A halogenated tetraphenyl ethenyl derivative fluorescent probe and a synthesis method and application thereof

Abstract

The application discloses a kind of two kinds of halogenated tetraphenyl ethenyl derivative fluorescent probes and synthesis method and application thereof.Halogenated tetraphenyl ethenyl derivative fluorescent probes 2FH2L, 2BrH2L synthesis method is as follows, compound B is prepared by compound A, compound B is dissolved in the mixed solvent of THF, methanol and water with LiOH, hydrolysis, then acidification treatment and the product 2FH2L is obtained by drying the precipitate by suction filtration.Halogenated tetraphenyl ethenyl derivative of the application exhibits significant AIE effect in different solvent proportions, and exhibits strong fluorescence emission in poor solvent.By the characteristics of halogenated tetraphenyl ethenyl derivative, it can be used as a kind of efficient Cu 2+ fluorescent probe.

Description

Technical Field

[0001] This invention relates to one or two examples of TPE-based fluorescent probes and their preparation. This invention also relates to the application of the copper ion fluorescent probe in the identification of copper ions, which belongs to the field of analytical detection. Background Technology

[0002] Copper, a crucial trace element, is an essential mineral for many organisms to maintain life and an indispensable metallic raw material for industrial production. However, when copper ion concentrations exceed a certain threshold, they can pollute the environment and threaten human health. Therefore, efficient and accurate detection of copper ion levels in the environment and organisms is crucial. Environmentally, factors such as industrial emissions, pesticide use, and urbanization lead to copper entering the natural environment, affecting water and soil quality. The application of fluorescent probe technology allows environmental protection departments to quickly identify copper ion exceedances and take timely measures to effectively prevent environmental pollution. In the fields of medicine and biology, copper, as an important element for cellular activity, participates in various physiological functions. However, its abnormal accumulation or homeostasis imbalance can trigger various neurological diseases, such as Wilson's disease, Alzheimer's disease, Parkinson's disease, and Meniere's disease. Therefore, monitoring the excessive presence of copper in the environment and the human body is of great significance for ensuring our survival and development.

[0003] Traditional fluorescent materials are limited by the ACQ effect, making it difficult to meet contemporary development needs. The discovery of the AIE phenomenon provides an important solution. In recent years, numerous fluorescent molecules with AIE properties, such as tetraphenylethylene (TPE) derivatives, cyano derivatives, pyran derivatives, Schiff base derivatives, and biphenyl derivatives, have been discovered and studied in depth. These AIE substances have been widely used in bioimaging, fluorescence sensing, LEDs, and color-changing luminescent materials. In particular, tetraphenylethylene derivatives have attracted much attention due to their simple synthesis, ease of modification, and excellent luminescent properties. With their typical AIE characteristics, they show broad application prospects in fluorescence sensing analysis and cell imaging. Various methods exist for detecting copper ions, including inductively coupled plasma mass spectrometry, ultraviolet-visible spectrophotometry, electrochemical analysis, and fluorescence spectroscopy.

[0004] In view of the above, this scheme innovatively designs a fluorescent probe solution, utilizing a fluorescence quenching mechanism to achieve the control of Cu. 2+ Rapid and selective detection was achieved after in-depth study of their AIE properties. It was found that these derivatives exhibit significant AIE effects under different solvent ratios, with particularly strong fluorescence emission in poor solvents. Through UV-Vis absorption and fluorescence spectroscopy analysis, we revealed the intrinsic relationship between the material's aggregation state and fluorescence properties. Furthermore, this study also developed a highly efficient Cu... 2+The fluorescent probe solution still exhibits activity against Cu even in environments where multiple metal ions coexist. 2+ The high selectivity and anti-interference ability of Cu were demonstrated, and the fluorescence emission of Cu was measured. 2+ The detection limit. Summary of the Invention

[0005] To address the problems mentioned in the background section, this invention provides a halotetraphenylyl derivative fluorescent probe, its synthesis method, and its application, overcoming the limitations of existing technologies where the probe solution reacts poorly to Cu in environments with multiple metal ions. 2+ The selectivity and anti-interference ability are poor.

[0006] To achieve the above objectives, in a first aspect, the present invention provides a halotetraphenylyl derivative fluorescent probe, wherein the molecular structure of the fluorescent probe is specifically shown in the following structural formula (I) or formula (II):

[0007] (I)

[0008] (II).

[0009] Secondly, the present invention provides a method for synthesizing a halotetraphenylyl derivative fluorescent probe, comprising the following steps: (1) Synthesize the aforementioned structural formula (I) Step 1: 4,4'-,difluorobenzophenone, 4,4'-,dibromobenzophenone, zinc powder, and THF (after redistillation and degassing) were placed together in a double-necked round-bottom flask. Under nitrogen protection, TiCl4 was slowly injected into the system in an ice-water bath. The reaction system was then stirred for 2 hours, followed by reflux at 80°C overnight. After cooling, the reaction was quenched with a 10% K2CO3 aqueous solution, and then extracted with CH2Cl2. The extracted solution was dried with anhydrous Na2SO4 and then concentrated using a rotary evaporator. The concentrated product was purified by column chromatography using CH2Cl2 and petroleum ether as eluents. The resulting product was dissolved in CH2Cl2 and then precipitated with petroleum ether to obtain a white solid. After filtration, compound A was obtained. Step 2: Compound A, 4-(methoxycarbonyl)phenylboronic acid, K2CO3, and Pd(PPh3)4 were added to a two-necked round-bottom flask equipped with a magnetic stir bar. The flask contained a degassed mixture of toluene, ethanol, and water. Nitrogen gas was then introduced, and the mixture was refluxed at 95°C overnight. The reaction progress was observed by TLC. The mixed product obtained from the reaction was extracted with CH2Cl2 and dried. Subsequently, it was concentrated by rotary evaporation. The system was purified by column chromatography using a mixed solution of CH2Cl2 and petroleum ether as the eluent. The petroleum ether was decanted in the CH2Cl2 solution to precipitate the solid, which was then filtered and dried to obtain compound B as a white solid. Step 3: Compound B was dissolved in a mixed solvent of THF, methanol, and water containing LiOH. The system was refluxed at room temperature for 4 hours. After cooling, the system was rotary evaporated to remove some of the THF and methanol, etc., organic solvents. Subsequently, the system was acidified with diluted hydrochloric acid solution until pH paper showed that the system was acidic, and a large amount of white flocculent precipitate was produced during the process. The precipitate was filtered and dried to obtain product 2FH2L, which was a pale yellow powder after filtration and drying. (2) Synthesize the structure (II) Step 1: 4,4'-,(2,2-diphenylvinyl-1,1-diyl)bis(bromobenzene), 4-(methoxycarbonyl)phenylboronic acid, and Pd(PPh3)4 were placed together in a three-necked round-bottom flask. A mixture of degassed toluene, ethanol, and water was also added to the flask, which was equipped with a magnetic stir bar. The flask was then filled with nitrogen and refluxed overnight at 95°C. The mixture was extracted with CH2Cl2, and the organic phase was washed with water and brine. The crude product was obtained by rotary evaporation and purified by column chromatography using CH2Cl2 and petroleum ether as eluents to give compound C, which was a white solid. Step 2: Dissolve compound C in CH2Cl2 and place the solution in a round-bottom flask equipped with a magnetic stir bar. Then slowly add liquid bromine. Stir at room temperature for 12 hours, quench the reaction with an ethanol solution of Na2S2O3, and adjust the pH to neutral using NaOH solution. Extract with CH2Cl2, dry the organic phase with anhydrous MgSO4, and after rotary evaporation, purify by column chromatography using a mixture of CH2Cl2 and petroleum ether as the eluent to obtain compound D. Step 3: Dissolve compound D in a mixed solvent of THF, methanol, and water in which NaOH is dissolved. Reflux the system at 80°C for 4 hours. After cooling, remove some of the THF and methanol by rotary evaporation. Then, dilute the solution with 1 mol / L of water. -1The system was acidified with hydrochloric acid solution until pH paper showed that the system was acidic, during which a large amount of white flocculent precipitate was produced. The precipitate was filtered and dried to obtain the product 2BrH2L.

[0010] Preferably, in step one, the volume ratio of CH2Cl2 to petroleum ether in the eluent is 1:5.

[0011] Preferably, in step two of synthesizing structural formula (I) and step one of synthesizing structural formula (II), the volumes of toluene, ethanol, and water are 50 mL, 15 mL, and 15 mL, respectively.

[0012] Preferably, in step two of synthesizing the structure (I), the volume ratio of CH2Cl2 to petroleum ether is 1:1.

[0013] Preferably, the volume ratio of the mixed solvent of THF, methanol and water in step three of the synthesis of structural formula (I) and structural formula (II) is 1:1:1, and is 20 mL for both.

[0014] Preferably, in steps one and two of synthesizing the structure (II), the volume ratio of CH2Cl2 to petroleum ether is 1:1.

[0015] Preferably, the reaction route for synthesizing the structure (I) is as follows:

[0016] 。

[0017] Preferably, the reaction route for synthesizing the structure (II) is as follows:

[0018] 。

[0019] Thirdly, this invention provides the above-mentioned halotetraphenylyl derivative fluorescent probe for recognizing Cu 2+ In the application of ions, the detection limit of the fluorescent probe for copper ions is determined by detecting the fluorescence emission levels of two fluorescent probe solutions in copper ion solutions of different concentrations.

[0020] Compared with the prior art, the beneficial effects of the present invention are: This invention successfully synthesized and characterized two TPE derivatives, 2FH₂L and 2BrH₂L, and investigated their AIE (Alternating Induction Emission) properties. These derivatives exhibited significant AIE effects in fluorescence performance under different solvent ratios, and showed strong fluorescence emission in poor solvents. Through UV-Vis absorption and fluorescence spectroscopy analysis, this method revealed the correlation between the aggregation state and fluorescence properties of these materials. A highly efficient method for detecting Cu was also discovered.2+ Fluorescent probes. Attached Figure Description

[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0022] Figure 1 The hydrogen NMR spectrum of 2FH2L; Figure 2 The hydrogen NMR spectrum of 2BrH2L; Figure 3 The UV absorption spectra of 2FH2L (20 mol / L) in mixed systems of DMF / H2O at different ratios are shown. Figure 4 The fluorescence spectra of 2FH2L (20 mol / L) in mixed systems of DMF / H2O at different ratios are shown. Figure 5 The particle size distribution of 2FH2L (20 mol / L) in a mixed system of DMF / H2O = 1 / 99; Figure 6 The UV absorption spectra of 2BrH2L (20 mol / L) in mixed systems of DMF / H2O at different ratios are shown. Figure 7 Fluorescence emission of 2BrH2L (20 mol / L) in mixed systems of DMF / H2O in different proportions; Figure 8 The particle size distribution of 2BrH2L (20 mol / L) in a mixed system of DMF / H2O = 1 / 99; Figure 9 Ion selectivity of 2FH2L fluorescent probe; Figure 10 Ion selectivity of the 2BrH2L fluorescent probe; Figure 11 The anti-interference ability of the 2FH2L fluorescent probe for detecting copper ions; Figure 12 The anti-interference ability of the 2BrH2L fluorescent probe for detecting copper ions; Figure 13 Fluorescence emission spectra of compound 2FH2L (10 mol / L) in copper ion solutions of different concentrations; Figure 14Fluorescence emission spectra of compound 2BrH2L (10 mol / L) in copper ion solutions of different concentrations. Detailed Implementation

[0023] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0024] Unless otherwise specified, the raw materials used in this invention are all from commercially available conventional products.

[0025] Example 1 This embodiment provides a method for preparing a copper ion fluorescent probe based on TPE, including the following steps: Preparation steps of 2FH2L: 4,4'-(2,2-Di(4-bromophenyl)ethylene-1,1-diyl)di(fluorobenzene) (Compound A) Preparation: 4,4'-,difluorobenzophenone, 4,4'-,dibromobenzophenone, zinc powder, and THF (redegassed by redistillation) were placed together in a double-necked round-bottom flask under nitrogen protection. TiCl4 was slowly added to the system in an ice-water bath, and the reaction mixture was stirred for 2 hours. The system was then refluxed overnight at 80°C. After cooling, the reaction was quenched with a 10% K2CO3 aqueous solution, followed by extraction with CH2Cl2. The extracted solution was dried over anhydrous Na2SO4 and then concentrated using a rotary evaporator. The concentrated product was purified by column chromatography using CH2Cl2:petroleum ether as the eluent. The resulting product was dissolved in CH2Cl2 and precipitated with petroleum ether to obtain a white solid, which was then filtered to obtain compound A.

[0026] 4',4'''-(2,2-bis(4-fluorophenyl)ethylene-1,1-diyl)bis([1,1'-biphenyl]-4-carboxylic acid)dimethyl ester (Compound B) Synthesis: Compound A, 4-(methoxycarbonyl)phenylboronic acid, K₂CO₃, and Pd(PPh₃)₄ were added to a two-necked round-bottom flask equipped with a magnetic stir bar. The flask contained a degassed mixture of toluene, ethanol, and water. Nitrogen gas was then introduced, and the mixture was refluxed overnight at 95°C. The reaction progress was observed via TLC. Once the reaction was relatively complete, it was stopped and cooled. The resulting mixture was extracted with CH₂Cl₂, dried, and then concentrated by rotary evaporation. The system was purified by column chromatography using a CH₂Cl₂:petroleum ether mixture as the eluent. Petroleum ether was precipitated in the CH₂Cl₂ solution, and the solid was filtered and dried to obtain compound B as a white solid.

[0027] 4',4'''-(2,2-bis(4-fluorophenyl)ethylene-1,1-diyl)bis(([1,1'-biphenyl]-4-carboxylic acid))( 2FH2L )

[0028] Synthesis: Compound B was dissolved in a mixed solvent of THF, methanol, and water containing LiOH. The system was refluxed at room temperature for 4 hours. After cooling, the system was rotary evaporated to remove some of the organic solvents such as THF and methanol. Subsequently, the system was acidified with diluted hydrochloric acid solution until pH paper showed that the system was acidic, during which a large amount of white flocculent precipitate was produced. The precipitate was filtered and dried to obtain product 2FH2L, which was a pale yellow powder after filtration and drying.

[0029] The molecular synthetic route is shown below. .

[0030] Preparation steps of 2BrH2L: 4',4'''-(2,2-diphenylethylene-1,1-diyl)bis([1,1'-biphenyl]-4-carboxylic acid) dimethyl ester (compound C)

[0031] Preparation: 4,4'-,(2,2-diphenylvinyl-1,1-diyl)di

[0032] (Bromobenzene), 4-(methoxycarbonyl)phenylboronic acid, and Pd(PPh3)4 were placed together in a three-necked round-bottom flask, along with degassed toluene, ethanol, and water. A magnetic stir bar was also provided. The flask was then filled with nitrogen and refluxed overnight at 95°C. The mixture was extracted with CH2Cl2, and the organic phase was washed with water and brine. The crude product was obtained by rotary evaporation and purified by column chromatography using CH2Cl2:petroleum ether as the eluent to give compound C as a white solid.

[0033] 4',4'''-(2,2-bis(4-bromophenyl)ethylene-1,1-diyl)bis([1,1'-biphenyl]-4-carboxylic acid) dimethyl ester (compound D) Preparation: Compound C was dissolved in CH2Cl2 and placed in a round-bottom flask equipped with a magnetic stir bar. Liquid bromine was then slowly added. The mixture was stirred at room temperature for 12 hours. The reaction was quenched by adding Na2SO3 and ethanol solution, and the pH was adjusted to neutral using NaOH solution. The mixture was then extracted with CH2Cl2, and the organic phase was dried over anhydrous MgSO4. After rotary evaporation, the compound was purified by column chromatography using a mixture of CH2Cl2 and petroleum ether as the eluent, yielding compound D in approximately 90% yield.

[0034] 4',4'''-(2,2-bis(4-bromophenyl)ethylene-1,1-diyl)bis(([1,1'-biphenyl]-4-carboxylic acid))( 2BrH2L ) Synthesis: Compound D was dissolved in a mixed solvent of THF, methanol, and water in which NaOH was dissolved. The system was refluxed at 80°C for 4 hours. After cooling, the system was rotary evaporated to remove some of the THF and methanol, and then diluted with 1 mol / L water. -1 The system was acidified with hydrochloric acid solution until pH paper indicated an acidic state, during which a large amount of white flocculent precipitate was produced. The precipitate was filtered and dried to obtain the product 2BrH2L. The synthetic route for this molecule is shown below. .

[0035] It should be noted that the characteristics of the TPE-based copper ion fluorescent probe are as follows: 1. AIE effect of copper ion probe DMF was selected as the good solvent and deionized water as the poor solvent. By varying the proportion of the poor solvent in the mixed solvent, specifically using 2FH₂L and 2BrH₂L, different volume ratios (DMF / H₂O = 1 / 99, 5 / 95, 10 / 90, 20 / 80, 40 / 60, 60 / 40, 80 / 20, 100 / 0) of DMF / H₂O mixed solutions were prepared (solution concentration C = 2 * 10⁻⁶). -5 We investigated the changes in UV absorption and fluorescence emission of these two compounds in a DMF / H2O mixed solution (mol / L), with an excitation wavelength of 360 nm. We also tested the particle size of aggregates in the DMF / H2O solution (V:V=1:99).

[0036] 2. Ultraviolet absorption and fluorescence spectral characterization of the 2FH2L copper ion probe The fluorescence emission and UV absorption spectra of 2FH2L molecules in mixed solutions of DMF / H2O at different volume ratios, as well as the particle size distribution of the mixed solutions at 99% water content, are shown in the following figure. Figure 3 As shown, 2FH2L produces a maximum ultraviolet absorption peak at around 320 nm; as Figure 4 As shown, when the volume fraction of water is less than 90%, the aggregation degree of fluorescent molecules is very low, and almost no fluorescence is produced; when the volume fraction of water is in the range of 90% to 99%, the aggregation degree of fluorescent molecules gradually increases. This is due to the gradual increase in molecular aggregation caused by the reduced solubility of fluorescent molecules in poor solvent systems, and also because the 2FH2L molecule has good AIE properties. Figure 5 As shown, 20 μmol / L compound 2FH2L exists as aggregates with a particle size of about 130 nm in a mixed system of DMF / H2O with a water volume fraction of 99%.

[0037] 3. Ultraviolet absorption and fluorescence spectral characterization of the 2BrH2L copper ion probe The UV absorption and fluorescence spectra of 2BrH2L molecules in a DMF / H2O mixed solution, as well as the particle size distribution at high water content (99%), are shown in the figure below. Figure 6 As shown, 2BrH2L produces a maximum ultraviolet absorption peak at around 320 nm; as Figure 7As shown, when the volume percentage of water is less than 90%, the aggregation degree of fluorescent molecules is low, and almost no fluorescence is produced. When the volume percentage of deionized water is between 90% and 99%, the increase in the unsuitable solvent water leads to a gradual increase in the aggregation degree of fluorescent molecules. This is due to the gradual decrease in the solubility of fluorescent molecules in the unsuitable solvent system, resulting in a gradual increase in the degree of molecular aggregation, and also because the 2BrH2L molecule has good AIE properties. Figure 8 As shown, 20 μmol / L compound 2BrH2L exists as aggregates with a particle size of approximately 175 nm in a mixed system of DMF / H2O with a water volume fraction of 99%.

[0038] Example 2 Two AIE fluorescent probe methods for the detection of copper ions: In the selective experiments of two compounds on copper ions, the prepared solutions of different metal ions were diluted to 100...

[0039] Prepare a 1.0 mmol / L solution. Take 9.9 mL of the diluted metal ion solution and add it to a 10 mL glass bottle. Finally, take 0.1 mL of the 1.0 mmol / L sample stock solution and add it to the 10 mL glass bottle to mix with the metal ion solution. The total volume of the mixed solution is 10 mL. Measure the fluorescence spectrum of the sample immediately after mixing.

[0040] Example 3 Methods for testing the anti-interference ability of three compounds: In a 10 mL glass bottle, 0.1 mL of a 10.0 mmol / L solution of another metal ions was first added, followed by 0.1 mL of a 1.0 mmol / L compound solution. The total volume was then adjusted, and deionized water was used to bring the volume to 10 mL. After mixing, the sample underwent its first fluorescence spectrum measurement. Following this measurement, 0.1 mL of a 10.0 mmol / L copper ion solution was added to the mixture, and a second fluorescence spectrum measurement was performed.

[0041] Example 4 Experimental methods for determining the detection limits of two compounds for copper ions: The previously configured 10 -2 The copper ion solution was diluted to 10 mol / L. -3 mol / L, 10 -4 mol / L, 10 -5 mol / L, 10 -6 mol / L, 10 -7 Next, 0.1 mL of a 10.0 mmol / L zinc ion solution was added to the diluted copper ion solution (the zinc ions were added to induce fluorescence in the previously non-luminescent 2FH₂L and 2BrH₂L solutions, and the detection limits of these two compounds for copper ions were determined by observing the effect of different copper ion concentrations on fluorescence intensity). Finally, 0.1 mL of a 1.0 mmol / L compound solution was added, bringing the total volume of the mixed solution to 10 mL. The fluorescence spectrum of the sample was measured immediately after mixing.

[0042] Specifically, the characteristics of halotetraphenylyl derivative fluorescent probes in copper ion detection are as follows: 1. Selectivity of compounds 2FH2L and 2BrH2L for the detection of copper ions. To investigate the selectivity of compounds 2FH₂L and 2BrH₂L for copper ions, fluorescence spectroscopy was used to study the three compounds on different metal cations, such as Al. 3+ Ba 2+ Cd 2+ Cr 3+ Fe 3+ K + Mg 2+ Na + Zn 2+ The changes in fluorescence intensity when present are as follows: Figure 9 , Figure 10 As shown. The results indicate that when 10 equivalents of different metal cations are added to a 10 μmol / L solution of the three compounds, all metal cations except copper ions enhance the luminescence intensity of the compound solution. However, as Cu... 2+ The addition of these compounds resulted in very low fluorescence intensity in the solution, or even no fluorescence at all. This clearly demonstrates that these two compounds can serve as effective fluorescent probes for detecting copper ions.

[0043] 2. Anti-interference properties of compounds 2FH2L and 2BrH2L for copper ion detection After investigating the selectivity of the three compounds for copper ions, the crucial next step is to investigate the interference resistance of the fluorescent probe. We added Cu to a 10 μmol / L solution of the three compounds... 2+ In addition to the solution, another metal cation was also added. The result was as follows: Figure 11 , Figure 12As shown, most metal ions did not significantly interfere with the solution. However, we found that chromium and iron ions weakened the fluorescence quenching effect produced by the combination of the three compounds (2FH2L, 2BrH2L) with copper ions.

[0044] 3. Detection limits of compounds 2FH₂L and 2BrH₂L for copper ions. After investigating the selectivity and anti-interference properties of the two compounds for copper ions, we further explored the detection limits of these two fluorescent probes for copper ions, which is also an important indicator for evaluating their detection performance. We determined the detection limits of the fluorescent probes for copper ions by measuring the fluorescence emission levels of the two fluorescent probe solutions in copper ion solutions of different concentrations. The results are as follows: Figure 13 , Figure 14 As shown in the data image, it can be observed that when the copper ion concentration is 10... - 3 mol / L and 10 -4 Fluorescence can be quenched at concentrations of mol / L, and when the copper ion concentration is less than 10 mol / L... -4 mol / L, concentration of 10 -5 mol / L, 10 -6 mol / L, 10 -7 At a concentration of mol / L, the fluorescence of the solution was actually enhanced. Therefore, we can conclude that the detection limit for copper ions for all three fluorescent probes is 10 mol / L. -4 mol / L.

[0045] This study successfully synthesized and characterized two TPE derivatives, 2FH₂L and 2BrH₂L, and investigated their AIE (Alternating Induction Emission) properties. These derivatives exhibited significant AIE effects in different solvent ratios and displayed strong fluorescence emission in poor solvents. UV-Vis absorption and fluorescence spectroscopy analyses revealed the correlation between the aggregation state and fluorescence properties of these materials. Furthermore, this study also discovered a highly efficient method for detecting Cu. 2+ Fluorescent probes. The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A halotetraphenylyl derivative fluorescent probe, characterized in that, The molecular structure of the fluorescent probe is shown in the following structural formula (I) or formula (II): （I） (II)。 2. A method for synthesizing a halotetraphenylyl derivative fluorescent probe as described in claim 1, characterized in that, Includes the following steps: (1) Synthesize the aforementioned structural formula (I) Step 1: 4,4'-difluorobenzophenone, 4,4'-dibromobenzophenone, zinc powder, and THF (after redistillation and degassing) were placed together in a double-necked round-bottom flask. Under nitrogen protection, TiCl4 was slowly injected into the system in an ice-water bath. The reaction system was then stirred for 2 hours, followed by reflux at 80°C overnight. After cooling, the reaction was quenched with 10% K2CO3 aqueous solution, and then extracted with CH2Cl2. The extracted solution was dried with anhydrous Na2SO4 and then concentrated using a rotary evaporator. The concentrated product was purified by column chromatography using CH2Cl2 and petroleum ether as eluents. The resulting product was dissolved in CH2Cl2 and then precipitated with petroleum ether to obtain a white solid. After filtration, compound A was obtained. Step 2: Compound A, 4-(methoxycarbonyl)phenylboronic acid, K2CO3, and Pd(PPh3)4 were added to a two-necked round-bottom flask equipped with a magnetic stir bar. The flask contained a degassed mixture of toluene, ethanol, and water. Nitrogen gas was then introduced, and the mixture was refluxed at 95°C overnight. The reaction progress was observed by TLC. The mixed product obtained from the reaction was extracted with CH2Cl2 and dried. Subsequently, it was concentrated by rotary evaporation. The system was purified by column chromatography using a mixed solution of CH2Cl2 and petroleum ether as the eluent. The petroleum ether was decanted in the CH2Cl2 solution to precipitate the solid, which was then filtered and dried to obtain compound B as a white solid. Step 3: Dissolve compound B in a mixed solvent of THF, methanol and water containing LiOH. Reflux the system at room temperature for 4 hours. After cooling, remove some of the THF and methanol organic solvent by rotary evaporation. Then acidify the system with diluted hydrochloric acid solution until the pH paper shows that the system is acidic. A large amount of white flocculent precipitate is generated during the process. Filter and dry the precipitate to obtain structural formula (I). After filtration and drying, structural formula (I) appears as a light yellow powder. The reaction route for synthesizing the structure (I) is as follows: ； (2) Synthesize the structure (II) Step 1: 4,4'-(2,2-diphenylvinyl-1,1-diyl)bis(bromobenzene), 4-(methoxycarbonyl)phenylboronic acid, and Pd(PPh3)4 were placed together in a three-necked round-bottom flask. A mixture of degassed toluene, ethanol, and water was also added to the flask, which was equipped with a magnetic stir bar. The flask was then filled with nitrogen and refluxed overnight at 95°C. The mixture was extracted with CH2Cl2, and the organic phase was washed with water and brine. The crude product was obtained by rotary evaporation and purified by column chromatography using CH2Cl2 and petroleum ether as eluents to give compound C as a white solid. Step 2: Dissolve compound C in CH2Cl2 and place it in a round-bottom flask with a magnetic stir bar. Then slowly add liquid bromine and stir at room temperature for 12 hours. Add an ethanol solution of Na2S2O3 to quench the reaction and adjust the pH to the neutral range using NaOH solution. Then extract with CH2Cl2, dry the organic phase with anhydrous MgSO4, and after rotary evaporation, perform column chromatography purification using a mixed solution of CH2Cl2 and petroleum ether as the eluent to obtain compound D. Step 3: Dissolve compound D in a mixed solvent of THF, methanol, and water in which NaOH is dissolved. Reflux the system at 80°C for 4 hours. After cooling, remove some of the THF and methanol organic solvent by rotary evaporation. Then, dilute the solution with 1 mol / L of water. -1 The system was acidified with hydrochloric acid solution until pH paper showed that the system was acidic. During the process, a large amount of white flocculent precipitate was generated. The precipitate was filtered and dried to obtain structural formula (II). The reaction route for synthesizing structure (II) is as follows: 。 3. The method for synthesizing a halotetraphenylyl derivative fluorescent probe according to claim 2, characterized in that, In step one, the volume ratio of CH2Cl2 to petroleum ether in the eluent is 1:

5.

4. The method for synthesizing a halotetraphenylyl derivative fluorescent probe according to claim 2, characterized in that, In step two of the synthesis of structural formula (I) and step one of the synthesis of structural formula (II), the volumes of toluene, ethanol and water are 50 mL, 15 mL and 15 mL, respectively.

5. The method for synthesizing a halotetraphenylyl derivative fluorescent probe according to claim 2, characterized in that, In step two of the synthesis of the structure (I), the volume ratio of CH2Cl2 to petroleum ether is 1:

1.

6. The method for synthesizing a halotetraphenylyl derivative fluorescent probe according to claim 2, characterized in that, In step three of the synthesis of structural formulas (I) and (II), the volume ratio of the mixed solvent of THF, methanol and water is 1:1:1, and the volume is 20 mL for both.

7. The method for synthesizing a halotetraphenylyl derivative fluorescent probe according to claim 2, characterized in that, In steps one and two of the synthesis of the structure (II), the volume ratio of CH2Cl2 to petroleum ether is 1:

1.

8. The application of the fluorescent probe as described in claim 1 in the identification of Cu²⁺ ions.

Images