Halogenated polysulfide aromatic hydrocarbon compound as well as preparation method and application thereof
Halogenated polythiophene compounds with hexathiophene cores address the limitations of light-chemical processes by enabling direct physical transitions and aggregation-induced emission, enhancing their suitability for bioimaging and organic light-emitting materials through simple and scalable synthesis.
Patent Information
- Application Number
- CN202510244848.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-03
- Publication Date
- 2025-07-15
AI Technical Summary
The existing photostimulus-responsive AIE materials have problems incomplete transformation, difficult structure to predict and by-products affect the properties of the material in photochemical reactions, and the biocompatibility of the materials and large-scale commercial applications are limited.
Halogenated polysulfur aromatic compounds were developed as photoluminescent materials, which achieved photostimulation response through physical processes. The synthesis route is simple, the raw materials are easy to obtain, and the aggregation-induced luminescence characteristics are suitable for organic and organic-water mixed solutions.
It realizes the efficient light response capability and aggregation-induced luminescent effect of photostimulus-responsive luminescent materials, has biocompatibility and commercialization potential, and is suitable for the fields of bioimaging and organic luminescent materials.
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Figure CN120309523A_ABST
Abstract
Description
Technical Field
[0001] The present disclosure relates to the technical field of organic light-emitting materials, and particularly to a halogenated polysulfur aromatic hydrocarbon compound, a preparation method thereof, and an application thereof. Background Art
[0002] In the process of exploring and utilizing various external stimulus means, light has rapidly established its position as an ideal stimulus source in the field of stimulus-responsive materials due to a series of remarkable advantages. Specifically, the primary advantage of light lies in its ability to serve as a remote and non-invasive triggering mechanism, enabling efficient non-contact control and ensuring the immediacy and accuracy of the response. Secondly, the regulation of the light reaction process and its parameters is flexible and precise. By adjusting the "on-off" state of light and controlling the irradiation wavelength and intensity, precise control of the light reaction process can be achieved. In addition, with its excellent spatio-temporal resolution, light provides strong support for precise manipulation in materials science. At the same time, as a safe and clean form of energy, light exhibits great application potential in a wide range of industrial and scientific fields. It is worth noting that light, as a typical orthogonal stimulus means, has significant advantages in developing diverse stimulus-responsive photoluminescence systems. Moreover, as a powerful triggering source, light can stimulate the photoluminescence phenomenon, thereby achieving an intuitive visualization effect, which is of great significance for the monitoring and evaluation of material properties. Given the unique and irreplaceable advantages demonstrated by light in terms of light stimulus response and aggregation-induced emission (AIE) performance, the present invention focuses on the research of light stimulus-responsive luminescent materials with AIE performance. Such materials not only have excellent optical properties but also exhibit broad application prospects in the fields of smart materials, sensors, displays, etc. Summary of the Invention
[0003] The present disclosure provides a halogenated polysulfur aromatic hydrocarbon compound, a preparation method thereof, and an application thereof to solve at least one of the technical problems existing in the prior art.
[0004] According to a first aspect of the present disclosure, there is provided a halogenated polysulfur aromatic hydrocarbon compound, the structural formula of which is shown in formula (I):
[0005] Wherein, X is one of F, Cl, and Br.
[0006] In an implementable embodiment, its synthesis route is as follows: Wherein, X is F, Cl or Br, and Y is F or Cl.
[0007] In one embodiment, 4-halobenzenethiol and hexasubstituted benzene are added to a DMF solvent, and at the same time, K2CO3 is added. The reaction is carried out at 55 - 60 °C for 12 - 24 hours under an inert gas atmosphere; the reaction is stopped. When cooled to room temperature, water is added to obtain an emulsion. An extractant is added to the emulsion, and liquid separation is performed to obtain an organic phase. This is repeated multiple times. The organic phases are combined, dried, and filtered by suction to obtain a solid;
[0008] Absolute ethanol is added to the solid, and it is stirred at 40 - 60 °C, cooled to room temperature, filtered by suction to obtain a solid, washed with absolute ethanol, and dried under vacuum to obtain the target compound.
[0009] In one embodiment, the 4-halobenzenethiol is p-fluorobenzenethiol, p-chlorobenzenethiol, or p-bromobenzenethiol;
[0010] The hexasubstituted benzene is hexafluorobenzene or hexachlorobenzene;
[0011] The DMF solvent can also be replaced by DMI;
[0012] The K2CO3 can also be replaced by Cs2CO3.
[0013] In one embodiment, the molar ratio of the hexasubstituted benzene, 4-halobenzenethiol, and K2CO3 is 1 - 2:6 - 12:6 - 15.
[0014] According to the second aspect of the present disclosure, the present invention provides the application of the halogenated polysulfur aromatic hydrocarbon compound or the halogenated polysulfur aromatic hydrocarbon compound obtained by the preparation method as a photoluminescent material.
[0015] According to the third aspect of the present disclosure, the present invention provides the application of the halogenated polysulfur aromatic hydrocarbon compound or the halogenated polysulfur aromatic hydrocarbon compound obtained by the preparation method in bioimaging technology.
[0016] In one embodiment, when the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material, it has a light-stimulus response property, and as the illumination time prolongs, the luminescence intensity of the halogenated polysulfur aromatic hydrocarbon compound also increases.
[0017] In one embodiment, when the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material, it exhibits aggregation-induced emission in an organic-aqueous mixed solution.
[0018] Compared with the prior art, the advantages of the present application are as follows: 1) The halogenated polysulfur aromatic hydrocarbon compound of the present application can be used as a photoluminescent material, which is a light-stimulus-responsive luminescent material. The molecular structural formula of the photoluminescent material is shown in Formula (1). In the molecular structural formula of the photoluminescent material, based on the hexathiophene unit as the core skeleton and modified by specific chemical groups, the material is endowed with unique light-stimulus-responsive characteristics. This innovative material not only exhibits excellent light response ability but also has the characteristic of enhanced aggregation-induced emission, which makes it have potential application value in the fields of bioimaging technology and organic light-emitting material applications, etc. 2) When the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material in the present application, it has the effect of aggregation-induced emission. The material can emit weakly in a pure organic solution and exhibit aggregation-induced emission in an organic-aqueous mixed solution (such as DMF-H2O, THF-H2O). The photoluminescent material with the aggregation-induced emission effect in the present application has good biocompatibility and no toxicity because it is in an aqueous solution environment. 3) The synthesis of the halogenated polysulfur aromatic hydrocarbon compound in the present application is relatively simple, the raw materials are cheap and easily available, and it is easy to be commercialized on a large scale.
[0019] It should be understood that the content described in this part is not intended to identify the key or important features of the embodiments of the present disclosure, nor is it used to limit the scope of the present disclosure. Other features of the present disclosure will become easily understood through the following description. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] By reading the following detailed description with reference to the accompanying drawings, the above and other objects, features, and advantages of the exemplary embodiments of the present disclosure will become easily understood. In the drawings, several embodiments of the present disclosure are shown in an exemplary rather than restrictive manner, where:
[0021] In the drawings, the same or corresponding reference numerals represent the same or corresponding parts.
[0022] Figure 1 Show the emission spectra of the photoluminescent materials 1-3 synthesized in the embodiments of the present disclosure before illumination and after illumination with 365 nm light for 30 s, 60 s, and 90 s;
[0023] Figure 2 Show the luminescence pictures of the photoluminescent material 1 synthesized in the embodiments of the present disclosure in a mixed solvent of THF and water with different ratios;
[0024] Figure 3 Show the luminescence pictures of the photoluminescent material 2 synthesized in the embodiments of the present disclosure in a mixed solvent of THF and water with different ratios;
[0025] Figure 4 Show the luminescence pictures of the photoluminescent material 3 synthesized in the embodiments of the present disclosure in a mixed solvent of THF and water with different ratios;
[0026] Figure 5 The proton nuclear magnetic resonance spectrum of the photoluminescent material 1 synthesized in the embodiments of the present disclosure is shown;
[0027] Figure 6 The proton nuclear magnetic resonance spectrum of the photoluminescent material 2 synthesized in the embodiments of the present disclosure is shown;
[0028] Figure 7 The proton nuclear magnetic resonance spectrum of the photoluminescent material 3 synthesized in the embodiments of the present disclosure is shown. Detailed implementation manners
[0029] To make the objectives, features, and advantages of the present disclosure more obvious and understandable, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the accompanying drawings in the embodiments of the present disclosure. Obviously, the described embodiments are only part of the embodiments of the present disclosure, rather than all the embodiments. Based on the embodiments in the present disclosure, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present disclosure.
[0030] Currently, most of the existing light-stimulus-responsive AIEs are based on the photochemical process of changing the chemical structure. However, there are some limitations in the in-situ regulation of the photochemical process. For example, the transformation in the photoreaction is usually incomplete, and the morphology and structure are difficult to predict. In addition, structural defects and by-products are common and will affect the properties and functions of the materials. In contrast, the physical process based on photoexcitation is more direct and can avoid the above-mentioned disadvantages of photochemistry.
[0031] The objective of the present invention is to combine the light-stimulus-responsive behavior with the aggregation-induced emission behavior, develop a preparation method of a polythioarene compound, synthesize a series of polythioarenes containing halogens, and explore their light-stimulus-responsive behavior.
[0032] Based on this, according to the first aspect of the present disclosure, the present invention provides a halogenated polythioarene compound, and its structural formula is shown as formula (I):
[0033] Wherein, X is one of F, Cl, and Br.
[0034] In the present application, the halogenated polysulfur aromatic hydrocarbon compound can be used as a photoluminescent material, which is a light-stimulus-responsive luminescent material. The molecular structural formula of this photoluminescent material is shown in Formula (1). In the molecular structural formula of this photoluminescent material, based on the hexathiophene unit as the core skeleton and modified by specific chemical groups, the material is endowed with unique light-stimulus-responsive characteristics. This innovative material not only exhibits excellent light response ability but also has the characteristic of enhanced aggregation-induced emission, which makes it have potential application value in the fields of bioimaging technology and organic light-emitting material applications, etc.
[0035] According to the second aspect of the present disclosure, the present invention also provides a synthetic route for the halogenated polysulfur aromatic hydrocarbon compound shown in Formula (1): Wherein, X is F, Cl or Br, and Y is F or Cl.
[0036] For example, the preparation method of this halogenated polysulfur aromatic hydrocarbon compound specifically includes: adding 4-halothiophenol and hexasubstituted benzene into a DMF (N,N-dimethylformamide) solvent, simultaneously adding K2CO3, and reacting at 55-60 °C for 12-24 hours under an inert gas atmosphere; stopping the reaction, adding water to obtain an emulsion when cooled to room temperature, adding an extractant to the emulsion, separating to obtain an organic phase, repeating multiple times, combining the organic phases, drying, and filtering by suction to obtain a solid;
[0037] Adding absolute ethanol to the solid, stirring at 40-60 °C, cooling to room temperature, filtering by suction to obtain a solid, washing with absolute ethanol, and drying in vacuo to obtain the target compound.
[0038] The synthesis of the halogenated polysulfur aromatic hydrocarbon compound in the present application is relatively simple, the raw materials are cheap and easily available, and it is easy to commercialize on a large scale.
[0039] For example, 4-halothiophenol is p-fluorothiophenol, p-chlorothiophenol or p-bromothiophenol.
[0040] For example, the hexasubstituted benzene is hexafluorobenzene or hexachlorobenzene. The DMF solvent can also be replaced by DMI (1,3-dimethyl-2-imidazolidinone). K2CO3 can also be replaced by Cs2CO3.
[0041] For example, the inert gas includes but is not limited to nitrogen, argon and helium. For example, the extractant is ethyl acetate. Drying is carried out using anhydrous sodium sulfate for drying.
[0042] For example, the molar ratio of the hexasubstituted benzene, 4-halothiophenol and K2CO3 is 1-2:6-12:6-15.
[0043] According to the third aspect of the present disclosure, the present invention also provides the application of the halogenated polysulfur aromatic hydrocarbon compound or the halogenated polysulfur aromatic hydrocarbon compound obtained by the above preparation method as a photoluminescent material.
[0044] In this application, when the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material, only physical changes from the ground state to the excited state occur under light stimulation, thereby achieving the purpose of light response.
[0045] For example, when the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material, it has the property of light stimulation response. As the illumination time prolongs, the luminescence intensity of the halogenated polysulfur aromatic hydrocarbon compound also increases.
[0046] The halogenated polysulfur aromatic hydrocarbon compound of this application has the property of light stimulation response. That is, when the compound in an organic solution is irradiated with ultraviolet light of 365 nm, the solution changes from a non-luminescent state to a green-light-emitting state; when the illumination is removed, it gradually returns to the non-luminescent state; this process is reversible. Through repeated introduction and removal of illumination, the oscillating luminescence characteristic is exhibited.
[0047] For example, when the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material, the aggregation-induced emission phenomenon appears in an organic-aqueous mixed solution. Specifically, the halogenated polysulfur aromatic hydrocarbon compound has the property of aggregation-induced emission, weakly emits light in a dilute tetrahydrofuran solution, and shows an obvious property of enhanced aggregation-induced emission as the proportion of water in the solution increases.
[0048] When the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material in this application, it has the effect of aggregation-induced emission. This material can weakly emit light in a pure organic solution and produce the phenomenon of aggregation-induced emission in an organic-aqueous mixed solution (such as DMF-H2O, THF-H2O). The photoluminescent material with the aggregation-induced emission effect in this application has good biocompatibility and no toxicity because the environment is an aqueous solution.
[0049] According to the fourth aspect of the present disclosure, the present invention also provides the application of the described halogenated polysulfur aromatic hydrocarbon compound or the halogenated polysulfur aromatic hydrocarbon compound obtained by the above preparation method in bioimaging technology.
[0050] The following further elaborates on this application with examples:
[0051] Example 1 (Synthesis of Luminescent Material)
[0052] A preparation method of a halogenated polysulfur aromatic hydrocarbon compound:
[0053] 10 mmol of 4-halobenzenethiol (specifically, p-fluorobenzenethiol) and 1 mmol of hexasubstituted benzene (specifically, hexachlorobenzene) were added to 20 mL of DMF solvent. Meanwhile, 10 mmol of K2CO3 was added. The reaction was carried out at 55 °C for 12 hours under a nitrogen atmosphere, and then the reaction was stopped. When cooled to room temperature, 100 mL of distilled water was added to produce a yellow emulsion. 50 mL of ethyl acetate was added to the emulsion for extraction, and the organic phase was obtained by liquid separation. This process was repeated three times. The combined organic phases were dried with anhydrous sodium sulfate, and the solvent was removed under reduced pressure to obtain a yellow solid. Anhydrous ethanol was added to the yellow solid, and the mixture was stirred at 50 °C for 2 hours. After cooling to room temperature, the yellow solid was collected by vacuum filtration and washed with anhydrous ethanol. The obtained solid was dried under vacuum conditions to obtain the target compound - a halogenated polysulfur aromatic hydrocarbon compound, denoted as "photoluminescent material 1".
[0054] Example 2
[0055] The preparation method of this Example 2 was generally the same as that of Example 1, except that p-chlorobenzenethiol was used as the 4-halobenzenethiol.
[0056] The halogenated polysulfur aromatic hydrocarbon compound prepared in Example 2 was denoted as "photoluminescent material 2".
[0057] Example 3
[0058] The preparation method of this Example 3 was generally the same as that of Example 1, except that p-bromobenzenethiol was used as the 4-halobenzenethiol.
[0059] The halogenated polysulfur aromatic hydrocarbon compound prepared in Example 3 was denoted as "photoluminescent material 3".
[0060] Example 4
[0061] The preparation method of this Example 4 was generally the same as that of Example 1, except that 6 mmol of 4-halobenzenethiol, 2 mmol of hexasubstituted benzene, and 6 mmol of K2CO3 were used.
[0062] Example 5
[0063] The preparation method of this Example 5 was generally the same as that of Example 1, except that 12 mmol of 4-halobenzenethiol, 1 mmol of hexasubstituted benzene, and 15 mmol of K2CO3 were used.
[0064] Relevant performance tests:
[0065] I): Photo-stimulus response phenomenon
[0066] 0.001 mmol of the halogenated polysulfur aromatic hydrocarbon compounds prepared in Examples 1 - 3 were weighed respectively, and 10 mL of tetrahydrofuran was added thereto and stirred until dissolved to obtain a test sample with a concentration of 10 -4Take 3 mL of the above sample to be tested in a cuvette. Using 365 nm as the excitation wavelength, detect the emission spectrum of the luminescent material in the wavelength range of 380 nm to 800 nm. Record its emission spectrum at different illumination times (30 s, 60 s, 90 s). The obtained emission spectra are as shown in Figure 1 as follows.
[0067] Among them, Figure 1 (a) is the emission spectrum diagram of the photoluminescent material 1 of Example 1, Figure 1 (b) is the emission spectrum diagram of the photoluminescent material 2 of Example 2, Figure 1 (c) is the emission spectrum diagram of the photoluminescent material 3 of Example 3.
[0068] From Figure 1 (a) to Figure 1 (c), it can be obtained that with the increase of the illumination time, the emission intensity of the photoluminescent material gradually increases. This shows that the halogenated polysulfur aromatic hydrocarbon compound of the present application has a photo-stimulus response property, that is, the halogenated polysulfur aromatic hydrocarbon compound can be used as a photo-stimulus response type luminescent material.
[0069] II): Aggregation-induced emission enhancement phenomenon
[0070] Prepare the photoluminescent materials obtained in Examples 1 to 3 respectively into dilution solutions with a concentration of 10 2 M using THF, and then add them to mixed solvents of THF and water with different ratios (the volume concentrations of water are 0%, 10%, 30%, 50%, 70%, 90%) to make the concentration of the luminescent material 10 -5 M, respectively obtaining mixed solutions. Then add the mixed solutions to fluorescence cuvettes respectively, and observe the luminescence of the luminescent material under the irradiation of 365 nm laser. The results are as shown in Figures 2 - 4 as follows, where Figure 2 is the luminescence of the photoluminescent material 1 prepared in Example 1, Figure 3 is the luminescence of the photoluminescent material 2 prepared in Example 2, Figure 4 is the luminescence of the photoluminescent material 3 prepared in Example 3.
[0071] From Figures 2 - 4 it can be obtained that with the increase of the volume ratio of water in the solution, the photoluminescent materials 1 to 3 all show obvious aggregation-induced emission enhancement phenomena, reaching the maximum when the volume fraction of the water phase is 50%, and continuing to increase the content of the water phase will lead to a weakening of the luminescence phenomenon.
[0072] Therefore, combining the results of the above photo-stimulus response phenomenon and aggregation-induced emission enhancement phenomenon, it can be obtained that the halogenated polysulfur aromatic hydrocarbon compound of the present application can be used as a photoluminescent material.
[0073] (III): Nuclear magnetic resonance hydrogen spectrum test
[0074] The photoluminescent materials 1, 2, and 3 obtained in Examples 1 to 3 were respectively subjected to nuclear magnetic resonance hydrogen spectrum tests, and the results are as Figures 5 - 7 shown. It can be obtained from Figures 5 - 7 that the photoluminescent materials 1, 2, and 3 of the present application were successfully prepared.
[0075] It should be understood that various forms of the processes shown above can be used, reordering, adding, or deleting steps. For example, the steps described in the present disclosure can be executed in parallel, sequentially, or in a different order, as long as the desired results of the technical solutions disclosed in the present disclosure can be achieved, and no limitations are imposed herein.
[0076] In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include at least one such feature. In the description of the present disclosure, "a plurality" means two or more unless otherwise specifically defined.
[0077] The above is only the specific implementation manner of the present disclosure, but the protection scope of the present disclosure is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present disclosure can easily think of changes or substitutions, which should all be covered within the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claimed rights.
Claims
1. A halogenated polysulfur aromatic hydrocarbon compound, characterized in that: Its structural formula is shown in formula (I): Among them, X is one of F, Cl, and Br.
2. The preparation method of the halogenated polysulfur aromatic hydrocarbon compound according to claim 1, characterized in that: The synthetic route is as follows: Wherein, X is F, Cl or Br, and Y is F or Cl.
3. The preparation method according to claim 2, wherein: Add 4-halobenzenethiol and hexasubstituted benzene into DMF solvent, and at the same time add K2CO3, and react at 55 - 60 °C for 12 - 24 hours under an inert gas atmosphere; Stop the reaction, add water when cooled to room temperature to obtain an emulsion, add an extractant to the emulsion, separate the organic phase, repeat multiple times, combine the organic phases, dry, and filter by suction to obtain a solid; Add absolute ethanol to the solid, stir at 40 - 60 °C, cool to room temperature, filter by suction to obtain a solid, wash with absolute ethanol, and dry under vacuum to obtain the target compound.
4. The preparation method according to claim 3, characterized in that: The 4-halobenzenethiol is p-fluorobenzenethiol, p-chlorobenzenethiol or p-bromobenzenethiol; The hexasubstituted benzene is hexafluorobenzene or hexachlorobenzene; The DMF solvent can also be replaced by DMI; The K2CO3 can also be replaced by Cs2CO3.
5. The preparation method according to claim 3, wherein: The molar ratio of the hexasubstituted benzene, 4-halobenzenethiol and K2CO3 is 1 - 2:6 - 12:6 - 15.
6. Application of the halogenated polysulfur aromatic hydrocarbon compound described in claim 1 or the halogenated polysulfur aromatic hydrocarbon compound obtained by the preparation method described in any one of claims 2 - 5 in the aspect of a photoluminescent material.
7. Application of the halogenated polysulfur aromatic hydrocarbon compound described in claim 1 or the halogenated polysulfur aromatic hydrocarbon compound obtained by the preparation method described in any one of claims 2 - 5 in bioimaging technology.
8. The application according to claim 6, characterized in that: When the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material, it has a photo-stimulus response property, and as the illumination time prolongs, the luminescence intensity of the halogenated polysulfur aromatic hydrocarbon compound also increases.
9. The application according to claim 6, characterized in that: When the halogenated polysulfur aromatic hydrocarbon compound is used as a photoluminescent material, it shows an aggregation-induced emission phenomenon in an organic-aqueous mixed solution.