CN113788779B - Acceptor-donating compound based on diphenyl sulfone and indole derivatives, and preparation method and application thereof - Google Patents
Acceptor-donating compound based on diphenyl sulfone and indole derivatives, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of organic luminescent materials, in particular to a series of donor-acceptor type compounds based on diphenyl sulfone and indole derivatives, and a preparation method and application thereof. The invention takes indole derivatives as electron donor (D) and diphenyl sulfone as electron acceptor (A) to form D-A or D-A-D type compound; the series of compounds have the characteristics of torsion intramolecular charge transfer and aggregation-induced luminescence, and are sensitive to the existence of water in an organic solvent; the concrete steps are as follows: in a certain range, as the water content increases, the maximum emission peak position appears in a red shift of the law, the intensity ratio of the red shift gradually increases, and the red shift and the intensity ratio all show good linear relation; thus, the series of compounds of the present invention can be used as a novel fluorescence sensor for real-time detection of water content in organic solvents at an intensity ratio and wavelength.
Description
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a series of donor-acceptor type compounds based on diphenyl sulfone and indole derivatives, and a preparation method and application thereof.
Background
The organic fluorescent material has the advantages of simple structure, stable luminescence and the like, and has wide application in the fields of fluorescent imaging, sensing, organic light emitting diodes and the like. However, common organic fluorescent materials are molecules which aggregate to cause quenching (ACQ), i.e., although having excellent luminescence properties in a dilute solution state, as the concentration increases, the pi-pi stacking degree in an aggregated state increases, resulting in a phenomenon that the luminescence intensity is drastically reduced or even fluorescence quenching occurs, and thus, the development thereof in the related art is greatly limited. To reduce the impact of ACQ effects, researchers such as Tang Benzhong have proposed a series of luminescent molecules (Y Hong, et al chem. Soc. Rev.,2011,40,5361) with aggregation-induced emission (AIE) and aggregation-induced enhanced emission (AIEE) properties, i.e., the molecules emit enhancement in the aggregated state. In recent years, due to the wide development prospect of AIE molecules, many researchers have been devoted to study the design principles, light-emitting mechanisms and links between structures and properties of AIE molecules. Until now, AIE molecules with excellent properties have attracted attention from a large number of researchers (Q Wang et al, j. Mater. Chem. B.,2016,4,4033.).
In addition, organic compounds composed of an electron donor (D) and an electron acceptor (a) have recently become popular materials in the photoelectric field because of their characteristic of intramolecular charge conversion (S Sasaki, et al, j. In polar environments, molecules with twisted intramolecular charge transfer undergo rapid intramolecular charge transfer processes between donor and acceptor, accompanied by a relaxed stacking mode, wherein the relaxation process from a high-energy local excited state is easily regulated by conditions such as molecular substituents and polarity, in addition to charge transfer from low energy, and thus molecules with twisted intramolecular charge transfer (tic) properties are widely used in various fields of biochemistry. Therefore, more and more researchers are focusing on designing molecules with AIE and TICT functions at the same time, so as to construct a fluorescent material with the synergistic action of TICT-AIE, and the application of the fluorescent molecules in fluorescent imaging and organic light emitting diodes is greatly promoted due to the strong emission in a dilute solution and an aggregation state.
However, this molecule is not widely used for the detection of water content in organic solvents. Since water is the most common impurity in organic solvents, detection and quantification of water is critical in both chemical reactions and industrial applications. At present, some traditional technologies for detecting trace water exist, such as karl fischer titration method, chromatography method, electrochemical method and the like (H Jung, chem. Soc. Rev.,2016,45,1242.), but generally, the methods have the defects of high cost, long time and the like, which greatly improve the operation requirement, so that it is necessary to design organic fluorescent molecules with simple structure and obvious color development to replace the traditional detection methods. In addition, in the existing water sensor, quantitative analysis of water is mostly carried out only through linear relation between intensity and water content, and certain errors exist in actual operation and may affect measurement accuracy.
By combining the research background, a three-dimensional detection sensor which is sensitive to trace water in an organic solvent and utilizes the double parameters of intensity ratio and wavelength variation along with the water content is developed, has important significance, can greatly improve the quantitative accuracy, and is suitable for quantitative detection of water in the organic solvent under the conditions of laboratory or industrial application and the like.
Disclosure of Invention
The invention aims to provide a series of acceptor-type compounds based on diphenyl sulfone and indole derivatives, a preparation method and application thereof, and overcome the defects of the prior art, and the novel fluorescent water sensor which is formed by taking indole derivatives as electron donors (D) and taking diphenyl sulfone as electron acceptors (A) and is formed by D-A or D-A-D type compounds is sensitive to the existence of water in an organic solvent due to the characteristics of torsion intramolecular charge transfer and aggregation-induced emission, and can be used for detecting the water content in the organic solvent in real time by ratio intensity and emission wavelength. .
The technical scheme adopted for solving the technical problems is as follows:
a series of acceptor-donating compounds based on diphenyl sulfone and indole derivatives are acceptor-donating compounds which are formed by taking indole derivatives as electron donors and taking diphenyl sulfone as electron acceptors, and the structural formula of the acceptor-donating compounds is shown as a general formula I or a general formula II:
wherein: r is hydrogen, or is a halogen atom, or is indole, or is indoline
The donor-acceptor type compound based on diphenyl sulfone and indole derivatives has the characteristics of charge transfer in torsion molecules and aggregation-induced luminescence, and can be used as a water sensor for detecting organic solvents.
A series of preparation methods of acceptor-donating compounds based on diphenyl sulfone and indole derivatives comprise the following steps: indole, 4 '-difluoro diphenyl sulfone and potassium carbonate are added into a reaction vessel, wherein the molar mass ratio of the indole, 4' -difluoro diphenyl sulfone to the potassium carbonate is 0.9-1.1mmol:1.8-2.2mmol:0.9-1.1mmol, under the protection of nitrogen, 2-12ml of N-methyl pyrrolidone is injected, the reaction is carried out for 0.5 hour at 100 ℃, the reaction liquid is poured into ice water, the extraction is carried out for three times by ethyl acetate, saturated saline water is used for washing, the organic phase is distilled off in a rotating way to remove the solvent, and the product 4-fluoro-4 '-indolyl phenylsulfone is obtained after separation and purification by column chromatography, wherein the 4-fluoro-4' -indolyl phenylsulfone is a compound shown as a general formula I.
A series of preparation methods of acceptor-donating compounds based on diphenyl sulfone and indole derivatives comprise the following steps: indole, 4 '-difluoro diphenyl sulfone and potassium carbonate are added into a reaction vessel, wherein the molar mass ratio of the indole, 4' -difluoro diphenyl sulfone to the potassium carbonate is 2-2.4mmol:0.9-1.1mmol:9-11mmol, under the protection of nitrogen, 2-12ml of N-methylpyrrolidone is injected, the reaction is carried out for 4 hours at 160 ℃, the temperature is naturally reduced to room temperature, the reaction liquid is poured into ice water under stirring, the ice water is extracted three times by ethyl acetate, saturated saline water is used for washing, the organic phase is distilled off to remove the solvent, and the product di (4-indolophenyl) sulfone is obtained through column chromatography separation and purification, wherein the product di (4-indolophenyl) sulfone is a compound shown as a general formula I.
A series of preparation methods of acceptor-donating compounds based on diphenyl sulfone and indole derivatives comprise the following steps: indoline, 4 '-difluoro diphenyl sulfone and potassium carbonate are added into a reaction vessel, wherein the molar mass ratio of the indoline, the 4,4' -difluoro diphenyl sulfone and the potassium carbonate is 0.9-1.1mmol:2-2.4mmol:9-11mmol, under the protection of nitrogen, 2-12ml of N-methyl pyrrolidone is injected, the reaction is carried out for 2 hours at 160 ℃, the reaction liquid is added into cold water, the ethyl acetate is used for extraction for three times, saturated saline water is used for washing, the organic phase is distilled off in a rotating way to remove the solvent, and the product 4-fluoro-4 '-indoline phenylsulfone is obtained through column chromatography separation and purification, wherein the 4-fluoro-4' -indoline phenylsulfone is a compound shown as a general formula II.
A series of preparation methods of acceptor-donating compounds based on diphenyl sulfone and indole derivatives comprise the following steps: indoline, 4 '-difluorodiphenyl sulfone and sodium hydride are added into a reaction vessel, wherein the molar mass ratio of the indoline to the 4,4' -difluorodiphenyl sulfone to the sodium hydride is 4-4.8mmol:0.9-1.1mmol:4-4.8mmol, under the protection of nitrogen, 2-12ml of N, N dimethylformamide is injected, the reaction is carried out for 10 hours at 100 ℃, the temperature is naturally reduced to room temperature, the reaction liquid is poured into ice water under stirring, the ice water is extracted three times by ethyl acetate, saturated saline water is used for washing, the organic phase is distilled off to remove the solvent, and the product of di (4-indoline phenyl) sulfone is obtained through column chromatography separation and purification, wherein the di (4-indoline phenyl) sulfone is a compound shown as a general formula II.
The synthetic routes of the four preparation methods are shown in the following formulas:
the 4-fluoro-4 '-indoline phenylsulfone is the compound C-1 in the reaction formula, the di (4-indoline phenylsulfone is the compound C-2, 4-fluoro-4' -indoline phenylsulfone is the compound C-3 in the reaction formula, and the di (4-indoline phenylsulfone is the compound C-4 in the reaction formula.
A series of acceptor-donating compounds based on diphenyl sulfone and indole derivatives are applied as fluorescent sensors to detect the water content of organic solvents.
Preferably, the use of a series of acceptor-donating compounds based on diphenyl sulfone and indole derivatives, the method of use comprising the steps of:
(1) Dissolving a compound of the general formula I or the general formula II in a mixed solution of water and tetrahydrofuran;
(2) And measuring the system luminescence change caused by the water integral change, thereby detecting the water content in the organic solvent.
The fluorescence spectrum shows regular changes with the change of the water content.
The invention synthesizes a series of donor-acceptor type compounds based on diphenyl sulfone and indole derivatives, and D-A or D-A-D type compounds formed by taking indole derivatives as electron donors (D) and diphenyl sulfone as electron acceptors (A); researches show that the series of compounds have the characteristics of torsion intramolecular charge transfer and aggregation-induced luminescence, and are sensitive to the existence of water in an organic solvent; the concrete steps are as follows: in a certain range, as the water content increases, the maximum emission peak position appears in a red shift of the law, the intensity ratio of the red shift gradually increases, and the red shift and the intensity ratio all show good linear relation; therefore, the series of compounds can be used as a novel fluorescence sensor for detecting the water content in the organic solvent in real time according to the intensity ratio and the wavelength.
The beneficial effects of the invention are as follows: compared with the prior art, the acceptor-donating compound based on diphenyl sulfone and indole derivatives and the preparation method and application thereof have the following advantages: the series of compounds provided by the invention have the characteristic of sensitivity to water, not only can detect the water content of the organic solvent according to the emission intensity, but also can detect the water content of the organic solvent according to the emission displacement change, and the raw materials are cheap and easy to obtain, are simple to synthesize and convenient to detect, so that the technical problems of higher detection cost and complex synthetic route in the prior art are solved, and the detection precision is effectively improved.
Drawings
FIG. 1 is a graph showing the fluorescence emission patterns of 4-fluoro-4' -indoline phenylsulfone, a compound with a concentration of 5. Mu. Mol/L, in mixed solution of tetrahydrofuran and water with different water volume contents in example 3 of the present invention;
FIG. 2 is a graph showing the relationship between the water volume fraction of 4-fluoro-4' -indoline phenylsulfone compound having a concentration of 5. Mu. Mol/L in a mixed solution of tetrahydrofuran and water and the ratio of emission wavelength and fluorescence intensity in example 3 of the present invention;
FIG. 3 is a graph showing the fluorescence emission patterns of the compound bis (4-indolinylphenyl) sulfone of example 4 of the present invention at a concentration of 5. Mu. Mol/L in a mixed solution of tetrahydrofuran and water at various water volume contents;
FIG. 4 is a graph showing the relationship between the water integral number and the ratio of emission wavelength and fluorescence intensity of bis (4-indolinylphenyl) sulfone compound of example 4 of the present invention at a concentration of 5. Mu. Mol/L in a mixed solution of tetrahydrofuran and water.
Detailed Description
Example 1
Indole (0.23 g,2 mmol), 4' -difluorodiphenyl sulfone (1.02 g,4 mmol) and potassium carbonate (0.28 g,2 mmol) were added to a 20mL round bottom flask, 5mL of N-methylpyrrolidone was injected under nitrogen protection, the reaction was allowed to react at 100℃for 0.5 hours, cooled to room temperature, the reaction solution was poured into 20mL ice water, extracted three times with ethyl acetate, washed with saturated brine, and the organic phase was distilled off in vacuo to give a pale yellow solid which was isolated and purified by column chromatography as petroleum ether: ethyl acetate = 10:1 (v/v) is used as eluent to obtain white solid 2-1, namely 4-fluoro-4' -indolyl phenylsulfone, and the yield is 68%.1H NMR (400 MHz, DMSO-d 6) delta (ppm): 8.19-8.09 (m, 4H), 7.91-7.84 (m, 2H), 7.76 (d, J=3.4 Hz, 1H), 7.68 (dd, J=11.0, 4.1Hz, 2H), 7.55-7.44 (m, 2H), 7.21 (dtd, J=14.8, 7.1,1.2Hz, 2H), 6.78 (dd, J=3.4, 0.6Hz, 1H).
Example 2
Indole (0.52 g,4.4 mmol), 4' -difluorodiphenyl sulfone (0.508 g,2 mmol) and potassium carbonate (2.76 g,20 mmol) were added to a 20mL round bottom flask, 10mL of N-methylpyrrolidone was injected under nitrogen protection, the reaction was carried out at 160℃for 4 hours, naturally cooled to room temperature, the reaction solution was poured into 50mL ice water under stirring, extracted three times with ethyl acetate, washed with saturated brine, the solvent was removed by rotary evaporation of the organic phase, and a pale yellow solid was obtained, which was isolated and purified by column chromatography as petroleum ether: ethyl acetate = 10:1 (v/v) is used as eluent to obtain white solid 2-2, namely bis (4-indolyl benzene) sulfone, and the yield is 81%.1H NMR (400 MHz, DMSO-d 6) delta (ppm): 8.22-8.14 (m, 4H), 7.90-7.86 (m, 4H), 7.75 (d, J=3.4 Hz, 2H), 7.67 (dd, J=12.8, 7.8Hz, 4H), 7.26-7.12 (m, 4H), 6.76 (d, J=3.4 Hz, 2H).
Example 3
Indoline (0.24 g,2 mmol), 4' -difluorodiphenyl sulfone (1.12 g,4.4 mmol) and potassium carbonate (2.76 g,20 mmol) were added to a 20mL round bottom flask, 10mL of N-methylpyrrolidone was injected under the protection of nitrogen, the reaction was carried out at 160 ℃ for 2 hours, naturally cooled to room temperature, the reaction solution was poured into 50mL ice water, extracted three times with ethyl acetate, washed with saturated saline, the solvent was removed by rotary evaporation of the organic phase, and a pale yellow solid was obtained, which was isolated and purified by column chromatography as petroleum ether: ethyl acetate = 10:1 (v/v) is used as an eluent to obtain off-white solid 2-3, namely 4-fluoro-4' -indoline phenylsulfone, and the yield is 69%.1H NMR (400 MHz, DMSO-d 6) delta (ppm): 8.04-7.7 (m, 2H), 7.90-7.83 (m, 2H), 7.50-7.40 (m, 2H), 7.40-7.34 (m, 2H), 7.32 (d, J=8.0 Hz, 1H), 7.28-7.20 (m, 1H), 7.12 (t, J=7.7 Hz, 1H), 6.86 (td, J=7.5, 0.7Hz, 1H), 4.00 (t, J=8.4 Hz, 2H), 3.21-3.02 (m, 2H).
Example 4
Indoline (1.04 g,8.8 mmol), 4' -difluorodiphenyl sulfone (0.508 g,2 mmol) and sodium hydride (0.22 g,8.8 mmol) were added to a 20mL round bottom flask, 10mL of anhydrous N, N-dimethylformamide was injected under the protection of nitrogen, the reaction was carried out at 100℃for 10 hours, the temperature was lowered to room temperature under natural conditions, the reaction solution was poured into 50mL ice water, extraction was carried out three times with ethyl acetate, washing with saturated brine, the organic phase was distilled off to remove the solvent, and a pale yellow solid was obtained, which was isolated and purified by column chromatography as petroleum ether: ethyl acetate = 10:1 (v/v) is used as eluent to obtain white solid 2-4, namely bis (4-indoline phenyl) sulfone, and the yield is 47%.1H NMR (400 MHz, DMSO-d 6) delta (ppm) 7.91-7.66 (m, 4H), 7.39-7.32 (m, 4H), 7.30 (d, J=8.0 Hz, 2H), 7.24 (dd, J=7.3, 0.8Hz, 2H), 7.11 (t, J=7.8 Hz, 2H), 6.85 (td, J=7.4, 0.8Hz, 2H), 4.00 (dd, J=15.2, 6.9Hz, 4H), 3.11 (t, J=8.4 Hz, 4H).
Test example 1
The compound obtained in example 3 was prepared as a mixed solution of tetrahydrofuran and water at a water ratio of 0%, 1%, 3%, 5%, 7% in order and at a concentration of 5. Mu. Mol/L. 2mL of the solution was added to a 1 cm. Times.1 cm. Times.4 cm cuvette with plugs, and the fluorescence emission spectrum was measured, λex=345 nm, and the results are shown in FIG. 1.
As can be seen from fig. 1, within a certain range, the fluorescence intensity gradually decreases and the emission wavelength gradually increases as the water content in the solution increases.
Test example 2
The compound obtained in example 3 was prepared as a mixed solution of tetrahydrofuran and water at a water ratio of 0%, 1%, 3%, 5%, 7% in order and at a concentration of 5. Mu. Mol/L. 2mL of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and the fluorescence emission spectrum, lambda ex The emission wavelength was observed as a function of water fraction at 345nm, and the results are shown in dashed line a of fig. 2.
As can be seen from FIG. 2, within a certain range, the emission wavelength shows a good linear relationship with the water content in the solution, R 2 ＝0.9982。
Test example 3
The compound obtained in example 3 was prepared as a mixed solution of tetrahydrofuran and water at a water ratio of 0%, 1%, 3%, 5%, 7% in order and at a concentration of 5. Mu. Mol/L. 2mL of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and the fluorescence emission spectrum, lambda ex =345 nm, observe itThe emission intensity ratio was varied with the water fraction, and the result was shown as a broken line B in fig. 2.
As can be seen from the attempt 2, the ratio of emission intensity and the water content in the solution show good linear relationship within a certain range, R 2 ＝0.9826。
Test example 4
The compound obtained in example 4 was prepared as a mixed solution of tetrahydrofuran and water at a water ratio of 0%, 1%, 3%, 5%, 7% in order and at a concentration of 5. Mu. Mol/L. 2mL of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and the fluorescence emission spectrum, lambda ex =350 nm, and the results are shown in fig. 3.
As can be seen from fig. 3, within a certain range, the fluorescence intensity gradually decreases and the emission wavelength gradually increases as the water content in the solution increases.
Test example 5
The compound obtained in example 4 was prepared as a mixed solution of tetrahydrofuran and water at a water ratio of 0%, 1%, 3%, 5%, 7% in order and at a concentration of 5. Mu. Mol/L. 2mL of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and the fluorescence emission spectrum, lambda ex The emission wavelength was observed as a function of water fraction, as shown by the dashed line C in fig. 4.
As can be seen from FIG. 4, within a certain range, the emission wavelength shows a good linear relationship with the water content in the solution, R 2 ＝0.9736。
Test example 6
The compound obtained in example 4 was prepared as a mixed solution of tetrahydrofuran and water at a water ratio of 0%, 1%, 3%, 5%, 7% in order and at a concentration of 5. Mu. Mol/L. 2mL of the solution was added to a cuvette with a plug of 1 cm. Times.1 cm. Times.4 cm, and the fluorescence emission spectrum, lambda ex The emission intensity ratio was observed as a function of water fraction, as shown by the dashed line D in fig. 4.
As can be seen from FIG. 4, the ratio of emission intensity and the water content in the solution show a good linear relationship within a certain range, R 2 ＝0.9889。
Similar results were obtained by the test of test examples 3 to 6 with the compounds prepared in example 1 and example 2.
The foregoing embodiments are merely examples of the present invention, and the scope of the present invention includes, but is not limited to, the forms and styles of the foregoing embodiments, and any suitable changes or modifications made by those skilled in the art, which are consistent with the claims of the present invention, shall fall within the scope of the present invention.
Claims (5)
1. A series of preparation methods of acceptor-donating compounds based on diphenyl sulfone and indole derivatives are characterized in that: is a donor-acceptor compound formed by using indole derivatives as electron donors and diphenyl sulfone as electron acceptors, and the structural formula of the donor-acceptor compound is shown as a general formula II:
wherein the compound of the general formula II is 4-fluoro-4' -indoline phenylsulfone or di (4-indoline phenylsulfone).
2. The process for the preparation of a series of acceptor-donating compounds based on diphenyl sulfone and indole derivatives according to claim 1, characterized in that: the preparation method comprises the following steps: indoline, 4 '-difluoro diphenyl sulfone and potassium carbonate are added into a reaction vessel, wherein the molar mass ratio of the indoline, the 4,4' -difluoro diphenyl sulfone and the potassium carbonate is 0.9-1.1mmol:2-2.4mmol:9-11mmol, under the protection of nitrogen, 2-12ml of N-methyl pyrrolidone is injected, the reaction is carried out for 2 hours at 160 ℃, the reaction liquid is added into cold water, the ethyl acetate is used for extraction for three times, saturated saline water is used for washing, the organic phase is distilled off in a rotating way to remove the solvent, and the product 4-fluoro-4 '-indoline phenylsulfone is obtained through column chromatography separation and purification, wherein the 4-fluoro-4' -indoline phenylsulfone is a compound shown as a general formula II.
3. The process for the preparation of a series of acceptor-donating compounds based on diphenyl sulfone and indole derivatives according to claim 1, characterized in that: the preparation method comprises the following steps: indoline, 4 '-difluorodiphenyl sulfone and sodium hydride are added into a reaction vessel, wherein the molar mass ratio of the indoline to the 4,4' -difluorodiphenyl sulfone to the sodium hydride is 4-4.8mmol:0.9-1.1mmol:4-4.8mmol, under the protection of nitrogen, 2-12ml of N, N dimethylformamide is injected, the reaction is carried out for 10 hours at 100 ℃, the temperature is naturally reduced to room temperature, the reaction liquid is poured into ice water under stirring, the ice water is extracted three times by ethyl acetate, saturated saline water is used for washing, the organic phase is distilled off to remove the solvent, and the product of di (4-indoline phenyl) sulfone is obtained through column chromatography separation and purification, wherein the di (4-indoline phenyl) sulfone is a compound shown as a general formula II.
4. Use of a series of acceptor-donating compounds based on diphenyl sulfone and indole derivatives according to any of claims 1-3, characterized in that: as a fluorescence sensor for detecting the water content of organic solvents.
5. The use of a series of acceptor-donating compounds based on diphenyl sulfone and indole derivatives according to claim 4, characterized in that: the application method comprises the following steps:
(1) Dissolving a compound of the general formula II in a mixed solution of water and tetrahydrofuran;
(2) And measuring the system luminescence change caused by the water integral change, thereby detecting the water content in the organic solvent.
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