A multi-branched aromatic tertiary amine supramolecular organic framework material and a preparation method thereof

Abstract

The application discloses a kind of multi-branched aromatic tertiary amine supramolecular organic framework materials and preparation method thereof, belong to supramolecular organic framework material field.The application is prepared by using aromatic primary amine and halogenated aromatic hydrocarbon coupling reaction in the catalytic system of carbonate, palladium salt and phosphine ligand, with six branches or eight branches of aromatic tertiary amine ligand, so that the supramolecular organic framework material constructed shows strong stability.The preparation method of multi-branched aromatic tertiary amine supramolecular organic framework material provided by the application has the advantages of short synthesis route, simple reaction system, mild reaction condition, simple operation, simple purification method, high product yield, etc., and the multi-branched aromatic tertiary amine ligand can be self-constructed into supramolecular organic framework material through recrystallization washing process, solving the problem that aromatic tertiary amine-based multi-branched supramolecular organic framework material with high stability and potential great application value is not limited by ligand synthesis difficulty.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of supermolecular organic framework materials, in particular to a multi-branched aromatic tertiary amine supermolecular organic framework material and a preparation method thereof. BACKGROUND

[0002] Supermolecular organic framework materials (SOFs) are a kind of crystalline materials with pore structure formed by weak non-covalent intermolecular interaction forces such as hydrogen bonds, van der Waals forces, pi-pi stacking, CH…pi, electrostatic interaction forces, etc. This new kind of molecular aggregate material with porous structure is considered as a special kind of supermolecular polymer with precise self-assembly structure, and has the advantages of light weight, high porosity, high specific surface area, adjustable pore size, solution processability, and repairable crystal structure, etc. and has broad application scenarios in the fields of gas storage and separation, light-emitting devices, biomedical probes, etc. However, due to the relatively weak strength of the supermolecular interaction force of the supermolecular organic framework material and the relatively small number of supermolecular construction sites, the supermolecular framework material usually exhibits relatively low stability, and has poor chemical and thermal stability.

[0003] Aromatic tertiary amines have very good luminescent properties and have wide application prospects in the field of light-emitting devices, and therefore have attracted more and more attention from researchers. The synthesis and construction of multi-branched aromatic tertiary amine supermolecular organic framework materials are difficult, and the synthesis and construction of early similar single-chain and few-branched supermolecular organic framework materials have the disadvantages of high reaction temperature, long reaction time, excessive metal reagents, many by-products, difficult purification, poor functional group tolerance, and serious pollution, etc. which limit the application of the material in the industry. For example, Arkaitz Correa et al. obtained a catalyst system by combining iron salt and chelating diamine derivatives to promote the N-arylation of primary amides and various N-heterocycles, and the yield of the obtained product was only about 30%, and the raw materials involved in the reaction were proved to be unsuitable substrates.

[0004] It can be seen that the prior art cannot achieve the synthesis and construction of multi-branched tertiary amine supermolecular organic framework materials with novel structures. SUMMARY

[0005] In view of the above shortcomings of the prior art, the present application aims to provide a novel multi-branched aromatic tertiary amine supermolecular organic framework material and a preparation method thereof, and aims to solve the problems of low stability of supermolecular organic framework materials and difficulty in synthesis and construction of multi-branched aromatic tertiary amine supermolecular organic framework materials.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0008] S1. A carbon salt, a palladium salt, a phosphine ligand, a halogenated aromatic hydrocarbon, and a solvent A are added to a round-bottom flask, magnetically stirred, and heated to reflux at 100 DEG C under inert gas protection for 30 min;

[0009] S2. After heating to reflux for 30 min, an aromatic primary amine dissolved in solvent A is added to the round-bottom flask for continued magnetic stirring and heating to reflux at 100 DEG C under oil bath;

[0010] S3. After the reaction is completed, the reaction is stopped, the reaction system is washed and filtered, and then the crude product is obtained by rotary evaporation under reduced pressure;

[0011] S4. The crude product is washed and filtered by recrystallization with solvent B, and finally dried to obtain the multi-branched aromatic tertiary amine ligand.

[0012] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the aromatic primary amine includes one of 1,3,5-tris(4-aminophenyl)benzene, tetra(4-aminophenyl)methane, tetraphenylstyrene tetramine, 1,3,6,8-tetra-(p-aminophenyl)-pyrene, 5”-(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1':4',1”:3”,1”':4”',1””-quaterphenyl]-4,4””-diamine.

[0013] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the halogenated aromatic hydrocarbon includes one of p-bromobenzoic acid methyl ester, p-bromobenzonitrile, bromobenzene, and p-bromonitrobenzene.

[0014] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the carbon salt includes one or more of potassium carbonate, cesium carbonate, and sodium carbonate.

[0015] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the palladium salt includes one or more of palladium acetate, bis(acetylacetone)palladium(II), and palladium chloride.

[0016] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the phosphine ligand includes one or more of 1,1'-binaphthalene-2,2'-diphenylphosphine, 1,2-bis(diphenylphosphino)ethane, and triphenylphosphine.

[0017] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the solvent A includes one or both of 1,4-dioxane and tetrahydrofuran.

[0018] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the solvent B is one of tetrahydrofuran, ethanol, acetone, ethyl acetate, 1,4-dioxane, methanol, dichloromethane, chloroform and acetonitrile.

[0019] In the preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material, the molar ratio of the aromatic primary amine, the halogenated aromatic hydrocarbon, the carbonate, the palladium salt and the phosphine ligand is 1:(8-14):(8-14):(0.3-0.8):(0.4-1.28).

[0020] The application further provides a supramolecular organic framework material, which is prepared by the above multi-branched aromatic tertiary amine supramolecular organic framework material preparation method.

[0021] Beneficial effects:

[0022] The application provides a novel multi-branched aromatic tertiary amine supramolecular organic framework material and a preparation method thereof. The aromatic tertiary amine ligand with six branched chains or eight branched chains is prepared by using the coupling reaction of aromatic primary amine and halogenated aromatic hydrocarbon in a catalytic system composed of carbonate, palladium salt and phosphine ligand. Since the aromatic tertiary amine ligand prepared by the application has multi-branched chains, the construction sites between the ligands are more when the supramolecular organic framework material is constructed. The novel supramolecular organic framework material constructed has the advantages of strong stability, rich structure, more adjustable channel shape and size, and easily modified channel surface, and the like. Therefore, the supramolecular organic framework material has special applications in the fields of gas adsorption and separation, sensing, catalysis, fluorescence and proton conduction, and the like.

[0023] The preparation method of the multi-branched aromatic tertiary amine supramolecular organic framework material provided by the application has the advantages of short synthesis route, simple reaction system, mild reaction conditions, simple operation, simple purification method and high product yield. After the multi-branched aromatic tertiary amine ligand is prepared, the multi-branched aromatic tertiary amine ligand can be self-constructed into a multi-branched aromatic tertiary amine supramolecular organic framework material in the recrystallization and washing process. Therefore, the application of the novel multi-branched aromatic tertiary amine supramolecular organic framework material with novel structure in the industry will not be limited by the difficulty in ligand synthesis and construction. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 The molecular structure formula of the ligand of the multi-branched aromatic tertiary amine supramolecular organic framework material prepared in Example 1 to Example 4.

[0025] Figure 2A molecular structure formula of a ligand of a multi-branched aromatic tertiary amine supramolecular organic framework material prepared for Example 5 to Example 8.

[0026] Figure 3 A molecular structure formula of a ligand of a multi-branched aromatic tertiary amine supramolecular organic framework material prepared for Example 9 to Example 11.

[0027] Figure 4 A single crystal structure diagram of a multi-branched aromatic tertiary amine supramolecular organic framework material prepared for Example 9.

[0028] Figure 5 A single crystal structure diagram of a multi-branched aromatic tertiary amine supramolecular organic framework material prepared for Example 10.

[0029] Figure 6 A thermogravimetric analysis curve of a multi-branched aromatic tertiary amine supramolecular organic framework material prepared for Example 9.

[0030] Figure 7 A thermogravimetric analysis curve of a multi-branched aromatic tertiary amine supramolecular organic framework material prepared for Example 10. DETAILED DESCRIPTION

[0031] The present application provides a multi-branched aromatic tertiary amine supramolecular organic framework material and a preparation method thereof, in order to make the purpose, technical scheme and effect of the present application more clear and definite, the present application is further explained in detail below with reference to the drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and not to limit the present application.

[0032] The present application provides a preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0033] S1. A carbonate, a palladium salt, a phosphine ligand, a halogenated aromatic hydrocarbon and a solvent A are added to a round-bottom flask, magnetically stirred, and heated to reflux at 100℃ under inert gas protection for 30min;

[0034] S2. After heating to reflux for 30min, the aromatic primary amine dissolved in solvent A is added to the round-bottom flask for continuous magnetic stirring, and the heating to reflux at 100℃ is continued;

[0035] S3. After the reaction is completed by monitoring by thin layer chromatography, the reaction is stopped, the reaction system is washed and suction filtered, and then the reaction crude product is obtained by rotary evaporation under reduced pressure;

[0036] S4. The reaction crude product is recrystallized, washed and suction filtered using a solvent B which is difficult to dissolve in the reaction crude product, and finally dried to obtain the multi-branched aromatic tertiary amine ligand.

[0037] The carbonate can provide alkaline conditions for the reaction system in the step S1, and promote the reaction; the palladium salt can promote the nitrogen arylation reaction of the halogenated aromatic hydrocarbon and the primary aromatic amine as a catalyst; and the phosphide can form a complex with the palladium ion as a ligand, so as to enhance the catalytic ability of the palladium salt. The carbonate, the palladium salt, the phosphine ligand and the halogenated aromatic hydrocarbon are first mixed in the solvent A, so that the halogenated aromatic hydrocarbon is uniformly mixed with other raw materials, and then reacts with the primary aromatic amine, so as to avoid the synthesis of other products due to unstable reaction, and improve the yield of the product.

[0038] In the step S3, the unreacted raw materials and some impurities in the reaction system can be removed by washing and filtration after the reaction, and the reduced pressure rotary evaporation operation can ensure that the crude product is obtained after the washing and filtration operation, so as to provide a guarantee for further purification of the product.

[0039] In the step S4, the by-products of the reaction product and the unreacted raw materials can be further removed from the crude reaction product by recrystallization washing and filtration of the crude reaction product using the solvent B which is difficult to dissolve in the crude reaction product, so as to greatly improve the purity of the reaction product.

[0040] The primary aromatic amine and the halogenated aromatic hydrocarbon are coupled in the catalytic system composed of the carbonate, the palladium salt and the phosphine ligand to prepare the primary aromatic amine ligand with six branches or eight branches, and then the primary aromatic amine ligand with multiple branches is washed and recrystallized to prepare the primary aromatic amine supramolecular organic framework material with multiple branches.

[0041] The primary aromatic amine ligand prepared by the present application has multiple branches, so that the construction site between the ligands is large when the supramolecular organic framework material is constructed, and the constructed supramolecular organic framework material exhibits strong stability.

[0042] In addition, the column is not needed when the primary aromatic amine ligand with multiple branches is purified, and the product with a purity greater than 98% can be obtained by simple recrystallization washing; and when the primary aromatic amine ligand with multiple branches is recrystallized, the primary aromatic amine ligand with multiple branches can construct the primary aromatic amine supramolecular organic framework material with multiple branches, so that the preparation method of the primary aromatic amine supramolecular organic framework material with multiple branches provided by the present application has the advantages of short synthesis route, simple reaction system, mild reaction conditions, simple operation, simple purification method and high product yield.

[0043] Further, the aromatic primary amine includes one of 1,3,5-tris(4-aminophenyl)benzene, tetra(4-aminophenyl)methane, tetraphenylthrene tetraamine, 1,3,6,8-tetra-(p-aminophenyl)-pyrene, 5''-(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1':4',1'':3'',1''':4''',1'''':4'''-quaterphenyl]-4,4'''-diamine. The halogenated aromatic hydrocarbon includes one of p-bromobenzoic acid methyl ester, p-bromobenzonitrile, bromobenzene, p-bromonitrobenzene. It should be noted that the aromatic primary amine is not used with any halogenated aromatic hydrocarbon, and when used, it needs to be matched with a specific halogenated aromatic hydrocarbon to synthesize a multi-branched aromatic tertiary amine ligand.

[0044] Further, the inert gas is nitrogen or argon.

[0045] Further, the carbonate salt includes one or more of sodium carbonate, potassium carbonate, cesium carbonate.

[0046] Further, the palladium salt includes one or more of palladium acetate, bis(acetylacetone)palladium(II), palladium chloride.

[0047] Further, the phosphine ligand includes one or more of triphenylphosphine, 1,1'-binaphthalene-2,2'-bis(diphenylphosphine), 1,2-bis(diphenylphosphino)ethane.

[0048] Further, the solvent A includes one or both of 1,4-dioxane and tetrahydrofuran.

[0049] Further, the solvent B is one of 1,4-dioxane, tetrahydrofuran, methanol, ethanol, acetone, dichloromethane, chloroform, acetonitrile. Since the solubility of the multi-branched aromatic tertiary amine ligand in different solvents is different, and the multi-branched aromatic tertiary amine ligand synthesized by different types of halogenated aromatic hydrocarbon and aromatic primary amine has differences in performance, therefore, before recrystallization and washing of the crude reaction product, the solvent B needs to be reselected according to the solubility difference of the multi-branched aromatic tertiary amine ligand in the solvent B.

[0050] Further, the molar ratio of the aromatic primary amine, halogenated aromatic hydrocarbon, carbonate salt, palladium salt, and phosphine ligand is 1:(8-14):(8-14):(0.3-0.8):(0.4-1.28). By adjusting the ratio of each raw material for preparing the multi-branched aromatic tertiary amine ligand, the molar ratio of the aromatic primary amine, halogenated aromatic hydrocarbon, carbonate salt, palladium salt, and phosphine ligand is 1:(8-14):(8-14):(0.3-0.8):(0.4-1.28), which can ensure the preparation of the multi-branched aromatic tertiary amine ligand. However, if the molar ratio of each raw material before the reaction is not within the above range, it will not be able to prepare the target product or there will be more by-products.

[0051] The present application also provides a supramolecular organic framework material, which is prepared by the method for preparing the multi-branched aromatic tertiary amine supramolecular organic framework material.

[0052] The supramolecular organic framework material constructed by the present application not only has strong stability, but also the application of the aromatic tertiary amine supramolecular organic framework material in the industry will not be limited by the difficulty in synthesizing ligands.

[0053] In order to further illustrate the multi-branched aromatic tertiary amine supramolecular organic framework material and the preparation method thereof provided by the present application, the following examples and comparative examples are provided.

[0054] Example 1

[0055] The method for preparing a multi-branched aromatic tertiary amine supramolecular organic framework material comprises the following steps:

[0056] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, methyl p-bromobenzoate and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0057] S2. After heating to reflux for 30 min, 1,3,5-tris(4-aminophenyl)benzene dissolved in 1,4-dioxane was added to the round-bottom flask for continuous magnetic stirring, and heated to reflux at 100°C for 3 days;

[0058] S3. The reaction was stopped after the completion of the reaction was confirmed by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0059] S4. The crude reaction product was washed and suction filtered by recrystallization with acetone, and finally dried at 60°C to obtain compound 4-({4-[3,5-bis(4-{bis[4-(methoxycarbonyl)phenyl]amino}phenyl)phenyl]phenyl}[4-(methoxycarbonyl)phenyl]amino)benzoic acid methyl ester with a yield of 97%.

[0060] In steps S1 and S2, the molar ratio of each reaction raw material is: the molar ratio of 1,3,5-tris(4-aminophenyl)benzene, methyl p-bromobenzoate, cesium carbonate, palladium acetate and 1,1'-binaphthalene-2,2'-diphenylphosphine is 1:10:13:0.8:1.0.

[0061] The compound obtained in this example is identified by 1 HNMR spectrum, and the nuclear magnetic resonance data are as follows: 1H NMR (600 MHz, Chloroform-d) δ 8.00 - 7.95 (m, 4H), 7.80 (s, 1H), 7.72 - 7.68 (m, 2H), 7.28 - 7.25 (m, 2H), 7.20 - 7.16 (m, 4H), 3.93 (s, 6H).

[0062] Example 2

[0063] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0064] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, p-bromobenzonitrile and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated under reflux at 100°C in an oil bath under nitrogen protection for 30 min;

[0065] S2. After heating under reflux in an oil bath for 30 min, 1,3,5-tris(4-aminophenyl)benzene dissolved in 1,4-dioxane was added to the round-bottom flask for continued magnetic stirring, and heated under reflux at 100°C in an oil bath for 3 days;

[0066] S3. The reaction was stopped after complete reaction was confirmed by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0067] S4. The crude reaction product was washed and suction filtered by recrystallization using tetrahydrofuran, and finally dried at 60°C to obtain compound 4-({4-[3,5-bis({4-[bis(4-cyanophenyl)amino]phenyl})phenyl]phenyl}(4-cyanophenyl)amino)benzonitrile, with a yield of 96%.

[0068] In steps S1 and S2, the molar ratio of each reaction raw material is: the molar ratio of 1,3,5-tris(4-aminophenyl)benzene, p-bromobenzonitrile, cesium carbonate, palladium acetate and 1,1'-binaphthalene-2,2'-diphenylphosphine is 1:10:12:0.8:1.0.

[0069] The compound obtained in this example was identified by 1 HNMR spectrum, and the nuclear magnetic resonance data are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.80 (s, 1H), 7.75 - 7.70 (m, 2H), 7.59 (d, J = 8.7 Hz, 4H), 7.28 (s, 2H), 7.20 (d, J = 8.7 Hz, 4H).

[0070] Example 3

[0071] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0072] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, methyl p-bromobenzoate, and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0073] S2. After heating to reflux for 30 min, tetra(4-aminophenyl)methane dissolved in 1,4-dioxane was added to the round-bottom flask for continued magnetic stirring, and heating to reflux at 100°C for 3 days;

[0074] S3. The reaction was stopped after complete reaction was confirmed by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude product was obtained by rotary evaporation under reduced pressure;

[0075] S4. The crude product was washed and suction filtered by recrystallization with ethyl acetate, and finally dried at 60°C to obtain compound hexamethyl 4,4',4',4”,4”',4”'-(((4-((3-(methoxycarbonyl)phenyl)(4-(methoxycarbonyl)phenylamino)phenyl)trimethyl)tris(phen-4,1-diyl))tris(azatril))hexabenzoate with a yield of 98%.

[0076] In steps S1 and S2, the molar ratio of each reaction raw material is: tetra(4-aminophenyl)methane:methyl p-bromobenzoate:cesium carbonate:palladium acetate:1,1'-binaphthalene-2,2'-diphenylphosphine = 1:8:11:0.6:0.9.

[0077] The compound obtained in the example is identified by 1 HNMR spectrum, and the nuclear magnetic resonance data are as follows: 1 H NMR (600 MHz, Chloroform-d) δ 7.95 (d, J = 8.4 Hz, 2H), 7.20 (t, J = 8.2 Hz, 1H), 7.12 (dd, J = 15.6, 8.3 Hz, 3H), 3.91 (s, 3H).

[0078] Example 4

[0079] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0080] S1. Cesium carbonate, palladium acetate, 1,2-bis(diphenylphosphino)ethane, p-bromobenzonitrile, and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0081] S2. After 30 min of heating under reflux in an oil bath, tetra(4- aminophenyl)methane dissolved in 1,4-dioxane was added to the round-bottom flask for continued magnetic stirring, and heating under reflux in an oil bath at 100°C for 2 days;

[0082] S3. The reaction was stopped after completion of the reaction, which was confirmed by TLC monitoring, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0083] S4. The crude reaction product was washed and suction filtered by recrystallization using ethanol, and finally dried at 60°C to obtain compound 4,4', 4", 4"", 4" ', 4" ", 4,"" ", 4,"" " "-((methane tetracarboxylic acid tetra(phenyl-4, 1-diyl)) tetra(azatriyl)) octyl benzyl cyanide, with a yield of 95%.

[0084] In steps S1 and S2, the molar ratio of each reaction raw material was: tetra(4- aminophenyl)methane: p-bromobenzyl cyanide: cesium carbonate: palladium acetate: 1,2- bis(diphenylphosphino)ethane = 1:8:9:0.4:0.6.

[0085] The compound obtained in this example was identified by 1 HNMR spectrum, and the nuclear magnetic data were as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.57 (s, 1H), 7.17 (d, J = 31.8 Hz, 2H).

[0086] Example 5

[0087] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0088] S1. Sodium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'- bisdiphenylphosphine, methyl p-bromobenzoate, and 1,4-dioxane were added to a round-bottom flask for magnetic stirring, and heating under reflux in an oil bath at 100°C for 30 min under nitrogen protection;

[0089] S2. After 30 min of heating under reflux in an oil bath, 5"-(4'-amino- [1,1'-biphenyl]-4-yl)-[1,1':4',1":3",1"' :4"',1""-quaterphenyl]-4,4""-diamine dissolved in 1,4-dioxane was added to the round-bottom flask for continued magnetic stirring, and heating under reflux in an oil bath at 100°C for 3 days;

[0090] S3. The reaction was stopped after completion of the reaction, which was confirmed by TLC monitoring, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0091] S4. The reaction crude product was washed and filtered by recrystallization with ethyl acetate, and finally dried at 60°C to obtain hexamethyl 4,4',4',4",4"',4'"-(benzene-1,3,5-triyl tri([1,1'-biphenyl]-4',4-diyl))tris(nitrogen triyl))hexabenzoate with a yield of 96%.

[0092] In steps S1 and S2, the molar ratio of each reaction raw material was: 5"-(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1':4',1":3",1"'4":3",1"'-quaterphenyl]-4,4"-diamine: methyl p-bromobenzoate: sodium carbonate: palladium acetate: 1,1'-binaphthalene-2,2'-diphenylphosphine = 1:8:8:0.3:0.4.

[0093] The compound obtained in this example was identified by 1 HNMR spectrum identification, nuclear magnetic resonance data as follows: 1 H NMR (500 MHz, DMSO-d6) δ 7.93 (s, 1H), 7.86 (d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.70 (d, J = 8.4 Hz, 2H), 7.57 (d, J = 8.7 Hz, 4H), 7.21 (d, J = 8.4 Hz, 2H), 7.15 (d, J = 8.7 Hz, 4H), 3.90 (s, 3H).

[0094] Example 6

[0095] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0096] S1. Cesium carbonate, palladium (II) bis(acetylacetone), 1,1'-binaphthalene-2,2'-diphenylphosphine, p-bromobenzonitrile and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0097] S2. After heating to reflux for 30 min, 5"-(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1':4',1":3",1"'4":3",1"' -quaterphenyl]-4,4"-diamine dissolved in 1,4-dioxane was added to the round-bottom flask for continued magnetic stirring, and heated to reflux at 100°C for 3 days;

[0098] S3. The reaction was stopped after the completion of the reaction was confirmed by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and filtration, and then rotary evaporation under reduced pressure to obtain the reaction crude product;

[0099] S4. The reaction crude product is washed and filtered by recrystallization using tetrahydrofuran, and finally dried at 60°C to obtain compound 4,4',4',4",4",4"-(benzene-1,3,5-triyl tri([1,1'-biphenyl]-4',4-diyl))tris(azatriyl))hexabenzonitrile, with a yield of 97%.

[0100] In steps S1 and S2, the molar ratio of each reaction raw material is: 5"-(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1':4',1":3",1"'4":3",1"'-quaterphenyl]-4,4"-diamine: p-bromobenzonitrile: cesium carbonate: bis(acetylacetonate)palladium(II): 1,1'-binaphthalene-2,2'-bisdiphenylphosphine = 1:8:10:0.3:0.5.

[0101] The compound obtained in this example is identified by 1 HNMR spectrum identification, nuclear magnetic resonance data are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.93 (s, 1H), 7.86 (d, J = 8.2 Hz, 2H), 7.76 (d, J = 8.2 Hz, 2H), 7.71 (d, J = 8.4 Hz, 2H), 7.59 (d, J = 8.7 Hz, 4H), 7.25 (d, J = 8.4 Hz, 2H), 7.21 (d, J = 8.7 Hz, 4H).

[0102] Example 7

[0103] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0104] S1. Potassium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-bisdiphenylphosphine, bromobenzene and 1,4-dioxane are added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0105] S2. After heating to reflux at 100°C for 30 min, tetraphenylthrene tetramine dissolved in 1,4-dioxane is added to the round-bottom flask for continuous magnetic stirring, and heated to reflux at 100°C for 3 days;

[0106] S3. The reaction is stopped after the reaction is confirmed to be complete by thin layer chromatography, 1,4-dioxane is added to the reaction system for washing and filtration, and then rotary evaporation under reduced pressure to obtain the reaction crude product;

[0107] S4. The reaction crude product is washed and filtered by recrystallization using tetrahydrofuran, and finally dried at 60°C to obtain compound 4,4',4',4"-(ethylene-1,1,2,2-tetrayl)tetra(N,N-diphenylaniline), with a yield of 98%.

[0108] The molar ratio of each reaction material in steps S1 and S2 is: tetraphenyl ethylene tetraamine: bromobenzene: potassium carbonate: palladium acetate: 1,1'-binaphthalene-2,2'-diphenylphosphine = 1:14:14:0.8:1.28.

[0109] The compound obtained in this example is identified by 1 HNMR spectrum, nuclear magnetic resonance data as follows: 1 H NMR (400 MHz, Chloroform-d) δ 7.90-7.12 (m, 4H), 7.06 (d, J = 8.0 Hz, 2H), 7.02-6.89 (m, 2H), 6.85 (d, J = 8.3 Hz, 2H).

[0110] Example 8

[0111] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0112] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, p-bromonitrobenzene and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0113] S2. After heating to reflux for 30 min, tetraphenyl ethylene tetraamine dissolved in 1,4-dioxane was added to the round-bottom flask for continuous magnetic stirring, and heated to reflux at 100°C for 3 days;

[0114] S3. The reaction was stopped after the completion of the reaction was confirmed by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude product was obtained by rotary evaporation under reduced pressure;

[0115] S4. The crude product was washed and suction filtered by recrystallization with tetrahydrofuran, and finally dried at 60°C to obtain compound 4,4',4',4'-(ethylene-1,1,2,2-tetrayl) tetrakis(N,N-bis(4-nitrophenyl) aniline) with a yield of 96%.

[0116] The molar ratio of each reaction material in steps S1 and S2 is: tetraphenyl ethylene tetraamine: p-bromonitrobenzene: cesium carbonate: palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine = 1:10:14:0.5:0.8.

[0117] The compound obtained in this example is identified by 1 HNMR spectrum, nuclear magnetic resonance data as follows: 1H NMR (400 MHz, DMSO-d6) δ 8.07 (d, J = 6.8 Hz, 2H), 7.24 (d, J = 11.4 Hz, 2H), 7.16 (d, 2H), 6.88 (d, J = 8.3 Hz, 2H).

[0118] Example 9

[0119] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0120] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, methyl p-bromobenzoate, and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0121] S2. After heating to reflux for 30 min, tetraphenylstyrene tetramine dissolved in 1,4-dioxane was added to the round-bottom flask for continued magnetic stirring, and heating to reflux at 100°C for 3 days;

[0122] S3. The reaction was stopped after complete reaction was confirmed by thin layer chromatography monitoring, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0123] S4. The crude reaction product was washed and suction filtered by recrystallization with ethyl acetate, and finally dried at 60°C to obtain compound 4,4',4',4'',4''',4'',4'''-(ethylene-1,1,2,2-tetrakis(phenyl-4,1-diyl)) tetra(nitrogen triyl)) octomethyl octoate with a yield of 98%.

[0124] In steps S1 and S2, the molar ratio of each reaction raw material is: tetraphenylstyrene tetramine:methyl p-bromobenzoate:cesium carbonate:palladium acetate:1,1'-binaphthalene-2,2'-diphenylphosphine = 1:10:14:0.5:0.8.

[0125] The compound obtained in this example was identified by 1 HNMR spectrum, and the nuclear magnetic data are as follows: 1 H NMR (600 MHz, Chloroform-d) δ 7.79-7.73 (m, 2H), 7.35-7.30 (m, 1H), 7.23-7.17 (m, 2H), 7.12-7.07 (m, 1H), 3.95 (s, 3H).

[0126] Figure 4 The single crystal structure diagram of the supramolecular organic framework material constructed by the multi-branched aromatic tertiary amine ligand prepared in this example is shown, from which Figure 4It can be seen that the constructed supramolecular organic framework material has a channel structure, so that the constructed supramolecular organic framework material has special functions in the fields of gas adsorption and separation, sensing, catalysis, fluorescence and proton conduction, etc. Figure 6 The TGA curve of the supramolecular organic framework material shown in the figure can be seen that the supramolecular framework material constructed in this embodiment has better stability before 400℃.

[0127] Example 10

[0128] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0129] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, p-bromobenzonitrile and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated under reflux at 100℃ in an oil bath under nitrogen protection for 30min;

[0130] S2. After heating under reflux in an oil bath for 30min, tetraphenyl ethylene tetramine dissolved in 1,4-dioxane was added to the round-bottom flask for continuous magnetic stirring, and heated under reflux at 100℃ in an oil bath for 2-3 days;

[0131] S3. The reaction was stopped by monitoring and confirming the completion of the reaction by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0132] S4. The crude reaction product was washed and suction filtered by recrystallization with tetrahydrofuran, and finally dried at 60℃ to obtain compound 4,4',4'',4''',4''',4''',4'''''',4'''''''-((ethylene-1,1,2,2-tetrayl tetra(phen-4,1-diyl)) tetra(azatrityl)) octylbenzene nitrile, with a yield of 97%.

[0133] In steps S1 and S2, the molar ratio of each reaction raw material is: tetraphenyl ethylene tetramine: p-bromobenzonitrile: cesium carbonate: palladium acetate: 1,1'-binaphthalene-2,2'-diphenylphosphine = 1:10:14:0.5:0.8.

[0134] The compound obtained in this embodiment is identified by 1 HNMR spectrum, and the nuclear magnetic resonance data are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 7.62 (d, J = 8.7 Hz, 1H), 7.16-7.10 (m, 1H), 7.03 (d, J = 8.7 Hz, 1H).

[0135] Figure 5 The single crystal structure diagram of the supramolecular organic framework material constructed by the multi-branched aromatic tertiary amine ligand prepared in this embodiment is shown, fromFigure 5 It can be seen that the constructed supramolecular organic framework material has a channel structure, so that the constructed supramolecular organic framework material has special functions in the fields of gas adsorption and separation, sensing, catalysis, fluorescence and proton conduction, etc. Figure 7 The TGA curve of the supramolecular organic framework material shown in the figure can be seen that the supramolecular framework material constructed in this embodiment has obvious weight loss at about 400℃, and the supramolecular framework material can maintain a certain stability before 400℃.

[0136] Example 11

[0137] A preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0138] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, methyl p-bromobenzoate and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated under reflux at 100℃ in an oil bath under nitrogen protection for 30min;

[0139] S2. After heating under reflux in an oil bath for 30min, 1,3,6,8-tetra-(p-aminophenyl)-pyrene dissolved in 1,4-dioxane was added to the round-bottom flask for continuous magnetic stirring, and heated under reflux at 100℃ in an oil bath for 3 days;

[0140] S3. The reaction was stopped after the completion of the reaction was confirmed by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0141] S4. The crude reaction product was washed and suction filtered by recrystallization with ethyl acetate, and finally dried at 60℃ to obtain compound 4,4',4',4'',4''',4'''-((1,5a1-dihydro-pyrene-1,3,6,8-tetrayl)tetra(phen-4,1-diyl))tetra(azanetriyl)octylic acid octyl ester with a yield of 99%.

[0142] In steps S1 and S2, the molar ratio of each reaction raw material is: 1,3,6,8-tetra-(p-aminophenyl)-pyrene: methyl p-bromobenzoate: cesium carbonate: palladium acetate: 1,1'-binaphthalene-2,2'-diphenylphosphine = 1:8:8:0.3:0.4.

[0143] The compound obtained in this embodiment was identified by 1 HNMR spectrum, and the nuclear magnetic data are as follows: 1H NMR (400 MHz, Chloroform-d) δ 8.32 (s, 1H), 8.04-7.90 (m, 4H), 7.73-7.58 (m, 2H), 7.40-7.28 (m, 2H), 7.25-7.10 (m, 4H), 3.92 (s, 6H).

[0144] Comparative Example 1

[0145] The present comparative example 1 provides a preparation method of a multi-branched aromatic tertiary amine supramolecular organic framework material, comprising the following steps:

[0146] S1. Cesium carbonate, palladium acetate, 1,1'-binaphthalene-2,2'-diphenylphosphine, p-bromobenzonitrile and 1,4-dioxane were added to a round-bottom flask, magnetically stirred, and heated to reflux at 100°C under nitrogen protection for 30 min;

[0147] S2. After heating to reflux for 30 min, 1,3,5-tris(4-aminophenyl)benzene dissolved in 1,4-dioxane was added to the round-bottom flask for continuous magnetic stirring, and heated to reflux at 100°C for 3 days; wherein the molar ratio of each reaction material is: 1,3,5-tris(4-aminophenyl)benzene: methyl p-bromobenzoate: cesium carbonate: palladium acetate: 1,1'-binaphthalene-2,2'-diphenylphosphine = 1:4:10:0.5:0.8;

[0148] S3. The reaction was stopped after the completion of the reaction was confirmed by thin layer chromatography, 1,4-dioxane was added to the reaction system for washing and suction filtration, and then the crude reaction product was obtained by rotary evaporation under reduced pressure;

[0149] S4. The crude reaction product was washed and suction filtered by recrystallization with methanol, and finally dried at 60°C. The dried reaction product was analyzed by thin layer chromatography, and it was found that the multi-branched aromatic tertiary amine ligand was not obtained.

[0150] In summary, the present application provides a new type of multi-branched aromatic tertiary amine supramolecular organic framework material and a preparation method thereof. By using the coupling reaction of aromatic primary amine and halogenated aromatic hydrocarbon in a catalytic system composed of carbonate, palladium salt and phosphine ligand, an aromatic tertiary amine ligand with six branches or eight branches is prepared. Since the aromatic tertiary amine ligand prepared by the present application has multiple branches, the construction sites between the ligands are more when constructing a supramolecular organic framework material, so that the new supramolecular organic framework material constructed not only has strong stability, but also has the advantages of rich structure, more adjustable shape and size of the channel, easy modification of the channel surface, etc., so that the supramolecular organic framework material has special applications in the fields of gas adsorption and separation, sensing, catalysis, fluorescence and proton conduction, etc.

[0151] The preparation method of the multi-branched aromatic tertiary amine super-molecular organic framework material has the advantages of short synthesis route, simple reaction system, mild reaction condition, simple operation, simple purification method and high product yield, etc. After the multi-branched aromatic tertiary amine ligand is prepared, the multi-branched aromatic tertiary amine ligand can be self-constructed into the multi-branched aromatic tertiary amine super-molecular organic framework material in the recrystallization and washing process, so that the application of the constructed aromatic tertiary amine super-molecular organic framework material with novel structure in the industry will not be limited due to the difficulty in ligand synthesis and construction.

Claims

1. A method for preparing a multi-branched aromatic tertiary amine supramolecular organic framework material, characterized in that, Includes the following steps: S1. Add carbonate, palladium salt, phosphine ligand, haloaromatic hydrocarbon and solvent A into a round-bottom flask, stir magnetically, and heat under inert gas protection in an oil bath at 100°C for reflux for 30 min. S2. After reflux in an oil bath for 30 min, add the aromatic primary amine dissolved in solvent A into a round-bottom flask, continue magnetic stirring, and continue reflux in an oil bath at 100°C. S3. After monitoring the reaction until it is complete by thin-layer chromatography, stop the reaction, wash and filter the reaction system, and then evaporate under reduced pressure to obtain the crude product. S4. The crude product was recrystallized, washed, and filtered using solvent B, and finally dried to obtain a multi-branched aromatic tertiary amine supramolecular organic framework material. The aromatic primary amine is one of 1,3,5-tris(4-aminophenyl)benzene, tetra(4-aminophenyl)methane, tetrastyrenetetramine, 1,3,6,8-tetra-(p-aminophenyl)pyrene, and 5”-(4'-amino-[1,1'-biphenyl]-4-yl)-[1,1':4',1”:3”,1”':4”',1””-pentaphenyl]-4,4””-diamine; The haloaromatic hydrocarbon is one of methyl p-bromobenzoate, p-bromobenzonitrile, bromobenzene, and p-bromonitrobenzene. The carbonate is one of potassium carbonate, cesium carbonate, and sodium carbonate; The palladium salt is one of palladium acetate and bis(acetylacetone)palladium(II); The phosphine ligand is one of 1,1'-binaphthyl-2,2'-bisdiphenylphosphine and 1,2-bis(diphenylphosphine)ethane; Solvent A is 1,4-dioxane; solvent B is one of tetrahydrofuran, ethanol, ethyl acetate, and 1,4-dioxane. The molar ratio of the aromatic primary amine, haloaromatic hydrocarbon, carbonate, palladium salt and phosphine ligand is 1:(8-14):(8-14):(0.3-0.8):(0.4-1.28).

2. A multi-branched aromatic tertiary amine supramolecular organic frame material, characterized in that, It is prepared by the method for preparing the multi-branched aromatic tertiary amine supramolecular organic framework material according to claim 1.

Images