Triphenylamine supramolecular polymers with tunable circular polarization, preparation methods and applications

Abstract

This invention discloses a triphenylamine supramolecular polymer capable of tunable circular polarization, its preparation method, and its applications. The polymer is formed by the co-assembly of a triphenylamine donor and a naphthyl monoamide acceptor through intermolecular non-covalent interactions. The preparation method of the triphenylamine donor is as follows: S1: Methyl gallate and bromododecane are added to DMF to react and obtain compound A; S2: Compound A and sodium hydroxide are added to ethanol to react and obtain compound B; S3: Compound B, 1-(4-bromophenyl)ethylamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide, and 4-dimethylaminopyridine are added to dichloromethane to react and obtain compound C; S4: Compound C, Pd(PPh3)2Cl2, CuI, and trimethylsilylacetylene are added to triethylamine under an inert atmosphere to react and obtain compound D; S5: Compound D, Pd(PPh3)2Cl2, CuI, and tris(4-iodophenyl)amine are added to triethylamine under an inert atmosphere to react and obtain the triphenylamine donor. This invention develops a CPL material with a wide range of adjustable properties.

Description

Technical Field

[0001] This invention relates to the field of circularly polarized light materials technology, and in particular to a triphenylamine supramolecular polymer for tunable circularly polarized light, its preparation method, and its applications. Background Technology

[0002] Practical applications of circularly polarized luminescent (CPL) materials in 3D displays and photonics require broad color tunability across the entire visible spectrum. Materials containing chiral π-aromatic luminescent groups are promising candidates for achieving this goal due to their well-defined structure, ease of modification, and ability to control multi-scale chirality. Tuning the π-conjugation length of the aromatic luminescent group is a feasible method for adjusting the emission color of CPL. Another option is to design D-π-A chiral luminescent groups with intramolecular charge transfer interactions (ICT), where D and A represent the electron donor and acceptor, respectively. However, both of these methods require cumbersome synthetic steps, thus limiting their practicality. Summary of the Invention

[0003] Based on the technical problems existing in the background technology, this invention proposes a triphenylamine supramolecular polymer with tunable circular polarization, its preparation method and application, and develops CPL materials with a wide range of tunable properties.

[0004] The present invention proposes a method for preparing a triphenylamine supramolecular polymer with tunable circular polarization, comprising the following steps: dissolving a triphenylamine donor and a naphthyl monoamide acceptor in an organic solvent, and co-assembling them through intermolecular non-covalent forces to form a triphenylamine supramolecular polymer with tunable circular polarization;

[0005] The triphenylamine donor has a structural formula of one of formulas 1 to 4:

[0006]

[0007] The naphthyl monoamide receptor is of formula 5 or formula 6:

[0008]

[0009] Preferably, the molar ratio of the triphenylamine donor to the naphthyl monoamide acceptor is 100:1-500.

[0010] Preferably, the organic solvent is one or more of methylcyclohexane, cyclohexane, n-hexane, n-decane, and decahydronaphthalene.

[0011] Preferably, the method for preparing the triphenylamine donor comprises the following steps:

[0012] S1: Compound A is prepared by reacting methyl gallate and dodecane bromide in DMF;

[0013] S2: Compound A and sodium hydroxide are reacted in ethanol to prepare compound B;

[0014] S3: Compound C was prepared by reacting compound B, 1-(4-bromophenyl)ethylamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine in dichloromethane;

[0015] S4: Compound D was prepared by reacting compound C, Pd(PPh3)2Cl2, CuI and trimethylsilylacetylene with triethylamine under an inert atmosphere;

[0016] S5: Compound D, Pd(PPh3)2Cl2, CuI and tris(4-iodophenyl)amine were reacted with triethylamine under an inert atmosphere to prepare a triphenylamine donor;

[0017] S6: Compound E was prepared by reacting compound C, pinacol diboronate, PdCl2 (dppf) and potassium acetate in 1,4-dioxane under an inert atmosphere.

[0018] S7: Compound E, Pd(PPh3)4 and tris(4-iodophenyl)amine were added to a mixture of toluene and ethanol, and K2CO3 was added under an inert atmosphere to react and obtain the triphenylamine donor.

[0019] Preferably, the molar ratio of methyl gallate to dodecane bromo in S1 is 1:4-8, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

[0020] Preferably, the molar ratio of compound A to sodium hydroxide in S2 is 1:6-10, the reaction temperature is 20-30℃, and the reaction time is 8-16 hours.

[0021] Preferably, the molar ratio of compound B, 1-(4-bromophenyl)ethylamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine in S3 is 1:1-1.2:2.2-2.6:1.5-2, the reaction temperature is 20-30℃, and the reaction time is 8-16 hours.

[0022] Preferably, the molar ratio of compound C, Pd(PPh3)2Cl2, CuI and trimethylsilylacetylene in S4 is 1:0.05-0.15:0.05-0.15:4-8, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

[0023] Preferably, the molar ratio of compound D, Pd(PPh3)2Cl2, CuI and tris(4-iodophenyl)amine in S5 is 1:0.01-0.03:0.01-0.03:0.2-0.4, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

[0024] Preferably, the molar ratio of compound C, pinacol diboronate, PdCl2(dppf), and potassium acetate in S6 is 1:1-2:0.01-0.03:2-4, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

[0025] Preferably, the molar ratio of compound E, Pd(PPh3)4 and tris(4-iodophenyl)amine in S7 is 1:0.005-0.015:0.2-0.4, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

[0026] The present invention provides a triphenylamine supramolecular polymer capable of tunable circular polarization prepared by the above-mentioned method.

[0027] The present invention relates to the application of the above-mentioned triphenylamine supramolecular polymer with tunable circularly polarized light in circularly polarized light-emitting materials.

[0028] Beneficial technical effects of the present invention:

[0029] 1. This invention introduces a novel circularly polarized luminescent supramolecular polymer material and its preparation process. By selecting low-cost, readily available low-molecular-weight chiral monomers and utilizing the synergistic effect of intermolecular hydrogen bonding and π-π stacking, a supramolecular polymer material with high-efficiency circularly polarized luminescence properties is successfully constructed. This method is not only low-cost and simple to operate, but also demonstrates significant potential and prospects for practical applications.

[0030] 2. The circularly polarized luminescent polymer material and its preparation method of the present invention adopt a supramolecular co-assembly strategy to achieve precise matching and efficient charge transfer between chiral donor molecules and non-chiral guest molecules, thereby achieving a full-spectrum circularly polarized luminescence range from blue, green, yellow to red light, and exhibiting a high asymmetric luminescence factor.

[0031] 3. The circularly polarized luminescent polymer assembly mechanism of this invention features a synergistic polymerization mechanism, endowing the material with the advantage of high molecular weight. This characteristic greatly enhances the material's applicability in solution processing, making it possible to prepare large-area, high-quality luminescent films, and providing new candidate materials for the application of optoelectronic devices, especially circularly polarized organic luminescent materials. Attached Figure Description

[0032] Figure 1 This is a schematic diagram illustrating the wide-range tunable circularly polarized luminescence achieved by the triphenylamine supramolecular polymer of the present invention.

[0033] Figure 2The following are the normalized CPL spectra of supramolecular polymer 1 and supramolecular donor-acceptor polymer 1.3 proposed in this invention: a: normalized CPL spectra of supramolecular polymer 2 and supramolecular donor-acceptor polymers 2.3 and 2.4; c: emission color coordinate diagrams of supramolecular polymers 1, 2, 1.3, 1.4, 2.3 and 2.4. Detailed Implementation

[0034] The present invention will be further explained below with reference to specific embodiments.

[0035] Example 1

[0036] The synthetic route for the compound of formula 1 proposed in this invention is as follows:

[0037]

[0038] The specific steps for synthesizing compound 1 are as follows:

[0039] S1: Methyl gallate (1.8 g, 10 mmol) and dodecane bromo (13.2 g, 60 mmol) were added to DMF (60 mL) and stirred overnight at 80 °C. After cooling the reaction solution to room temperature, the solvent was removed by rotary evaporation. The mixture was extracted with CH2Cl2 and water, and the organic phase was dried over anhydrous Na2SO4 and concentrated. The reactants were purified by silica gel column chromatography (petroleum ether / CHCl3 = 10:1, v / v) to give a white solid product, denoted as compound A.

[0040] S2: Compound A (3.4 g, 5 mmol) and sodium hydride (1.6 g, 40 mmol) were added to ethanol (60 mL) and stirred overnight at room temperature. The mother liquor was gradually added to an aqueous solution of hydrochloric acid at pH 1 (500 mL) to obtain a white solid. The white solid was purified by silica gel column chromatography (petroleum ether / CHCl3 = 10:1, v / v) to obtain a white solid product, denoted as compound B.

[0041] S3: Compound B (5 g, 7.4 mmol), (R)-(+)-1-(4-bromophenyl)ethylamine (1.6 g, 8.1 mmol), EDC (3.4 g, 17.8 mmol), and DMAP (12.6 g, 12.6 mmol) were added to dichloromethane (100 mL) and stirred overnight at room temperature. The solvent was removed by rotary evaporation. After extraction with CH2Cl2 and water, the organic phase was dried over anhydrous Na2SO4 and concentrated. The reactants were purified by silica gel column chromatography (petroleum ether / CHCl3 = 10:1, v / v) to give a white solid product, denoted as compound C. 1H NMR (400MHz, CDCl3) δ7.47(d,J=8.4Hz,2H),7.27(s,1H),7.25(s,1H),6.93(s,2H),6.16(d,J=8.1Hz,1H),5.28–5.22(m,1H) ,4.01–3.96(m,6H),1.83–1.71(m,6H),1.58–1.56(m,3H),1.50–1.40(m,6H),1.34–1.22(m,48H),0.88(t,J=6.8Hz,9H).13C NMR (100MHz, CDCl3, 298K) δ166.8,153.4,142.7,141.7,132.0,129.4,128.3,121 .5,106.1,73.8,69.7,63.4,49.1,32.3,30.1,30.0,29.7,26.4,23.0,22.0,14.5.

[0042] S4: Pd(PPh3)2Cl2 (121 mg, 0.17 mmol), CuI (33 mg, 0.17 mmol), compound C (1.5 g, 1.7 mmol), and trimethylsilylacetylene (1.1 g, 10.3 mmol) were added to triethylamine (Et3N, 20 mL) under a nitrogen atmosphere and stirred overnight at 80 °C. After cooling the reaction solution to room temperature, the solvent was removed by rotary evaporation. The mixture was extracted with CH2Cl2 and water, and the organic phase was dried over anhydrous Na2SO4 and concentrated. The reactants were purified by silica gel column chromatography (petroleum ether / CHCl3 = 10:1, v / v) to give a white solid, designated as compound D.

[0043] S5: Pd(PPh3)2Cl2 (20 mg, 0.03 mmol), CuI (5 mg, 0.03 mmol), compound D (1080 mg, 1.35 mmol), and tris(4-iodophenyl)amine (240 mg, 0.39 mmol) were added to triethylamine (Et3N, 50 mL) under a nitrogen atmosphere and stirred overnight at 80 °C. After the reaction mixture cooled to room temperature, the solvent was removed by rotary evaporation. The organic phase was extracted with CH2Cl2 and water, dried over anhydrous Na2SO4, and concentrated. The reactants were purified by silica gel column chromatography (petroleum ether / CHCl3 / CH3CN = 250:250:6, v / v / v) to give a pale yellow solid (R)-1 (272 mg, 0.10 mmol, 26.6%). 1H NMR (400MHz, CDCl3, 293K) δ (ppm): 7.51 (d, J = 8.3Hz, 6H), 7.44 (d, J = 8.7Hz, 6H), 7.37 (d, J = 8.3Hz, 6H), 7.08 (d, J = 8.7Hz, 6H), 6.95 (s, 6H), 6.20 (d, J=7.7Hz, 3H), 5.36–5.26 (m, 3H), 4.04–3.94 (m, 18H), 1.86–1.66 (m, 18H), 1.52–1.40 (m, 27H), 1.39 (s, 144H), 0.92–0.82 (m, 27H). 13C NMR (101MHz, CDCl3, 293K) δ (ppm): 166.5, 153.2, 146.7, 143.2, 141.4, 132.8, 131.9, 129.3, 126.3, 124.0, 122.5, 117.9, 105.9, 8 9.4, 89.0, 77.4, 77.0, 76.7, 73.6, 69.5, 49.1, 32.0, 30.3, 29.8, 29.7, 29.7, 29.7, 29.6, 29.4, 29.4, 29.4, 26.1, 22.7, 21.6, 14.1. MALDI-TOF-MS: m / z 2646.02[M+H]+.

[0044] Example 2

[0045] The specific steps of the method for synthesizing the compound of formula 2 proposed in this invention are as follows:

[0046] The enantiomeric compound (S)-1 was synthesized by replacing (R)-(+)-1-(4-bromophenyl)ethylamine in S3 of Example 1 with (S)-(+)-1-(4-bromophenyl)ethylamine, while all other conditions were the same as in Example 1. A pale yellow solid (S)-1 (284 mg, 0.11 mmol, 27.9%) was obtained. 1H NMR (400MHz, CDCl3, 293K): δ (ppm): 7.51 (d, J=8.3Hz, 6H), 7.44 (d, J=8.7Hz, 6H), 7.37 (d, J=8.3Hz, 6H), 7.08 (d, J=8.7Hz, 6H), 6.95 (s, 6H) , 6.20 (d, J=7.7Hz, 3H), 5.36–5.26 (m, 3H), 4.04–3.94 (m, 18H), 1.86– 1.66 (m, 18H), 1.52–1.40 (m, 27H), 1.39 (s, 144H), 0.92–0.82 (m, 27H).

[0047] Example 3

[0048] The synthetic route for compound formula 3 proposed in this invention is as follows:

[0049]

[0050] The specific steps for synthesizing compound 3 are as follows:

[0051] S1: Methyl gallate (1.8 g, 10 mmol) and dodecane bromo (13.2 g, 60 mmol) were added to DMF (60 mL) and stirred overnight at 80 °C. After cooling the reaction solution to room temperature, the solvent was removed by rotary evaporation. The mixture was extracted with CH2Cl2 and water, and the organic phase was dried over anhydrous Na2SO4 and concentrated. The reactants were purified by silica gel column chromatography (petroleum ether / CHCl3 = 10:1, v / v) to give a white solid product, denoted as compound A.

[0052] S2: Compound A (3.4 g, 5 mmol) and sodium hydride (1.6 g, 40 mmol) were added to ethanol (60 mL) and stirred overnight at room temperature. The mother liquor was gradually added to an aqueous solution of hydrochloric acid at pH 1 (500 mL) to obtain a white solid. The white solid was purified by silica gel column chromatography (petroleum ether / CHCl3 = 10:1, v / v) to obtain a white solid product, denoted as compound B.

[0053] S3: Compound B (5 g, 7.4 mmol), (R)-(+)-1-(4-bromophenyl)ethylamine (1.6 g, 8.1 mmol), EDC (3.4 g, 17.8 mmol), and DMAP (12.6 g, 12.6 mmol) were added to dichloromethane (100 mL) and stirred overnight at room temperature. The solvent was removed by rotary evaporation. After extraction with CH2Cl2 and water, the organic phase was dried over anhydrous Na2SO4 and concentrated. The reactants were purified by silica gel column chromatography (petroleum ether / CHCl3 = 10:1, v / v) to give a white solid product, denoted as compound C. 1H NMR (400MHz, CDCl3) δ7.47(d,J=8.4Hz,2H),7.27(s,1H),7.25(s,1H),6.93(s,2H),6.16(d,J=8.1Hz,1H),5.28–5.22(m,1H) ,4.01–3.96(m,6H),1.83–1.71(m,6H),1.58–1.56(m,3H),1.50–1.40(m,6H),1.34–1.22(m,48H),0.88(t,J=6.8Hz,9H).13C NMR (100MHz, CDCl3, 298K) δ166.8,153.4,142.7,141.7,132.0,129.4,128.3,121 .5,106.1,73.8,69.7,63.4,49.1,32.3,30.1,30.0,29.7,26.4,23.0,22.0,14.5.

[0054] S4: PdCl2 (dppf) (22 mg, 0.03 mmol), compound C (1200 mg, 1.4 mmol), and pinacol diboronate (533 mg, 2.1 mmol) were added to 1,4-dioxane (20 mL). Under a nitrogen atmosphere, potassium acetate (401 mg, 4.2 mmol) was added to the flask. The mixture was stirred overnight at 80 °C. The solvent was removed by rotary evaporation. The residue was extracted with CH2Cl2 and water, and the organic layer was dried over anhydrous Na2SO4 and concentrated. The residue was purified by silica gel column chromatography (petroleum ether / CHCl3 / CH3CN = 250:250:6, v / v / v) to give a white solid product, denoted as compound E.

[0055] S5: Pd(PPh3)4 (20 mg, 0.02 mmol), compound E (1270 mg, 1.4 mmol), and tris(4-iodophenyl)amine (250 mg, 0.40 mmol) were added to toluene (20 mL) and anhydrous ethanol (10 mL). Under a nitrogen atmosphere, 2 M K2CO3 (580 mg, 4.2 mmol, dissolved in 2 mL of deionized water) was injected into the flask. The mixture was stirred overnight at 90 °C. The solvent was removed by rotary evaporation. The residue was extracted with CH2Cl2 and water, and the organic layer was dried over anhydrous Na2SO4 and concentrated. The residue was purified by silica gel column chromatography (petroleum ether / CHCl3 / CH3CN = 250:250:6, v / v / v) to give a white solid product (R)-2 (322 mg, 0.13 mmol, 31%). 1HNMR (400MHz, CDCl3, 293K) δ (ppm): 7.59 (d, J=8.3Hz, 6H), 7.51 (d, J=8.7H z, 6H), 7.46 (d, J=8.4Hz, 6H), 7.23 (d, J=8.6Hz, 6H), 6.97 (s, 6H), 6.23 (d, J =7.8Hz, 3H), 5.41–5.30 (m, 3H), 4.07–3.92 (m, 18H), 1.86–1.68 (m, 18H), 1. 65 (d, J=6.9Hz, 9H), 1.52–1.40 (m, 18H), 1.26 (s, 144H), 0.93–0.81 (m, 27H). 13C NMR (101MHz, CDCl3, 293K) δ (ppm): 166.6, 153.2, 146.9, 141.9, 141.4, 139.9, 135.3, 129.5, 127.9, 127.3, 127.1, 126.9, 124.5 , 106.0, 77.3, 77.1, 76.9, 73.6, 69.6, 58.5, 49.1, 32.0, 30.4, 29.8, 29.8, 29.7, 29.4, 26.8, 26.2, 22.8, 21.7, 19.8, 18.5, 14.2. MALDI-TOF-MS: m / z2574.76[M+H]+.

[0056] Example 4

[0057] The specific steps for synthesizing the compound of formula 4 proposed in this invention are as follows:

[0058] The enantiomeric compound (S)-2 was synthesized by replacing (R)-(+)-1-(4-bromophenyl)ethylamine in S3 of Example 3 with (S)-(+)-1-(4-bromophenyl)ethylamine, while all other conditions were the same as in Example 3. A white solid (S)-2 (290 mg, 0.12 mmol, 28%) was obtained. 1H NMR (400MHz, CDCl3, 293K) δ (ppm): 7.59 (d, J=8.3Hz, 6H), 7.51 (d, J=8.7Hz, 6H), 7.46 (d, J=8.4Hz, 6H), 7.23 (d, J=8.6Hz, 6H), 6.97 (s, 6H), 6.23 (d, J= 7.8Hz, 3H), 5.41–5.30 (m, 3H), 4.07–3.92 (m, 18H), 1.86–1.68 (m, 18H), 1.6 5(d, J=6.9Hz, 9H), 1.52–1.40(m, 18H), 1.26(s, 144H), 0.93–0.81(m, 27H).

[0059] Example 5

[0060] The preparation method of the triphenylamine supramolecular polymer with tunable circularly polarized light proposed in this invention comprises the following steps: A triphenylamine donor and a naphthyl monoamide acceptor are dissolved in methylcyclohexane (MCH) at a molar ratio of 1:1. The concentration of the supramolecular polymer is 40 mg / mL. The above mixed solution is spin-coated (1000 r / min, 60 s) onto a quartz plate to form a film. Subsequently, the film is heated to 80 °C, held for 5 minutes, and then cooled to room temperature.

[0061] like Figure 1 As shown, the triphenylamine donor of this invention forms a one-dimensional supramolecular homopolymer under the promotion of triple hydrogen bonds. The helical orientation of the supramolecular polymer is controlled by the long-range chiral transfer from the alkyl stereocenter on the triphenylamine donor to the internal triphenylamine core, resulting in a blue CPL signal. When the triphenylamine donor is mixed with a naphthylamide acceptor, the resulting supramolecular donor-acceptor polymer exhibits green, yellow, orange, and red CPL. These color changes are achieved by adjusting the charge transfer intensity through subtle structural modifications to the donor or acceptor units. Notably, subtle structural modifications to the triphenylamine donor lead to distinctly different donor-acceptor arrangements at the supramolecular level. Specifically, triphenylamine donors containing acetylene linkages induce ground-state charge transfer toward the naphthylamide guest. Triphenylamine donors without acetylene linkages, under the same conditions, promote excited-state charge transfer, resulting in differences in luminescence lifetime.

[0062] like Figure 2 As shown, the (R)-1 supramolecular polymer exhibits a blue CPL signal (λmax: 472 nm). Figure 2a) Equimolar mixing of (R)-1 and compound 3 (Formula 5) resulted in green emission. By modifying the structure of the triphenylamine donor or naphthalene monoimide acceptor, the supramolecular homologous polymer of (R)-2 exhibited blue ring-polarized emission at 453 nm. Figure 2 b); The mixed compound (R)-2 and compound 3 (Equation 5) undergo non-covalent donor-acceptor polymerization, producing an orange ring-polarized emission signal centered at 558 nm (|glum|: 5.6 × 10⁻³, τ: 53.4 ns, Figure 2 b).

[0063] In summary, triphenylamine donors (R)-1 and (R)-2 emit blue light in their supramolecular homopolymer state. The charge-transfer complex between triphenylamine and naphthalene monoimide results in red-shifted cyclopolarized luminescence, the direction of which depends on the triphenylamine donor. Modifying the acetylene bond on the triphenylamine donor to tune the HOMO level, and adding a bromine atom to the naphthalene monoimide acceptor to alter the LUMO level, yielded supramolecular donor-acceptor polymers of complexes 1.3, 1.4, 2.3, and 2.4, exhibiting cyclopolarized luminescence signals in green, yellow, orange, and red, respectively. Figure 2 c), wherein compound 1 is of formula 1, compound 2 is of formula 2, compound 3 is of formula 5, and compound 4 is of formula 6.

[0064] In this invention, (S)-1 and (S)-2 are chiral enantiomers of (R)-1 and (R)-2, respectively, used to achieve luminescent chiral signals opposite to those of (R)-1 and (R)-2; for example, the (S)-1 supramolecular polymer emits left-handed circularly polarized light under ultraviolet light excitation; then, the (R)-1 supramolecular polymer emits right-handed circularly polarized light under ultraviolet light excitation.

Claims

1. A method for preparing triphenylamine supramolecular polymers with tunable circularly polarized light, characterized in that, The method steps are as follows: the triphenylamine donor and the naphthyl monoamide acceptor are dissolved in an organic solvent and co-assembled through intermolecular non-covalent forces to form a triphenylamine supramolecular polymer that can be tunably circularly polarized; The triphenylamine donor has a structural formula of one of formulas 1 to 4: ， The naphthyl monoamide receptor is of formula 5 or formula 6: 。 2. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 1, characterized in that, The molar ratio of the triphenylamine donor to the naphthyl monoamide acceptor is 100:1-500.

3. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 1, characterized in that, The organic solvent is one or more of methylcyclohexane, cyclohexane, n-hexane, n-decane, and decahydronaphthalene.

4. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 1, characterized in that, The method for preparing the triphenylamine donor is as follows: S1: Compound A is prepared by reacting methyl gallate and dodecane bromide in DMF; S2: Compound A and sodium hydroxide are reacted in ethanol to prepare compound B; S3: Compound C was prepared by reacting compound B, 1-(4-bromophenyl)ethylamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine in dichloromethane; S4: Compound D was prepared by reacting compound C, Pd(PPh3)2Cl2, CuI and trimethylsilylacetylene with triethylamine under an inert atmosphere; S5: Compound D, Pd(PPh3)2Cl2, CuI and tris(4-iodophenyl)amine were reacted with triethylamine under an inert atmosphere to prepare a triphenylamine donor; S6: Compound E was prepared by reacting compound C, pinacol diboronate, PdCl2 (dppf) and potassium acetate in 1,4-dioxane under an inert atmosphere. S7: Compound E, Pd(PPh3)4 and tris(4-iodophenyl)amine were added to a mixture of toluene and ethanol, and K2CO3 was added under an inert atmosphere to react and obtain the triphenylamine donor.

5. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 4, characterized in that, In S1, the molar ratio of methyl gallate to dodecane bromo is 1:4-8, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

6. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 4, characterized in that, In S2, the molar ratio of compound A to sodium hydroxide is 1:6-10, the reaction temperature is 20-30℃, and the reaction time is 8-16 hours.

7. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 4, characterized in that, In S3, the molar ratio of compound B, 1-(4-bromophenyl)ethylamine, 1-ethyl-(3-dimethylaminopropyl)carbodiimide and 4-dimethylaminopyridine is 1:1-1.2:2.2-2.6:1.5-2, the reaction temperature is 20-30℃, and the reaction time is 8-16 hours.

8. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 4, characterized in that, The molar ratio of compounds C, Pd(PPh3)2Cl2, CuI and trimethylsilylacetylene in S4 is 1:0.05-0.15:0.05-0.15:4-8, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

9. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 4, characterized in that, The molar ratio of compounds D, Pd(PPh3)2Cl2, CuI and tris(4-iodophenyl)amine in S5 is 1:0.01-0.03:0.01-0.03:0.2-0.4, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

10. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 4, characterized in that, In S6, the molar ratio of compound C, pinacol diboronate, PdCl2 (dppf), and potassium acetate is 1:1-2:0.01-0.03:2-4, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

11. The method for preparing the triphenylamine supramolecular polymer with tunable circular polarization according to claim 4, characterized in that, In S7, the molar ratio of compound E, Pd(PPh3)4 and tris(4-iodophenyl)amine is 1:0.005-0.015:0.2-0.4, the reaction temperature is 70-90℃, and the reaction time is 10-14 hours.

12. A triphenylamine supramolecular polymer with tunable circularly polarized light prepared by the method of any one of claims 1-11.

13. The application of the triphenylamine supramolecular polymer with tunable circular polarization as described in claim 12 in circularly polarized luminescent materials.

Images