A UV-responsive organic single-molecule material and its preparation method and application

Abstract

The present invention discloses an ultraviolet light responsive organic single molecule material and its preparation method and application, which relates to the technical field of photoelectric materials. The ultraviolet light responsive organic single molecule material is A or B; the chemical formula of A is C 25 H 20 OS2, the chemical structural formula is formula I; the chemical molecular formula of B is C 29 H 22 OS2, with the chemical formula of Formula II. The UV-responsive organic monomolecular materials provided by the present invention exhibit excellent conductivity change effects under UV illumination. For phenyl-substituted organic monomolecular photoelectric materials, the conductivity under UV illumination can reach 275.4% of that under unilluminated conditions; for naphthyl-substituted organic monomolecular photoelectric materials, the conductivity under UV illumination can reach 182.0% of that under unilluminated conditions.

Description

Technical Field

[0001] The present invention belongs to the technical field of photoelectric materials, and in particular relates to an ultraviolet light responsive organic single molecule material and a preparation method and application thereof. Background Art

[0002] Optoelectronic materials are materials that can generate, convert, transmit, process, and store photonic signals. Commercially available inorganic semiconductors and organic optoelectronic materials are already widely used in various fields. However, optoelectronic materials in integrated circuits also face the physical size limitations of materials brought about by circuit miniaturization. This can lead to control failures of traditional optoelectronic materials in highly integrated circuits. Therefore, developing optoelectronic materials suitable for use in microelectronic components is a key solution for building future high-performance, highly integrated optoelectronic devices.

[0003] Molecules that respond to UV light can achieve structural transformations under UV illumination. For example, diarylethenes and spiropyrans can undergo ring-switching under UV light, transforming their molecular structure and bringing about changes in various physical properties, particularly electrical conductivity.

[0004] Therefore, it is necessary to develop optoelectronic materials with ultraviolet light signal response for use in integrated circuit devices. Summary of the Invention

[0005] In view of this, the present invention provides an ultraviolet light responsive organic single molecule material and its preparation method and application, the main purpose of which is to solve the technical problem that the electrical conductivity of ultraviolet light responsive photoelectric materials needs to be improved.

[0006] In one aspect, the present invention provides an ultraviolet light responsive organic single molecule material, wherein the organic single molecule material is A or B;

[0007] The chemical formula of A is C 25 H 20 OS2, chemical structure is Formula I;

[0008] The chemical formula of B is C 29 H 22 OS2, chemical structure is Formula II;

[0009]

[0010] In a second aspect, the present invention provides a method for preparing the above-mentioned ultraviolet light-responsive organic monomolecular material, the method comprising the following steps:

[0011] S1: Mix 4-thiomethylphenylacetylene, n-butyl lithium, and reactant C at -70-80°C, raise the temperature to room temperature, and react I to obtain product I. Obtain an organic phase of product I, which is concentrated and purified to obtain intermediate product a.

[0012] S2: The intermediate product a in step S1 is mixed with manganese dioxide, and reacted with product II at room temperature to obtain product II, and a filtrate of the product II is obtained. The filtrate is concentrated and purified to obtain intermediate product b;

[0013] S3: Mixing 4-thiomethylphenylacetylene, n-butyl lithium, and the intermediate product b at -70-80°C, heating to room temperature, and reacting III to obtain product III. An organic phase of the product III is obtained, and the organic phase is concentrated and purified to obtain the final product.

[0014] Wherein, when the reactant C is benzaldehyde, the final product is C 25 H 20 OS2;

[0015] When the reactant C is naphthaldehyde, the final product is C 29 H 22 OS2.

[0016] Optionally, the temperature of the raw material mixing in step S1 is minus 78°C.

[0017] Optionally, the temperature of the raw material mixing in step S3 is minus 78°C.

[0018] Optionally, in step S1, the molar ratio of the 4-thiomethylphenylacetylene, the n-butyl lithium and the reactant C is 1:(1-1.2):(1-1.5).

[0019] Optionally, in step S1, the molar ratio of the n-butyl lithium to the 4-thiomethylphenylacetylene is selected from any value of 1, 1.1, 1.2, or a range between any two values.

[0020] Optionally, in step S1, the molar ratio of the reactant C to the 4-thiomethylphenylacetylene is selected from any value of 1, 1.1, 1.2, 1.3, 1.4, 1.5, or a range between any two values.

[0021] Optionally, in step S2, the molar ratio of the intermediate product a to the manganese dioxide is 1:3.5-4.

[0022] Optionally, in step S2, the molar ratio of the manganese dioxide to the intermediate product a is selected from any value among 3.5, 3.6, 3.7, 3.8, 3.9, 4, or a range between any two values.

[0023] Optionally, in step S3, the molar ratio of the 4-thiomethylphenylacetylene to n-butyl lithium is 1:1 to 1.2.

[0024] Optionally, in step S3, the molar ratio of the n-butyl lithium to the 4-thiomethylphenylacetylene is selected from any value of 1, 1.1, 1.2, or a range between any two values.

[0025] Optionally, both reaction I in step S1 and reaction III in step S3 are quenched with a saturated ammonium chloride solution.

[0026] Optionally, the organic phase of the product I in step S1 is extracted with ethyl acetate, and the organic phase is dried, concentrated, and purified to obtain the intermediate product a;

[0027] The product II in step 2 is filtered to obtain a filtrate, and the filtrate is concentrated and purified by vacuum distillation to obtain the intermediate product b;

[0028] The organic phase of the product III in step S3 is extracted with ethyl acetate, and the organic phase is dried, concentrated, and purified to obtain the final product.

[0029] Optionally, the yield of the intermediate product a is 75% to 85%; the yield of the intermediate product b is 95% to 99%.

[0030] Optionally, the yield of the intermediate product a is 80.0%; the yield of the intermediate product b is 97.1%.

[0031] In a third aspect, the present invention provides an ultraviolet light responsive solution, wherein the ultraviolet light responsive organic single molecule material or the ultraviolet light responsive organic single molecule material obtained by the above preparation method and a solvent are mixed together to form the ultraviolet light responsive solution.

[0032] Optionally, the mixing ratio of the ultraviolet light responsive organic single molecule material and the solvent is 0.3-0.5 mg: 10-15 mL.

[0033] Optionally, the mass of the ultraviolet light responsive organic single molecule material is selected from any value among 0.3, 0.35, 0.4, 0.45, 0.5, or a range between any two values, in mg;

[0034] The volume of the solvent is selected from any value among 10, 11, 12, 13, 14, 15 or any range between two values, and the unit is mL.

[0035] Optionally, the solvent is selected from at least one of benzene, toluene, 1,3,5-trimethylbenzene and 1,2,4-trichlorobenzene.

[0036] In a fourth aspect, the present invention provides the use of the above-mentioned ultraviolet light-responsive organic single-molecule material or the ultraviolet light-responsive organic single-molecule material obtained by the above-mentioned preparation method or the above-mentioned ultraviolet light-responsive solution in optoelectronic materials.

[0037] In a fifth aspect, the present invention provides a photoelectric material, which includes the above-mentioned ultraviolet light-responsive organic single-molecule material or the ultraviolet light-responsive organic single-molecule material obtained by the above-mentioned preparation method or the above-mentioned ultraviolet light-responsive solution.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] 1) The ultraviolet light-responsive organic single-molecule material provided by the present invention has a simple and easy-to-operate synthesis route and a non-toxic and harmless final structure.

[0040] 2) The ultraviolet light-responsive organic single-molecule material provided by the present invention has a good conductivity change effect under ultraviolet light; for the phenyl-substituted organic single-molecule photoelectric material, its conductivity under ultraviolet light can reach 275.4% of that under non-illumination conditions; for the naphthyl-substituted organic single-molecule photoelectric material, its conductivity under ultraviolet light can reach 182.0% of that under non-illumination conditions.

[0041] 3) The ultraviolet-responsive organic single-molecule material provided by the present invention can realize the conductivity control of single-molecule conductive materials under ultraviolet light and can be used in the design of light-controlled molecular logic circuits.

[0042] 4) Compared with traditional solid-state optoelectronic materials, the ultraviolet light-responsive organic single-molecule material provided by the present invention can effectively break through the physical size limit of optoelectronic materials in integrated circuits. It has the advantages of small size, easy structure modification, and sensitive response to optical signals. It is a very promising optoelectronic material. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 The organic single-molecule photoelectric material C of Example 1 of the present invention 25 H 20 OS2 molecular structure diagram;

[0044] Figure 2 The organic single-molecule photoelectric material C of Example 2 of the present invention 29 H 22 OS2 molecular structure diagram;

[0045] Figure 3 The organic single-molecule photoelectric material C of Example 1 of the present invention 25 H 20 OS2 H NMR spectrum;

[0046] Figure 4 The organic single-molecule photoelectric material C of Example 2 of the present invention 29 H 22 OS2 H NMR spectrum;

[0047] Figure 5The organic single-molecule photoelectric material C of Example 1 of the present invention 25 H 20 Schematic diagram of the OS2 synthesis route;

[0048] Figure 6 The organic single-molecule photoelectric material C of Example 2 of the present invention 29 H 22 Schematic diagram of the OS2 synthesis route;

[0049] Figure 7 The organic single-molecule photoelectric material C of Example 1 of the present invention 25 H 20 One-dimensional statistical plot of single-molecule conductance of OS2 before illumination (left) and under 365nm UV illumination (right);

[0050] Figure 8 The organic single-molecule photoelectric material C of Example 2 of the present invention 29 H 22 One-dimensional statistical plot of the single-molecule conductance of OS2 before illumination (left) and under 365nm UV illumination (right). DETAILED DESCRIPTION

[0051] The present application will be further described below in conjunction with specific embodiments. The following description is merely a few embodiments of the present application and does not limit the present application in any form. Although the present application discloses the preferred embodiments below, it is not intended to limit the present application. Any person skilled in the art who, without departing from the scope of the technical solution of the present application, makes slight changes or modifications using the above disclosed technical content is equivalent to an equivalent implementation case and falls within the scope of the technical solution.

[0052] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

[0053] In the embodiment of the present invention, C 25 H 20 OS2 and C 29 H 22 OS2 uses Bruker AVANCEⅢ400M nuclear magnetic resonance spectrometer to test the nuclear magnetic resonance hydrogen spectrum.

[0054] In the embodiment of the present invention, C 25 H 20 OS2 and C 29 H 22OS2 uses the Xiamen Micro-Ray Precision Instruments STMBJ3.0 single-molecule conductivity tester to test single-molecule conductance. The ultraviolet light source uses the Zhongjiao Jinyuan CEL-PF300-T8 xenon lamp light source combined with the UVREF reflector to produce ultraviolet light in the 200-400nm wavelength range. The single-molecule conductance data processing program uses the Pi-Lab open source basic_analysis program.

[0055] Example 1 (C 25 H 20 OS2)

[0056] 1) A 1:1 molar ratio of n-butyllithium solution was added to a solution of 4-thiomethylphenylacetylene in anhydrous tetrahydrofuran at -78°C. A 1:1 molar ratio of benzaldehyde was added to the vessel and the temperature was raised to room temperature. After allowing the reaction to proceed overnight, the reaction was quenched with saturated ammonium chloride solution and the solution was extracted with ethyl acetate. The organic phase was separated, dried, concentrated, and purified by flash column chromatography to afford intermediate a in an 80.0% yield.

[0057] 2) Intermediate a from step 1) was dissolved in dichloromethane, and manganese dioxide was added at a 1:4 molar ratio. The mixture was stirred at room temperature and monitored by thin-layer chromatography. After completion of the reaction, the reaction solution was filtered, concentrated by vacuum distillation, and the product was purified by flash column chromatography to obtain intermediate b in a 97.1% yield.

[0058] 3) At -78°C, a 1:1 molar ratio of n-butyllithium solution was added to a solution of 4-thiomethylphenylacetylene in anhydrous tetrahydrofuran. A 1:1 equivalent of product b from step 2) was added to the container and the temperature was raised to room temperature. After reacting overnight, the reaction was quenched with saturated ammonium chloride solution and the solution was extracted with ethyl acetate. The organic phase was separated, dried, concentrated, and then purified by flash column chromatography to obtain product C. 25 H 20 OS2, yield 70.0%; C 25 H 20 The synthetic route of OS2 is as follows Figure 5 shown.

[0059] C 25 H 20 The nuclear magnetic resonance hydrogen spectrum characterization data of OS2 are as follows:

[0060] 1 H NMR (400MHz, CDCl3): δ7.93 (d, J=7.3Hz, 2H), 7.50-7.34 (m, 7H), 7.18 (d, J=8.5Hz, 4H), 3.05 (s, 1H), 2.48 (s, 6H).

[0061] H NMR spectra Figure 3 As shown; Figure 3 The signal integration of each hydrogen atom is correct and the peak splitting is clear and correct, indicating that the structure is correct and has high purity.

[0062] The final product C synthesized in Example 1 was identified 25 H 20 The molecular structure of OS2 is as follows Figure 1 shown.

[0063] C 25 H 20 The UV response solution of OS2 is prepared as follows: 25 H 20 0.45 mg of OS2 material was placed in a 2 ml glass sample bottle, and 1 ml of 1,2,4-trichlorobenzene solution was added. After the material was completely dissolved, 0.1 ml of the solution was taken with a pipette and injected into another 2 ml glass sample bottle containing 0.9 ml of 1,2,4-trichlorobenzene solution to obtain C. 25 H 20 OS2 UV-responsive solution.

[0064] C 25 H 20 The single-molecule conductivity test results of OS2 UV-responsive solution are as follows: Figure 7 As shown, C 25 H 20 One-dimensional statistical plot of single-molecule conductance of OS2 before illumination (left) and under 200-400nm UV illumination (right); Figure 7 Indicates C 25 H 20 OS2 has a sensitive conductivity response to ultraviolet light in the wavelength range of 200-400nm in solution.

[0065] Example 2 (C 29 H 22 OS2)

[0066] 1) A 1:1 molar ratio of n-butyllithium solution was added to a solution of 4-thiomethylphenylacetylene in anhydrous tetrahydrofuran at -78°C. A 1:1 molar ratio of naphthaldehyde was added to the vessel and the temperature was raised to room temperature. After allowing the reaction to react overnight, the reaction was quenched with saturated ammonium chloride solution and the solution was extracted with ethyl acetate. The organic phase was separated, dried, concentrated, and purified by flash column chromatography to afford intermediate a in an 84.0% yield.

[0067] 2) Intermediate a from step 1) was dissolved in dichloromethane, and manganese dioxide was added at a 1:4 molar ratio. The mixture was stirred at room temperature and monitored by thin-layer chromatography. After completion of the reaction, the reaction solution was filtered, concentrated by vacuum distillation, and the product was purified by flash column chromatography to obtain intermediate b in an 89.8% yield.

[0068] 3) At -78°C, a 1:1 molar ratio of n-butyllithium solution was added to a solution of 4-thiomethylphenylacetylene in anhydrous tetrahydrofuran. A 1:1 equivalent of product b from step 2) was added to the container and the temperature was raised to room temperature. After reacting overnight, the reaction was quenched with saturated ammonium chloride solution and the solution was extracted with ethyl acetate. The organic phase was separated, dried, concentrated, and then purified by flash column chromatography to obtain product C. 29 H 22 OS2, yield 87.6%; C 29 H 22 The synthetic route of OS2 is as follows Figure 6 shown.

[0069] C 29 H 22 The nuclear magnetic resonance hydrogen spectrum characterization data of OS2 are as follows:

[0070] 1 H NMR (400MHz, CDCl3): δ8.98(d,J=8.5Hz,1H),8.21(d,J=7.2Hz,1H),7.90(t,J=7.7Hz,2H),7.59(t,J=7. 1Hz, 1H), 7.51 (q, J = 8.2Hz, 2H), 7.38 (d, J = 8.4Hz, 4H), 7.15 (d, J = 8.4Hz, 4H), 3.31 (s, 1H), 2.46 (s, 6H).

[0071] H NMR spectra Figure 4 As shown in the figure, the signal integration of each hydrogen atom is correct and the peak splitting is clear and correct, indicating that the structure is correct and has high purity.

[0072] The final product C synthesized in Example 2 was identified 29 H 22 The molecular structure of OS2 is as follows Figure 2 shown.

[0073] C 29 H 22 The UV response solution of OS2 is prepared as follows: 29 H 22 0.45 mg of OS2 material was placed in a 2 ml glass sample bottle, and 1 ml of 1,2,4-trichlorobenzene solution was added. After the material was completely dissolved, 0.1 ml of the solution was taken with a pipette and injected into another 2 ml glass sample bottle containing 0.9 ml of 1,2,4-trichlorobenzene solution to obtain C. 29 H 22 OS2 UV-responsive solution.

[0074] C 29 H 22The single-molecule conductivity test results of OS2 UV-responsive solution are as follows: Figure 8 As shown, C 29 H 22 One-dimensional statistical plot of single-molecule conductance of OS2 before illumination (left) and under 200-400nm UV illumination (right); Figure 8 Indicates C 29 H 22 OS2 has a sensitive conductivity response to ultraviolet light in the wavelength range of 200-400nm in solution.

[0075] The ultraviolet light responsive organic single molecule material provided in Example 1 or Example 2 of the present invention is C 29 H 22 OS2 or C 29 H 22 OS2 chemical structure ( Figure 1 or Figure 2 ) and the sulfur-containing benzene acetylene group and the benzene ring (or naphthalene) group work together to achieve ultraviolet response.

[0076] The synthesis route of the ultraviolet light-responsive organic single-molecule material provided in Example 1 or Example 2 of the present invention is simple and easy to operate, and the final structure is non-toxic and harmless.

[0077] The ultraviolet light-responsive organic single-molecule material synthesized in Example 1 or Example 2 of the present invention has a good conductivity change effect under ultraviolet light; for the phenyl-substituted organic single-molecule photoelectric material synthesized in Example 1, its conductivity under ultraviolet light can reach 275.4% of that under non-illumination conditions; for the naphthyl-substituted organic single-molecule photoelectric material synthesized in Example 2, its conductivity under ultraviolet light can reach 182.0% of that under non-illumination conditions.

[0078] The ultraviolet light-responsive organic single-molecule material synthesized in Example 1 or Example 2 of the present invention can realize the conductivity control of the single-molecule conductive material under ultraviolet light, and can be used in the design of light-controlled molecular logic circuits.

[0079] Compared with traditional solid-state optoelectronic materials, the ultraviolet light-responsive organic single-molecule materials synthesized in Example 1 or Example 2 of the present invention can effectively break through the physical size limit of optoelectronic materials in integrated circuits. They have the advantages of small size, easy structure modification, and sensitive response to optical signals. They are a type of optoelectronic material with great potential.

[0080] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. An ultraviolet light responsive organic single molecule material, characterized in that: The organic single molecule material is A or B; The chemical formula of A is C 25 H 20 OS2, chemical structure is Formula I; The chemical formula of B is C 29 H 22 OS2, chemical structure is Formula II; Formula I; Formula II.

2. The method for preparing the ultraviolet light responsive organic monomolecular material according to claim 1, characterized in that: The method comprises the following steps: S1: Mix 4-thiomethylphenylacetylene, n-butyl lithium, and reactant C at -70-80°C, raise the temperature to room temperature, and react I to obtain product I. Obtain an organic phase of product I, which is then concentrated and purified to obtain intermediate product a. S2: The intermediate product a in step S1 is mixed with manganese dioxide, and reacted with product II at room temperature to obtain product II, and a filtrate of the product II is obtained. The filtrate is concentrated and purified to obtain intermediate product b; S3: Mixing 4-thiomethylphenylacetylene, n-butyl lithium, and the intermediate product b at -70-80°C, heating to room temperature, and reacting III to obtain product III. An organic phase of the product III is obtained, and the organic phase is concentrated and purified to obtain the final product. Wherein, when the reactant C is benzaldehyde, the final product is C 25 H 20 OS2; When the reactant C is naphthaldehyde, the final product is C 29 H 22 OS2.

3. The method for preparing an ultraviolet-responsive organic monomolecular material according to claim 2, wherein: In step S1, the molar ratio of the 4-thiomethylphenylacetylene, the n-butyl lithium and the reactant C is 1:(1-1.2):(1-1.5).

4. The method for preparing an ultraviolet-responsive organic monomolecular material according to claim 2, wherein: In step S2, the molar ratio of the intermediate product a to the manganese dioxide is 1:3.5-4.

5. The method for preparing an ultraviolet-responsive organic monomolecular material according to claim 2, wherein: In step S3, the molar ratio of 4-thiomethylphenylacetylene to n-butyl lithium is 1:1-1.

2.

6. The method for preparing an ultraviolet-responsive organic monomolecular material according to claim 2, wherein: Both reaction I in step S1 and reaction III in step S3 are quenched with a saturated ammonium chloride solution.

7. The method for preparing an ultraviolet-light-responsive organic monomolecular material according to claim 2, wherein: The organic phase of the product I in step S1 is extracted with ethyl acetate, and the organic phase is dried, concentrated, and purified to obtain the intermediate product a; The product II in step 2 is filtered to obtain a filtrate, and the filtrate is concentrated and purified by vacuum distillation to obtain the intermediate product b; The organic phase of the product III in step S3 is extracted with ethyl acetate, and the organic phase is dried, concentrated, and purified to obtain the final product.

8. A UV-responsive solution, characterized in that The ultraviolet light responsive organic single molecule material according to claim 1 or the ultraviolet light responsive organic single molecule material obtained by the preparation method according to any one of claims 2 to 7 and a solvent is a solution obtained by mixing the ultraviolet light responsive organic single molecule material according to claim 1 and a solvent.

9. The ultraviolet light responsive solution according to claim 8, characterized in that: The mixing ratio of the ultraviolet light responsive organic single molecule material and the solvent is 0.3-0.5 mg: 10-15 mL.

10. The ultraviolet light responsive solution according to claim 8, characterized in that: The solvent is selected from at least one of benzene, toluene, 1,3,5-trimethylbenzene and 1,2,4-trichlorobenzene.

11. Use of the ultraviolet light responsive organic single molecule material according to claim 1, the ultraviolet light responsive organic single molecule material obtained by the preparation method according to any one of claims 2 to 7, or the ultraviolet light responsive solution according to any one of claims 8 to 10 in optoelectronic materials.

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