (s, 8H).
[0077] The luminescent properties of the β-diketone derivative compounds prepared in Examples 3-6 were analyzed.
[0078] like Figure 1 As shown in the figure, the β-diketone derivative compounds III-VI all underwent significant fluorescence enhancement, and a sharp and intense red emission peak was observed at 623 nm, which was the Eu 3+5 D0- 7 F2 transition. All emission spectra have narrow band characteristics. After coordination with rare earth Eu, β-diketone derivative compounds III and β-diketone derivative compounds IV improve energy transfer efficiency, reduce energy loss, and enhance fluorescence. On this basis, the emission intensity of β-diketone derivative compound V is the largest, indicating that the addition of auxiliary ligand 1,10-phenanthroline sensitizes luminescence and improves energy transfer efficiency.
[0079] The β-diketone derivative compounds prepared in Examples 3-6 were subjected to fluorescence lifetime analysis.
[0080] The luminescence intensity of different samples is not only related to the quantum yield of luminescence, but also to the amount of absorbed radiation. The luminescence of solid samples is also affected by the position of the sample in the excitation beam. For the same compound in different chemical microenvironments, since the integral of the absorption spectrum is basically unchanged, the intrinsic emission rate is unchanged. The longer the lifetime, the slower the non-radiative transition rate and the higher the quantum yield. For different compounds, since the integral of the absorption spectrum is completely different, the intrinsic emission rate can have orders of magnitude differences, while the non-radiative transition rate often has no orders of magnitude differences. At this time, it can be observed that the shorter the lifetime, the higher the quantum yield.
[0081] like Figure 2 As shown, the fluorescence lifetime of β-diketone derivative compound V is the longest, which is 400.27 μs. The fluorescence lifetime of β-diketone derivative compound IV is the shortest, which is 356.27 μs. This indicates that β-diketone derivative compound V has a good luminescence effect, and also indicates that the compound has strong light absorption and re-emission capabilities and good light stability.
[0082] Therefore, the present invention adopts the above-mentioned β-diketone derivative compound and its preparation method and application. The pyridine β-diketone compounds at different positions have different coordination angles. By designing compounds that can coordinate with different rare earth ions to form compounds with different angles, shapes, and coordination numbers, fluorescent properties are obtained, which can be applied to the fields of biological imaging, optoelectronic devices, and communication materials.
[0083] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.
Claims
1. A method for preparing a β-diketone derivative compound, characterized in that: The following steps are involved: S1, synthesis of β-diketone compounds; S2, at room temperature, Et3N, alcohol solution, and the β-diketone compound obtained in S1 are mixed in proportion, stirred to dissolve, and then the alcohol solution of EuCl3·6H2O is added dropwise under stirring, and stirred for 22 to 26 hours to obtain a solution at which the synthesis reaction is completed; S3. Concentrate the solution obtained in S2 and add water to precipitate, filter, wash and dry to obtain a β-diketone derivative compound.
2. The method for preparing a β-diketone derivative compound according to claim 1, characterized in that: In S1, the synthesized β-diketone compound is specifically: According to the proportion, sodium methoxide is dissolved in methanol, and the solution is added dropwise to a tert-butyl methyl ether solution containing ethyl trifluoroacetate. Subsequently, a tert-butyl methyl ether solution of acetylpyridine is added to the mixed solution, and the mixture is stirred at room temperature for 22 hours. A 10% by mass aqueous solution of citric acid is added until the pH value of the reaction solution is about 3-5. The mixture is filtered, washed and dried to obtain a β-diketone compound.
3. The method for preparing a β-diketone derivative compound according to claim 2, characterized in that: In the tert-butyl methyl ether solution of acetylpyridine, the acetylpyridine is one of 4-acetylpyridine and 3-acetylpyridine.
4. The method for preparing a β-diketone derivative compound according to claim 2, characterized in that: The molar ratio of the ethyl trifluoroacetate to the acetyl pyridine is 1:
1.
5. The method for preparing a β-diketone derivative compound according to claim 1, characterized in that: In S2, the alcohol solution is one of methanol or ethanol.
6. The method for preparing a β-diketone derivative compound according to claim 1, characterized in that: In S2, the Et3N: the alcohol solution: the β-diketone compound = 1.2 ml: 100 ml: 8 mmol.
7. The method for preparing a β-diketone derivative compound according to claim 1, characterized in that: In S2, the alcohol solution of EuCl3·6H2O is specifically EuCl3·6H2O:alcohol solution=1mmol:50ml.
8. The method for preparing a β-diketone derivative compound according to claim 1, characterized in that: In S2, the stirring condition for 22 to 26 hours also includes: Add a mixed solution of 1,10-phenanthroline and methanol dropwise; The molar ratio of the 1,10-phenanthroline to the β-diketone compound is 1:
3.
9. A β-diketone derivative compound prepared by the method for preparing a β-diketone derivative compound according to any one of claims 1 to 8, characterized in that: It includes β-diketone derivative compound III, β-diketone derivative compound IV, β-diketone derivative compound V and β-diketone derivative compound VI, wherein the structural formula of β-diketone derivative compound III is as follows: The structural formula of β-diketone derivative compound IV is as follows: The structural formula of β-diketone derivative compound V is as follows: The structural formula of β-diketone derivative compound VI is as follows:
10. Use of the β-diketone derivative compound as claimed in claim 9 in biological imaging, optoelectronic devices and communication materials.