Tunable porphyrin-cadmium complex mayernan nonlinear optical material and preparation and application thereof

Abstract

The present application relates to a kind of tunable porphyrin-cadmium complex maykine nanometer nonlinear optical material and its preparation and application, the rotatability of single bond in organic matter is designed two porphyrin-cadmium complex, and it is connected to the surface of two-dimensional few-layer maykine by substitution reaction key.The porphyrin-cadmium complex of one of them occurs rotation due to different bridging groups, different steric hindrance, induces the conjugation degree of organic component to change greatly, to cause two materials to generate response for different pulse scale (nanosecond and femtosecond) laser respectively.Compared with prior art, the material configuration is changed by bridging group in the present application, so as to change the coupling degree of material, excited state lifetime and its nonlinear optical performance, so that the material has selectivity for laser of different pulse scale, and has good application potential for the screening and switching type scene of complex laser.

Description

Technical Field

[0001] This invention belongs to the technical field of organic-inorganic hybrid nanomaterials and third-order nonlinear optical materials, and relates to a tunable porphyrin-cadmium complex micene nano-nonlinear optical material and its preparation and application. Background Technology

[0002] Nonlinear optics is fundamental to many applications, such as harmonic generation, all-optical data processing, information technology, optical sensors, and four-wave mixing. With the increasing applications of lasers in civilian, industrial, and academic fields, research on nonlinear optical (NLO) materials has become crucial for the continued development of optoelectronics. Nonlinear optical absorption refers to the phenomenon that a material's absorption coefficient differs under low and high irradiance light. High-performance nonlinear optical absorption materials are essential for pulsed laser generation (mode-locked or Q-switched), optical limiting, multiphoton-pumped lasers, and subbandgap photodetectors. Among potential nonlinear optical materials, two-dimensional (2D) materials have particular advantages due to their strong exciton effects, ultrafast carrier dynamics, and efficient charge delocalization. Significant progress has been made in the nonlinear optical absorption properties of various 2D materials such as graphene, graphyne, black phosphorus, metal chalcogenides, and two-dimensional mixed Ruddlesden-Popper halide perovskites (RPPs). MXene is a recently developed 2D material with the chemical formula M n+1 X n T x (n = 1-3), where M is a transition metal (e.g., Ti, Nb, Mo), X is carbon and / or nitrogen, and T is a surface terminal group (e.g., -O, -OH, -F). Interestingly, MXenes exhibit excellent electrical conductivity and are currently used as transparent conductors, electrocatalysts, sensors, electromagnetic interference shields, energy storage, and photothermal conversion. Their nonlinear optical (NLO) properties were first reported by Jhon et al. in 2017, and the NLO properties and applications of MXenes are attracting increasing attention.

[0003] However, the commercialization of two-dimensional nonlinear optical materials is hindered by inconsistent performance. Their nonlinear optical properties are closely related to the synthesis method and material structure; similar structures of the same material may yield different or even opposite performance results. Furthermore, the influence of the degree of conjugation on NLO performance has been extensively studied. However, besides extending the material system, the material configuration can also significantly affect the degree of conjugation and the final nonlinear optical performance. The distribution of its band structure is highly susceptible to the influence of the degree of conjugation. Improving nonlinear optical performance requires the development of reproducible synthesis methods and the establishment of structure-performance relationships, but to date, very few related studies have been published. Summary of the Invention

[0004] The purpose of this invention is to provide a tunable porphyrin-cadmium complex micene nanomaterial for nonlinear optical applications, its preparation, and its application. By altering the material configuration through bridging groups, the coupling degree, excited-state lifetime, and nonlinear optical properties of the material can be changed. This results in the material exhibiting selectivity for lasers of different pulse scales, and it has good application potential for screening complex lasers and switching scenarios.

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

[0006] In one aspect, the present invention provides a method for preparing tunable porphyrin-cadmium complex micene nanomaterials as nonlinear optical nanomaterials, comprising the following steps:

[0007] (1) Configure Mikeene Ti3C2T x Solution;

[0008] (2) Dissolve the porphyrin-cadmium complex in a dichloromethane / ethanol mixture, and then transfer it to a micronized Ti3C2T solution. x After thorough mixing and stirring in the solution, the mixture is separated to obtain the target product.

[0009] The porphyrin-cadmium complex is a conjugated porphyrin-cadmium complex 1 and / or a non-conjugated porphyrin-cadmium complex 2;

[0010] The chemical structural formula of the conjugated porphyrin-cadmium complex 1 is as follows:

[0011]

[0012] The chemical structural formula of the non-conjugated porphyrin-cadmium complex 2 is as follows:

[0013]

[0014] Furthermore, the micene Ti3C2T x The mass ratio of porphyrin-cadmium complex is 4:(5-7), preferably 4:6.

[0015] Furthermore, the stirring reaction is carried out under a nitrogen atmosphere, the temperature of the stirring reaction is 50-70℃, preferably 60℃, and the time is 8-16h, preferably 12h.

[0016] Furthermore, before stirring the reaction, K2CO3 was added to the reaction system, which reacts with the methyl methacrylate (Ti3C2T). x The mass ratio is (2.5~3.5):4, preferably 3:4.

[0017] Furthermore, in the dichloromethane / ethanol mixed solution, the volume ratio of dichloromethane to ethanol is 1:0.8 to 1.2.

[0018] Furthermore, the porphyrin-cadmium complex is prepared by the following process:

[0019] 5-(4-benzoyl)-10,15,20-triphenylporphyrin or 5-formyl-10,15,20-triphenylporphyrin were prepared by the propionic acid method.

[0020] Under alkaline conditions, 5-(4-benzoyl)-10,15,20-triphenylporphyrin and / or 5-formyl-10,15,20-triphenylporphyrin were used as porphyrin raw materials and reacted with 2-acetylpyridine via Michael addition reaction to obtain tripyridine-substituted porphyrin.

[0021] Tripyridine-substituted porphyrins react with cadmium halides to give porphyrin-cadmium complexes;

[0022] The chemical structural formula of the tripyridine-substituted porphyrin is:

[0023] (The solid hexagon represents a benzene ring), and the corresponding synthesized porphyrin-cadmium complex is conjugated porphyrin-cadmium complex 1; or the chemical structural formula of the tripyridine-substituted porphyrin is... The corresponding synthesized porphyrin-cadmium complex is non-conjugated porphyrin-cadmium complex 2.

[0024] Furthermore, the synthesis of tripyridine-substituted porphyrins is carried out in steps: first, the porphyrin raw material is dissolved in dichloromethane, then triethylamine is added, and the reaction is carried out under reflux in one step.

[0025] Then, 2-acetylpyridine and triethylamine were added to the reaction system, and the mixture was refluxed twice.

[0026] Finally, an excess of ammonium acetate ethanol solution was added, and the mixture was refluxed three times to obtain a brownish-red solution. After cooling to room temperature, the solution was recrystallized from ethanol to obtain tripyridine-substituted porphyrin.

[0027] More preferably, the molar ratio of porphyrin raw material to 2-acetylpyridine is 1:1;

[0028] During the first reflux reaction, the ratio of porphyrin feedstock, dichloromethane, and triethylamine added was 2.5 mmol: 100 mL: 10 mL.

[0029] During the secondary reflux reaction, the volume ratio of triethylamine to dichloromethane added is 40:100;

[0030] The time for the first reflux reaction is 6-10 hours, the time for the second reflux reaction is 6-10 hours, and the time for the third reflux reaction is 4-6 hours.

[0031] In a second aspect, the present invention provides a tunable porphyrin-cadmium complex micene nanomaterial for nonlinear optical applications, which is prepared using any of the methods described above. Porphyrin-cadmium complex 1, due to the presence of a benzene ring as a bridge, exhibits high conjugation between the pyridine complex and the porphyrin. Porphyrin-cadmium complex 2, due to its greater steric hindrance, exhibits lower conjugation between the pyridine complex and the porphyrin, resulting in a more perpendicular relationship between them. This leads to the final modified micene nanosheets possessing excellent laser pulse selectivity.

[0032] In a third aspect, the present invention provides an application of tunable porphyrin-cadmium complex micene nanomaterials in laser pulse-selective or switching laser devices. Specifically, conjugated porphyrin-cadmium complex micene nanosheets exhibit ultrafast response to femtosecond lasers, while non-conjugated porphyrin-cadmium complex micene nanosheets only respond to nanosecond lasers.

[0033] Furthermore, the laser conditions for the response of the conjugated porphyrin-cadmium complex micene nanosheets are 35 fs, 5155 nm, and 1000 Hz.

[0034] Furthermore, the laser conditions for the response of the non-conjugated porphyrin-cadmium complex micene nanosheets are 15 ns, 532 nm, and 10 Hz.

[0035] Compared with the prior art, the present invention has the following advantages:

[0036] I. The porphyrin-cadmium complex micene nano-nonlinear optical material prepared in this invention exhibits good air and light stability after some end groups are replaced.

[0037] Second, the porphyrin-cadmium complex micene nanomaterials in this invention exhibit pulse-dependent third-order nonlinear optical properties. The conjugated porphyrin-cadmium complex micene nanosheets have an ultrafast response to femtosecond lasers, while the non-conjugated porphyrin-cadmium complex micene nanosheets only respond to nanosecond lasers, demonstrating a strong correlation between material structure and nonlinear optical properties.

[0038] Third, the porphyrin-cadmium complex micene nano-nonlinear optical material prepared in this invention has good selectivity for laser pulses of different scales, can meet the screening requirements of complex lasers, and has good application potential in the fields of optical sieving and optical switching. Attached Figure Description

[0039] Figure 1 This is a schematic diagram illustrating the specific synthesis process of conjugated porphyrin-cadmium complex 1 and non-conjugated porphyrin-cadmium complex 2;

[0040] Figure 2 These are the morphology and elemental distribution of the porphyrin-cadmium complex micene nano-nonlinear optical material prepared in this invention;

[0041] Figure 3 These are thin film images of the porphyrin-cadmium complex micene nano-nonlinear optical material prepared according to this invention;

[0042] Figure 4 These are atomic force microscopy images and thickness files of the porphyrin-cadmium complex micene nano-nonlinear optical material prepared according to this invention;

[0043] Figure 5 The results are Z-scans of the non-conjugated porphyrin-cadmium complex micene nano-nonlinear optical material prepared in this invention under nanosecond laser irradiation.

[0044] Figure 6 The Z-scan results of the conjugated porphyrin-cadmium complex micene nano-nonlinear optical material prepared in this invention under femtosecond laser irradiation are shown.

[0045] Figure 7 A schematic diagram illustrating the process for preparing porphyrin-cadmium complex micene nanomaterials as nonlinear optical materials;

[0046] Figure 8 The image shows the detection results of the product prepared in Comparative Example 1. Detailed Implementation

[0047] 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.

[0048] In the following embodiments, unless otherwise specified, the raw materials or processing techniques are conventional commercial products or conventional processing techniques in the art.

[0049] Example 1:

[0050] The preparation of the conjugated porphyrin-cadmium complex 1 specifically includes the following steps:

[0051] 5-(4-benzoyl)-10,15,20-triphenylporphyrin from references [1] It was synthesized.

[0052] The specific structural chemical formula is as follows:

[0053]

[0054] 2-Acetylpyridine (0.3 g, 2.5 mmol) and 5-(4-benzoyl)-10,15,20-triphenylporphyrin (1.6 g, 2.5 mmol) were dissolved in 100 mL of dichloromethane, and 10 mL of triethylamine was added. The reaction was carried out at 40 °C under reflux for 8 hours. After the reaction was completed, another molar equivalent of 2-acetylpyridine (0.3 g, 2.5 mmol) and 40 mL of triethylamine were added to the reaction system, and the reaction was monitored in real time by thin-layer chromatography. After refluxing at 40 °C for another 8 hours, acetic acid was added to terminate the reaction, resulting in a brown viscous mixture. After pH testing showed that the system was slightly acidic, excess ammonium acetate ethanol solution (1.8 g, 25.0 mL) was added, and the mixture was refluxed at 70 °C for another 5 hours, resulting in a brownish-brown solution. After cooling to room temperature, tripyridine porphyrin was obtained by recrystallization from ethanol as purplish-brown crystals (0.6 g, 40.0%).

[0055] 1 H NMR (CDCl3, 600MHz, TMS, δ / ppm): -2.78(2H,s,-NH),7.31(4H,d,H-Ph),7.67-7.78(8H,m,Hβ-pyrrole),8.05-8.11(8H,m,H Ph),8.22(2H,d,H Ph),8.31(4H,m,H Ph),8.45(1H,m,H Ph),8.51(4H,m,H Py),8.78(2H,d,H Py).

[0056] MS (MALDI-TOF): C 59 H 39 Theoretical value of N7 m / z: 846.01; calculated value: 845.29 [M] + ].

[0057] CdBr2 (108.4 mg, 0.4 mmol) was sonicated and dissolved in 15 mL of ethanol solution. Tripyridine porphyrin (0.3 g, 0.33 mmol) was dissolved in 20 mL of dichloromethane. After sonication and centrifugation, the supernatant of both was retained. Cadmium halide solution was then slowly added to the upper layer of porphyrin solution. After standing for 3 days, porphyrin-cadmium complex 1 was obtained.

[0058] MS (MALDI-TOF): C 59 H 39 Theoretical m / z value of Br2CdN7: 1117.01; Calculated value: 1115.94 [M] + ].

[0059] Example 2:

[0060] Preparation of non-conjugated porphyrin-cadmium complex 2:

[0061] 5-Formyl-10,15,20-triphenylporphyrin from references [2] The non-conjugated porphyrin-cadmium complex 2 was synthesized using a method similar to that of conjugated porphyrin-cadmium complex 1, requiring only the replacement of the reactant 5-(4-benzoyl)-10,15,20-triphenylporphyrin with an equivalent amount of 5-formyl-10,15,20-triphenylporphyrin. The specific steps are as follows:

[0062] 2-Acetylpyridine (0.3 g, 2.5 mmol) and 5-formyl-10,15,20-triphenylporphyrin (1.4 g, 2.5 mmol) were dissolved in 100 mL of dichloromethane, and 10 mL of triethylamine was added. The mixture was refluxed for 8 hours. After the reaction was complete, another molar equivalent of 2-acetylpyridine (0.3 g, 2.5 mmol) and 40 mL of triethylamine were added to the reaction system, and the reaction was monitored in real time by thin-layer chromatography. After reflux for another 8 hours, acetic acid was added to terminate the reaction, yielding a brownish-yellow viscous mixture. After pH testing showed that the system was slightly acidic, excess ammonium acetate ethanol solution (1.8 g, 25.0 mL) was added, and the mixture was refluxed for another 5 hours, yielding a brown solution. After cooling to room temperature, recrystallization from ethanol yielded tripyridineporphyrin without a benzene ring as a bridge, as brown crystals (0.5 g, 35.0%).

[0063] 1 H NMR (CDCl3, 600MHz, TMS, δ / ppm): -2.64(2H,s,-NH),7.71-7.87(8H,m,Hβ-pyrrole),8.24-8.31(8H,m,H Ph),8.45(2H,d,H Ph),8.66(4H,m,H Ph),8.81(1H,m,H Ph),8.91(4H,m,H Py),9.04(2H,d,H Py).

[0064] MS (MALDI-TOF): C 53 H 35 Theoretical value of N7 m / z: 769.30; calculated value: 768.67 [M] + ].

[0065] CdBr2 (108.4 mg, 0.4 mmol) was sonicated and dissolved in 15 mL of ethanol solution. The above-mentioned tripyridine porphyrin (0.2 g, 0.33 mmol) was dissolved in 20 mL of dichloromethane. After sonication and dispersion, the supernatant of both was retained by centrifugation. Then, cadmium halide solution was slowly added to the upper layer of porphyrin solution. After standing for 3 days, porphyrin-cadmium complex 2 was obtained.

[0066] MS (MALDI-TOF): C 53 H 35 Theoretical m / z value of Br2CdN7: 1047.07; Calculated value: 1046.00 [M] + ].

[0067] Example 3:

[0068] The porphyrin-cadmium complex micene nanomaterial for nonlinear optical applications specifically includes the following steps:

[0069] Ti3C2T x According to the literature [3] Synthesized using mild LiF and HCl. The etched micene was dispersed in distilled water in colloidal form and further freeze-dried to obtain approximately 120 mg of fluffy solid.

[0070] Take the above-mentioned micene solid (Ti3C2T) x 4.0 mg was transferred to a round-bottom flask, anhydrous ethanol (5.0 mL) was added, and the mixture was ultrasonically dispersed to obtain a suspension. The cadmium porphyrin complex (6.0 mg) obtained in Example 1 or 2 was dispersed in 5 mL of anhydrous dichloromethane, and the resulting solution was transferred to Ti3C2T x In the ethanol suspension, K2CO3 (3 mg) was added to the mixture. After stirring and refluxing at 60 °C for 12 hours under nitrogen protection, the mixture was separated by high-speed centrifugation at 8000 rpm. The substrate was washed multiple times with dichloromethane. Some samples were dried in a vacuum drying oven, and some samples were dispersed in ethanol solution for testing.

[0071] Comparative Example 1:

[0072] Compared with Examples 1 and 2, tripyridine porphyrin and micene were directly stirred to verify whether non-complexed metal ions could cause a configurational change.

[0073] Testing revealed that tripyridine porphyrin and micene did not react. After thorough ultrasonic cleaning, it was found that tripyridine porphyrin could not form a stable hybrid material with micene (see...). Figure 8 (After thorough elution, only the absorption of micene is observed), and the tripyridine porphyrin structure in the elution product remains unchanged.

[0074] Comparative Example 2:

[0075] Compared with Examples 1 and 2, the reaction of tripyridine porphyrin and cadmium halide uses a single solvent, verifying the importance of mixed solvents for complexation reactions.

[0076] It is known that tripyridine porphyrin is soluble in organic solvents, while cadmium halide is an inorganic salt. Using a single solvent for the reaction prevents the two from reacting completely. Mass spectrometry confirms that most of the product is still tripyridine porphyrin, with only a very small amount of complexed porphyrin.

[0077] MS (MALDI-TOF): Theoretical m / z value: Calculated value, 1047.07, found 768.67, a few 1046.00 [M + ].

[0078] Figure 1 This is a schematic diagram illustrating the specific synthetic process of conjugated porphyrin-cadmium complex 1 and non-conjugated porphyrin-cadmium complex 2, which are obtained through stepwise Michael addition reactions.

[0079] Figure 2 The images show the morphology and elemental distribution of the conjugated porphyrin-cadmium complex Mikene nano-nonlinear optical material prepared in Example 3. The presence of N and Cd elements proves that the tripyridine porphyrin in the Mikene nanosheets has successfully complexed with cadmium halide.

[0080] Figure 3 These are thin film images of the conjugated porphyrin-cadmium complex micene nano-nonlinear optical material prepared in Example 3, demonstrating that this type of material has good dispersibility and high linear optical transmittance.

[0081] Figure 4 This is an atomic force microscopy morphology and thickness file of the conjugated porphyrin-cadmium complex micene nano-nonlinear optical material prepared in Example 3, dispersed in ethanol. The thickness is about 5 nm, which proves that the micene modified with porphyrin-cadmium complex has fewer layers than the etched micene and is less prone to aggregation due to van der Waals forces.

[0082] Figure 5 The two materials prepared in Example 3 were subjected to Z-scan tests under laser conditions of 35 fs, 515 nm, 1000 Hz and 15 ns, 532 nm, 10 Hz, respectively. The non-conjugated porphyrin-cadmium complex micene nano-nonlinear optical material showed a response under nanosecond laser irradiation with a minimum modulation depth of 59%, while the conjugated porphyrin-cadmium complex micene nano-nonlinear optical material showed no absorption at nanosecond laser irradiation.

[0083] Figure 6 The two materials prepared in Example 3 were subjected to Z-scan tests under laser conditions of 35 fs, 515 nm, 1000 Hz and 15 ns, 532 nm, 10 Hz, respectively. The conjugated porphyrin-cadmium complex micene nano-nonlinear optical material responded under femtosecond laser irradiation with a minimum modulation depth of 23%, while the conjugated porphyrin-cadmium complex micene nano-nonlinear optical material showed no absorption under femtosecond laser irradiation.

[0084] Meanwhile, the two types of porphyrin-cadmium complex micene nano-nonlinear optical materials prepared in Example 3 were tested. It was found that the laser conditions for the response of the conjugated porphyrin-cadmium complex micene nanosheets were 35 fs, 5155 nm, and 1000 Hz; while the laser conditions for the response of the non-conjugated porphyrin-cadmium complex micene nanosheets were 15 ns, 532 nm, and 10 Hz.

[0085] As described above, the porphyrin-cadmium complex micene nanomaterial, through the simplest bridging group benzene ring, alters the steric hindrance between the tripyridine cadmium complex unit and the porphyrin unit. This results in one porphyrin-cadmium complex being conjugated and the other perpendicular to each other, leading to a significant change in configuration. This configurational change alters the degree of conjugation of the porphyrin-cadmium complex, thereby affecting its energy level arrangement, linear absorption, and excited-state lifetime, ultimately altering its nonlinear optical properties.

[0086] Meanwhile, their distinct conjugated structures enable them to produce nonlinear responses under nanosecond and femtosecond pulsed lasers, respectively, making them one of the important candidate materials for screening different pulsed lasers and optical switches.

[0087] 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 tunable porphyrin-cadmium complex micene nanomaterial for nonlinear optical applications, characterized in that, Includes the following steps: (1) Configuring Mikeene Ti3C2T x Solution; (2) Dissolve cadmium halide in ethanol solution and porphyrin in dichloromethane, then mix and react the two to obtain a porphyrin-cadmium complex, which is then transferred to a micronized olefin Ti3C2T. x After thorough mixing and stirring in the solution, the mixture is separated to obtain the target product. The porphyrin-cadmium complex is a conjugated porphyrin-cadmium complex 1 and / or a non-conjugated porphyrin-cadmium complex 2; The chemical structural formula of the conjugated porphyrin-cadmium complex 1 is as follows: ， The chemical structural formula of the non-conjugated porphyrin-cadmium complex 2 is as follows: 。 2. The method for preparing a tunable porphyrin-cadmium complex micene nano-nonlinear optical material according to claim 1, characterized in that, The Maxene Ti3C2T x The mass ratio of the porphyrin-cadmium complex is 4:(5~7).

3. The method for preparing a tunable porphyrin-cadmium complex micene nano-nonlinear optical material according to claim 1, characterized in that, The stirring reaction was carried out under a nitrogen atmosphere at a temperature of 50-70 °C for 8-16 h.

4. The method for preparing a tunable porphyrin-cadmium complex micene nano-nonlinear optical material according to claim 1, characterized in that, Before stirring the reaction, K2CO3 was added to the reaction system, which reacted with the methyl methacrylate (Ti3C2T). x The mass ratio is (2.5~3.5):

4.

5. The method for preparing a tunable porphyrin-cadmium complex micene nano-nonlinear optical material according to claim 1, characterized in that, The porphyrin-cadmium complex was prepared by the following process: 5-(4-benzoyl)-10,15,20-triphenylporphyrin or 5-formyl-10,15,20-triphenylporphyrin were prepared by the propionic acid method. Under alkaline conditions, 5-(4-benzoyl)-10,15,20-triphenylporphyrin and / or 5-formyl-10,15,20-triphenylporphyrin were used as porphyrin raw materials and reacted with 2-acetylpyridine via Michael addition reaction to obtain tripyridine-substituted porphyrin. Tripyridine-substituted porphyrins react with cadmium halides to give porphyrin-cadmium complexes; The chemical structural formula of the tripyridine-substituted porphyrin is: The corresponding synthesized porphyrin-cadmium complex is conjugated porphyrin-cadmium complex 1; or the chemical structural formula of the tripyridine-substituted porphyrin is... The corresponding synthesized porphyrin-cadmium complex is a non-conjugated porphyrin-cadmium complex 2.

6. The method for preparing a tunable porphyrin-cadmium complex micene nano-nonlinear optical material according to claim 5, characterized in that, The synthesis of tripyridine-substituted porphyrins is carried out in steps. First, the porphyrin raw material is dissolved in dichloromethane, then triethylamine is added, and the reaction is carried out under reflux in one step. Then, 2-acetylpyridine and triethylamine were added to the reaction system, and the mixture was refluxed twice. Finally, an excess of ammonium acetate ethanol solution was added, and the mixture was refluxed three times to obtain a brownish-red solution. After cooling to room temperature, the solution was recrystallized from ethanol to obtain tripyridine-substituted porphyrin.

7. The method for preparing a tunable porphyrin-cadmium complex micene nano-nonlinear optical material according to claim 6, characterized in that, The molar ratio of porphyrin raw material to 2-acetylpyridine is 1:1; During the first reflux reaction, the ratio of porphyrin feedstock, dichloromethane, and triethylamine added was 2.5 mmol: 100 mL: 10 mL. During the secondary reflux reaction, the volume ratio of triethylamine to dichloromethane added is 40:100; The time for the first reflux reaction is 6-10 hours, the time for the second reflux reaction is 6-10 hours, and the time for the third reflux reaction is 4-6 hours.

8. A tunable porphyrin-cadmium complex micene nano-nonlinear optical material, which is prepared by the preparation method described in any one of claims 1-7.

9. The application of the tunable porphyrin-cadmium complex micene nano-nonlinear optical material as described in claim 8 in laser pulse selective or switching laser devices.

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