Photothermal dual-logic gated tricrylamide-based photochromic materials, their synthesis methods and applications

Abstract

This invention relates to a photothermal dual-logic-gated triarylethylene-based photochromic material, its synthesis method, and its applications. A tetraphenylbenzene derivative is introduced into the triphenylbenzene structure. Tetraphenylbenzene consists of four phenyl groups replacing hydrogen atoms on the central benzene ring. Since the benzene ring in the group can rotate freely, various conformations of tetraphenylbenzene can be formed by changing the temperature, thus creating a novel triarylethylene-based photochromic material with photothermal dual-logic-gated properties. This type of material exhibits advantages such as fast photochromic response, high saturated absorbance of the photochromic product, and long-lasting color change. This invention relates to a compound synthesis process that is simple, has mild synthesis conditions, low process cost, high yield, and is easy to purify. The series of materials are suitable for applications such as multi-layer anti-counterfeiting and encryption, complex logic gates, molecular optical switches, decoration, and optical information storage.

Description

Technical Field

[0001] This invention belongs to the field of photochromic materials technology, and relates to a photothermal dual-logic gated tristyrene-based photochromic material and its synthesis method, as well as its applications in multi-layer anti-counterfeiting and encryption, complex logic gates, molecular optical switches, decoration and optical information storage. Background Technology

[0002] Photochromism is a chemical-physical phenomenon encompassing the chemical and physical reactions that occur in organic, inorganic, biological, and polymeric substances under light-induced conditions. Photochromism refers to the reversible chemical reaction that occurs when specific molecules are exposed to light of a certain wavelength, accompanied by a significant change in their absorption spectrum; and the ability of these molecules to revert to their initial state upon exposure to light of another specific wavelength or under heating conditions. Pure and Applied Chemistry. 2001, 73, 639-665. Photochromic compounds, as important optical information materials, have wide applications in materials science and information science, and can be used in optical information storage materials, optical imaging materials, optical decorative materials, and anti-counterfeiting identification technologies.

[0003] Research on organic photochromic chemistry and materials has been continuously expanded and deepened in recent years. Organic photochromic compounds can be broadly classified into the following categories according to their type: arginine anhydrides, diarylethylene compounds, spiropyrans, azo compounds, etc. Since Irie et al. reported the photochromic properties of cis-diarylethylene heterocycles and proved that this compound simultaneously possesses excellent thermal stability and fatigue resistance, diarylethylene has been widely studied as an important photochromic system, becoming one of the most promising photochromic materials for current applications. Chemical reviews (2000, 100, 1685-1716). However, diarylethene only exhibits photochromic properties in its cis conformation. Therefore, in research, a five-membered ring must be bridged to the olefin bond to fix the cis conformation. This makes the diarylethene molecule complex, difficult to synthesize and modify, thus limiting the practical application of diarylethene materials. Therefore, designing simple, easily synthesized photochromic molecules is an important trend in the development of photochromic materials.

[0004] Triarylethylene photochromic materials have simple molecular structures and, while maintaining excellent photoresponse performance, are easy to synthesize and modify, making them a promising new type of photochromic material with application value. In recent years, Yu et al. have successively reported several triarylethylene compounds with excellent photochromic properties (…). Chem. Sci. ,2016, 7,5302-5306; Mater. Chem. Front ., 2017, 1, 1900-1904; J. Mater. Chem. C(2021, 9, 11126-11131). However, most of the triarylethylene photochromic compounds reported so far only have photoresponsiveness and low color purity, which limits their application in fields such as complex information encryption. Therefore, it is necessary to further develop multi-stimulus responsive photochromic materials. Summary of the Invention

[0005] Technical problems to be solved

[0006] To avoid the shortcomings of existing technologies, this invention proposes a photothermal dual-logic-gated styrene-based photochromic material, its synthesis method, and its application.

[0007] The purpose of this invention is to provide a photothermal dual-logic-gated tristyrene-based photochromic material, which can change the photochromic absorption wavelength of the compound under heating conditions, and has the advantages of photothermal dual-logic gate, fast photochromic response speed, and high photochromic saturation absorbance.

[0008] The second objective of this invention is to provide a method for synthesizing the above-mentioned photothermal dual-logic-gated tristyrene-based photochromic materials. These methods are simple in process, have high yield, are easy to purify, and can adjust the photochromic absorption wavelength, photoresponse speed, and fatigue resistance of the target product by changing the functional groups.

[0009] The third objective of this invention is to apply the aforementioned photothermal dual-logic gated tristyrene-based photochromic materials to fields such as multi-information anti-counterfeiting and encryption, complex logic gates, optical information storage, decoration, and bioimaging.

[0010] Technical solution

[0011] A photothermal dual-logic gated tricrylamide-based photochromic material, characterized by the following general molecular structure formula:

[0012]

[0013] Wherein, R0 is tetraphenylbenzene or its derivative, and R1 and R2 may be the same or different, and are selected from alkyl, halogen, nitro, carboxyl, hydroxyl, amino, aldehyde, cyano, aromatic ring or aromatic heterocyclic substituents.

[0014] The R0 mentioned above is selected from the following structures:

[0015]

[0016] Among them, R3, R4, R5, R6, and R7 may be the same or different, and are selected from hydrogen, trimethylsilyl, alkyl, halogen, alkoxy, nitro, carboxyl, amino, cyano, aromatic ring, or aromatic heterocyclic substituent.

[0017] When R1 and R2 are aromatic rings or aromatic heterocyclic substituents, they are selected from the following structures:

[0018]

[0019] Wherein: R8 and R9 may be the same or different, and are selected from hydrogen, alkyl, halogen, alkoxy, nitro, carboxyl, amino, aldehyde or cyano.

[0020] A method for synthesizing the photothermal dual-logic-gated tristyrene-based photochromic material is characterized by: using a Diels-Alder reaction, a compound containing tetraphenylcyclopentadienone is reacted with a tristyrene derivative containing alkynyl groups at one, two, or three ends, and the mixture is heated under reflux to obtain the photothermal dual-logic-gated tristyrene-based photochromic material.

[0021] The heating and reflux process involves heating and refluxing at 180°C for 24 hours to obtain a photothermal dual-logic-gated tristyrene-based photochromic material.

[0022] A method for synthesizing the photothermal dual-logic-gated tristyrene-based photochromic material is characterized by: using a Suzuki coupling reaction to combine a halogen-containing tetraphenylbenzene compound with a tristyrene derivative containing boron aromatic rings or aromatic heterocyclic substituents at one, two, or three ends to obtain the photothermal dual-logic-gated tristyrene-based photochromic material.

[0023] The Suzuki coupling reaction is carried out in an alkaline environment with a palladium catalyst.

[0024] An application of the aforementioned photothermal dual-logic gated tristyrene-based photochromic material is characterized by its use in the preparation of multi-layer anti-counterfeiting products, photothermal dual-logic gated materials, optical information storage products, decorative and bio-imaging products.

[0025] Beneficial effects

[0026] This invention proposes a photothermal dual-logic-gated triphenylethylene-based photochromic material, its synthesis method, and its application. A tetraphenylbenzene derivative is introduced into the triphenylene structure. Tetraphenylbenzene consists of four phenyl groups replacing hydrogen atoms on the central benzene ring. Since the benzene ring in the group can rotate freely, various conformations of tetraphenylbenzene can be formed by changing the temperature. This creates a novel triarylethylene-based photochromic material with photothermal dual-logic-gated properties. Furthermore, this type of material has advantages such as fast photochromic response, high saturated absorbance of the photochromic product, and long-lasting color change.

[0027] This invention relates to a compound synthesis process that is simple, has mild synthesis conditions, low process cost, high yield, and is easy to purify. The synthesized photochromic materials have excellent and tunable photochromic properties, good erasure and rewriteability, and the color of the photochromic product after light exposure can be controlled by changing the ambient temperature. This makes the series of materials suitable for multiple anti-counterfeiting and encryption, complex logic gates, molecular optical switches, decoration, and optical information storage. Attached Figure Description

[0028] Figure 1 The images show a comparison of the solid powder of the final product of Example 1 of this invention at 25 ℃ and 80 ℃ before and after photochromism, as well as a comparison of their ultraviolet-visible reflectance spectra. Before heating, the solid powder on the left is white before photochromism, and the solid powder on the right turns pink after photochromism. After heating to 80 ℃, the crystal on the left is white before photochromism, and the solid powder on the right turns yellow after photochromism.

[0029] Figure 2 The images show a comparison of the solid powder of the final product of Example 2 of this invention at 25 ℃ and 80 ℃ before and after photochromism, as well as a comparison of their ultraviolet-visible reflectance spectra. Before heating, the solid powder on the left is white before photochromism, and the solid powder on the right turns pink after photochromism. After heating to 80 ℃, the crystal on the left is white before photochromism, and the solid powder on the right turns yellow after photochromism.

[0030] Figure 3 : This shows the trend of the maximum reflection wavelength of the photochromic products in Examples 1 and 2 as a function of temperature. Detailed Implementation

[0031] The present invention will now be further described in conjunction with the embodiments and accompanying drawings:

[0032] A method for synthesizing photothermal dual-logic gated tricresyl-based photochromic materials includes the following methods:

[0033] Method (1): The target product is obtained by reacting a compound containing tetraphenylcyclopentadienone with a triphenylphenyl derivative containing alkynyl groups at one, two, or three ends via a Diels-Alder reaction. Preferably, Method (1) involves providing a compound containing tetraphenylcyclopentadienone and a triphenylphenyl derivative containing alkynyl groups, and heating the mixture in a diphenyl ether solution under reflux at 180°C for 24 hours to finally obtain the target product.

[0034] Method (2): The target product is obtained by Suzuki coupling reaction of a halogen-containing tetraphenylbenzene compound and a triphenylbenzene derivative having boron aromatic ring or aromatic heterocyclic substituents at one, two, or three ends; preferably, the method (2) is to provide a halogen-containing tetraphenylbenzene compound and a triphenylbenzene derivative having boron aromatic ring or aromatic heterocyclic substituents at one, two, or three ends, and react them in a tetrahydrofuran solution under the action of potassium carbonate aqueous solution and palladium catalyst to obtain the target product.

[0035] The aforementioned photothermal dual-logic gated triphenylene-based photochromic materials can be applied to the preparation of multi-layer anti-counterfeiting products, photothermal dual-logic gated materials, optical information storage products, decorative and bio-imaging products.

[0036] The present invention will be further illustrated by specific embodiments below, but the present invention is not limited to these specific examples.

[0037] Example 1:

[0038] (1) Synthesis of intermediate [1,1-bis(4-fluorobenzene)-2-(2-iodophenyl)ethylene]

[0039]

[0040] Under an argon atmosphere, 2-iodobenzyl bromide (5.00 g, 16.84 mmol) and triethyl phosphite (4.20 g, 25.26 mmol) were added to a 250 mL two-necked flask. The mixture was refluxed at 85 °C for 6 h, then the heating was stopped, and the mixture was cooled to room temperature to obtain the phosphorus ylide reagent, diethyl 2-iodophenyl phosphate. Then, tetrahydrofuran (50 mL) and 4,4'-difluorobenzophenone (4.41 g, 20.21 mmol) were added to the flask in an ice-water bath. After the reagents were completely dissolved, potassium tert-butoxide (5.67 g, 50.52 mmol) was slowly added. The reaction was stopped after stirring at room temperature for 3 h. The tetrahydrofuran solvent was removed by vacuum distillation, and the mixture was extracted with dichloromethane and saturated brine. The organic phase was collected, dried over anhydrous sodium sulfate, and filtered to obtain a clear solution. The crude product was purified by silica gel column chromatography, with hexane as the eluent. The product was recrystallized from dichloromethane / n-hexane to give 4.87 g of a pale yellow solid, with a yield of 69.14%.

[0041] (2) Synthesis of intermediate [1,1-bis(4-fluorobenzene)-2-(2-trimethylsilylethynylphenyl)ethylene]

[0042]

[0043] Under a light-protected environment and argon atmosphere, 1,1-bis(4-fluorobenzene)-2-(2-iodophenyl)ethylene (3.00 g, 7.17 mmol), cuprous iodide (68.11 mg, 0.36 mmol), and the catalyst bis(triphenylphosphine)palladium dichloride (0.05 g, 0.07 mmol) were added to a 250 mL two-necked flask. Then, ultra-dry tetrahydrofuran (40 mL) and triethylamine (12 mL) were added, followed by the dropwise addition of trimethylethynylsilane (1.53 mL, 10.76 mmol). The reaction was stopped after stirring at room temperature for 24 h. The reaction solution was concentrated by vacuum distillation, extracted with dichloromethane and saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and filtered to obtain a clear, transparent liquid. The crude product was purified by silica column chromatography, with hexane as the eluent. The product was recrystallized from dichloromethane / hexane to give 2.03 g of a pale yellow solid, with a yield of 72.86%.

[0044] (3) Synthesis of intermediate [1,1-bis(4-fluorobenzene)-2-(2-ethynylphenyl)ethylene]

[0045]

[0046] Under an argon atmosphere, 1,1-bis(4-fluorobenzene)-2-(2-ethynylbenzene)ethylene (2.00 g, 5.15 mmol) and anhydrous potassium carbonate (2.13 g, 15.44 mmol) were added to a 250 mL two-necked flask, followed by methanol (30 mL) and dichloromethane (15 mL). The reaction was stopped after stirring at room temperature for 12 h. The reaction solution was concentrated by vacuum distillation, and the mixture was extracted with dichloromethane and saturated brine. The organic phase was collected, dried over anhydrous sodium sulfate, and filtered to obtain a clear liquid. The crude product was purified by silica gel column chromatography, with the eluent being a 2:1 (v / v) mixture of n-hexane and dichloromethane. The product was recrystallized from dichloromethane / n-hexane to give 1.55 g of a pale yellow solid, with a yield of 95.16%.

[0047] (4) Synthesis of the target product in Example 1

[0048]

[0049] Under an argon atmosphere, 1,1-bis(4-fluorobenzene)-2-(2-ethynylbenzene)ethylene (1.00 g, 3.16 mmol) and tetraphenylcyclopentadienone (1.82 g, 4.74 mmol) were added to a 250 mL two-necked flask, followed by the addition of diphenyl ether (10 mL). The reaction was refluxed at 180 °C for 24 h, and then cooled to room temperature. Using hexane as the eluent, the reaction mixture was passed through a Buchner funnel filled with silica gel to remove the solvent diphenyl ether. Then, using dichloromethane as the eluent, the remaining crude product was collected. The reaction mixture was concentrated by vacuum distillation, extracted with dichloromethane and saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and filtered to obtain a clear, transparent liquid. The crude product was purified by silica column chromatography, with the eluent being a mixed solution of n-hexane and dichloromethane in a volume ratio of 2:1. The product was recrystallized from dichloromethane / n-hexane to give 1.89 g of white solid, with a yield of 88.56%.

[0050] In this embodiment, the final product initially exhibits photochromic properties. Under irradiation with a 365 nm ultraviolet light source, the compound powder changes from white to pink. Heating the compound alters its photochromic properties; under irradiation with a 365 nm ultraviolet light source at 80 °C, the compound powder changes from white to yellow. Comparison photos and measured ultraviolet-visible reflectance spectra of the compound before and after heating and before and after photochromic changes are provided. Figure 1 As shown.

[0051] Example 2:

[0052] (1) Synthesis of intermediate [1,1-bis(4-chlorobenzene)-2-(2-iodophenyl)ethylene]

[0053]

[0054] Referring to step (1) of Example 1, the target product was synthesized by replacing 4,4'-difluorobenzophenone with 4,4'-dichlorobenzophenone, with a yield of 65.43%.

[0055] (2) Synthesis of intermediate [1,1-bis(4-chlorobenzene)-2-(2-trimethylsilylethynylphenyl)ethylene]

[0056]

[0057] Referring to step (2) of Example 1, the target product was synthesized by replacing 1,1-di(4-chlorobenzene)-2-(2-iodophenyl)ethylene with 1,1-di(4-fluorobenzene)-2-(2-iodophenyl)ethylene, with a yield of 76.82%.

[0058] (3) Synthesis of intermediate [1,1-bis(4-chlorobenzene)-2-(2-ethynylphenyl)ethylene]

[0059]

[0060] Referring to step (3) of Example 1, the target product was synthesized by replacing 1,1-bis(4-chlorobenzene)-2-(2-trimethylsilylethynylbenzene)ethylene with 1,1-bis(4-fluorobenzene)-2-(2-trimethylsilylethynylbenzene)ethylene, with a yield of 93.49%.

[0061] (4) Synthesis of the target product in Example 2

[0062]

[0063] Referring to step (4) of Example 1, the target product was synthesized by replacing 1,1-bis(4-chlorobenzene)-2-(2-ethynylbenzene)ethylene with 1,1-bis(4-fluorobenzene)-2-(2-ethynylbenzene)ethylene, with a yield of 84.63%.

[0064] In this embodiment, the final product initially exhibits photochromic properties. Under irradiation with a 365 nm ultraviolet light source, the compound powder changes from white to pink. Heating the compound alters its photochromic properties; under irradiation with a 365 nm ultraviolet light source at 80 °C, the compound powder changes from white to yellow. Comparison photos and measured ultraviolet-visible reflectance spectra of the compound before and after heating and before and after photochromic changes are provided. Figure 2 As shown.

[0065] The trends of the maximum reflection wavelength of the photochromic products in Examples 1 and 2 as a function of temperature are as follows: Figure 3 As shown.

[0066] Example 3:

[0067] (1) Synthesis of intermediate [1,1-bis(4-bromophenyl)-2-(2-iodophenyl)ethylene]

[0068]

[0069] Referring to step (1) of Example 1, the target product was synthesized by replacing 4,4'-difluorobenzophenone with 4,4'-dibromobenzophenone, with a yield of 67.80%.

[0070] (2) Synthesis of intermediate [1,1-bis(4-bromophenyl)-2-(2-trimethylsilylethynylphenyl)ethylene]

[0071]

[0072] Referring to step (2) of Example 1, the target product was synthesized by replacing 1,1-di(4-bromobenzene)-2-(2-iodobenzene)ethylene with 1,1-di(4-fluorobenzene)-2-(2-iodobenzene)ethylene, with a yield of 80.23%.

[0073] (3) Synthesis of intermediate [1,1-bis(4-bromophenyl)-2-(2-ethynylphenyl)ethylene]

[0074]

[0075] Referring to step (3) of Example 1, the target product was synthesized by replacing 1,1-di(4-bromobenzene)-2-(2-trimethylsilylethynylbenzene)ethylene with 1,1-di(4-fluorobenzene)-2-(2-trimethylsilylethynylbenzene)ethylene, with a yield of 94.87%.

[0076] (4) Synthesis of the target product in Example 3

[0077]

[0078] Referring to step (4) of Example 1, the target product was synthesized by replacing 1,1-bis(4-fluorobenzene)-2-(2-ethynylbenzene)ethylene with 1,1-bis(4-fluorobenzene)-2-(2-ethynylbenzene)ethylene, with a yield of 89.93%.

[0079] Example 4:

[0080] (1) Synthesis of intermediate [1,1-bis(4-fluorophenyl)-2-(2-bromophenyl)ethylene]

[0081]

[0082] Following step (1) of Example 1, the target product was synthesized by replacing 2-iodobenzyl bromide with 2-bromobenzyl bromide, with a yield of 61.15%.

[0083] (2) Synthesis of intermediate [1,1-bis(4-fluorobenzene)-2-(2-boronate phenyl)ethylene]

[0084]

[0085] Under an argon atmosphere, 1,1-bis(4-fluorobenzene)-2-(2-bromobenzene)ethylene (3.00 g, 8.08 mmol), pinacol diborate (3.08 g, 12.12 mmol), potassium acetate (2.38 g, 24.24 mmol), and the catalyst 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride (0.05 g, 0.07 mmol) were added to a 250 mL two-necked flask. Then, 1,4-dioxane (40 mL) was added, and the reaction was stopped after reflux at 85 °C for 24 h. The reaction solution was concentrated by vacuum distillation, extracted with dichloromethane and saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and filtered to obtain a clear liquid. The crude product was purified by silica column chromatography, with hexane as the eluent. The product was recrystallized from dichloromethane / hexane to give 1.82 g of white solid, with a yield of 53.81%.

[0086] (3) Synthesis of the target product in Example 4

[0087]

[0088] Under an argon atmosphere, 1,1-bis(4-fluorobenzene)-2-(2-boronate-phenyl)ethylene (1.8 g, 4.30 mmol), 1-iodo,2-trimethylsilyl,(3,4,5,6-tetraphenyl)benzene (3.00 g, 5.16 mmol), potassium carbonate (1.78 g, 12.91 mmol), deionized water (2 mL), and the catalyst tetraphenylphosphine palladium (0.05 g, 0.07 mmol) were added to a 250 mL two-necked flask. Then, tetrahydrofuran (40 mL) was added, and the reaction was stopped after reflux at 85 °C for 24 h. The reaction solution was concentrated by vacuum distillation, extracted with dichloromethane and saturated brine, and the organic phase was collected, dried over anhydrous sodium sulfate, and filtered to obtain a clear, transparent liquid. The crude product was purified by silica column chromatography with hexane as the eluent. The product was recrystallized from dichloromethane / hexane to give 1.72 g of white solid, with a yield of 53.56%.

[0089] Table 1. Maximum fluorescence emission wavelength and maximum UV-Vis reflection wavelength at 25 °C and 80 °C of the final product solids in Examples 1-4

[0090]

[0091] Note: The emission spectrum of the solid was measured using a Marine Optics QE65PRO spectrometer in conjunction with a Marine Optics R600-125F reflection probe.

[0092] To highlight the advantages of the product of this invention, the properties of similar products under the same technology are compared. The structures of Comparative Examples 1-4 are shown below, and the relevant parameters are shown in Table 2.

[0093]

[0094] Table 2. Maximum fluorescence emission wavelength, maximum UV-Vis reflection wavelength at 25 °C, physical state at 80 °C, and maximum UV-Vis reflection wavelength of the final solid products of Examples 1 and Comparative Examples 1-4.

[0095]

[0096] As shown in Table 2, the product of this invention possesses unique photothermal dual-logic-gated photochromic properties. Other similar products do not possess this property.

[0097] In summary, this invention relates to a photothermal dual-logic-gated tricresyl-based photochromic material, which possesses advantages such as photothermal dual-logic gates, fast photochromic response speed, and high photochromic saturation absorbance. It can be applied to the preparation of multi-layer anti-counterfeiting and encryption, complex logic gates, molecular optical switches, decoration, and optical information storage. Those skilled in the art can make various corresponding changes and modifications based on the technical solutions and concepts of this invention, and all such changes and modifications should fall within the protection scope of the claims of this invention.

Claims

1. A photothermal dual-logic gated tricrylamide-based photochromic material, characterized in that... The general molecular formula is: R1 and R2 may be the same or different, and are selected from halogens; The R0 mentioned above is selected from the following structures: R3 is selected from hydrogen or trimethylsilyl; R4, R5, R6, and R7 are all selected from hydrogen.

2. A method for synthesizing the photothermal dual-logic gated styrene-based photochromic material as described in claim 1, characterized in that: The photothermal dual-logic gated tristyrene photochromic materials were obtained by reacting a compound containing tetraphenylcyclopentadienone with a tristyrene derivative containing an alkynyl group at one end under reflux using the Diels-Alder reaction.

3. The method for synthesizing the photothermal dual-logic gated styrene-based photochromic material according to claim 2, characterized in that: The heating and reflux process involves heating and refluxing at 180°C for 24 hours to obtain a photothermal dual-logic-gated tristyrene-based photochromic material.

4. A method for synthesizing the photothermal dual-logic gated styrene-based photochromic material as described in claim 1, characterized in that: By employing the Suzuki coupling reaction, a halogen-containing tetraphenylbenzene compound and a triphenylphenyl derivative containing a boron aromatic ring or aromatic heterocyclic substituent at one end are combined to obtain photothermal dual-logic-gated triphenylphenyl photochromic materials.

5. The method for synthesizing the photothermal dual-logic gated styrene-based photochromic material according to claim 4, characterized in that: The Suzuki coupling reaction is carried out in an alkaline environment with a palladium catalyst.

6. An application of the photothermal dual-logic gated tristyrene-based photochromic material as described in claim 1, characterized in that: It is used to manufacture multi-layer anti-counterfeiting products, optical information storage products, decorative products, and bio-imaging products.

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