Chiral rare earth metal polymers and methods for their preparation

Abstract

The application discloses a preparation method of a chiral rare earth metal polymer, and particularly comprises the following steps: step 1, preparing 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethanone; 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(diphenylphosphinyl oxygen)-1,1'-binaphthalene; step 4, preparing a rare earth complex according to the product obtained in step 2 and the product obtained in step 3; and step 5, preparing the chiral rare earth metal polymer according to the product obtained in step 4 and methyl methacrylate. The application further discloses the chiral rare earth metal polymer prepared by using the above preparation method. The polymer prepared by the application not only makes the complex have chiral activity, but also avoids the fluorescence quenching of ion coordination of solvent molecules and Eu 3+ .

Description

Technical Field

[0001] This invention belongs to the field of luminescent materials technology, and relates to chiral rare earth metal polymers. This invention also relates to a method for preparing chiral rare earth metal polymers. Background Technology

[0002] Chiral rare-earth metal polymers possess high fluorescence efficiency, narrow emission peaks, and long fluorescence lifetimes, leading to their widespread application in numerous fields, including fluorescent probes, medical imaging, optical coding, biological detectors, acid-base detectors, and advanced information encryption. Among these, chiral rare-earth metal polymers offer unique advantages in the precise control of fluorescence color, energy transfer, luminescence efficiency, and circularly polarized fluorescence; however, current research on chiral rare-earth polymers is limited. Developing a simple and efficient strategy for preparing chiral polymer materials is of practical significance. Summary of the Invention

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

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

[0005] The first technical solution adopted in this invention is a method for preparing chiral rare earth metal polymers, specifically including the following steps:

[0006] Step 1: Prepare 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethane-1-one;

[0007] Step 2: Prepare 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione based on the product obtained in Step 1;

[0008] Step 3: Prepare chiral bis(diphenylphosphinooxy)-1,1'-binaphthylene;

[0009] Step 4: Prepare rare earth complexes based on the products obtained in Step 2 and Step 3;

[0010] Step 5: Prepare a chiral rare earth metal polymer based on the product obtained in Step 4 and methyl methacrylate.

[0011] The first technical solution of this invention is further characterized by:

[0012] The specific process of step 1 is as follows:

[0013] Step 1.1: Dissolve 0.3g to 0.9g of 4-vinylphenylboronic acid and 0.2g to 0.6g of 4-bromoacetophenone in 2g to 6g of sodium carbonate aqueous solution, then add 30mg to 90mg of catalyst and 5mL to 15mL of reaction solvent, and heat in an oil bath at 80℃ to 100℃ and react in a N2 environment;

[0014] Step 1.2: Pour the product from the reaction in Step 1.1 into a single-necked flask and rotary evaporate it at 40℃~45℃ to remove the solvent toluene. Then add C4H8O2 to the residue after rotary evaporation and extract the aqueous phase with C4H8O2. Filter the mixture and rotary evaporate the collected organic matter at 30℃~35℃ to remove C4H8O2, obtaining a solid. Dissolve the solid in dichloromethane and purify it by silica gel column chromatography. Place the purified product in a vacuum drying oven and dry it 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 tetra(triphenylphosphine)palladium(0), and the reaction solvent is toluene.

[0016] The specific process of step 2 is as follows: Dissolve 0.15g to 0.45g of product T1 in 4mL to 12mL of tetrahydrofuran, stir in an ice-water bath and N2 environment, then add 0.3g to 0.9g of NaH and stir for 0.5 to 1h, then add 0.3mL to 0.9mL of ethyl trifluoroacetate, then transfer to an oil bath and heat for 3 to 4 hours. After the reaction is completed and cooled to room temperature, the crude product is obtained. Add ice water to the crude product, add hydrochloric acid dropwise to adjust the pH value to 2 to 3, and stir continuously until a precipitate appears. Filter the precipitate, wash it 3 times with deionized water, and then dry it 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℃~95℃.

[0018] The specific process of step 3 is as follows: Dissolve 0.1-0.3 g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthylene in 10-30 mL of tetrahydrofuran, cool to 0℃, add 6-20 mL of H2O2, and after the reaction is complete, pour into a single-necked flask for rotary evaporation to remove tetrahydrofuran. Then add 50 mL of CH2Cl2 to the residue after rotary evaporation and extract the aqueous phase with CH2Cl2. Add anhydrous Na2SO4 to the lower layer solution after extraction to absorb water until there are no suspended water droplets. Filter, and rotary evaporate the collected organic matter to remove CH2Cl2, and obtain a solid. Dry the obtained solid in a vacuum drying oven to obtain chiral-bis(diphenylphosphino)-1,1'-binaphthylene.

[0019] The specific process of step 4 is as follows: Dissolve 0.4g to 1.2g of product T2 from step 2 in 15mL to 45mL of methanol, then add 0.02g to 0.06g of NaOH, react at room temperature for 0.5 to 1h, and then add 0.2g to 0.6g of EuCl. 3. The product of step 3, chiral bis(diphenylphosphinooxy)-1,1'-binaphthylene, was heated in an oil bath at 50℃ to 70℃ and reacted under N2 environment for 12 to 13 hours. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. The precipitate was filtered, washed with deionized water, and then vacuum dried to obtain the rare earth complex T2-Eu-R / S-BINAPO.

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

[0021] The second technical solution adopted in this invention is a chiral rare earth metal polymer, which is prepared by the above-mentioned method for preparing chiral rare earth metal polymers.

[0022] The beneficial effects of this invention are that it prepares β-diketone (T2) through a simple and easily synthesized method. β-diketone rare earth complexes, with their excellent luminescence efficiency, energy transfer efficiency, chemical stability, and ability to exist in solid or liquid forms, have become the class of rare earth complexes with the most outstanding luminescence efficiency. By coordinating β-diketone (T2) with lanthanide metal ions and R / S-BINAPO to form chiral rare earth complexes, and then polymerizing these complexes with methyl methacrylate, chiral rare earth metal polymers are obtained, which possess excellent fluorescence properties and have good application prospects in the fields of fluorescent probes, host-guest recognition, bioimaging, optical devices, and magnetic and superconducting materials. Attached Figure Description

[0023] Figure 1 This is the ultraviolet-visible infrared absorption spectrum of product T1 prepared by Example 1 of the preparation method of chiral rare earth metal polymer of the present invention.

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

[0025] Figure 3(a) is the fluorescence spectrum of the product T2-Eu-S-BINAPO prepared by Example 1 of the preparation method of chiral rare earth metal polymer of the present invention;

[0026] Figure 3(b) is the fluorescence spectrum of the product T2-Eu-R-BINAPO prepared by Example 1 of the preparation method of 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 by Example 1 of the preparation method of 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 by Example 1 of the preparation method of chiral rare earth metal polymer of the present invention. Detailed Implementation

[0029] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

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

[0031] Step 1, prepare 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethane-1-one, i.e., product T1, the process is as follows:

[0032] 4-Vinylphenylboronic acid (0.3g–0.9g) and 4-bromoacetophenone (0.2g–0.6g) were dissolved in an aqueous solution of sodium carbonate (2g–6g). Tetra(triphenylphosphine)palladium(0) (30mg–90mg) and toluene (5mL–15mL) were added as catalyst. The reaction was carried out in an N2 environment by purging and releasing N2 three times. The reaction was heated in an oil bath (80℃–100℃) for 12 hours. The product was poured into a single-necked flask and rotary evaporated (40℃–45℃) to remove the toluene solvent. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2. After filtration, the collected organic matter was rotary evaporated (30℃–35℃) to remove C4H8O2, yielding a solid. The solid was dissolved in dichloromethane and purified by silica gel column chromatography. The purified product was dried in a vacuum drying oven (45℃) to obtain product T1.

[0033] Step 2: Prepare 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione, i.e., β-diketone T2, based on product T1 obtained in Step 1:

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

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

[0036] Dissolve 0.1–0.3 g of R / S-BINAP (2,2'-bis(diphenylphosphino-1,1'-binaphthyl)) in 10–30 mL of THF (tetrahydrofuran). After cooling to 0 °C, add 6–20 mL of 30% H₂O₂ and react for 30 min, stirring at room temperature for 4 h. Pour into a single-necked flask and rotary evaporate (30–35 °C) to remove THF. Add 50 mL of CH₂Cl₂ to the residue, and extract the aqueous phase with 30 mL of CH₂Cl₂ (add CH₂Cl₂ to the upper layer of water). Extract three times, and add anhydrous Na₂SO₄ to the lower layer of solution to absorb water until no suspended water droplets remain. Filter. Rotary evaporate the collected organic matter (35 °C) to remove CH₂Cl₂, obtaining a solid. Dry in a vacuum drying oven at 45 °C for 24 h to obtain the product R / S-BINAPO.

[0037] Step 4: Prepare T2-Eu-R / S-BINAPO based on the products obtained in Steps 2 and 3:

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

[0039] Step 5: Prepare chiral rare earth metal polymer (TMR / S) based on the product obtained in Step 4 and methyl methacrylate.

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

[0041] Example 1

[0042] 4-Vinylphenylboronic acid (0.3 g) and 4-bromoacetophenone (0.2 g) were dissolved in an aqueous solution of sodium carbonate (2 g). Tetra(triphenylphosphine)palladium (0) (30 mg) catalyst and toluene (5 mL) reaction solvent were added. The reaction was carried out in an N2 environment by purging and releasing N2 three times. The reaction was heated in an oil bath (80 °C) for 12 hours. The product after the reaction was completed was poured into a single-necked flask and rotary evaporated (45 °C) to remove the solvent toluene. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2. After filtration, the collected organic matter was rotary evaporated (35 °C) to remove C4H8O2, and a solid was obtained. The solid was dissolved in dichloromethane and purified by silica gel column chromatography. The purified product was dried in a vacuum drying oven (45 °C) to obtain product T1.

[0043] The product T1 (0.15 g) from step 1 was dissolved in THF (4 mL) and stirred in an ice-water bath and N2 environment. Then, NaH (0.3 g) was added and stirred for 0.5 h. Then, ethyl trifluoroacetate (0.3 mL) was added, and the mixture was transferred to an oil bath and heated for 3 hours. After the reaction was completed and cooled to room temperature, the crude 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 three times with deionized water, and then dried in a vacuum drying oven (45 °C) to obtain the final product T2.

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

[0045] The product T2 (0.4 g) from step 2 was dissolved in methanol (15 mL), and NaOH (0.02 g) was added to create 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) from step 3 were added. The mixture was heated in an oil bath (50 °C) and reacted under N2 environment for 12 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. 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 the product from step 4, 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, followed by 40 mg of the initiator azobisisobutyronitrile (AIBN). The mixture was heated in an oil bath at 80 °C and reacted under N2 atmosphere for 20 h. After the reaction was completed and cooled to room temperature, ethanol was added to precipitate the product three times. The resulting solid product was collected by filtration and dried under vacuum at 45 °C to obtain the chiral rare earth metal polymer (TMR / S).

[0047] Figure 1 The UV-Vis infrared absorption spectrum of T1 in Example 1, Figure 2 The UV-Vis-IR absorption spectrum of T2 shows a shift in its peak, indicating a change in its intramolecular structure, i.e., the synthesis of β-diketone T2. Figures 3(a) and 3(b) are the fluorescence spectra of T2-Eu-S-BINAPO and T2-Eu-S-BINAPO in DMF solution, respectively, under 396 nm light excitation. 5 D0 to ground state 7 F J (J = 0, 1, 2, 3, 4) transitions to form Eu 3+ Characteristic red light of ions. Among them, 578nm is... 5 D0→ 7 F0, 588-595nm is 5D0→ 7 F1, 613nm is 5 D0→ 7 F2, 651nm is 5 D0→ 7 F3, 703nm is 5 D0→ 7 The F4's leap has its strongest launch position at λ. em =613nm, the intensity is significantly higher than the other four peaks, this is because 5 D0→ 7 The F2 transition has the highest sensitivity. Figure 4 This is the CD spectrum of Example 1 of the rare earth complex preparation method of the present invention. After introducing the chiral auxiliary ligand R-BINAPO, T2-Eu-R-BINAPO showed "+", "-", and "-" signals at wavelengths of 255 nm, 300 nm, and 340 nm, respectively. The CD signal peak of T2-Eu-S-BINAPO prepared after introducing the chiral auxiliary ligand S-BINAPO is mirrored that of T2-Eu-R-BINAPO, indicating that T2-Eu-S-BINAPO and T2-Eu-R-BINAPO are enantiomers. This shows that the rare earth complex induces chiral transfer through coordination with (R / S)-BINAPO, thereby modulating the optical properties of T2-Eu-R / S-BINAPO. Figure 5 This is the UV-Vis infrared absorption spectrum of TMR / S in DMF solution, which indirectly proves that the rare earth complex polymerizes with methyl methacrylate.

[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). Tetra(triphenylphosphine)palladium (0) (60 mg) catalyst and toluene (10 mL) solvent were added. The reaction was carried out in an N2 environment by purging and releasing N2 three times. The reaction was heated in an oil bath (90 °C) for about 12 hours. The product was poured into a single-necked flask and rotary evaporated (42 °C) to remove the toluene solvent. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2. After filtration, the collected organic matter was rotary evaporated (32 °C) to remove C4H8O2, yielding a solid. The solid was dissolved in dichloromethane and purified by silica gel column chromatography. The purified product was dried in a vacuum drying oven (45 °C) to obtain product T1.

[0050] The product T1 (0.3 g) from step 1 was dissolved in THF (8 mL) and stirred in an ice-water bath and N2 environment. Then, NaH (0.6 g) was added and stirred for 0.8 h. Then, ethyl trifluoroacetate (0.6 mL) was added, and the mixture was transferred to an oil bath and heated for 3 hours. After the reaction was completed and cooled to room temperature, the crude 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 three times with deionized water, and then dried in a vacuum drying oven (45 °C) to obtain the final product T2.

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

[0052] The product T2 (0.8 g) from step 2 was dissolved in methanol (30 mL), and NaOH (0.04 g) was added to create 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) from step 3 were added. The mixture was heated in an oil bath (60 °C) under N2 environment for 12.5 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. 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 the product from step 4, 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, followed by 80 mg of the initiator azobisisobutyronitrile (AIBN). The mixture was heated in an oil bath at 90 °C and reacted under N2 atmosphere for 22 h. After the reaction was completed and cooled to room temperature, ethanol was added to precipitate the product three times. The resulting solid product was collected by filtration and dried under vacuum at 45 °C to obtain the chiral rare earth metal polymer (TMR / S).

[0054] Example 3

[0055] 4-Vinylphenylboronic acid (0.9 g) and 4-bromoacetophenone (0.6 g) were dissolved in an aqueous solution of sodium carbonate (6 g). Tetra(triphenylphosphine)palladium (0) (90 mg) catalyst and toluene (15 mL) solvent were added. The reaction was carried out in an N2 environment by purging and releasing N2 three times. The mixture was heated in an oil bath (100 °C) for approximately 12 hours. The product was then transferred to a single-necked flask and rotary evaporated (40 °C) to remove the toluene solvent. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2. After filtration, the collected organic matter was rotary evaporated (30 °C) to remove C4H8O2, yielding a solid. The solid was dissolved in dichloromethane and purified by silica gel column chromatography. The purified product was dried in a vacuum drying oven (45 °C) to obtain product T1.

[0056] The product T1 (0.45 g) from step 1 was dissolved in THF (12 mL) and stirred in an ice-water bath and N2 environment. Then, NaH (0.9 g) was added and stirred for 1 h. Then, ethyl trifluoroacetate (0.9 mL) was added and the mixture was transferred to an oil bath and heated for 4 h. After the reaction was completed and cooled to room temperature, the 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. While stirring continuously, a precipitate was formed. The precipitate was filtered, washed three times with deionized water, and then dried in a vacuum drying oven (45 °C) to obtain the final product T2.

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

[0058] Finally, the product T2 (1.2 g) from step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to make it alkaline. After reacting at room temperature for 1 h, EuCl3·6H2O (0.6 g) and the product R / S-BINAPO (0.12 g) from step 3 were added. The mixture was heated in an oil bath (70 °C) and reacted in a N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. 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 the product from step 4, 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, followed by 120 mg of the initiator azobisisobutyronitrile (AIBN). The mixture was heated in an oil bath at 100 °C and reacted under N2 atmosphere for 24 h. After the reaction was completed and cooled to room temperature, ethanol was added to precipitate the product three times. The resulting solid product was collected by filtration and dried under vacuum at 45 °C to obtain the chiral rare earth metal polymer (TMR / S).

[0060] Example 4

[0061] 4-Vinylphenylboronic acid (0.4 g) and 4-bromoacetophenone (0.4 g) were dissolved in an aqueous solution of sodium carbonate (4 g). Tetra(triphenylphosphine)palladium (0) (80 mg) catalyst and toluene (8 mL) reaction solvent were added. The mixture was charged and discharged three times with N2 to ensure the reaction proceeded in an N2 environment. The mixture was heated in an oil bath (100 °C) for approximately 12 hours. The product was then transferred to a single-necked flask and rotary evaporated (40 °C) to remove the toluene solvent. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2. After filtration, the collected organic matter was rotary evaporated (30 °C) to remove C4H8O2, yielding a solid. The solid was dissolved in dichloromethane and purified by silica gel column chromatography. The purified product was dried in a vacuum drying oven (45 °C) to obtain product T1.

[0062] The product T1 (0.45 g) from step 1 was dissolved in THF (12 mL) and stirred in an ice-water bath and N2 environment. Then, NaH (0.9 g) was added and stirred for 1 h. Then, ethyl trifluoroacetate (0.9 mL) was added and the mixture was transferred to an oil bath and heated for 4 h. After the reaction was completed and cooled to room temperature, the 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. While stirring continuously, a precipitate was formed. The precipitate was filtered, washed three times with deionized water, and then dried in a vacuum drying oven (45 °C) to obtain the final product T2.

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

[0064] Finally, the product T2 (1.2 g) from step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to make it alkaline. After reacting at room temperature for 1 h, EuCl3·6H2O (0.6 g) and the product R / S-BINAPO (0.12 g) from step 3 were added. The mixture was heated in an oil bath (70 °C) and reacted in a N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. 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 the product from step 4, 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, followed by 120 mg of the initiator azobisisobutyronitrile (AIBN). The mixture was heated in an oil bath at 100 °C and reacted under N2 atmosphere for 24 h. After the reaction was completed and cooled to room temperature, ethanol was added to precipitate the product three times. The resulting solid product was collected by filtration and dried under vacuum at 45 °C to obtain the chiral rare earth metal polymer (TMR / S).

[0066] Example 5

[0067] 4-Vinylphenylboronic acid (0.4 g) and 4-bromoacetophenone (0.4 g) were dissolved in an aqueous solution of sodium carbonate (4 g). Tetra(triphenylphosphine)palladium (0) (80 mg) catalyst and toluene (8 mL) solvent were added. The reaction was carried out in an N2 environment by purging and releasing N2 three times. The mixture was heated in an oil bath (100 °C) for approximately 12 hours. The product was then transferred to a single-necked flask and rotary evaporated (40 °C) to remove the toluene solvent. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2. After filtration, the collected organic matter was rotary evaporated (32 °C) to remove C4H8O2, yielding a solid. The solid was dissolved in dichloromethane and purified by silica gel column chromatography. The purified product was dried in a vacuum drying oven (45 °C) to obtain product T1.

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

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

[0070] Finally, the product T2 (1.2 g) from step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to make it alkaline. After reacting at room temperature for 1 h, EuCl3·6H2O (0.6 g) and the product R / S-BINAPO (0.12 g) from step 3 were added. The mixture was heated in an oil bath (70 °C) and reacted in a N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. 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 the product from step 4, 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, followed by 120 mg of the initiator azobisisobutyronitrile (AIBN). The mixture was heated in an oil bath at 100 °C and reacted under N2 atmosphere for 24 h. After the reaction was completed and cooled to room temperature, ethanol was added to precipitate the product three times. The resulting solid product was collected by filtration and dried under vacuum at 45 °C to obtain the chiral rare earth metal polymer (TMR / S).

[0072] Example 6

[0073] 4-Vinylphenylboronic acid (0.4 g) and 4-bromoacetophenone (0.4 g) were dissolved in an aqueous solution of sodium carbonate (4 g). Tetra(triphenylphosphine)palladium (0) (80 mg) catalyst and toluene (8 mL) reaction solvent were added. The mixture was charged and discharged three times with N2 to ensure the reaction proceeded in an N2 environment. The mixture was heated in an oil bath (100 °C) for approximately 12 hours. The product was then transferred to a single-necked flask and rotary evaporated (40 °C) to remove the toluene solvent. Ethyl acetate (C4H8O2) was added to the residue, and the aqueous phase was extracted with C4H8O2. After filtration, the collected organic matter was rotary evaporated (30 °C) to remove C4H8O2, yielding a solid. The solid was dissolved in dichloromethane and purified by silica gel column chromatography. The purified product was dried in a vacuum drying oven (45 °C) to obtain product T1.

[0074] The product T1 (0.45 g) from step 1 was dissolved in THF (12 mL) and stirred in an ice-water bath and N2 environment. Then, NaH (0.9 g) was added and stirred for 1 h. Then, ethyl trifluoroacetate (0.9 mL) was added and the mixture was transferred to an oil bath and heated for 4 h. After the reaction was completed and cooled to room temperature, the 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. While stirring continuously, a precipitate was formed. The precipitate was filtered, washed three times with deionized water, and then dried in a vacuum drying oven (45 °C) to obtain the final product T2.

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

[0076] Finally, the product T2 (0.9 g) from step 2 was dissolved in methanol (45 mL), and NaOH (0.06 g) was added to create 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) from step 3 were added. The mixture was heated in an oil bath (70 °C) and reacted under N2 environment for 13 h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. 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 the product from step 4, 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, followed by 120 mg of the initiator azobisisobutyronitrile (AIBN). The mixture was heated in an oil bath at 100 °C and reacted under N2 atmosphere for 24 h. After the reaction was completed and cooled to room temperature, ethanol was added to precipitate the product three times. The resulting solid product was collected by filtration and dried under vacuum at 45 °C to obtain the chiral rare earth metal polymer (TMR / S).

[0078] This invention constructs chiral rare earth complexes using a chiral transfer strategy. Specifically, it prepares a novel β-diketone-sensitized rare earth ion and then introduces R / S-BINAPO as an auxiliary ligand into the complex via coordination. This not only endows the complex with chiral activity but also avoids interference from solvent molecules (containing NH, OH, and CH groups) and Eu. 3+ Ion-coordinated fluorescence quenching not only endows the complex with excellent rare-earth luminescence properties but also unique circular dichroism. The synthesized complex is then polymerized with methyl methacrylate to form a polymer, resulting in a simple and efficient preparation of chiral polymer materials with good chiral optical properties and luminescence performance. This expands its application potential in many fields, such as fluorescent probes, medical imaging, optical coding, and advanced information encryption.

Claims

1. A method for preparing chiral rare earth metal polymers, characterized in that: Specifically, the steps include the following: Step 1, prepare 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethane-1-one; Step 2: Prepare 4,4,4-trifluoro-1-(4'-vinyl-[1,1'-biphenyl]-4-yl)butane-1,3-dione from the product obtained in Step 1; Step 3: Prepare chiral bis(diphenylphosphinooxy)-1,1'-binaphthylene; Step 4: Prepare rare earth complexes based on the products obtained in Step 2 and Step 3; Step 5: Prepare a chiral rare earth metal polymer based on the product obtained in Step 4 and methyl methacrylate.

2. The method for preparing chiral rare earth metal polymers according to claim 1, characterized in that: The specific process of step 1 is as follows: Step 1.1: Dissolve 0.3g~0.9g of 4-vinylphenylboronic acid and 0.2g~0.6g of 4-bromoacetophenone in 2g~6g of sodium carbonate aqueous solution, then add 30mg~90mg of catalyst and 5mL~15mL of reaction solvent, heat in an oil bath at 80℃~100℃ and react in a N2 environment; Step 1.2: Pour the product from Step 1.1 into a single-necked flask and rotary evaporate at 40℃~45℃ to remove the reaction solvent. Then add C4H8O2 to the residue after rotary evaporation and extract the aqueous phase with C4H8O2. Filter and rotary evaporate the collected organic matter at 30℃~35℃ to remove C4H8O2, obtaining a solid. Dissolve the solid in dichloromethane and purify it by silica gel column chromatography. Place the purified product in a vacuum drying oven to dry, obtaining 1-(4'-vinyl-[1,1'-biphenyl]-4-yl)ethane-1-one, i.e., product T1.

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

4. The method for preparing chiral rare earth metal polymers according to claim 2, characterized in that: The specific process of step 2 is as follows: Dissolve 0.15g~0.45g of product T1 in 4mL~12mL of tetrahydrofuran, stir in an ice-water bath and N2 environment, then add 0.3g~0.9g of NaH and stir for 0.5~1h, then add 0.3mL~0.9mL of ethyl trifluoroacetate, then transfer to an oil bath and heat for 3~4 hours. After the reaction is completed and cooled to room temperature, the crude product is obtained. Add ice water to the crude product, add hydrochloric acid dropwise to adjust the pH value to 2~3, and stir continuously until a precipitate appears. Filter the precipitate, wash it 3 times with deionized water, and then dry it 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 chiral rare earth metal polymers according to claim 4, characterized in that: In step 2, the reaction temperature in the oil bath is 75℃~95℃.

6. The method for preparing chiral rare earth metal polymers according to claim 4, characterized in that: The specific process of step 3 is as follows: 0.1~0.3g of 2,2'-bis(diphenylphosphino)-1,1'-binaphthylene is dissolved in 10~30mL of tetrahydrofuran, cooled to 0℃, and then 6~20mL of H2O2 is added and reacted for 30min. The mixture is stirred at room temperature for 4h, and then poured into a single-necked flask for rotary evaporation to remove tetrahydrofuran. 50mL 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 no suspended water droplets are present. The mixture is filtered, and the collected organic matter is rotary evaporated to remove CH2Cl2, resulting in a solid. The solid is dried in a vacuum drying oven to obtain chiral-bis(diphenylphosphino)-1,1'-binaphthylene.

7. The method for preparing chiral rare earth metal polymers according to claim 6, characterized in that: The specific process of step 4 is as follows: Dissolve 0.4g~1.2g of product T2 from step 2 in 15mL~45mL of methanol, then add 0.02g~0.06g of NaOH, react at room temperature for 0.5~1h, and then add 0.2g~0.6g of EuCl3. . The product of step 3, chiral bis(diphenylphosphinooxy)-1,1'-binaphthylene, was heated in an oil bath at 50℃~70℃ and reacted under N2 environment for 12h~13h. After the reaction was completed and cooled to room temperature, deionized water was added to quench the precipitate. The precipitate was filtered, washed with deionized water, and then vacuum dried to obtain the rare earth complex T2-Eu-R / S-BINAPO.

8. The method for preparing chiral rare earth metal polymers according to claim 7, characterized in that: The specific process of step 5 is as follows: Dissolve 0.16g~0.48g of the product T2-Eu-R / S-BINAPO from step 4 in 10mL~30mL of anhydrous and oxygen-free 1,2-dichlorobenzene, add 3mL~9mL of methyl methacrylate, and finally add 40mg~120mg of the initiator azobisisobutyronitrile (AIBN). Heat in an oil bath at 80℃~100℃ and react in a N2 environment for 20h~24h. After the reaction is completed and cooled to room temperature, add ethanol to precipitate 3 times, collect the obtained solid product by filtration, and dry it under vacuum at 45℃ to obtain the chiral rare earth metal polymer (TMR / S).

9. A chiral rare earth metal polymer, prepared by the method for preparing chiral rare earth metal polymers as described in any one of claims 1 to 8.

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