Chiral rare earth metal polymer and preparation method thereof

Abstract

The invention discloses a preparation method of a chiral rare earth metal polymer, which specifically comprises the following steps: step 1, preparing 1-(4 '-vinyl-[1, 1'-biphenyl]-4-yl) ethane-1-ketone; step 2, preparing 4, 4, 4-trifluoro-1-(4 '-vinyl-[1, 1'-biphenyl]-4-yl) butane-1, 3-diketone according to the product obtained in the step 1; step 3, preparing chiral-bis (diphenyl phosphino oxygen)-1, 1 '-binaphthalene; 4, preparing a rare earth compound according to the product obtained in the step 2 and the product obtained in the step 3; and 5, preparing the chiral rare earth metal polymer according to the product obtained in the step 4 and methyl methacrylate. The invention also discloses the chiral rare earth metal polymer prepared by the preparation method, and the polymer prepared by the invention not only endows a complex with chiral activity, but also avoids fluorescence quenching of coordination of solvent molecules and Eu < 3 + > ions.

Description

Technical Field

[0001] The invention belongs to the technical field of luminescent materials, relates to chiral rare earth metal polymers, and also relates to a preparation method of the chiral rare earth metal polymers. Background Art

[0002] Chiral rare earth metal polymers have the characteristics of high fluorescence efficiency, narrow emission peak, and long fluorescence lifetime. They will be widely used in many fields, including fluorescent probes, medical imaging, optical coding, biological application detectors, acid-base detectors, and encryption fields such as advanced information. Among them, chiral rare earth metal polymers have special advantages in the precise control of fluorescence color, energy transfer, luminous efficiency, and circularly polarized fluorescence, but there are few studies on chiral rare earth polymers. It is of practical significance to develop a simple and efficient preparation strategy for chiral polymer materials. Summary of the invention

[0003] The purpose of the present invention is to provide a method for preparing chiral rare earth metal polymers. The polymers prepared by the method not only make the complexes have chiral activity, but also avoid the solvent molecules and Eu 3+ Fluorescence quenching by ion coordination.

[0004] Another object of the present invention is to provide chiral rare earth metal polymers.

[0005] The first technical solution adopted by the present invention is a method for preparing a chiral rare earth metal polymer, which specifically comprises the following steps:

[0006] Step 1, preparing 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethan-1-one;

[0007] Step 2, preparing 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione according to the product obtained in step 1;

[0008] Step 3, preparing chiral-bis(diphenylphosphinooxy)-1,1'-binaphthyl;

[0009] Step 4, preparing a rare earth complex according to the product obtained in step 2 and the product obtained in step 3;

[0010] Step 5, preparing a chiral rare earth metal polymer according to the product obtained in step 4 and methyl methacrylate.

[0011] The first technical solution of the present invention is also characterized in that:

[0012] The specific process of step 1 is:

[0013] Step 1.1, dissolving 0.3 g to 0.9 g of 4-vinylbenzeneboronic acid and 0.2 g to 0.6 g of 4-bromoacetophenone in 2 g to 6 g of sodium carbonate aqueous solution, adding 30 mg to 90 mg of catalyst and 5 mL to 15 mL of reaction solvent, heating in an oil bath at 80° C. to 100° C. and reacting in a N2 environment;

[0014] Step 1.2, pour the product after the reaction in step 1.1 into a single-necked flask and perform rotary evaporation at 40°C to 45°C to remove the solvent toluene, then add C4H8O2 to the residue after rotary evaporation, extract the aqueous phase with C4H8O2, filter, and perform rotary evaporation on the collected organic matter at 30°C to 35°C to remove C4H8O2 to obtain a solid, dissolve the solid in dichloromethane and purify it with a silica gel column, and place the purified product in a vacuum drying oven to dry to obtain 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethane-1-one, i.e., product T1.

[0015] In step 1.1, the catalyst is tetrakis(triphenylphosphine)palladium(0), and the reaction solvent is toluene.

[0016] The specific process of step 2 is as follows: 0.15g to 0.45g of product T1 is dissolved in 4mL to 12mL of tetrahydrofuran, stirred in an ice-water bath and N2 environment, then 0.3g to 0.9g of NaH is added and stirred for 0.5 to 1h, and then 0.3mL to 0.9mL of ethyl trifluoroacetate is added, and then the mixture is transferred to an oil bath and stirred and heated for 3 to 4 hours. After the reaction is completed and cooled to room temperature, a crude reaction product is obtained, ice water is added to the crude product, and hydrochloric acid is added dropwise to adjust the pH value to 2 to 3, and the mixture is continuously stirred until a precipitate appears, the precipitate is filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven to obtain 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione, i.e., product T2.

[0017] In step 2, the reaction temperature in the oil bath is 75°C to 95°C.

[0018] The specific process of step 3 is as follows: 0.1-0.3 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl is dissolved in 10-30 mL of tetrahydrofuran, cooled to 0°C and then 6-20 mL of H2O2 is added. After the reaction is completed, the mixture is poured into a single-necked flask and subjected to rotary evaporation to remove tetrahydrofuran. 50 mL of CH2Cl2 is added to the residue after rotary evaporation, and the aqueous phase is extracted with CH2Cl2. Anhydrous Na2SO4 is added to the lower layer solution after extraction to absorb water until there are no suspended water droplets. The mixture is filtered, and the collected organic matter is subjected to rotary evaporation to remove CH2Cl2 to obtain a solid. The obtained solid is dried in a vacuum drying oven to obtain chiral-bis(diphenylphosphino)-1,1'-binaphthyl.

[0019] The specific process of step 4 is as follows: 0.4 g to 1.2 g of the product T2 of step 2 is dissolved in 15 mL to 45 mL of methanol, and then 0.02 g to 0.06 g of NaOH is added. After reacting at room temperature for 0.5 to 1 h, 0.2 g to 0.6 g of EuCl is added. 3. 6H2O and 0.06g-0.12g of the product of step 3, chiral-bis(diphenylphosphinoyloxy)-1,1'-binaphthyl, are heated in an oil bath at 50°C-70°C and reacted under a N2 environment for 12h-13h. After the reaction is completed and cooled to room temperature, deionized water is added to quench the precipitate. The precipitate is filtered, washed with deionized water, and then dried in vacuo to obtain the rare earth complex T2-Eu-R / S-BINAPO.

[0020] The specific process of step 5 is as follows: 0.16g to 0.48g of the product T2-Eu-R / S-BINAPO of step 4 is dissolved in 10mL to 30mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 3mL to 9mL of methyl methacrylate is added, and finally 40mg to 120mg of initiator azobisisobutyronitrile is added, and the mixture is heated in an oil bath at 80°C to 100°C and reacted under a N2 environment for 20h to 24h. After the reaction is completed and cooled to room temperature, ethanol is added and precipitated for 3 times, and the obtained solid product is collected by filtration, and dried under vacuum at 45°C to obtain a chiral rare earth metal polymer TMR / S.

[0021] The second technical solution adopted by the present invention is that the chiral rare earth metal polymer is prepared by the above-mentioned preparation method of the chiral rare earth metal polymer.

[0022] The beneficial effect of the present invention is that the present invention prepares β-diketone (T2) through a simple and easy-to-synthesize method. The β-diketone rare earth complex has the most outstanding luminescence efficiency among rare earth complexes due to its excellent luminescence efficiency, energy transfer efficiency, chemical stability and the characteristics of being able to exist in solid or liquid form. The β-diketone (T2) is coordinated with lanthanide metal ions and R / S-BINAPO to form a chiral rare earth complex, and then the complex is polymerized with methyl methacrylate to obtain a chiral rare earth metal polymer, so that it has its excellent fluorescence properties and has good application prospects in the fields of fluorescent probes, host-guest recognition, bioimaging, optical devices, magnetic and superconducting materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the ultraviolet-visible infrared absorption spectrum of the product T1 prepared in Example 1 of the method for preparing the chiral rare earth metal polymer of the present invention;

[0024] Figure 2 This is the ultraviolet-visible infrared absorption spectrum of the product T2 prepared in Example 1 of the method for preparing the chiral rare earth metal polymer of the present invention;

[0025] FIG3( a ) is a fluorescence spectrum of T2-Eu-S-BINAPO, a product prepared in Example 1 of the method for preparing a chiral rare earth metal polymer of the present invention;

[0026] FIG3( b ) is a fluorescence spectrum of the product T2-Eu-R-BINAPO prepared in Example 1 of the method for preparing a chiral rare earth metal polymer of the present invention;

[0027] Figure 4 This is the CD spectrum of the product T2-Eu-R / S-BINAPO prepared in Example 1 of the method for preparing the chiral rare earth metal polymer of the present invention;

[0028] Figure 5 This is the ultraviolet-visible infrared absorption spectrum of the product (TMR / S) prepared in Example 1 of the method for preparing chiral rare earth metal polymers of the present invention. DETAILED DESCRIPTION

[0029] The present invention is described in detail below with reference to the accompanying drawings and specific embodiments.

[0030] The method for preparing the chiral rare earth metal polymer of the present invention specifically comprises the following steps:

[0031] Step 1, preparing 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethane-1-one, i.e., product T1, by the following process:

[0032] 4-Vinylbenzeneboronic acid (0.3g-0.9g) and 4-bromoacetophenone (0.2g-0.6g) were dissolved in an aqueous solution of sodium carbonate (2g-6g), and a catalyst tetrakis(triphenylphosphine)palladium(0) (30mg-90mg) and a reaction solvent of toluene (5mL-15mL) were added. N2 was charged and discharged three times to allow the reaction to proceed in a N2 environment. The mixture was heated in an oil bath (80°C-100°C) for 12 hours. The product after the reaction was poured into a single-necked flask and subjected to rotary evaporation (40°C-45°C) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2 and filtered. The collected organic matter was rotary evaporated (30°C-35°C) to remove C4H8O2 to obtain a solid. The solid was dissolved in dichloromethane and purified by a silica gel column. The purified product was placed in a vacuum drying oven and dried (45°C) to obtain product T1.

[0033] Step 2, according to the product T1 obtained in step 1, prepare 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione, i.e. β-diketone T2:

[0034] The product T1 (0.15 g to 0.45 g) of step 1 was dissolved in tetrahydrofuran THF (4 mL to 12 mL), stirred in an ice-water bath and N2 environment, and then NaH (0.3 g to 0.9 g) was added and stirred for 0.5 to 1 h, and then ethyl trifluoroacetate (0.3 mL to 0.9 mL) was added, and then transferred to an oil bath (75° C. to 95° C.) and stirred and heated for 3 to 4 hours. After the reaction was completed and cooled to room temperature, a crude reaction product was obtained. Ice water was added to the crude product, and hydrochloric acid was added dropwise to adjust the pH value to 2 to 3. The product was stirred continuously until a precipitate appeared, and the precipitate was filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven (45° C.) to obtain the final product T2.

[0035] Step 3, preparation of chiral (R / S)-bis(diphenylphosphinooxy)-1,1'-binaphthyl, i.e., R / S-BINAPO:

[0036] Dissolve 0.1-0.3g R / S-BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthyl) in 10-30mL THF (tetrahydrofuran), cool to 0℃, add 6-20mL H2O2 (30%), react for 30min, and stir at room temperature for 4h. Pour into a single-necked flask and evaporate (30-35℃) to remove THF. Add 50mL CH2Cl2 to the residue, and extract the aqueous phase with 30mL CH2Cl2 (add CH2Cl2 to the upper water layer), extract 3 times, and add anhydrous Na2SO4 to the lower solution to absorb water until there are no suspended water droplets, and filter. Evaporate the collected organic matter (35℃) to remove CH2Cl2 to obtain a solid. Dry in a vacuum oven at 45℃ for 24h. Obtain the product R / S-BINAPO.

[0037] Step 4, preparing T2-Eu-R / S-BINAPO according to the products obtained in steps 2 and 3:

[0038] The product T2 (0.4 g to 1.2 g) of step 2 was dissolved in methanol (15 mL to 45 mL), and NaOH (0.02 g to 0.06 g) was added to make it in an alkaline environment. After reacting at room temperature for 0.5 to 1 h, EuCl was added. 3. 6H2O (0.2g-0.6g) and the product R / S-BINAPO (0.06g-0.12g) of step 3 are heated in an oil bath (50℃-70℃) and reacted under N2 environment for 12h-13h. After the reaction is completed and cooled to room temperature, deionized water is added to quench the precipitate. The precipitate is filtered, washed with deionized water, and then vacuum dried (45℃) to obtain the product T2-Eu-R / S-BINAPO.

[0039] Step 5, preparing a chiral rare earth metal polymer (TMR / S) according to the product obtained in step 4 and methyl methacrylate.

[0040] 0.16 g to 0.48 g of the product T2-Eu-R / S-BINAPO in step 4 was dissolved in 10 mL to 30 mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 3 mL to 9 mL of methyl methacrylate was added, and finally 40 mg to 120 mg of initiator azobisisobutyronitrile (AIBN) was added, and the mixture was heated in an oil bath at 80°C to 100°C and reacted under a N2 environment for 20 h to 24 h. After the reaction was completed and cooled to room temperature, ethanol was added and precipitated three times, and the obtained solid product was collected by filtration and dried under vacuum at 45°C to obtain a chiral rare earth metal polymer (TMR / S).

[0041] Example 1

[0042] 4-Vinylbenzeneboronic acid (0.3 g) and 4-bromoacetophenone (0.2 g) were dissolved in an aqueous solution of sodium carbonate (2 g). A catalyst tetrakis(triphenylphosphine)palladium(0) (30 mg) and a reaction solvent of toluene (5 mL) were added. N2 was charged and discharged three times to allow the reaction to proceed in a N2 environment. The mixture was heated in an oil bath (80° C.) for 12 hours. The product after the reaction was poured into a single-necked flask and subjected to rotary evaporation (45° C.) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2 and filtered. The collected organic matter was rotary evaporated (35° C.) to remove C4H8O2 to obtain a solid. The solid was dissolved in dichloromethane and purified by a silica gel column. The purified product was placed in a vacuum drying oven and dried (45° C.) to obtain product T1.

[0043] The product T1 (0.15 g) of step 1 was dissolved in THF (4 mL), stirred in an ice-water bath and N2 environment, and then NaH (0.3 g) was added and stirred for 0.5 h, and then ethyl trifluoroacetate (0.3 mL) was added, and then transferred to an oil bath and stirred and heated for 3 hours. After the reaction was completed and cooled to room temperature, a crude reaction product was obtained. Ice water was added to the crude product, and hydrochloric acid was added dropwise to adjust the pH value to 2. The mixture was stirred continuously until a precipitate appeared. The precipitate was filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven (45° C.) to obtain the final product T2.

[0044] Dissolve 0.1g R / S-BINAP in 10mL THF, cool to 0℃, add 6mL H2O2 (30%) for 30min, and stir at room temperature for 4h. Pour into a single-necked flask and evaporate (30℃) to remove THF. Add 50mL CH2Cl2 to the residue, and extract the aqueous phase with 3x30mL CH2Cl2 (add CH2Cl2 to the upper water layer), add anhydrous Na2SO4 to the lower solution to absorb water until there are no suspended water droplets, and filter. Evaporate the collected organic matter (35℃) to remove CH2Cl2 to obtain a solid. Dry in a vacuum oven at 45℃ for 24h. Obtain R / S-BINAPO.

[0045] The product T2 (0.4 g) of step 2 was dissolved in methanol (15 mL), and NaOH (0.02 g) was added to make it in an alkaline environment. After reacting at room temperature for 0.5 h, EuCl3.6H2O (0.2 g) and the product R / S-BINAPO (0.06 g) of step 3 were added, and heated in an oil bath (50°C) and reacted under a N2 environment for 12 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate, and the precipitate was filtered, washed with deionized water, and then vacuum dried (45°C) to obtain the product T2-Eu-R / S-BINAPO.

[0046] 0.16 g of step 4 product T2-Eu-R / S-BINAPO was dissolved in 10 mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 3 mL of methyl methacrylate was added, and finally 40 mg of initiator azobisisobutyronitrile (AIBN) was added. The mixture was heated in an oil bath at 80° C. and reacted for 20 h under a N2 environment. After the reaction was completed and cooled to room temperature, ethanol was added and precipitated three times. The resulting solid product was collected by filtration and dried under vacuum at 45° C. to obtain a chiral rare earth metal polymer (TMR / S).

[0047] Figure 1 The UV-visible infrared absorption spectrum of T1 in Example 1, Figure 2 FIG3 (a) and FIG3 (b) are the fluorescence spectra of T2-Eu-S-BINAPO and T2-Eu-S-BINAPO in DMF solution of the present invention, respectively. Under 396 nm light excitation, the emission energy level is 5 D0 to ground state 7 F J (J=0,1,2,3,4) transition to form Eu 3+ Ion characteristic red light. 578nm is 5 D0→ 7 F0, 588-595nm 5D0→ 7 F1, 613nm 5 D0→ 7 F2, 651nm 5 D0→ 7 F3, 703nm 5 D0→ 7 The transition of F4, the strongest emission position is at λ em =613nm, the intensity is obviously higher than the other four peaks, this is due to 5 D0→ 7 F2 transition has the highest sensitivity. Figure 4 This is the CD spectrum of Example 1 of the method for preparing rare earth complexes of the present invention. After the introduction of the chiral auxiliary ligand R-BINAPO, T2-Eu-R-BINAPO shows "+", "-", "-" signals at 255nm, 300nm and 340nm wavelengths, respectively. The CD signal peaks of T2-Eu-S-BINAPO prepared after the introduction of the chiral auxiliary ligand S-BINAPO are mirror images of T2-Eu-R-BINAPO, indicating that T2-Eu-S-BINAPO and T2-Eu-R-BINAPO are enantiomers of each other. This indicates that the rare earth complex causes chirality transfer by coordinating with (R / S)-BINAPO, thereby regulating the optical properties of T2-Eu-R / S-BINAPO. Figure 5 It is the ultraviolet-visible infrared absorption spectrum of TMR / S in the DMF solution of the present invention, which indirectly proves that the rare earth complex and methyl methacrylate are polymerized.

[0048] Example 2

[0049] 4-Vinylphenylboronic acid (0.6 g) and 4-bromoacetophenone (0.4 g) were dissolved in an aqueous solution of sodium carbonate (4 g), and a catalyst tetrakis(triphenylphosphine)palladium(0) (60 mg) and a reaction solvent of toluene (10 mL) were added. N2 was charged and discharged three times to allow the reaction to proceed in a N2 environment. The mixture was heated in an oil bath (90° C.) for about 12 hours. The product after the reaction was poured into a single-necked flask and subjected to rotary evaporation (42° C.) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2 and filtered. The collected organic matter was rotary evaporated (32° C.) to remove C4H8O2 to obtain a solid. The solid was dissolved in dichloromethane and purified by a silica gel column. The purified product was placed in a vacuum drying oven and dried (45° C.) to obtain product T1.

[0050] The product T1 (0.3 g) of step 1 was dissolved in THF (8 mL), stirred in an ice-water bath and N2 environment, and then NaH (0.6 g) was added and stirred for 0.8 h, and then ethyl trifluoroacetate (0.6 mL) was added, and then transferred to an oil bath and stirred and heated for 3 hours. After the reaction was completed and cooled to room temperature, a crude reaction product was obtained. Ice water was added to the crude product, and hydrochloric acid was added dropwise to adjust the pH value to 2. The mixture was stirred continuously until a precipitate appeared. The precipitate was filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven (45° C.) to obtain the final product T2.

[0051] Dissolve 0.2g R / S-BINAP in 20mL THF, cool to 0℃, add 15mL H2O2 (30%) and react for 30min, stir at room temperature for 4h. Pour into a single-necked flask and evaporate (30℃) to remove THF. Add 50mL CH2Cl2 to the residue, and extract the aqueous phase with 3x30mL CH2Cl2 (add CH2Cl2 to the upper water layer), add anhydrous Na2SO4 to the lower solution to absorb water until there are no suspended water droplets, and filter. Evaporate the collected organic matter (35℃) to remove CH2Cl2 to obtain a solid. Dry in a vacuum oven at 45℃ for 24h. Obtain R / S-BINAPO.

[0052] The product T2 (0.8 g) of step 2 was dissolved in methanol (30 mL), and NaOH (0.04 g) was added to make it in an alkaline environment. After reacting at room temperature for 0.8 h, EuCl3.6H2O (0.4 g) and the product R / S-BINAPO (0.09 g) of step 3 were added, and heated in an oil bath (60°C) and reacted under a N2 environment for 12.5 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate, and the precipitate was filtered, washed with deionized water, and then vacuum dried (45°C) to obtain the product T2-Eu-R / S-BINAPO.

[0053] 0.32 g of step 4 product T2-Eu-R / S-BINAPO was dissolved in 20 mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 6 mL of methyl methacrylate was added, and finally 80 mg of initiator azobisisobutyronitrile (AIBN) was added. The mixture was heated in an oil bath at 90° C. and reacted for 22 h under a N2 environment. After the reaction was completed and cooled to room temperature, ethanol was added and precipitated three times. The resulting solid product was collected by filtration and dried under vacuum at 45° C. to obtain a chiral rare earth metal polymer (TMR / S).

[0054] Example 3

[0055] 4-Vinylbenzeneboronic acid (0.9 g) and 4-bromoacetophenone (0.6 g) were dissolved in an aqueous solution of sodium carbonate (6 g). A catalyst tetrakis(triphenylphosphine)palladium(0) (90 mg) and a reaction solvent of toluene (15 mL) were added. N2 was charged and discharged three times to allow the reaction to proceed in a N2 environment. The mixture was heated in an oil bath (100° C.) for about 12 hours. The product after the reaction was poured into a single-necked flask and subjected to rotary evaporation (40° C.) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2 and filtered. The collected organic matter was rotary evaporated (30° C.) to remove C4H8O2 to obtain a solid. The solid was dissolved in dichloromethane and purified by a silica gel column. The purified product was placed in a vacuum drying oven and dried (45° C.) to obtain product T1.

[0056] The product T1 (0.45 g) of step 1 was dissolved in THF (12 mL), and stirred in an ice-water bath and N2 environment. NaH (0.9 g) was then added and stirred for 1 h. Ethyl trifluoroacetate (0.9 mL) was added, and the mixture was transferred to an oil bath and stirred and heated for 4 hours. After the reaction was completed and cooled to room temperature, a crude product was obtained. Ice water was added to the crude product, and hydrochloric acid was added dropwise to adjust the pH value to 3. The mixture was stirred continuously until a precipitate appeared. The precipitate was filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven (45° C.) to obtain the final product T2.

[0057] Dissolve 0.3g R / S-BINAP in 30mL THF, cool to 0℃, add 20mL H2O2 (30%) and react for 30min, stir at room temperature for 4h. Pour into a single-necked flask and evaporate (35℃) to remove THF. Add 50mL CH2Cl2 to the residue, and extract the aqueous phase with 3x30mL CH2Cl2 (add CH2Cl2 to the upper water layer), add anhydrous Na2SO4 to the lower solution to absorb water until there are no suspended water droplets, and filter. Evaporate the collected organic matter (35℃) to remove CH2Cl2 to obtain a solid. Dry in a vacuum oven at 45℃ for 24h. Obtain R / S-BINAPO.

[0058] Finally, the product T2 (1.2 g) of step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to make it in an alkaline environment. After reacting at room temperature for 1 h, EuCl3.6H2O (0.6 g) and the product R / S-BINAPO (0.12 g) of step 3 were added, and heated in an oil bath (70°C) and reacted under a N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate, and the precipitate was filtered, washed with deionized water, and then vacuum dried (45°C) to obtain the product T2-Eu-R / S-BINAPO.

[0059] 0.48 g of step 4 product T2-Eu-R / S-BINAPO was dissolved in 30 mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 9 mL of methyl methacrylate was added, and finally 120 mg of initiator azobisisobutyronitrile (AIBN) was added, heated in an oil bath at 100° C. and reacted for 24 h under a N2 environment. After the reaction was completed and cooled to room temperature, ethanol was added and precipitated three times, and the resulting solid product was collected by filtration and dried under vacuum at 45° C. to obtain a chiral rare earth metal polymer (TMR / S).

[0060] Example 4

[0061] 4-Vinylbenzeneboronic acid (0.4 g) and 4-bromoacetophenone (0.4 g) were dissolved in an aqueous solution of sodium carbonate (4 g), and a catalyst tetrakis(triphenylphosphine)palladium(0) (80 mg) and a reaction solvent of toluene (8 mL) were added. N2 was charged and discharged three times to allow the reaction to proceed in a N2 environment. The mixture was heated in an oil bath (100° C.) for about 12 hours. The product after the reaction was poured into a single-necked flask and subjected to rotary evaporation (40° C.) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2 and filtered. The collected organic matter was rotary evaporated (30° C.) to remove C4H8O2 to obtain a solid. The solid was dissolved in dichloromethane and purified by a silica gel column. The purified product was placed in a vacuum drying oven and dried (45° C.) to obtain product T1.

[0062] The product T1 (0.45 g) of step 1 was dissolved in THF (12 mL), and stirred in an ice-water bath and N2 environment. NaH (0.9 g) was then added and stirred for 1 h. Ethyl trifluoroacetate (0.9 mL) was added, and the mixture was transferred to an oil bath and stirred and heated for 4 hours. After the reaction was completed and cooled to room temperature, a crude product was obtained. Ice water was added to the crude product, and hydrochloric acid was added dropwise to adjust the pH value to 3. The mixture was stirred continuously until a precipitate appeared. The precipitate was filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven (45° C.) to obtain the final product T2.

[0063] Dissolve 0.3g R / S-BINAP in 30mL THF, cool to 0℃, add 20mL H2O2 (30%) and react for 30min, stir at room temperature for 4h. Pour into a single-necked flask and evaporate (35℃) to remove THF. Add 50mL CH2Cl2 to the residue, and extract the aqueous phase with 3x30mL CH2Cl2 (add CH2Cl2 to the upper water layer), add anhydrous Na2SO4 to the lower solution to absorb water until there are no suspended water droplets, and filter. Evaporate the collected organic matter (35℃) to remove CH2Cl2 to obtain a solid. Dry in a vacuum oven at 45℃ for 24h. Obtain R / S-BINAPO.

[0064] Finally, the product T2 (1.2 g) of step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to make it in an alkaline environment. After reacting at room temperature for 1 h, EuCl3.6H2O (0.6 g) and the product R / S-BINAPO (0.12 g) of step 3 were added, and heated in an oil bath (70°C) and reacted under a N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate, and the precipitate was filtered, washed with deionized water, and then vacuum dried (45°C) to obtain the product T2-Eu-R / S-BINAPO.

[0065] 0.48 g of step 4 product T2-Eu-R / S-BINAPO was dissolved in 30 mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 9 mL of methyl methacrylate was added, and finally 120 mg of initiator azobisisobutyronitrile (AIBN) was added, heated in an oil bath at 100° C. and reacted for 24 h under a N2 environment. After the reaction was completed and cooled to room temperature, ethanol was added and precipitated three times, and the resulting solid product was collected by filtration and dried under vacuum at 45° C. to obtain a chiral rare earth metal polymer (TMR / S).

[0066] Example 5

[0067] 4-Vinylbenzeneboronic acid (0.4 g) and 4-bromoacetophenone (0.4 g) were dissolved in an aqueous solution of sodium carbonate (4 g), and a catalyst tetrakis(triphenylphosphine)palladium(0) (80 mg) and a reaction solvent of toluene (8 mL) were added. N2 was charged and discharged three times to allow the reaction to proceed in a N2 environment. The mixture was heated in an oil bath (100° C.) for about 12 hours. The product after the reaction was poured into a single-necked flask and subjected to rotary evaporation (40° C.) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2 and filtered. The collected organic matter was rotary evaporated (32° C.) to remove C4H8O2 to obtain a solid. The solid was dissolved in dichloromethane and purified by a silica gel column. The purified product was placed in a vacuum drying oven and dried (45° C.) to obtain product T1.

[0068] The product T1 (0.23 g) of step 1 was dissolved in THF (8 mL), stirred in an ice-water bath and N2 environment, then NaH (0.6 g) was added and stirred for 1 h, and then ethyl trifluoroacetate (0.4 mL) was added, and then transferred to an oil bath and stirred and heated for 4 hours. After the reaction was completed and cooled to room temperature, a crude reaction product was obtained. Ice water was added to the crude product, and hydrochloric acid was added dropwise to adjust the pH value to 3. The mixture was stirred continuously until a precipitate appeared. The precipitate was filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven (45° C.) to obtain the final product T2.

[0069] Dissolve 0.3g R / S-BINAP in 30mL THF, cool to 0℃, add 20mL H2O2 (30%) and react for 30min, stir at room temperature for 4h. Pour into a single-necked flask and evaporate (35℃) to remove THF. Add 50mL CH2Cl2 to the residue, and extract the aqueous phase with 3x30mL CH2Cl2 (add CH2Cl2 to the upper water layer), add anhydrous Na2SO4 to the lower solution to absorb water until there are no suspended water droplets, and filter. Evaporate the collected organic matter (35℃) to remove CH2Cl2 to obtain a solid. Dry in a vacuum oven at 45℃ for 24h. Obtain R / S-BINAPO.

[0070] Finally, the product T2 (1.2 g) of step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to make it in an alkaline environment. After reacting at room temperature for 1 h, EuCl3.6H2O (0.6 g) and the product R / S-BINAPO (0.12 g) of step 3 were added, and heated in an oil bath (70°C) and reacted under a N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate, and the precipitate was filtered, washed with deionized water, and then vacuum dried (45°C) to obtain the product T2-Eu-R / S-BINAPO.

[0071] 0.48 g of step 4 product T2-Eu-R / S-BINAPO was dissolved in 30 mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 9 mL of methyl methacrylate was added, and finally 120 mg of initiator azobisisobutyronitrile (AIBN) was added, heated in an oil bath at 100° C. and reacted for 24 h under a N2 environment. After the reaction was completed and cooled to room temperature, ethanol was added and precipitated three times, and the resulting solid product was collected by filtration and dried under vacuum at 45° C. to obtain a chiral rare earth metal polymer (TMR / S).

[0072] Example 6

[0073] 4-Vinylbenzeneboronic acid (0.4 g) and 4-bromoacetophenone (0.4 g) were dissolved in an aqueous solution of sodium carbonate (4 g), and a catalyst tetrakis(triphenylphosphine)palladium(0) (80 mg) and a reaction solvent of toluene (8 mL) were added. N2 was charged and discharged three times to allow the reaction to proceed in a N2 environment. The mixture was heated in an oil bath (100° C.) for about 12 hours. The product after the reaction was poured into a single-necked flask and subjected to rotary evaporation (40° C.) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2 and filtered. The collected organic matter was rotary evaporated (30° C.) to remove C4H8O2 to obtain a solid. The solid was dissolved in dichloromethane and purified by a silica gel column. The purified product was placed in a vacuum drying oven and dried (45° C.) to obtain product T1.

[0074] The product T1 (0.45 g) of step 1 was dissolved in THF (12 mL), and stirred in an ice-water bath and N2 environment. NaH (0.9 g) was then added and stirred for 1 h. Ethyl trifluoroacetate (0.9 mL) was added, and the mixture was transferred to an oil bath and stirred and heated for 4 hours. After the reaction was completed and cooled to room temperature, a crude product was obtained. Ice water was added to the crude product, and hydrochloric acid was added dropwise to adjust the pH value to 3. The mixture was stirred continuously until a precipitate appeared. The precipitate was filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven (45° C.) to obtain the final product T2.

[0075] Dissolve 0.2g R / S-BINAP in 15mL THF, cool to 0℃, add 30mL H2O2 (30%) and react for 30min, stir at room temperature for 4h. Pour into a single-necked flask and evaporate (35℃) to remove THF. Add 50mL CH2Cl2 to the residue, and extract the aqueous phase with 3x30mL CH2Cl2 (add CH2Cl2 to the upper water layer), add anhydrous Na2SO4 to the lower solution to absorb water until there are no suspended water droplets, and filter. Evaporate the collected organic matter (35℃) to remove CH2Cl2 to obtain a solid. Dry in a vacuum oven at 45℃ for 24h. Obtain R / S-BINAPO.

[0076] Finally, the product T2 (0.9 g) of step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to make it in an alkaline environment. After reacting at room temperature for 1 h, EuCl3.6H2O (0.6 g) and the product R / S-BINAPO (0.12 g) of step 3 were added, and heated in an oil bath (70°C) and reacted under a N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate, and the precipitate was filtered, washed with deionized water, and then vacuum dried (45°C) to obtain the product T2-Eu-R / S-BINAPO.

[0077] 0.48 g of step 4 product T2-Eu-R / S-BINAPO was dissolved in 30 mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 9 mL of methyl methacrylate was added, and finally 120 mg of initiator azobisisobutyronitrile (AIBN) was added, heated in an oil bath at 100° C. and reacted for 24 h under a N2 environment. After the reaction was completed and cooled to room temperature, ethanol was added and precipitated three times, and the resulting solid product was collected by filtration and dried under vacuum at 45° C. to obtain a chiral rare earth metal polymer (TMR / S).

[0078] The present invention constructs a chiral rare earth complex through a chiral transfer strategy, that is, a novel β-diketone sensitized rare earth ion is prepared, and then R / S-BINAPO is introduced into the complex as an auxiliary ligand through coordination, which not only makes the complex chiral active, but also avoids the solvent molecules (containing NH, OH, CH groups) and Eu 3+ Fluorescence quenching of ion coordination. The complex not only has excellent rare earth luminescence properties, but also has unique circular diffraction characteristics. The synthesized complex is then polymerized with methyl methacrylate to form a polymer, and a chiral polymer material is prepared simply and efficiently, which has good chiral optical properties and luminescence properties, broadening its application potential in many fields, such as fluorescent probes, medical imaging, optical coding, and advanced information encryption.

Claims

1. A method for preparing a chiral rare earth metal polymer, characterized in that: The specific steps include: Step 1, preparing 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethan-1-one; Step 2, preparing 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione according to the product obtained in step 1; Step 3, preparing chiral-bis(diphenylphosphinooxy)-1,1'-binaphthyl; Step 4, preparing a rare earth complex according to the product obtained in step 2 and the product obtained in step 3.

2. The method for preparing a chiral rare earth metal polymer according to claim 1, characterized in that: The specific process of step 1 is as follows: Step 1.1, dissolving 0.3 g to 0.9 g of 4-vinylbenzeneboronic acid and 0.2 g to 0.6 g of 4-bromoacetophenone in 2 g to 6 g of sodium carbonate aqueous solution, adding 30 mg to 90 mg of catalyst and 5 mL to 15 mL of reaction solvent, heating in an oil bath at 80° C. to 100° C. and reacting in a N2 environment; Step 1.2, pour the product after the reaction in step 1.1 into a single-necked flask and perform rotary evaporation at 40°C to 45°C to remove the solvent toluene, then add C4H8O2 to the residue after rotary evaporation, extract the aqueous phase with C4H8O2, filter, and perform rotary evaporation on the collected organic matter at 30°C to 35°C to remove C4H8O2 to obtain a solid, dissolve the solid in dichloromethane and purify it with a silica gel column, and place the purified product in a vacuum drying oven to dry to obtain 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethane-1-one, i.e., product T1.

3. The method for preparing a chiral rare earth metal polymer according to claim 2, characterized in that: In the step 1.1, the catalyst is tetrakis(triphenylphosphine)palladium(0), and the reaction solvent is toluene.

4. The method for preparing a chiral rare earth metal polymer according to claim 2, characterized in that: The specific process of step 2 is as follows: 0.15g to 0.45g of the product T1 is dissolved in 4mL to 12mL of tetrahydrofuran, and the mixture is stirred in an ice-water bath and N2 environment, and then 0.3g to 0.9g of NaH is added and stirred for 0.5 to 1h, and then 0.3mL to 0.9mL of ethyl trifluoroacetate is added, and the mixture is transferred to an oil bath and stirred and heated for 3 to 4 hours. After the reaction is completed and cooled to room temperature, a crude reaction product is obtained, ice water is added to the crude product, and hydrochloric acid is added dropwise to adjust the pH value to 2 to 3, and the mixture is stirred continuously until a precipitate appears, and the precipitate is filtered, washed with deionized water 3 times, and then dried in a vacuum drying oven to obtain 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione, i.e., product T2.

5. The method for preparing a chiral rare earth metal polymer according to claim 4, characterized in that: In the step 2, the reaction temperature in the oil bath is 75°C to 95°C.

6. The method for preparing a chiral rare earth metal polymer according to claim 4, characterized in that: The specific process of step 3 is as follows: 0.1-0.3 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl is dissolved in 10-30 mL of tetrahydrofuran, cooled to 0°C, 6-20 mL of H2O2 is added, the reaction is carried out for 30 min, stirred at room temperature for 4 h, poured into a single-necked flask and subjected to rotary evaporation to remove tetrahydrofuran, 50 mL of CH2Cl2 is added to the residue after rotary evaporation, and the aqueous phase is extracted with CH2Cl2, anhydrous Na2SO4 is added to the lower layer solution after extraction to absorb water until there are no suspended water droplets, filtered, and the collected organic matter is subjected to rotary evaporation to remove CH2Cl2 to obtain a solid, and the obtained solid is dried in a vacuum drying oven to obtain chiral-bis(diphenylphosphinooxy)-1,1'-binaphthyl.

7. The method for preparing a chiral rare earth metal polymer according to claim 6, characterized in that: The specific process of step 4 is as follows: 0.4 g to 1.2 g of the product T2 of step 2 is dissolved in 15 mL to 45 mL of methanol, 0.02 g to 0.06 g of NaOH is added, and after reacting at room temperature for 0.5 to 1 h, 0.2 g to 0.6 g of EuCl is added.

3. 6H2O and 0.06g-0.12g of the product of step 3, chiral-bis(diphenylphosphinoyloxy)-1,1'-binaphthyl, are heated in an oil bath at 50°C-70°C and reacted under a N2 environment for 12h-13h. After the reaction is completed and cooled to room temperature, deionized water is added to quench the precipitate. The precipitate is filtered, washed with deionized water, and then dried in vacuo to obtain the rare earth complex T2-Eu-R / S-BINAPO.

8. The method for preparing a chiral rare earth metal polymer according to claim 7, characterized in that: The specific process of step 5 is as follows: 0.16g to 0.48g of the product T2-Eu-R / S-BINAPO in step 4 is dissolved in 10mL to 30mL of anhydrous and oxygen-free 1,2-dichlorobenzene, 3mL to 9mL of methyl methacrylate is added, and finally 40mg to 120mg of initiator azobisisobutyronitrile is added, and the mixture is heated in an oil bath at 80°C to 100°C and reacted under a N2 environment for 20h to 24h. After the reaction is completed and cooled to room temperature, ethanol is added and precipitated three times, and the obtained solid product is collected by filtration, and dried under vacuum at 45°C to obtain a chiral rare earth metal polymer TMR / S.

9. A chiral rare earth metal polymer prepared by the method for preparing a chiral rare earth metal polymer according to any one of claims 1 to 8.

Images