Diphenylacrylonitrile-based flexible crystalline materials, their preparation methods and applications

Abstract

This invention discloses a diphenylacrylonitrile-based flexible crystal material, its preparation method, and its applications, relating to the field of organic optoelectronic functional materials. The basic structure of this organic fluorescent material consists of a diphenylacrylonitrile core with different substituents as substituent groups. The deep red or near-infrared flexible fluorescent organic crystal material is obtained by dissolving the powdered material in a suitable solvent and slowly evaporating it. The fluorescent material prepared by this invention uses inexpensive and readily available raw materials, and the preparation method is simple. The flexible crystal can be bent to a semi-circle at any angle. The material prepared by this invention has good elastic mechanical properties and can be applied to flexible optoelectronic devices, display materials, information storage materials, or optical waveguide materials.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic functional materials, specifically to a flexible crystalline material based on diphenylacrylonitrile, its preparation method, and its applications. Background Technology

[0002] In recent years, flexible electronic products have developed rapidly and are gradually becoming more common in people's daily lives. Organic crystal materials have advantages such as few defects, long-range structural order, good photostability and thermal stability, and high carrier mobility, making them ideal materials for fabricating flexible organic electronic devices. However, traditional organic crystal materials are usually brittle and easily break under external forces, unable to deform, which greatly limits their application in the field of organic optoelectronics, especially in flexible electronic devices. Therefore, how to design and synthesize flexible pure organic light-emitting crystal materials has become a key research focus in this field. Pure organic flexible crystal materials exhibit elasticity or plasticity under various external forces, but pure organic flexible crystal materials with deep red and near-infrared fluorescence are extremely rare. However, the emission position of practical active optical waveguides is generally located in the deep red to near-infrared region. The emission position of existing organic crystal-based flexible active optical waveguide materials generally does not reach the near-infrared region, making it difficult to be compatible with existing standards.

[0003] Chinese patent document CN115286607A discloses a flexible crystal material of ketones, its preparation method and application. Its phosphorescence emission peak falls in the obvious green light wavelength emission region, which is not well compatible with existing optical waveguide application standards. Summary of the Invention

[0004] (a) Technical problems to be solved

[0005] To address the aforementioned technical problems, the present invention aims to develop a class of flexible deep-red or near-infrared fluorescent crystal materials based on diphenylacrylonitrile (DIC) that are simple to prepare and produce good results. It provides a method for preparing flexible crystals based on DIC derivatives and their application as flexible fluorescent crystal materials. The crystals prepared by this invention exhibit good elasticity and can realize active optical waveguide functions, providing a reference for the future application of fluorescent crystal materials in flexible devices, active optical waveguides, and other fields.

[0006] (II) Technical Solution

[0007] A flexible crystalline material based on diphenylacrylonitrile, prepared from diphenylacrylonitrile compounds;

[0008] The structural formula of diphenylacrylonitrile compounds is formula (I):

[0009]

[0010] The Ar structure consists of a benzene ring containing different substituents, which are one or more groups selected from halogen, cyano, nitro, methyl, trifluoromethyl, or phenyl.

[0011] Furthermore, the Ar structure includes:

[0012] Diphenylacrylonitrile molecules are flexible crystals, and their unit cell parameters include the following:

[0013] (1) The chemical formula is C 19 H 17 N2, this crystalline material belongs to the monoclinic crystal system, and its space group is P121 / c1. α = 90°, β = 98.793°, γ = 90°, Z = 6, cell volume

[0014] (2) The chemical formula is C 20 H 19 N2, this crystalline material belongs to the orthorhombic crystal system, and its space group is Pna21. α = 90°, β = 90°, γ = 90°, Z = 8, cell volume

[0015] (3) The chemical formula is C 25 H 22 N2 is a monoclinic crystal material with space group P121 / n1. α = 90°, β = 101.919°, γ = 90°, Z = 4, cell volume

[0016] (4) The chemical formula is C 19 H 17 FN2 is a monoclinic crystal material with space group C12 / c1. α = 90°, β = 104.405°, γ = 90°, Z = 8, cell volume

[0017] (5) The chemical formula is C 19 H 16 F2N2 is a crystalline material belonging to the monoclinic crystal system, with space group C12 / c1. α = 90°, β = 106.082°, γ = 90°, Z = 8, cell volume

[0018] (6) The chemical formula is C 19 H 15 F3N2 is a monoclinic crystal material with space group C12 / c1. α = 90°, β = 105.6190°, γ = 90°, Z = 8, cell volume

[0019] (7) The chemical formula is C 20 H 16 F3N2 is a monoclinic crystal material with space group P121 / c1. α = 90°, β = 102.252°, γ = 90°, Z = 4, cell volume

[0020] (8) The chemical formula is C 20 H 16 F3N2 is a crystalline material belonging to the orthorhombic crystal system with space group Pbca. α = 90°, β = 90°, γ = 90°, Z = 8, cell volume

[0021] (9) The chemical formula is C 20 H 16 N3 is a monoclinic crystal material with space group P121 / c1. α = 90°, β = 92.132°, γ = 90°, Z = 4, cell volume

[0022] (10) The chemical formula is C 19 H 17 N3O2 is a triclinic crystal material with space group P-1. α = 82.983°, β = 89.166°, γ = 64.384°, Z = 2, cell volume

[0023] Furthermore, flexible crystalline materials of diphenylacrylonitrile molecules can be bent into semi-circular rings under external force.

[0024] Furthermore, flexible crystalline materials based on diphenylacrylonitrile molecules can achieve deep red or near-infrared fluorescence emission under ultraviolet light irradiation.

[0025] Furthermore, the preparation method of the diphenylacrylonitrile flexible crystal material includes the following steps: dissolving diphenylacrylonitrile molecular powder in a good solvent, then adding a poor solvent, and slowly evaporating the solvent at room temperature until needle-like elastic crystals are obtained, thus obtaining the diphenylacrylonitrile flexible crystal material.

[0026] Furthermore, good solvents include dichloromethane, trichloromethane, and acetone.

[0027] Furthermore, undesirable solvents include petroleum ether, n-hexane, methanol, and ethanol.

[0028] Furthermore, the application of diphenylacrylonitrile-based flexible crystal materials as fluorescent materials in flexible active optical waveguides.

[0029] Furthermore, by placing a flexible crystal material of diphenylacrylonitrile molecules on a silicon wafer and irradiating one end of the flexible crystal with ultraviolet light, waveguide emission of the crystal material can be observed at the other end of the crystal.

[0030] Furthermore, the intensity of ultraviolet light is ≥80mW / cm². 2 The wavelength range is 300–400 nm.

[0031] (III) Beneficial Technical Effects

[0032] This invention utilizes simple molecular design and different substituent groups to modify the diphenylacrylonitrile skeleton to prepare such molecules with HPLC-grade purity. Excellent elastic pure organic crystal materials can be grown by slowly evaporating the solvent, and the elastic crystals can still maintain the deep red or near-infrared fluorescence properties of the initial state when bent at any angle.

[0033] The material of this invention exhibits stable luminescence properties and can be used in an air atmosphere without the need for inert gas protection or a vacuum environment. All raw materials used are pure organic compounds, widely available, readily accessible, inexpensive, simple to synthesize, and easy to prepare. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in this invention. For those skilled in the art, other drawings can be obtained based on these drawings.

[0035] Figure 1 Fluorescence spectra of the diphenylacrylonitrile-based flexible crystal material prepared for the example were obtained by excitation at 365 nm.

[0036] Figure 2 The images shown are of the flexible crystalline material of diphenylacrylonitrile before and after bending in the examples;

[0037] Figure 3 This is a schematic diagram illustrating the application of diphenylacrylonitrile-based flexible crystal materials in active optical waveguides in the embodiments. Detailed Implementation

[0038] The present invention will be described in detail below with reference to specific embodiments and examples, thereby making the advantages and various effects of the present invention more clearly apparent. Those skilled in the art should understand that these specific embodiments and examples are for illustrative purposes only and are not intended to limit the present invention.

[0039] Example 1:

[0040] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 1 and diphenylacrylonitrile flexible crystal material 1: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by the addition of 5 mmol of benzyl acetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 1, with the structural formula shown below. The chemical formula is C 19 H 18 N2. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 1 in chloroform:n-hexane = 2:3 (volume ratio, total 5 mL), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which is the diphenylacrylonitrile flexible crystal material 1.

[0041] Example 2:

[0042] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 2 powder and diphenylacrylonitrile flexible crystal material 2: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of p-methylphenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 2, with the structural formula shown below. The chemical formula is C 20 H 20 N2. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 2 in dichloromethane:petroleum ether = 2:3 (volume ratio, total 5 mL), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which is the diphenylacrylonitrile flexible crystal material 2.

[0043] Example 3:

[0044] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 3 powder and diphenylacrylonitrile flexible crystal material 3: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of p-phenylphenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 3, with the structural formula shown below. The chemical formula is C 25 H 22 N2. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 3 in chloroform:ethanol = 2:3 (volume ratio, total 5 mL), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which are the diphenylacrylonitrile flexible crystal materials 3.

[0045] Example 4:

[0046] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 4 powder and diphenylacrylonitrile flexible crystal material 4: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of p-fluorophenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 4, with the structural formula shown below. The chemical formula is C 19 H 17 FN2. 15 mg of the above-mentioned diphenylacrylonitrile compound 4 was dissolved in dichloromethane:methanol = 2:3 (volume ratio, total 5 mL), and the solvent was slowly evaporated at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which is the diphenylacrylonitrile flexible crystal material 4.

[0047] Example 5:

[0048] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 5 powder and diphenylacrylonitrile flexible crystal material 5: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of 2,4-difluorophenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 5, with the structural formula shown below. The chemical formula is C 19 H 16 F2N2. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 5 in dichloromethane:methanol = 2:3 (volume ratio, total 5 mL), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which are the diphenylacrylonitrile flexible crystal materials 5.

[0049] Example 6:

[0050] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 6 powder and diphenylacrylonitrile flexible crystal material 6: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of 2,3,4-trifluorophenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 6, with the structural formula shown below. The chemical formula is C 19 H 15 F3N2. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 6 in dichloromethane:petroleum ether = 2:4 (volume ratio, 6 mL in total), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which are the diphenylacrylonitrile flexible crystal materials 6.

[0051] Example 7:

[0052] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 7 powder and diphenylacrylonitrile flexible crystal material 7: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of p-trifluoromethylphenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 7, with the structural formula [structure omitted]. The chemical formula is C 20 H 17 F3N2. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 7 in chloroform:n-hexane = 3:4 (volume ratio, total 7 mL), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which are the diphenylacrylonitrile flexible crystal materials 7.

[0053] Example 8:

[0054] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 8 powder and diphenylacrylonitrile flexible crystal material 8: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of 3-trifluoromethylphenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 8, with the structural formula shown below. The chemical formula is C 20 H 17 F3N2. 15 mg of the above-mentioned diphenylacrylonitrile compound 8 was dissolved in acetone:petroleum ether = 3:4 (volume ratio, total 7 mL). The solvent was slowly evaporated at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which is the diphenylacrylonitrile flexible crystal material 8.

[0055] Example 9:

[0056] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 9 powder and diphenylacrylonitrile flexible crystal material 9: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of p-cyanophenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 9, with the structural formula [insert structural formula here]. The chemical formula is C 20 H 17 N3. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 9 in chloroform:petroleum ether = 2:4 (volume ratio, 6 mL in total), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which are the diphenylacrylonitrile flexible crystal materials 9.

[0057] Example 10:

[0058] Please see Figures 1-3 Preparation of diphenylacrylonitrile compound 10 powder and diphenylacrylonitrile flexible crystal material 10: 5 mmol of p-dimethylaminocinnamaldehyde and 5 mmol of sodium methoxide were added to a 100 mL double-necked flask, followed by 5 mmol of p-nitrophenylacetonitrile and 50 mL of methanol. The mixture was stirred at room temperature for 5 hours. After returning to room temperature, the mixture was filtered to obtain diphenylacrylonitrile compound 10, with the structural formula shown below. The chemical formula is C 19 H 17 N3O2. Dissolve 15 mg of the above-mentioned diphenylacrylonitrile compound 10 in dichloromethane:n-hexane = 2:3 (volume ratio, total 5 mL), and slowly evaporate the solvent at room temperature for 4 days to obtain needle-like elastic crystals with excellent elasticity, which are the diphenylacrylonitrile flexible crystal material 10.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A flexible crystalline material based on diphenylacrylonitrile, characterized in that: The diphenylacrylonitrile-based flexible crystal material is prepared from diphenylacrylonitrile compounds; The structural formula of the diphenylacrylonitrile compound is formula (I): (I)； The preparation method of the diphenylacrylonitrile flexible crystal material includes the following steps: dissolving diphenylacrylonitrile molecular powder in a good solvent, then adding a poor solvent, and slowly evaporating the solvent at room temperature until needle-like elastic crystals are obtained, thereby obtaining the diphenylacrylonitrile flexible crystal material. The good solvent is selected from dichloromethane, trichloromethane, and acetone; The unsuitable solvents are selected from petroleum ether, n-hexane, methanol, and ethanol; The Ar structure is as follows: , , , , , , , , , ; The diphenylacrylonitrile molecule is a flexible crystal with the following unit cell parameters: (1) The chemical formula is C 19 H 17 N2, this crystal material belongs to the monoclinic crystal system, its space group is P121 / c1, a=7.5710(8)Å, b=17.6435(18)Å, c=16.8668(19)Å, α=90°, β=98.793°, γ=90°, Z=6, and the unit cell volume V=2226.6(4)Å. 3 ; (2) The chemical formula is C 20 H 19 N2, this crystal material belongs to the orthorhombic crystal system, its space group is Pna21, a=11.1327(10)Å, b=36.568(3)Å, c=7.7230(5)Å, α=90°, β=90°, γ=90°, Z=8, and the unit cell volume V=3144.0(4)Å. 3 ; (3) The chemical formula is C 25 H 22 N2, this crystal material belongs to the monoclinic crystal system, its space group is P121 / n1, a=12.3853(10)Å, b=6.0975(4)Å, c=23.2010(18)Å, α=90°, β=101.919°, γ=90°, Z=4, and the unit cell volume V=1714.3(2)Å. 3 ; (4) The chemical formula is C 19 H 17 FN2 is a monoclinic crystal material with space group C12 / c1, a = 33.420(2) Å, b = 3.9340(3) Å, c = 22.9549(16) Å, α = 90°, β = 104.405°, γ = 90°, Z = 8, and cell volume V = 2923.1(4) Å. 3 ; (5) The chemical formula is C 19 H 16 F2N2 is a monoclinic crystal material with space group C12 / c1, a = 34.992(3) Å, b = 3.9927(2) Å, c = 23.0491(14) Å, α = 90°, β = 106.082°, γ = 90°, Z = 8, and cell volume V = 3094.2(3) Å. 3 ; (6) The chemical formula is C 19 H 15 F3N2 is a monoclinic crystal material with space group C12 / c1, a = 34.7691(11) Å, b = 4.00920(10) Å, c = 23.5274(8) Å, α = 90°, β = 105.6190°, γ = 90°, Z = 8, and cell volume V = 3158.53(17) Å. 3 ; (7) The chemical formula is C 20 H 16 F3N2 is a monoclinic crystal material with space group P121 / c1, a = 12.6197(8) Å, b = 6.0908(4) Å, c = 23.2499(16) Å, α = 90°, β = 102.252°, γ = 90°, Z = 4, and cell volume V = 1746.4(2) Å. 3 ; (8) The chemical formula is C 20 H 16 F3N2 is a crystal material belonging to the orthorhombic crystal system with space group Pbca, a = 13.5622(4) Å, b = 10.0093(3) Å, c = 25.2061(8) Å, α = 90°, β = 90°, γ = 90°, Z = 8, and cell volume V = 3421.68(18) Å. 3 ; (9) The chemical formula is C 20 H 16 N3, this crystal material belongs to the monoclinic crystal system, its space group is P121 / c1, a=4.3143(4)Å, b=10.9207(10)Å, c=34.499(3)Å, α=90°, β=92.132°, γ=90°, Z=4, and the unit cell volume V=1624.3(3)Å. 3 ; (10) The chemical formula is C 19 H 17 N3O2, this crystalline material belongs to the triclinic crystal system, with space group P-1, a=6.6635(8)Å, b=7.2294(9)Å, c=18.521(3)Å, α=82.983°, β=89.166°, γ=64.384°, Z=2, and cell volume V=797.76(18)Å. 3 .

2. The flexible crystalline material of diphenylacrylonitrile according to claim 1, characterized in that: The diphenylacrylonitrile-based flexible crystal material can be bent into a semi-circular ring under external force.

3. The flexible crystalline material of diphenylacrylonitrile according to claim 1, characterized in that: The aforementioned flexible crystalline material of diphenylacrylonitrile molecules can achieve deep red or near-infrared fluorescence emission under ultraviolet light irradiation.

4. The application of the diphenylacrylonitrile-based flexible crystal material according to any one of claims 1-3 as a fluorescent material in flexible active optical waveguides.

5. The application of the diphenylacrylonitrile-based flexible crystal material as a fluorescent material in flexible active optical waveguides according to claim 4, characterized in that: By placing a flexible crystal material of diphenylacrylonitrile molecules on a silicon wafer and irradiating one end of the flexible crystal with ultraviolet light, waveguide emission of the crystal material can be observed at the other end of the crystal.

6. The application of the diphenylacrylonitrile-based flexible crystal material as a fluorescent material in flexible active optical waveguides according to claim 5, characterized in that; The intensity of the ultraviolet light is ≥80mW / cm 2 The wavelength range is 300–400 nm.

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