Dual recognition of fluoride ion by chiral photoactive molecules based on triarylamine

Abstract

This invention provides a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines. By co-assembling a unique supramolecular assembly with a non-chiral inorganic anionic material, circular dichroism (CD) absorption spectroscopy signal amplification is achieved, enabling latent recognition of F ions. Simultaneously, under ultraviolet light irradiation, the supramolecular system containing F ions exhibits a completely different color development compared to other anions, demonstrating overt recognition of F ions.

Description

Technical Field

[0001] This invention belongs to the field of inorganic anion detection, specifically relating to a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamine, which is applicable to fluoride ion detection material systems. Background Technology

[0002] In supramolecular chemistry, particularly the self-assembly of chiral molecules, enormous application potential has been shown in sensing, nanotechnology, and materials science. However, achieving precise control over the chiral expression within these systems, especially under specific stimuli, remains a significant challenge. Fluorine, the smallest atomically and most electronegative element in the halogen group, typically exists in the natural environment as fluoride ions. Adequate fluoride intake is crucial for dental health, preventing tooth decay and promoting mineral deposition in bones. However, excessive fluoride intake can cause dental fluorosis and may interfere with normal bone development, leading to skeletal fluorosis. Furthermore, excessive fluoride can damage kidney and liver function, affecting the health of the nervous and circulatory systems. At high concentrations, fluoride ions can interfere with the normal metabolism of the immune system, potentially causing immune dysfunction by inhibiting protein and DNA synthesis. Beyond its impact on human health, fluoride pollution also enters the environment through human activities such as coal combustion, fertilizer application, aluminum smelting, and the production of ceramics, bricks, and glass, posing a threat to human and ecosystem health. Excessive fluoride content in soil can inhibit plant metabolism and photosynthesis, thereby reducing crop yield. Given the importance of fluoride ions to human health and ecological balance, developing a highly selective, highly sensitive, and easy-to-operate method for detecting fluoride ions is of great significance for scientific research and environmental monitoring. Summary of the Invention

[0003] The purpose of this invention is to provide a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines. Furthermore, the detection method is simple and highly operable.

[0004] The present invention provides a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines, which involves: using circular dichroism spectroscopy to detect the intensity change of the self-assembly of chiral triarylamine derivative molecules before and after the addition of fluoride ions to achieve latent recognition of F ions; or using ultraviolet light to distinguish the color change of the self-assembly of chiral triarylamine derivative molecules before and after the addition of fluoride ions to achieve explicit recognition of F ions.

[0005] Specifically, the dual recognition method for fluoride ions based on triarylamine chiral photosensitive molecules includes the following steps:

[0006] 1) Detect the circular dichroism (CD) intensity CD0 of the self-assembled chiral triarylamine derivative molecule and the circular dichroism (CD) intensity CD1 of the self-assembled chiral triarylamine derivative molecule containing anions. If CD1 is significantly enhanced compared to CD0, then the anion is determined to be a fluoride ion or includes fluoride ions.

[0007] 2) If a chiral triarylamine derivative molecule self-assembled system containing anions turns red under ultraviolet light, then the anion is determined to be a fluoride ion or includes fluoride ions.

[0008] When detecting whether an anion detection material system contains fluoride ions, one or both of the above steps 1) and 2) can be performed without any order restriction.

[0009] In the above method, the self-assembled chiral triarylamine derivative molecule exists in a mixed solvent, wherein the mixed solvent is DMF / DCM, and the volume ratio of DMF to DCM can be 0.02-0.5:1, specifically 0.02-0.25:1 or 0.25:1;

[0010] The significant enhancement is described as an enhancement of more than 10 times;

[0011] The chiral triarylamine derivative molecular self-assembly was prepared by a method comprising the following steps:

[0012] The chiral triarylamine derivative molecule is obtained by supramolecular assembly in a mixed solvent.

[0013] The self-assembled system of the anion-containing chiral triarylamine derivative molecules was prepared by a method comprising the following steps:

[0014] The anionic compound and the chiral triarylamine derivative molecule are obtained by supramolecular assembly in a mixed solvent;

[0015] The mixed solvent is DMF / DCM, and the volume ratio of DMF to DCM can be 0.02-0.5:1, specifically 0.02-0.25:1 or 0.25:1.

[0016] The concentration of chiral triarylamine derivative molecules in the mixed solvent is 0.088-1.0 mg / mL, specifically 0.88 mg / mL;

[0017] The chiral triarylamine derivative molecule is S or R-UNTA, and its structural formula is shown below:

[0018]

[0019] The chiral triarylamine derivative molecule (S / R-UNTA) was prepared by reacting 4,4',4'-triaminotriphenylamine and (S) / (R)-(+)-1-(1-naphthyl)isocyanate as raw materials.

[0020] Specifically, the chiral triarylamine derivative molecule (S-UNTA) is formulated according to... Figure 1 The synthetic route shown was prepared by a method comprising the following steps: 4,4',4'-triaminotriphenylamine (580 mg, 2 mmol) and (S)-(+)-1-(1-naphthyl)isocyanate (1305.5 mg, 6.6 mmol) were added to a round-bottom flask, followed by the addition of tetrahydrofuran (THF). The mixture was heated under reflux for 24 hours with stirring in an oil bath. After the reaction was complete, the mixture was filtered and the precipitate was collected. Subsequently, the filter cake was recrystallized from DMF and DCM and dried under vacuum for 24 hours to obtain a white solid in 65.2% S-UNTA.

[0021] R-UNTA is synthesized using the same procedure as S-UNTA.

[0022] This molecule has been reported in previous literature: DOI:10.1002 / smtd.202400538.

[0023] The molar ratio of the self-assembled body to the F ion (the detected unit) can be 1:1-3, specifically 1:3.

[0024] The application of chiral triarylamine derivative molecules or self-assembled chiral triarylamine derivative molecules in F ion detection is also within the scope of protection of this invention.

[0025] The present invention also provides an F ion recognition material.

[0026] The F ion recognition material provided by this invention is the above-mentioned chiral triarylamine derivative molecule or a self-assembled chiral triarylamine derivative molecule, wherein the chiral triarylamine derivative molecule may specifically be S / R-UNTA.

[0027] The triarylamine-based chiral photosensitive molecule described in this invention avoids the cumbersome enantiomer synthesis and response to external stimuli. It is a unique and tunable chiral optical material with significant applications in the recognition of fluoride ions.

[0028] The present invention has the following advantages:

[0029] (1) This invention prepares nanofibers through supramolecular assembly. Figure 9 It can exhibit a significantly enhanced circular dichroism absorption spectrum signal after the addition of F ions.

[0030] (2) This invention combines chiral materials with non-chiral inorganic anions, which can form a distinct helical fiber structure after the addition of F ions. Figure 9 This has become a new type of tunable F ion recognition material.

[0031] (3) The present invention co-assembles chiral materials with F ions, which can exhibit completely different color reactions after ultraviolet light irradiation, and can be used as a new type of visual F ion recognition material.

[0032] (4) The tunable F ion recognition material prepared by the present invention has a simple preparation method, provides a new idea for the study of F ion recognition materials, and provides a new choice for optical materials in the field of anion recognition.

[0033] This invention investigates the specific recognition of fluoride ions by the triarylamine derivative molecule UNTA in a DMF-DCM mixed solvent. The circular dichroism absorption spectrum of the UNTA system with added fluoride ions is enhanced by more than 15 times. Furthermore, UNTA turns green after UV irradiation in the DMF-DCM mixed solvent, while UNTA + fluoride ions turn red after UV irradiation in an organic solvent, achieving naked-eye recognition of fluoride ions. This invention realizes the dual recognition of fluoride ions by chiral supramolecular molecules in an organic system. Attached Figure Description

[0034] Figure 1 This is a synthetic route diagram for chiral triarylamine derivative molecules (S / R-UNTA).

[0035] Figure 2 The CD absorption spectrum of the assembly UNTA prepared in Example 1 of this invention and the F-axis absorption spectrum of the assembly UNTA+ are shown. - The CD absorption spectrum.

[0036] Figure 3 The CD spectrum is obtained by adding different equivalent amounts of F ions to the assembly UNTA in Embodiment 2 of the present invention.

[0037] Figure 4 This is the g obtained by adding different equivalent amounts of F ions to the assembly UNTA in Example 2 of the present invention. abs statistics.

[0038] Figure 5 The assembly prepared in Example 3 of this invention is supplemented with different anions (F). - ,Cl - ,Br - NO3 - CH3SO3 - The difference in solution color after irradiation with ultraviolet light and the macroscopic color difference after a period of time. The anions added from left to right are: blank, F... -, Cl - , Br - NO3 - CH3SO3 - .

[0039] Figure 6 The changes in the ultraviolet absorption spectrum of the assembly prepared in Example 4 of this invention after adding 3 equivalents of F ions under ultraviolet light irradiation for different time periods are shown.

[0040] Figure 7 The curves showing the changes in the absorption peak at 500 nm in the ultraviolet absorption spectra of the assembly prepared in Example 4 of this invention after adding 3 equivalents of F ions and irradiating it with ultraviolet light for different durations are fitted curves.

[0041] Figure 8 The difference lies in the circular dichroism absorption spectra of the assembly prepared in Example 5 of this invention after adding 3 equivalents of different anions.

[0042] Figure 9 The images show the microstructures of the assemblies formed by R / S-UNTA assembly. Among them, a is the nanofiber structure formed by the self-assembly of R-UNTA in a mixed solvent (DMF:DCM=1:4), b is the nanospiral fiber structure formed by the co-assembly of R-UNTA and F ions in a mixed solvent (DMF:DCM=1:4) (the molar ratio of F ions to UNTA is 3:1), and c is the nanospiral fiber structure formed by the co-assembly of S-UNTA and F ions in a mixed solvent (DMF:DCM=1:4) (the molar ratio of F ions to UNTA is 3:1). Detailed Implementation

[0043] The present invention will now be described in further detail with reference to specific embodiments. The given embodiments are merely illustrative of the invention and not intended to limit its scope. The embodiments provided below can serve as a guide for further improvements by those skilled in the art and do not constitute a limitation on the invention in any way.

[0044] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, performed according to the techniques or conditions described in the literature in this field or according to the product instructions. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0045] In the following examples, the chiral triarylamine derivative molecule (S-UNTA) is prepared according to... Figure 1The synthetic route shown was prepared by a method comprising the following steps: 4,4',4'-triaminotriphenylamine (580 mg, 2 mmol) and (S)-(+)-1-(1-naphthyl)isocyanate (1305.5 mg, 6.6 mmol) were added to a round-bottom flask, followed by the addition of tetrahydrofuran (THF). The mixture was heated under reflux for 24 hours with stirring in an oil bath. After the reaction was complete, the mixture was filtered and the precipitate was collected. Subsequently, the filter cake was recrystallized from DMF and DCM and dried under vacuum for 24 hours to obtain a white solid in 65.2% S-UNTA.

[0046] The preparation method of R-UNTA is the same as above, except that (S)-(+)-1-(1-naphthyl)isocyanate ethyl ester is replaced with (R)-(+)-1-(1-naphthyl)isocyanate ethyl ester.

[0047] Example 1

[0048] This embodiment provides a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines, including the following steps:

[0049] (1) 4.4 mg of R / S-UNTA molecules were dispersed in 1 mL of DMF, heated to form a transparent solution, and then cooled to 25°C. After 10 minutes, 0.2 mL of a fixed concentration (4.4 mg / mL) UNTA solution was obtained. A DMF solution of UNTA was prepared according to the calculated ratio, and 0.8 mL of a poor solvent (DCM) was added. After 30 minutes, the self-assembled UNTA was obtained.

[0050] (2) The preparation method of F ion co-assemblies is similar to the above method. First, F ions (tetrabutylammonium fluoride (F...) are prepared at room temperature... - The ions were dissolved in DCM and then co-assembled with UNTA according to the calculated ratio (the molar ratio of F ions to UNTA was 3:1). Some assemblies were taken from the sample tube and placed in a 0.1 mm cuvette for spectral analysis.

[0051] (3) In a DMF / DCM solvent mixture, UNTA assembles itself into a self-assembled structure. This is achieved by adding fluoride ions (tetrabutylammonium fluoride (F...)... -After introducing this system, a significant enhancement of UNTA chirality was observed, particularly upon co-assembly with F ions. The CD spectrum of the R-UNTA assembly was mirror-image of that of the S-UNTA assembly. Adding three equivalents of F ions to the R-UNTA and S-UNTA systems and performing CD spectral analysis on the resulting co-assemblies, S-UNTA showed a significant positive CD signal from 250 nm to 400 nm, intersecting at 333 nm. After co-assembly with F ions, R-UNTA exhibited a CD spectrum mirror-image of S-UNTA, characterized by a negative CD signal appearing in the same wavelength range (see...). Figure 2 ).

[0052] Among them, the tetrabutylammonium fluoride (F) used - Purchased from Innocare Reagents Co., Ltd.

[0053] Example 2

[0054] This embodiment provides a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines, including the following steps:

[0055] (1) 4.4 mg of R / S-UNTA molecules were dispersed in 1 mL of DMF, heated to form a clear solution, and then cooled to 25°C. After 10 minutes, 0.2 mL of a fixed concentration (4.4 mg / mL) UNTA solution was obtained. A DMF solution of UNTA was prepared according to the calculated ratio, and 0.8 mL of a poor solvent (DCM) was added. After 30 minutes, the self-assembled UNTA was obtained.

[0056] (2) The preparation method of F ion co-assemblies is similar to the above method. First, F ions (tetrabutylammonium fluoride (F...) are prepared at room temperature... - The assemblies were dissolved in DCM and then co-assembled with UNTA according to the calculated ratio. Some assemblies were taken from the sample tube and placed in a 0.1 mm cuvette for spectral analysis.

[0057] (3) F-ion titration experiments were performed on R-UNTA at a constant concentration. Different amounts of F-ions were added to R-UNTA solutions, and their CD spectra were subsequently analyzed. The addition of F-ions led to an enhancement of the R-UNTA CD signal (see...). Figure 3 ). For g in a mixed system containing different F ion concentrations abs Further analysis showed that with increasing F ion content, the g of R-UNTA at 310 nm... abs Gradually increase (see) Figure 4 This indicates that the addition of F ions to the system can significantly enhance the intensity of the CD absorption spectrum of UNTA, and the F ions in the system can be implicitly identified through CD spectroscopy.

[0058] Among them, the tetrabutylammonium fluoride (F) used - Purchased from Innocare Reagents Co., Ltd.

[0059] Example 3

[0060] This embodiment provides a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines, including the following steps:

[0061] (1) 4.4 mg of R / S-UNTA molecules were dispersed in 1 mL of DMF, heated to form a clear solution, and then cooled to 25°C. After 10 minutes, 0.2 mL of a fixed concentration (4.4 mg / mL) UNTA solution was obtained. A DMF solution of UNTA was prepared according to the calculated ratio, and 0.8 mL of a poor solvent (DCM) was added. After 30 minutes, the UNTA assembly was obtained.

[0062] (2) The preparation method of the anion co-assembly is similar to the above method. First, various inorganic anions (F...) are prepared at room temperature. - Cl - ,Br - NO3 - CH3SO3 - (Tetrabutylammonium fluoride (F)) - ), tetrabutylammonium chloride (Cl - ), Tetrabutylammonium bromide (Br - Tetrabutylammonium nitrate (NO3) - ), Tetrabutylammonium methanesulfonate (CH3SO3) - The anion was dissolved in DCM and then co-assembled with UNTA according to the calculated ratio (molar ratio of anion to UNTA was 3:1). Some assemblies were taken from the sample tube and placed in a 0.1 mm cuvette for spectral analysis.

[0063] (3) Recognition experiments of different anions were conducted on R-UNTA at a constant concentration. R-UNTA was reacted with various inorganic anions (F... - Cl - ,Br - NO3 - CH3SO3 - A comparative study was conducted on the co-assembled solutions. The resulting solutions were initially colorless and transparent. After irradiation with 365nm ultraviolet light for 10 minutes, a significant visual difference appeared: the solutions containing F... - The system showed a distinct red color, while systems containing other anions showed a green color (see...). Figure 5 This clearly demonstrates R-UNTA's influence on F. - The specific selectivity manifests as macroscopic color changes that can be observed with the naked eye.

[0064] Among them, the tetrabutylammonium fluoride (F) used - ), tetrabutylammonium chloride (Cl - ), Tetrabutylammonium bromide (Br - Tetrabutylammonium nitrate (NO3) - ), Tetrabutylammonium methanesulfonate (CH3SO3) - Purchased from Inokai Reagent Co., Ltd.

[0065] Example 4

[0066] This embodiment provides a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines, including the following steps:

[0067] (1) 4.4 mg of R / S-UNTA molecules were dispersed in 1 mL of DMF, heated to form a clear solution, and then cooled to 25°C. After 10 minutes, 0.2 mL of a fixed concentration (4.4 mg / mL) UNTA solution was obtained. A DMF solution of UNTA was prepared according to the calculated ratio, and 0.8 mL of a poor solvent (DCM) was added. After 30 minutes, the UNTA assembly was obtained.

[0068] (2) The preparation method of F ion co-assemblies is similar to the above method. First, F ions (tetrabutylammonium fluoride (F...) are prepared at room temperature... - The assemblies were dissolved in DCM and then co-assembled with UNTA according to the calculated ratio. Some assemblies were taken from the sample tube and placed in a 0.1 mm cuvette for spectral analysis.

[0069] (3) Conduct an experiment on the change of ultraviolet absorption spectrum of UNTA+F ion assembly at constant concentration with light exposure time.

[0070] Three equivalents of F ions were added to an R-UNTA solution, followed by irradiation of the F-ion-containing system with 365 nm ultraviolet light. With varying irradiation time, the system exhibited an absorption peak at 500 nm that increased over time. Analysis of the intensity of the 500 nm ultraviolet absorption peak showed an initial rapid increase followed by a slow enhancement (see...). Figure 6 and Figure 7 This indicates that after adding F ions to the system and then irradiating it with ultraviolet light, UNTA exhibits a strong absorption peak at 500 nm in its ultraviolet absorption spectrum, corresponding to its color change after ultraviolet irradiation. Furthermore, it is highly sensitive to F ions, responding rapidly to ultraviolet irradiation and producing changes in color and spectrum.

[0071] Among them, the tetrabutylammonium fluoride (F) used - Purchased from Innocare Reagents Co., Ltd.

[0072] Example 5

[0073] This embodiment provides a dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines, including the following steps:

[0074] (1) 4.4 mg of R / S-UNTA molecules were dispersed in 1 mL of DMF, heated to form a clear solution, and then cooled to 25°C. After 10 minutes, 0.2 mL of a fixed concentration (4.4 mg / mL) UNTA solution was obtained. A DMF solution of UNTA was prepared according to the calculated ratio, and 0.8 mL of a poor solvent (DCM) was added. After 30 minutes, the UNTA assembly was obtained.

[0075] (2) The preparation method of the anion co-assembly is similar to the above method. First, various inorganic anions (F...) are prepared at room temperature. - Cl - ,Br - NO3 - CH3SO3 - (Tetrabutylammonium fluoride (F)) - ), tetrabutylammonium chloride (Cl - ), Tetrabutylammonium bromide (Br - Tetrabutylammonium nitrate (NO3) - ), Tetrabutylammonium methanesulfonate (CH3SO3) - The assemblies were dissolved in DCM and then co-assembled with UNTA according to the calculated ratio. Some assemblies were taken from the sample tube and placed in a 0.1 mm cuvette for spectral analysis.

[0076] (3) Recognition experiments of different anions were conducted on R-UNTA at a constant concentration. R-UNTA was reacted with various inorganic anions (F... - Cl - ,Br - NO3 - CH3SO3 - A comparative study was conducted on the co-assemblies. Their CD spectra were analyzed. The addition of F ions led to an enhancement of the R-UNTA CD signal. However, the CD intensity of mixed systems containing different anions other than F ions did not change significantly (see [link to study]. Figure 8 This indicates that the addition of F ions to the system significantly enhances the intensity of the UNTA CD absorption spectrum, while other anions do not achieve the same effect. Therefore, the F ions in the system can be implicitly identified through CD spectroscopy.

[0077] Among them, the tetrabutylammonium fluoride (F) used - ), tetrabutylammonium chloride (Cl - ), Tetrabutylammonium bromide (Br - Tetrabutylammonium nitrate (NO3)- ), Tetrabutylammonium methanesulfonate (CH3SO3) - Purchased from Inokai Reagent Co., Ltd.

[0078] The present invention has been described in detail above. Those skilled in the art will recognize that the invention can be practiced in a wide range of ways with equivalent parameters, concentrations, and conditions without departing from its spirit and scope, and without requiring unnecessary experiments. While specific embodiments have been provided, it should be understood that further modifications can be made to the invention. In summary, according to the principles of the invention, this application is intended to include any changes, uses, or improvements to the invention, including changes made using conventional techniques known in the art that depart from the scope disclosed herein.

Claims

1. A dual recognition method for fluoride ions based on chiral photosensitive molecules of triarylamines, comprising: using circular dichroism spectroscopy to detect the intensity change of the self-assembly of chiral triarylamine derivative molecules before and after the addition of fluoride ions to achieve latent recognition of F ions; or using ultraviolet light to distinguish the color change of the self-assembly of chiral triarylamine derivative molecules before and after the addition of fluoride ions to achieve dominant recognition of F ions. The chiral triarylamine derivative molecular self-assembly was prepared by a method comprising the following steps: The chiral triarylamine derivative molecule is obtained by supramolecular assembly in a mixed solvent; The chiral triarylamine derivative molecule is S or R-UNTA, and its structural formula is shown below: The chiral triarylamine derivative molecule S-UNT was prepared by a method comprising the following steps: 4,4',4'-triaminotriphenylamine and (S)-(+)-1-(1-naphthyl)isocyanate were added to a round-bottom flask, followed by the addition of tetrahydrofuran. The mixture was heated under reflux for 24 hours with stirring in an oil bath. After the reaction was completed, the mixture was filtered and the precipitate was collected. Subsequently, the filter cake was recrystallized from DMF and DCM and dried under vacuum for 24 hours to obtain S-UNTA as a white solid. By replacing (S)-(+)-1-(1-naphthyl)isocyanate with (R)-(+)-1-(1-naphthyl)isocyanate in the above method, R-UNTA is prepared.

2. The method according to claim 1, characterized in that, The method for dual recognition of fluoride ions by chiral photosensitive molecules based on triarylamines includes the following steps: 1) Detect the circular dichroism spectral intensity CD0 of the self-assembled chiral triarylamine derivative molecule, and detect the circular dichroism spectral intensity CD1 of the self-assembled chiral triarylamine derivative molecule containing anions. If CD1 is significantly enhanced compared to CD0, then the anion is determined to be a fluoride ion or includes fluoride ions. 2) If a chiral triarylamine derivative molecule self-assembled system containing anions turns red under ultraviolet light, then the anion is determined to be a fluoride ion or includes fluoride ions. The self-assembled system of the anion-containing chiral triarylamine derivative molecules was prepared by a method comprising the following steps: The anionic compound and the chiral triarylamine derivative molecule are obtained by supramolecular assembly in a mixed solvent.

3. The method according to claim 2, characterized in that, The self-assembled chiral triarylamine derivative molecules exist in a mixed solvent, wherein the mixed solvent is DMF / DCM, and the volume ratio of DMF to DCM is 0.02-0.5:

1.

4. The method according to claim 2, characterized in that, In step 1), the significant enhancement is an enhancement of more than 10 times.

5. The method according to claim 2, characterized in that, The concentration of the chiral triarylamine derivative molecule in the mixed solvent is 0.088-1.0 mg / mL.

6. The method according to claim 2, characterized in that, The molar ratio of the self-assembled body to F ions is 1:1-3.

7. Application of chiral triarylamine derivative molecules or self-assembled chiral triarylamine derivative molecules in the detection of F ions; The chiral triarylamine derivative molecule is S or R-UNTA, and its structural formula is shown below: The chiral triarylamine derivative molecule S-UNT was prepared by a method comprising the following steps: 4,4',4'-triaminotriphenylamine and (S)-(+)-1-(1-naphthyl)isocyanate were added to a round-bottom flask, followed by the addition of tetrahydrofuran. The mixture was heated under reflux for 24 hours with stirring in an oil bath. After the reaction was completed, the mixture was filtered and the precipitate was collected. Subsequently, the filter cake was recrystallized from DMF and DCM and dried under vacuum for 24 hours to obtain S-UNTA as a white solid. By replacing (S)-(+)-1-(1-naphthyl)isocyanate with (R)-(+)-1-(1-naphthyl)isocyanate in the above method, R-UNTA is obtained; The chiral triarylamine derivative molecular self-assembly was prepared by a method comprising the following steps: The chiral triarylamine derivative molecule is obtained by supramolecular assembly in a mixed solvent.

8. An F ion recognition material, which is a chiral triarylamine derivative molecule or a self-assembled chiral triarylamine derivative molecule, wherein the chiral triarylamine derivative molecule is S or R-UNTA, and its structural formula is shown below: The chiral triarylamine derivative molecule S-UNT was prepared by a method comprising the following steps: 4,4',4'-triaminotriphenylamine and (S)-(+)-1-(1-naphthyl)isocyanate were added to a round-bottom flask, followed by the addition of tetrahydrofuran. The mixture was heated under reflux for 24 hours with stirring in an oil bath. After the reaction was completed, the mixture was filtered and the precipitate was collected. Subsequently, the filter cake was recrystallized from DMF and DCM and dried under vacuum for 24 hours to obtain S-UNTA as a white solid. By replacing (S)-(+)-1-(1-naphthyl)isocyanate with (R)-(+)-1-(1-naphthyl)isocyanate in the above method, R-UNTA is obtained; The chiral triarylamine derivative molecular self-assembly was prepared by a method comprising the following steps: The chiral triarylamine derivative molecule is obtained by supramolecular assembly in a mixed solvent.

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