Thiodiazole five-membered fused heterocyclic conjugated organic small molecules, their preparation methods and applications

Abstract

This invention discloses a thiodiazole five-membered fused heterocyclic conjugated organic small molecule, its preparation method, and its applications. This conjugated organic small molecule has the structure shown in formula (I), where n is any integer value from 0, 1, 2, to 3; R1, R2, R3, R4, R5, and R6 are each one of hydrogen, alkyl, alkoxy, or alkylthio; X1, X2, and X3 are each one of oxygen, sulfur, selenium, or tellurium; and R1-R6 are not all hydrogen simultaneously. This conjugated organic small molecule is easy to synthesize, has stable properties, and possesses near-infrared absorption capabilities. Its derivatives, after self-assembly modification, can be applied in the field of photocatalytic hydrogen evolution; the nanoscale crystals of its derived conjugated organic small molecule can be applied in reactive oxygen species therapy drugs, all demonstrating good technical effects.

Description

Technical Field

[0001] This invention relates to the field of new materials, specifically to a thiodiazole pentagonal fused heterocyclic conjugated organic small molecule, its preparation method, and its application. Background Technology

[0002] Solar energy is the most abundant renewable resource on Earth, existing stably in nature. Converting sunlight into other forms of energy can be used in photocatalysis, photothermal conversion, and photoelectric conversion to achieve catalytic water splitting, carbon dioxide reduction, nitrogen fixation, degradation of organic pollutants, seawater desalination, and the development of solar cells. However, the low energy density of sunlight reaching the Earth's surface makes the collection, conversion, and utilization of sunlight challenging. Of the sunlight reaching Earth, ultraviolet light accounts for 5%, visible light for 46%, and the infrared portion for 49%. Therefore, using materials with near-infrared absorption can improve the utilization rate of sunlight. Furthermore, materials with absorption extending into the near-infrared region show great promise in the biological field, enabling photoacoustic imaging, photothermal therapy, and photodynamic therapy. Therefore, designing and fabricating novel materials with near-infrared absorption is of great significance.

[0003] Currently, rare earth materials with near-infrared absorption require complex preparation by combining them with other photosensitizers; quantum dots and carbon nanotubes have poor biocompatibility; and precious metal materials are expensive, hindering large-scale application. In contrast, small organic molecules offer advantages such as ease of preparation, tunable structure, stable performance, and good biocompatibility, making them more suitable for applications in photocatalysis, photoelectric conversion, and biological fields.

[0004] Therefore, how to provide a small organic molecule that can be applied to photocatalysis, photoelectric conversion, and the biological field is a research direction in this field. Summary of the Invention

[0005] In view of the current research status and the technical problems existing in this field, the purpose of this invention is to provide a thiodiazole five-membered fused heterocyclic conjugated organic small molecule, its preparation method, and its applications. This conjugated organic small molecule is easy to synthesize, has stable performance, and possesses near-infrared absorption capabilities. Its derivatives, after self-assembly modification, can be applied in the field of photocatalytic hydrogen evolution; the nanoscale crystals of its derived conjugated organic small molecule can be applied in reactive oxygen species therapy drugs, all demonstrating good technical effects.

[0006] The first aspect of the present invention is to provide a conjugated small organic molecule of the thiodiazole pentagonal fused heterocyclic class, having the structure shown in formula (I).

[0007]

[0008] In formula (I), n may be the same or different, and each is any integer value among 0, 1, 2, and 3; R1, R2, R3, R4, R5, and R6 may be the same or different, and each is one of hydrogen, alkyl, alkoxy, or alkylthio; X1, X2, and X3 may be the same or different, and each is one of oxygen, sulfur, selenium, or tellurium.

[0009] R1, R2, R3, R4, R5, and R6 are not all hydrogen at the same time.

[0010] According to the present invention, R1, R2, R3, R4, R5 and R6 can each be selected from a wide range. In a preferred embodiment of the present invention, R1, R2, R3, R4, R5 and R6 are each one of H (and R1, R2, R3, R4, R5 and R6 are not all hydrogen at the same time), C1-C24 alkyl, C1-C24 alkoxy, and C1-C24 alkylthio.

[0011] Preferably, R1, R2, R3, R4, R5, and R6 are each H, a C1-C24 alkyl group, a C1-C24 alkoxy group, or a C1-C24 alkylthio group; more preferably, R1, R2, R3, R4, R5, and R6 are each H, a C1-C12 alkyl group, a C1-C12 alkoxy group, or a C1-C12 alkylthio group. That is, R1-R6 are each H, -C m H 2m+1 -OC m H 2m+1 -SC m H 2m+1 , where m = 1-12.

[0012] According to the present invention, the C1-C12 alkyl groups mentioned in R1, R2, R3, R4, R5 and R6 above may, for example, be alkyl groups with C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 and C12 carbon atoms respectively.

[0013] According to the present invention, R1, R2, R3, R4, R5 and R6 each refer to alkoxy groups of C1-C12, for example, each of which can be an alkoxy group of C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 and C12 carbon atoms.

[0014] According to the present invention, the C1-C12 alkylthio groups mentioned in R1, R2, R3, R4, R5 and R6 above can be, for example, alkylthio groups with C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11 and C12 carbon atoms respectively.

[0015] Specifically, it can be a straight-chain or branched alkyl, alkoxy, alkylthio group, etc., for example, the following structures:

[0016]

[0017] The second aspect of the present invention is to provide a method for preparing the conjugated organic small molecule described in the first aspect, comprising coupling a tetraphenylethylene derivative of formula (III) with a thiodiazole pentane fused heterocyclic compound of formula (II);

[0018]

[0019] In formula (II), Y is a halogen.

[0020] According to the present invention, Y can be selected from a wide range. In a preferred embodiment of the present invention, Y in formula (II) is Br or I.

[0021] According to the present invention, the molar ratio of the tetraphenylethylene derivative to the thiodiazolium pentagonal fused heterocyclic compound can be selected within a wide range. In a preferred embodiment of the present invention, the molar ratio of the tetraphenylethylene derivative to the thiodiazolium pentagonal fused heterocyclic compound is (3.5-4.5):1, preferably (3.7-4.3):1.

[0022] In a preferred embodiment of the invention, the coupling reaction is carried out under anaerobic conditions and in the presence of a catalyst and a solvent.

[0023] According to the present invention, the catalyst can be selected from a wide range. In a preferred embodiment of the present invention, the catalyst is selected from palladium salts, preferably at least one of tetra(triphenylphosphine)palladium, bis(diphenylphosphine)ferrocene palladium dichloride, and bis(dibenzylacetone)palladium.

[0024] According to the present invention, the amount of palladium salt can be selected within a wide range. In a preferred embodiment of the present invention, the amount of palladium salt is 0.02-0.2 mmol relative to 1 mmol of the tetraphenylethylene derivative.

[0025] In a preferred embodiment of the present invention, the coupling reaction is carried out in the presence of a base; according to the present invention, the base can be selected from a wide range, and in a preferred embodiment of the present invention, the base is selected from carbonates, more preferably from at least one of sodium carbonate, potassium carbonate and cesium carbonate; and / or, the molar ratio of the catalyst to the base is 1:(50-100).

[0026] According to the present invention, the solvent can be selected from a wide range. In a preferred embodiment of the present invention, the solvent is selected from a mixed solution of an organic solvent and water; preferably, the organic solvent is at least one of tetrahydrofuran, toluene and dioxane.

[0027] According to the present invention, the solvent can be selected from a wide range. In a preferred embodiment of the present invention, the amount of solvent used is 5-20 mL relative to 1 mmol of the tetraphenylethylene derivative.

[0028] According to the present invention, the conditions for the coupling reaction can be selected within a wide range. In a preferred embodiment of the present invention, the conditions for the coupling reaction include a temperature of 70-115°C.

[0029] According to the present invention, the time conditions of the coupling reaction can be selected within a wide range. In a preferred embodiment of the present invention, the time is 8-18 hours.

[0030] In a preferred embodiment of the present invention, the oxygen-free condition is a nitrogen and / or inert gas atmosphere.

[0031] In a preferred embodiment of the present invention, the method includes: adding a tetraphenylethylene derivative and a thiodiazolium pentagonal fused heterocyclic compound under anaerobic conditions, dissolving the compound in a mixed solvent of tetrahydrofuran and water, and reacting at 70-115°C for 8-18 hours to obtain the conjugated organic small molecule material. The molar ratio of the tetraphenylethylene diffractometer to the thiodiazolium pentagonal fused heterocyclic compound is (3.5-4.5):1, preferably (3.7-4.3):1. In the mixed solution of tetrahydrofuran and water, the volume ratio of tetrahydrofuran to water is (3-5):1, more preferably (3.5-4.5):1.

[0032] In a preferred embodiment of the present invention, the preparation process of the DAD-structure-based conjugated organic small molecule material of the present invention follows the following reaction route:

[0033]

[0034] A third aspect of the present invention is to provide a method for self-assembly modification of the conjugated organic small molecule described in the first aspect, comprising mixing the conjugated organic small molecule with a surfactant to obtain a self-assembled modified conjugated organic small molecule.

[0035] According to the present invention, the surfactant can be selected from a wide range. In a preferred embodiment of the present invention, the surfactant is selected from at least one of Triton X-100, hexadecyltrimethylammonium bromide, sodium n-octyl sulfate, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, decadecyltrimethylammonium bromide and n-octyltrimethylammonium bromide.

[0036] According to the present invention, the source of the surfactant can be selected from a wide range. In a preferred embodiment of the present invention, the surfactant is derived from an aqueous solution containing the surfactant.

[0037] According to the present invention, the mixing method can be selected within a wide range. In a preferred embodiment of the present invention, the mixing method is stirring, with a preferred rotation speed of 600-1500 rpm and / or a mixing time of 6-54 h.

[0038] According to the present invention, the amount of the conjugated organic small molecule is such that the concentration of the conjugated organic small molecule in the mixture can be selected within a wide range. In a preferred embodiment of the present invention, the amount of the conjugated organic small molecule is such that the concentration of the conjugated organic small molecule in the mixture is 0.01-1 mol / L.

[0039] In a more preferred embodiment of the present invention, the self-assembly modification method comprises: mixing 1-5 volumes of a solution containing the conjugated organic small molecules with 50-200 volumes of a surfactant at a concentration of 1×10⁻⁶. -5 -2×10 -1 Mix the mol / L aqueous solution containing the surfactant and stir at 600-1500 rpm for 6-54 hours.

[0040] More specifically, this invention proposes a self-assembly preparation process for the conjugated organic small molecule TTD-TPE-2OMe for photocatalytic hydrogen evolution experiments, comprising the following steps:

[0041] (1) Dissolve TTD-TPE-2OMe in tetrahydrofuran solvent to prepare a solution;

[0042] (2) Add 50-200 mL of deionized water to the conical flask, then add the appropriate amount of surfactant. Dissolve the surfactant completely by sonication to prepare a solution with a concentration of 1×10⁻⁶. -5 -2×10 -1 A surfactant aqueous solution of mol / L, wherein the surfactant is selected from Triton X-100, hexadecyltrimethylammonium bromide, sodium octadecyl sulfate, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, decadecyltrimethylammonium bromide, and octadecyltrimethylammonium bromide;

[0043] (3) Place the prepared surfactant aqueous solution on a magnetic stirrer and stir at a speed of 600-1500 rpm. Then, take 1-5 mL of the solution from step (1) and add it dropwise to the aqueous solution using a pipette;

[0044] (4) After stirring at room temperature for 6-54 hours, TTD-TPE-2OMe self-assembled bodies were obtained.

[0045] In a more preferred embodiment of the present invention, the self-assembly modification method includes the following steps:

[0046] The conjugated organic small molecule material was dissolved in tetrahydrofuran solution and added to a prepared aqueous solution of surfactant under stirring at room temperature. The stirring speed was 600-1500 rpm, the concentration of the conjugated organic small molecule was 0.01-1 mol / L, and the stirring time was 6-54 h to obtain the self-assembled modified conjugated organic small molecule material.

[0047] The specific surfactants that can be used are: Triton X-100, polyethylene glycol, hexadecyltrimethylammonium bromide, sodium n-octyl sulfate, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, decadecyltrimethylammonium bromide, and n-octyltrimethylammonium bromide.

[0048] More preferably, the stirring speed is 800-1200 rpm and / or the concentration of small organic molecules is 0.05-0.5 mol / L and / or the stirring time is 12-36 h.

[0049] A fourth aspect of the present invention is to provide a self-assembled modified conjugated organic small molecule prepared by the self-assembly modification method described in the third aspect.

[0050] The fifth aspect of the present invention is to provide an application of the conjugated organic small molecule described in the first aspect or the self-assembled modified conjugated organic small molecule described in the fourth aspect in the field of photocatalytic hydrogen evolution.

[0051] In a more preferred embodiment of the present invention, the conjugated organic small molecule material prepared by the method of the present invention can be used for photocatalytic water splitting to obtain hydrogen and obtain clean energy. The application process includes the following steps:

[0052] (1) Add the self-assembled conjugated organic small molecule (e.g., TTD-TPE-2OMe) solution to the reaction vessel. The concentration of the self-assembled conjugated organic small molecule is 0.01-1 mol / L.

[0053] (2) Add a sacrificial agent to the reaction system in step (1) above. The concentration of the sacrificial agent is 1-10 times the concentration of the self-assembled conjugated organic small molecules. 4 The sacrificial agent is any one of triethanolamine, ascorbic acid, ethylene glycol, methanol, and silver nitrate;

[0054] (3) Irradiate the mixed solution in step (2) using a PLS-SXE 300 xenon lamp as the light source. The power of the light source used is 400-700 mW / cm². 2Meanwhile, the mixed solution was stirred using a magnetic stirrer at a speed of 600-1500 rpm, and a circulating condenser was used to maintain the test temperature of the entire system at 0-25℃.

[0055] (4) Every 30 minutes, a quantitative amount of gas is automatically taken out from the reactor and sent to a gas chromatograph for detection to obtain the composition and amount of the generated gas.

[0056] A sixth aspect of the present invention is to provide a method for preparing nanoscale crystals of conjugated organic small molecules, comprising:

[0057] The conjugated organic small molecules described in the first aspect are dissolved in a solvent under heating conditions, cooled and allowed to stand to obtain micron-sized crystals, and then the micron-sized crystals are added to an aqueous solution containing polyethylene glycol and ultrasonically broken to obtain nano-sized crystals of the conjugated organic small molecules.

[0058] According to the present invention, the solvent can be selected from a wide range of options. In a preferred embodiment of the present invention, the solvent is selected from chloroform and ethyl acetate in a volume ratio of 1:(1.5-3); and / or,

[0059] The ultrasonic fragmentation time is 3-10 hours.

[0060] According to the present invention, the mass ratio of the micron-sized crystals to polyethylene glycol can be selected within a wide range. In a preferred embodiment of the present invention, the mass ratio of the micron-sized crystals to polyethylene glycol is 1:(3-7).

[0061] According to the present invention, the polyethylene glycol is selected from polyethylene glycol with a number average molecular weight that can be selected from a wide range. In a preferred embodiment of the present invention, the polyethylene glycol is selected from polyethylene glycol with a number average molecular weight of 1000-5000.

[0062] In a preferred embodiment of the present invention, the method for preparing nanoscale crystals based on DAD structure conjugated organic small molecule materials includes the following steps:

[0063] The conjugated organic small molecule material was dissolved in a solvent of chloroform and ethyl acetate with a volume ratio of 1:(1.5-3) under heating conditions, and then cooled and allowed to stand to obtain micron-sized crystals. The micron-sized crystals were added to polyethylene glycol and dispersed in water, and then sonicated using a cell disruptor for 3-10 hours to obtain nano-sized crystals of the conjugated organic small molecule material. Preferably, the mass ratio of micron-sized crystals to polyethylene glycol is 1:(3-7).

[0064] More preferably, the volume ratio of ethyl acetate to chloroform solvent is (1.7-2.6):1, and the ultrasonic time of the cell disruptor is 6-9 hours.

[0065] In a more preferred embodiment of the present invention, taking TTD-TPE-2OMe as an example, the present invention proposes a preparation process for nanoscale crystals of conjugated organic small molecule materials, comprising the following steps:

[0066] (1) Add TTD-TPE-2OMe to 40-160 mL of a mixed solvent of chloroform and ethyl acetate, wherein the volume ratio of chloroform to ethyl acetate is 1:(1.5-3);

[0067] (2) Heat the solution in step (1) to 60-120°C to completely dissolve it, and let it stand and cool to precipitate micron-sized crystals;

[0068] (3) Add the micron-sized crystals obtained in step (2) to 10 mL of aqueous solution containing DSPE-PEG-2000, wherein the mass ratio of micron-sized crystals to DSPE-PEG-2000 is 1:3-7. Use a cell disruptor to sonicate for 3-10 h to obtain TTD-TPE-2OMe nano-sized crystal material.

[0069] A seventh aspect of the present invention is to provide a nanoscale crystal of a conjugated organic small molecule prepared by the preparation method described in the sixth aspect.

[0070] The eighth aspect of the present invention is to provide the application of nanoscale crystals of conjugated organic small molecules as described in the seventh aspect of the present invention in reactive oxygen species therapeutic agents.

[0071] According to the above technical solution, the conjugated organic small molecule system of the present invention is prepared by introducing a DAD structure and connecting different tetraphenylethylene derivatives as donor units to the 1,2,5-thiodiazolidine five-membered fused heterocyclic acceptor unit. The reaction route is simple and easy to operate, and the structure can be effectively regulated. The maximum absorption edge of this conjugated organic small molecule material is about 876 nm in the liquid state and about 1019 nm in the solid state, exhibiting a wide absorption range. Moreover, it has a band gap of 1.38 eV, and its oxidation and reduction potentials relative to the standard hydrogen energy level are -0.98 V and 0.40 V, respectively, which match the hydrogen production potential (-0.41 V) and the superoxide radical generation potential (-0.33 V), enabling effective redox reactions.

[0072] By modifying the self-assembly of this conjugated organic small molecule, an assembly of the organic small molecule was obtained. This assembly has good water contact performance, as well as electron-hole separation capability and effective carrier transport capability, and can be used in the field of photocatalytic hydrogen evolution.

[0073] This invention prepares nanoscale crystals of conjugated organic small molecule materials based on DAD structure. The ordered stacking arrangement is more conducive to charge transport performance and has a stronger superoxide radical generation ability compared to disordered nanoparticles.

[0074] The inventors of this invention believe that the organic small molecules and their derivatives possess the above advantages because, through research and verification, the reasons are as follows:

[0075] The high planarity and high conjugation of small organic molecules facilitate π-π stacking, broadening the absorption range. The introduction of DA structures increases intermolecular charge delocalization, further redshifting the absorption. This invention achieves the regulation of the molecular absorption range through specific structures and altered aggregation states, obtaining broad-absorption organic conjugated small molecule materials that can fully absorb sunlight and convert it into chemical energy, internal energy, and other forms of energy, thus achieving efficient utilization of solar energy. This invention increases conjugation by connecting thiophene units to both ends of the 1,2,5-thiodiazolidine five-membered fused heterocyclic unit, broadening the molecular absorption. Simultaneously, the strong DA interactions are used to construct highly conjugated small organic molecules, enhancing intramolecular charge transfer and resulting in broad absorption. Attached Figure Description

[0076] Figure 1 The product of Example 1 1 HNMR spectrum.

[0077] Figure 2 Absorption spectra of conjugated organic small molecules based on DAD structure in solution and solid states in Example 1.

[0078] Figure 3 Electrochemical cyclic voltammetry spectrum of a DAD-based conjugated organic small molecule in Example 1.

[0079] Figure 4 : Photocurrent response spectrum of conjugated organic small molecules based on DAD structure in Example 1.

[0080] Figure 5 Photocatalytic hydrogen evolution rate curves of DAD-structured conjugated organic small molecule assembly materials in Examples 2-3.

[0081] Figure 6 Transmission electron microscopy image of DAD-structured conjugated organic small molecule nanocrystal material in Example 4.

[0082] Figure 7 Example 4: Superoxide radical generation of DAD-structured conjugated organic small molecule nanocrystal materials.

[0083] Figure 8 : Product of Comparative Example 3 1 HNMR spectrum. Detailed Implementation

[0084] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0085] 1 HNMR was used for characterization; absorption spectroscopy was used to test the absorption spectrum of molecules; electrochemical cyclic voltammetry curves and photocurrent response spectra were tested using an electrochemical workstation; photocatalytic hydrogen evolution efficiency was tested using an all-glass automated online trace gas analysis system and gas chromatography; molecular morphology and lattice diffraction spots were characterized using transmission electron microscopy; and the generation of superoxide radicals was characterized by detecting changes in fluorescence intensity using dihydrorhodamine 123 (DHR123) as an indicator.

[0086] Example 1

[0087] The synthetic route for the DAD-structured conjugated organic small molecule TTD-TPE-2OMe proposed in this invention includes the following steps:

[0088]

[0089] (1) Under anhydrous and oxygen-free conditions, 0.5 mmol of 4,6-bis(5-bromo-2-thienyl)thieno[3,4-c][1,2,5]thiadiazole, 2 mmol of 2-(4-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane, 8 mmol of K2CO3 and 0.1 mmol of Pd(PPh3)4 were added to a 50 mL double-necked round-bottom flask;

[0090] (2) Add the deoxygenated THF (16 mL) and water (4 mL) mixed solvent to the reaction flask, then heat to 86℃ and react for 16 h;

[0091] (3) After the reaction was completed, the THF and water solvent were removed by vacuum distillation in a rotary evaporator, and then extracted three times to obtain the crude product TTD-TPE-2OMe.

[0092] (4) The crude product in step (3) was purified by column chromatography using 200-mesh silica gel powder as packing material and petroleum ether and dichloromethane as eluents to obtain the green target product TTD-TPE-2OMe.

[0093] The product of Example 1 1 See the HNMR spectrum. Figure 1 ,Depend on Figure 1 As can be seen, both the number of hydrogen atoms and the chemical shift correspond to the target product, proving that the product in this embodiment is TTD-TPE-2OMe. The absorption spectra of the DAD-based conjugated organic small molecule in solution and solid states from Example 1 are shown below. Figure 2 ,Depend on Figure 2 It can be seen that its maximum absorption wavelength in solution is 876 nm, and its maximum absorption range in solid state is 1019 nm, proving that TTD-TPE-2OMe has a wide absorption range.

[0094] The electrochemical cyclic voltammetry spectrum of the DAD-based conjugated organic small molecule in Example 1 is shown below. Figure 3 ,Depend on Figure 3 As can be seen, its oxidation potential is 0.20V and its reduction potential is -1.18V. The reduction and oxidation potentials converted to standard hydrogen potentials are -0.98V and 0.40V, respectively, demonstrating that TTD-TPE-2OMe has the ability to generate hydrogen and superoxide radicals. The photocurrent response spectrum of the DAD-based conjugated organic small molecule in Example 1 is shown below. Figure 4 ,Depend on Figure 4 It is evident that its current increases under illumination and recovers under darkness, proving that TTD-TPE-2OMe can generate charge separation under illumination.

[0095] Example 2

[0096] This invention proposes a self-assembly preparation process for the conjugated organic small molecule TTD-TPE-2OMe for photocatalytic hydrogen evolution experiments, comprising the following steps:

[0097] (1) Dissolve TTD-TPE-2OMe in tetrahydrofuran solvent to prepare a tetrahydrofuran solution with a concentration of 5 mmol / L;

[0098] (2) Add 100 mL of deionized water to an Erlenmeyer flask, then add the appropriate amount of surfactant. Dissolve the surfactant completely by sonication to prepare solutions with a concentration of 2.6 × 10⁻⁶. -1 mol L -1 Octyltrimethylammonium bromide, 6.8 × 10 - 2 mol L -1 Decyltrimethylammonium bromide, 1.6 × 10 -2 mol L -1 Dodecyltrimethylammonium bromide, 2.1 × 10 -3 molL -1Tetradecyltrimethylammonium bromide, 9.2 × 10 -4 mol L -1 cetyltrimethylammonium bromide;

[0099] (3) Place the prepared surfactant aqueous solution on a magnetic stirrer and stir at 1000 rpm. Then take 2 mL of the solution from step (1) and add it dropwise to the aqueous solution using a pipette. At this time, the concentration of TTD-TPE-2OMe is 0.1 mmol / L.

[0100] (4) After stirring at room temperature for 48 hours, a self-assembled TTD-TPE-2OMe was obtained.

[0101] Example 3

[0102] The conjugated organic small molecule materials prepared by the method of this invention can be used for photocatalytic water splitting to obtain hydrogen and obtain clean energy. The application process includes the following steps:

[0103] (1) Add the self-assembled TTD-TPE-2OMe solution from Example 2 to the reaction vessel;

[0104] (2) Add a sacrificial agent to the reaction system in step (1) above. The concentration of the sacrificial agent is 1000 times that of TTD-TPE-2OMe. The sacrificial agent is ascorbic acid.

[0105] (3) The mixed solution in step (2) was irradiated using a PLS-SXE 300 xenon lamp as the light source, with a power of 660 mW / cm². 2 Meanwhile, the mixed solution was stirred using a magnetic stirrer at a speed of 1000 rpm, and a circulating condenser was used to maintain the test temperature of the entire system at 6°C.

[0106] (4) Every 30 minutes, a quantitative amount of gas is automatically taken out from the reactor and sent to a gas chromatograph for detection to obtain the composition and amount of the generated gas.

[0107] The results are as follows Figure 5 As shown, Figure 5 The figures in the middle are the photocatalytic hydrogen evolution rate curves of the assembled samples obtained in Example 2, consisting of TTD-TPE-2OMe and octaalkyltrimethylammonium bromide, decaalkyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, and hexadecyltrimethylammonium bromide. Figure 5 It is evident that as the alkyl chain length in the surfactant decreases, the photocatalytic hydrogen evolution efficiency of the TTD-TPE-2OMe assembly continuously increases, proving that the alkyl chain length of the surfactant affects the photocatalytic hydrogen evolution efficiency of the TTD-TPE-2OMe assembly.

[0108] Example 4

[0109] This invention proposes a process for preparing nanoscale crystals of conjugated organic small molecule materials, comprising the following steps:

[0110] (1) Add TTD-TPE-2OMe to 120 mL of a mixed solvent of chloroform and ethyl acetate, wherein the volume ratio of chloroform to ethyl acetate is 1:2;

[0111] (2) Heat the solution in step (1) to 100°C to completely dissolve it, and let it stand to cool and precipitate micron-sized crystals;

[0112] (3) The micron-sized crystals obtained in step (2) above are added to 10 mL of aqueous solution containing DSPE-PEG-2000, wherein the mass ratio of micron-sized crystals to DSPE-PEG-2000 is 1:5. The mixture is sonicated for 8 h using a cell disruptor to obtain TTD-TPE-2OMe nano-sized crystal material.

[0113] The transmission electron microscope (TEM) image of the DAD-structured conjugated organic small molecule nanocrystalline material (TTD-TPE-2OMe nanocrystalline material) in this embodiment is shown below. Figure 6 As shown, by Figure 6 As can be seen, its sheet-like structure, with a size of about 200 nm, exhibits lattice diffraction fringes when subjected to Fourier transform, proving that TTD-TPE-2OMe is a nanoscale crystalline material.

[0114] The generation of superoxide radicals in the DAD-structured conjugated organic small molecule nanocrystal material in this embodiment was verified by using DHR123 as a fluorescent indicator. The results are as follows: Figure 7 As shown, Figure 7 The curves showing the superoxide radical generation in samples with only a fluorescent indicator, a fluorescent indicator and TTD-TPE-2OMe nanoscale crystal material, and a fluorescent indicator and TTD-TPE-2OMe nanoparticle material, respectively, are shown. Figure 7 It is evident that the fluorescence intensity of the sample with only the fluorescent indicator does not change under light irradiation. The fluorescence enhancement is weak after adding TTD-TPE-2OMe nanoparticles, but the fluorescence intensity is significantly enhanced after adding TTD-TPE-2OMe nanoscale crystals. This demonstrates that TTD-TPE-2OMe nanoscale crystals have a strong superoxide radical generation capacity under light irradiation.

[0115] Compare with Example 1

[0116] TTD-TPE-2OMe was dissolved in tetrahydrofuran solution and added to a pure aqueous solution under stirring at room temperature. The stirring speed was 1000 rpm, the concentration of TTD-TPE-2OMe was 0.1 mol / L, and the stirring time was 48 h. The mixture was then added to a reactor along with a sacrificial agent, and tests showed that it did not produce hydrogen gas under light irradiation.

[0117] Compare with Example 2

[0118] 2 mg of TTD-TPE-2OMe and 10 mg of DSPE-PEG-2000 were dissolved in 0.5 mL of tetrahydrofuran. The tetrahydrofuran solutions of the two were then poured together and mixed evenly. The mixture was then added dropwise to 9 mL of water under a cell disruptor to prepare TTD-TPE-2OMe nanoparticles.

[0119] According to the examples, its superoxide radical generation capacity was tested and found to be 3.6 times lower than that of TTD-TPE-2OMe nanoscale crystal material.

[0120] Example 5

[0121] (1) Under anhydrous and oxygen-free conditions, 0.5 mmol of 4,6-bis(5-bromo-2-thienyl)thieno[3,4-c][1,2,5]thiadiazole, 2 mmol of 2-(4-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane, 8 mmol of K2CO3 and 0.1 mmol of Pd(PPh3)4 were added to a 50 mL double-necked round-bottom flask;

[0122] (2) Add the deoxygenated THF (16 mL) and water (4 mL) mixed solvent to the reaction flask, then heat to 86℃ and react for 10 h;

[0123] (3) After the reaction was completed, the product was removed by vacuum distillation in a rotary evaporator to remove THF and water solvent, and then extracted three times to obtain the crude product.

[0124] (4) The crude product in step (3) was purified by column chromatography using 200-mesh silica gel powder as packing material and petroleum ether and dichloromethane as eluents, and the green target product TTD-TPE-2OMe was still obtained.

[0125] Example 6

[0126] (1) Under anhydrous and oxygen-free conditions, 0.50 mmol of 4,6-bis(5-bromo-2-thienyl)thieno[3,4-c][1,2,5]thiadiazole, 1.76 mmol of 2-(4-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)phenyl)-4,4,5,5-tetramethyl-1,3,2-dioxoborane, 8.12 mmol of K2CO3 and 0.12 mmol of Pd(PPh3)4 were added to a 50 mL double-necked round-bottom flask;

[0127] (2) Add the deoxygenated THF (16 mL) and water (4 mL) mixed solvent to the reaction flask, then heat to 86℃ and react for 12 h;

[0128] (3) After the reaction was completed, the product was removed by vacuum distillation in a rotary evaporator to remove THF and water solvent, and then extracted three times to obtain the crude product.

[0129] (4) The crude product in step (3) was purified by column chromatography using 200-mesh silica gel powder as packing material and petroleum ether and dichloromethane as eluents to obtain the green target product TTD-TPE-2OMe.

[0130] Compare with Example 3

[0131]

[0132] (1) Under anhydrous and oxygen-free conditions, 0.2 mmol of 4,6-bis(5-bromo-2-thienyl)thieno[3,4-c][1,2,5]thiadiazole, 0.8 mmol of 1-(4-phenylboronic acid pinacol ester)-1,2,2-tristyrene, 3.2 mmol of K2CO3 and 0.04 mmol of Pd(PPh3)4 were added to a 50 mL double-necked round-bottom flask;

[0133] (2) Add the deoxygenated THF (8 mL) and water (2 mL) mixed solvent to the reaction flask, then heat to 86℃ and react for 16 h;

[0134] (3) After the reaction was completed, the product was removed by vacuum distillation in a rotary evaporator to remove THF and water solvent, and then extracted three times to obtain the crude product.

[0135] (4) The crude product in step (3) was purified by column chromatography using 200-mesh silica gel powder as packing material and petroleum ether and dichloromethane as eluents to obtain the green target product TTD-TPE.

[0136] The product of Comparative Example 3 1 See the HNMR spectrum. Figure 8 ,Depend on Figure 8As can be seen, both the number of hydrogen atoms and the chemical shift correspond to the target product, proving that the product of this embodiment is TTD-TPE.

[0137] The products in Examples 5-6 and Comparative Example 3 were verified according to the method for detecting superoxide radicals in Example 4, except that the products in Examples 5-6 and Comparative Example 3 were replaced with the product in Example 1. The results are shown in Table 1.

[0138] Table 1

[0139] Superoxide radical generation capacity Example 1 powerful Example 5 powerful Example 6 powerful Comparative Example 3 none

[0140] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

[0141] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0142] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0143] The endpoints and any values ​​of the ranges disclosed in this application are not limited to the precise ranges or values; such ranges or values ​​should be understood to include values ​​close to them. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein. In principle, various technical solutions can be combined with each other to obtain new technical solutions, which should also be considered as specifically disclosed herein.

[0144] In the context of this specification, except where expressly stated otherwise, any matters or issues not mentioned shall apply directly to those known in the art without any modification.

[0145] Furthermore, any implementation described herein can be freely combined with one or more other implementations described herein, and the resulting technical solutions or technical ideas shall be regarded as part of the original disclosure or original record of the present invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider the combination to be obviously unreasonable.

Claims

1. A method for self-assembly modification of a conjugated organic small molecule, comprising mixing the conjugated organic small molecule with a surfactant to obtain a self-assembled modified conjugated organic small molecule; The surfactant is selected from at least one of hexadecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, decadecyltrimethylammonium bromide, and n-octyltrimethylammonium bromide; The conjugated organic molecule is a thiodiazole five-membered fused heterocyclic conjugated organic molecule with the structure shown in formula (I). （I）， in, In formula (I), n is 1, R1, R2, R3, R4, R5 and R6 are the same or different, R1, R2, R3, R4, R5 and R6 are each one of H, C1 alkoxy, C2 alkoxy and C3 alkoxy; X1, X2 and X3 are each sulfur. R1, R2, R3, R4, R5, and R6 are not all hydrogen at the same time.

2. The self-assembly modification method according to claim 1, characterized in that: The surfactant is derived from an aqueous solution containing the surfactant; and / or, The mixing method is stirring, and / or the mixing time is 6-54 hours.

3. The self-assembly modification method according to claim 1, characterized in that: The mixing method is stirring, with a rotation speed of 600-1500 rpm.

4. The self-assembly modification method according to claim 1, characterized in that: The amount of the conjugated organic small molecule used is such that the concentration of the conjugated organic small molecule in the mixture is 0.01-1 mol / L.

5. The self-assembly modification method according to claim 1, characterized in that: The self-assembly modification method includes: Mix 1-5 volumes of a solution containing the aforementioned conjugated small organic molecules with 50-200 volumes of a surfactant at a concentration of 1×10⁻⁶. -5 -2×10 -1 Mix the mol / L aqueous solution containing the surfactant and stir at 600-1500 rpm for 6-54 hours.

6. The self-assembled modified conjugated organic small molecule prepared by the self-assembly modification method according to any one of claims 1-5.

7. The application of the self-assembled modified conjugated organic small molecule as described in claim 6 in the field of photocatalytic hydrogen evolution.

8. A method for preparing nanoscale crystals of conjugated organic small molecules, comprising: Conjugated organic small molecules are dissolved in a solvent under heating conditions, cooled and allowed to stand to obtain micron-sized crystals, and then the micron-sized crystals are added to an aqueous solution containing polyethylene glycol and ultrasonically broken to obtain nano-sized crystals of conjugated organic small molecules. The conjugated organic molecule is a thiodiazole five-membered fused heterocyclic conjugated organic molecule with the structure shown in formula (I). （I）， In formula (I), n is 1, R1, R2, R3, R4, R5 and R6 are the same or different, R1, R2, R3, R4, R5 and R6 are each one of H, C1 alkoxy, C2 alkoxy and C3 alkoxy; X1, X2 and X3 are each sulfur. R1, R2, R3, R4, R5, and R6 are not all hydrogen at the same time; The solvent is selected from chloroform and ethyl acetate in a volume ratio of 1:(1.5-3); The ultrasonic fragmentation time is 3-10 hours; The mass ratio of the micron-sized crystals to polyethylene glycol is 1:(3-7). The polyethylene glycol is selected from polyethylene glycols with a number average molecular weight of 1000-5000.

9. A nanoscale crystal of a conjugated organic small molecule prepared by the preparation method of claim 8.

10. The use of the nanoscale crystals of the conjugated organic small molecules according to claim 9 in the preparation of reactive oxygen species therapeutic drugs.

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