CN114805796B - Two-dimensional strong fluorescence polyaniline material with metal ion detection performance and preparation method thereof - Google Patents
Two-dimensional strong fluorescence polyaniline material with metal ion detection performance and preparation method thereof Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
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Abstract
The invention relates to the technical field of organic synthesis, and relates to a two-dimensional strong fluorescence polyaniline material with metal ion detection performance and a preparation method thereof, wherein the structural formula of a polymer of the two-dimensional strong fluorescence polyaniline material is as follows:wherein n=5 to 30; r is R 1 ‑R 3 H, CH respectively 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 13 、C 7 H 15 、C 8 H 17 、CH(C 5 H11) 2 、OH、OCH 3 、OC 2 H 5 、OC 3 H 7 、OC 4 H 9 、OC 8 H 17 Any of the substituents having an aromatic structure, F, cl, br, I, phenyl, and the like may be the same or different; r is R 4 Is H or CN; ar is any one of B1 to B4:the polyaniline material can effectively capture copper ions, iron ions and ruthenium ions, and has great application potential in the fields of ion detection, cell and biological imaging, photoelectric application and the like.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a two-dimensional strong fluorescence polyaniline material with metal ion detection performance and a preparation method thereof.
Background
Polyaniline has important applications in some fields of energy, communication, biological imaging, sensing, catalysis, photoelectricity and the like, but the development of polyaniline in the sensing field is limited by non-fluorescence. Thus, the preparation of polyaniline fluorescent materials is a great challenge, especially two-dimensional strong fluorescent polyaniline materials. Compared with the traditional material, the two-dimensional layered material has the advantages of unique single-layer structure, more reaction sites, increased activity and the like. Therefore, the molecular design is the key for preparing the two-dimensional strong fluorescence polyaniline material, and the invention skillfully utilizes double bonds to construct a large molecular conjugated system, thereby successfully preparing the two-dimensional strong fluorescence polyaniline material.
Disclosure of Invention
The invention aims to provide a two-dimensional strong fluorescence polyaniline material with metal ion detection performance, which greatly enhances the conjugation degree between whole molecules in a mode of constructing double bonds between benzene rings, greatly enhances charge transfer in the molecules and shows excellent metal ion sensing performance.
The second purpose of the invention is to provide a preparation method of the two-dimensional strong fluorescence polyaniline material with metal ion detection performance, which has the advantages of simple synthesis method, high universality and strong operability.
The scheme adopted by the invention for achieving one of the purposes is as follows: a two-dimensional strong fluorescence polyaniline material with metal ion detection performance has a polymer structure formula as follows:
wherein n=5 to 30;
R 1 -R 3 h, CH respectively 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 13 、C 7 H 15 、C 8 H 17 、CH(C 5 H11) 2 、OH、OCH 3 、OC 2 H 5 、OC 3 H 7 、OC 4 H 9 、OC 8 H 17 Any of the substituents having an aromatic structure, F, cl, br, I, phenyl, and the like may be the same or different;
R 4 is H or CN;
ar is any one of B1 to B4:
for example, when R 1 ，R 2 And R is 3 Is H, R 4 The structural formula of the polymer of the two-dimensional strong fluorescence polyaniline material is any one of the following formulas P11 to P44 when Ar is B1 to B4 is-H or-CN:
the scheme adopted by the invention for achieving the second purpose is as follows: the preparation method of the two-dimensional strong fluorescence polyaniline material with metal ion detection performance comprises the steps of preparing corresponding double nitro monomers by reacting a nitro-containing compound with any one of terephthalaldehyde, 1, 4-p-dichlorobenzyl derivatives, 2, 5-thiophene dicarboxaldehyde and 9-hexyl-9H-carbazole-3, 6-dicarboxaldehyde, reducing the double nitro monomers to obtain final monomers, and polymerizing the final monomers in a bulk mode to obtain the two-dimensional strong fluorescence polyaniline material.
Preferably, the method comprises the following steps:
(1) Uniformly mixing a nitro-containing compound with any one of terephthalaldehyde, 1, 4-p-dichlorobenzyl derivative, 2, 5-thiophene dicarboxaldehyde and 9-hexyl-9H-carbazole-3, 6-dicarboxaldehyde in an organic solvent, and reacting under the condition of a catalyst to prepare a corresponding dinitrate monomer;
(2) Reducing the dinitrate monomer obtained in the step (1) to obtain corresponding amine, and purifying to obtain a final monomer;
(3) And (3) dissolving the final monomer obtained in the step (2) in an organic solvent, adding an aqueous solution of acid, heating the mixture, stirring until the reaction is complete, filtering the reacted mixture, and washing and drying the obtained filter residues to obtain a polymer, wherein the polymer is the two-dimensional strong-fluorescence polyaniline material.
Preferably, the structural formula of the nitro-containing compound is any one of the following formulas A1 to A3:
wherein R is 1 ，R 2 And R is 3 Is divided into H, CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 13 、C 7 H 15 、C 8 H 17 、CH(C 5 H11) 2 、OH、OCH 3 、OC 2 H 5 、OC 3 H 7 、OC 4 H 9 、OC 8 H 17 Any of the substituents having an aromatic structure, F, cl, br, I, phenyl, and the like may be the same or different.
Preferably, the final monomer has the structural formula:
wherein R is 1 -R 3 H, CH respectively 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 13 、C 7 H 15 、C 8 H 17 、CH(C 5 H11) 2 、OH、OCH 3 、OC 2 H 5 、OC 3 H 7 、OC 4 H 9 、OC 8 H 17 Any of the substituents having an aromatic structure, F, cl, br, I, phenyl, and the like may be the same or different;
R 4 is H or CN;
ar is any one of B1 to B4:
preferably, in the step (1), the molar ratio of the nitro-containing compound to any one of terephthalaldehyde, 1, 4-p-dichlorobenzyl derivative, 2, 5-thiophenedicarboxyaldehyde and 9-hexyl-9H-carbazole-3, 6-dicarboxaldehyde is 2:1, the catalyst is sodium hydroxide or piperidine, the molar ratio of the catalyst to the nitrobenzene-containing compound is 100-150:1, and the organic solvent is dichloromethane or methanol.
Preferably, in the step (2), the reducing system is tin powder, ethanol solution of hydrochloric acid or ethanol solution of iron powder and ammonium chloride, and when the ethanol solution of tin powder and hydrochloric acid is used as the reducing system: the mol ratio of the dinitrate monomer to the tin powder to the hydrochloric acid is 1 (2-5) (4.7-6), and the concentration of the dinitrate monomer in the ethanol is 0.25-0.5 mol.L -1 When the ethanol solution of iron powder and ammonium chloride is used as a reduction system, the molar ratio of the dinitrate monomer to the iron powder and the ammonium chloride is 1 (5-20) (10-20), and the concentration of the dinitrate monomer in the ethanol is 0.25-0.5 mol.L -1 。
Preferably, in the step (3), the organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and tetrahydrofuran.
Preferably, in the step (3), the acid is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran, the feeding ratio of the final monomer, ammonium persulfate, acid, water and organic solvent is 250 mmol/1 mmol/3 mL/1 mL (3-10 mL), and the reaction temperature is 60-90 ℃.
Preferably, in the step (3), the filter residue is washed with a hydrazine hydrate solution, a 5% sodium hydroxide solution and a methanol solution in this order.
In the step (1), the 2-nitrobenzyl bromide derivative or the 1, 4-p-dichlorobenzyl derivative is obtained by refluxing 2-nitrobenzyl bromide or 1, 4-p-dichlorobenzyl and triphenylphosphine in chloroform solution, evaporating the solvent, and washing and purifying the solid with dimethylbenzene. The catalyst is sodium hydroxide or piperidine, and the solution is dichloromethane or methanol.
For example, when the nitro-group-containing compound has the structural formula A1, A2 and the terephthalaldehyde (B1), 1, 4-p-dichlorobenzyl derivative (B2), R 1 ，R 2 And R is 3 Is H;
the monomer has the structural formula:
the polymer has the structural formula:
in the ion detection, P11 and P22 are found to have strong selectivity and sensitivity to iron ions and copper ions, P33 has strong selectivity and sensitivity to copper ions, and P44 has strong selectivity and sensitivity to iron ions, copper ions and ruthenium ions.
The invention has the following advantages and beneficial effects:
(1) The two-dimensional strong fluorescence polyaniline material with metal ion detection performance provided by the invention takes benzene rings as skeletons as fluorescence luminous groups, amino groups as metal ion binding points, can effectively capture copper ions, iron ions and ruthenium ions, and can be used as a fluorescence material with great application potential in the fields of ion detection, cell and biological imaging, photoelectric application and the like.
(2) The two-dimensional strong fluorescence polyaniline material with metal ion detection performance greatly enhances the conjugation degree between the whole molecules by constructing double bonds between benzene rings, and simultaneously greatly enhances the charge transfer in the molecules.
(3) Compared with the existing polyaniline material, the two-dimensional strong fluorescence polyaniline material with metal ion detection performance has strong fluorescence and shows a two-dimensional layered microscopic morphology.
(4) The preparation method of the invention is simple, moderate and high in operability.
Drawings
FIG. 1 is a schematic diagram of the synthetic flow of a two-dimensional strongly fluorescent polyaniline-like material monomer according to the present invention;
FIG. 2 is a schematic diagram of the synthetic flow of the two-dimensional strong fluorescent polyaniline-like material polymer according to the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of compound 1 in example 1 of the present invention;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the compound 6 in example 1 of the present invention;
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the compound M1 of example 1 of the present invention;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of the compound P11 in example 1 of the present invention;
FIG. 7 is a nuclear magnetic resonance hydrogen spectrum of compound 7 in example 2 of the present invention;
FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of the compound M2 in example 2 of the present invention;
FIG. 9 is a nuclear magnetic resonance hydrogen spectrum of the compound P22 in example 2 of the present invention;
FIG. 10 is a nuclear magnetic resonance hydrogen spectrum of compound 2 in example 3 of the present invention;
FIG. 11 is a nuclear magnetic resonance hydrogen spectrum of compound 3 in example 3 of the present invention;
FIG. 12 is a nuclear magnetic resonance hydrogen spectrum of compound 8 in example 3 of the present invention;
FIG. 13 is a nuclear magnetic resonance hydrogen spectrum of the compound M3 in example 3 of the present invention;
FIG. 14 is a nuclear magnetic resonance hydrogen spectrum of the compound P33 in example 3 of the present invention;
FIG. 15 is a nuclear magnetic resonance hydrogen spectrum of compound 4 in example 4 of the present invention;
FIG. 16 is a nuclear magnetic resonance hydrogen spectrum of compound 5 in example 4 of the present invention;
FIG. 17 is a nuclear magnetic resonance hydrogen spectrum of compound 9 in example 4 of the present invention;
FIG. 18 is a nuclear magnetic resonance hydrogen spectrum of the compound M4 in example 4 of the present invention;
FIG. 19 is a nuclear magnetic resonance hydrogen spectrum of compound P44 in example 4 of the present invention;
FIG. 20 is an infrared spectrum of compounds M1 and P11 in example 1 of the present invention;
FIG. 21 is an infrared spectrum of compounds M2 and P22 of example 2 of the present invention;
FIG. 22 is an infrared spectrum of compounds M3 and P33 of example 3 of the present invention;
FIG. 23 is an infrared spectrum of compounds M4 and P44 of example 4 of the present invention;
FIG. 24 is a graph showing the fluorescence emission spectrum of polymer P11 in example 1 of the present invention;
FIG. 25 is a graph showing the fluorescence emission spectrum of polymer P22 in example 2 according to the present invention;
FIG. 26 is a graph showing the fluorescence emission spectrum of polymer P33 in example 3 according to the present invention;
FIG. 27 is a graph showing the fluorescence emission spectrum of polymer P44 in example 4 of the present invention.
Detailed Description
For a better understanding of the present invention, the following examples are further illustrative of the present invention, but the contents of the present invention are not limited to the following examples only.
In the examples below, the specific operations, which do not involve temperature, are all carried out at room temperature.
The design of the synthetic monomer varies due to the choice of the original compound substrate. FIG. 1 is a schematic diagram of the synthetic flow of a two-dimensional strongly fluorescent polyaniline-like material monomer according to the present invention; FIG. 2 is a schematic diagram of the synthetic flow of the two-dimensional strong fluorescent polyaniline-like material polymer according to the present invention.
Example 1: detailed description of the synthetic procedures of each compound using 1, 4-p-dichlorobenzene as the starting material
1, 4-P-dichlorobenzene is taken as a raw material, triphenylphosphine is added into a chloroform solution to obtain a1, 4-P-dichlorobenzene derivative (1), then the 1, 4-P-dichlorobenzene derivative (1) and o-nitrobenzaldehyde are reacted to obtain yellow powder 1, 4-bis ((E) -2-nitrostyryl) benzene (6), the obtained product is reduced under the conditions of tin powder and hydrochloric acid to obtain a final monomer M1, and the monomer M1 is reacted in the presence of a phosphoric acid aqueous solution and ammonium persulfate to generate a polymer P11, wherein the polymer is the two-dimensional strong-fluorescence polyaniline material containing double bond units.
(1) Synthesis of Compound 1
In a 250mL three-necked flask, 1.74g (10 mmol) of 1, 4-p-dichlorobenzyl, 5.24g (20 mmol) of triphenylphosphine and 50mL of chloroform were charged, and the mixture was refluxed with a reflux condenser equipped with a drying tube, and refluxed with an oil bath for 2 hours. After the reaction, the chloroform was distilled off and the reaction mixture was further purified15mL of dimethylbenzene is added into a reaction bottle, fully mixed by shaking and filtered. The crystals were washed with a small amount of xylene and the product was dried in an oven at 110℃for 1h for further use. The yield was 92%. 1 H NMR(400MHz,CDCl 3 )δ7.72(t,6H),7.67(t,12H),7.61(d,12H),6.91(s,4H),5.43(d,6H)ppm.
(2) Synthesis of Compound 6
In a 250mL three-necked flask, 1.40g (2 mmol) of Compound 1,0.91g (6 mmol) of o-nitrobenzaldehyde and 15mL of methylene chloride were charged, and the mixture was poured into a reflux condenser. 1.0mL of 50% aqueous sodium hydroxide solution was slowly dropped from the side of the three-necked flask with sufficient stirring to keep the flask slightly boiling. After the completion of the dropwise addition, stirring was continued for 24 hours. After the reaction, filtering the solution, adding absolute ethyl alcohol into the residue to recrystallize to obtain the compound 6 with the yield of 69%. 1 H NMR(400MHz,DMSO-d 6 )δ8.12(d,2H),7.60(t,2H),7.55(t,2H),7.25(d,2H),6.89(t,6H),6.59(d,2H)ppm.
(3) Synthesis of Compound M1
1.86g (5 mmol) of compound 6 and 1.19g (10 mmol) of tin powder obtained were added to 20mL of absolute ethanol under nitrogen atmosphere, and 2mL of 36% hydrochloric acid solution was added dropwise at 0 ℃. After the completion of the dropwise addition, stirring overnight at room temperature, carefully adding a saturated aqueous sodium bicarbonate solution and adjusting the pH of the solution to 7, stirring for 0.5h, extracting with dichloromethane, combining the organic phases, removing the solvent under reduced pressure, and purifying with a chromatographic column to give a pale yellow powder, namely the compound M1, with a yield of 64%. 1 H NMR(400MHz,DMSO-d 6 )δ7.06(s,4H),6.95(t,2H),6.88(d,2H),6.68(d,2H),6.47(d,4H),6.40(m,2H,)ppm.
(4) Synthesis of Polymer P11
1.56g (10 mmol) of compound M1 was dissolved in 15mL of dry N, N-dimethylformamide, 8mL of a mixed solution of phosphoric acid and water in a volume ratio of 3:1 was added, followed by heating to 90℃and stirring for 5min, then 1mL of a 0.04mM ammonium persulfate aqueous solution was added and stirring was carried out for 24 hours, after the reaction was completed, filtration was carried out, and the filter residue was washed with a hydrazine hydrate solution, 5% sodium hydroxide and a methanol solution in this order, and dried in a vacuum oven at 90℃for use in a yield of 51%.
As shown in fig. 3, the nuclear magnetic resonance spectrum of the compound 1 in this example is shown in the figure: at 5.4ppmThe nuclear magnetic shift is the methylene (-CH) of compound 1 2 ) Indicating that we successfully synthesized compound 1.
As shown in fig. 4, the nuclear magnetic resonance spectrum of the compound 6 in this example is shown as follows: the nuclear magnetic shift peaks of the double bond are respectively 6.7 and 6.9ppm, which shows that the compound is successfully synthesized.
As shown in fig. 5, the nuclear magnetic resonance hydrogen spectrum of the compound M1 in this example is shown in the figure: the nuclear magnetic shift peak of the amine group was at 4.9ppm, indicating that the nitro compound had been completely converted to an amine compound.
As shown in fig. 6, the nuclear magnetic resonance hydrogen spectrum of the compound P11 in this example is shown in the figure: the nuclear magnetic shift peak of monomer M1 has substantially disappeared, indicating that the polymer has been successfully prepared.
As shown in fig. 20, the infrared spectra of the compounds M1 and P11 in this example are shown in the figure: the comparison of the IR spectra of the monomers and polymers can be seen at 1500-1800cm -1 The fine monomer infrared peak has been converted to a broad polymer peak, indicating that the monomer has been completely converted to polymer.
As shown in fig. 24, the ion-selective fluorescence emission spectrum of the polymer P11 in this example is shown, and it can be seen from the figure: when Fe is added to a solution of polymer P11 in N, N-dimethylformamide 3+ ，Zn 2+ After 13 metal ions, only metal ions Fe 3+ And Cu 2+ The fluorescence emission peak of the polymer P11 at 525nm is obviously reduced and other metal ions are almost unchanged after the polymer P11 is added, so the polymer can be used as Fe 3+ And Cu 2+ Is provided.
Example 2: details of the synthetic procedures of the respective compounds using terephthalaldehyde as the raw material
The method comprises the steps of taking terephthalaldehyde as a raw material, adding o-nitrophenylacetonitrile into a methanol solution to react to obtain (2Z, 2 'Z) -3,3' - (1, 4-phenylene) bis (2- (2-nitrophenyl) acrylonitrile) (7), reducing the obtained product under the conditions of tin powder and hydrochloric acid to obtain a final monomer M2, and reacting the monomer M2 in the presence of a phosphoric acid aqueous solution and ammonium persulfate to generate a polymer P22, wherein the polymer is a double bond unit-containing two-dimensional strong-fluorescence polyaniline material.
(1) Synthesis of Compound 7
In a 250mL three-necked flask, 1.34g (10 mmol) of terephthalaldehyde, 3.24g (20 mmol) of o-nitrophenylacetonitrile and 30mL of methanol were charged, and the flask was equipped with a reflux condenser. 2.0mL of piperidine solution was slowly dropped from the three-necked flask side with sufficient stirring. After the completion of the dropwise addition, the temperature is raised to 70 ℃ and stirring is continued for 24 hours. After the reaction, the reaction mixture was filtered to obtain yellow powder, namely compound 7 in 75% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.26(d,2H),7.96(s,4H),7.84(t,2H),7.72(m,6H)ppm.
(2) Synthesis of Compound M2
2.11g (5 mmol) of compound 7 and 1.19g (10 mmol) of tin powder obtained were added to 20mL of absolute ethanol under nitrogen atmosphere, and 2mL of 36% hydrochloric acid solution was added dropwise at 0 ℃. After the completion of the dropwise addition, stirring overnight at room temperature, carefully adding a saturated aqueous sodium bicarbonate solution and adjusting the pH of the solution to 7, stirring for 0.5h, extracting with dichloromethane, combining the organic phases, removing the solvent under reduced pressure, and purifying with a chromatographic column to give a pale yellow powder, namely the compound M2, with a yield of 58%. 1 H NMR(400MHz,CDCl 3 )δ7.95(s,4H),7.34(s,2H),7.21(t,4H),6.83(t,2H),6.75(d,2H),3.99(s,4H)ppm.
(3) Synthesis of Polymer P22
1.81g (5 mmol) of compound M2 was dissolved in 15mL of dry N, N-dimethylformamide, 8mL of a mixed solution of phosphoric acid and water in a volume ratio of 3:1 was added, followed by heating to 90℃and stirring for 5min, then 1mL of an aqueous solution of 0.04mM ammonium persulfate was added and stirring was carried out for 24 hours, after the reaction was completed, filtration was carried out, and the filter residue was washed with a hydrazine hydrate solution, 5% sodium hydroxide and a methanol solution in this order, and dried in a vacuum oven at 90℃for use, and the yield was 55%.
As shown in fig. 7, the nuclear magnetic resonance spectrum of the compound 7 in this example is shown as follows: the double bond nuclear magnetic shift of compound 7 was observed at 7.8ppm, indicating that compound 7 was successfully synthesized.
As shown in fig. 8, the nuclear magnetic resonance hydrogen spectrum of the compound M2 in this example is shown in the figure: amino (-NH) 2 ) The nuclear magnetic shift peak of (2) was 4.0ppm, indicating that the nitro group wasThe compound has been completely converted into an amine-based compound.
As shown in fig. 9, the nuclear magnetic resonance hydrogen spectrum of the compound P22 in this example is shown in the figure: the nuclear magnetic shift peak of monomer M2 has substantially disappeared, indicating that the polymer has been successfully prepared.
As shown in fig. 21, the infrared spectra of the compounds M2 and P22 in this example are shown in the figure: of the monomers-NH-around 3300 2 Has been converted to broad vibrational peaks in the polymer due to the-NH-vibration peaks 2 Polymerization takes place.
As shown in fig. 25, the ion-selective fluorescence emission spectrum of the polymer P22 in this example is shown, and it can be seen from the figure: when Fe is added to a solution of polymer P22 in N, N-dimethylformamide 3+ ，Zn 2+ After 13 metal ions, only Fe 3+ And Cu 2+ The fluorescence emission peak of the polymer P22 at 472nm is obviously reduced and other metal ions are almost unchanged after the ions are added, so the polymer can be used as metal ions Fe 3+ And Cu 2+ Is provided.
Example 3: the steps for synthesizing each compound are detailed by taking thiophene as raw material
Thiophene is used as a raw material, N-butyllithium and anhydrous N, N-dimethylformamide are added into tetrahydrofuran solution to react to obtain 2, 5-thiophene dicarboxaldehyde (3), then the compound (3) and the 2-nitrobenzyl bromide derivative (2) react to obtain reddish brown powder 2, 5-bis ((E) -2-nitrostyryl) thiophene (8), the obtained product is reduced under the conditions of tin powder and hydrochloric acid to obtain a final monomer M3, the monomer M3 reacts under the existence of phosphoric acid aqueous solution and ammonium persulfate to generate a polymer P33, and the polymer is the two-dimensional strong-fluorescence polyaniline material containing double bond units.
(1) Synthesis of Compound 2
In a 250mL three-necked flask, 1g (4.65 mmol) of nitrobenzyl bromide and 1.5g (5.73 mmol) of triphenylphosphine are placed in a single-necked flask, 15mL of chloroform is added, the mixture is condensed and refluxed for 2 hours at 66 ℃, after the reaction is finished, the chloroform is distilled off, 5mL of dimethylbenzene is added, shaking and mixing are carried out, white solid precipitation is observed, suction filtration is carried out, and petroleum ether is used for washing, thus obtaining the compoundThe product of 2 was dried in an oven at 110℃for 1h, ready for use in 97% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.08(d,1H),7.96(t,3H),7.78(m,7H),7.70(t,1H),7.66(t,6H),7.43(d,1H),5.50(d,2H)ppm.
(2) Synthesis of Compound 3
In a 250mL three-necked flask, 12mL (30 mmol) of N-butyllithium and 1mL (13 mmol) of thiophene were added to a freshly distilled mixed solution of 4mL of tetramethylethylenediamine and 50mL of hexane under a nitrogen atmosphere, and 20mL of dry tetrahydrofuran and 3.5mL of anhydrous N, N-dimethylformamide were added to the mixture. The reaction mixture was refluxed at 70 ℃ for 1.5h. The reaction mixture was cooled to room temperature. To the mixture was added 5% hydrochloric acid (50 mL), and the mixture was stirred for 0.5h. 100mL of ethyl acetate solution was added and the mixture was washed with hydrochloric acid (100 mL) and saturated sodium chloride (100 mL). Purification by chromatography column gave a pale yellow powder, compound 3, 70% yield. 1 H NMR(400MHz,DMSO-d 6 )δ10.10(d,2H),8.18(d,2H),ppm.
(3) Synthesis of Compound 8
In a 250mL three-necked flask, 0.7g (5 mmol) of Compound 3,4.78g (10 mmol) of Compound 2 and 30mL of dichloromethane were added, and the mixture was charged with a reflux condenser. 5.0mL of 50% aqueous sodium hydroxide solution was slowly dropped from the side of the three-necked flask with sufficient stirring to keep the flask slightly boiling. After the completion of the dropwise addition, stirring was continued for 24 hours. After the reaction was completed, the solution was filtered off, and absolute ethanol was added to the residue to recrystallize to obtain a yellow solid, compound 8, in 90% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.03(t,4H),7.78(t,2H),7.62(m,4H),7.32(m,4H)ppm.
(4) Synthesis of Compound M3
1.89g (5 mmol) of compound 8 and 1.19g (10 mmol) of tin powder obtained were added to 20mL of absolute ethanol under nitrogen atmosphere, and 2mL of 36% hydrochloric acid solution was added dropwise at 0 ℃. After the completion of the dropwise addition, stirring overnight at room temperature, carefully adding a saturated aqueous sodium bicarbonate solution and adjusting the pH of the solution to 7, stirring for 0.5h, extracting with dichloromethane, combining the organic phases, removing the solvent under reduced pressure, and purifying with a chromatographic column to obtain a pale yellow powder, namely the compound M3, with a yield of 82%. 1 H NMR(400MHz,DMSO-d 6 )δ7.43(d,2H),7.20(m,6H),7.01(t,2H),6.71(d,2H),6.61(t,2H),5.31(s,4H)ppm.
(5) Synthesis of Polymer P33
1.59g (5 mmol) of compound M3 was dissolved in 15mL of dry N, N-dimethylformamide, 8mL of a mixed solution of phosphoric acid and water in a volume ratio of 3:1 was added, followed by heating to 90℃and stirring for 5min, then 1mL of an aqueous solution of 0.04mM ammonium persulfate was added and stirring was carried out for 24 hours, after the reaction was completed, filtration was carried out, and the filter residue was washed with a hydrazine hydrate solution, 5% sodium hydroxide and a methanol solution in this order, and dried in a vacuum oven at 90℃for use, with a yield of 50%.
As shown in fig. 10, the nuclear magnetic resonance spectrum of the compound 2 in this example is shown as follows: methylene (-CH) of Compound 2 2 ) Is observed at 5.4ppm, indicating that compound 2 was successfully synthesized.
As shown in fig. 11, the nuclear magnetic resonance hydrogen spectrum of the compound 3 in this example is shown as follows: the nuclear magnetic shift peak of aldehyde (-CHO) was at 10.12ppm, indicating that compound 3 was successfully synthesized.
As shown in fig. 12, the nuclear magnetic resonance spectrum of the compound 8 in this example is shown as follows: the double bond nuclear magnetic shift of compound 8 was observed at 7.7ppm, indicating that compound 8 was successfully synthesized.
As shown in fig. 13, the nuclear magnetic resonance hydrogen spectrum of the compound M3 in this example is shown in the figure: amino (-NH) 2 ) The nuclear magnetic shift peak of (2) is 5.2ppm, which indicates that the nitro compound has been completely converted into an amine compound.
As shown in fig. 14, the nuclear magnetic resonance hydrogen spectrum of the compound P33 in this example is shown in the figure: the nuclear magnetic shift peak of monomer M3 has substantially disappeared, indicating that the polymer has been successfully prepared.
As shown in fig. 22, the infrared spectra of the compounds M3 and P33 in this example are shown in the figure: of the monomers-NH-around 3300 2 Has been converted to broad vibrational peaks in the polymer due to the-NH-vibration peaks 2 Polymerization takes place.
As shown in fig. 25, the ion-selective fluorescence emission spectrum of the polymer P33 in this example is shown, and it can be seen from the figure: when N, N-dimethyl into Polymer P33Adding Fe into solution of formamide 3+ ，Zn 2+ After waiting 13 metal ions, only Cu 2+ After the ion is added, the fluorescence emission peak of the polymer P33 at 525nm is obviously increased and other metal ions are almost unchanged, so the polymer can be used as metal ion Cu 2+ Is provided.
Example 4: the synthesis steps of each compound are described in detail by taking carbazole as raw material
Carbazole is used as a raw material, potassium hydroxide powder and bromohexane are added into a dimethyl sulfoxide solution to react to obtain 9-hexyl carbazole (4), phosphorus oxychloride and anhydrous N, N-dimethylformamide are added into a1, 2-dichloroethane solution of the compound (4) to obtain 9-hexyl-9H-carbazole-3, 6-dicarbaldehyde (5), and then the compound (5) and the 2-nitrobenzyl bromide derivative (2) react to obtain yellow powder 9-hexyl-3, 6-bis ((E) -2-nitrostyryl) -9H-carbazole (9). The product is reduced under the conditions of tin powder and hydrochloric acid to obtain a final monomer M4, and the monomer M4 reacts in the presence of phosphoric acid aqueous solution and ammonium persulfate to generate a polymer P44, wherein the polymer is the two-dimensional strong-fluorescence polyaniline material containing double bond units.
(1) Synthesis of Compound 4
In a 250mL three-necked flask, 2.48g (15 mmol) of 1-bromohexane was slowly dropped into a mixed solution of 1.67g (10 mmol) of carbazole and 15mL of dimethyl sulfoxide under a nitrogen atmosphere. The reaction mixture was reacted at 90℃for 24 hours. The reaction mixture was cooled to room temperature. To the mixture was added 50mL of water and the reaction mixture was extracted with 100mL of petroleum ether. The organic phases were combined, the solvent was removed under reduced pressure, and purified by column chromatography to give compound 4 as a white solid in 91% yield. 1 H NMR(400MHz,DMSO-d 6 )δ8.15(d,2H),7.57(d,2H),7.47(d,2H),7.20(s,2H),4.35(s,2H),1.73(t,2H,)1.26(m,6H),0.78(t,3H)ppm.
(2) Synthesis of Compound 5
1.53g (10 mmol) of phosphorus oxychloride and 0.73g (10 mmol) of anhydrous N, N-dimethylformamide are slowly added dropwise to a1, 2-dichloroethane solution of compound 4 in a 250mL three-necked flask under nitrogen atmosphere at 0deg.C. The reaction mixture was refluxed at 90 ℃ for 72h. The reaction mixture was cooled to room temperature. 50mL of the mixture was addedThe mixture was stirred with water for 0.5h. The reaction mixture was extracted with 100mL of dichloromethane. The organic phases were combined, the solvent was removed under reduced pressure, and purified by column chromatography to give compound 5 as a white solid in 47% yield. 1 H NMR(400MHz,DMSO-d 6 )δ10.11(t,2H),8.93(s,2H),8.09(s,2H),7.91(t,2H),4.54(s,2H),1.79(s,2H),1.23(m,6H),0.81(t,3H)ppm.
(3) Synthesis of Compound 9
In a 250mL three-necked flask, 3.07g (10 mmol) of Compound 5,9.56g (20 mmol) of Compound 2 and 30mL of dichloromethane were added, and the mixture was charged into a reflux condenser. 5.0mL of 50% aqueous sodium hydroxide solution was slowly dropped from the side of the three-necked flask with sufficient stirring to keep the flask slightly boiling. After the completion of the dropwise addition, stirring was continued for 24 hours. After the reaction was completed, the solution was filtered off, and absolute ethanol was added to the residue to recrystallize to obtain a yellow solid, namely compound 9, in a yield of 51%. 1 H NMR(400MHz,CDCl 3 )δ8.18(s,1H),7.92(t,2H),7.77(t,2H),7.64(d,1H),7.59(t,2H),7.54(t,2H),7.32(m,6H),7.20(d,1H),7.09(d,1H),4.22(m,2H),1.81(m,2H),1.31(t,2H),1.18(m,4H),0.82(t,3H)ppm.
(4) Synthesis of Compound M4
2.73g (5 mmol) of compound 9 and 1.19g (10 mmol) of tin powder obtained were added to 20mL of absolute ethanol under nitrogen atmosphere, and 2mL of 36% hydrochloric acid solution was added dropwise at 0 ℃. After the completion of the dropwise addition, stirring overnight at room temperature, carefully adding a saturated aqueous sodium bicarbonate solution and adjusting the pH of the solution to 7, stirring for 0.5h, extracting with dichloromethane, combining the organic phases, removing the solvent under reduced pressure, and purifying with a chromatographic column to give a pale yellow powder, namely the compound M4, with a yield of 58%. 1 H NMR(400MHz,DMSO-d 6 )δ8.43(s,2H),7.81(d,2H),7.61(d,2H),7.51(m,4H),7.21(d,2H),7.01(t,2H),6.72(d,2H),6.63(t,2H),5.34(s,4H),4.44(t,2H),1.83(t,2H),1.30(t,2H),1.25(t,4H),0.85(t,3H)ppm.
(5) Synthesis of Polymer P44
2.43g (5 mmol) of compound M4 are dissolved in 15mL of dry N, N-dimethylformamide, 8mL of a mixed solution of phosphoric acid and water in a volume ratio of 3:1 is added, then the temperature is raised to 90 ℃ and the mixture is stirred for 5min, then 1mL of 0.04mM ammonium persulfate aqueous solution is added and stirred for 24h, after the reaction is finished, the mixture is filtered, filter residues are washed by hydrazine hydrate solution, 5% sodium hydroxide and methanol solution in sequence, and the mixture is dried in a vacuum oven at 90 ℃ for later use, and the yield is 62%.
As shown in fig. 15, the nuclear magnetic resonance hydrogen spectrum of the compound 4 in this example is shown in the figure: the nuclear magnetic shift of the alkyl chain of compound 4 was observed at 0.5-4.5ppm, indicating that compound 4 was successfully synthesized.
As shown in fig. 16, the nuclear magnetic resonance spectrum of the compound 5 in this example is shown as follows: the nuclear magnetic shift peak of aldehyde (-CHO) was at 10.10ppm, indicating that compound 5 was successfully synthesized.
As shown in fig. 17, the nuclear magnetic resonance hydrogen spectrum of the compound 9 in this example is shown in the figure: the double bond nuclear magnetic shift of compound 9 was observed at 7.5ppm, indicating that compound 9 was successfully synthesized.
As shown in fig. 18, the nuclear magnetic resonance hydrogen spectrum of the compound M4 in this example is shown in the figure: amino (-NH) 2 ) The nuclear magnetic shift peak of (2) was 5.4ppm, which indicates that the nitro compound had been completely converted to an amine compound.
As shown in fig. 19, the nuclear magnetic resonance hydrogen spectrum of the compound P44 in this example is shown in the figure: the nuclear magnetic shift peak of monomer M4 has substantially disappeared, indicating that the polymer has been successfully prepared.
As shown in fig. 23, the infrared spectra of the compounds M4 and P44 in this example are shown in the figure: of the monomers-NH-about 3400 2 Has been converted to broad vibrational peaks in the polymer due to the-NH-vibration peaks 2 Polymerization takes place.
As shown in fig. 27, the ion-selective fluorescence emission spectrum of the polymer P44 in this example is shown, which can be seen: when Fe is added to a solution of polymer P44 in N, N-dimethylformamide 3+ ，Zn 2+ After 13 metal ions, only Fe 3+ ，Cu 2+ And Ru (Rust) 3+ After the ion is added, the fluorescence emission peak of the polymer P44 at 530nm is obviously reduced and other metal ions are almost unchanged, so the polymer can be used as metal ion Fe 3+ ，Cu 2+ And Ru (Rust) 3+ Is provided.
While the invention has been described with respect to the preferred embodiments, it will be understood that the invention is not limited thereto, but is capable of modification and variation without departing from the spirit of the invention, as will be apparent to those skilled in the art.
Claims (8)
1. A two-dimensional strong fluorescence polyaniline material with metal ion detection performance is characterized in that: the structural formula of the polymer of the two-dimensional strong fluorescence polyaniline material is as follows:
；
wherein n=5-30;
R 1 -R 3 h, CH respectively 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 13 、C 7 H 15 、C 8 H 17 、CH(C 5 H 11 ) 2 、OH、OCH 3 、OC 2 H 5 、OC 3 H 7 、OC 4 H 9 、OC 8 H 17 Any of the substituents having an aromatic structure, F, cl, br, I, phenyl, and the like may be the same or different;
R 4 is H or CN;
ar is any one of B2-B4:
。
2. the method for preparing the two-dimensional strong-fluorescence polyaniline material with metal ion detection performance according to claim 1, wherein the method comprises the following steps: the two-dimensional strong fluorescence polyaniline material is prepared by reacting a nitro-containing compound with any one of terephthalaldehyde, 1, 4-p-dichlorobenzyl derivative, 2, 5-thiophene dicarboxaldehyde and 9-hexyl-9H-carbazole-3, 6-dicarboxaldehyde to prepare corresponding dinitrate monomers, reducing the dinitrate monomers to obtain final monomers, and polymerizing the final monomers in a bulk manner to obtain the two-dimensional strong fluorescence polyaniline material;
the structural formula of the nitro-containing compound is any one of the following formulas A1-A3:
，
wherein R is 1 ，R 2 And R is 3 Is divided into H, CH 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 13 、C 7 H 15 、C 8 H 17 、CH(C 5 H 11 ) 2 、OH、OCH 3 、OC 2 H 5 、OC 3 H 7 、OC 4 H 9 、OC 8 H 17 Any of the substituents having an aromatic structure, F, cl, br, I, phenyl, and the like may be the same or different;
the 1, 4-p-dichlorobenzyl derivative is obtained by refluxing 1, 4-p-dichlorobenzyl and triphenylphosphine in chloroform solution, evaporating the solvent, and washing and purifying the solid with xylene.
3. The method for preparing the two-dimensional strong-fluorescence polyaniline-like material with metal ion detection performance according to claim 2, comprising the steps of:
(1) Uniformly mixing a nitro-containing compound with any one of terephthalaldehyde, 1, 4-p-dichlorobenzyl derivative, 2, 5-thiophene dicarboxaldehyde and 9-hexyl-9H-carbazole-3, 6-dicarboxaldehyde in an organic solvent, and reacting under the condition of a catalyst to prepare a corresponding dinitrate monomer;
(2) Reducing the dinitrate monomer obtained in the step (1) to obtain corresponding amine, and purifying to obtain a final monomer;
(3) And (3) dissolving the final monomer obtained in the step (2) in an organic solvent, adding an aqueous solution of acid, heating the mixture, stirring until the reaction is complete, filtering the reacted mixture, and washing and drying the obtained filter residues to obtain a polymer, wherein the polymer is the two-dimensional strong-fluorescence polyaniline material.
4. The method for preparing the two-dimensional strong-fluorescence polyaniline material with metal ion detection performance according to claim 2, comprising the following steps: the final monomer has the structural formula:
，
wherein R is 1 -R 3 H, CH respectively 3 、C 2 H 5 、C 3 H 7 、C 4 H 9 、C 5 H 11 、C 6 H 13 、C 7 H 15 、C 8 H 17 、CH(C 5 H 11 ) 2 、OH、OCH 3 、OC 2 H 5 、OC 3 H 7 、OC 4 H 9 、OC 8 H 17 Any of the substituents having an aromatic structure, F, cl, br, I, phenyl, and the like may be the same or different;
R 4 is H or CN;
ar is any one of B2-B4:
。
5. the method for preparing the two-dimensional strong-fluorescence polyaniline material with metal ion detection performance according to claim 3, wherein the method comprises the following steps: in the step (1), the molar ratio of the nitro-containing compound to any one of terephthalaldehyde, 1, 4-p-dichlorobenzyl derivative, 2, 5-thiophene dicarboxaldehyde and 9-hexyl-9H-carbazole-3, 6-dicarboxaldehyde is 2:1, the catalyst is sodium hydroxide or piperidine, the molar ratio of the catalyst to the nitrobenzene-containing compound is 100-150:1, and the organic solvent is dichloromethane or methanol.
6. The method for preparing the two-dimensional strong-fluorescence polyaniline material with metal ion detection performance according to claim 3, wherein the method comprises the following steps: in the step (2), the reducing system is tin powder, ethanol solution of hydrochloric acid or ethanol solution of iron powder and ammonium chloride, and when the ethanol solution of tin powder and hydrochloric acid is adopted as the reducing system: the mol ratio of the dinitrate monomer to the tin powder to the hydrochloric acid is 1 (2-5) (4.7-6), and the concentration of the dinitrate monomer in the ethanol is 0.25-0.5 mol.L -1 When the ethanol solution of iron powder and ammonium chloride is used as a reduction system, the molar ratio of the dinitrate monomer to the iron powder and the ammonium chloride is 1 (5-20) (10-20), and the concentration of the dinitrate monomer in the ethanol is 0.25-0.5 mol.L -1 。
7. The method for preparing the two-dimensional strong-fluorescence polyaniline material with metal ion detection performance according to claim 3, wherein the method comprises the following steps: in the step (3), the organic solvent is any one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and tetrahydrofuran.
8. The method for preparing the two-dimensional strong-fluorescence polyaniline material with metal ion detection performance according to claim 3, wherein the method comprises the following steps: in the step (3), the filter residue is washed by hydrazine hydrate solution, 5% sodium hydroxide solution and methanol solution in sequence.
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