Covalent organic polycyclic material and synthesis method thereof

Abstract

The invention relates to the technical field of organic synthesis and functional materials, and particularly discloses a covalent organic polycyclic material and a synthesis method thereof.The synthesis method comprises the steps that a first monomer and a second monomer are added into an organic solvent and subjected to a heating reaction under the action of a catalyst, centrifugation, washing and drying are conducted after the reaction is finished, and the obtained solid is the covalent organic polycyclic material; the monomer I is aldehyde containing alkoxy, and the monomer II is amine containing alkoxy. According to the method, the covalent organic polycyclic material with a clear structure can be synthesized, and the obtained covalent organic polycyclic material has good solubility and excellent thermal stability.

Description

Technical Field

[0001] The present invention belongs to the technical fields of organic synthesis and functional materials, and particularly relates to a covalent organic polycyclic material and a synthesis method thereof. Background Art

[0002] The construction of cyclic structures is one of the most important goals in materials science, chemistry, and physics. These cyclic structures with well-defined cavities have important theoretical and experimental values and broad application prospects in gas storage / separation, proton conduction, catalysis, sensing, optoelectronics, biomedicine, etc. Therefore, considerable progress has been made in constructing various cyclic structures through the covalent assembly of molecular building blocks. Summary of the Invention

[0003] The first object of the present invention is to provide a synthesis method of a covalent organic polycyclic material with good solubility and excellent thermal stability.

[0004] The second object of the present invention is to provide a covalent organic polycyclic material obtained by the above method.

[0005] The object of the present invention is specifically realized by the following technical solutions: A synthesis method of a covalent organic polycyclic material, wherein monomer one and monomer two are added to an organic solvent and heated for reaction under the action of a catalyst. After the reaction is completed, centrifugation, washing, and drying are carried out, and the obtained solid is the covalent organic polycyclic material. The monomer one is an aldehyde containing an alkoxy group, and the monomer two is an amine containing an alkoxy group.

[0006] Preferably, the monomer one is 5-[(3-{[3,5-diformyl-4-(hexyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(hexyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(hexyloxy)benzene-1,3-dicarbaldehyde or 5-[(3-{[3,5-diformyl-4-(decyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(decyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(decyloxy)benzene-1,3-dicarbaldehyde, and the monomer two is 3-[(3-{[3-amino-5-(hexyloxy)phenyl]ethynyl}-5-(hexyloxy)phenyl)ethynyl]-5-(hexyloxy)aniline or 3-[(3-{[3-amino-5-(decyloxy)phenyl]ethynyl}-5-(decyloxy)phenyl)ethynyl]-5-(decyloxy)aniline.

[0007] More preferably, the catalyst is trifluoroacetic acid.

[0008] Preferably, the molar ratio of the monomer one, monomer two, and catalyst is 3:9:80.

[0009] Preferably, the organic solvent is a mixed solvent of N,N-dimethylformamide and mesitylene.

[0010] More preferably, the volume ratio of N,N-dimethylformamide to mesitylene is 3:1.

[0011] Preferably, the concentration of the first monomer in the organic solvent is 1-100 μmol / mL.

[0012] Preferably, the reaction temperature of the heating reaction is 25-180 °C, and the reaction time is 1-15 days.

[0013] Preferably, the reaction vessel for the heating reaction uses a glass bottle, a thick-walled pressure-resistant tube or an ampoule bottle.

[0014] The covalent organic polycyclic material obtained by any of the above methods.

[0015] The method of the present invention involves designing specific organic building blocks that can covalently connect in a predetermined manner to form a target covalent organic polycyclic structure. The geometric configurations of the building blocks are crucial as they directly determine the final structure and connectivity. The monomers of the present invention have rigid three-armed Y-shaped and U-shaped structural units, containing aldehyde and amine active functional groups. Under solvothermal conditions with a catalyst of trifluoroacetic acid, an imine-linked covalent organic polycyclic material is constructed through a Schiff base reaction. This material has a well-defined structure and exhibits good solubility in conventional organic solvents.

[0016] The present invention has the following advantages compared with the prior art: The synthesis method of the present invention can construct covalent organic polycyclic materials with good structures. The obtained covalent organic polycyclic materials have good solubility and excellent thermal stability. Description of the Drawings

[0017] Figure 1 is the 1 1H NMR spectrum of COM-1 synthesized by the present invention; Figure 2 is the 13 13C NMR spectrum of COM-1 synthesized by the present invention; Figure 3 is the matrix-assisted laser desorption / ionization time-of-flight mass spectrum of COM-1 synthesized by the present invention; Figure 4 is the gel permeation chromatography of COM-1 synthesized by the present invention; Figure 5 is the Fourier transform infrared spectrum of COM-1 synthesized by the present invention and the raw materials; Figure 6is the powder X-ray diffraction pattern of the synthesized COM-1 and the raw materials of the present invention; Figure 7 is the thermogravimetric analysis curve of the synthesized COM-1 of the present invention; Figure 8 are the pictures of the synthesized COM-1 of the present invention dissolved in different solvents; Figure 9 is of the synthesized COM-2 of the present invention 1 1H NMR spectrum; Figure 10 is of the synthesized COM-2 of the present invention 13 13C NMR spectrum; Figure 11 is the matrix-assisted laser desorption / ionization time-of-flight mass spectrum of the synthesized COM-2 of the present invention; Figure 12 is the gel permeation chromatogram of the synthesized COM-2 of the present invention; Figure 13 is the Fourier transform infrared spectrum of the synthesized COM-2 and the raw materials of the present invention; Figure 14 is the powder X-ray diffraction pattern of the synthesized COM-2 and the raw materials of the present invention; Figure 15 is the thermogravimetric analysis curve of the synthesized COM-2 of the present invention. Specific Embodiments

[0018] The following describes the preferred embodiments of the present invention. It should be understood that the preferred embodiments described herein are only for the purpose of illustration and explanation of the present invention, and are not intended to limit the present invention.

[0019] Unless otherwise specified, the raw materials in the embodiments of the present invention are all purchased through commercial channels. The sources of some raw materials are as follows: Tetrahydrofuran (THF), dichloromethane (DCM), N,N-dimethylformamide (DMF), 2-butanone, absolute ethanol, triethylamine, and acetone are provided by Tianlong Bohua (Tianjin) Pharmaceutical and Chemical Co., Ltd., all in 500 mL specifications. Mesitylene (500 mL) is purchased from Alfa Aesar. Trifluoroacetic acid (TFA, 500 mL) is purchased from Shanghai Macklin Biochemical Co., Ltd. 1,3,5-Triiodobenzene (25 g) and 1-bromo-3,5-dinitrobenzene (25 g) are purchased from Leyan. Pyridinium chlorochromate (PCC, 500 g), Pd(PPh 3 ) 2 Cl 2 (25 g), SnCl 2 ·2H 2 O(500 g), Pd(PPh 3 ) 4(5 g), 1-bromoalkane (500 mL), alkyl alcohol (500 mL), trimethylsilylacetylene (100 mL), 3,5-dibromophenol (25 g) and 4-bromophenol (100 g) were all purchased from Energy Chemical.

[0020] Synthesis of Monomers (1) Synthesis of Monomer 1.

[0021] Synthesis of Compound S1 Under argon protection, formaldehyde (37%, 150 mL) was added to a mixed solution of 4-bromophenol (25.5 g, 147 mmol), KOH (11.0 g, 197 mmol) and isopropyl alcohol (50 mL). Then the mixture was stirred and heated at 40 °C for 4 days. The resulting solution was cooled to room temperature, poured into 0.1 mol / L HCl (1000 mL) and stirred, and then left to stand for 6 h. A red oil was precipitated at the bottom of the beaker. The supernatant was transferred to another clean beaker for further precipitation and left to stand for more than 2 days. The solid was precipitated from the solution. Then the solid was separated by filtration, washed with chloroform and dried to obtain a white crude product, which was directly used in the next step. Under argon protection, the white crude product (6.00 g), 1-bromohexane (5.12 g, 31.0 mmol) or 1-bromodecane (6.86 g, 31.0 mmol), K 2 CO 3 (7.19 g, 52.0 mmol) were added to 125 mL of 2-butanone, and the mixture was refluxed at 90 °C overnight. After the reaction was completed, the mixture was cooled to room temperature. The solvent was removed under reduced pressure, water was added, and the mixture was extracted with DCM (3×100 mL). The organic phase was dried with anhydrous Na 2 SO 4 After removing the solvent under reduced pressure, the resulting product was added to a mixed solution of PCC (16.1 g, 75.0 mmol), diatomaceous earth (10.0 g) and DCM (200 mL), stirred at room temperature for 4 h, filtered and concentrated under reduced pressure. The crude product was purified by silica gel column chromatography (PE / DCM = 5 / 1, v / v) to obtain product S1a (white solid, 5.10 g, yield: 63%) / S1b (white solid, 5.60 g, yield: 59%).

[0022] Synthesis of Compound S2 Compound S1 (12.0 mmol), Pd(PPh 3 ) 2 Cl 2(253 mg, 0.36 mmol), CuI (25.0 mg, 0.13 mmol) were added to a two-necked flask. Under argon protection, 65 mL of THF and 25 mL of triethylamine were added to the flask. The reaction mixture was stirred at room temperature for 15 min, then trimethylsilylacetylene (1.77 g, 18.0 mmol) was added via syringe. The reaction system was stirred at 50 °C for 4 h, then filtered and concentrated by evaporation under reduced pressure. K 2 CO 3 (1.66 g, 12.0 mmol), 20 mL of methanol were added, and the mixture was stirred at room temperature for 3 h. After the reaction was completed, DCM was added to dissolve the mixture, and it was washed with saturated NaHCO 3 solution, water, and saturated brine. The organic phase was dried over anhydrous Na 2 SO 4 and concentrated by evaporation under reduced pressure to obtain the crude product. Then the crude product was purified by silica gel column chromatography (PE / DCM: 5 / 1, v / v) to obtain the corresponding product S2a (light yellow solid, 2.47 g, yield: 80%) / S2b (white solid, 3.05 g, yield: 81%).

[0023] Synthesis of Compound 1 1,3,5-Triiodobenzene (590 mg, 1.30 mmol), Pd(PPh 3 ) 4 (231 mg, 0.20 mmol), CuI (76 mg, 0.4 mmol) were added to a two-necked flask. Under argon protection, 10 mL of THF and 30 mL of triethylamine were added to the flask. The reaction mixture was stirred at room temperature for 15 min, then Compound S2 (4.00 mmol) was dissolved in 10 mL of THF and slowly added via syringe. The reaction was stirred at 50 °C for 24 h. After the reaction was completed, the mixture was cooled to room temperature, then the solvent was removed under reduced pressure and DCM was added to dissolve it. It was washed with saturated NH 4 Cl solution, water, and saturated brine. The organic phase was dried over anhydrous Na 2 SO 4 and concentrated by evaporation under reduced pressure to obtain the crude product. It was purified by silica gel column chromatography (PE / DCM, 3 / 1, V / V) to obtain the corresponding product 1a (light yellow solid, 0.85 g, yield: 77%) / 1b (light yellow solid, 1.05 g, yield: 80%) (Monomer 1). (2) Synthesis of Monomer 2 Synthesis of Compound S3 Under argon protection, 3,5-dibromophenol (5.00 g, 19.8 mmol), 1-bromohexane (3.43 g, 20.8 mmol) or 1-bromodecane (4.60 g, 20.8 mmol), and NaOH (0.84 g, 21.0 mmol) were refluxed in 125 mL of ethanol at 90 °C overnight. Then the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and the residue was dissolved in DCM, washed with saturated brine, and the organic phase was dried over anhydrous Na 2 SO 4 After drying, the solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography using PE as the eluent to obtain the corresponding products S3a (colorless oil, 5.1 g, yield: 77%) / S3b (colorless oil, 6.8 g, yield: 87%).

[0024] Synthesis of Compound S4 Under argon protection, S3 (10.0 mmol), Pd(PPh 3 ) 2 Cl 2 (351 mg, 0.50 mmol), CuI (95 mg, 0.50 mmol), and PPh 3 (131 mg, 0.50 mmol) were added to a two-necked flask. 50 mL of triethylamine was added to the flask, and the reaction mixture was stirred at room temperature for 15 min. Then trimethylsilylacetylene (3.93 g, 40.0 mmol) was added via syringe, and the resulting solution was stirred at 60 °C overnight. The resulting mixture was filtered and then concentrated under reduced pressure. KOH (0.84 g, 15.0 mmol), 50 mL of methanol, and 50 mL of THF were added, and the mixture was stirred at room temperature for 2 h. After adding water, the organic phase was separated, and the aqueous phase was extracted with DCM. The combined organic phases were washed with saturated brine and dried over anhydrous Na 2 SO 4 After drying and evaporation in vacuo, the crude product was obtained. The crude product was purified by silica gel column chromatography using PE as the eluent to obtain the corresponding products S4a (yellow solid, 2.08 g, yield: 92%) / S4b (yellow solid, 2.50 g, yield: 89%).

[0025] Synthesis of Compound S5 n-Hexanol (8.17 g, 80.0 mmol) or n-decanol (12.66 g, 80.0 mmol) and KOH (4.49 g, 80.0 mmol) were added to 40 mL of DMF. Then, a solution of 1-bromo-3,5-dinitrobenzene (9.88 g, 40.0 mmol) in DMF (40 mL) was added to the mixture with stirring. The reaction mixture was stirred at 90 °C for 20 h, then cooled to room temperature, poured into water, and the mixture was extracted with DCM. The combined organic phases were washed with saturated brine and dried over anhydrous Na 2 SO 4 . The solvent was evaporated under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography using PE as the eluent to obtain the corresponding products S5a (yellow oil, 8.0 g, yield: 66%) / S5b (yellow solid, 8.1 g, yield: 56%).

[0026] Synthesis of Compound 2 Under argon protection, S5 (12.0 mmol), Pd(PPh 3 ) 4 (289 mg, 0.25 mmol), and CuI (48 mg, 0.25 mmol) were added to a two-necked flask. 50 mL of triethylamine and 10 mL of THF were added to the flask. The reaction mixture was stirred at room temperature for 15 min. S4 (5.00 mmol) was dissolved in 20 mL of THF and then added via syringe, and the resulting solution was stirred at 70 °C for 24 h. Then, the mixture was cooled to room temperature and the solvent was removed under reduced pressure. The residue was dissolved in DCM and washed with saturated NH 4 Cl solution, water, and saturated brine. The organic phase was dried over anhydrous Na 2 SO 4 . The solvent was evaporated in vacuo to obtain the crude product. SnCl 2 ·2H 2 O (11.3 g, 50.0 mol) was refluxed in 50 mL of ethanol under argon at 90 °C overnight. Then, the mixture was cooled to room temperature and poured into an aqueous solution (50 mL) of NaOH (2.10 g, 52.5 mmol) at 0 °C. The mixture was basified with 10% NaOH, then diluted with water and extracted with DCM. The organic phase was extracted with brine and dried over anhydrous Na 2 SO 4 . The organic phase was evaporated in vacuo to obtain the crude product, which was purified by silica gel column chromatography using DCM as the eluent to obtain the corresponding products 2a (light brown solid, 2.6 g, yield: 86%) / 2b (light brown solid, 2.8 g, yield: 72%) (monomer di).

[0027] Example 1 1a (12.7 mg, 0.015 mmol) and 2a (28.0 mg, 0.045 mmol) were weighed into a 5 mL glass vial. N,N-dimethylformamide (2.10 mL) and mesitylene (0.70 mL) were added to the mixture, and it was sonicated until completely dissolved. Then, 0.20 mL of a 2 M N,N-dimethylformamide solution of trifluoroacetic acid was added, and it was gently shaken to ensure uniform mixing. The glass vial was placed in an oven at 50 °C and left standing for 3 days. After cooling to room temperature, the solid was separated by centrifugation and washed with DMF (3 × 5 mL), ethanol (3 × 5 mL), and acetone (2 × 5 mL). Subsequently, the powder was dried at room temperature to obtain a pale white product COM-1 (35.8 mg, yield: 93%). As Figure 1 、 Figure 2 , 1 The 1H NMR spectrum provided clear and distinct resonances and integrations, which were in complete agreement with the molecular structure of COM-1. In addition, 13 The 13C NMR spectrum confirmed the molecular structure, and the observed signals corresponded to the carbon atoms within the molecule.

[0028] As Figure 3 ,matrix-assisted laser desorption / ionization time-of-flight mass spectrometry analysis provided further evidence for the successful synthesis of COM-1, and the expected protonated molecular ion peak was detected at an m / z value of 2566.74.

[0029] As Figure 4 ,gel permeation chromatography analysis of COM-1 gave a single and narrow peak, and the polydispersity index (Đ) was 1.10, indicating that no high molecular weight polymers were formed.

[0030] As Figure 5 , Figure 5 -COM-1 corresponds to the infrared absorption curve of COM-1, where Figure 5-1 a corresponds to 5-[(3-{[3,5-diformyl-4-(hexyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(hexyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(hexyloxy)benzene-1,3-dicarbaldehyde, Figure 5-2 a corresponds to 3-[(3-{[3-amino-5-(hexyloxy)phenyl]ethynyl}-5-(hexyloxy)phenyl)ethynyl]-5-(hexyloxy)aniline.

[0031] As Figure 6, By comparing the powder X-ray diffraction patterns of COM-1 and the raw materials, it can be found that a new crystalline material has been successfully synthesized by the method of the present invention. Among them Figure 6-1 a corresponds to 5-[(3-{[3,5-diformyl-4-(hexyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(hexyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(hexyloxy)benzene-1,3-dicarbaldehyde, Figure 6-2 a corresponds to 3-[(3-{[3-amino-5-(hexyloxy)phenyl]ethynyl}-5-(hexyloxy)phenyl)ethynyl]-5-(hexyloxy)aniline.

[0032] As Figure 7 , Through thermogravimetric analysis, it can be found that COM-1 can be stable to at least 320 °C in a nitrogen atmosphere without obvious decomposition.

[0033] As Figure 8 , COM-1 can be dissolved in THF and chloroform, indicating its good solubility.

[0034] Example 2 1b (15.2 mg, 0.015 mmol) and 2b (35.0 mg, 0.045 mmol) were weighed into a 5 mL glass vial. N,N-dimethylformamide (2.10 mL) and mesitylene (0.70 mL) were added to the mixture, and it was sonicated until completely dissolved. Then, 0.20 mL of a N,N-dimethylformamide solution of 2 M trifluoroacetic acid was added, and it was gently shaken to ensure uniform mixing. The glass vial was placed in an oven at 50 °C and left standing for 3 days. After cooling to room temperature, the solid was separated by centrifugation and washed with DMF (3 × 5 mL), ethanol (3 × 5 mL), and acetone (2 × 5 mL). Subsequently, the powder was dried at room temperature to obtain a pale yellow product COM-2 (41.1 mg, yield: 85%).

[0035] The above results show that the types and numbers of alkoxy groups on the amine and aldehyde can be changed to introduce different groups into the covalent organic polycyclic material.

[0036] As Figure 9 , Figure 10 , 1 The 1H NMR spectrum provides clear and distinct resonances and integrations, which are completely consistent with the molecular structure of COM-2. In addition, 13 The 13C NMR spectrum confirms the molecular structure, and the observed signals correspond to the carbon atoms within the molecule.

[0037] As Figure 11, Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis provided further evidence for the successful synthesis of COM-2, and the expected protonated molecular ion peak was detected at an m / z value of 3239.21.

[0038] As Figure 12 , Gel permeation chromatography (GPC) analysis of COM-2 gave a single and narrow peak with a polydispersity index (Đ) of 1.13, indicating that no high molecular weight polymers were formed.

[0039] As Figure 13 , Figure 13 -COM-2 corresponds to the infrared absorption curve of COM-2, where Figure 13-1 b corresponds to 5-[(3-{[3,5-diformyl-4-(decyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(decyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(decyloxy)benzene-1,3-dicarbaldehyde, Figure 13-2 b corresponds to 3-[(3-{[3-amino-5-(decyloxy)phenyl]ethynyl}-5-(decyloxy)phenyl)ethynyl]-5-(decyloxy)aniline.

[0040] As Figure 14 , By comparing the powder X-ray diffraction patterns of COM-2 and the starting materials, it was found that a new crystalline material was successfully synthesized by the method of the present invention. Among them Figure 14-1 b corresponds to 5-[(3-{[3,5-diformyl-4-(decyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(decyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(decyloxy)benzene-1,3-dicarbaldehyde, Figure 14-2 b corresponds to 3-[(3-{[3-amino-5-(decyloxy)phenyl]ethynyl}-5-(decyloxy)phenyl)ethynyl]-5-(decyloxy)aniline.

[0041] As Figure 15 , Thermogravimetric analysis showed that COM-2 was stable up to at least 330 °C in a nitrogen atmosphere without significant decomposition.

[0042] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for synthesizing a covalent organic polycyclic material, characterized in that: Monomer 1 and monomer 2 are added to an organic solvent, and heated to react under the action of a catalyst. After the reaction is completed, the solid is centrifuged, washed, and dried to obtain a covalent organic polycyclic material. Monomer 1 is an aldehyde containing an alkoxy group, and monomer 2 is an amine containing an alkoxy group.

2. The method for synthesizing a covalent organic polycyclic material according to claim 1, characterized in that: The first monomer is 5-[(3-{[3,5-diformyl-4-(hexyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(hexyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(hexyloxy)benzene-1,3-dicarbaldehyde or 5-[(3-{[3,5-diformyl-4-(decyloxy)phenyl]ethynyl}-5-{[3-formyl-4-(decyloxy)-5-vinylphenyl]ethynyl}phenyl)ethynyl]-2-(hexyloxy)benzene-1,3-dicarbaldehyde The monomer is 3-[(3-{[3-amino-5-(hexyloxy)phenyl]ethynyl}-5-(hexyloxy)phenyl)ethynyl]-5-(hexyloxy)aniline or 3-[(3-{[3-amino-5-(decyloxy)phenyl]ethynyl}-5-(decyloxy)phenyl)ethynyl]-5-(decyloxy)aniline.

3. The method for synthesizing a covalent organic polycyclic material according to claim 2, characterized in that: The catalyst is trifluoroacetic acid.

4. The method for synthesizing a covalent organic polycyclic material according to any one of claims 1 to 3, characterized in that: The molar ratio of the monomer 1, the monomer 2 and the catalyst is 3:9:

80.

5. The method for synthesizing a covalent organic polycyclic material according to claim 1, characterized in that: The organic solvent is a mixed solvent of N,N-dimethylformamide and mesitylene.

6. The method for synthesizing a covalent organic polycyclic material according to claim 5, characterized in that: The volume ratio of the N,N-dimethylformamide to mesitylene is 3:

1.

7. The method for synthesizing a covalent organic polycyclic material according to claim 1, characterized in that: The concentration of the monomer 1 in the organic solvent is 1-100 μmol / mL.

8. The method for synthesizing a covalent organic polycyclic material according to claim 1, characterized in that: The reaction temperature of the heating reaction is 25-180° C., and the reaction time is 1-15 days.

9. The method for synthesizing a covalent organic polycyclic material according to claim 1, characterized in that: The reaction container for the heating reaction is a glass bottle, a thick-walled pressure-resistant tube or an ampoule.

10. A covalent organic polycyclic material obtained according to any one of claims 1 to 9.

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