Macrocyclic hybrid elastomer material, preparation method and reversible switching method

Abstract

The invention belongs to the technical field of stimuli-responsive color-changing materials, and particularly relates to a macrocyclic hybrid elastomer material as well as a preparation method and a reversible switching method thereof. According to the invention, a functionalized macrocyclic compound is doped into an aminated polyurethane matrix to prepare the macrocyclic hybrid elastomer. According to the design, the problem of fluorescence quenching in a macrocyclic compound powder state is effectively solved, so that the macrocyclic compound realizes fluorescence'opening 'in a matrix, and meanwhile, the inherent ring stress dependence reversible photoluminescence characteristic in a macrocyclic compound solution is completely reserved. In addition, the substrate endows the film with good flexibility, elasticity and remoldability, and the micro-scale elastic characteristic of the film realizes the reversible near-infrared light-emitting switch function of methanol response. The prepared elastomer film has multiple advantages of an optical switch, methanol response, near-infrared luminescence, flexibility, elasticity, reusability and the like, can be applied to the fields of methanol identification, information encryption, anti-counterfeiting, reusable labels and the like, and provides an innovative design strategy for constructing a multi-stimulus fluorescent elastomer.

Description

Technical Field

[0001] This invention belongs to the field of stimulus-responsive color-changing materials technology, specifically relating to a macrocyclic hybrid elastomer material, its preparation method, and a reversible switching method. Background Technology

[0002] Stimulus-induced color-changing materials (SCMs) exhibit significant color or luminescence changes in response to external stimuli, attracting considerable attention due to their immense potential in fields such as color-changing fabrics, anti-counterfeiting, data recording, information security, camouflage, sensors, and smart windows. Stimulus-induced functional materials are typically prepared by introducing stimulus-responsive functional groups or molecular stacks into the material via covalent or non-covalent bonds. Most SCMs are single-stimulus responsive materials, making the achievement of multi-stimulus responses in a single system extremely challenging. In recent years, significant progress has been made in multi-stimulus responsive advanced materials, greatly promoting their application in the aforementioned fields. Furthermore, among stimulus-responsive materials, stimulus-responsive fluorescent materials (SFCMs) with controllable luminescence properties have garnered significant attention due to their advantages, including being invisible under sunlight, exhibiting high sensitivity, direct visual visibility, and high information confidentiality.

[0003] However, the application of SFCMs is still limited to aggregated, highly luminescent chromophores, as they are typically used in solid or aggregated states. The application of traditional chromophores, which exhibit high luminescence in solution but are susceptible to aggregation quenching (ACQ), in stimulated fluorescence materials is severely restricted. In recent years, organic light-emitting macrocyclic compounds have been widely used in SFCMs due to their unique host-guest interactions, guest-modulated luminescence properties, and strain dependence. Unique strain-dependent stimulated fluorescence behavior can be achieved through tunable ring stress induced by ring binding.

[0004] Currently, existing macrocyclic compound materials are limited to solid-state high-luminescence macrocyclic compounds in powder form, and the stimulating factors are limited to solvents, mechanical forces, temperature and guest molecules, making it difficult to achieve efficient solid-state fluorescence modulation and multi-stimulus response fluorescence mutagenesis. Summary of the Invention

[0005] To address the aforementioned issues, this invention provides a macrocyclic hybrid elastomer material, its preparation method, and a reversible switching method. Using hydrogen bonding as a connecting bridge, a carboxyl-functionalized macrocyclic compound containing PDI photoelectric units and photo-switching diarylethene (DTE) units is precisely incorporated into an amino polyurethane (PU-NH2) system. This enables fluorescence "on" within the PU-NH2 matrix while fully preserving the inherent ring stress-dependent reversible photofluorescence properties of the macrocyclic compound solution, achieving precise construction of a multi-stimulus responsive fluorescent elastomer. Furthermore, the polyurethane matrix endows the film with excellent flexibility, elasticity, and reshapeability, and its microscale elastic properties enable a methanol-responsive reversible near-infrared emission switching function.

[0006] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0007] The first objective of this invention is to provide a macrocyclic hybrid elastomer material comprising a functionalized polyurethane matrix with free amine groups on its side chains or chain ends, and a carboxyl-functionalized conjugated opto-macrocyclic material doped into the matrix via hydrogen bonds and / or covalent bonds as connecting bridges, wherein the carboxyl-functionalized conjugated opto-macrocyclic material has the following general structural formula: ; Wherein, R is -(CH2)6COOCH3.

[0008] Furthermore, the doping amount of the carboxyl-functionalized conjugated optoelectronic macrocyclic material is 1 wt.% to 5 wt.% of the matrix.

[0009] Furthermore, a method for preparing a functionalized polyurethane matrix with free amine groups on the side chains or chain ends includes the following steps: S1. Using functional monomers ID, polytetramethylene ether glycol and dicyclohexylmethane diisocyanate as raw materials, a polymerization reaction is carried out in a catalyst and solvent system to obtain polyurethane containing imine bonds.

[0010] S2. Using polyurethane containing imine bonds and n-butylamine as raw materials, an ammonolysis reaction is carried out to obtain functionalized polyurethane with free amine groups on the side chain or chain end.

[0011] The structure of the functional unit ID is shown below: .

[0012] Furthermore, the molar ratio of polytetramethylene ether glycol to functional monomer ID is 1:1, the amount of dicyclohexylmethane diisocyanate is the sum of the molar amounts of polytetramethylene ether glycol and functional monomer ID, the molar ratio of catalyst to polytetramethylene ether glycol is 1:0.03 to 0.08, the catalyst is dibutyltin dilaurate, the polymerization temperature is 70℃ to 90℃, and the time is 2h to 4h.

[0013] Furthermore, the molar ratio of polyurethane containing imine bonds to n-butylamine is 1:100. During the ammonolysis reaction, the solvent is ammonia water, the reaction temperature is 60℃~100℃, and the reaction time is 2h~4h.

[0014] Furthermore, the preparation method of carboxyl-functionalized conjugated photoelectric macrocyclic materials includes the following steps: S1. Using brominated compounds of perylene imide derivatives and 2,2'-(((perfluorocyclopent-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) as raw materials, a Suzuki coupling reaction was carried out under the action of a metal catalyst to obtain conjugated organic macrocyclic compound materials with side-chain modified groups.

[0015] S2. Under alkaline conditions, the ester groups of the conjugated organic macrocyclic compound material with side chain modification groups are hydrolyzed to obtain carboxyl-functionalized conjugated optoelectronic macrocyclic materials.

[0016] Furthermore, the molar ratio of the brominated compound of the perylene imide derivative to 2,2'-(((perfluorocyclopentan-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) is 1:1 to 1.5, the metal catalyst is a palladium catalyst, and the molar ratio of the palladium catalyst to the brominated compound of the perylene imide derivative is 0.25 to 0.35:1. The Suzuki coupling reaction is carried out at a temperature of 70°C to 90°C for a time of 36 h to 72 h.

[0017] Furthermore, the alkali is a 1M sodium hydroxide solution, the molar ratio of the conjugated organic optoelectronic macrocyclic material with side-chain modified groups to sodium hydroxide is 1:4 to 8, the hydrolysis reaction temperature is 50℃ to 70℃, and the time is 36h to 48h.

[0018] Furthermore, the structures of the brominated compounds of perylene imide derivatives are shown below: .

[0019] A second objective of this invention is to provide a method for preparing the above-mentioned macrocyclic hybrid elastomer material, comprising the following steps: Macrocyclic hybrid elastomer films were prepared by solvent casting using anhydrous THF as solvent and functionalized polyurethane matrix with free amine groups on the side chain or chain end and carboxyl-functionalized conjugated optoelectronic macrocyclic materials as raw materials.

[0020] A third objective of this invention is to provide a reversible switching method for the aforementioned macrocyclic hybrid elastomer material, characterized by comprising the following steps: Applying light with a wavelength of 300 nm to 365 nm to the macrocyclic hybrid elastomer material causes it to switch from an open-ring state to a closed-ring state, turning off near-infrared luminescence. Then, applying light with a wavelength of 450 nm to 520 nm restores it to an open-ring state, turning on near-infrared luminescence. Alternatively, immersing the macrocyclic hybrid elastomer material in a methanol solution causes it to switch from a near-infrared luminescence state to a fluorescence quenching state, turning off near-infrared luminescence. Then, heating restores it to a near-infrared luminescence state, turning on near-infrared luminescence.

[0021] Compared with the prior art, the present invention has the following advantages: The macrocyclic hybrid elastomer material provided by this invention uses hydrogen bonds and / or covalent bonds as connecting bridges to precisely incorporate carboxyl-functionalized macrocyclic compounds containing PDI photoelectric units and photo-switchable diarylethene (DTE) units into an amino polyurethane (PU-NH2) system. This yields a perylene imide (PDI) macrocyclic hybrid elastomer with photo / methanol-switchable dual on / off near-infrared luminescence characteristics, enabling fluorescence "on" in the PU-NH2 matrix while fully preserving the inherent ring stress-dependent reversible photofluorescence properties of the macrocyclic compound in solution. This achieves the precise construction of a multi-stimulus responsive fluorescent elastomer. Addressing the technical challenge of complete fluorescence quenching of high near-infrared luminescent macrocyclic compounds in solid-state conditions due to the significant aggregation-induced quenching (ACQ) effect inherent in PDI molecules, this invention effectively overcomes this light-blocking problem through the synergistic effect of the macrocyclic compound and the PU-NH2 system. This allows the ring stress-dependent reversible photofluorescence behavior in solution to be fully preserved in the elastomer film, achieving efficient regulation of fluorescence performance. In addition, the polyurethane matrix endows the film with good flexibility, elasticity and reshapeability, and its microscale elastic properties enable the methanol-responsive reversible near-infrared emission switching function.

[0022] The macrocyclic hybrid elastomer material prepared by this invention possesses excellent multi-stimulus responsive fluorescence properties, good flexibility and elasticity, and remodelability. It not only overcomes the limitations of existing ACQ-effect macrocyclic materials in achieving efficient solid-state fluorescence regulation and functional applications, but also provides a more efficient and flexible technical solution for the application of multi-stimulus responsive smart materials in detection, encryption, and other fields, pioneering the construction of multi-stimulus fluorescent elastomers based on ACQ-effect macrocyclic compounds. Specifically, it exhibits: excellent light / methanol dual-switching fluorescence performance: achieving dual regulation of near-infrared emission via light-controlled on / off and methanol-response on / off, with reversible photofluorescence behavior, high sensitivity, and strong stability; wide range of applications: relying on the above core characteristics, the prepared elastomer film has been successfully applied in multiple fields such as rapid methanol detection, information encryption, sun protection reminders, anti-counterfeiting labels, and reusable labels, demonstrating significant application value; innovative and universal strategies: the innovative design strategy proposed in this invention, based on the composite of ACQ-effect macrocyclic compounds and polyurethane systems, provides a completely new approach for the construction of multi-stimulus responsive fluorescent elastomers, possessing good technical universality and scalability. Attached Figure Description

[0023] Figure 1 These are photographs of the macrocyclic compound solid powder of the present invention under ultraviolet light irradiation, photographs of the macrocyclic hybrid elastomer film under ultraviolet light irradiation, and photographs of the macrocyclic hybrid elastomer film before and after light and methanol induction.

[0024] Figure 2 The image shows the 1H NMR characterization results of the PDI of this invention.

[0025] Figure 3 The image shows the 1H NMR characterization results of the DAE of this invention.

[0026] Figure 4 The image shows the 1H NMR characterization results of the ester-functionalized [4+4]-COOCH3 of this invention.

[0027] Figure 5 The image shows the Maldi-tof characterization results of the ester-functionalized [4+4]-COOCH3 of this invention.

[0028] Figure 6 The infrared spectra of [4+4]-COOCH3 and [4+4]-COOH are shown in this invention.

[0029] Figure 7 The UV-Vis absorption and photoluminescence spectra of the [4+4]-COOH macrocyclic compound of this invention under 365 nm and 460 nm light irradiation are shown.

[0030] Figure 8 This is a schematic diagram showing the conformational and luminescence switching of the [4+4]-COOH macrocyclic compound of the present invention.

[0031] Figure 9 This study tested the reversible cyclic switching between the "open ring" and "closed ring" conformations of the [4+4]-COOH macrocyclic compound of this invention.

[0032] Figure 10 This is a diagram illustrating the fluorescence energy transfer switching mechanism of the photochromic reaction based on diarylethylene derivatives in this invention.

[0033] Figure 11 The absorption spectra of the open-loop / closed-loop DAE and PDI of this invention, and the emission spectrum of PDI.

[0034] Figure 12 The UV-Vis absorption and photoluminescence spectra of [4+4]-COOH in pure tetrahydrofuran and a tetrahydrofuran / methanol = 1 / 1 mixed solvent are shown in the figure.

[0035] Figure 13 This is a process diagram of the macrocyclic hybrid elastomer film (o-[4+4]@PU-NH2) of the present invention.

[0036] Figure 14 The UV-Vis absorption spectra of o-[4+4]@PU-NH2 and c-[4+4]@PU-NH2 of the present invention and their optical photographs under 365nm illumination are shown.

[0037] Figure 15 This is a schematic diagram illustrating the interconversion between o-[4+4]@PU-NH2 and c-[4+4]@PU-NH2 in this invention.

[0038] Figure 16 This is a test diagram of the reversible cyclic switching between the "open-loop" and "closed-loop" states of the [4+4]@PU-NH2 of the present invention.

[0039] Figure 17 The diagram and photographs show how the [4+4]@PU-NH2 of this invention achieves pattern writing and erasure by alternating irradiation with 365nm and 460nm light and a mask.

[0040] Figure 18 The images show the UV-Vis absorption spectra of o-[4+4]@PU-NH2 before and after treatment with methanol solution, as well as photographs under 365nm irradiation.

[0041] Figure 19 The images are photographs of the [4+4]-COOH in methanol solution and during the heating process of this invention.

[0042] Figure 20 This is a test diagram of the reversible cyclic switching of o-[4+4]@PU-NH2 in methanol solution and alternating heating treatment according to the present invention.

[0043] Figure 21 This is a schematic diagram illustrating the mechanism by which o-[4+4]@PU-NH2 achieves fluorescence switching in methanol solution and under heat treatment according to the present invention.

[0044] Figure 22 The images show the o-[4+4]@PU-NH2 of the present invention after being soaked in different solvents for 30 minutes.

[0045] Figure 23 This is a schematic diagram of the internal structure of [4+4]-co-PU-NH2 of the present invention.

[0046] Figure 24 These are photographs of the [4+4]-co-PU-NH2 of the present invention before and after light and methanol induction. Detailed Implementation

[0047] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0048] Currently, existing macrocyclic compound materials are limited to solid-state high-luminescence macrocyclic compounds in powder form, and the stimulating factors are limited to solvents, mechanical forces, temperature, and guest molecules, making it difficult to achieve efficient solid-state fluorescence modulation and multi-stimulus-responsive fluorescence mutagenesis. Therefore, overcoming the ACQ effect of solid-state non-luminescent materials, introducing the stimuli-fluorescence behavior of macrocyclic compounds, and ultimately developing novel multi-stimulus-responsive macrocyclic SFCMs that transcend powder form is challenging but extremely valuable.

[0049] Based on this, the present invention provides a macrocyclic hybrid elastomer material with switchable near-infrared emission characteristics of light / methanol and its preparation method, in order to solve the technical problem of developing multi-stimulus responsive fluorescent chromogenic materials based on aggregation-induced quenching (ACQ) chromophores, as detailed below: On one hand, the present invention provides a macrocyclic hybrid elastomer material, comprising a functionalized polyurethane matrix with free amine groups on the side chains or chain ends, and a carboxyl-functionalized conjugated opto-macrocyclic material doped in the matrix via hydrogen bonds and / or covalent bonds as connecting bridges, wherein the carboxyl-functionalized conjugated opto-macrocyclic material has the following general structural formula: ; Wherein, R is -(CH2)6COOCH3.

[0050] In this invention, the carboxyl-functionalized conjugated optoelectronic macrocyclic material is a [4+4]-functionalized macrocyclic compound. Based on the isomerization of the DTE unit from an open conformation to a closed conformation, it exhibits significant photo-induced switching absorption spectrum and color change (i.e., possible photo-induced switching behavior). Its reversible photo-switching behavior demonstrates high fatigue resistance and reusability. However, the [4+4]-functionalized macrocyclic compound is prone to fluorescence quenching under stimulating factors such as methanol solvent and light. Therefore, to address the fluorescence quenching problem of the [4+4]-functionalized macrocyclic compound in powder form, this invention incorporates the [4+4]-functionalized macrocyclic compound into an amino polyurethane (PU-NH2) using hydrogen bonds as a connecting bridge. A macrocyclic hybrid elastomer film was prepared using a PU-NH2 matrix. This design effectively solved the fluorescence quenching problem of the [4+4] macrocyclic compound powder, enabling it to achieve fluorescence "on" in the PU-NH2 matrix. Simultaneously, it fully preserved the inherent ring stress-dependent reversible photofluorescence characteristics of the macrocyclic compound in solution, resulting in a perylene diimide (PDI) macrocyclic hybrid elastomer with switchable near-infrared emission characteristics (light / methanol switching). Through the synergistic effect of the macrocyclic compound and the PU-NH2 system, this light-blocking problem was effectively overcome, allowing the ring stress-dependent reversible photofluorescence behavior in solution to be fully preserved in the elastomer film, achieving efficient regulation of fluorescence performance. Furthermore, the polyurethane matrix endows the film with good flexibility, elasticity, and reshapeability, and its microscale elastic properties enable the methanol-responsive reversible near-infrared emission switching function. The prepared elastomer film has multiple advantages such as optical switching, methanol response, near-infrared luminescence, flexibility and elasticity, and reusability. It can be applied to methanol identification, information encryption, anti-counterfeiting and reusable labels, and provides an innovative design strategy for constructing multi-stimulation fluorescent elastomers.

[0051] In some embodiments, the doping amount of the carboxyl-functionalized conjugated optoelectronic macrocyclic material is 1 wt.% to 5 wt.% of the matrix. In this invention, excessive doping of the carboxyl-functionalized conjugated optoelectronic macrocyclic material can easily lead to: 1. Exacerbated fluorescence quenching (ACQ effect recurrence). The macrocyclic material itself contains large conjugated planar structures such as PDI, which are prone to π–π stacking. Excessive doping leads to excessive aggregation of macrocyclic molecules in the polymer matrix, resulting in excessively strong intermolecular interactions and significant fluorescence quenching, causing a decrease in near-infrared luminescence intensity, a decrease in optical switching contrast (ON / OFF ratio), and a decrease in fluorescence response sensitivity. 2. Deterioration of elastomer mechanical properties. The macrocyclic material itself is a rigid, hydrophobic molecule with limited compatibility with the flexible polyurethane matrix. Excessive doping can easily lead to phase separation, micro-agglomeration, pores, and defects, resulting in decreased tensile strength, reduced toughness, reduced elastic recovery rate, and brittle and cracked films.

[0052] In some embodiments, a method for preparing a functionalized polyurethane matrix with free amine groups on the side chains or chain ends includes the following steps: S1. Using functional monomers ID, polytetramethylene ether glycol and dicyclohexylmethane diisocyanate as raw materials, a polymerization reaction is carried out in a catalyst and solvent system to obtain polyurethane containing imine bonds.

[0053] In this invention, a one-step method is used to synthesize polyurethane containing imine bonds. Polytetramethylene ether glycol (PTMG) is used as the soft segment, and dicyclohexylmethane diisocyanate (HMDI) and a synthesized monomer (ID) with a conjugated structure are used as the hard segment. Polymerization yields the polyurethane containing imine bonds. The conjugated monomer facilitates the subsequent release of free amino groups. This structure can first protect the amino groups, allowing them to polymerize with other functional monomers to form a polymer. Subsequently, a simple ammonolysis reaction can release the free amino groups. The amino groups can form hydrogen bonds with the fluorine and carboxyl groups in the macrocycle, thereby improving the dispersibility of the macrocycle in the polymer.

[0054] The molar ratio of polytetramethylene ether glycol to functional monomer ID is 1:1, the amount of dicyclohexylmethane diisocyanate is the sum of the molar amounts of polytetramethylene ether glycol and functional monomer ID, the molar ratio of catalyst to polytetramethylene ether glycol is 1:0.03 to 0.08, the catalyst is dibutyltin dilaurate, the polymerization temperature is 70℃ to 90℃, and the time is 2h to 4h.

[0055] S2. Using polyurethane containing imine bonds and excess n-butylamine as raw materials, an ammonolysis reaction is carried out to obtain functionalized polyurethane with free amine groups on the side chains or chain ends.

[0056] In this invention, during the ammonolysis reaction, the imine bonds in the polyurethane side chains break, releasing free amine groups. These amine groups can form hydrogen bonds with the fluorine and carboxyl groups in the macrocycle, resulting in good dispersibility of the macrocycle in the polymer. The free amine groups inhibit macrocycle aggregation through hydrogen bonding, resolving ACQ hydrogen bonds and allowing the macrocycle to be uniformly dispersed in the polyurethane, thus preserving the photo-switching, near-infrared luminescence, and methanol response. Furthermore, the released free amine groups can undergo amidation with the -COOH group on the [4+4] ring to form an amide bond -CONH-, achieving covalent doping of the macrocycle.

[0057] The molar ratio of polyurethane containing imine bonds to n-butylamine is 1:100. During the ammonolysis reaction, the solvent is ammonia water, the reaction temperature is 60℃~100℃, and the reaction time is 2h~4h.

[0058] The structure of the functional unit ID is shown below: .

[0059] In some embodiments, the method for preparing a functional monomer ID includes the following steps: Using benzaldehyde and 2-amino-1,3-propanediol as starting materials, a Mannich reaction was carried out in a solvent under a protective gas atmosphere to obtain the functional monomer ID. The synthetic route is as follows: .

[0060] In some embodiments, the preparation method of carboxyl-functionalized conjugated optoelectronic macrocyclic materials includes the following steps: S1. Using a brominated compound of perylene imide derivative and 2,2'-(((perfluorocyclopentan-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) as starting materials, a Suzuki coupling reaction was carried out under the action of a metal catalyst to obtain a conjugated organomacyclic compound with a side-chain modified group. The synthetic route is as follows:

[0061] .

[0062] The molar ratio of the brominated compound of the perylene imide derivative to 2,2'-(((perfluorocyclopentan-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) was 1:1 to 1.5. The metal catalyst was a palladium catalyst, and the molar ratio of the palladium catalyst to the brominated compound of the perylene imide derivative was 0.25 to 0.35:1. The Suzuki coupling reaction was carried out at a temperature of 70℃ to 90℃ for 36 h to 72 h.

[0063] S2. Under alkaline conditions, the ester groups of conjugated organic macrocyclic compounds with side-chain modified groups are hydrolyzed to obtain carboxyl-functionalized conjugated optoelectronic macrocyclic materials. The synthetic route is as follows:

[0064] .

[0065] The alkali is a 1M sodium hydroxide solution, the molar ratio of the conjugated organic optoelectronic macrocyclic material with side-chain modified groups to sodium hydroxide is 1:4 to 8, the hydrolysis reaction temperature is 50℃ to 70℃, and the time is 36h to 48h.

[0066] In some embodiments, the structures of the brominated compounds of perylene imide derivatives are shown below: .

[0067] In some embodiments, a method for preparing brominated compounds of perylene imide derivatives includes the following steps: Using 1,7-dibromo-3,4,9,10-perylenetetracarboxylic dianhydride and methyl 7-aminoheptanoate hydrochloride as starting materials, an alkylation modification reaction was carried out under a Lewis acid catalyst and a protective gas atmosphere to obtain brominated perylene imide derivatives. The synthetic reaction formula is shown below:

[0068] .

[0069] The molar ratio of 1,7-dibromo-3,4,9,10-perylenetetracarboxylic dianhydride to methyl 7-aminoheptanoate hydrochloride was 1:2–3. The molar ratio of Lewis acid catalyst to 1,7-dibromo-3,4,9,10-perylenetetracarboxylic dianhydride was 0.045–0.05:1. The Lewis acid catalyst was zinc acetate. The alkylation modification reaction was carried out at 120–180℃ for 6–10 h. During the alkylation modification reaction, quinoline was used as the reaction solvent. Sodium carbonate, a strong base-weak acid salt, was added to neutralize the hydrogen ions generated by methyl 7-aminoheptanoate hydrochloride during the reaction, ensuring the smooth progress of the reaction. The molar ratio of sodium carbonate to 1,7-dibromo-3,4,9,10-perylenetetracarboxylic dianhydride was 1–1.5:1.

[0070] In some embodiments, the preparation method of 2,2'-(((perfluorocyclopent-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) includes the following steps: Starting with 3,3'-(perfluorocyclopentan-1-en-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) and pinacol diboronate, a Suzuki-Miyaura coupling reaction was carried out under a metal catalyst to yield 2,2'-(((perfluorocyclopentan-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane). The synthetic reaction formula is shown below:

[0071] .

[0072] The molar ratio of 3,3'-(perfluorocyclopentan-1-en-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) to pinacol diborate was 1:2–4, the molar ratio of the metal catalyst to 3,3'-(perfluorocyclopentan-1-en-1,2-diyl)bis(5-(4-bromophenyl)-2-methylthiophene) was 1–2:10, the metal catalyst was palladium, and the Suzuki–Miyaura coupling reaction was carried out at 90–110 °C for 8–16 h. Toluene was used as the reaction solvent in the Suzuki–Miyaura coupling reaction; potassium acetate, an inorganic base, was also added to activate the palladium catalyst, and the molar ratio of potassium acetate to pinacol diborate was 2:1.

[0073] On the other hand, the present invention also provides a method for preparing the above-mentioned macrocyclic hybrid elastomer material, comprising the following steps: Macrocyclic hybrid elastomer films were prepared by solvent casting using anhydrous tetrahydrofuran as solvent and functionalized polyurethane matrix with free amine groups on the side chain or chain end and carboxyl-functionalized conjugated optoelectronic macrocyclic materials as raw materials.

[0074] In this invention, anhydrous tetrahydrofuran (THF) is added to the PU-NH2 matrix and the [4+4] macrocyclic compound, and the mixture is stirred at room temperature until PU-NH2 and the [4+4] macrocyclic compound form a mixed solution. The solvent is slowly evaporated at room temperature, and a film is formed naturally. After vacuum drying, a macrocyclic hybrid elastomer film is obtained. Alternatively, ethyl dimethylaminopropylcarbodiimide (EDC), 4-dimethylaminopyridine (DMAP) and THF are added to the PU-NH2 matrix and the [4+4] macrocyclic compound, and the mixture is stirred at room temperature to form a mixed solution. Then, PU-NH2 is added to carry out an amidation reaction, and a film is formed naturally. After vacuum drying, a macrocyclic hybrid elastomer film is obtained.

[0075] Furthermore, the present invention also provides a method for optically reversible switching of the above-mentioned macrocyclic hybrid elastomer material, comprising the following steps: Applying light with a wavelength of 300 nm to 365 nm to the macrocyclic hybrid elastomer material causes it to switch from an open-ring state to a closed-ring state, turning off near-infrared emission. Then, applying light with a wavelength of 450 nm to 520 nm restores it to an open-ring state, turning on near-infrared emission.

[0076] Furthermore, the present invention also provides a method for reversibly switching the methanol solvent of the above-mentioned macrocyclic hybrid elastomer material, comprising the following steps: The macrocyclic hybrid elastomer material is immersed in a methanol solution to switch it from a near-infrared luminescent state to a fluorescence quenched state, thus turning off near-infrared luminescence. Then, it is heated to restore the near-infrared luminescent state and turn on near-infrared luminescence.

[0077] like Figure 1As shown in the photographs of the powdered macrocyclic compound under ultraviolet light and the macrocyclic hybrid elastomer film under ultraviolet light, it is evident that doping the macrocyclic compound with the ACQ effect into the polymer matrix suppresses ACQ, thus enabling the application of the ACQ-effect macrocyclic compound in the solid state. Based on this, this invention, through the synergistic effect of the [4+4] macrocyclic compound and the PU-NH2 matrix, fully preserves the reversible photofluorescence behavior in the elastomer film under methanol solution or light irradiation, achieving efficient regulation of fluorescence performance. It realizes dual regulation of near-infrared luminescence on / off and methanol response on / off, and the photofluorescence behavior is reversible, highly responsive, and stable. The prepared elastomer film possesses multiple advantages, including photo-switching, methanol response, near-infrared luminescence, flexibility, and reusability. This not only overcomes the limitations of existing technologies but also provides more efficient and flexible technical solutions for methanol identification, information encryption, anti-counterfeiting, and reusable labels.

[0078] The following specific examples will provide further explanation.

[0079] Example 1 A macrocyclic hybrid elastomer material comprises a functionalized polyurethane (PU-NH2) matrix with free amine groups, and a carboxyl-functionalized conjugated optoelectronic macrocyclic material ([4+4] macrocyclic compound) doped into the matrix via hydrogen bonds as a connecting bridge, wherein the doping amount of the [4+4] macrocyclic compound is 5 wt.% of PU-NH2. The carboxyl-functionalized conjugated optoelectronic macrocyclic material has the following general structural formula:

[0080] .

[0081] Wherein, R is -(CH2)6COOCH3.

[0082] The preparation method of the above-mentioned macrocyclic hybrid elastomer material includes the following steps: Preparation of brominated compounds of perylene imide derivatives: 1,7-dibromopyrene-3,4,9,10-tetracarboxylic dianhydride (0.2203 g, 0.4 mmol), methyl 7-aminoheptanoate hydrochloride (0.1672 g, 1.05 mmol), zinc acetate (0.0040 g, 0.018 mmol), inorganic base Na₂CO₃ (0.1145 g, 1.05 mmol), and quinoline (4 mL) were weighed and placed in a reaction flask. The mixture was reacted at 140 °C for 24 hours under nitrogen protection and then cooled to room temperature. The reaction was terminated with 20 mL of H₂O and 30 mL of methanol. The precipitate was collected by vacuum filtration and washed with a methanol-water mixture. The crude product was dried at 100℃ for 12 hours and further purified by silica gel column chromatography (eluent: EA / DCM = 3:100, v / v) to obtain a red powder product PDI (0.1826 g, 55%). The 1H NMR spectrum is shown below. Figure 2 As shown. Its synthetic route is as follows:

[0083] .

[0084] Preparation of S2, 2,2'-(((perfluorocyclopent-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane): Weigh the reactant 3,3'-(perfluorocyclopent-1-en-1,2-diyl)bis(5-(3-bromophenyl)-2-methylthiophene) (1.3211 g, 1.95 mmol), and the reaction mixture... Pinacol boronic acid ester (1.2383 g, 4.88 mmol), catalyst PdCl2(dppf)·CH2Cl2 (0.1597 g, 0.195 mmol), inorganic potassium acetate KOAc (0.9555 g, 9.75 mmol), and 40 mL of toluene were placed in a reaction flask and subjected to a Suzuki-Miyaura coupling reaction under nitrogen protection at 90 °C for 24 hours. After the reaction was completed, the solvent was removed under reduced pressure, and the crude product was purified by silica gel column chromatography using a gradient elution of petroleum ether:dichloromethane = 2:1 to 1:2 to obtain a white powder, namely 2,2'-(((perfluorocyclopentan-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane), named DAE (yield 85%). 1H NMR spectrum as follows Figure 3 As shown. Its synthetic route is as follows:

[0085] .

[0086] Preparation of S3, Conjugated Organic Macrocyclic Compound Material with Side-Chain Modification: Under a nitrogen atmosphere, reactants PDI (0.2 mmol), DAE (0.2 mmol), catalyst Pd(PPh3)4 (0.056 mmol), and inorganic base K2CO3 (4 mmol) were suspended in a mixed solvent of 216 mL tetrahydrofuran and 43.2 mL deionized water. The reaction mixture was stirred at 80 °C for 48 hours to carry out Suzuki coupling reaction. After the reaction was completed, 100 mL of water was added to quench the reaction, and the organic phase was extracted with dichloromethane (100 mL × 3), then washed three times with deionized water (50 mL × 3), and the organic phase was dried with anhydrous sodium sulfate. The crude product was purified by silica gel column chromatography, eluting with a gradient of dichloromethane:ethyl acetate = 50:1 to 20:1 (volume ratio), to obtain a reddish-brown powder, which was the macrocyclic compound material with side-chain modification, named [4+4]-COOCH3 (yield 1%). The 1H NMR spectrum is shown below. Figure 4 As shown, Maldi-tof characterization is as follows: Figure 5 As shown. Its synthetic route is as follows:

[0087] .

[0088] S4. Preparation of carboxyl-functionalized conjugated photoelectric macrocyclic materials: [4+4]-COOCH3 (0.1 mmol), 8 mL of tetrahydrofuran solvent, and 8 mL of 1 M sodium hydroxide solution were added to a 50 mL capped glass bottle. The reaction was carried out at 60 °C with stirring for 48 hours. After the reaction was completed, the mixture was cooled to room temperature, and 7-9 mL of 2 M hydrochloric acid solution was added to neutralize the unreacted sodium hydroxide. Subsequently, 8 mL of deionized water was added to precipitate the product, and the reddish-brown powder [4+4]-COOH (yield 95%) was obtained by vacuum filtration. The infrared spectrum is shown below. Figure 6 As shown. Its synthetic route is as follows:

[0089] .

[0090] S5. Preparation of the conjugated functional monomer ID: 0.1 mol of benzaldehyde and 0.11 mol of 2-amino-1,3-propanediol were dissolved in 50 mL of ethanol and refluxed at 60 °C for 12 hours under nitrogen protection to carry out the Mannich reaction. After the reaction, the product was purified by vacuum distillation. The obtained molecule was named ID (benzaldehyde derivative). Its synthetic route is as follows:

[0091] .

[0092] S6. Preparation of functionalized polyurethane with free amino groups: Polytetramethylene ether glycol (PTMG) was used as the soft segment, and dicyclohexylmethane diisocyanate (HMDI) and synthetic monomer (ID) with conjugated structure were used as the hard segment. Specifically, PTMG (1 mol), ID (1 mol), HMDI (2 mol) and the catalyst dibutyltin dilaurate (DBTDL, 0.1 mol) were weighed and placed in a reaction flask. 80 mL of anhydrous N,N-dimethylformamide (DMF) was added. The reaction was carried out at 80 °C for 3 hours under nitrogen protection. The solvent was removed by vacuum distillation of the reaction product, and then the product was dried under vacuum at 80 °C for 24 hours to obtain polyurethane (PU) containing imine bonds. Subsequently, polyurethane (PU) containing imine bonds and excess n-butylamine were reacted and heated (reaction temperature: 80℃, reaction time: 3h) to trigger the cleavage of imine bonds in the side chains of the polyurethane (PU), resulting in an ammonolysis reaction that released free amino groups. The reaction product was then subjected to vacuum distillation to remove the solvent, followed by vacuum drying at 80℃ for 24 hours to obtain an amino-containing polyurethane material (PU-NH2). The synthetic route is as follows:

[0093] .

[0094] S7. Preparation of macrocyclic hybrid elastomer film [4+4]@PU-NH2: Accurately weigh 100 mg of PU-NH2 matrix polymer and 5 mg of dopant component [4+4]-COOH, and add them together to a clean 3 cm diameter polytetrafluoroethylene (PTFE) petri dish; then slowly add 15 mL of anhydrous tetrahydrofuran (THF, purity ≥99.9%) as solvent to the petri dish, place the petri dish on a magnetic stirrer, and stir at 300 r / min at room temperature for 1 h until PU-NH2 and [4+4]-COOH are completely dissolved, forming a homogeneous, transparent mixed solution without obvious particulate impurities. After stirring, place the petri dish in a fume hood to allow the solvent to evaporate slowly at room temperature (evaporation time is about 24 h), allowing the mixed solution to form a film naturally at the bottom of the petri dish. After the solvent has mostly evaporated, the resulting preliminary film, along with the culture dish, is placed in a vacuum drying oven and dried at 60℃ and -0.09MPa for 24 hours to completely remove any residual trace solvent from the film, ultimately yielding a uniform [4+4]@PU-NH2 film with a smooth surface. The preparation route is as follows:

[0095] The macrocyclic compound [4+4]-COOH prepared in Example 1 and the macrocyclic hybrid elastomer film material [4+4]@PU-NH2 were studied. The specific research methods and results are shown below: 1. Study on the properties of [4+4]-COOH macrocyclic compounds in solution: The reversible photochromic behavior of the macrocyclic compound was evaluated in THF solution. Figure 7 The diagram shows the reversible photochromic behavior of the 4+4]-COOH macrocyclic compound of this invention after light irradiation, as shown below. Figure 7 As shown, after irradiation with 365 nm light, the [4+4]-COOH macrocyclic compound solution (concentration 1×10⁻⁶) -5 M) exhibits a significant photoinduced switching absorption spectrum and color change (from red to deep purple). Figure 8 This is a schematic diagram illustrating the conformational and luminescence switching of the [4+4]-COOH macrocyclic compound of the present invention, as shown below. Figure 8 As shown, these photo-induced switching behaviors originate from the isomerization of DTE units from open to closed conformations. Figure 9 This is a test diagram showing the reversible cyclic switching between the "open ring" and "closed ring" conformations of the [4+4]-COOH macrocyclic compound of this invention, as shown in the figure. Figure 9 As shown, when the [4+4]-COOH macrocyclic compound is exposed to 365 nm light to its static state (PSS365 state), its solution color and absorption spectrum can be restored to their original state when exposed to 460 nm visible light, indicating that the DTE closed-ring conformation was successfully reversed to the open-ring state. This reversible light-switching behavior can be repeated. After 10 open-ring / closed-ring cycles, no significant change was observed in the characteristic absorption peaks of 650 nm to 800 nm, indicating that it has high fatigue resistance and reusability.

[0096] At the same time, such as Figure 7 As shown, opto-switchable near-infrared emission was observed in the [4+4] macrocyclic compound, with a mode matching the opto-switchable absorption. Specifically, upon reaching the PSS365 state, the [4+4] macrocyclic compound with bright near-infrared fluorescence was completely quenched, exhibiting the highest fluorescence quenching efficiency, with a PL on / off ratio of approximately 7. After visible light irradiation, the emission color of the PSS365 solution could be restored to the original bright red. Similar to the opto-switchable absorption characteristics, this opto-switchable emission is reversible and reproducible. Figure 10 This is a diagram illustrating the fluorescence energy transfer switching mechanism of the photochromic reaction based on diarylethene derivatives in this invention. Figure 10 As shown, this switchable light emission is attributed to the Foster resonance energy transfer (FRET) from the PDI (energy donor) to the closed-state DAE unit (energy acceptor). Figure 11 The images show the absorption spectra of the open-ring / closed-ring DAE and PDI of this invention, as well as the emission spectrum of PDI. Figure 11As shown, the emission spectrum of PDI and the absorption spectrum of the closed-ring DAE show significant overlap, confirming the existence of an energy transfer process between PDI and the closed-ring DAE. The UV-Vis absorption and photoluminescence spectra of [4+4]-COOH in pure tetrahydrofuran and a tetrahydrofuran / methanol = 1 / 1 mixed solvent are also shown. The emission spectrum of the PDI unit and the absorption spectrum of the non-luminescent closed-ring DTE group show good overlap, indicating an effective fluorescence resonance energy transfer (FRET) process from PDI to the closed-ring DTE, accompanied by effective fluorescence quenching.

[0097] In addition, the macrocyclic compound [4+4]-COOH exhibits methanol-induced irritant coloration behavior in solution. Figure 12 The UV-Vis absorption and photoluminescence spectra of [4+4]-COOH in pure tetrahydrofuran and a tetrahydrofuran / methanol = 1 / 1 mixed solvent are shown below. Figure 12 As shown, the addition of an equal volume of methanol to a THF solution of a macrocyclic compound almost completely quenched the red fluorescence, laying the foundation for solvent-based colorimetric applications. The significant red shift in the absorption spectrum indicates that the macrocyclic compound aggregates into a PDI dimer through strong J-type π-π interactions after the addition of methanol, resulting in strong nonradiative energy dissipation and significant fluorescence quenching.

[0098] 2. Properties of [4+4]-COOH macrocyclic compounds in powder form: Figure 13 This is a diagram showing the near-infrared luminescence activity and photo-switchable fluorescence characteristics of the powdered [4+4]-COOH macrocyclic compound of this invention. Figure 13 In the diagram, 'a' represents the state after irradiation, and 'b' represents the state before irradiation. For example... Figure 13 As shown, strong π-π stacking interactions exist between PDI molecules, an inherent characteristic that leads to a significant aggregation-induced quenching (ACQ) effect in the synthesized macrocyclic compounds. This effect causes the macrocyclic compounds to completely lose their near-infrared luminescence activity and photo-switchable fluorescence properties in the solid powder state. Specifically, the [4+4]-COOH powder did not exhibit bright red fluorescence or photo-switchable fluorescence properties under 365 nm light irradiation, which limits the application of the [4+4]-COOH macrocyclic compounds in the solid state.

[0099] 3. Properties of macrocyclic hybrid elastomer films [4+4]@PU-NH2: The photochromic and methanol-induced color-changing properties of the aforementioned macrocyclic molecules are completely preserved in their polymer matrix films. This property avoids the common problem that single-molecule properties in solution are difficult to realize in the solid state, paving the way for their practical applications.

[0100] Figure 14The image shows the UV-Vis absorption spectra of o-[4+4]@PU-NH2 and c-[4+4]@PU-NH2 of this invention, and their optical photographs under 365nm illumination. Figure 14 As shown, o-[4+4]@PU-NH2 is in the open-ring state (strong red fluorescence), and c-[4+4]@PU-NH2 is in the closed-ring state (the strong red fluorescence disappears after irradiation with 365nm light). The [4+4]@PU-NH2 film exhibits significant photochromic behavior. Specifically, after irradiation with ultraviolet light, the film's bright near-infrared fluorescence is highly quenched, and a new absorption band appears in the 650nm–750nm range, corresponding to the closed-ring DTE state. When irradiated with 460nm light, the film can completely recover to its initial state. These results are consistent with the photo-switching behavior of macrocyclic compounds in solution, indicating that macrocyclic compounds can also undergo reversible photoisomerization in solid films (e.g., ...). Figure 15 (As shown). Figure 16 This is a test diagram of the reversible cyclic switching between the "open-loop" and "closed-loop" states of the [4+4]@PU-NH2 of the present invention, as shown in the figure. Figure 16 As shown, after ten cycles, the characteristic absorption peak of the film in the 650nm-800nm ​​band did not change significantly, indicating that the solid film still has excellent fatigue resistance.

[0101] Based on the above research, macrocyclic hybrid [4+4]@PU-NH2 is used as a reusable tag. Figure 17 The diagram and photographs show how the [4+4]@PU-NH2 of this invention achieves pattern writing and erasure by alternating irradiation with 365nm and 460nm light and a mask. Figure 17 In the diagram, a represents the initial thin film, b represents 365nm illumination, c represents 460nm illumination, and d represents 365nm secondary illumination. For example... Figure 17 As shown, after being illuminated with 365nm light, the first high-resolution pattern information (pumpkin) can be easily written through a photomask, and this information can be completely erased by 460nm light. Subsequently, the erased paper can be rewritten using different photomasks, and the second pineapple pattern information can be photolithographically printed by illuminating it with 365nm light.

[0102] Figure 18 The images show the UV-Vis absorption spectra of o-[4+4]@PU-NH2 before and after treatment with methanol solution, as well as photographs under 365nm irradiation. Figure 18 As shown, the [4+4]@PU-NH2 film exhibits a significant methanol-induced color change phenomenon. Figure 19 These are photographs of the [4+4]-COOH of this invention in methanol solution and during the heat treatment process. Figure 19As shown, specifically, when the [4+4]@PU-NH2 film is immersed in methanol, its red fluorescence gradually weakens and almost completely quenches after 90 seconds of immersion. The original red fluorescence can be restored after the quenched film is heated to remove the adsorbed methanol. Figure 20 This is a test diagram of the reversible cyclic switching of o-[4+4]@PU-NH2 in methanol solution and alternating heating treatment according to the present invention. Figure 20 As shown, the film has excellent fatigue resistance and can be reused more than 500 times.

[0103] Figure 21 This is a schematic diagram illustrating the mechanism by which o-[4+4]@PU-NH2 achieves fluorescence switching in methanol solution and under heat treatment according to the present invention. Figure 21 As shown, PDI, as a chromophore forming exciton clusters, exhibits good dispersion of its groups in the initially relaxed network in the absence of methanol, resulting in monomer-dominated fluorescence. When the film is immersed in methanol, the dispersion of macrocyclic molecules in the polyurethane network is significantly reduced. Strong J-type π-π interactions between PDI units lead to the formation of micron- or nano-scale aggregates. Simultaneously, strong interactions between PDI units and polymer chains via hydrogen bonds induce deformation of the polymer chains at the microscale. Under these conditions, emission is mainly dominated by PDI excitons, exhibiting strong nonradiative energy dissipation and significant fluorescence quenching. Upon removal of methanol, the stress in the deformed polymer chains is released, restoring them to their initial state and driving the depolymerization of PDI aggregates, causing the emission mode to change from exciton emission to monomer-dominated bright red fluorescence. Figure 22 These are photographs of o-[4+4]@PU-NH2 of the present invention after being immersed in different solvents for 30 minutes, as shown. Figure 22 As shown, other commonly used solvents do not induce fluorescence quenching in this type of film, highlighting the uniqueness of the methanol-induced solvent fluorescence color change effect. Therefore, the [4+4]@PU-NH2 thin-film "indicator" shows great potential in the field of simple methanol detection.

[0104] Example 2 A method for preparing a macrocyclic covalent elastomer thin film material with switchable near-infrared emission properties (light / methanol switching) includes the following steps: S1. The preparation of carboxyl-functionalized conjugated optoelectronic macrocyclic materials is the same as in Example 1.

[0105] S2. The preparation of functionalized polyurethane with free amino groups is the same as in Example 1.

[0106] S3. Preparation method of macrocyclic covalent elastomer thin film material: Carboxyl-functionalized conjugated optoelectronic macrocyclic material (0.051 g, 0.011 mmol), ethyldimethylaminopropylcarbodiimide (0.015 g, 0.1 mmol), 4-dimethylaminopyridine (0.012 g, 0.1 mmol), and 10 mL of THF solution were added to a 50 mL glass container and stirred at room temperature for 30 minutes. Then, 20 mL of PU-NH2 stock solution (c(THF) = 0.5 g·mL⁻¹) was added. -1 An amidation reaction was carried out at room temperature for 48 hours. The precipitate was collected by vacuum filtration and washed with a mixture of methanol and water. The crude product was placed in a 3 cm diameter PTFE petri dish using 20 mL of THF as solvent. After the THF evaporated, the [4+4]-co-PU-NH2 film (5 wt%) was dried under vacuum for 24 hours. After the solvent had mostly evaporated, the resulting pre-prepared film, along with the petri dish, was placed in a vacuum drying oven and dried at 60 °C and -0.09 MPa for 24 hours to completely remove any residual trace amounts of solvent inside the film, finally yielding a uniform and smooth covalent film [4+4]-co-PU-NH2. A schematic diagram of the internal structure is shown below. Figure 23 As shown.

[0107] The macrocyclic covalently hybrid elastomer thin film material [4+4]-co-PU-NH2 prepared in Example 2 was studied, and the results showed that the characteristics of photofluorescence intensity change and methanol-induced fluorescence intensity change of the macrocyclic hybrid elastomer thin film material through covalent bonding still exist. Specifically, Figure 24 These are photographs of the [4+4]-co-PU-NH2 of the present invention before and after treatment with methanol solution, and before and after irradiation with 365nm light. Figure 24 As shown, the [4+4]-co-PU-NH2 covalent film exhibits significant photochromic behavior (from strong red fluorescence to weak red fluorescence) and significant methanol-induced color change (from strong red fluorescence to weak red fluorescence).

[0108] It should be noted that when numerical ranges are involved in this invention, it should be understood that both endpoints of each numerical range and any value between the two endpoints can be selected. Since the steps and methods used are the same as in the embodiments, preferred embodiments are described here to avoid redundancy. Although preferred embodiments of the invention have been described, those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments as well as all changes and modifications falling within the scope of this invention.

[0109] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.

Claims

1. A macrocyclic hybrid elastomer material, characterized in that, The invention comprises a functionalized polyurethane matrix with free amine groups on its side chains or chain ends, and a carboxyl-functionalized conjugated photoelectric macrocyclic material doped into the matrix via hydrogen bonds and / or covalent bonds as connecting bridges. The carboxyl-functionalized conjugated photoelectric macrocyclic material has the following general structural formula: ； Wherein, R is -(CH2)6COOCH3.

2. The macrocyclic hybrid elastomer material according to claim 1, characterized in that, The doping amount of carboxyl-functionalized conjugated optoelectronic macrocyclic materials is 1 wt.% to 5 wt.% of the matrix.

3. The macrocyclic hybrid elastomer material according to claim 1, characterized in that, A method for preparing a functionalized polyurethane matrix with free amine groups on the side chains or chain ends includes the following steps: Using functional monomer ID, polytetramethylene ether glycol and dicyclohexylmethane diisocyanate as raw materials, a polymerization reaction is carried out in a catalyst and solvent system to obtain polyurethane containing imine bonds; Using polyurethane containing imine bonds and n-butylamine as raw materials, an ammonolysis reaction is carried out to obtain functionalized polyurethane with free amine groups on the side chain or chain end. The structure of the functional unit ID is shown below: 。 4. The macrocyclic hybrid elastomer material according to claim 3, characterized in that, The molar ratio of polytetramethylene ether glycol to functional monomer ID is 1:

1. The amount of dicyclohexylmethane diisocyanate is the sum of the molar amounts of polytetramethylene ether glycol and functional monomer ID. The molar ratio of catalyst to polytetramethylene ether glycol is 1:0.03 to 0.

08. The catalyst is dibutyltin dilaurate. The polymerization temperature is 70℃ to 90℃, and the time is 2h to 4h.

5. The macrocyclic hybrid elastomer material according to claim 3, characterized in that, The molar ratio of polyurethane containing imine bonds to n-butylamine is 1:

100. During the ammonolysis reaction, the solvent is ammonia water, the reaction temperature is 60℃~100℃, and the reaction time is 2h~4h.

6. The macrocyclic hybrid elastomer material according to claim 3, characterized in that, A method for preparing carboxyl-functionalized conjugated optoelectronic macrocyclic materials includes the following steps: Using brominated compounds of perylene imide derivatives and 2,2'-(((perfluorocyclopent-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) as raw materials, a Suzuki coupling reaction was carried out under the action of a metal catalyst to obtain conjugated organic macrocyclic compound materials with side-chain modified groups; Under alkaline conditions, the ester groups of conjugated organic macrocyclic compounds with side-chain modified groups are hydrolyzed to obtain carboxyl-functionalized conjugated optoelectronic macrocyclic materials.

7. The macrocyclic hybrid elastomer material according to claim 6, characterized in that, The molar ratio of the brominated compound of perylene imide derivative to 2,2'-(((perfluorocyclopentan-1-en-1,2-diyl)bis(5-methylthiophene-4,2-diyl))bis(4,1-phenylene))bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane) was 1:1 to 1.

5. The metal catalyst was palladium catalyst, and the molar ratio of palladium catalyst to the brominated compound of perylene imide derivative was 0.25 to 0.35:

1. The Suzuki coupling reaction was carried out at a temperature of 70℃ to 90℃ for 36 h to 72 h. The alkali was a 1M sodium hydroxide solution. The molar ratio of the conjugated organic optoelectronic macrocyclic material with side-chain modified groups to sodium hydroxide was 1:4 to 8. The hydrolysis reaction was carried out at a temperature of 50℃ to 70℃ for 36 to 48 hours.

8. The macrocyclic hybrid elastomer material according to claim 6, characterized in that, The structures of brominated compounds of perylene imide derivatives are shown below: 。 9. A method for preparing a macrocyclic hybrid elastomer material according to any one of claims 1 to 8, characterized in that, Includes the following steps: Macrocyclic hybrid elastomer films were prepared by solvent casting using anhydrous tetrahydrofuran as solvent and functionalized polyurethane matrix with free amine groups on the side chain or chain end and carboxyl-functionalized conjugated optoelectronic macrocyclic materials as raw materials.

10. A reversible switching method for a macrocyclic hybrid elastomer material according to any one of claims 1 to 8, characterized in that, Includes the following steps: Applying light with a wavelength of 300 nm to 365 nm to the macrocyclic hybrid elastomer material causes it to switch from an open-ring state to a closed-ring state, turning off near-infrared luminescence. Then, applying light with a wavelength of 450 nm to 520 nm restores it to an open-ring state and turns on near-infrared luminescence. Alternatively, the macrocyclic hybrid elastomer material can be immersed in a methanol solution to switch it from a near-infrared luminescent state to a fluorescence quenching state, thus turning off near-infrared luminescence. Then, heating can restore it to a near-infrared luminescent state, thus turning on near-infrared luminescence.

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