An organic fluorescent material and its preparation method and application

Abstract

The present invention relates to the technical field of organic fluorescent materials, and discloses a method for preparing an organic fluorescent material, comprising the following steps: (1) dropping a 1,3,5-benzenetricarboxylic acid chloride solution into a mixed solution of a naphthalene dicarboxamide derivative and triethylamine, stirring until the reaction is complete, standing, recrystallizing, filtering, and drying to obtain a compound T; (2) dissolving the compound T in an organic solvent, then adding a sodium hydroxide solution, mixing and stirring until the reaction is complete, adjusting the pH value, collecting the precipitated product, and vacuum drying to obtain an organic fluorescent material. The organic fluorescent material prepared by the present invention has a simple synthesis process, strong economic efficiency, strong photochemical stability, no photobleaching and photodegradation phenomenon, and a long fluorescence lifetime. The organic fluorescent material has a high fluorescence lifetime at 1×10 －4 Metal ions can be detected under low concentration conditions of M, and it has strong anti-interference ability, which greatly reduces its cost of use as a probe.

Description

Technical Field

[0001] The present invention relates to the technical field of organic fluorescent materials, and in particular to an organic fluorescent material and a preparation method and application thereof. Background Art

[0002] Organic fluorescent materials have good fluorescence properties. They can be widely used as fluorescent probes in medical research, chemical testing, modern biology and other fields. They can also be used to analyze and detect various trace elements or harmful substances in the biological environment. Organic fluorescent materials have the advantages of high sensitivity, low detection limit, strong anti-interference, fast detection speed, good repeatability, and no radiation during the detection process. Organic fluorescent materials have the characteristics of broad market, wide application fields, high added value, and broad potential application prospects. Nowadays, they have achieved rapid development, have been industrialized and used in mainstream smartphones, tablets, car videos and other devices on the market.

[0003] However, to date, poor photochemical stability, serious photobleaching and photodegradation phenomena, and short fluorescence lifetime of organic dyes are still long-standing problems that need to be solved in the development of organic fluorescent materials. Therefore, while maintaining the existing advantages of organic fluorescent materials, developing organic fluorescent materials with strong photochemical stability, no photobleaching and photodegradation phenomena, and long fluorescence lifetime has become a major challenge for the development of the organic fluorescent materials industry. Summary of the invention

[0004] In view of this, the present invention provides an organic fluorescent material and a preparation method thereof to solve the technical problems of poor photochemical stability, serious photobleaching and photodegradation, and short fluorescence lifetime of existing organic fluorescent materials.

[0005] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0006] A method for preparing an organic fluorescent material comprises the following steps:

[0007] (1) adding a 1,3,5-benzenetricarboxylic acid chloride solution dropwise to a mixed solution of a naphthalene dicarboxamide derivative and triethylamine, stirring until the reaction is complete, standing, recrystallizing, filtering, and drying to obtain a compound T;

[0008] (2) The compound T is dissolved in an organic solvent, and then a sodium hydroxide solution is added, and the mixture is mixed and stirred until the reaction is complete. The pH value is adjusted, and the precipitated product is collected and vacuum dried to obtain an organic fluorescent material (hereinafter referred to as "DT").

[0009] Preferably, in the method for preparing the organic fluorescent material, the molar ratio of the 1,3,5-benzenetricarboxylic acid chloride to the naphthalene dicarboxamide derivative is 9:(30-40);

[0010] The ratio of the naphthalene dicarboxamide derivative to the triethylamine is 6 g: (1-10) ml.

[0011] Preferably, in the method for preparing the organic fluorescent material, the 1,3,5-benzenetricarboxylic acid chloride solution in step (1) is obtained by dissolving 1,3,5-benzenetricarboxylic acid chloride in an ultra-dry tetrahydrofuran solution;

[0012] The mixed solution of the naphthalene dicarboxamide derivative and triethylamine is obtained by dissolving the naphthalene dicarboxamide derivative and triethylamine in an ultra-dry tetrahydrofuran solution.

[0013] Preferably, in the above-mentioned method for preparing the organic fluorescent material, the chemical structural formula of the naphthalene dicarboxamide derivative is:

[0014]

[0015] Preferably, in the method for preparing the organic fluorescent material, the stirring time in step (1) is 10-20 hours and the temperature is 20-30°C.

[0016] Preferably, in the above-mentioned method for preparing the organic fluorescent material, the organic solvent in step (2) is selected from dimethylformamide; wherein dimethylformamide is selected mainly because it is miscible with water, is easy to post-process, has good chemical stability, has a large polarity and is easy to dissolve raw materials and products.

[0017] The molar ratio of the compound T to the sodium hydroxide is (2-10):75;

[0018] The concentration of the solution after the compound T is dissolved in the organic solvent is 0.01-0.02 mol / L, and the concentration of the sodium hydroxide solution is 0.5-1.0 mol / L.

[0019] Preferably, in the method for preparing the organic fluorescent material, in step (2), the pH value is adjusted to acidic by adding an acidic solution.

[0020] Preferably, in the method for preparing the organic fluorescent material, the stirring time in step (2) is 8-15 hours and the temperature is 20-30°C.

[0021] The present invention also provides an organic fluorescent material prepared by the above method, wherein the organic fluorescent material is a macromolecular organic compound formed by condensing three naphthalene dicarboxamide derivatives with isophthaloyl chloride as the main body, and the structural formula thereof is:

[0022]

[0023] The present invention also provides an application of the organic fluorescent material prepared by the above method, wherein the organic fluorescent material is used as a probe to detect paramagnetic metal ions.

[0024] Preferably, in the application of the above-mentioned organic fluorescent material, the paramagnetic metal ions include Fe 3+ 、Ni 2+ , Cu 2+ .

[0025] The present invention provides an organic fluorescent material and a preparation method thereof. Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The organic fluorescent material DT prepared by the present invention has an excitation wavelength of 350-400nm and an emission wavelength of 500-650nm. It has the characteristics of being excited by ultraviolet light and short-wave visible light, and has strong absorption in the visible light range of 400-570nm. In addition, the synthesis process of the organic fluorescent material of the present invention is simple and economical, which lays a foundation for its future industrial production.

[0027] (2) The organic fluorescent material DT prepared by the present invention with three electron-withdrawing groups (carboxyl groups) provides a new reference for solving the long-standing problems of poor photochemical stability, serious photobleaching and photodegradation, and short fluorescence lifetime of organic dyes in organic fluorescent materials. It is an organic fluorescent material with strong photochemical stability, no photobleaching and photodegradation, and long fluorescence lifetime. The fluorescent probe performance of DT was tested and the results showed that DT can effectively identify Fe 3 + 、Ni 2+ , Cu 2+ Paramagnetic metal ions; and DT fluorescence is strong, at 1×10 －4 Metal ions can be detected under low concentration conditions of M, and it has strong anti-interference ability, which greatly reduces its cost of use as a probe. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying creative work.

[0029] Figure 1 The synthetic route map of organic fluorescent material DT;

[0030] Figure 2 For compound T 1 H NMR;

[0031] Figure 3 is the high-resolution mass spectrum of compound T;

[0032] Figure 4 For organic fluorescent material DT 1 H NMR;

[0033] Figure 5 This is the high-resolution mass spectrum of the organic fluorescent material DT;

[0034] Figure 6 This is a photo of the organic fluorescent material DT;

[0035] Figure 7 It is the ultraviolet absorption spectrum of the organic fluorescent material DT;

[0036] Figure 8 It is the fluorescence spectrum of the organic fluorescent material DT;

[0037] Fig. 9 This is the experimental diagram of the detection of metal ions using organic fluorescent material DT as a fluorescent probe. DETAILED DESCRIPTION

[0038] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0039] Example 1

[0040] like Figure 1 As shown, this embodiment provides a method for preparing an organic fluorescent material DT, comprising the following steps:

[0041] (1) Synthesis of Compound T

[0042] A super-dry THF solution of 1,3,5-benzenetricarboxylic acid chloride (0.09 mmol, 0.024 g) was slowly added dropwise to a mixture of a naphthalene dicarboxamide derivative (0.367 mmol, 0.12 g) and triethylamine (0.1 mL) in a super-dry THF solution, and the mixture was stirred at 25° C. for 15 hours; after the reaction was completed, the solvent was removed, the residue was recrystallized in DMF and ethanol, washed with ethanol and water, the product was collected by filtration, and dried under vacuum to obtain compound T, and the yield of compound T was 62.2%.

[0043] Compound T is 2,2',2''-tris(tris(benzene-1,3,5-tricarbonyl)tris(nitrogen diyl))tris(ethane-2,1-diyl)tris((nitrogen diacyl))triacetate trimethyl ester; Figure 2Shown is compound T 1 H NMR, Figure 3 is the high-resolution mass spectrum of compound T. 1 H NMR (400MHz,) δ 8.69 (d, 3H), 8.60 (d, J = 7.3Hz, 1H), 8.54 (s, 2H), 8.44 (d, 3H), 8.27 (d, 3H), 8.09 (s, 3H), 7.95 (s, 3H), 7.71(t, 3H), 6.97(d, 3H), 4.78(s, 6H), 3.68(s, 9H), 3.64(s, 12H).MS: m / z: calcd: 1137.3505; found: 1136.3534[M-H + ].

[0044] (2) Synthesis of organic fluorescent material DT

[0045] A solution of NaOH (0.75 mmol, 0.03 g) in water (1.0 mL) was added dropwise to a solution of compound T (0.057 mmol, 0.065 g) in DMF (4.0 mL), and the mixture was stirred at 25°C overnight. Dilute hydrochloric acid was added to the reaction mixture to adjust the pH to acidic. The product precipitated in the solution. The product was collected and dried under vacuum to obtain an organic fluorescent material DT. The yield of the organic fluorescent material DT was 90.3%.

[0046] The organic fluorescent material DT is 2,2',2''-tris(tris(benzene-1,3,5-tricarbonyl)tris(nitrogen diyl))tris(ethane-2,1-diyl)tris((nitrogen diacyl)tris(1,3-dioxy-1H-benzo[de]isoquinoline-6,2(3H)-diyl))triacetic acid; Figure 4 The organic fluorescent material DT is shown 1 H NMR, Figure 5 This is the high-resolution mass spectrum of DT, an organic fluorescent material. Figure 6 This is a photo of the organic fluorescent material DT. 1 H NMR (400MHz, DMSO) δ9.03 (d, 3H), 8.69 (s, 3H), 8.53 (d, 3H), 8.45 (d, 3H), 8.29 (d, 3H), 8.05 (s, 3H), 7 .72(t, 3H), 6.98(d, 3H), 4.69(s, 6H), 3.64(s, 12H).MS: m / z: calcd: 1905.3035; found: 1905.2985[M + ].

[0047] Next, the fluorescent probe performance of the organic fluorescent material DT is tested through experiments.

[0048] 1. DT as a fluorescent probe for the detection of paramagnetic metal ions

[0049] Dissolve DT in dimethyl sulfoxide to prepare 12 bottles of 2.0 mL of 1×10 －4 M DT solution, and use a 20.0 μL pipette to transfer 20.0 μL of 1 M Ni 2+ , K + , Cd 2+ , Mn 2+ , Na + , Zn 2+ , Al 3+ ,Mg 2+ , Fe 3+ , Ca 2 + , Cu 2+ The aqueous solution was added to the 11 bottles of DT solution, one metal ion solution was added to each bottle, and 20.0 μL of pure water was added to the 12th bottle as a control group. After mixing evenly, it was irradiated with 365 nm ultraviolet light to observe the phenomenon. It was found that DT can 3+ 、Ni 2+ , Cu 2+ The metal ions are recognized and fluorescence quenching occurs. Figure 7 The figure shows the ultraviolet absorption spectrum of the organic fluorescent material DT. Figure 8 This is the fluorescence spectrum of the organic fluorescent material DT. Fig. 9 This is a diagram of the experimental detection of metal ions using the organic fluorescent material DT as a fluorescent probe.

[0050] DT as a fluorescent probe for detecting Fe 3+ 、Ni 2+ , Cu 2+ Anti-interference experiment

[0051] The volume was 2.0 mL and the concentration was 1×10 －4 Fe was added to the DT solution of M 3+ and other metal ions, all of which caused fluorescence quenching; －4 Cu was added to the DT solution of M 2+ and other metal ions, all of which caused fluorescence quenching; －4 Ni was added to the DT solution of M 2+ and other metal ions, all of which caused fluorescence quenching, indicating that DT can selectively bind to Fe in solutions containing multiple metal ions. 3+ 、Ni 2+ , Cu 2+Fluorescence quenching occurs upon binding, and the cell has strong anti-interference ability.

[0052] Example 2

[0053] This embodiment provides a method for preparing an organic fluorescent material DT, comprising the following steps:

[0054] (1) Synthesis of Compound T

[0055] A super-dry THF solution of 1,3,5-benzenetricarboxylic acid chloride (0.09 mmol) was slowly added dropwise to a mixture of a naphthalene dicarboxamide derivative (0.38 mmol) and triethylamine (0.1 mL) in a super-dry THF solution, and the mixture was stirred at 25° C. for 15 hours; after the reaction was completed, the solvent was removed, the residue was recrystallized in DMF and ethanol, washed with ethanol and water, the product was collected by filtration, and dried under vacuum to obtain compound T, and the yield of compound T was 55.3%.

[0056] (2) Synthesis of organic fluorescent material DT

[0057] A solution of NaOH (0.75 mmol) in water (1.0 mL) was added dropwise to a solution of compound T (0.067 mmol) in DMF (4.0 mL), and the mixture was stirred at 25°C overnight. Dilute hydrochloric acid was added to the reaction mixture to adjust the pH to acidic. The product precipitated in the solution. The product was collected and dried under vacuum to obtain an organic fluorescent material DT. The yield of the organic fluorescent material DT was 87.2%.

[0058] Example 3

[0059] This embodiment provides a method for preparing an organic fluorescent material DT, comprising the following steps:

[0060] (1) Synthesis of Compound T

[0061] A solution of 1,3,5-benzenetricarboxylic acid chloride (0.09 mmol) in ultra-dry THF was slowly added dropwise to a mixture of a naphthalene dicarboxamide derivative (0.40 mmol) and triethylamine (0.1 mL) in ultra-dry THF, and the mixture was stirred at 25° C. for 15 hours. After the reaction was completed, the solvent was removed, the residue was recrystallized in DMF and ethanol, washed with ethanol and water, the product was collected by filtration, and dried under vacuum to obtain compound T with a yield of 48.1%.

[0062] (2) Synthesis of organic fluorescent material DT

[0063] A solution of NaOH (0.75 mmol) in water (1.0 mL) was added dropwise to a solution of compound T (0.10 mmol) in DMF (4.0 mL), and the mixture was stirred at 25°C overnight. Dilute hydrochloric acid was added to the reaction mixture to adjust the pH to acidic. The product precipitated in the solution. The product was collected and dried under vacuum to obtain an organic fluorescent material DT with a yield of 86.5%.

[0064] Comparative Example 1

[0065] This comparative example provides a method for preparing an organic fluorescent material DT, comprising the following steps:

[0066] (1) Synthesis of Compound T

[0067] A solution of 1,3,5-benzenetricarboxylic acid chloride (0.09 mmol, 0.024 g) in ultra-dry THF was slowly added dropwise to a mixture of a naphthalene dicarboxamide derivative (0.367 mmol, 0.12 g) and triethylamine (0.1 mL) in ultra-dry THF, and the mixture was stirred at 25° C. for 10 hours; after the reaction was completed, the solvent was removed, the residue was recrystallized in DMF and ethanol, washed with ethanol and water, the product was collected by filtration, and dried under vacuum to obtain compound T with a yield of 50.2%.

[0068] (2) Synthesis of organic fluorescent material DT

[0069] A solution of NaOH (0.75 mmol, 0.03 g) in water (1.0 mL) was added dropwise to a solution of compound T (0.057 mmol, 0.065 g) in DMF (4.0 mL), and the mixture was stirred at 10°C overnight. Dilute hydrochloric acid was added to the reaction mixture to adjust the pH to acidic. The product precipitated in the solution. The product was collected and dried under vacuum to obtain an organic fluorescent material DT with a yield of 83.3%.

[0070] Comparative Example 2

[0071] This comparative example provides a method for preparing an organic fluorescent material DT, comprising the following steps:

[0072] (1) Synthesis of Compound T

[0073] A solution of 1,3,5-benzenetricarboxylic acid chloride (0.09 mmol) in ultra-dry THF was slowly added dropwise to a mixture of a naphthalene dicarboxamide derivative (0.367 mmol) and triethylamine (0.1 mL) in ultra-dry THF, and the mixture was stirred at 25° C. for 20 hours. After the reaction was completed, the solvent was removed, the residue was recrystallized in DMF and ethanol, washed with ethanol and water, the product was collected by filtration, and dried under vacuum to obtain compound T with a yield of 63.1%.

[0074] (2) Synthesis of organic fluorescent material DT

[0075] A solution of NaOH (0.75 mmol) in water (1.0 mL) was added dropwise to a solution of compound T (0.057 mmol) in DMF (4.0 mL), and the mixture was stirred at 35°C overnight. Dilute hydrochloric acid was added to the reaction mixture to adjust the pH to acidic. The product precipitated in the solution. The product was collected and dried under vacuum to obtain an organic fluorescent material DT with a yield of 85.2%.

[0076] Comparative Example 3

[0077] This comparative example provides a method for preparing an organic fluorescent material DT, comprising the following steps:

[0078] (1) Synthesis of Compound T

[0079] A solution of 1,3,5-benzenetricarboxylic acid chloride (0.09 mmol) in ultra-dry THF was slowly added dropwise to a mixture of a naphthalene dicarboxamide derivative (0.367 mmol) and triethylamine (0.1 mL) in ultra-dry THF, and the mixture was stirred at 10° C. for 15 hours; after the reaction was completed, the solvent was removed, the residue was recrystallized in DMF and ethanol, washed with ethanol and water, the product was collected by filtration, and dried under vacuum to obtain compound T with a yield of 50.3%.

[0080] (2) Synthesis of organic fluorescent material DT

[0081] A solution of NaOH (0.75 mmol) in water (1.0 mL) was added dropwise to a solution of compound T (0.057 mmol) in DMF (4.0 mL), and the mixture was stirred at 15°C overnight. Dilute hydrochloric acid was added to the reaction mixture to adjust the pH to acidic. The product precipitated in the solution. The product was collected and dried under vacuum to obtain an organic fluorescent material DT with a yield of 80.3%.

[0082] The fluorescent probe performance of the organic fluorescent material DT prepared in the above examples and comparative examples was tested. The results showed that the prepared organic fluorescent material DT can effectively 3+ 、Ni 2+ , Cu 2+ In addition, DT can selectively bind to Fe and other metal ions in solutions containing various metal ions. 3+ 、Ni 2+ , Cu 2+ The combination causes fluorescence quenching, which has strong anti-interference ability; however, the ratio of raw materials, reaction conditions, etc. will have a great influence on the yield of organic fluorescent materials. Only by precisely controlling the reaction process can the yield of the product be improved.

[0083] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the scheme disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0084] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing an organic fluorescent material, characterized in that: The following steps are involved: (1) adding a 1,3,5-benzenetricarboxylic acid chloride solution dropwise to a mixed solution of a naphthalene dicarboxamide derivative and triethylamine, stirring until the reaction is complete, standing, recrystallizing, filtering, and drying to obtain a compound T; (2) dissolving the compound T in an organic solvent, then adding a sodium hydroxide solution, mixing and stirring until the reaction is complete, adjusting the pH value, collecting the precipitated product, and vacuum drying to obtain an organic fluorescent material; The compound T is 2,2',2''-tris(tris(benzene-1,3,5-tricarbonyl)tris(nitrogen diyl))tris(ethane-2,1-diyl)tris((nitrogen diacyl))triacetate trimethyl ester, and the organic fluorescent material is a macromolecular organic compound formed by condensing three naphthalene dicarboxamide derivatives with isophthaloyl chloride as the main body. 3+ 、Ni 2+ , Cu 2+ Recognition is performed and fluorescence quenching occurs. Its structural formula is:

2. The method for preparing an organic fluorescent material according to claim 1, characterized in that: The molar ratio of the 1,3,5-benzenetricarboxylic acid chloride to the naphthalene dicarboxamide derivative is 9:(30-40); The ratio of the naphthalene dicarboxamide derivative to the triethylamine is 6 g: (1-10) ml.

3. The method for preparing an organic fluorescent material according to claim 1 or 2, characterized in that: The 1,3,5-benzenetricarboxylic acid chloride solution in step (1) is obtained by dissolving 1,3,5-benzenetricarboxylic acid chloride in an ultra-dry tetrahydrofuran solution; The mixed solution of the naphthalene dicarboxamide derivative and triethylamine is obtained by dissolving the naphthalene dicarboxamide derivative and triethylamine in an ultra-dry tetrahydrofuran solution.

4. The method for preparing an organic fluorescent material according to claim 3, characterized in that: The chemical structural formula of the naphthalene dicarboxamide derivative is:

5. The method for preparing an organic fluorescent material according to claim 1, characterized in that: The stirring time in step (1) is 10-20 hours and the temperature is 20-30°C.

6. The method for preparing an organic fluorescent material according to claim 1, characterized in that: The organic solvent in step (2) is selected from N,N-dimethylformamide; The molar ratio of the compound T to the sodium hydroxide is (2-10):75; The concentration of the solution after the compound T is dissolved in the organic solvent is 0.01-0.02 mol / L, and the concentration of the sodium hydroxide solution is 0.5-1.0 mol / L.

7. The method for preparing an organic fluorescent material according to claim 1, characterized in that: In step (2), the pH value is adjusted to acidic by adding an acidic solution.

8. The method for preparing an organic fluorescent material according to claim 1, characterized in that: The stirring time in step (2) is 8-15 hours and the temperature is 20-30°C.

9. An application of an organic fluorescent material prepared by the method according to any one of claims 1 to 8, characterized in that: The organic fluorescent material is used as a probe to detect paramagnetic metal ions.

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