Circularly polarized chiral organic fluorescent light-emitting material, preparation method and application thereof

Abstract

A kind of circularly polarized chiral organic fluorescent light emitting material and its preparation method and application belong to the technical field of design, preparation and application of chiral polymer functional materials.The chiral binaphthyl compound R / S-2 prepared as chiral monomer is coupled with the monomer of fluorenyl chromophore group with single bond, double bond and triple bond connector to prepare three intrinsic chiral polymer functional fluorescent light emitting materials R / S-P1, R / S-P2 and R / S-P3 with different conjugated main chain conformations by Suzuki, Heck and Sonogashira coupling polymerization reaction, and their photophysical properties and chiral luminescence performance in thin film state are studied.The experiment proves that the product prepared by the application embodies the controllable photophysical properties in test, and has certain circular dichroism and circularly polarized luminescence properties, indicating that it is expected to be applied in the field of chiral solid-state display material and optoelectronic device.

Description

Technical Field

[0001] This invention belongs to the field of design, preparation and application technology of chiral polymer functional materials, specifically relating to a circularly polarized chiral organic fluorescent luminescent material and its preparation method and application. Background Technology

[0002] With in-depth research into chiral properties, it has been discovered that chiral molecules possess unique chiral optical properties, such as optical rotation, circular dichroism (CD), and circularly polarized luminescence (CPL). Unlike optical rotation and CD, which express ground-state chiral structure information, CPL can directly reflect the excited-state structure information of a chiral luminescent system. Due to its rich optical information and angle independence, it is widely used in various technologies and devices, such as quantum computing and information encryption, asymmetric synthesis, 3D display, bioimaging, and chiral recognition.

[0003] Two key factors need to be considered when designing and developing CPL materials: the luminescence asymmetry factor (g) em ) and luminous efficacy (ФF). g em The main measure is the degree of polarization of the CPL, and the calculation formula is g. em = 2(IL-IR) / (IL+IR) ≈ 4cosθ|m| / |μ|, where IL and IR refer to the intensities of left-handed and right-handed polarized light, respectively; m and μ refer to the magnetic and electric dipole transition moments, respectively; θ is the angle between them; g em The value ranges from [-2, 2]. Therefore, chiral luminescent materials with magnetic dipole transition allowance and electric dipole transition forbidden properties can emit strong left- or right-hand circularly polarized light [Sanchez-Carnerero, EM; Agarrabeitia, AR; Moreno, F.; Maroto, BL; Muller, G.; Ortiz, MJ; Moya, de la S. Circularly polarized luminescence from simple organic molecules. Chem. Eur. J. 2015, 21, 13488-13500].

[0004] Existing CPL materials include chiral organometallic complexes, chiral organomolecules, chiral polymers, and chiral supramolecular molecules. While chiral organometallic complexes possess permitted magnetic dipole transitions and high gamma-ray polarization (GLP), they are still relatively limited in their application. em (~10 -1 However, their low ФF limits their practical applications, such as chiral lanthanide metal complexes. While chiral small organic molecules possess good ФF, the magnetic dipole transition restriction inherent in their structure leads to limited gamma. em The value is usually in the range of 10.-5 ~10 -3 Within the scope [Han, J.; Guo, S.; Lu, H.; Liu, S.; Zhao, Q.; Huang, W. Recent progress on circularly polarized luminescentmaterials for organic optoelectronic devices. Adv. Optical Mater. 2018, 6,1800538].

[0005] Compared to chiral organic small molecules, chiral polymers possess a more ordered helical structure and film-forming properties, with multiple small molecules arranged in a regular helical pattern, which is beneficial for enhancing their luminescence properties and polarization degree [Li, SY; Xu, L.; Gao, RT; Chen, Z.; Liu, N.; Wu, ZQ Advances in circularly polarized luminescence materials based on helical polymers. J. Mater. Chem. C 2023, 11, 1242-1250]. However, research on chiral polymer CPL materials has mainly focused on side-chain polymers, while research on main-chain conjugated chiral polymers is relatively limited. Summary of the Invention

[0006] This invention aims to reveal a new and feasible route and method for preparing chiral binaphthyl polymers with different main chain conformations, thereby proposing a circularly polarized chiral organic fluorescent luminescent material and its preparation method and application. The product exhibits tunable photophysical properties in testing, and has certain circular dichroism and circularly polarized luminescence properties, thus expanding its application potential in chiral optoelectronic devices, solid-state displays and lighting.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] First, this invention proposes a circularly polarized chiral organic fluorescent luminescent material, the structural formula of which is shown as R / S-P1, R / S-P2, or R / S-P3 in the following formula:

[0009]

[0010] In the formula, R / S represents the R or S configuration.

[0011] Secondly, this invention also proposes a method for preparing this circularly polarized chiral organic fluorescent luminescent material:

[0012] First, the chiral binaphthyl compound R / S-2 is prepared via step a:

[0013] Step a: Compound 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2 was prepared by dissolving binaphthol R / S-1 in diiodomethane and reacting it with n-butyllithium, wherein the molar ratio of binaphthol, diiodomethane, and n-butyllithium was 0.5~1.5∶0.5~1.5∶2~4;

[0014] Secondly, using the chiral binaphthyl compound R / S-2 as a chiral monomer and a fluorenyl chromophore with single, double, and triple bonds as a monomer, three intrinsically chiral polymer functional fluorescent materials R / S-P1, R / S-P2, and R / S-P3 with different conjugated backbone conformations were prepared via Suzuki, Heck, and Sonogashira coupling polymerization reactions. The preparation steps are given in steps b, c, and e, respectively.

[0015] Step b: A poly(2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthylidine[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-2, 9,9-dioctylfluorene-2,7-bis(pinacolyl borate) M1, potassium carbonate, and methyltrioctylammonium chloride were prepared by reacting the compounds 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-P1 with single bonds through phenylboronic acid and bromobenzene end-capping treatment. The molar ratio of R / S-2, M1, potassium carbonate, methyltrioctylammonium chloride, and tetra(triphenylphosphine)palladium was 0.5~1.5∶0.5~1.5∶5~15∶0.05~0.15∶0.05~0.15.

[0016] Step c: Compounds 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-2, 9,9-dioctyl-2,7-divinyl-9H-fluorene M2, and potassium carbonate are dissolved in an organic solvent and reacted under the catalysis of tetra(triphenylphosphine)palladium and palladium acetate. The reaction is then followed by end-capping with bromobenzene and styrene to prepare vinyl-containing poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-P2, wherein the molar ratio of R / S-2, M2, potassium carbonate, tetra(triphenylphosphine)palladium, and palladium acetate is 0.5~1.5∶0.5~1.5∶5~15∶0.5~1∶0.05~0.15;

[0017] Step d: The compound 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2, 2,7-diethynyl-9,9-dioctyl-9H-fluorene M3, and cuprous iodide were reacted under the catalysis of tetra(triphenylphosphine)palladium, and the reaction was followed by end-capping with bromobenzene and phenylacetylene to prepare poly(2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-P3 containing triple bonds. The molar ratio of R / S-2, M3, cuprous iodide, and tetra(triphenylphosphine)palladium was 0.5~1.5∶0.5~1.5∶0.05~0.15∶0.05~0.15.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] (1) The present invention prepared three chiral polymers with different main chain conformations. Among them, poly-2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxane (R / S-P1) with single bond as linker can achieve more effective intramolecular chiral transfer between its chiral source naphthalene moiety and fluorenyl luminescent group. After testing, it not only has ground state circular dichroism but also circular polarization luminescence properties.

[0020] (2) The preparation route proposed in this invention is mainly a coupling polymerization reaction. During the preparation process, an oxygen-free environment should be maintained as much as possible. In addition, end-capping treatment should be performed before the reaction ends to suppress any active groups that may exist at the polymer ends and eliminate interference with its photophysical properties and chiral luminescence properties.

[0021] (3) This invention proposes a new and feasible route and method for preparing intrinsic chiral polymers. The prepared products exhibit controllable photophysical properties in the test, and have certain circular dichroism and circular polarization emission properties, indicating that they are expected to be applied in fields such as chiral solid-state display materials and optoelectronic devices. Attached Figure Description

[0022] Figure 1 This is the chiral monomeric small molecule 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene (R / S-2) prepared in Example 1. 1 H NMR spectrum.

[0023] Figure 2 This is the chiral monomeric small molecule 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene (R / S-2) prepared in Example 1. 13 C NMR spectrum.

[0024] Figure 3 It is the chiral backbone polymer poly(2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P1) prepared in Example 1. 1 H NMR spectrum.

[0025] Figure 4 It is the chiral backbone polymer poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinadiazine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P2) prepared in Example 1. 1 H NMR spectrum.

[0026] Figure 5 It is the chiral main-chain polymer 2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinadiazine [2,1-d:1',2'-f][1,3]dioxolane (R / S-P3) prepared in Example 1. 1 H NMR spectrum.

[0027] Figure 6 The images show the thin-film UV absorption (a) and fluorescence emission spectra (b) of the three chiral main-chain polymers prepared in Example 1.

[0028] Figure 7 These are the circular dichroism and circular polarization spectra of the three chiral main-chain polymer thin films prepared in Example 1. Figure 7 (a) and (d) correspond to the circular dichroism spectrum and circular polarization spectrum of R / S-P1, respectively. Figure 7 (b) and (e) correspond to the circular dichroism spectrum and circular polarization spectrum of R / S-P2, respectively. Figure 7 (c) and (f) correspond to the circular dichroism spectrum and circular polarization spectrum of R / S-P3, respectively. Detailed Implementation

[0029] This invention uses the prepared chiral binaphthalene compound 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenylene (R / S-2) as a chiral monomer, and fluorenyl chromophores having single, double, and triple bonds as monomers, respectively, to prepare three intrinsically chiral polymer functional luminescent dyes with different conjugated backbone conformations via Suzuki, Heck, and Sonogashira coupling polymerization reactions: poly(2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)binaphthidine[2,1-d:1',2'-f][1,3]dioxopentenylene (R / S-2). The photophysical properties and chiral luminescence properties of poly(2'-f][1,3]dioxolane (R / S-P1), poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P2), and poly(2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P3) in thin film state were investigated.

[0030] The present invention will be further described in detail below with reference to the embodiments and accompanying drawings.

[0031] Example 1

[0032] The preparation route for circularly polarized chiral organic fluorescent luminescent materials is as follows:

[0033]

[0034] The specific preparation steps are as follows:

[0035] Step a, Preparation of 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene (R / S-2):

[0036] Add 1.2 g (4.2 mmol) of naphthol (R / S-1, Shanghai Bied Pharmaceutical Technology Co., Ltd.), 0.34 mL (4.2 mmol) of diiodomethane, 1.73 g (12.56 mmol) of anhydrous potassium carbonate, and 40 mL of acetonitrile to a 50 mL reaction flask. Heat the reaction system to 80 °C and maintain the temperature for 12 h.

[0037] The reaction was monitored by TLC. After the reaction was completed, the mixture was cooled to room temperature and then water (60 mL) was added to the reaction system for dilution. A large amount of pale yellow solid precipitated out. The solid was filtered and the filter cake was dried in a vacuum drying oven to obtain 1.26 g of pale yellow solid.

[0038] Weigh out the pale yellow solid (1.0 g, 3.35 mmol), add an appropriate amount of anhydrous diethyl ether, and add n-butyllithium (5.16 mL, 13.41 mmol) dropwise to the reaction system under ice bath conditions. After the addition is complete, heat the reaction system to room temperature and react for 2 h. Then, cool the reaction system to -20 °C again, and slowly add elemental iodine (2.5 g) to the reaction system. After the addition is complete, slowly heat the reaction system to room temperature and continue the reaction for 12 h.

[0039] After the reaction was completed, sodium bisulfite solution was added to the reaction system, and the mixture was separated. The organic phase was washed with water, and the organic phases were combined and the reaction solvent was evaporated to obtain the crude product. The crude product was purified by column chromatography (eluent: petroleum ether / ethyl acetate = 80 / 1, v / v) to finally obtain a white solid, namely 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentene (R / S-2), with a yield of 53%.

[0040] R / S-2 1 H NMR spectrum ( Figure 1 (As shown) Data: 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.50(s, 2H), 7.83 (d, J = 8.4 Hz, 2H), 7.47-7.43 (m, 2H), 7.40 (d, J = 8.8 Hz,2H), 7.32-7.28 (m, 2H), 5.67 (s, 2H).

[0041] R / S-2 13 C NMR spectrum ( Figure 2 (As shown) Data: 13 C NMR (101 MHz, CDCl3) δ 149.57,139.67, 133.07, 131.82, 127.37, 126.82, 126.74, 126.53, 125.97, 102.02,89.91.

[0042] Step b, preparation of poly-2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthidine [2,1-d:1',2'-f][1,3]dioxolane (R / S-P1):

[0043] 9,9-Dioctylfluorene-2,7-bis(pinacol borate) (M1) (192.8 mg, 0.3 mmol), 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene (R / S-2) (165 mg, 0.3 mmol), potassium carbonate (414 mg, 3 mmol), methyltrioctylammonium chloride (10 mol%, 0.03 mmol, 12.1 mg), and tetrakis(triphenylphosphine)palladium (10 mol%, 0.03 mmol, 35 mg) were sequentially added to a reaction flask containing a mixed solvent of 10 mL toluene and 2 mL water. The reaction was carried out under a nitrogen atmosphere. The resulting mixture was stirred at 85 °C for 72 h.

[0044] The end-capping reaction was carried out by sequentially adding phenylboronic acid (3.7 mg, 0.03 mmol) and bromobenzene (4.7 mg, 0.03 mmol) (85 °C, 6 h). After the reaction was completed, the mixture was cooled to room temperature, poured into 50 mL of water, and extracted with ethyl acetate (30 mL each time, 3 times). The organic layers were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under vacuum to obtain the crude product.

[0045] The crude product was dissolved in 2 mL of dichloromethane, and then added dropwise to 100 mL of acetone under magnetic stirring to precipitate the polymer. After standing for 1 h, the polymer was collected by filtration, washed several times with acetone, and finally dried under vacuum to obtain a white solid, namely poly(2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P1), with a yield of 62%.

[0046] GPC: Mw = 15984, Mn = 8475, PDI = 1.88.

[0047] R / S-P1 1 H NMR spectrum ( Figure 3 (As shown) Data: 1H NMR (400 MHz, CDCl3) δ (ppm): 8.16-8.12 (m, 2H), 8.09-8.00 (m, 2H), 7.79-7.74 (m, 2H), 7.70-7.68 (m, 2H), 7.65-7.60 (m, 4H), 7.54-7.46 (m, 2H), 7.40-7.33 (m, 2H), 5.17 (s, 2H), 2.03-1.86(m, 4H), 1.11-0.94 (m, 20H), 0.79-0.69 (m, 4H), 0.67 (t, J = 7.1 Hz, 6H).

[0048] Step c, Preparation of poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P2):

[0049] 9,9-Dioctyl-2,7-divinyl-9H-fluorene (M2) (132.8 mg, 0.3 mmol), 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene (R / S-2) (165 mg, 0.3 mmol), potassium carbonate (414 mg, 3 mmol), tetrakis(triphenylphosphine)palladium (56.65 mg, 0.216 mmol), and palladium acetate (10 mol%, 0.03 mmol, 6.8 mg) were sequentially dissolved in 10 mL of DMF. The reaction was carried out under a nitrogen atmosphere. The mixture was stirred at 120 °C for 72 h.

[0050] Bromobenzene (4.7 mg, 0.03 mmol) and styrene (3.1 mg, 0.03 mmol) were added sequentially for end-capping reaction (85 °C, 6 h). After the reaction solution cooled to room temperature, it was filtered through diatomaceous earth, and the filtrate was collected and concentrated under vacuum to obtain the crude product.

[0051] The crude product was dissolved in 2 mL of dichloromethane, and then added dropwise to 100 mL of acetone under magnetic stirring to precipitate the polymer. After standing for 1 h, the polymer was collected by filtration, washed several times with acetone, and finally dried under vacuum to obtain a light yellow solid product, namely poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P2), with a yield of 54%.

[0052] GPC: Mw = 9015, Mn = 5562, PDI = 1.62.

[0053] R / S-P2 1 H NMR spectrum ( Figure 4 (As shown) Data: 1 H NMR (400 MHz, CDCl3) δ (ppm): 8.34-7.93 (m, 4H), 7.73-7.63 (m, 4H), 7.60-7.54 (m, 4H), 7.50-7.4 (m, 4H), 7.36-7.29 (m,2H), 6.85-6.76 (m, 1H), 5.83-5.73 (m, 2H), 5.28-5.24 (m, 1H), 2.06-1.93 (m, 4H), 1.25-1.05 (m, 20H), 0.83-0.66 (m, 10H).

[0054] Step d, preparation of poly-2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P3):

[0055] Under a nitrogen atmosphere, 2,7-diethynyl-9,9-dioctyl-9H-fluorene (M3) (131.6 mg, 0.3 mmol), 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene (R / S-2) (165 mg, 0.3 mmol), cuprous iodide (10 mol%, 0.03 mmol, 5.7 mg), tetrakis(triphenylphosphine)palladium (10 mol%, 0.03 mmol, 35 mg), and tetrahydrofuran (10 mL) were added to a 100 mL Shrek flask. Triethylamine (5 mL) was then added dropwise to the solution, and the solution was heated to 70 °C and stirred for 72 h.

[0056] After the reaction was complete, bromobenzene (4.7 mg, 0.03 mmol) and phenylacetylene (3.0 mg, 0.03 mmol) were added sequentially for end-capping treatment (85℃, 6 h). After the reaction was completed, the mixture was filtered through diatomaceous earth, and the filtrate was collected and concentrated under vacuum to obtain the crude product.

[0057] The crude product was dissolved in 2 mL of dichloromethane, and then added dropwise to 100 mL of acetone under magnetic stirring to precipitate the polymer. After standing for 1 h, the polymer was collected by filtration, washed several times with acetone, and finally dried under vacuum to obtain a light yellow solid, namely poly(2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P3), with a yield of 65%.

[0058] GPC: Mw = 10628, Mn = 6770, PDI = 1.57.

[0059] R / S-P3 1 H NMR spectrum ( Figure 5 Data (shown): 1H NMR (400 MHz, CDCl3) δ (ppm): 8.30 (s, 2H), 7.96–7.92 (m, 2H), 7.73–7.68 (m, 2H), 7.61–7.58 (m, 4H), 7.52–7.47 (m, 4H), 7.36–7.30 (m, 2H), 5.99 (s, 2H), 2.05–2.00 (m, 4H), 1.22–1.07 (m, 20H), 0.81–0.78 (m, 6H), 0.67–0.63 (m, 4H).

[0060] Example 2

[0061] Taking the three chiral main-chain polymers prepared in Example 1—poly(2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P1), poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P2), and 2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane (R / S-P3)—as examples, their applications in photophysical properties and circularly polarized luminescence were studied. The three chiral main-chain polymers were all represented by abbreviations.

[0062] To investigate the photophysical properties of the three chiral backbone polymers, polymers with the R configuration were selected, and their UV absorption and fluorescence emission spectra in thin films were tested. For example... Figure 6As shown, R-P1, R-P2, and R-P3 all exhibit high-energy absorption bands below 300 nm, which is attributed to the binaphthyl framework. Compared to R-P1, the maximum absorption wavelengths of R-P2 and R-P3 are red-shifted to 373 nm and 357 nm, respectively. Figure 6 (a) shows the maximum fluorescence emission peaks of R-P1, R-P2, and R-P3, respectively, at 404 nm, 465 nm, and 454 nm. Figure 6 (b) shows. Notably, compared to R-P1, the fluorescence emission of R-P2 and R-P3 exhibits a significant redshift, with shifts as high as 61 nm and 50 nm, respectively, indicating that the n-π* conjugation along the chiral polymer backbone is more effective. These results demonstrate that different linkage modes of chiral backbone polymers can significantly affect their photophysical properties.

[0063] To verify the chiral luminescence properties regulated by the main chain structure of the chiral polymers, the ground-state and excited-state properties of three chiral polymers in thin film were measured using circular dichroism (CD) spectroscopy and CPL spectroscopy. Figure 7 As shown, in the spin-coated films, all three polymer enantiomers exhibited distinct mirror-image CD signals, with alternating positive and negative Cotton effects in the 200 nm to 400 nm range. Notably, R / S-P1 showed a stronger CD signal compared to R / S-P2 and R / S-P3. Figure 7 (a), 7(b), and 7(c) are shown). Further CPL testing was then conducted, and the results showed that the chiral polymer R / S-P1 with single-bond linkers exhibited a significant CPL signal |g em | ≈ 0.001, while the chiral polymers R / S-P2 and R / S-P3, which use double and triple bonds as linkers, both showed silent CPL signals ( Figure 7 (d), 7(e), 7(f)) show that chiral polymers polymerized by single bond linkage are more conducive to achieving intramolecular chiral transfer.

[0064] Therefore, the above results all indicate that the photophysical properties and chiral luminescence properties of chiral polymers can be regulated by the main chain linker mechanism.

Claims

1. A circularly polarized chiral organic fluorescent luminescent material, characterized in that, Its structural formula is shown in the following formula as R / S-P1, R / S-P2 or R / S-P3: In the formula, R / S represents the R or S configuration.

2. The method for preparing the circularly polarized chiral organic fluorescent luminescent material as described in claim 1, characterized in that, The preparation route is as follows: The specific preparation method steps are as follows: First, the chiral binaphthyl compound R / S-2 is prepared via step a: Step a: Compound 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2 was prepared by dissolving binaphthol R / S-1 in diiodomethane and reacting it with n-butyllithium, wherein the molar ratio of binaphthol, diiodomethane, and n-butyllithium was 0.5~1.5∶0.5~1.5∶2~4; Secondly, using the chiral binaphthyl compound R / S-2 as a chiral monomer and a fluorenyl chromophore with single, double, and triple bonds as a monomer, three intrinsically chiral polymer functional fluorescent materials R / S-P1, R / S-P2, and R / S-P3 with different conjugated backbone conformations were prepared via Suzuki, Heck, and Sonogashira coupling polymerization reactions. The preparation steps are given in steps b, c, and e, respectively. Step b: A poly(2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthylidine[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-2, 9,9-dioctylfluorene-2,7-bis(pinacolyl borate) M1, potassium carbonate, and methyltrioctylammonium chloride were prepared by reacting the compounds 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-P1 with single bonds through phenylboronic acid and bromobenzene end-capping treatment. The molar ratio of R / S-2, M1, potassium carbonate, methyltrioctylammonium chloride, and tetra(triphenylphosphine)palladium was 0.5~1.5∶0.5~1.5∶5~15∶0.05~0.15∶0.05~0.

15. Step c: Compounds 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-2, 9,9-dioctyl-2,7-divinyl-9H-fluorene M2, and potassium carbonate are dissolved in an organic solvent and reacted under the catalysis of tetra(triphenylphosphine)palladium and palladium acetate. The reaction is then followed by end-capping with bromobenzene and styrene to prepare vinyl-containing poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-P2, wherein the molar ratio of R / S-2, M2, potassium carbonate, tetra(triphenylphosphine)palladium, and palladium acetate is 0.5~1.5∶0.5~1.5∶5~15∶0.5~1∶0.05~0.15; Step d: The compound 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2, 2,7-diethynyl-9,9-dioctyl-9H-fluorene M3, and cuprous iodide were reacted under the catalysis of tetra(triphenylphosphine)palladium, and the reaction was followed by end-capping with bromobenzene and phenylacetylene to prepare poly(2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxopentenylene R / S-P3 containing triple bonds. The molar ratio of R / S-2, M3, cuprous iodide, and tetra(triphenylphosphine)palladium was 0.5~1.5∶0.5~1.5∶0.05~0.15∶0.05~0.

15.

3. The preparation method according to claim 2, characterized in that, Step a specifically involves: adding 4.2 mmol of naphthol R / S-1, 4.2 mmol of diiodomethane, 12.56 mmol of anhydrous potassium carbonate, and 40 mL of acetonitrile to a reaction vessel; heating the reaction system to 80 °C and maintaining the temperature for 12 h; cooling to room temperature after the reaction, then adding water to dilute the reaction system to precipitate the product, filtering and drying to obtain a pale yellow solid; weighing 1.0 g of the pale yellow solid and adding an appropriate amount of anhydrous diethyl ether, and adding 13.41 mmol of n-butyllithium dropwise to the reaction system under ice bath conditions; after the addition is complete, heating the reaction system to room temperature and reacting for 2 h; then cooling the reaction system to -20 °C again, and then slowly adding 2.5 g of elemental iodine to the reaction system; after the addition is complete, slowly heating the reaction system to room temperature and continuing the reaction for 12 h. h; After the reaction was completed, the final white solid obtained after purification was 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2.

4. The preparation method according to claim 2, characterized in that, Step b specifically involves: adding 0.3 mmol of 9,9-dioctylfluorene-2,7-bis(pinacol borate)M1, 0.3 mmol of 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2, 3 mmol of potassium carbonate, 0.03 mmol of methyltrioctylammonium chloride, and 0.03 mmol of tetra(triphenylphosphine)palladium sequentially to a reaction vessel containing a mixed solvent of toluene and water. The reaction is carried out under a nitrogen atmosphere, and the resulting mixture is stirred at 85 °C for 72 h. Then, 0.03 mmol of phenylboronic acid and 0.03 mmol of bromobenzene are added sequentially, and an end-capping reaction is carried out at 85 °C for 6 hours. h; The reaction product was purified and precipitated with acetone to finally obtain a white solid, namely poly(2-methyl-6-(7-methyl-9,9-dioctyl-9H-furan-2-yl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane R / S-P1.

5. The preparation method according to claim 2, characterized in that, Step c specifically involves dissolving 0.3 mmol of 9,9-dioctyl-2,7-divinyl-9H-fluorene M2, 0.3 mmol of 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2, 3 mmol of potassium carbonate, 0.216 mmol of tetrakis(triphenylphosphine)palladium, and 0.03 mmol of palladium acetate sequentially in DMF. The reaction system is carried out under a nitrogen atmosphere, and the mixture is stirred at 120 °C for 72 h. Then, 0.03 mmol of bromobenzene and 0.03 mmol of styrene are added sequentially, and an end-capping reaction is carried out at 85 °C for 6 hours. h; The reaction product was purified and precipitated with acetone to finally obtain a light yellow solid product, namely poly(2-methyl-6-(2-(7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane R / S-P2.

6. The preparation method according to claim 2, characterized in that, Step d specifically involves: under a nitrogen atmosphere, adding 0.3 mmol of 2,7-diethynyl-9,9-dioctyl-9H-fluorene M3, 0.3 mmol of 2,6-diiododibenzo[2,1-d:1',2'-f][1,3]dioxopentenene R / S-2, 0.03 mmol of cuprous iodide, 0.03 mmol of tetra(triphenylphosphine)palladium, and 10 mL of tetrahydrofuran to the reaction vessel; then adding 5 mL of triethylamine dropwise to the above solution, heating the solution to 70 °C and stirring for 72 h; then, adding 0.03 mmol of bromobenzene and 0.03 mmol of phenylacetylene sequentially, and carrying out the end-capping reaction at 85 °C for 6 hours. h; The reaction product was purified and precipitated with acetone to finally obtain a light yellow solid, namely poly(2-methyl-6-((7-methyl-9,9-dioctyl-9H-furan-2-yl)vinyl)dinaphthidine[2,1-d:1',2'-f][1,3]dioxolane R / S-P3.

7. The application of the circularly polarized chiral organic fluorescent luminescent material as described in claim 1 in chiral solid-state display materials and optoelectronic devices.

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