WO2019033611A1 - Porphyrin conjugated organic framework material and preparation method therefor - Google Patents

Abstract

A porphyrin conjugated organic framework material and a preparation method therefor, falling within the technical fields of new materials and preparation therefor. Said material is a two-dimensional laminar structure material formed by linking structural units. The structural units are porphyrin and porphyrin derivatives, all structural units are linked by covalent bonds, and intermolecular force is present between layers. In the preparation method of the present invention, a five-membered heterocycle and a polyaldehyde in a certain ratio are used as reactants, and are subjected to a polymerization reaction under the action of an acid and an oxidizing agent, thereby directly obtaining the porphyrin conjugated organic framework material by means of a one-pot process. The present invention designs a framework material of which the structure and properties can be effectively regulated on a molecular scale, realizing one-step synthesis of a porphyrin conjugated organic framework material. The method is simple in operation, has low costs, can be easily enlarged, and effectively promotes basic research and preparation of organic skeleton materials, thus providing new possibilities for practical application of organic framework materials.

Description

Porphyrin conjugated organic skeleton material and preparation method thereof Technical field

The invention belongs to the technical field of new material design and preparation, and particularly relates to a preparation method of a porphyrin conjugated organic skeleton material.

Background technique

The development and application level of materials is a sign of the degree of civilization of human society, and the discovery and application of new materials is one of the important driving forces for the reform of human society. The development of metal materials has greatly enhanced the level of social productivity and promoted the industrial revolution of the 19th century. The popularity of polymer materials such as rubber, plastics, and fibers has greatly improved our standard of living. With the first observation of clear carbon nanotube structure in 1991 by Iijima (Iijima S. Nature, 1991, 354 (6348): 56-58), Geim stripped in 2004 to obtain single-layer graphene (Novoselov K S et al., Science , 2004, 306 (5696): 666-669), the concept of nanomaterials and low-dimensional materials has made a fundamental change in our understanding of materials. The rapid development of contemporary social economy and the urgent need for the emergence of new materials.

The regulation of the structure and properties of materials at the molecular atomic level is a key issue in material design and synthesis. Traditional materials are limited by their own properties and synthetic methods, and it is difficult to achieve precise control of material structure, especially in terms of nano-materialization and low-dimensionality of materials. Therefore, the bottom-up small molecule chemical assembly is considered to be an effective means to achieve controlled synthesis of materials. In 2005, Omar M. Yaghi et al. reported for the first time a two-dimensional conjugated organic framework material of borate esters, marking the arrival of an era of precise design and synthesis of materials at the molecular level (Adrien P. Cote et al., Science, 2005, 310, 1166-1170). The synthesis strategy of organic framework materials is based on organic synthesis methodology. The organic small molecules are connected by covalent bonds and extend infinitely in three-dimensional space to obtain regularly arranged framework materials. By designing the substrate structure and synthesis method, the organic framework material can easily realize the modulation of its chemical structure, and obtain a material system with regular pore structure, ultra-high specific surface area and rich coordination sites.

The research on the structural design and synthesis methods of organic framework materials has received extensive attention. Kuhn et al. reported the synthesis and properties of triazine organic framework materials (Pieree Kuhn et al., J. Am. Chem. Soc. 2008, 130, 13333-13337); Zhu Junjiang et al. (Zhu Junjiang et al., Patent Publication No.: CN103224264A) The use of such triazine organic framework materials for the removal of organic dyes in aqueous phases; Yaghi et al. reported the synthesis of three-dimensional covalent organic framework materials in 2009 (Fernando J. Uribe-Romo et al., J. Am .Chem. Soc. 2009, 131, 4570-4571). However, the structural design of conjugated organic framework materials has not been fully developed, and its synthesis and separation methods are complex, involving multiple organic reactions, and it is difficult to achieve large-scale, high-quality, high-yield preparation, thus greatly limiting the organic framework. The application of materials in practical systems.

Summary of the invention

The object of the present invention is to overcome the difficulty that the general materials are difficult to precisely control, and design a class of porphyrin conjugated organic skeleton materials based on covalent bond connection, thereby realizing precise controllable preparation and chemical structure control of the skeleton materials at the molecular level; The synthesis method of organic framework materials is complex, and it is difficult to realize the bottleneck of large-scale preparation and application. A one-step direct synthesis of porphyrin conjugated organic framework materials is proposed, which can effectively promote the mass production of organic framework materials, and is a practical application of organic framework materials. Offer possible.

The technical solution of the present invention is as follows:

A porphyrin conjugated organic framework material, characterized in that the porphyrin conjugated organic framework material is a two-dimensional sheet structure material obtained by linking structural units, and the structural unit is derived from porphyrin and porphyrin. The structural units are all connected by covalent bonds.

Further, the inner ring hetero atom of the porphyrin and the porphyrin derivative is one or more of N, O and S.

Further, the structural unit is connected in a two-dimensional sheet structure, and the force between the sheets is an intermolecular force.

The method for preparing a porphyrin conjugated organic skeleton material according to the present invention comprises the following steps:

1) using a five-membered heterocyclic ring and a polyaldehyde as a substrate, fully dissolving it in an organic solvent, and uniformly mixing the acid and the oxidizing agent; wherein the ratio of the amount of the five-membered heterocyclic ring and the polyaldehyde is 1:0.1-1 :10;

2) The above mixture is reacted at a temperature of 40 to 220 ° C for a reaction time of 30 minutes to 72 hours.

Further, the five-membered heterocyclic ring is one or more of pyrrole, furan and thiophene; the polyaldehyde is three carbons or more and has two or more aldehyde functional groups.

Further, the acid is one or more of formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluorocarboxylic acid, and trifluoroacetic acid; the oxidizing agent is air, One or more of oxygen, nitrobenzene, dinitrobenzene, trinitrobenzene, potassium nitrate, sodium nitrate and ammonium nitrate; the organic solvent is methanol, ethanol, propanol, isopropanol, B Glycol, propylene glycol, glycerol, toluene, ethylbenzene, xylene, trimethylbenzene, dichloromethane, chloroform, tetrachloromethane, dioxane, tetrahydrofuran, N-methylpyrrolidone, N, N-di One or more of methyl formamide and N,N-dimethylacetamide.

The porphyrin conjugated organic framework material of the invention realizes the precise design and regulation of the framework material at the molecular level, has the diversity and stability of the chemical structure; the synthesis method is simple and efficient, and the preparation condition is mild. The preparation method greatly simplifies the synthesis route, can effectively realize the mass preparation of the porphyrin conjugated organic skeleton material, obtains the high quality porphyrin conjugated organic skeleton material, has simple process and low cost, and is suitable for engineering enlargement and batch preparation. It can help promote the application of public organic skeleton materials in practical systems, and provide new possibilities for the renewal of material systems.

DRAWINGS

Figure 1 is a scanning electron micrograph of a porphyrin conjugated organic framework material synthesized using pyrrole and terephthalaldehyde as substrates.

2 is a transmission electron micrograph of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as substrates.

Figure 3 is a high resolution transmission electron micrograph of a porphyrin conjugated organic framework material synthesized using pyrrole and terephthalaldehyde as substrates.

4 is an atomic force microscope photograph of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as substrates.

Figure 5 is an infrared spectrum of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as substrates.

Fig. 6 is an X-ray diffraction spectrum of a porphyrin conjugated organic skeleton material synthesized using pyrrole and terephthalaldehyde as a substrate.

Detailed ways

The invention is further illustrated by several specific examples.

The porphyrin conjugated organic framework material proposed by the invention is a two-dimensional sheet structural material formed by connecting structural units, wherein the structural unit is a porphyrin and a porphyrin derivative, and all structural units are covalently bonded. connection. The inner ring hetero atom of the porphyrin and the porphyrin derivative is one or more of N, O and S. The structural unit is connected in a two-dimensional sheet structure, and the force between the sheets is an intermolecular force.

The method for preparing a porphyrin conjugated organic skeleton material provided by the invention comprises the following steps:

1) using a five-membered heterocyclic ring and a polyaldehyde as a substrate, fully dissolving it in an organic solvent, and uniformly mixing the acid and the oxidizing agent; wherein the ratio of the amount of the five-membered heterocyclic ring and the polyaldehyde is 1:0.1-1 :10; the five-membered heterocyclic ring is generally one or more of pyrrole, furan and thiophene; the polyaldehyde is three carbons and more than three carbons, and has two or more aldehyde functional groups; the acid uses formic acid And one or more of acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, trifluorocarboxylic acid and trifluoroacetic acid; the oxidizing agent is air, oxygen, nitrobenzene, dinitrogen One or more of benzene, trinitrobenzene, potassium nitrate, sodium nitrate and ammonium nitrate; the organic solvent is methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, glycerol , toluene, ethylbenzene, xylene, trimethylbenzene, dichloromethane, chloroform, tetrachloromethane, dioxane, tetrahydrofuran, N-methylpyrrolidone, N,N-dimethylformamide and N,N One or more of dimethylacetamide.

2) The above mixture is reacted at a temperature of 40 to 220 ° C for a reaction time of 30 minutes to 72 hours.

Example 1: A nitrogen porphyrin conjugated organic skeleton material was obtained by a one-pot method using pyrrole and terephthalaldehyde as substrates.

13.4 g of terephthalaldehyde was weighed and added to 200 mL of ethanol, stirred, fully dissolved, and transferred to a 500 mL flask. To the flask, 6.9 mL of pyrrole, 10 mL of concentrated hydrochloric acid, and 5 mL of nitrobenzene were added, and the mixture was uniformly mixed with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 60 ° C for 12 h. The obtained product was filtered, washed with ethanol, and dried to obtain a nitrogen porphyrin conjugated organic skeleton material. The reaction yield was 98%.

Example 2: A cobalt-coordinated nitrogen porphyrin conjugated organic framework material was obtained by one-pot method using pyrrole and malondialdehyde as substrates.

Weigh 14.4 g of malondialdehyde into 250 mL of tetrachloromethane, stir well, and transfer to a 500 mL flask. To the flask, 13.8 mL of pyrrole, 5 mL of trifluoroacetic acid, 2 g of potassium nitrate, and 6 g of cobalt nitrate were added, and the mixture was sufficiently dissolved with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 140 ° C for 1 h. The obtained product was filtered, washed with ethanol, and dried to obtain a cobalt-coordinated nitrogen porphyrin conjugated organic skeleton material. The reaction yield was 94%.

Example 3: A thioporphyrin conjugated organic framework material was obtained by a one-pot method using pyrrole, thiophene and terephthalaldehyde as substrates.

13.4 g of terephthalaldehyde, 3.5 mL of pyrrole, and 15 mL of thiophene were weighed and added to 150 mL of isopropyl alcohol, stirred, fully dissolved, and transferred to a 500 mL flask. 150 mL of acetic acid and 3 g of trinitrobenzene were added to the flask, and the mixture was sufficiently dissolved with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 120 ° C for 72 h. The obtained product was filtered, washed with ethanol, and dried to obtain a thioporphyrin conjugated organic skeleton material. The reaction yield was 92%.

Example 4: An oxoporphyrin conjugated organic skeleton material was obtained by a one-pot method using pyrrole, furan and terephthalaldehyde as substrates.

13.4 g of terephthalaldehyde, 3.5 mL of pyrrole, and 13 mL of furan were weighed and added to 200 mL of chloroform, stirred, sufficiently dissolved, and transferred to a 500 mL flask. 10 mL of concentrated hydrochloric acid, 150 mL of acetic acid, and 1.6 g of sodium nitrate were added to the flask, and the mixture was sufficiently dissolved with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 200 ° C for 36 h. The obtained product was filtered, washed with ethanol, and dried to obtain an oxyporphyrin conjugated organic skeleton material. The reaction yield was 97%.

Example 5: Iron-complexed nitrogen porphyrin conjugated organic framework material was obtained by one-pot method using pyrrole and adipaldehyde as substrates.

15.0 g of adipaldehyde was weighed and added to 200 mL of toluene, stirred, sufficiently dissolved, and transferred to a 500 mL flask. 7.4 mL of pyrrole, 15 mL of trifluoroformic acid, 2.5 mL of trinitrobenzene, and 7.6 g of ferric chloride were added to the flask, and the mixture was uniformly mixed with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 95 ° C for 48 h. The obtained product was subjected to filtration, ethanol washing, and dried to obtain an iron-coordinated nitrogen porphyrin conjugated organic skeleton material. The reaction yield was 95%.

Example 6: An oxoporphyrin conjugated organic framework material was obtained by a one-pot method using pyrrole, furan and succinaldehyde as substrates.

17.2 g of succinaldehyde, 6.9 mL of pyrrole, and 23 mL of furan were weighed and added to 100 mL of trimethylbenzene and 150 mL of dioxane, and the mixture was sufficiently dissolved and transferred to a 500 mL flask. 15 mL of p-toluenesulfonic acid and 3.0 g of potassium nitrate were added to the flask, and the mixture was sufficiently dissolved with stirring. The flask was placed in an oil bath and kept stirring and reacted at 150 ° C for 18 h. The obtained product was filtered, washed with ethanol, and dried to obtain an oxyporphyrin conjugated organic skeleton material. The reaction yield was 93%.

Example 7: A nitrogen porphyrin conjugated organic framework material was obtained by a one-pot method using pyrrole and biphenyldialdehyde as substrates.

21.0 g of biphenyldialdehyde and 6.9 mL of pyrrole were weighed and added to 180 mL of N-methylpyrrolidone, stirred, fully dissolved, and transferred to a 500 mL flask. 2 mL of sulfuric acid, 5.8 g of nickel acetate were added to the flask, and the mixture was thoroughly stirred. The flask was placed in an oil bath, kept stirring, and oxygen was introduced and reacted at 40 ° C for 12 h. The obtained product was subjected to filtration, ethanol washing, and dried to obtain a nickel-coordinated nitrogen porphyrin conjugated organic skeleton material. The reaction yield was 98%.

Example 8: A thioporphyrin conjugated organic framework material was obtained by one-pot method using pyrrole, thiophene and glutaraldehyde as substrates.

18.5 g of glutaraldehyde, 7.4 mL of pyrrole, and 17.4 mL of thiophene were weighed into 200 mL of N,N-dimethylacetamide, dissolved sufficiently, and transferred to a 500 mL flask. 15 mL of concentrated hydrochloric acid and 5.0 g of ammonium nitrate were added to the flask, and the mixture was sufficiently dissolved with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 70 ° C for 48 h. The obtained product was filtered, washed with ethanol, and dried to obtain a thioporphyrin conjugated organic skeleton material. The reaction yield was 93%.

Example 9: A nitrogen porphyrin conjugated organic skeleton material was obtained by a one-pot method using pyrrole and 2,4-dimethylterephthalaldehyde as a substrate.

24.8 g of 2,4-dimethyl-terephthalaldehyde and 8.9 mL of pyrrole were weighed and added to 200 mL of glycerin, stirred well, and then transferred to a 500 mL flask. 5 mL of trifluoroacetic acid 50 mL of acetic acid and 5 mL of nitrobenzene were added to the flask, and the mixture was sufficiently dissolved with stirring. The flask was placed in an oil bath, kept stirring, and reacted at 200 ° C for 20 h. The obtained product was filtered, washed with ethanol, and dried to obtain a nitrogen porphyrin conjugated organic skeleton material. The reaction yield was 95%.

Claims (8)

A porphyrin conjugated organic framework material, characterized in that the porphyrin conjugated organic framework material is a two-dimensional sheet structure material obtained by linking structural units, and the structural unit is derived from porphyrin and porphyrin. The structural units are all connected by covalent bonds. The porphyrin conjugated organic skeleton material according to claim 1, wherein the inner ring hetero atom of the porphyrin and the porphyrin derivative is one or more of N, O and S. A porphyrin conjugated organic skeleton material according to claim 1 or 2, wherein the force between said two-dimensional sheet structures is an intermolecular force. A method for preparing a porphyrin conjugated organic skeleton material according to claim 1, wherein the method comprises the steps of: 1) using a five-membered heterocyclic ring and a polyaldehyde as a substrate, fully dissolving it in an organic solvent, and uniformly mixing the acid and the oxidizing agent; wherein the ratio of the amount of the five-membered heterocyclic ring and the polyaldehyde is 1:0.1-1 :10; 2) The above mixture is reacted at a temperature of 40 to 220 ° C for a reaction time of 30 minutes to 72 hours. The method for producing a porphyrin conjugated organic skeleton material according to claim 4, wherein the five-membered heterocyclic ring is one or more of pyrrole, furan and thiophene; 3 carbons or more, having more than two aldehyde functional groups. The method for preparing a porphyrin conjugated organic skeleton material according to claim 4, wherein the acid is formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, three One or more of fluorocarboxylic acid and trifluoroacetic acid. The method for preparing a porphyrin conjugated organic skeleton material according to claim 4, wherein the oxidizing agent is air, oxygen, nitrobenzene, dinitrobenzene, trinitrobenzene, potassium nitrate, nitric acid One or more of sodium and ammonium nitrate. The method for preparing a porphyrin conjugated organic skeleton material according to claim 4, wherein the organic solvent is methanol, ethanol, propanol, isopropanol, ethylene glycol, propylene glycol, glycerin, Toluene, ethylbenzene, xylene, trimethylbenzene, dichloromethane, chloroform, tetrachloromethane, dioxane, tetrahydrofuran, N-methylpyrrolidone, N,N-dimethylformamide and N,N- One or more of dimethylacetamide.

Images