CN113816974B - Porphyrin covalent connection sym-triazacyclonium compound and preparation and application thereof - Google Patents
Porphyrin covalent connection sym-triazacyclonium compound and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to a porphyrin covalent connection homotriazacyclonorcinol compound and preparation and application thereof, which take cheap and easily-obtained 2, 3-dichloronitrobenzene as a raw material, obtain a homotriazacyclonorcinol core intermediate through copper catalytic coupling, reduction reaction, amidation reaction and coupling reaction, and then obtain a target product through the covalent connection of porphyrin molecules in the form of carbon-carbon single bonds and carbon-carbon triple bonds through the coupling reaction. The inventive sym-triazacyclon has decisive action for enhancing nonlinear optical response of material due to pi extension conjugated system of its molecular internal plane, and donor (D) -acceptor (A) charge transfer system is formed between porphyrin and sym-triazacyclon through covalent connection of porphyrin, thereby enhancing nonlinear optical absorption of material. The organic material prepared by the invention has good photochemical and thermal stability, high product purity and good solubility, so the organic material prepared by the invention provides reference for expanding the application of the field of organic nonlinear optical materials.
Description
Technical Field
The invention belongs to the technical field of polycyclic aromatic hydrocarbon compounds, and relates to a porphyrin covalent connection homotriazacyclonium compound, and preparation and application thereof.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are simple hydrocarbon molecules composed of a plurality of aromatic rings, and such molecules can also be regarded as basic constituent units of carbon materials such as graphene and carbon nanotubes. Owing to their pi-conjugated systems, such molecules have excellent charge transport and fluorescence properties and are therefore widely used in the fields of organic photovoltaics, field effect transistors, solar cells, fluorescence imaging and nonlinear optics.
Under the condition of not changing the plane structure of the polycyclic aromatic hydrocarbon, changing the lattice structure of the aromatic ring of the polycyclic aromatic hydrocarbon by chemically doping atoms is an effective strategy for regulating the physicochemical property and the photoelectric property of the polycyclic aromatic hydrocarbon, wherein the typical example is the homotriazacyclon, the photoelectric property of the polycyclic aromatic hydrocarbon is regulated and controlled by doping nitrogen atoms, so that the polycyclic aromatic hydrocarbon has electron deficiency, and when a small molecular donor and a porphyrin macrocyclic structure are introduced, the intramolecular electron induced transfer can be effectively promoted, and the nonlinear optical effect of synergistic action is shown.
Moreover, porphyrin is taken as a highly conjugated macrocyclic aromatic system, the excited state absorption is larger than the ground state absorption, and good nonlinear optical properties are shown. Has the advantages of good absorbance, good photochemistry and thermal stability, easy modification, mature synthesis method and easy operation. By chemical modification, it is possible to serve as a good donor unit.
Therefore, the polycyclic aromatic hydrocarbon compound of the triazacyclon and the porphyrin compound are organically combined, and the respective defects can be made up. The nonlinear optical performance of the compound can be effectively and systematically enhanced through effective intramolecular charge transfer between the porphyrin donor and the homotriazacyclono acceptor. However, there are still few reports on the synthesis of such compounds and research in the field of organic nonlinear optics.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
The invention aims to provide a porphyrin covalent connection homotriazacyclonium compound and preparation and application thereof.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a porphyrin covalent connection homotriazacyclonium compound, which has a structure shown in a formula I or a formula II:
wherein R is any one of alkyl of C6-C12.
The second technical scheme of the invention provides a preparation method of porphyrin covalent connection homotriazacyclono compounds, which comprises the following steps:
(1) mixing 2, 3-dichloronitrobenzene, copper powder and N, N-dimethylformamide, carrying out coupling reaction, adding ammonia water after the reaction is finished, filtering and purifying to obtain a compound 1;
(2) dissolving the compound 1 in a mixed solution of ethyl acetate and ethanol, adding palladium carbon, then refluxing and heating, continuously adding hydrazine hydrate, reacting, and performing suction filtration and separation on an obtained reaction product to obtain a compound 2;
(3) dissolving the compound 2 and triethylamine in tetrahydrofuran to form a solution A; dissolving p-iodobenzoyl chloride in tetrahydrofuran to form a solution B; then dropwise adding the solution A into the solution B, stirring for reaction, filtering, cleaning and drying the obtained reaction product to obtain a compound 3;
(4) taking the compound 3, sodium chloride and aluminum chloride to perform solid-phase reaction, cooling after the reaction is finished, adding a sodium hydroxide solution, performing ultrasonic dispersion, filtering, and recrystallizing to obtain a compound 4;
(5) adding the compound 4, potassium acetate and 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride into dimethyl sulfoxide, heating and stirring for reaction, adding pinacol diboron, continuing heating and stirring for reaction, after the reaction is finished, performing reduced pressure spin drying on a solvent, and performing column chromatography separation to obtain a compound 11;
(6) dissolving a compound 4, cuprous iodide and bis (triphenylphosphine) palladium dichloride in triethylamine and tetrahydrofuran, heating and refluxing, adding triisopropyl silyl acetylene, continuously refluxing and heating, drying a solvent in a spinning mode, dissolving a crude product in tetrahydrofuran, then adding a tetrabutylammonium fluoride solution, continuously stirring for reaction, quenching deionized water after the reaction is finished, and washing the crude product after the solvent is removed by using dichloromethane to obtain a compound 12;
(7) adding the compound 10, the compound 11 and potassium phosphate into DMF and toluene, adding palladium tetratriphenylphosphine, heating, stirring, reacting, filtering, washing, drying, and purifying the obtained crude product with a silica gel chromatographic column to obtain a porphyrin covalent connection homotriazacyclonium compound with the structure shown in the formula I;
(8) adding the compound 10, the compound 12 and cuprous iodide into triethylamine and DMF, then adding palladium tetratriphenylphosphine, heating, stirring, refluxing, reacting, filtering, washing and drying after the reaction is finished, and purifying the obtained crude product by using a silica gel chromatographic column to obtain a porphyrin covalent connection homotriazacyclonium compound with the structure shown in the formula II;
the compound 10 is 5-bromo-10, 20-bis- (2, 6-dihexylphenyl) zinc porphyrin.
Furthermore, in the step (1), the molar ratio of the 2, 3-dichloronitrobenzene to the copper powder is 1: 6-9, and preferably 15.63: 93.75.
Further, in the step (1), the temperature of the coupling reaction is 140-170 ℃, preferably 155 ℃, and the time is 10-12h, preferably 12 h.
Further, in the step (2), the adding amount ratio of the compound 1, palladium carbon and hydrazine hydrate is (80-120) mg: (50-70) mg: 0.5mL, preferably 100 mg: 60 mg: 0.5mL, wherein the mass fraction of hydrazine hydrate is 80-90%, preferably 85 wt%. Preferably, the mass fraction of palladium in the palladium on carbon is preferably 10%.
Further, in the step (2), the temperature of reflux heating is 75-80 ℃, and preferably 77 ℃. Meanwhile, after hydrazine hydrate is added, the reaction is continued for 9 to 10 hours, preferably 10 hours.
Further, in the step (3), the mass ratio of the compound 2, triethylamine and p-iodobenzoyl chloride is 100: (200-240): (200-240), preferably 100:222: 231.
Further, in the step (3), the stirring reaction is carried out at normal temperature for 15-25 h, preferably 20 h.
Further, in the step (4), the mass ratio of the compound 3, sodium chloride and aluminum chloride is 65: (180-220): (140-170), preferably 65:205: 156.
Further, in the step (4), the temperature of the solid phase reaction is 200-240 ℃, preferably 220 ℃, and the time is 3-5 hours, preferably 4 hours.
Further, in the step (5), the molar ratio of the compound 4, potassium acetate, 1' -bis-diphenylphosphino ferrocene palladium dichloride and pinacol bisborate is (0.3-0.4): (1.8-2.4): 0.05: (1.8-2.4), preferably 0.35:2.1:0.05: 2.1.
Further, in the step (5), the temperature of the heating and stirring reaction is 70-90 ℃, and preferably 80 ℃.
Further, in the step (6), the addition ratio of the compound 4, cuprous iodide, bis triphenylphosphine palladium dichloride, triisopropyl silyl acetylene and tetrabutylammonium fluoride solution is (45-50) mg: (6-10) mg: (25-30) mg: (57-63) μ L: (180-220) μ L, preferably, 48 mg: 8 mg: 28 mg: 59.33 μ L: 206 μ L.
Further, in the step (6), the concentration of the tetrabutylammonium fluoride solution is 0.8-1.2 mol/L, preferably 1mol/L, and the temperature of heating reflux is 70-90 ℃, preferably 80 ℃.
Further, in the step (7), the mass ratio of the compound 10 to the compound 11 to potassium phosphate to palladium tetratriphenylphosphine is (150 to 175): (22-28): (27-33): 40, preferably, 166:25:30: 40.
Further, in the step (7), the temperature for heating and stirring reaction is 80-100 ℃, preferably 90 ℃, and the time is 10-14 h, preferably 12 h.
Further, in the step (8), the mass ratio of the compound 10 to the compound 12 to the cuprous iodide to the palladium tetratriphenylphosphine is (320-350): (30-40): (5-7): (18 to 20), preferably 335:34:6: 19. Furthermore, the temperature of the heating, stirring and refluxing reaction is 80-100 ℃, preferably 90 ℃, and the time is 10-14 hours, preferably 12 hours.
Further, the compound 10 is prepared by the following method:
(A) dissolving a compound 6 and a compound 7 in dichloromethane, adding trifluoroacetic acid, stirring under the protection of inert gas for reaction, adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone, continuing the reaction, quenching the reaction, and separating to obtain a compound 8;
(B) dissolving the compound 8 in dichloromethane to form a solution A; dissolving N-bromosuccinimide in dichloromethane to form a solution B; then, under the protection of inert gas, dropwise adding the solution B into the solution A, continuously stirring for reaction, quenching the reaction, and separating, drying and purifying the obtained reaction product to obtain a compound 9;
(C) putting the compound 9 and zinc acetate dihydrate into a reaction container, adding dichloromethane and methanol, stirring for reaction, and separating and drying an obtained reaction product to obtain a compound 10;
the chemical structural formula of the compound 6 is as follows:
The chemical structural formula of the compound 7 is as follows:
Further, in the step (A), the ratio of the amounts of the compound 6, the compound 7, trifluoroacetic acid and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone added is (1.5 to 1.8) g: (0.5-0.8) g: (0.28-0.35) mL: (1.4-1.7), preferably, 1.67 g: 0.67 g: 0.31 mL: 1.57 g.
Furthermore, in the step (B), the mass ratio of the compound 8 to the N-bromosuccinimide is (280-340): (60-70), preferably 310: 67.
Furthermore, in the step (C), the ratio of the addition amounts of the compound 9, zinc acetate dihydrate, methylene chloride and methanol is (460 to 480) mg: (1.0-1.2) g: (80-120) mL: 50mL, preferably, 471 mg: 1.1 g: 100mL of: 50 mL.
The third technical scheme of the invention provides application of porphyrin covalently linked homotriazacyclonium compound, and the porphyrin covalently linked homotriazacyclonium compound is used as an organic nonlinear optical material. The porphyrin molecule is introduced to promote effective charge transfer between the porphyrin molecule as a donor (D) and the sym-triazacyclon as an acceptor (A), and the nonlinear optical absorption coefficient of the porphyrin molecule is enhanced.
The porphyrin covalent connection sym-triazacyclon compound (I) (II) prepared by the invention contains a planar pi conjugated structure of triazacyclon and a macrocyclic pi conjugated structure of porphyrin. Meanwhile, a large number of alkyl chains introduced into porphyrin improve the defect of poor solubility of triazacyclon due to planarity, can be dissolved in conventional organic solvents such as dichloromethane, chloroform, tetrahydrofuran, DMF and the like, and improve the photochemical and thermal stability of organic molecules.
The porphyrin covalent connection sym-triazacyclon compound (I) (II) prepared by the invention combines the donor property of porphyrin molecules and the electron deficiency acceptor property of triazacyclon, forms an effective electron donor (D) -electron acceptor (A) system, and promotes the effective charge transfer in molecules.
The quinoline covalently linked homotriazacyclon compound (I) (II) prepared by the invention shows that due to an effective pi conjugated system between porphyrin and triazacyclon, effective intramolecular charge transfer between porphyrin and triazacyclon enhances dipole moment of molecular transition, and improves nonlinear optical response of organic molecules. The nonlinear absorption coefficients of the compounds (I) and (II) under the laser irradiation of 800nm and 34fs are higher than those of the monomer compounds of the compounds, and the excellent synergistic effect is shown. Meanwhile, compared with the compound (I), the compound (II) has a longer conjugated connecting bridge, expands the flow of pi electrons, enhances the charge transfer between donors and acceptors, and shows higher nonlinear absorption coefficient. Therefore, the method has great application prospect in the field of organic nonlinear optics.
Drawings
FIG. 1 is a synthetic route of porphyrin covalently linked triazacyclonane compounds prepared by the present invention.
FIG. 2 shows nuclear magnetic hydrogen spectrum of Compound 4 prepared according to the present invention.
FIG. 3 shows nuclear magnetic hydrogen spectrum of compound 11 prepared by the present invention.
FIG. 4 is a nuclear magnetic hydrogen spectrum of Compound 12 prepared in accordance with the present invention.
FIG. 5 shows nuclear magnetic hydrogen spectra of porphyrin covalently linked triazacyclono compounds (I) prepared by the present invention, wherein R is hexyloxy.
FIG. 6 shows nuclear magnetic hydrogen spectra of porphyrin covalently linked triazacyclono compounds (II) prepared by the present invention, wherein R is hexyloxy.
FIG. 7 shows the nonlinear optical absorption spectra of porphyrin covalent-bonded triazacyclono compounds (I) and (II) prepared by the invention, wherein R is hexyloxy, and the monomer compounds 4 and 10 thereof under the irradiation of laser at 800nm and 34 fs.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the starting materials 2, 6-dihexyloxybenzaldehyde (compound 6) and dipyrromethane (compound 7) were used, the syntheses all being prior art:
reference may be made to the following documents:
1、Splan,K.E.；Hupp,J.T.,Permeable Nonaggregating Porphyrin Thin Films That Display Enhanced Photophysical Properties.Langmuir 2004,20(24),10560-10566.；
2、Singh,K.；Sharma,S.；Sharma,A.,Unique versatility of Amberlyst 15.An acid and solvent-free paradigm towards synthesis of bis(heterocyclyl)methane derivatives.Journal of Molecular Catalysis A:Chemical 2011,347(1),34-37.。
meanwhile, glassware used for synthesis is strictly washed and dried by deionized water. Unless otherwise specified, all of the organic solvents used in the examples of the present invention are commercially available products.
In addition, the rest of the material or processing technology, if not specifically stated, indicates that it is the conventional commercial material or conventional processing technology in this field.
Example 1:
referring to the process scheme shown in fig. 1, this example 1 provides a method for the preparation of porphyrin covalently linked homotriazacyclono compounds:
1. synthesis of 4,8, 12-tris- (p-iodophenyl) -1,5, 9-triazacyclon (compound 4):
synthesis of Compound 1:
weighing 2, 3-dichloronitrobenzene (3.0g,15.63mmol) and copper powder (6.0g, 93.75mmol), adding into a two-necked bottle, adding 30mL of anhydrous DMF, heating to 155 ℃ under the protection of nitrogen, refluxing for 12h, cooling to 120 ℃ after the reaction is finished, adding prepared diluted ammonia water (100mL of ammonia water and 400mL of deionized water), slowly pouring the mixed solution into the diluted ammonia water, stirring vigorously, filtering the generated precipitate to obtain a filter residue, and drying in vacuum for 6 h. Grinding the solid to powder, adding 30mL of acetone, refluxing at 58 deg.C for 30min, and filtering again to obtain filter residueAnd the residue was washed with hot acetone several times to give compound 1 in 42% yield. 1 H NMR(600MHz,CDCl 3 ):δ8.15(dd,J＝8.4,1.1Hz,3H),7.93(dd,J＝7.8,1.1Hz,3H),7.68(t,J＝8.1Hz,3H).
Synthesis of Compound 2:
compound 1(100mg, 0.275mmol) was weighed into a two-necked flask, 10mL of ethyl acetate and 8mL of ethanol were added thereto, and nitrogen gas was purged three times or more. Palladium on carbon (10% w/w,60mg) was added thereto, followed by heating to 77 ℃ under nitrogen. Then a solution of hydrazine hydrate (85% wt,0.5mL) was carefully added dropwise and the reaction was continued for 10 h. After completion of the reaction, filtration was carried out by suction to obtain a filtrate, the solvent was spin-dried under reduced pressure, and the crude product was purified by silica gel column chromatography (eluent: petroleum ether/ethyl acetate: 3/1) to obtain compound 2. The yield was 50%. 1 H NMR(600MHz,DMSO-d 6 )δ8.20(d,J＝8.0Hz,3H),7.15(dd,J1＝J2＝8.0Hz,3H),6.86(d,J＝8.0Hz,3H),5.33(s,6H).
Synthesis of Compound 3:
compound 2(100mg, 0.37mmol) and triethylamine (222mg, 2.196mmol) were dissolved in 2mL of anhydrous tetrahydrofuran to form solution A. P-iodobenzoyl chloride (231mg, 1.65mmol) was dissolved in 1.8mL of anhydrous tetrahydrofuran to form solution B. Then, the solution A is slowly added into the solution B in a dropwise manner, and the reaction is stirred for 20 hours at normal temperature under the protection of nitrogen. After the reaction was completed, direct filtration was performed, and the obtained residue was repeatedly washed with a saturated sodium bicarbonate solution and dichloromethane, and the solid was dried overnight in a vacuum oven to obtain compound 3 in 83% yield. 1 H NMR(600MHz,DMSO-d 6 )δ10.79(s,1H),7.97(d,J＝8.0Hz,2H),7.83(d,J＝8.0Hz,2H),7.50(d,J＝7.6Hz,1H),7.41(t,J＝7.9Hz,1H).
Synthesis of 4,8, 12-tris- (p-iodophenyl) -1,5, 9-triazacyclon (compound 4):
adding compound 3(65mg, 0.07mmol), sodium chloride (205mg, 3.5mmol) and aluminum chloride (156mg, 1.2mmol) into a reaction flask, charging nitrogen gas for more than three times, heating to 220 ℃ under nitrogen protection, and stirring for reaction for 4 h. After the reaction is finished, cooling the reaction bottle to room temperature, adding 15% sodium hydroxide solution, performing ultrasonic treatment to further disperse the sodium hydroxide solution, filtering to obtain filter residue, and measuring the volume of the filter residueThe mixed solution of methanol and dichloromethane with the ratio of 1:10 is recrystallized to obtain the compound 4 with the yield of 80 percent. 1 H NMR(600MHz,CDCl 3 )δ9.22(d,J＝9.5Hz,1H),9.16(d,J＝8.9Hz,1H),8.13(d,J＝7.9Hz,1H),7.94(d,J＝7.7Hz,1H).
2. Synthesis of 5-bromo-10, 20-bis- (2, 6-dihexylphenyl) zinc porphyrin:
synthesis of compound 8:
compound 6(1.67g, 4.6mmol) and compound 7(0.67g, 4.6mmol) were dissolved in 600mL of dichloromethane, added to a 1L two-necked flask, degassed for 30min with a long needle inserted. Trifluoroacetic acid (0.31mL, 4.14mmol) was added with a pipette under the exclusion of light, and the reaction was stirred at room temperature under nitrogen for 4 h. Then, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (1.57g, 6.9mmol) was added thereto, the reaction was further carried out for 1 hour, and then 1mL of triethylamine was added to quench the reaction. Then quickly passing through a flash column by using a mixed solution (volume ratio is 1:1) of dichloromethane and petroleum ether, then carrying out decompression and spin-drying on the solvent, and recrystallizing by using dichloromethane and petroleum ether to obtain the compound 8. The yield was 43%. 1 H NMR(600MHz,CDCl 3 )δ10.14(s,2H),9.26(d,J＝4.4Hz,4H),8.97(d,J＝4.4Hz,4H),7.70(t,J＝8.5Hz,2H),7.02(d,J＝8.6Hz,4H),3.83(t,J＝6.4Hz,8H),0.90(m,8H),0.51(m,16H),0.41(m,8H),0.26–0.21(m,12H),-3.02(s,2H).
Synthesis of compound 9:
compound 8(310mg, 0.36mmol) was dissolved in 150mL of dichloromethane to form solution A. N-bromosuccinimide (67mg, 0.38mmol) was dissolved in 40mL of dichloromethane to form solution B. And then dropwise adding the solution B into the solution A under the protection of nitrogen at 0 ℃, and continuously stirring for reacting for more than 4 hours. After completion of the reaction, the reaction was quenched with 5mL of acetone, and then the organic phase was washed with deionized water and dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation of the organic phase under reduced pressure, and the crude product was purified by a silica gel column chromatography (eluent: petroleum ether/dichloromethane ═ 1/1) to obtain Compound 9. The yield was 61%. . 1 H NMR(600MHz,CDCl 3 )δ10.01(s,1H),9.62(d,J＝4.6Hz,2H),9.17(d,J＝4.3Hz,2H),8.88(t,J＝5.1Hz,4H),7.70(t,J＝8.5Hz,2H),7.00(d,J＝8.6Hz,4H),3.83(t,J＝6.3Hz,8H),0.94–0.90(m,8H),0.53–0.49(m,16H),0.41–0.38(m,8H),0.23(t,J＝6.8Hz,12H),-2.88(s,2H).
Synthesis of 5-bromo-10, 20-bis- (2, 6-dihexylphenyl) zinc porphyrin (Compound 10) Compound 9(471mg, 0.5mmol) and zinc acetate dihydrate (1.1g, 5mmol) were weighed into a two-necked flask, and 100mL of dichloromethane and 50mL of methanol were added thereto. The reaction was stirred at room temperature under an air atmosphere for 3-5h, and the degree of reaction was checked by thin layer chromatography. After the reaction is completed, the organic phase is washed with deionized water and dried with anhydrous sodium sulfate, the solvent is removed by rotary evaporation of the organic phase under reduced pressure, and the crude product is recrystallized from petroleum ether dichloromethane to obtain compound 10. The yield was 95%. 1 H NMR(600MHz,CDCl 3 )δ10.01(s,1H),9.62(d,J＝4.6Hz,2H),9.17(d,J＝4.3Hz,2H),8.88(t,J＝5.1Hz,4H),7.70(t,J＝8.5Hz,2H),7.00(d,J＝8.6Hz,4H),3.83(t,J＝6.3Hz,8H),0.94–0.90(m,8H),0.53–0.49(m,16H),0.41–0.38(m,8H),0.23(t,J＝6.8Hz,12H).
3. Synthesis of porphyrin covalently bound homotriazacyclono compounds (I) (wherein R is hexyloxy):
synthesis of compound 11:
compound 4(318mg, 0.35mmol), potassium acetate (206mg, 2.1mmol) and 1,1' -bisdiphenylphosphinoferrocene palladium dichloride (39mg, 0.05mmol) were weighed into a two-necked flask, charged with nitrogen gas three times or more, and then added with 20mL of anhydrous dimethyl sulfoxide. Then bubbling with nitrogen with a long needle for 10min, and heating to 80 ℃ under the protection of nitrogen. Then, pinacol diboron (533mg, 2.1mmol) was added, and stirring was continued for 10h under reflux. After the reaction was completed, the solution was poured into celite and filtered, the celite was washed with ethyl acetate to obtain an organic phase, the organic phase was washed with a saturated sodium carbonate solution, deionized water and brine in this order, dried over anhydrous sodium sulfate, the solvent was removed by rotary evaporation under reduced pressure, and the crude product was purified by a silica gel column chromatography (eluent: petroleum ether/ethyl acetate: 1/1) to obtain compound 11. The yield was 84%. 1 H NMR(600MHz,CDCl 3 )δ9.19(d,J＝8.8Hz,3H),9.12(d,J＝8.8Hz,3H),8.20(q,J＝7.2Hz,12H),1.46(d,J＝1.8Hz,36H).
Synthesis of porphyrin covalent linkage homotriazacyclono compounds (i): weighing Compound 10(166mg, 0.17mmol), Compound11(25mg, 0.03mmol) and potassium phosphate (30mg, 0.14mmol) were charged into a two-necked flask, nitrogen gas was purged three times or more, and then 15mL of DMF and 7mL of toluene were added thereto and dissolved by stirring. Tetratriphenylphosphine palladium (40mg, 0.03mmol) was added, and the mixture was heated to 90 ℃ under nitrogen atmosphere for reaction for 12 h. After the reaction is finished, pouring the solution into diatomite to remove impurities, washing the solution with dichloromethane to obtain an organic phase, washing the organic phase with saturated sodium carbonate solution, deionized water and brine in sequence, drying the organic phase with anhydrous sodium sulfate, carrying out rotary evaporation under reduced pressure to remove the solvent, and purifying a crude product by using a silica gel chromatographic column (eluent: dichloromethane/petroleum ether/tetrahydrofuran ═ 1/1/0.1) to obtain the porphyrin covalent bonding homotriazacyclonine compound (I). The yield was 61%. 1 H NMR(600MHz,CDCl 3 )δ10.17(s,3H),9.89(d,J＝8.6Hz,3H),9.64(d,J＝8.6Hz,3H),9.35(d,J＝4.2Hz,6H),9.24(d,J＝4.4Hz,6H),9.08(d,J＝4.3Hz,12H),8.69(d,J＝9.2Hz,12H),7.74(t,J＝8.6Hz,6H),7.06(d,J＝8.7Hz,12H),3.89(t,J＝6.3Hz,24H),1.01–0.84(m,30H),0.54–0.45(m,42H),0.40–0.36(m,24H),0.24(t,J＝6.9Hz,36H).
4. Synthesizing porphyrin covalent connection sym-triazacyclono compound (II) wherein R is hexyloxy):
synthesis of compound 12: compound 4(48mg, 0.05mmol), cuprous iodide (8mg, 0.04mmol), and palladium bis (triphenylphosphine) dichloride (28mg, 0.04mmol) were weighed into a two-necked flask, charged with nitrogen gas three times or more, and then added with 10mL of triethylamine and 2mL of tetrahydrofuran. The solid was dissolved by heating to 80 ℃, and then triisopropylsilylacetylene (59.33 μ L, 0.3mmol) was added slowly, and the reaction was stirred under nitrogen for 5 h. After the reaction is completed, the solvent is dried by spinning under reduced pressure to obtain a crude product. The crude product was dissolved in 15mL tetrahydrofuran, and tetrabutylammonium fluoride solution (206. mu.L, 1M in THF) was added at 0 ℃ under nitrogen, and the reaction was stirred for an additional 1h at 0 ℃. After the reaction was completed, the reaction mixture was quenched with deionized water, extracted with ethyl acetate to obtain an organic phase, and the organic phase was washed with deionized water several times and dried over anhydrous sodium sulfate. After removal of the solvent, recrystallization from petroleum ether and ethyl acetate gave compound 12. The yield was 62%.
Synthesis of porphyrin covalent linkage homotriazacyclono compound (ii):compound 10(335mg, 0.33mmol), compound 12(34mg, 0.06mmol) and cuprous iodide (6mg, 0.03mmol) were weighed into a two-necked flask, and charged with nitrogen gas three times or more. Then, 20mL of anhydrous triethylamine and 10mL of anhydrous DMF were added thereto, and after stirring and dissolving, palladium tetratriphenylphosphine (19mg, 0.02mmol) was added thereto. The mixture is heated to 90 ℃ under the protection of nitrogen and stirred for reaction for 12 hours. . After the reaction is finished, pouring the solution into diatomite to remove impurities, washing the solution with dichloromethane to obtain an organic phase, washing the organic phase with saturated sodium carbonate solution, deionized water and brine in sequence, drying the organic phase with anhydrous sodium sulfate, carrying out rotary evaporation under reduced pressure to remove the solvent, and purifying a crude product by using a silica gel chromatographic column (eluent: dichloromethane/petroleum ether/tetrahydrofuran ═ 1/3/0.1) to obtain the porphyrin covalent linkage homotriazacyclonium compound (II). The yield was 43%. 1 H NMR(600MHz,CDCl 3 )δ10.10(s,3H),9.93(d,J＝4.5Hz,6H),9.57(d,J＝8.9Hz,3H),9.41(d,J＝9.0Hz,3H),9.27(d,J＝4.3Hz,6H),9.07(d,J＝4.5Hz,6H),8.98(d,J＝4.3Hz,6H),8.48(q,J＝8.2Hz,12H),7.73(t,J＝8.6Hz,6H),7.05(d,J＝8.6Hz,12H),3.88(t,J＝6.4Hz,24H),0.99–0.94(m,24H),0.89–0.83(m,6.7Hz,36H),0.57–0.43(m,48H),0.41–0.36(m,24H).
Referring to FIGS. 2-6, the nuclear magnetic hydrogen spectra of compound 4, compound 11 and compound 12, which are derivatives of homotriazacyclonium and their derivatives, and the nuclear magnetic hydrogen spectra of porphyrin covalent-linked homotriazacyclonium compounds (I) (II) are highlighted and the chemical structures of these compounds are confirmed.
Example 2:
the application of porphyrin synthesized in embodiment 1 in covalently connecting homotriazacyclonium compounds (I) (II) (wherein R is hexyloxy) in the field of developing organic nonlinear optical materials is as follows:
compound (I) (II) (wherein R is hexyloxy), Compound 4 and Compound 10 (as a reference) were formulated at a concentration of 10 -4 M in chloroform. They were placed in quartz cuvettes of 1mm thickness, respectively, and their nonlinear optical properties were measured under laser irradiation at 800nm,34fs, respectively. The results show that the nonlinear absorption coefficient of porphyrin covalently linked homotriazacyclono compounds (I) (II) (where R is hexyloxy) is significantly better than that of their monomersA non-linear absorption coefficient.
Referring to FIG. 7, the results of the open-cell Z-scan test of compounds 4, 10, (I) and (II) under laser irradiation at 800nm and 34fs are shown. Porphyrin covalent attachment homotriazacyclononane compounds (i) and (ii) both exhibit better nonlinear optical responses than their monomeric compounds 4 and 10, which is also a significant feature of covalent functionalized attachment. This is due to the charge donating properties of the porphyrin molecules and the shortcomings of homotriazacyclonos that make them an efficient donor-acceptor system, facilitating efficient charge transfer, enhancing their nonlinear optical response. In addition, compared with the compound (I), the compound (II) has longer conjugated connecting bridges by connecting carbon-carbon triple bonds with the homotriazacyclon and porphyrin molecules, effectively promotes the pi electron flow of a plane conjugated system of the homotriazacyclon and the charge transfer of a D-A system, and has more excellent nonlinear optical performance compared with the compound (I). According to the Z-scanning test result, the porphyrin covalent connection triazacyclon compound is judged to have better nonlinear optical performance, so that a new thought is provided for designing and preparing organic nonlinear optical materials with more flexibility and better performance.
The raw material reagents and their addition amounts, and the process parameters and conditions of the reaction, etc. used in the above examples may be arbitrarily adjusted within the following ranges (i.e., arbitrarily adjusted to their end values, or any intermediate value) as required:
the molar ratio of the 2, 3-dichloronitrobenzene to the copper powder is 1: 6-9, the temperature of the coupling reaction is 140-170 ℃, and the time is 10-12 hours;
the adding amount ratio of the compound 1, palladium carbon and hydrazine hydrate is (80-120) mg: (50-70) mg: 0.5mL, wherein the mass fraction of hydrazine hydrate is 80-90%;
the mass ratio of the compound 2 to the triethylamine to the p-iodobenzoyl chloride is 100: (200-240): (200 to 240);
the mass ratio of the compound 3 to the sodium chloride to the aluminum chloride is 65: (180-220): (140-170);
the molar ratio of the compound 4, potassium acetate, 1' -bis (diphenylphosphino) ferrocene palladium dichloride and pinacol diboron is (0.3-0.4): (1.8-2.4): 0.05: (1.8-2.4);
the addition ratio of the compound 4, cuprous iodide, bis (triphenylphosphine) palladium dichloride, triisopropyl silyl acetylene and tetrabutylammonium fluoride solution is (45-50) mg: (6-10) mg: (25-30) mg: (57-63) μ L: (180-220) mu L; the concentration of the tetrabutylammonium fluoride solution is 0.8-1.2 mol/L;
the mass ratio of the compound 10 to the compound 11 to the potassium phosphate to the palladium tetratriphenylphosphine is (150-175): (22-28): (27-33): 40;
the mass ratio of the compound 10 to the compound 12 to the cuprous iodide to the palladium tetratriphenylphosphine is (320-350): (30-40): (5-7): (18-20);
the addition amount ratio of the compound 6, the compound 7, trifluoroacetic acid and 2, 3-dichloro-5, 6-dicyan-p-benzoquinone is (1.5-1.8) g: (0.5-0.8) g: (0.28-0.35) mL: (1.4-1.7) g;
the mass ratio of the compound 8 to the N-bromosuccinimide is (280-340): (60-70);
the addition amount ratio of the compound 9, zinc acetate dihydrate, dichloromethane and methanol is (460-480) mg: (1.0-1.2) g: (80-120) mL: 50mL, preferably, 471 mg: 1.1 g: 100mL of: 50 mL.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (13)
1. A porphyrin covalent connection homotriazacyclon compound is characterized by having a structure shown as a formula I or a formula II:
wherein R is any one of C6-C12 alkyl.
2. The method for preparing porphyrin covalent connection homotriazacyclononane compound according to claim 1, characterized by comprising the following steps:
(1) mixing 2, 3-dichloronitrobenzene, copper powder and N, N-dimethylformamide, carrying out coupling reaction, adding ammonia water after the reaction is finished, filtering and purifying to obtain a compound 1;
(2) dissolving the compound 1 in a mixed solution of ethyl acetate and ethanol, adding palladium carbon, then refluxing and heating, continuously adding hydrazine hydrate, reacting, and performing suction filtration and separation on an obtained reaction product to obtain a compound 2;
(3) dissolving the compound 2 and triethylamine in tetrahydrofuran to form a solution A; dissolving p-iodobenzoyl chloride in tetrahydrofuran to form a solution B; then dropwise adding the solution A into the solution B, stirring for reaction, filtering, cleaning and drying the obtained reaction product to obtain a compound 3;
(4) taking the compound 3, sodium chloride and aluminum chloride to perform solid-phase reaction, cooling after the reaction is finished, adding a sodium hydroxide solution, performing ultrasonic dispersion, filtering, and recrystallizing to obtain a compound 4;
(5) adding the compound 4, potassium acetate and 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride into dimethyl sulfoxide, heating and stirring for reaction, adding pinacol diboron, continuing heating and stirring for reaction, after the reaction is finished, performing reduced pressure spin-drying on a solvent, and performing column chromatography separation to obtain a compound 11;
(6) adding the compound 10, the compound 11 and potassium phosphate into DMF and toluene, adding palladium tetratriphenylphosphine, heating, stirring, reacting, filtering, washing, drying, and purifying the obtained crude product with a silica gel chromatographic column to obtain a porphyrin covalent connection homotriazacyclonium compound with the structure shown in the formula I;
the compound 10 is 5-bromo-10, 20-bis- (2, 6-dihexylphenyl) zinc porphyrin;
the chemical structural formula of the compound 1 is as follows:
the chemical structural formula of the compound 2 is as follows:
the chemical structural formula of the compound 3 is as follows:
the chemical structural formula of the compound 4 is as follows:
the chemical structural formula of the compound 11 is as follows:
3. the method for preparing porphyrin covalent connection homotriazacyclononane compound according to claim 1, characterized by comprising the following steps:
(a) mixing 2, 3-dichloronitrobenzene, copper powder and N, N-dimethylformamide, carrying out coupling reaction, adding ammonia water after the reaction is finished, filtering and purifying to obtain a compound 1;
(b) dissolving the compound 1 in a mixed solution of ethyl acetate and ethanol, adding palladium carbon, then refluxing and heating, continuously adding hydrazine hydrate, reacting, and performing suction filtration and separation on an obtained reaction product to obtain a compound 2;
(c) dissolving the compound 2 and triethylamine in tetrahydrofuran to form a solution A; dissolving p-iodobenzoyl chloride in tetrahydrofuran to form a solution B; then dropwise adding the solution A into the solution B, stirring for reaction, filtering, cleaning and drying the obtained reaction product to obtain a compound 3;
(d) taking the compound 3, sodium chloride and aluminum chloride to perform solid-phase reaction, cooling after the reaction is finished, adding a sodium hydroxide solution, performing ultrasonic dispersion, filtering, and recrystallizing to obtain a compound 4;
(e) dissolving a compound 4, cuprous iodide and bis (triphenylphosphine) palladium dichloride in triethylamine and tetrahydrofuran, heating and refluxing, adding triisopropyl silyl acetylene, continuously refluxing and heating, drying a solvent in a spinning mode, dissolving a crude product in tetrahydrofuran, then adding a tetrabutylammonium fluoride solution, continuously stirring for reaction, quenching deionized water after the reaction is finished, and washing the crude product after the solvent is removed by using dichloromethane to obtain a compound 12;
(f) adding the compound 10, the compound 12 and cuprous iodide into triethylamine and DMF, then adding palladium tetratriphenylphosphine, heating, stirring, refluxing, reacting, filtering, washing and drying after the reaction is finished, and purifying the obtained crude product by using a silica gel chromatographic column to obtain a porphyrin covalent connection homotriazacyclonium compound with the structure shown in the formula II;
the compound 10 is 5-bromo-10, 20-bis- (2, 6-dihexylphenyl) zinc porphyrin; the chemical structural formula of the compound 1 is as follows:
the chemical structural formula of the compound 2 is as follows:
the chemical structural formula of the compound 3 is as follows:
the chemical structural formula of the compound 4 is as follows:
the chemical structural formula of the compound 12 is as follows:
4. the preparation method of the porphyrin covalent connection homotriazacyclononane compound as claimed in claim 2 or 3, wherein in the step (1) and the step (a), the molar ratio of 2, 3-dichloronitrobenzene to copper powder is 1: 6-9;
the temperature of the coupling reaction is 140-170 ℃, and the time is 10-12 h.
5. The method for preparing a porphyrin covalent bonding homotriazacyclonium compound according to claim 2 or 3, characterized in that in step (2) and step (b), the ratio of the addition amounts of compound 1, palladium on carbon and hydrazine hydrate is (80-120) mg: (50-70) mg: 0.5mL, wherein the mass fraction of hydrazine hydrate is 80-90%;
the temperature of reflux heating is 75-80 ℃.
6. The method for preparing a porphyrin covalent linking homotriazacyclononane compound according to claim 2 or 3, wherein in step (3) and step (c), the mass ratio of compound 2, triethylamine and p-iodobenzoyl chloride is 100: (200-240): (200 to 240);
the stirring reaction is carried out at normal temperature for 15-25 h.
7. The method for preparing a porphyrin covalent linking homotriazacyclononane compound according to claim 2 or 3, wherein in the step (4) and the step (d), the mass ratio of the compound 3 to the sodium chloride to the aluminum chloride is 65: (180-220): (140-170);
the temperature of the solid phase reaction is 200-240 ℃, and the time is 3-5 h.
8. The method for preparing a porphyrin covalent connection sym-triazacyclonorchis compound according to claim 2, wherein in step (5), the molar ratio of the compound 4, potassium acetate, 1' -bis-diphenylphosphino ferrocene palladium dichloride and pinacol bisborate is (0.3-0.4): (1.8-2.4): 0.05: (1.8-2.4), and the temperature for heating, stirring and reacting is 70-90 ℃.
9. The method for preparing a porphyrin covalent connection homotriazacyclonium compound as claimed in claim 3, wherein in step (e), the addition ratio of the compound 4, cuprous iodide, bis (triphenylphosphine) palladium dichloride, triisopropylsilylacetylene, tetrabutylammonium fluoride solution is (45-50) mg: (6-10) mg: (25-30) mg: (57-63) μ L: (180-220) mu L, wherein the concentration of the tetrabutylammonium fluoride solution is 0.8-1.2 mol/L, and the temperature of heating reflux is 70-90 ℃.
10. The method for preparing a porphyrin covalent-linking sym-triazacyclonium compound according to claim 2, wherein in step (6), the mass ratio of the compound 10 to the compound 11 to potassium phosphate to palladium tetratriphenylphosphine is (150-175): (22-28): (27-33): and 40, heating and stirring for reaction at the temperature of 80-100 ℃ for 10-14 hours.
11. The preparation method of the porphyrin covalent connection sym-triazacyclonium compound as claimed in claim 3, wherein in step (f), the mass ratio of the compound 10 to the compound 12 to the cuprous iodide to the palladium tetratriphenylphosphine is (320-350): (30-40): (5-7): (18-20), the temperature of the heating, stirring and refluxing reaction is 80-100 ℃, and the time is 10-14 h.
12. The method for preparing porphyrin covalent linkage homotriazacyclonos compound as claimed in claim 2, characterized in that said compound 10 is prepared by the following method:
(A) dissolving a compound 6 and a compound 7 in dichloromethane, adding trifluoroacetic acid, stirring under the protection of inert gas for reaction, adding 2, 3-dichloro-5, 6-dicyan p-benzoquinone, continuing the reaction, quenching the reaction, and separating to obtain a compound 8;
(B) dissolving the compound 8 in dichloromethane to form a solution A; dissolving N-bromosuccinimide in dichloromethane to form a solution B; then, under the protection of inert gas, dropwise adding the solution B into the solution A, continuously stirring for reaction, quenching the reaction, and separating, drying and purifying the obtained reaction product to obtain a compound 9;
(C) putting the compound 9 and zinc acetate dihydrate into a reaction container, adding dichloromethane and methanol, stirring for reaction, and separating and drying an obtained reaction product to obtain a compound 10;
the chemical structural formula of the compound 6 is as follows:
the chemical structural formula of the compound 7 is as follows:
the chemical structural formula of the compound 8 is as follows:
the chemical structural formula of the compound 9 is as follows:
13. use of a porphyrin covalently linked homotriazacyclononane compound as claimed in claim 1, wherein the porphyrin is covalently linked to the homotriazacyclononane compound as an organic nonlinear optical material.
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