Carbon-carbon double bond connected cyanine dye conjugated organic framework material as well as preparation method and application thereof

Abstract

The invention relates to a carbon-carbon double bond connected cyanine dye conjugated organic framework material as well as a preparation method and application thereof, and belongs to the technical field of conjugated polymer materials. The carbon-carbon double bond connected cyanine dye conjugated organic framework material prepared by introducing a cyanine dye into a conjugated organic framework material has excellent optical properties, the absorption spectrum can be expanded to 2000 nm, the material has excellent photo-thermal conversion properties under near-infrared laser irradiation, the ultrahigh temperature of 450 DEG C can be reached, and the stability is good; the preparation method is simple in process and low in cost; and carbon-carbon double bonds can be broken under the action of reductive amine and are degraded into monomers, so that raw materials are recycled.

Description

Technical Field

[0001] This invention relates to a carbon-carbon double-bonded cyanine dye conjugated organic framework material, its preparation method, and its application, belonging to the field of conjugated polymer materials technology. Background Technology

[0002] Covalent organic frameworks (COFs) are porous crystalline materials composed of organic monomers linked by covalent bonds. They possess highly ordered structures, large specific surface areas, and tunable functionality, showing broad application prospects in gas storage, catalysis, and photoelectric conversion. Traditional COF materials are mainly constructed based on imine bonds, typically using aniline molecules as amine sources, which are then condensed with aromatic aldehyde molecules to form a network structure linked by carbon-nitrogen double bonds. Fully conjugated covalent organic frameworks based on carbon-carbon double bonds are a class of highly promising semiconductor materials that have attracted much attention in recent years. Compared to carbon-nitrogen double bonds, strongly conjugated carbon-carbon double bonds not only maintain the stability of the framework under extreme conditions but also provide extended π-conjugation throughout the framework, thereby achieving efficient electron transport and endowing these sp²-carbon linked COFs with excellent photoelectric properties. The formation of cyano-substituted carbon-carbon double bonds through aldol condensation between arylacetonitrile and aromatic aldehydes is currently the main strategy for designing and synthesizing sp²-carbon linked COFs. In addition, electron-deficient triazine molecules or pyridinium molecules can also react efficiently with aromatic aldehydes to synthesize sp² carbon-linked COFs. However, due to the poor reversibility of carbon-carbon double bond formation, the synthesis of sp² carbon-linked COFs remains a significant challenge.

[0003] Of particular note is that there are currently no reports of using cyanine dye molecules as monomers to synthesize novel COFs based on C=C bonds. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a carbon-carbon double bond-linked cyanine dye conjugated organic framework material, its preparation method and its application.

[0005] To achieve the above objectives, the technical solution of the present invention is as follows.

[0006] A carbon-carbon double-bonded cyanine dye conjugated organic framework material, wherein the repeating unit structure of the material is as follows:

[0007] ; Where R is -H or -OH; The structure is as follows (1) or (2): ; X is Cl, Br, or I; n is an integer from 1 to 3; R1 and R2 are alkyl groups with 1 to 6 carbon atoms; It is one of the following structures: .

[0008] A method for preparing a cyanine dye conjugated organic framework material with carbon-carbon double bonds, the method comprising the following steps: (1) Preparation of solid chemical compound 1 by reaction of 1,8-naphthimide with liquid bromine: Dissolve 1,8-naphthimide in chloroform, add liquid bromine dropwise, stir the reaction for 10-12 h, filter, wash, and obtain solid compound 1; (2) Solid compound 1 and 1-haloalkanes react to prepare solid compound 2: Solid compound 1, 1-haloalkanes and sodium carbonate are dissolved in an organic solvent and reacted at 80~90℃ for 10~12h. After the reaction is completed, the reaction solution is filtered to remove sodium carbonate, concentrated and separated to obtain solid compound 2. (3) NATO-nAr is prepared by reacting solid compound 2 and reactant 1. The structural formula of reactant 1 is: n is an integer from 1 to 3, and Y is borate or tin alkyl: Under a protective gas atmosphere, solid compound 2 and reactant 1 are dissolved in an organic solvent, and then tetrakis(triphenylphosphine)palladium and sodium carbonate are added. The reaction is carried out at 80-110°C for 10-12 h. After the reaction is completed, the mixture is extracted, dried, concentrated, and separated by column chromatography to obtain solid compound NATO-nAr. (4) NATO-nAr first reacts with methylmagnesium chloride, then hydrohalic acid is added until the solution changes color, and then reactant 2 is added to prepare the solution. The reaction is a cyanine dye conjugated organic framework material with carbon-carbon double bonds linked by NAT-nX. Reactant 2 is pyromellitic methylformaldehyde or trialdehyde phloroglucinol: Under a protective gas atmosphere, NATO-nAr is added to anhydrous tetrahydrofuran, followed by the dropwise addition of methyl magnesium chloride. The reaction is carried out at 55-65℃ for 1-2 hours, then cooled. Hydrohalic acid is added until the solution changes color, and then the tetrahydrofuran-ethanol organic solvent of reactant 2 is added. The reaction continues for more than 24 hours. The resulting solid is washed to obtain... A cyanine dye conjugated organic framework material (NAT-nAr-COF) with carbon-carbon double bonds linked by NAT-nX. The reaction equation is: ; The repeating structural unit of NAT-nAr-COF is one of the following structures: .

[0009] Preferably, in step (1), the molar ratio of 1,8-naphthalimide to liquid bromine is 1:1 to 1.5.

[0010] Preferably, in step (2), the molar ratio of the solid compound 1, 1-haloalkane and sodium carbonate is 1:1~1.5:2~2.5.

[0011] Preferably, in step (3), the molar ratio of the solid compound 2 to the reactant 1 is 2~3:1.

[0012] Preferably, in step (4), the molar ratio of NATO-nAr, methyl magnesium chloride, and reactant 2 is 1:5~6:0.5~1.

[0013] A method for preparing a cyanine dye conjugated organic framework material with carbon-carbon double bonds, the method comprising the following steps: (1) 2,3,3-Trimethyl-5-bromo-3H-indole reacts with reactant 1 to prepare cured compound 3. The structural formula of reactant 1 is: n is an integer from 1 to 3, and Y is borate or tin alkyl: Under a protective atmosphere, 2,3,3-trimethyl-5-bromo-3H-indole, reactant 1 and tetratriphenylphosphine palladium are dissolved in an organic solvent and heated under reflux at 80-110°C for 12-16 h. After the reaction is complete, the mixture is extracted with dichloromethane, the organic phase is dried with anhydrous sodium sulfate, concentrated and separated by column chromatography to obtain solid compound 3; (2) Preparation of ID-nAr by reaction of solid compound 3 and 1-haloalkanes: solid compound 3 and 1-haloalkanes were dissolved in anhydrous acetonitrile and reacted at 60~80℃ for 5~8h. After the reaction was completed, the mixture was filtered and washed to obtain yellow solid ID-nAr. (3) Preparation by reaction of ID-nAr and reactant 2 For ID-nX carbon-carbon double-bonded cyanine dye conjugated organic framework materials, reactant 2 is pyromellitic trimethylolpropionate or trialdehyde phloroglucinol: ID-nAr and reactant 2 are dissolved in a tetrahydrofuran-ethanol mixed solvent and reacted at 80-90℃ for more than 24 hours. The resulting solid is washed to obtain... A cyanine dye conjugated organic framework material with carbon-carbon double bonds linked by ID-nX (ID-nAr-COF). The reaction equation is: ; The repeating structural unit of ID-nAr-COF is one of the following structures: .

[0014] Preferably, in step (1), the molar ratio of 2,3,3-trimethyl-5-bromo-3H-indole to reactant 1 is 2~3:1.

[0015] Preferably, in step (2), the molar ratio of the solid compound 3 and the 1-haloalkane is 1:1 to 1.5.

[0016] Preferably, in step (3), the molar ratio of ID-nAr to reactant 2 is 1:0.5~1.

[0017] Application of a carbon-carbon double-bonded cyanine dye conjugated organic framework material as a photothermal conversion material.

[0018] Application of a carbon-carbon double-bonded cyanine dye conjugated organic framework material as a near-infrared laser ignition photothermal agent.

[0019] A method for recovering raw materials of cyanine dye conjugated organic framework materials with carbon-carbon double bonds, the method comprising the following steps: dispersing the cyanine dye conjugated organic framework material with carbon-carbon double bonds in a mixed solvent of ethanol and dichloroethane, adding reducing amine, heating and stirring at 60±5℃ for more than 24 hours, filtering, separating the filtrate by column chromatography, and recovering pyromellitic methyl pyrogallol or trialdehyde pyrogallol.

[0020] Beneficial effects This invention introduces cyanine dyes into conjugated organic conjugated framework materials (COFs) to prepare carbon-carbon double-bonded organic conjugated framework materials. Cyanine dye molecules are a class of analogues containing positively charged indole salts. Their electron-deficient properties endow the terminal methyl groups with high reactivity, enabling them to undergo efficient aldol condensation reactions with aromatic aldehyde groups to form stable carbon-carbon double bonds. These double bonds are reversible, allowing for degradation and recovery of raw materials in the presence of reducing amines, thus providing a potential alternative monomer for the synthesis of sp2-carbon linked COFs. Furthermore, cyanine dyes possess strong light-harvesting capabilities due to their unique conjugated structure and photosensitivity. Integrating these molecules into COF frameworks not only allows for the synthesis of COFs with higher conjugation but also endows the materials with excellent optical properties, significantly enhancing the potential of COFs in optoelectronic, photothermal, and biomedical applications. Moreover, the reversibility of the carbon-carbon double bond enables the reversible degradation of the synthesized polymer materials, facilitating the recovery of raw materials, which is of great significance for resource conservation and utilization.

[0021] This invention introduces cyanine dyes into conjugated organic framework materials to prepare carbon-carbon double-bonded cyanine dye conjugated organic framework materials. These materials possess excellent optical properties, with an absorption spectrum extending to 2000 nm. Under near-infrared laser irradiation, they exhibit excellent photothermal conversion properties, reaching ultra-high temperatures of 450℃ and demonstrating good stability. The preparation method is simple and low-cost. Furthermore, the carbon-carbon double bonds can be broken and degraded into monomers under the action of reducing amines, thereby recovering the raw materials. This invention has potential applications in the resource recovery and utilization of organic materials. Attached Figure Description

[0022] Figure 1 These are the XRD patterns of the final products in Examples 1-4 of this invention.

[0023] Figure 2 These are the diffuse reflectance spectra of the final products in Examples 1-4 of this invention.

[0024] Figure 3 This refers to the photothermal conversion efficiency of NAT-B-COF1 in this embodiment of the invention.

[0025] Figure 4 These are actual images of NAT-B-COF1 before and after degradation in an application example of this invention.

[0026] Figure 5 These are NMR images of NAT-B-COF1 before and after degradation in an application example of this invention. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to specific embodiments.

[0028] Example 1 Taking R=H, R1=CH2(CH2)4CH3, Ar as benzene, and n=1 as an example, this embodiment provides a method for synthesizing NAT-B-COF1.

[0029] The synthesis route is as follows: .

[0030] The structure of NAT-B-COF1 is as follows: .

[0031] The specific preparation method is as follows: 1,8-Naphthimide (1.69 g, 10 mmol) was dissolved in 50 mL of chloroform, and liquid bromine (1.92 g, 12 mmol) was added dropwise. The mixture was stirred at room temperature for 12 hours. After the reaction was complete, the solution was poured into 200 mL of saturated sodium thiosulfate solution, filtered, and the precipitate was washed with water to give a yellow solid compound 1 (2.36 g, 95%).

[0032] Compound 1 (1 g, 3.01 mmol), 1-bromohexane (596 mg, 3.61 mmol), and sodium carbonate (638 mg, 6.02 mmol) were dissolved in 30 mL of anhydrous acetonitrile and anhydrous tetrahydrofuran (v:v = 2:1), and the mixture was heated under reflux at 80 °C for 12 hours. After the reaction was completed, the reaction solution was filtered to remove sodium carbonate, and the filtrate was concentrated and separated by column chromatography with petroleum ether / dichloromethane in a volume ratio of 2:1 to give a yellow solid compound 2 (829 mg, 83%).

[0033] Compound 2 (500 mg, 1.51 mmol) and 1,4-diphenylboronic acid (116 mg, 0.70 mmol) were dissolved in a mixture of 16 mL tetrahydrofuran and 4 mL water, and the mixture was subjected to a freeze-elution reaction three times. After the third freeze-elution, tetra(triphenylphosphine)palladium (162 mg, 0.14 mmol) and sodium carbonate (297 mg, 2.8 mmol) were added under a nitrogen atmosphere, and the mixture was further evacuated for five minutes. After thawing, the mixture was refluxed at 90 °C for 16 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography with petroleum ether / ethyl acetate (v / v) to give a yellow solid compound NATO-B (337 mg, 83%).

[0034] Under a nitrogen atmosphere, NATO-B (30 mg, 0.052 mmol) and 0.5 mL of anhydrous tetrahydrofuran were added to a Schlenk flask, followed by a 3M tetrahydrofuran solution of magnesium methyl chloride (0.09 mL, 0.27 mmol). The reaction was carried out at 60 °C for 1 hour. After cooling, hydrochloric acid was added under a nitrogen atmosphere until the solution turned red. Then, 4 mL of ethanol and 0.5 mL of a tetrahydrofuran solution of trimesaldehyde (5.6 mg, 0.035 mmol) were added, and the reaction was carried out at 90 °C for 24 hours. The resulting black precipitate was filtered, washed with tetrahydrofuran, water, and ethanol, respectively, and then freeze-dried to obtain NAT-B-COF1.

[0035] The XRD pattern of NAT-B-COF1 was obtained using an X-ray diffractometer, as follows: Figure 1 As shown.

[0036] The diffuse reflectance map of NAT-B-COF1 was obtained using a violet-visible-near-infrared spectrophotometer, as follows: Figure 2 As shown. From Figure 2 It can be seen that NAT-B-COF1 has a broad absorption spectrum, from 400 nm to 2000 nm, with a maximum absorption wavelength at 850 nm, which is far greater than the absorption wavelength of COF materials reported so far.

[0037] Calculations show that the photothermal conversion efficiency of NAT-B-COF1 under 1064nm laser irradiation is 92.16%. Figure 3 As shown.

[0038] Example 2 Taking R=OH, R1=CH2(CH2)4CH3, Ar as furan, and n=2 as an example, this embodiment provides a method for synthesizing NAT-2F-COF2, with the following structural formula:

[0039] The synthesis route is as follows:

[0040] The specific preparation method is as follows: Under a nitrogen atmosphere, compound 2 (500 mg, 1.51 mmol), 5,5'-bis(trimethyltinyl)-2,2'-bifuran (322 mg, 0.70 mmol), and tetrakis(triphenylphosphine)palladium (162 mg, 0.14 mmol) were dissolved in anhydrous toluene and heated to reflux at 110 °C for 14 hours. After the reaction was complete, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography with petroleum ether / ethyl acetate in a volume ratio of 2:1 to give a yellow solid NATO-2F (190 mg, 74%).

[0041] Under a nitrogen atmosphere, NATO-2F (30 mg, 0.047 mmol) and 0.5 mL of anhydrous tetrahydrofuran were added to a Schlenk flask, followed by a 3M tetrahydrofuran solution of magnesium methyl chloride (0.08 mL, 0.24 mmol). The mixture was heated to reflux at 60 °C for 1 hour. After cooling, hydrochloric acid was added under a nitrogen atmosphere until the solution turned red. Then, a tetrahydrofuran solution of 4 mL ethanol and 0.5 mL of trialdehyde phloroglucinol (5.1 mg, 0.031 mmol) was added, and the mixture was reacted at 60 °C for 24 hours. The resulting black precipitate was filtered, washed with tetrahydrofuran, water, and ethanol, and then freeze-dried to obtain NAT-2F-COF2.

[0042] The XRD pattern of NAT-2F-COF2 was obtained using an X-ray diffractometer, as follows: Figure 1 As shown.

[0043] The diffuse reflectance of NAT-2F-COF2 was obtained using a violet-visible-near-infrared spectrophotometer, as shown below. Figure 2 As shown.

[0044] Example 3 Taking R=H, R1=CH3, Ar as benzene, and n=1 as an example, this embodiment provides a method for synthesizing ID-B-COF1, with the following structural formula:

[0045] The synthesis route is as follows:

[0046] The specific preparation method is as follows: 2,3,3-Trimethyl-5-bromo-3H-indole (520 mg, 2.18 mmol) and 1,4-diphenylboronic acid (166 mg, 1.00 mmol) were dissolved in a mixture of 16 mL tetrahydrofuran and 4 mL water, and the mixture was subjected to a freeze-elution reaction three times. After the third freeze-elution, tetratetraphenylphosphine palladium (231 mg, 0.20 mmol) and sodium carbonate (424 mg, 4.00 mmol) were added under a nitrogen atmosphere, and the mixture was further evacuated for five minutes. After thawing, the mixture was refluxed at 90 °C for 16 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography with petroleum ether / ethyl acetate (v / v) to give a yellow solid compound 3 (318 mg, 81%).

[0047] Compound 3 (100 mg, 0.25 mmol) and 0.1 mL of iodomethane were dissolved in 10 mL of anhydrous acetonitrile and reacted at 80°C for 5 hours. After the reaction was complete, the solution was poured into anhydrous diethyl ether, filtered, and the precipitate was washed with diethyl ether to give a yellow solid ID-B (166 mg, 98%).

[0048] ID-B (30 mg, 0.044 mmol) and trimesin (4.8 mg, 0.029 mmol) were dissolved in 4 mL of ethanol and 1 mL of tetrahydrofuran solution, and the mixture was subjected to freeze-elution three times. The reaction was carried out at 90 °C for 24 hours under a nitrogen atmosphere. The resulting black precipitate was filtered and washed with tetrahydrofuran, water, and ethanol, respectively, and then freeze-dried to obtain ID-B-COF1.

[0049] The XRD pattern of ID-B-COF1 was obtained using an X-ray diffractometer, as follows: Figure 1 As shown.

[0050] The diffuse reflectance map of ID-B-COF1 was obtained using a violet-visible-near-infrared spectrophotometer, as shown below. Figure 2 As shown.

[0051] Example 4 Taking R=OH, R1=CH3, Ar as furan, and n=2 as an example, this embodiment provides a method for synthesizing ID-2F-COF2, with the following structural formula:

[0052] The synthesis route is as follows:

[0053] The specific preparation method is as follows: Under a nitrogen atmosphere, 2,3,3-trimethyl-5-bromo-3H-indole (520 mg, 2.18 mmol), 5,5'-bis(trimethyltinyl)-2,2'-bifuran (460 mg, 1.00 mmol), and tetraphenylphosphine palladium (231 mg, 0.20 mmol) were dissolved in anhydrous toluene and the mixture was refluxed at 110 °C for 14 hours. After the reaction was complete, the mixture was extracted with dichloromethane, dried over anhydrous sodium sulfate, concentrated, and separated by column chromatography with petroleum ether / ethyl acetate in a volume ratio of 2:1 to give a yellow solid 4 (359 mg, 80%).

[0054] Compound 4 (100 mg, 0.22 mmol) and 0.1 mL of iodomethane were dissolved in 10 mL of anhydrous acetonitrile and reacted at 80°C for 5 hours. After the reaction was completed, the solution was poured into anhydrous diethyl ether, filtered, and the precipitate was washed with diethyl ether to give a yellow solid ID-2F (155 mg, 96%).

[0055] ID-2F (30 mg, 0.041 mmol) and trimesin (4.4 mg, 0.027 mmol) were dissolved in 4 mL of ethanol and 1 mL of tetrahydrofuran solution, and the mixture was subjected to freeze-elution three times. The reaction was carried out at 60 °C for 24 hours under a nitrogen atmosphere. The resulting black precipitate was filtered and washed with tetrahydrofuran, water, and ethanol, respectively, and then freeze-dried to obtain ID-2F-COF.

[0056] The XRD pattern of ID-2F-COF2 was obtained using an X-ray diffractometer, as shown below. Figure 1 As shown.

[0057] The diffuse reflectance of ID-2F-COF2 was obtained using a violet-visible-near-infrared spectrophotometer, as shown below. Figure 2 As shown.

[0058] Example 5 NAT-2B-COF1 was synthesized using 4,4'-biphenyldiboronic acid instead of 1,4-diphenylboronic acid, as described in Example 1.

[0059] Example 6 NAT-3B-COF1 was synthesized using 1,1':4'-,1''-triphenyl]-4,4'-dimethyldiboronic acid instead of 1,4-diphenylboronic acid, as described in Example 1.

[0060] Example 7 NAT-3F-COF2 was synthesized using 3F-2Sn instead of 5,5'-bis(trimethylstanyl)-2,2'-bifuran, as described in Example 2. The synthetic route for 3F-Sn is as follows:

[0061] The specific preparation method is as follows: Furan (10 g, 147.06 mmol) and NBS (55 g, 309.0 mmol) were weighed and added to a 500 mL round-bottom flask. 200 mL of tetrahydrofuran was added, and the mixture was stirred at room temperature for 12 hours. After removing the solution, 150 mL of water was added to the mixture. The mixture was extracted with n-hexane (30 mL × 3), the organic phase was washed with sodium thiosulfate solution, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography (using n-hexane as eluent) to give compound 5, a colorless liquid (3.3 g, 10% yield).

[0062] Compound 5 (2 g, 8.88 mmol), tributyl(furan-2-yl)stanane (6.67 g, 18.67 mmol), and tetrakis(triphenylphosphine)palladium (1.5 g, 1.33 mmol) were weighed and added to a 250 mL Schlenk flask. Under a nitrogen atmosphere, 100 mL of anhydrous toluene was added, and the mixture was reacted at 110 °C for 12 hours. After the reaction was complete, toluene was removed by rotary evaporation. The mixture was then stirred with a saturated potassium fluoride aqueous solution and extracted with n-hexane (30 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by column chromatography (using petroleum ether as eluent) to give compound 6 as a white solid (1.2 g, 70% yield).

[0063] Compound 6 (0.5 g, 2.5 mmol) was weighed and added to a 50 mL Schlenk flask. 5 mL of anhydrous tetrahydrofuran was added under a nitrogen atmosphere, and the mixture was stirred at -78 °C for 30 minutes. Butyllithium (2.5 M, 2.2 mL, 5.5 mmol) was slowly added dropwise. After the addition was complete, the mixture was stirred at -78 °C for 2 hours, then at -40 °C for 1 hour. Trimethyltin chloride (1 M, 6 mL, 6.0 mmol) was added dropwise to the mixture. After slowly warming to room temperature, water was added to the mixture, and the mixture was extracted with n-hexane (30 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product obtained did not require purification.

[0064] Example 8 NAT-2T-COF2 was synthesized using 5,5'-bis(trimethylstanyl)-2,2'-bithiophene instead of 5,5'-bis(trimethylstanyl)-2,2'-bifuran, as described in Example 2.

[0065] Example 9 NAT-3T-COF2 was synthesized using 3T-2Sn instead of 5,5'-bis(trimethylstanyl)-2,2'-bifuran, as described in Example 2. The synthetic route of 3T-Sn is as follows:

[0066] The specific preparation method is as follows: Thiophene (10 g, 119.05 mmol) and NBS (46.62 g, 261.9 mmol) were weighed and added to a 500 mL round-bottom flask. 200 mL of tetrahydrofuran was added, and the mixture was stirred at room temperature for 12 hours. After removing the solution, 150 mL of water was added to the mixture. The mixture was extracted with n-hexane (30 mL × 3), the organic phase was washed with sodium thiosulfate solution, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product was purified by column chromatography (using n-hexane as eluent) to give compound 7, a colorless liquid (7.8 g, 27% yield).

[0067] Compound 7 (2 g, 6.85 mmol), tributyl(thiophen-2-yl)stanane (5.62 g, 15.07 mmol), and tetrakis(triphenylphosphine)palladium (1.29 g, 1.03 mmol) were weighed and added to a 250 mL Schlenk flask. Under a nitrogen atmosphere, 100 mL of anhydrous toluene was added, and the mixture was reacted at 110 °C for 12 hours. After the reaction was complete, toluene was removed by rotary evaporation. The mixture was then stirred with a saturated potassium fluoride aqueous solution and extracted with n-hexane (30 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated. The crude product was purified by column chromatography (using petroleum ether as eluent) to give compound 8 as a white solid (1.4 g, 82% yield).

[0068] Compound 7 (0.5 g, 2.02 mmol) was weighed and added to a 50 mL Schlenk flask. 5 mL of anhydrous tetrahydrofuran was added under a nitrogen atmosphere, and the mixture was stirred at -78 °C for 30 minutes. Butyllithium (2.5 M, 1.78 mL, 4.44 mmol) was slowly added dropwise. After the addition was complete, the mixture was stirred at -78 °C for 2 hours, then at -40 °C for 1 hour. Trimethyltin chloride (1 M, 4.5 mL, 4.5 mmol) was added dropwise to the mixture. After slowly raising the temperature to room temperature, water was added to the mixture, and the mixture was extracted with n-hexane (30 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation. The crude product obtained did not require purification.

[0069] Example 10 ID-2B-COF1 was synthesized using 4,4'-biphenyldiboronic acid instead of 1,4-diphenylboronic acid, as described in Example 3.

[0070] Example 11 ID-3B-COF1 was synthesized using 1,1':4'-,1''-triphenyl]-4,4'-dimethyldiboronic acid instead of 1,4-diphenylboronic acid, as described in Example 3.

[0071] Example 12 ID-3F-COF2 was synthesized using 3F-2Sn instead of 5,5'-bis(trimethylstanyl)-2,2'-bifuran, as described in Example 4. The synthesis of 3F-2Sn was described in Example 7.

[0072] Example 13 ID-2T-COF2 was synthesized using 5,5'-bis(trimethylstanyl)-2,2'-bithiophene instead of 5,5'-bis(trimethylstanyl)-2,2'-bifuran, as described in Example 4.

[0073] Example 14 ID-3T-COF2 was synthesized using 3T-2Sn instead of 5,5'-bis(trimethylstanyl)-2,2'-bifuran, as described in Example 2. The synthesis of 3T-Sn was described in Example 9.

[0074] Application Example 1 The carbon-carbon double-bonded cyanine dye conjugated organic framework material from Example 1 was attached to the red phosphorus of a match using a small amount of glue. An 808 nm laser was set to a power density of 1.0 W / cm². 2 A match was placed 10 cm from the laser, and within twenty seconds, the match ignited because the material's temperature rose above the ignition point of red phosphorus. The 1064 nm laser was set to a power density of 0.8 W / cm². 2 When the match is 5 cm away from the laser, it is ignited within 10 seconds because the material heats up and exceeds the ignition point of red phosphorus.

[0075] Application Example 2 The carbon-carbon double bond-linked cyanine dye conjugated organic framework materials from Examples 1-4 were degraded by trimethylamine to recover the raw material, trimesin. The operation steps are as follows: COFs based on cyanine dyes were dispersed in a mixed solution of ethanol and dichloroethane, and an aqueous solution of trimethylamine was added. The mixture was heated and stirred at 60°C for 24 hours. After filtration, extraction with dichloromethane, and concentration, the filtrate was separated by column chromatography to obtain the starting material pyromellitic aldehyde and compound A. Figure 4 , 5 As shown, Figure 4 These are images of NATB-COF materials before and after degradation. Figure 5 The NMR spectra of the recovered trimethylbenzene and compound A are compared with those of the raw materials.

[0076] In summary, the invention includes, but is not limited to, the above embodiments. Any equivalent substitutions or partial improvements made under the spirit and principles of this invention shall be considered to be within the protection scope of this invention.

Claims

1. A cyanine dye conjugated organic framework material with carbon-carbon double bonds, characterized in that: The repeating unit structure of the material is as follows: ； Where R is -H or -OH; The structure is as follows (1) or (2): ； X is Cl, Br, or I; n is an integer from 1 to 3; R1 and R2 are alkyl groups with 1 to 6 carbon atoms; It is one of the following structures: 。 2. A method for preparing a cyanine dye conjugated organic framework material with carbon-carbon double bonds as described in claim 1, characterized in that: The method steps include: (1) Solid chemical 1 was prepared by reacting 1,8-naphthalimide with liquid bromine; (2) Solid compound 1 was reacted with a 1-haloalkane to prepare solid compound 2; (3) NATO-nAr is prepared by reacting solid compound 2 and reactant 1. The structural formula of reactant 1 is: n is an integer from 1 to 3, and Y is a borate or tin alkyl group; (4) NATO-nAr first reacts with methylmagnesium chloride, then hydrohalic acid is added until the solution changes color, and then reactant 2 is added to prepare the solution. The NAT-nX carbon-carbon double bond-linked cyanine dye conjugated organic framework material, reactant 2 is pyromellitic trimethylol or trialdehyde phloroglucinol; The reaction equation is: ； The repeating structural unit of NAT-nAr-COF is one of the following structures: 。 3. The method for preparing a carbon-carbon double-bonded cyanine dye conjugated organic framework material as described in claim 2, characterized in that: (1) Dissolve 1,8-naphthalimide in chloroform, add liquid bromine dropwise, stir for 10-12 h, filter, wash, and obtain solid compound 1; (2) Dissolve solid compound 1, 1-haloalkane and sodium carbonate in an organic solvent and react at 80~90℃ for 10~12h. After the reaction is completed, filter the reaction solution to remove sodium carbonate, concentrate and separate to obtain solid compound 2. (3) Under a protective gas atmosphere, solid compound 2 and reactant 1 were dissolved in an organic solvent, and then tetra-triphenylphosphine palladium and sodium carbonate were added. The reaction was carried out at 80~110℃ for 10~12h. After the reaction was completed, the mixture was extracted, dried, concentrated, and separated by column chromatography to obtain solid compound NATO-nAr. (4) Under a protective gas atmosphere, NATO-nAr was added to anhydrous tetrahydrofuran, and methyl magnesium chloride was added dropwise. After reacting at 55-65℃ for 1-2 hours, the temperature was lowered, and hydrohalic acid was added until the solution changed color. Then, tetrahydrofuran-ethanol organic solvent of reactant 2 was added, and the reaction was continued for more than 24 hours. The obtained solid was washed to obtain... A cyanine dye conjugated organic framework material with carbon-carbon double bonds linked by NAT-nX.

4. The method for preparing a carbon-carbon double-bonded cyanine dye conjugated organic framework material as described in claim 2 or 3, characterized in that: In step (1), the molar ratio of 1,8-naphthalimide to liquid bromine is 1:1 to 1.5; And / or, in step (2), the molar ratio of the solid compound 1, 1-haloalkane and sodium carbonate is 1:1~1.5:2~2.5; And / or, in step (3), the molar ratio of the solid compound 2 to reactant 1 is 2~3:1; And / or, in step (4), the molar ratio of NATO-nAr, methyl magnesium chloride, and reactant 2 is 1:5~6:0.5~1.

5. A method for preparing a cyanine dye conjugated organic framework material with carbon-carbon double bonds as described in claim 1, characterized in that: The method steps include: (1) 2,3,3-Trimethyl-5-bromo-3H-indole reacts with reactant 1 to prepare cured compound 3. The structural formula of reactant 1 is: n is an integer from 1 to 3, and Y is a borate or tin alkyl group; (2) Preparation of ID-nAr by reaction of solid compounds 3- and 1-haloalkanes; (3) Preparation by reaction of ID-nAr and reactant 2 The cyanine dye conjugated organic framework material is a carbon-carbon double bond linked by ID-nX, and reactant 2 is pyromellitic methylaldehyde or trialdehyde phloroglucinol. The reaction equation is: ； The repeating structural unit of ID-nAr-COF is one of the following structures: 。 6. The method for preparing a carbon-carbon double-bonded cyanine dye conjugated organic framework material as described in claim 5, characterized in that: (1) Under a protective gas atmosphere, 2,3,3-trimethyl-5-bromo-3H-indole, reactant 1 and tetratriphenylphosphine palladium were dissolved in an organic solvent and heated under reflux at 80~110℃ for 12~16h. After the reaction was completed, the mixture was extracted with dichloromethane, the organic phase was dried with anhydrous sodium sulfate, concentrated and separated by column chromatography to obtain solid compound 3. (2) Dissolve solid compound 3 and 1-haloalkane in anhydrous acetonitrile and react at 60~80℃ for 5~8h. After the reaction is completed, filter and wash to obtain yellow solid ID-nAr; (3) Dissolve ID-nAr and reactant 2 in a tetrahydrofuran-ethanol mixed solvent and react at 80-90℃ for more than 24 hours. Wash the resulting solid to obtain A cyanine dye conjugated organic framework material with carbon-carbon double bonds linked by ID-nX.

7. A method for preparing a carbon-carbon double-bonded cyanine dye conjugated organic framework material as described in claim 5 or 6, characterized in that: In step (1), the molar ratio of 2,3,3-trimethyl-5-bromo-3H-indole to reactant 1 is 2~3:1; And / or, in step (2), the molar ratio of the solid compound 3 and the 1-haloalkane is 1:1 to 1.5; And / or, in step (3), the molar ratio of ID-nAr to reactant 2 is 1:0.5~1.

8. The application of the carbon-carbon double-bonded cyanine dye conjugated organic framework material of claim 1 as a photothermal conversion material.

9. The application of the carbon-carbon double-bonded cyanine dye conjugated organic framework material of claim 1 as a near-infrared laser ignition photothermal agent.

10. A method for recovering raw materials from a cyanine dye conjugated organic framework material with carbon-carbon double bonds as described in claim 1, characterized in that: The method includes: dispersing a carbon-carbon double-bonded cyanine dye conjugated organic framework material in a mixed solvent of ethanol and dichloroethane, adding a reducing amine, heating and stirring at 60±5℃ for more than 24 hours, filtering, separating the filtrate by column chromatography, and recovering pyromellitic methyl pyrogallol or trialdehyde pyrogallol.

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