Zinc phthalocyanine derivative as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of functional organic materials, and particularly discloses a zinc phthalocyanine derivative as well as a preparation method and application thereof. The preparation method comprises the following steps: performing chloromethylation reaction on zinc phthalocyanine and a chloromethylation reagent under the condition of a Lewis acid catalyst to obtain a chloromethylated zinc phthalocyanine intermediate; and then carrying out nucleophilic substitution reaction on the chloromethylated zinc phthalocyanine intermediate and an amine substance to obtain the zinc phthalocyanine derivative. According to the invention, chloromethyl is introduced to the phthalocyanine ring, so that the phthalocyanine ring can be further subjected to nucleophilic substitution reaction with various nucleophilic reagents, and amine groups with various functions are introduced to the phthalocyanine macroring. The dissolvability and dispersity of phthalocyanine can be remarkably improved, and the hydrophilicity / hydrophobicity, the electronic effect and the interface interaction with biomolecules or electrode materials can be accurately regulated and controlled by selecting different amines.

Description

Technical Field

[0001] This invention relates to the field of functional organic materials technology, and in particular to a zinc phthalocyanine derivative, its preparation method, and its application. Background Technology

[0002] Phthalocyanines are a class of macrocyclic compounds with an 18π-electron conjugated system, their structure resembling that of porphyrins found in nature. Metal phthalocyanines, especially zinc phthalocyanine (ZnPc), exhibit excellent light absorption and photophysicochemical activity in the near-infrared region (650–800 nm), making them one of the core materials in photodynamic therapy, photothermal therapy, and photocatalysis. Zinc phthalocyanine, as a typical representative of phthalocyanine compounds, has advantages such as low synthesis cost, good chemical stability, and high singlet oxygen generation efficiency. However, traditional zinc phthalocyanines suffer from poor water solubility, easy aggregation, and limited functionality, which restricts their practical applications.

[0003] To improve the solubility and functionalization of zinc phthalocyanine, structural modification through chemical modification is a key approach to address the aforementioned issues. During the research and development process, it was discovered that introducing various functional amine groups onto the phthalocyanine macrocycle not only significantly improves the solubility and dispersibility of phthalocyanine, but also allows for precise control of its hydrophilic / hydrophobic properties, electronic effects, and interfacial interactions with biomolecules or electrode materials by selecting different amines.

[0004] However, traditional amino functionalization methods may involve steps such as nitration and reduction or the use of highly reactive and hard-to-obtain amination reagents, resulting in problems such as long routes, high costs, and complex operations.

[0005] There is still a lack of systematic, efficient, and high-yield synthetic routes for the systematic preparation of a series of zinc phthalocyanine derivatives with specific functions (such as targeting, high solubility, and specific energy levels) through efficient chloromethylation reactions and further reactions with structurally diverse amine compounds. Therefore, developing a universal and efficient preparation method to obtain novel zinc phthalocyanine derivatives to meet the application needs of different fields is of significant practical importance. Summary of the Invention

[0006] The present invention aims to provide a method for synthesizing zinc phthalocyanine derivatives that is efficient and easy to scale up, and to obtain a series of novel derivatives with excellent solubility and optical properties, thereby promoting their application in photocatalysis, organic optoelectronics and chemical sensing.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: A zinc phthalocyanine derivative, wherein the structure of the zinc phthalocyanine derivative is as follows:

[0008] Wherein, Y includes H and / or Cl; X is -CH2-NR1R2 or -CH2-R3, and R1 and R2 are independently selected from hydrogen, C1~C1, C2, and C2, respectively. 12 The alkyl group or a cycloalkyl group of C3 to C8; wherein R3 is a nitrogen-containing heterocycle formed by R1, R2 and a nitrogen atom or R1, R2, a nitrogen atom and a heteroatom, wherein the heteroatom includes N, O or S; wherein the nitrogen-containing heterocycle is connected to the methylene group in X via a nitrogen atom; Both m and n are non-negative integers, and m+n=4, m≥1.

[0009] Preferably, the nitrogen-containing heterocycle is selected from one of pyrrolidinyl, piperidinyl, morpholinyl, and piperazineyl.

[0010] Another object of the present invention is to provide a method for preparing zinc phthalocyanine derivatives, comprising the following steps: 1) Zinc phthalocyanine and a chloromethylating agent were subjected to a chloromethylation reaction under Lewis acid catalyst conditions to obtain a chloromethylated zinc phthalocyanine intermediate; 2) The chloromethylated zinc phthalocyanine intermediate was reacted with an amine under acid-binding conditions to undergo a nucleophilic substitution reaction to obtain a zinc phthalocyanine derivative.

[0011] Preferably, the chloromethylating agent includes one or more of thionyl chloride, phosphorus oxychloride, chloromethyl methyl ether, chloromethyl diethyl ether, chloromethyl phenyl ether, dichloromethyl ether, a mixture of paraformaldehyde and hydrogen chloride, and a mixture of formaldehyde and hydrogen chloride. The Lewis acid catalyst includes one or more of zinc chloride, ferric chloride, and aluminum chloride.

[0012] Preferably, the molar ratio of zinc phthalocyanine, chloromethylating agent and Lewis acid catalyst is 1:4~10:0.5~1.2.

[0013] Preferably, the temperature of the chloromethylation reaction in step 1) is 50~120℃ and the time is 2~24h.

[0014] Preferably, the molar ratio of the chloromethylated zinc phthalocyanine intermediate, the amine substance, and the acid-binding agent is 1:2~50:2~20.

[0015] Preferably, the amines include one or more of propylamine, dimethylamine, aniline, o-phenylenediamine, morpholine, piperidine, carbazole, etc. The acid-binding agent includes one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, N,N-diisopropylethylamine, and pyridine.

[0016] Preferably, the nucleophilic substitution reaction in step 2) is carried out at a temperature of 20-80°C for a time of 4-48 hours.

[0017] Another object of the present invention is to provide an application of zinc phthalocyanine derivatives as photocatalytic reaction catalysts, photoelectroactive layer materials, or sensor sensitive materials.

[0018] The introduction of a chloromethyl group (-CH₂Cl) onto the phthalocyanine ring is a crucial intermediate step in this invention. As an excellent leaving group and reaction site, the chloromethyl group can further undergo nucleophilic substitution reactions with various nucleophiles (such as amine compounds), thereby introducing a variety of functional amine groups onto the phthalocyanine macrocycle. This not only significantly improves the solubility and dispersibility of phthalocyanines but also allows for precise control of their hydrophilic / hydrophobic properties, electronic effects, and interfacial interactions with biomolecules or electrode materials by selecting different amines.

[0019] As can be seen from the above technical solution, compared with the prior art, the present invention has the following beneficial effects: 1. Product diversity: By changing the structure of amines, various functional groups can be easily introduced to prepare a series of zinc phthalocyanine derivatives with different physicochemical properties (such as solubility, hydrophilicity / hydrophobicity, and electronic energy levels) to meet the needs of different application scenarios.

[0020] 2. High versatility of the method: The two-step synthesis method provided by this invention has high versatility, is applicable to a variety of amine compounds, has mild reaction conditions, is simple to operate, and is easy to control.

[0021] 3. Excellent product performance: The prepared zinc phthalocyanine derivatives significantly improve the solubility of zinc phthalocyanine in common organic solvents (such as DMF, THF, chloroform, etc.) by introducing amino groups with different structures, which is beneficial for subsequent solution processing. At the same time, the introduction of amino groups effectively modulates the electronic effect of the phthalocyanine macrocycle, allowing its light absorption, energy level and other properties to be customized according to application requirements.

[0022] 4. Low-cost and flexible synthesis of zinc phthalocyanine: The chloromethylating reagents and amine compounds used in this invention are widely available and relatively inexpensive. In particular, a variety of primary and secondary amines with different structures can be used, providing a flexible and universal platform for the targeted design and synthesis of zinc phthalocyanine derivatives with specific properties (such as different solubilities, electronic properties, and biological targeting).

[0023] 5. Broad application prospects: The obtained zinc phthalocyanine derivatives retain the excellent optical properties of the phthalocyanine core and show good application prospects in photocatalysis, organic optoelectronic materials and chemical sensing. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0025] Figure 1 Characterization diagram of the zinc phthalocyanine derivative prepared in Example 1; Figure 2 Characterization diagram of the zinc phthalocyanine derivative prepared in Example 2; Figure 3 Characterization diagram of the zinc phthalocyanine derivative prepared in Example 3; Figure 4 Characterization diagram of the zinc phthalocyanine derivative prepared in Example 4; Figure 5 Characterization diagram of the zinc phthalocyanine derivative prepared in Example 5; Figure 6 The image shows the characterization of the zinc phthalocyanine derivative prepared in Example 6. Detailed Implementation

[0026] This invention provides a zinc phthalocyanine derivative, the structure of which is as follows:

[0027] Wherein, Y includes H and / or Cl; X is -CH2-NR1R2 or -CH2-R3, and R1 and R2 are independently selected from hydrogen, C1~C1, C2, and C2, respectively. 12 The alkyl group or a cycloalkyl group of C3 to C8; wherein R3 is a nitrogen-containing heterocycle formed by R1, R2 and a nitrogen atom or R1, R2, a nitrogen atom and a heteroatom, wherein the heteroatom includes N, O or S; wherein the nitrogen-containing heterocycle is connected to the methylene group in X via a nitrogen atom; Both m and n are non-negative integers, and m+n=4, m≥1; the specific value of m can be 1, 2, 3, or 4.

[0028] In this invention, the nitrogen-containing heterocycle is selected from one of pyrrolidinyl, piperidinyl, morpholinyl, and piperazineyl.

[0029] This invention also provides a method for preparing a zinc phthalocyanine derivative, comprising the following steps: 1) Zinc phthalocyanine and a chloromethylating agent were subjected to a chloromethylation reaction under Lewis acid catalyst conditions to obtain a chloromethylated zinc phthalocyanine intermediate; 2) The chloromethylated zinc phthalocyanine intermediate was reacted with an amine under acid-binding conditions to undergo a nucleophilic substitution reaction to obtain a zinc phthalocyanine derivative.

[0030] In this invention, the chloromethylating agent includes one or more of thionyl chloride, phosphorus oxychloride, chloromethyl methyl ether, chloromethyl ethyl ether, chloromethyl phenyl ether, dichloromethyl ether, a mixture of paraformaldehyde and hydrogen chloride, and a mixture of formaldehyde and hydrogen chloride.

[0031] In this invention, the Lewis acid catalyst includes one or more of zinc chloride, ferric chloride, and aluminum chloride.

[0032] In this invention, the molar ratio of zinc phthalocyanine, chloromethylating agent and Lewis acid catalyst is 1:4~10:0.5~1.2, preferably 1:5~8:0.6~1, and more preferably 1:6:0.8.

[0033] In this invention, the temperature of the chloromethylation reaction in step 1) is 50~120℃, specifically 60℃, 70℃, 80℃, 90℃, 100℃, or 110℃; the time is 2~24h, specifically 4h, 5h, 6h, 8h, 10h, 12h, 15h, 18h, 20h, or 22h.

[0034] In this invention, the molar ratio of the chloromethylated zinc phthalocyanine intermediate, the amine substance and the acid-binding agent is 1:2~50:2~20, preferably 1:10~40:5~15, and more preferably 1:20~30:10.

[0035] In this invention, the amine substances include one or more of propylamine, dimethylamine, aniline, o-phenylenediamine, morpholine, piperidine, carbazole, etc.

[0036] In this invention, the acid-binding agent includes one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, N,N-diisopropylethylamine, and pyridine.

[0037] In this invention, the temperature of the nucleophilic substitution reaction in step 2) is 20~80℃, specifically 30℃, 40℃, 50℃, 60℃, or 70℃; the time is 4~48h, specifically 5h, 6h, 8h, 10h, 12h, 15h, 18h, 20h, 24h, 30h, 36h, or 42h.

[0038] In this invention, an inorganic alkaline substance or an organic alkaline substance is preferably used to adjust the pH value; the inorganic alkaline substance is preferably one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide; the organic alkaline substance is preferably one or more of triethylamine, N,N-diisopropylethylamine, and pyridine.

[0039] This invention also provides an application of zinc phthalocyanine derivatives as photocatalytic reaction catalysts, photoelectric active layer materials, or sensor sensitive materials.

[0040] In this invention, zinc phthalocyanine derivatives can be used as catalysts in photocatalytic reactions, as photoelectric active layer materials in the preparation of organic solar cells, organic field-effect transistors or organic light-emitting diodes, and as sensitive materials in the preparation of chemielectric resistive gas sensors.

[0041] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0042] Example 1

[0043] Synthesis of zinc phthalocyanine tetra(N,N-dimethylamino) derivative (compound 1)

[0044] In a 1000 mL three-necked flask equipped with a magnetic induction valve, condenser, and nitrogen protection, zinc phthalocyanine (10 g, 17.3 mmol) and chloromethyl methyl ether (8.0 mL, 106.3 mmol) were added. Anhydrous chlorobenzene (300 mL) was then slowly added as a solvent, and anhydrous zinc chloride (2.2 g, 16.1 mmol) was added as a catalyst. The reaction mixture was heated to 80 °C under nitrogen protection and stirred under reflux for 12 hours. After the reaction was complete, it was cooled to room temperature, and the reaction solution was slowly poured into ice water to quench it. The mixture was filtered, and the resulting solid was washed successively with water, ethanol, and n-hexane, and dried under vacuum to give a dark blue solid chloromethylated zinc phthalocyanine intermediate (12.2 g). Mass spectrometry confirmed that it was mainly a product with an average degree of substitution of 4.

[0045] The chloromethylated zinc phthalocyanine intermediate (5.2 g, 6.7 mmol) and a THF solution of dimethylamine (2.0 mol / L, 150 mL, 300 mmol dimethylamine) obtained above were added to a 500 mL round-bottom flask. Triethylamine (10 mL, 71.9 mmol) was added as an acid-binding agent, and anhydrous THF (200 mL) was added as a solvent. The reaction mixture was stirred at 40 °C for 24 hours. After the reaction was completed, most of the solvent was removed by vacuum distillation. The residue was dissolved in dichloromethane and washed three times with water. The organic phase was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (eluent: dichloromethane / methanol = 20 / 1, v / v) to give compound 1 (4.5 g, 85% yield), a dark blue solid product. The structural formula is as follows:

[0046] Characterization diagram of compound 1 is shown below Figure 1 As shown, the characterization data is as follows: LCMS: m / z [M C 44 H 48 N 12 Zn: Measured value 810.33.

[0047] UV-Vis (DMSO): λmax = 675 nm.

[0048] 1 H NMR (400 MHz, DMSO-d6): δ (ppm) 8.18-7.72 (m, 4H, Pc-H), 7.66-7.33(m, 8H, Pc-H), 3.67(s, 8H, -CH2-), 2.22 (s, 24H, -N(CH3)2).

[0049] Example 2: Synthesis of zinc phthalocyanine tetra(N-morpholinyl) derivative (compound 2)

[0050] The procedure was the same as in Example 1, except that in the second step, morpholine was used instead of dimethylamine. After purification by column chromatography, a dark blue solid compound 2 (4.8 g, 80% yield) was obtained. Its structural formula is as follows:

[0051] Characterization diagram of compound 2 is shown below Figure 2 As shown, the characterization data is as follows: LCMS: m / z [M C 52 H 52 N 12 O4Zn: Measured value 974.45.

[0052] UV-Vis (DMSO): λmax = 678 nm.

[0053] 1 H NMR (400 MHz, DMSO-d6): δ (ppm) 8.15-7.63 (m, 4H, Pc-H), 7.56-7.24(m, 8H, Pc-H), 3.66 (s, 8H, -CH2-), 3.57 (t, J = 4.8 Hz, 16H, -O-CH2-), 2.42(br s, 16H, -N-CH2-).

[0054] Example 3: Synthesis of a zinc phthalocyanine tetra(4-methylimidazolyl) derivative (compound 3)

[0055] The operating procedure is the same as in Example 1, except that 4-methylimidazole is used instead of dimethylamine in the second step. After cooling, the solid is poured into 200 mL of water, and a dark green solid precipitates. The solid is filtered, washed with water until neutral, washed with ethanol / ether, and then subjected to silica gel column chromatography (C10). C The target product was obtained with a ratio of / MeOH = 20:1, in a yield of 78%. The structural formula is:

[0056] Characterization diagram of compound 3 as follows Figure 3 As shown, the characterization data is as follows: LCMS: m / z [M : m / z C 48 H 34 N 16 Zn: Measured value 900.29.

[0057] 1 ¹H NMR (400 MHz, DMSO-d6): δ (ppm) 8.12–7.27 (m, phthalocyanine ring 12H), 7.46–7.15 (m, imidazole ring 8H), 4.40 (s, -CH 2H), 2.23 (s, -CH312H).

[0058] Example 4: Synthesis of a zinc phthalocyanine tetra(2-aminopyridyl) derivative (compound 4)

[0059] The operating procedure was the same as in Example 1, except that in the second step, dimethylamine was replaced with excess 2-aminopyridine, the reaction temperature was 70°C, and the reaction time was 18 h. The product was a blue-green powder with a yield of 72%. UV-Vis analysis showed that the Q band was located at 712 nm (in DMF), a red shift of 32 nm compared to the parent compound. The structural formula is:

[0060] Characterization diagram of compound 4 is shown below Figure 4 As shown, the characterization data is as follows: LCMS: m / z [M : m / z C 52 H 34 N 16 Zn: Measured value 950.35.

[0061] ¹H NMR (400 MHz, DMSO-d6): δ (ppm) 8.36 (s, -NH- 4H), 8.03–6.73 (m, pyridine ring 16H), 7.64–6.93 (m, phthalocyanine ring 12H), 4.38 (s, -CH- 2H).

[0062] Example 5: Synthesis of a zinc phthalocyanine tetra(N-methylpiperazinyl) derivative (compound 5)

[0063] The procedure was the same as in Example 1, except that in step two, an equimolar amount of N-methylpiperazine was used instead of dimethylamine, the reaction temperature was 70°C, and the reaction time was 10 hours. After purification, a dark blue solid was obtained with a yield of 82%. The structural formula is:

[0064] Characterization diagram of compound 5 as follows Figure 5 As shown, the characterization data is as follows: LCMS: m / z [M : m / z C 56 H 66 N 16 Zn: Measured value 1028.64.

[0065] 1 ¹H NMR (400 MHz, DMSO): δ 8.15–7.28 (m, phthalocyanine ring - 12H), 4.4 (s, 2H, -CH-), 3.66 (s, 8H, -N-CH2-), 2.48–2.34 (m, 32H, piperazine ring - N-CH2-), 2.14 (s, 12H, -N-CH3).

[0066] Example 6: Synthesis of zinc phthalocyanine-tetra(piperidinyl) derivative (compound 6)

[0067] The procedure was the same as in Example 1, except that in step two, excess piperidine replaced dimethylamine. The reaction mixture was heated to 60°C and stirred under a nitrogen atmosphere for 24 hours. The reaction progress was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and poured into 200 mL of ice water, resulting in the precipitation of a blue solid. The solid was filtered and washed with water. The crude product was purified by silica gel column chromatography (eluent: dichloromethane / methanol = 20 / 1, v / v). The blue main band was collected, and the solvent was removed by rotary evaporation to obtain a dark blue solid product (4.5 g). The yield was 75%. The structural formula is:

[0068] Characterization diagram of compound 6 is shown below Figure 6 As shown, the characterization data is as follows: LCMS: m / z [M : m / z C 56 H 62 N 12 Zn: Measured value 968.58.

[0069] 1 ¹H NMR (400 MHz, DMSO-d6): δ(ppm) 8.15–7.28 (m, phthalocyanine ring 12H), 4.4 (s, -CH- 2H), 4.56 (s, -CH2N- 8H), 2.53–2.42 (m, piperidine ring 16H), 1.54–1.40 (m, piperidine ring 24H).

[0070] Ultraviolet-visible absorption spectrum (DMF): λmax 672 nm, 351 nm.

[0071] Experimental Example

[0072] Taking the zinc phthalocyanine derivative prepared in Example 1 as an example, the zinc phthalocyanine derivative prepared in Example 1 was dissolved in chloroform to prepare a solution with a concentration of 2 mg / mL. A spin-coating method (1500 rpm, 60 seconds) was used to form a film on a SiO2 / Si substrate with a pre-prepared active drain electrode (gold electrode). Subsequently, the film was vacuum annealed at 80°C for 1 hour to remove residual solvent and optimize molecular arrangement. Using the above film as an organic semiconductor layer, a bottom-gate top-contact OFET device was constructed. Using a semiconductor parameter analyzer, the transfer characteristic curves (fixed source-drain voltage V_ds, scanned gate voltage V_g) and output characteristic curves (fixed V_g, scanned V_ds) of the device were measured under vacuum or inert gas atmosphere. The results showed that the derivative film exhibited typical p-type semiconductor characteristics. Calculations showed that its hole mobility could reach 1. 3 ~1 2 The current ratio is on the order of cm² / V·s, and the on / off current ratio (I_on / I_off) is > 10. 4 The introduced dimethylamino side chain improves the solubility of the molecule in organic solvents, enabling solution processing, and can also modulate the microstructure and charge transport channels of the film through intermolecular interactions.

[0073] Taking the zinc phthalocyanine derivative prepared in Example 2 as an example, 50 ml of a prepared 10 mg / L Rhodamine B aqueous solution was taken, and 10 mg of the zinc phthalocyanine amino-functionalized derivative was added as a photocatalyst. Under visible light (λ > 420 nm) irradiation, samples were taken at regular intervals, centrifuged, and the concentration of Rhodamine B in the supernatant was measured. The results showed that this derivative could effectively catalyze the degradation of Rhodamine B under visible light irradiation, with a degradation rate exceeding 90% within 60 minutes, indicating its excellent photocatalytic performance.

[0074] Taking the zinc phthalocyanine derivative prepared in Example 6 as an example, the TiO2 electrode was modified with the derivative of Example 6, and dye-sensitized solar cells (DSSCs) were assembled. Under AM 1.5 illumination, the photoelectric conversion efficiency reached 6.2%, which was better than that of unmodified ZnPc (η=4.5%).

[0075] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0076] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A zinc phthalocyanine derivative, characterized in that, The structure of the zinc phthalocyanine derivative is as follows: Wherein, Y includes H and / or Cl; X is -CH2-NR1R2 or -CH2-R3, and R1 and R2 are independently selected from hydrogen, C1~C1, C2, and C2, respectively. 12 The alkyl group or a cycloalkyl group of C3 to C8; wherein R3 is a nitrogen-containing heterocycle formed by R1, R2 and a nitrogen atom or R1, R2, a nitrogen atom and a heteroatom, wherein the heteroatom includes N, O or S; wherein the nitrogen-containing heterocycle is connected to the methylene group in X via a nitrogen atom; Both m and n are non-negative integers, and m+n=4, m≥1.

2. A zinc phthalocyanine derivative according to claim 1, characterized in that, The nitrogen-containing heterocycle is selected from one of pyrrolidinyl, piperidinyl, morpholinyl, and piperazineyl.

3. The method for preparing a zinc phthalocyanine derivative according to claim 1 or 2, characterized in that, Includes the following steps: 1) Zinc phthalocyanine and a chloromethylating agent were subjected to a chloromethylation reaction under Lewis acid catalyst conditions to obtain a chloromethylated zinc phthalocyanine intermediate; 2) The chloromethylated zinc phthalocyanine intermediate was reacted with an amine under acid-binding conditions to undergo a nucleophilic substitution reaction to obtain a zinc phthalocyanine derivative.

4. The method for preparing a zinc phthalocyanine derivative according to claim 3, characterized in that, The chloromethylating agent includes one or more of the following: thionyl chloride, phosphorus oxychloride, chloromethyl methyl ether, chloromethyl diethyl ether, chloromethyl phenyl ether, dichloromethyl ether, a mixture of paraformaldehyde and hydrogen chloride, and a mixture of formaldehyde and hydrogen chloride. The Lewis acid catalyst includes one or more of zinc chloride, ferric chloride, and aluminum chloride.

5. The method for preparing a zinc phthalocyanine derivative according to claim 4, characterized in that, The molar ratio of zinc phthalocyanine, chloromethylating agent and Lewis acid catalyst is 1:4~10:0.5~1.

2.

6. A method for preparing a zinc phthalocyanine derivative according to any one of claims 3 to 5, characterized in that, The chloromethylation reaction in step 1) is carried out at a temperature of 50~120℃ for 2~24h.

7. The method for preparing a zinc phthalocyanine derivative according to claim 6, characterized in that, The molar ratio of the chloromethylated zinc phthalocyanine intermediate, the amine, and the acid-binding agent is 1:2~50:2~20.

8. The method for preparing a zinc phthalocyanine derivative according to claim 7, characterized in that, The amines include one or more of the following: propylamine, dimethylamine, aniline, o-phenylenediamine, morpholine, piperidine, carbazole, etc. The acid-binding agent includes one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, triethylamine, N,N-diisopropylethylamine, and pyridine.

9. A method for preparing a zinc phthalocyanine derivative according to claim 7 or 8, characterized in that, The nucleophilic substitution reaction in step 2) is carried out at a temperature of 20-80°C for 4-48 hours.

10. The application of a zinc phthalocyanine derivative as described in claim 1 or 2 as a photocatalytic reaction catalyst, a photoelectric active layer material, or a sensor sensitive material.

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