Dopamine-type organic polymer tightly coated miche nanononlinear optical material, preparation and application thereof

Abstract

This invention relates to a dopamine-type organic polymer-coated micene nanomaterial for nonlinear optical applications, its preparation, and its application. Utilizing the self-polymerization behavior of a porphyrin-based dopamine-type compound, a few-layer micene layer is tightly "coated" with the material after being etched and peeled away with hydrofluoric acid. The dopamine-type compound spontaneously polymerizes while interacting with the micene surface, completely isolating its terminal functional groups (-OH, =O, -F) from air. Compared to existing technologies, this invention significantly improves the environmental stability of micene by functionalizing the porphyrin core polymer to adjust the surface exposure, making its broadband nonlinear optical properties more promising for practical use. This invention inspires further development of micene to obtain specific photoelectric properties and is of great significance for the widespread practical application of micene, especially as an optoelectronic device.

Description

Technical Field

[0001] This invention belongs to the field of organic-inorganic hybrid third-order nonlinear optical materials technology, and relates to a dopamine-type organic polymer tightly coated micene nano-nonlinear optical material and its preparation and application. Background Technology

[0002] Since the invention of the first laser, lasers have attracted increasing attention and have gradually become an important component of data storage and processing, optical sensors, mode-locking, optical limiting, and optical communication systems. Therefore, ultrafast optical signal processing based on nonlinear optical (NLO) materials is currently a hot research direction. Two-dimensional layered materials, possessing unique mechanical, physical, and chemical properties different from bulk materials, have become powerful candidate optical signal modulation materials to meet the miniaturization, integration, high efficiency, high performance, and multifunctionality requirements of optoelectronic devices. Examples include graphene, metal oxide hydroxides, black phosphorus, topological insulators, transition metal sulfides, and hexagonal boron nitride. However, the inherent zero-bandgap structure of graphene, the instability of black phosphorus, and the difficulty in refining the manufacturing process of transition metal sulfides have limited their practicality to some extent. Overcoming the current limitations in the manufacturing, application, and performance of two-dimensional materials is key to realizing their full potential in advanced photonics and optoelectronics applications. Developing novel and promising two-dimensional nonlinear optical materials remains a long-term goal in the optoelectronic field.

[0003] In recent years, micene, as a new member of the two-dimensional layered material system, has attracted the interest of researchers in various fields due to its excellent properties, including superior light transmittance, high elastic modulus, excellent electrical conductivity, tunable bandgap, versatility in environmental fabrication, and compatibility with organic solvents and water. However, research on the nonlinear optical applications of micene is very limited. micene is generated from the bulk MAX phase. n+1 X n T x This is the general formula for MXene, where M represents a transition metal (such as V, Nb, Ti, etc.), X represents C or N, T represents a surface terminator (hydroxyl, oxygen, or fluorine), and n can be 1, 2, or 3. The layered accordion-like two-dimensional structure of MXene can be achieved by etching the A layer (usually aluminum) with HF or HCl / LiF solution, producing excellent two-dimensional MXene. Its preparation imparts a large number of hydrophilic terminator groups, resulting in relatively weak environmental stability. According to density functional theory (DFT)-based studies, its electrical and optical properties are also significantly affected by its surface terminators. Therefore, overcoming the environmental and photoinstability of MXene is the most important problem to be solved in realizing its application in nonlinear optics. This invention is based on this premise. Summary of the Invention

[0004] The purpose of this invention is to provide a dopamine-type organic polymer-coated micene nano-nonlinear optical material, its preparation and application. By using porphyrin core polymer functionalization to adjust the surface exposure of micene, the environmental stability of micene is greatly improved, and its broadband nonlinear optical function is more promising for practical use, which inspires the possibility of further developing micene to obtain specific photoelectric properties.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] Dopamine, similar to the special adhesive proteins produced by mussels, enables mussels to firmly adhere to almost any type of surface. This is mainly due to the large number of phenol, pyrrole, and pyridine functional groups in dopamine, which allow it to undergo oxidative self-polymerization to form a robust polydopamine coating. These groups impart strong adhesion to other surfaces through reactions such as Michael addition, Schiff base formation, and single-electron radical polymerization.

[0007] Based on this, in one aspect, the present invention provides a method for preparing dopamine-type organic polymer-coated micene nano-nonlinear optical materials, comprising the following steps:

[0008] (1) Configure Mikeene Ti3C2T x Solution;

[0009] (2) After dissolving dopamine hydrochloride and dopamine-like porphyrin, the solution is transferred to the macene Ti3C2T x In the solution, the reaction is stirred, and then the reaction products are separated to obtain the target product;

[0010] The dopamine-like porphyrins are dopamine-like porphyrin Por1 and / or dopamine-like porphyrin Por2, and their chemical structural formulas are as follows:

[0011]

[0012] Furthermore, the MIC Ti3C2T x The solution can be obtained using conventional techniques in the art. Specifically, it can be synthesized using mild LiF and HCl. For example, it can be prepared according to the following references (Alhabeb, M.; Maleski, K.; Anasori, B.; Lelyukh, P.; Clark, L.; Sin, S.; Gogotsi, Y. Guidelines for synthesis and processing of two-dimensional titanium carbide (Ti3C2T). xMXene).Chem.Mater.2017,29(18),7633-7644.), the final product is obtained in the form of a colloidal dispersion and its concentration can be adjusted.

[0013] Furthermore, the molar ratio of dopamine hydrochloride to dopamine-like porphyrin is 3-5:1.

[0014] Furthermore, the MIC (Ti3C2T) x The concentration of the solution is 0.8–1.2 mg / mL, and the ratio of its concentration to the amount of dopamine hydrochloride added is 4 mL: (0.015–0.025) mmol.

[0015] Furthermore, in step (2), the stirring reaction is carried out at room temperature for 6-18 hours.

[0016] Furthermore, the dopamine-like porphyrin Por1 is prepared by the following method:

[0017] Take 5-(3,5-dimethoxyphenyl)dipyrrolemethane and di-tert-butyl dicarbonate (Diboc)-protected amino-p-benzaldehyde, which can be (4-formylphenylethyl)carbamate tert-butyl ester, and react them to give porphyrin 3. Then, porphyrin 3 is deprotected twice to give dopamine-like porphyrin Por1 with diamino and dihydroxy groups.

[0018] The synthetic route for dopamine-like porphyrin Por1 can be found below:

[0019]

[0020] Furthermore, the reagents used for the two deprotection processes of porphyrin 3 are boron tribromide and dioxane hydrochloride, respectively. More preferably, the two deprotection processes are as follows:

[0021] First unprotection process:

[0022] Boron tribromide dissolved in dichloromethane was added to the dichloromethane coolant of porphyrin 3, stirred at room temperature, and then methanol was added until the color changed from green to light red. Then, the mixture was washed, dried, and purified to obtain porphyrin 4, the structure of which is described in the above process route.

[0023] Second deprotection process:

[0024] Add HCl·dioxane solution dropwise to the porphyrin 4 dioxane solution, then stir at room temperature, extract, wash, dry, and purify to complete the process.

[0025] Furthermore, the dopamine-like porphyrin Por2 is prepared by the following method:

[0026] First, synthesize asymmetric porphyrin 8;

[0027] Suzuki-Miyaura modification was performed on the exposed meso site of asymmetric porphyrin 8 to obtain porphyrin 9 with dihydroxyl groups;

[0028] The remaining meso site of porphyrin 9 was further modified with bromine atoms and subjected to a second Suzuki-Miyaura reaction to obtain dopamine-like porphyrin Por2;

[0029] The chemical structural formula of the asymmetric porphyrin 8 is as follows:

[0030]

[0031] The chemical structural formula of porphyrin 9 is as follows:

[0032]

[0033] Here, the process for synthesizing asymmetric porphyrin 8 can be prepared according to the literature (Plater, MJ; Aiken, S.; Bourhill, GA new synthetic route to donor-acceptor porphyrins. Tetrahedron 2002, 58, 2405-2413.).

[0034] The specific synthetic route of dopamine-like porphyrin Por2 in this invention is as follows:

[0035]

[0036] Furthermore, the Suzuki-Miyaura modification process is as follows:

[0037] Weigh out asymmetric porphyrin 8 and dissolve it in anhydrous tetrahydrofuran. Add 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)benzene-1,3-diol, K3PO4, and Pd(PPh3)4. Then stir at 65-70℃ for 12-24 h under a nitrogen atmosphere. The ratio of the amount of asymmetric porphyrin 8, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)benzene-1,3-diol, K3PO4, and Pd(PPh3)4 is 410 mg: 4.6 mmol: 12.5 mmol: 7.6 mg.

[0038] Furthermore, the further modification process of porphyrin 9 is as follows:

[0039] Porphyrin 9 was dissolved in chloroform, and 4 equivalents of NBS (N-bromosuccinimide) were added. The mixture was stirred to obtain porphyrin 10.

[0040] Porphyrin 10 was dissolved in anhydrous tetrahydrofuran, tert-butyl (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)phenethyl)carbamate, K3PO4 and Pd(PPh3)4;

[0041] The ratio of added porphyrin 10, tert-butyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)phenethyl)carbamate, K3PO4 and Pd(PPh3)4 is 300mg:4.5mmol:11.1mmol:5.8g.

[0042] On the other hand, this invention provides a dopamine-type organic polymer-coated micene nanomaterial for nonlinear optical applications, prepared using any of the methods described above. During the preparation process, the porphyrin precursors Por1 and Por2 both possess dopamine-like functional groups and structures, enabling them to undergo self-polymerization, which is simple and efficient. The modified micene nanosheets exhibit excellent air / light stability; the prepared film remains stable in air for over 6 months and is undamaged after laser radiation below 200 μW, demonstrating stable properties.

[0043] During the preparation process, such as

[0044] In a third aspect, this invention provides an application of a dopamine-type organic polymer-coated micene nanomaterial for nonlinear optical applications under complex laser irradiation conditions. Specifically, it exhibits excellent third-order nonlinear optical properties under complex laser irradiation conditions (different wavelengths, different energies).

[0045] For example, the response covers different wavelength ranges of femtosecond lasers from 400 to 1550 nm; the response covers different energy ranges of femtosecond lasers from 0 to 4 mJ / cm². 2 The preferred value is not 0.

[0046] Compared with the prior art, the present invention has the following advantages:

[0047] I. The dopamine-type organic polymer tightly coated micene nanostructured nonlinear optical material prepared in this invention exhibits very high air and laser stability, which is beneficial for the practical application of the material system. Simultaneously, it demonstrates good solution and thin-film stability, exhibiting excellent broadband nonlinear optical properties under femtosecond laser irradiation at different wavelengths.

[0048] Second, the dopamine-type organic polymer tightly encapsulates the micene nano-nonlinear optical material in this invention, which has excellent third-order nonlinear optical properties and is an important candidate material for ultrafast laser signal modulation.

[0049] Third, the dopamine-type organic polymer tightly coated with micene nano-nonlinear optical film prepared in this invention can meet the requirements of complex laser applications and exhibits excellent nonlinear optical performance under laser irradiation of multiple power and multiple wavelengths, thus meeting the needs of more laser application scenarios. Attached Figure Description

[0050] Figure 1 It is the specific synthesis process of dopamine-type organic polymers;

[0051] Figure 2 This is a schematic diagram of the thin film preparation process of the dopamine-type organic polymer tightly coating the micene nano-nonlinear optical material prepared in this invention;

[0052] Figure 3 The structural characterization (infrared, X-ray diffraction and X-ray photoelectron spectroscopy) of the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in this invention is shown.

[0053] Figure 4 This is the absorption spectrum of the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in this invention;

[0054] Figure 5 The results of the Z-scan at 800 nm are for the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in this invention.

[0055] Figure 6 The results of Z-scan at 1300 nm are for the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in this invention.

[0056] Figure 7 The results are Z-scans at 1550 nm for the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in this invention. Detailed Implementation

[0057] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0058] In the following examples, tert-butyl (4-formylphenethyl)carbamate (CAS: 421551-75-9), 5-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)phenyl-1,3-diol (CAS: 1352134-72-5), and tert-butyl (4-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl)phenethyl)carbamate (CAS: 360792-43-4) were all purchased directly from the exploration platform (Titan Reagent Co., Ltd.).

[0059] Unless otherwise specified, the raw materials or processing techniques are conventional commercial products or conventional processing techniques in this field.

[0060] Example 1:

[0061] The preparation of the precursor porphyrin Por1 includes the following steps:

[0062] A solution of 3,5-dimethoxybenzaldehyde (3.0 g, 18.0 mmol) and pyrrole (50.0 mL, 720.0 mmol) was degassed by argon bubbling for 15 min, followed by the addition of trifluoroacetic acid (138.0 mL, 1.8 mmol). After 1 hour, the reaction mixture was neutralized with triethylamine (Et3N, 0.4 mL, 3.2 mmol). Unreacted pyrrole was removed by vacuum distillation, the mixture was diluted with toluene, and washed with 10% NaCl aqueous solution (2–100 mL). The organic phase was dried over MgSO4, filtered, and the solvent was removed under vacuum. Finally, the residue was separated by silica gel column chromatography, eluting with (hexane / ethyl acetate / triethylamine; 80:20:1). Target compound 1 was recrystallized from hexane / ethyl acetate at 0–8 °C, washed with hexane (100 mL), and (3.6 g) 5-(3,5-dimethoxyphenyl)dipyrrolemethane was obtained in 71% yield.

[0063] (4-Formylphenylethyl)carbamate tert-butyl ester (3.0 g, 13.8 mmol) was added to a solution of 5-(3,5-dimethoxyphenyl)dipyrrolemethane 1 (2.00 g, 13.8 mmol) in dichloromethane (2400 ml). The mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere and in the presence of trifluoroacetic acid (30 drops). The oxidant 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) (4.5 g, 19.8 mmol) was added, and the solution was stirred for another 2 hours. After alkalizing the solution with Et3N (approximately 5 ml), the mixture was immediately subjected to rapid column chromatography to remove residual DDQ. Further purification by column chromatography (silica gel, 5:1 petroleum ether / CH2Cl2) yielded porphyrin 3 (1800 mg, 38.0%) as a purple powder. In this preparation step, the amount of trifluoroacetic acid added did not exceed one-thousandth of the solvent volume.

[0064] Boron tribromide (1.0 mL, 10.5 mmol) dissolved in 10.0 mL of dichloromethane was added to a 200 mL pre-dried solution of porphyrin 3 (2.0 g, 2.72 mmol) in dichloromethane. The mixture was stirred at room temperature for 2 hours, and then 5 mL of methanol was added. The mixture was neutralized with ammonia until the color changed from green to pale red. It was washed with water, dried over anhydrous sodium sulfate, and evaporated to dryness. The precipitate was dissolved in ethyl acetate, eluted with ethyl acetate, and purified on silica gel. The eluent was evaporated, and the precipitate was precipitated with petroleum ether. The yield of porphyrin 4 was 0.9 g (98%).

[0065] HCl·dioxane (concentrated in 10 mL of dioxane) was added dropwise to a solution of porphyrin 4 (0.7 g, 3.0 mmol) and porphyrin 4. The mixture was then stirred at 25 °C for 4 hours. The solvent was removed under reduced pressure, and the residue was dissolved in water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product, which was purified by column chromatography to give a purple solid, Por1 (0.4 g, 89% yield).

[0066] 1 H NMR (600MHz, CHCl3-d, TMS, δ / ppm): -1.96(2H,s,-NH), 1.56-1.61(8H,m,-CH2-), 2.76(4H,s,-NH2 ), 6.86 (8H, d, Hβ-pyrrole), 7.68 (8H, d, H-Ph), 8.10 (4H, d, H-Ph), 8.49 (2H, s, H-Ph), 9.07 (4H, s, -OH).

[0067] MS (MALDI-TOF): C 48 H 40 Theoretical value of N6O4 m / z: 764.89; calculated value: 763.31 [M] + ].

[0068] Example 2:

[0069] The preparation of the precursor porphyrin Por2 includes the following steps:

[0070] Benzaldehyde (1.0 g, 4.7 mmol) was added to a solution of 2,2'-dipyrrolithane (1.0 g, 6.2 mmol) in dichloromethane (800 mL). The mixture was stirred at room temperature for 3 hours under a nitrogen atmosphere and in the presence of trifluoroacetic acid (30 drops). The oxidant 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) (4.5 g, 19.8 mmol) was added, and the solution was stirred for another 2 hours. After alkalization with Et3N (approximately 5 mL), the mixture was immediately subjected to rapid column chromatography to remove residual DDQ. Further purification by column chromatography (silica, 5:1 petroleum ether / dichloromethane) yielded a purple powder of porphyrin 7 (1.8 g, 38.0%).

[0071] Porphyrin 7 (0.1 mmol) was dissolved in chloroform (25.0 mL) at room temperature. After cooling the solution in a salt bath to approximately -15 °C, NBS (20.0 mg, 0.11 mmol, 1.1 equivalents) was added, and the reaction mixture was stirred for 10 minutes. The NBS was then quenched by adding acetone (0.5 mL). The reaction mixture was concentrated under reduced pressure, and the resulting crude solid was not directly passed through... 1 ¹H NMR spectroscopy analysis. The solid residue was purified on a short silica gel column to obtain a mixture of monobromide and dibromide-related compounds, which were difficult to separate in this step. Therefore, they were separated in the following coupling reaction step.

[0072] Porphyrin 8 (crude product, 410.0 mg) was dissolved in anhydrous tetrahydrofuran (150 mL) and added to a dry Schlenk flask. Further additions of 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhexacyclopentan-2-yl)benzene-1,3-diol (1205.7 mg, 4.6 mmol), K3PO4 (2653.0 mg, 12.5 mmol), and Pd(PPh3)4 (7.6 mg, 10% mol) were made. The mixture was stirred at 67 °C for 18 hours under a nitrogen atmosphere, cooled to room temperature, and extracted with dichloromethane (3 × 20 mL). The organic layer was dried over anhydrous Na2SO4, filtered, and concentrated. Purification by gradient column chromatography (silica, dichloromethane / hexane = 3:7 to 5:5 to 6:4) yielded a purple solid porphyrin 9 (40.0 mg, 90%).

[0073] Porphyrin 9 (0.05 mmol) was redissolved in chloroform (25 mL) at room temperature. The solution was cooled in an ice bath, and NBS (40.0 mg, 0.2 mmol, 4 equivalents) was added. The reaction mixture was stirred for 10 minutes, and then quenched by adding acetone (0.5 mL). The reaction mixture was concentrated under reduced pressure, and the solid residue was purified on a short silica gel column to give porphyrin 10 (101 mg, 89%).

[0074] Porphyrin 10 (300.0 mg, 0.51 mmol) was dissolved in 100 mL of pre-dehydrated and deoxygenated anhydrous tetrahydrofuran and added to a dry Schlenk flask. Tert-butyl (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)phenethyl)carbamate (700 mg, 4.5 mmol), K3PO4 (2167.0 mg, 11.1 mmol), and Pd(PPh3)4 (5.8 mg, 10% mol content) were added. The mixture was stirred at 67 °C for 18 hours under nitrogen, cooled to room temperature, and extracted with dichloromethane (3 × 20 mL). The organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was dissolved directly in 10 mL of dioxane to form a suspension, to which HCl-dioxane (1.5 mL, 6 mmol, 4 M dioxane solution) was added dropwise. The mixture was then stirred at 25°C for 4 hours. The solvent was removed under reduced pressure, and the residue was dissolved in water and extracted with ethyl acetate (3 × 50 mL). The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, and concentrated to give a crude product, which was purified by column chromatography to give Por2 (0.67 g, 74% yield) as a purple solid.

[0075] 1 H NMR (600MHz, CHCl3-d, TMS, δ / ppm): -1.96(2H,s,-NH),1.58-1.63(4H,m,-CH2-), 2.86(1H,s,-NH2),6.56(4H,d,Hβ-pyrrole), 6.76 (4H, d, Hβ-pyrrole), 7.48-7.52 (10H, d, H-Ph), 7.70 (4H, d, H-Ph), 7.99 (2H, d, H-Ph), 8.12 (1H, s, H-Ph), 9.06 (2H, s, -OH).

[0076] MS (MALDI-TOF): C 46 H 35 Theoretical N₅O₂ m / z value: 691.28; Actual value: 689.13 [M] 2+ ].

[0077] Example 3:

[0078] Preparation of dopamine-type organic polymer tightly coated with micene nanomaterials.

[0079] Specifically, the following steps are included:

[0080] Ti3C2T xAccording to the literature (Alhabeb, M.; Maleski, K.; Anasori, B.; Lelyukh, P.; Clark, L.; Sin, S.; Gogotsi, Y. Guidelines for synthesis and processing of two-dimensional titanium carbide (Ti3C2T x (MXene). Chem. Mater. 2017, 29(18), 7633-7644.) was synthesized using mild LiF and HCl. The final product was obtained as a colloidal dispersion, adjusted to a concentration of approximately 1 mg / mL. -1 .

[0081] A portion of the newly synthesized dispersion was freeze-dried and stored in a glove box. Take the above Ti3C2T... x The dispersion (4.0 mL) was transferred to a round-bottom flask and stirred slowly at 400 rpm. Dopamine hydrochloride (4.0 mg, 0.02 mmol) and the precursor porphyrins Por1 or Por2 (0.005 mmol) prepared in Examples 1 and 2 were dissolved in water / ethanol (1:1, 5.0 mL, v / v) and stirred until dissolved. The solution was then transferred to Ti3C2T x The suspension immediately turned brownish-red. After stirring for 12 hours, the mixture was separated by high-speed centrifugation at 8000 rpm. The supernatant containing excess free dopamine was removed by pipetting, and the remaining substrate was resuspended in water (2.0 mL) and the process of centrifugation and rinsing was repeated several times.

[0082] The final particles were redispersed in water (2.0 mL) and then sonicated (30 s) to obtain a deep yellow colloidal dispersion. This dispersion was then spin-coated onto a quartz substrate at 1000 rpm for 8 seconds, followed by spin-coating at 5000 rpm for 30 seconds. The sample was then dried in a vacuum oven and finally annealed at 150°C for 10 minutes.

[0083] Comparative Example 1:

[0084] Compared to Example 1, porphyrin 3 was retained as a control. This porphyrin has similar functional groups to Por1, but does not possess the basic functional group of dopamine.

[0085] Comparative Example 2:

[0086] Compared to Example 2, the presence of the tert-butoxycarbonyl (Boc) group is retained, resulting in a final porphyrin that does not have a bare amino structure and cannot self-polymerize.

[0087] Figure 1The preparation processes of two types of dopamine-type porphyrin precursors with porphyrin as the core are presented.

[0088] Figure 2 A schematic diagram of the thin film preparation process of dopamine-type organic polymer tightly coating micene nano-nonlinear optical material is given. By adding a dispersion of the final product with different concentrations at different rotation speeds, materials of different thicknesses are obtained.

[0089] Figure 3 The structural characterization (infrared, X-ray diffraction and X-ray photoelectron spectroscopy) of the dopamine-type organic polymer tightly coated with the micene nano-nonlinear optical material prepared in Example 3 demonstrates that the dopamine-like porphyrin is dispersed on the surface of the micene nanosheets in a conjugated and self-polymerized form, rather than simply attached.

[0090] Figure 4 The absorption spectrum of the dopamine-type organic polymer tightly coated with the micene nano-nonlinear optical material prepared in Example 3 above once again proves that the dopamine-like porphyrin underwent an oxidative self-polymerization reaction, resulting in conjugation enhancement and a red shift in absorption.

[0091] Figure 5 The results are the Z-scan at 800 nm for the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in Example 3, Ti3C2T. x (Por1) y It has the best performance, with a modulation depth of 78%.

[0092] Figure 6 The results are Z-scans at 1300 nm for the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in Example 3, Ti3C2T. x (Por2) y The performance is optimal, with a modulation depth of 41%.

[0093] Figure 7 The results are Z-scans at 1550 nm for the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material prepared in Example 3, Ti3C2T. x (Por1) y Two-photon absorption is dominant, with a modulation depth of 50%.

[0094] In summary, based on the above embodiments and other content, the dopamine-type organic polymer tightly coating micene nano-nonlinear optical material of the present invention, inspired by mussel protein and dopamine structure, uses porphyrin, one of the antisaturated absorbers, as the core, and undergoes a similar self-polymerization reaction, which enhances the conjugation of porphyrin molecules. At the same time, it is firmly and impermeably adsorbed on the surface of micene, isolating the micene structure from damage by air and water, thereby greatly improving its air and laser stability, and significantly increasing the application scenarios and practical range of the material.

[0095] Meanwhile, its enhanced conjugated structure enables the thin film of this material to have a very good broadband nonlinear response under ultrafast pulsed laser, specifically manifested as antisaturation absorption and two-photon absorption in the range of 400-1550 nm.

[0096] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a dopamine-type organic polymer-coated micene nano-nonlinear optical material, characterized in that, Includes the following steps: (1) Configuring Mikeene Ti3C2T x Solution; (2) After dissolving dopamine hydrochloride and dopamine-like porphyrin, the solution is transferred to the micene Ti3C2T x In the solution, the reaction is stirred, and then the reaction products are separated to obtain the target product; The dopamine-like porphyrins are dopamine-like porphyrin Por1 and / or dopamine-like porphyrin Por2, and their chemical structural formulas are as follows: 、 ； The molar ratio of dopamine hydrochloride to dopamine-like porphyrin is 3-5:1; The Maxene Ti3C2T x The concentration of the solution is 0.8~1.2 mg / mL, and the ratio of its concentration to the amount of dopamine hydrochloride added is 4mL:(0.015~0.025)mmol.

2. The method for preparing a dopamine-type organic polymer-coated micene nano-nonlinear optical material according to claim 1, characterized in that, In step (2), the stirring reaction is carried out at room temperature for 6-18 hours.

3. The method for preparing a dopamine-type organic polymer-coated micene nano-nonlinear optical material according to claim 1, characterized in that, The dopamine-like porphyrin Por1 was prepared by the following method: 5-(3,5-dimethoxyphenyl)dipyrrolemethane and (4-formylphenylethyl)carbamate tert-butyl ester were reacted to obtain porphyrin 3. Porphyrin 3 was then deprotected twice to obtain dopamine-like porphyrin Por1 with diamino and dihydroxy groups.

4. The method for preparing a dopamine-type organic polymer-coated micene nano-nonlinear optical material according to claim 3, characterized in that, The reagents used for the two deprotection processes of porphyrin 3 were boron tribromide and dioxane hydrochloride, respectively.

5. The method for preparing a dopamine-type organic polymer-coated micene nano-nonlinear optical material according to claim 1, characterized in that, The dopamine-like porphyrin Por2 was prepared by the following method: First, synthesize asymmetric porphyrin 8; Suzuki-Miyaura modification was performed on the exposed meso site of asymmetric porphyrin 8 to obtain porphyrin 9 with dihydroxyl groups; The remaining meso site of porphyrin 9 was further modified with bromine atoms and subjected to a second Suzuki-Miyaura reaction to obtain dopamine-like porphyrin Por2; The chemical structural formula of the asymmetric porphyrin 8 is as follows: ； The chemical structural formula of porphyrin 9 is as follows: 。 6. The method for preparing a dopamine-type organic polymer-coated micene nano-nonlinear optical material according to claim 5, characterized in that, The Suzuki-Miyaura modification process is as follows: Weigh out asymmetric porphyrin 8 and dissolve it in anhydrous tetrahydrofuran. Add 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)benzene-1,3-diol, K3PO4, and Pd(PPh3)4. Then stir at 65-70℃ for 12-24 h under a nitrogen atmosphere. The ratio of the amount of asymmetric porphyrin 8, 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborhecyclopentan-2-yl)benzene-1,3-diol, K3PO4, and Pd(PPh3)4 is 410 mg: 4.6 mmol: 12.5 mmol: 7.6 mg. The further modification process of porphyrin 9 is as follows: Porphyrin 9 was dissolved in chloroform, and 4 equivalents of NBS were added. The mixture was stirred and reacted to obtain porphyrin 10. Porphyrin 10 was dissolved in anhydrous tetrahydrofuran, and tert-butyl (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)phenethyl)carbamate, K3PO4 and Pd(PPh3)4 were added. The ratio of porphyrin 10, tert-butyl(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)phenethyl)carbamate, K3PO4 and Pd(PPh3)4 was 300 mg: 4.5 mmol: 11.1 mmol: 5.8 g.

7. A dopamine-type organic polymer tightly coated micene nano-nonlinear optical material, which is prepared by the preparation method according to any one of claims 1-6.

8. The application of the dopamine-type organic polymer tightly coated micene nano-nonlinear optical material according to claim 7 under complex laser irradiation conditions.

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