Circularly polarized luminescent complex material and application thereof

Abstract

The application discloses a circularly polarized luminescent complex material, which comprises a compound represented by the following formula: wherein M is platinum or palladium; A, B, C and D are each independently selected from nitrogen or a carbene carbon atom; ring L1, ring L2, ring L3 and ring L4 are each independently selected from a polyaromatic ring, an aromatic heterocycle, an aromatic ring or an aromatic heterocycle with one or more substituents. The application also discloses applications of the circularly polarized luminescent complex material. The circularly polarized luminescent complex material has the characteristics of wide chiral source, high asymmetric factor, good luminescent performance and good thermal stability, and is not related to the material itself, and can drive the helical chirality, axial chirality and planar chirality circularly polarized luminescent material. Different types of ligands are designed to construct different helical chirality, axial chirality and planar chirality circularly polarized complexes, which can be used as different applications.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of organic light-emitting materials, and particularly relates to a circularly polarized luminescence complex material and application thereof. BACKGROUND

[0002] In recent years, chiral optical functional materials with circularly polarized luminescence (CPL) have attracted more and more attention due to their wide potential applications in three-dimensional optical display, information encryption transmission and storage, biological coding, optoelectronic devices, etc. In the development of CPL materials, a key problem is to obtain a high luminescence asymmetry factor (g lum ) value. In order to quantify CPL, the formula g lum = 2 x (I L -I R ) / (I L + I R ) is usually used for calculation, wherein I L and I R are the left / right circularly polarized light emission intensities. The maximum value of |g lum | is 2, which represents complete left or right circularly polarized light. Although the highest g lum currently comes from chiral lanthanide metal complexes, however, these materials exhibit very small luminescent efficiency in some aspects such as electroluminescent devices, therefore, scientists gradually put their research interest into developing transition metal complexes and small organic molecules with CPL activity.

[0003] Generally, the design strategy of new circularly polarized luminescence materials mainly introduces a chiral unit into a chromophore through a covalent bond or a coordination bond, and then realizes circularly polarized luminescence through chiral transmission. However, most of the chiral molecules constructed by this strategy exhibit weak CPL signals, and the types of chiral sources are limited. In order to improve the CPL signal, some researchers have proved that the |g lum | value of a perylene-bisimide system can be improved from 0.003 to 0.008 by using supramolecular self-assembly. Although this strategy can effectively improve the CPL signal, under general conditions, not only is it difficult to select the materials for self-assembly, but also the self-assembly process is relatively harsh, and it is usually necessary to accurately control the proportion between the phases, as well as the required solvents, concentration, temperature and other external conditions, and it is not suitable for the preparation of OLED devices. SUMMARY

[0004] Therefore, the technical problem to be solved by the present application is that the types of chiral sources are limited and the racemization barrier is low in the prior art, so as to provide a circularly polarized luminescence complex material and application thereof.

[0005] To this end, the present application adopts the following technical solutions:

[0006] The present application provides a circularly polarized luminescent complex material, which comprises a compound represented by Formula I:

[0007]

[0008] wherein M is platinum or palladium;

[0009] A, B, C and D are each independently selected from nitrogen or a carbene carbon atom;

[0010] Ring L1, ring L2, ring L3 and ring L4 are each independently selected from a polyaromatic ring, an aromatic heterocycle, an aromatic ring or an aromatic heterocycle having one or more substituents, each of which is independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, a straight-chain alkane of C1-C30, a branched-chain alkane of C3-C30, a cycloalkyl of C3-C30, an alkoxy / alkylmercapto of C1-C30, an aryl / heteroaryl / ether / aryloxyether of C6-C60; wherein the heteroatom of the heteroaryl can be independently selected from Si, Ge, N, P, O, S, Se;

[0011] The symbol represents the position of a chiral center; one or more can exist;

[0012] The symbol represents that the adjacent ring L1, ring L2, ring L3 and ring L4 are connected to each other or exist independently, and the connection is by a chemical bond or is fused into a ring;

[0013] Ring L1, ring L2, ring L3 and ring L4 are each not chiral, or are easily racemized, are not sufficient to meet the application of chirality, or the chiral center of ring L1, ring L2, ring L3 and ring L4 is irrelevant to the chiral center constructed by the present application.

[0014] Further, the compound represented by Formula I comprises the following structure:

[0015]

[0016] wherein the bond structures X and Y are atoms or groups connecting the aromatic ring or the aromatic heterocycle, each of which is independently selected from -C-, -N-, -Si-, -S-, an aromatic ring or an aromatic heterocycle, an aromatic ring or an aromatic heterocycle having one or more substituents;

[0017] wherein each of the substituents is independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH, -NH2, straight-chain alkane of C1-C30, branched alkane of C3-C30, cycloalkyl of C3-C30, alkoxy / alkylmercapto of C1-C30, aryl / heteroaryl / ether / arylheteroether of C6-C60; wherein the heteroatom of the heteroaryl can be independently selected from Si, Ge, N, P, O, S, Se.

[0018] M and any two or more rings of L1, L2, L3, or L4 form a chiral center by coordination

[0019]

[0020] X and Y are each independently selected from the following bond structures:

[0021]

[0022] The compound represented by Formula I has a structure represented by any one of Chemical Formula 1-1 to Chemical Formula 11-39:

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049] The preparation method of the circularly polarized luminescent complex material is as follows: taking an achiral compound as a raw material, constructing a new chiral center in organic synthesis, realizing the chiral property of the molecule, specifically, anchoring the structure that can rotate freely through metal coordination, combining steric effect, making the target compound produce enantiomers, and then separating the enantiomers through chiral preparation to obtain the chiral compound, and the complex includes helical chirality, axial chirality and planar chirality.

[0050] The application also provides application of the circularly polarized luminescent complex material, which is applied to chiral drugs, chiral pesticides, chiral liquid crystal materials, chiral conductive polymer materials, chiral mesoporous materials, chiral nanomaterials and chiral electroluminescent materials.

[0051] The technical scheme of the application has the following advantages:

[0052] (1) The circularly polarized luminescent complex material has the characteristics of wide chiral source, high asymmetric factor, good luminescent performance and good thermal stability, and the chiral property is irrelevant to the material itself, and the helical chirality or axial chirality circularly polarized luminescent material is driven through coordination.

[0053] (2) The present application induces large steric hindrance to generate helical chirality, axial chirality and planar chirality through coordination, the designed ligand does not contain a chiral center, is not subject to the type of chiral raw materials, and is more free in molecular design. The designed molecule has large steric hindrance, and the molecular skeleton is entirely a conjugated structure, which is relatively rigid. The molecule cannot form a planar configuration and has a large racemization barrier due to large steric hindrance (racemization does not occur in the preparation of Examples 1-1, 1-7, 1-12, 1-14 and 1-15, which includes a sublimation operation at high temperature, indicating that the racemization barrier is large). The chiral performance is maintained under extreme conditions such as high temperature, so that the coordination cannot form a plane to generate helical chirality. At the same time, the large steric hindrance makes the complex molecule as a whole form a spatial stereoscopic configuration, which can effectively inhibit the aggregation between molecules and obtain good electroluminescent performance. BRIEF DESCRIPTION OF DRAWINGS

[0054] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the drawings needed in the specific embodiments or prior art description will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0055] Figure 1 It is the effect picture of chiral HPLC test for Example 1;

[0056] Figure 2 It is the effect picture of chiral HPLC test for Example 3;

[0057] Figure 3 It is the effect picture of chiral HPLC test for Example 4;

[0058] Figure 4 It is the effect picture of chiral HPLC test for Example 12;

[0059] Figure 5 It is the effect picture of chiral HPLC test before preparation of Example 1;

[0060] Figure 6 It is the effect picture of chiral HPLC test of peak 1 after preparation of Example 1;

[0061] Figure 7 It is the effect picture of chiral HPLC test of peak 2 after preparation of Example 1;

[0062] Figure 8 It is the circular dichroism absorption spectrum of two components after chiral resolution of Example 1;

[0063] Figure 9 It is the circular dichroism absorption spectrum of two components after chiral resolution of Example 1;

[0064] Figure 10 Figure 2 shows the asymmetric factor test chart of the two components after chiral resolution of Example 1 in dichloromethane solution;

[0065] Figure 11 Figure 3 shows the circularly polarized luminescence spectrum of the two components after chiral resolution of Example 1 in pure film state;

[0066] Figure 12 Figure 4 shows the asymmetric factor test chart of the two components after chiral resolution of Example 1 in pure film state. DETAILED DESCRIPTION

[0067] The following examples are provided to better enable those skilled in the art to further understand and practice the application, and are not intended to limit the scope of the application in any way. Any product derived from the application or from the combination of the application and other prior art features is within the scope of the application.

[0068] When the specific experimental procedures or conditions are not mentioned in the examples, the operations or conditions can be carried out according to the conventional experimental procedures described in the literature in the field.

[0069] The following specific examples are further illustrations of the application and are not intended to limit the scope of the application. The examples are provided to better enable those skilled in the art to further understand and practice the application, and are not intended to limit the scope of the application in any way. Any product derived from the application or from the combination of the application and other prior art features is within the scope of the application.

[0070] Example 1

[0071] The present example provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0072]

[0073] (1) Compound 1 (1 g, 4.69 mmol), compound 2 (734 mg, 4.69 mmol) and tetrakis triphenylphosphine palladium (228 mg) were added to a 100 mL round-bottom two-neck flask, and vacuum was applied and argon was injected repeatedly three times, and then toluene (40 mL), ethanol (10 mL) and 3.5 M potassium carbonate aqueous solution (10 mL) were sequentially injected. The reaction was carried out at 85°C for 20 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected, and the solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain 1.2 g of white solid, i.e. compound 3, with a yield of 89%. 1H NMR (400 MHz, Chloroform-d) δ 9.47 (d, J = 8.1 Hz, 1H), 8.36 (t, J = 1.9 Hz, 1H), 8.27 - 8.15 (m, 2H), 7.97 (d, J = 8.3 Hz, 1H), 7.94 - 7.88 (m, 1H), 7.84 - 7.66 (m, 4H), 7.52 - 7.41 (m, 2H).

[0074] (2) Compound 3 (1.1 g, 3.81 mmol), 3,5-di-tert-butylaniline (390 mg, 1.9 mmol), palladium acetate (40 mg), tri-tert-butylphosphonium tetrafluoroborate (230 mg), sodium tert-butoxide (1.10 g), and heavy toluene (30 mL) were added to a 100 mL round bottom flask, which was evacuated and filled with argon three times. The reaction was carried out at 130 °C for 24 hours. After cooling to room temperature, extraction was performed with dichloromethane and water, and the organic layer was collected. The organic solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 1.1 g of white product, which was compound 4, with a yield of 81%. 1 H NMR (400 MHz, Chloroform-d) δ 9.35 - 9.28 (m, 2H), 8.21 - 8.13 (m, 4H), 8.02 (dt, J = 7.7, 1.3 Hz, 2H), 7.92 (d, J = 8.4 Hz, 2H), 7.89 - 7.83 (m, 2H), 7.76 (d, J = 8.8 Hz, 2H), 7.69 - 7.59 (m, 6H), 7.47 (t, J = 7.9 Hz, 2H), 7.35 - 7.30 (m, 2H), 7.21 (dd, J = 15.6, 1.8 Hz, 3H), 7.06 (s, 1H), 1.30 (s, 18H).

[0075] (3) Compound 4 (500 mg, 0.7 mmol), potassium chloroplatinate (321 mg, 0.77 mmol), and acetic acid (40 mL) were added to a 100 mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 48 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography to obtain 330 mg of dark red product, which was the circularly polarized luminescent complex material 1-1, with a yield of 52%. 1H NMR (400 MHz, Chloroform-d) δ 9.65 (d, J = 8.3 Hz, 2H), 8.17 (d, J = 8.4 Hz, 2H), 8.03 (d, J = 8.3 Hz, 2H), 7.58 (t, J = 1.8 Hz, 1H), 7.56 (d, J = 7.4 Hz, 2H), 7.39 - 7.31 (m, 4H), 7.24 (s, 2H), 7.19 (dd, J = 8.3, 7.4 Hz, 2H), 7.12 (d, J = 8.7 Hz, 2H), 7.05 (ddd, J = 8.0, 6.9, 1.2 Hz, 2H), 6.54 (ddd, J = 8.3, 7.0, 1.3 Hz, 2H), 6.42 (d, J = 8.3 Hz, 2H), 1.40 (s, 18H).

[0076] Example 2:

[0077] The present embodiment provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0078]

[0079] (1) 5 (7 g, 20.6 mmol), 1-bromoquinoline (4.3, 20.6 mmol), and tetrakis triphenylphosphine palladium (238 mg) were added into a 100 mL round-bottom two-neck flask, vacuumed and filled with argon for three times, and then toluene (150 mL), ethanol (50 mL), and 2M potassium carbonate aqueous solution (50 mL) were sequentially injected. The reaction was carried out at 85°C for 20 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected. The solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography to obtain 5.1 g of white solid, i.e., compound 6, with a yield of 73%. 1 H NMR (400 MHz, Chloroform-d), δ (ppm): 8.18 (s, 1H), 8.16 (s, 1H), 8.11 (t, J = 1.7 Hz, 1H), 8.09 (t, J = 1.7 Hz, 1H), 7.79 (s, 1H), 7.77 (s, 1H), 7.71 (t, J = 7.7 Hz, 1H), 7.61 (t, J = 1.9 Hz, 1H), 7.50 (t, J = 7.0 Hz, 1H), 1.39 (s, 9H).

[0080] (2) Compound 6 (1.5 g, 4.4 mmol), 3,5-di-tert-butylaniline (0.45, 2.2 mmol), palladium acetate (25 mg), tri-tert-butylphosphonium tetrafluoroborate (100 mg), sodium tert-butoxide (0.43 g, 4.4 mmol) and heavy toluene (50 mL) were added to a 100 mL round bottom flask, vacuumed and purged with argon for 3 times. Reaction was carried out at 130 °C for 24 hours. After cooling to room temperature, extraction was carried out with dichloromethane and water, and the organic layer was collected. The organic solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 1.3 g of white product, compound 7, with a yield of 81%. 1 H NMR (400 MHz, Chloroform-d), d (ppm): 8.15 - 8.09 (m, 4H), 7.84 (t, J = 1.7 Hz, 2H), 7.80 - 7.75 (m, 2H), 7.73 - 7.66 (m, 6H), 7.48 (ddd, J = 8.1, 6.9, 1.2 Hz, 2H), 7.34 (t, J = 1.9 Hz, 2H), 7.08 (s, 3H), 1.35 (s, 18H), 1.26 (s, 18H). 13 C NMR (101 MHz, Chloroform-d), d (ppm): 158.16, 152.62, 151.42, 148.27, 148.18, 146.95, 140.39, 136.54, 129.76, 129.46, 127.39, 127.10, 126.08, 122.72, 120.46, 119.62, 118.82, 118.70, 116.61, 35.06, 34.96, 31.49, 31.41.

[0081] (3) Compound 7 (1 g, 1.4 mmol), potassium chloroplatinate (0.7 g, 1.7 mmol) and acetic acid (40 mL) were added to a 100 mL two-necked round bottom flask. After bubbling with argon for 30 minutes, reaction was carried out at 135 °C for 48 hours. After cooling to room temperature, filtration was carried out, and the solid was collected. The crude product was separated by column chromatography to obtain 900 mg of dark red product, circularly polarized luminescent complex material 1-7, with a yield of 70%. 1H NMR (400 MHz, DMSO-d6), d (ppm): 8.72 (d, J = 8.8 Hz, 2H), 8.58 (d, J = 8.9 Hz, 2H), 8.10 (dd, J = 8.2, 1.4 Hz, 2H), 7.83 - 7.73 (m, 4H), 7.64 (t, J = 1.8 Hz, 1H), 7.46 (t, J = 7.5 Hz, 2H), 7.17 (d, J = 1.8 Hz, 2H), 6.99 (ddd, J = 8.5, 6.8, 1.4 Hz, 2H), 6.43 (d, J = 1.6 Hz, 2H), 1.41 (s, 18H), 1.23 (s, 18H). MALDI-MS (m / z) calcd for C 52 H 55 N3Pt·[M] + :917.11.Found:917.37.Analy.Calcl.for C 52 H 55 N3Pt·H2O:C,66.79;H;6.14;N,4.49;found:C,67.12,H,6.77,N,4.46.

[0082] Example 3:

[0083] The present example provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0084]

[0085] (1) Compound 8 (5.15 g, 42.2 mmol), compound 9 (10 g, 42.2 mmol) and tetraphenylphosphonium palladium (500 mg, 0.43 mmol) were added into a 500 mL round-bottom flask, and then toluene (60 mL), ethanol (20 mL) and 2M potassium carbonate aqueous solution (20 mL) were sequentially injected, and the vacuum was repeatedly filled with argon for three times. The reaction was carried out at 85°C for 12 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected, and the solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain 9.3 g of yellow oily product, i.e. compound 10, with a yield of 95%. 1 H NMR (500 MHz, Chloroform-d) δ 8.11 (d, J = 8.5 Hz, 1H), 7.58 - 7.55 (m, 2H), 7.48 (t, J = 7.7 Hz, 3H), 7.44 (d, J = 8.5 Hz, 1H).

[0086] (2) Compound 10 (9.0 g, 38.5 mmol) and triphenylphosphine (50.4 g, 192.3 mmol) were added to a 250 mL round-bottom flask, vacuumed and filled with argon three times, and then o-dichlorobenzene (100 ml) was injected. The reaction was performed at 85°C for 12 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain 3.5 g of a yellowish powder, which was compound 11, at a yield of 46%. 1 H NMR (400 MHz, Chloroform-d) δ 8.36 (dd, J = 7.9, 1.0 Hz, 1H), 8.20 (s, 1H), 7.70 (d, J = 8.5 Hz, 1H), 7.54 (ddd, J = 8.2, 7.0, 1.2 Hz, 1H), 7.47 (dt, J = 8.2, 1.0 Hz, 1H), 7.36 - 7.34 (m, 1H), 7.34 - 7.32 (m, 1H).

[0087] (3) Compound 11 (3.5 g, 17.3 mmol), iodobenzene (5.3 g, 26 mmol), cuprous iodide (986 mg, 5.2 mmol), L-trans-1,2-cyclohexanediamine (591 mg, 5.2 mmol), potassium phosphate (7.33 g, 34.6 mmol) were added to a 250 mL round-bottom flask, vacuumed and filled with argon three times, and then 1,4-dioxane (100 ml) was injected. The reaction was performed at 110°C for 12 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain 3.8 g of a white powder, which was compound 12, at a yield of 80%. 1 H NMR (400 MHz, Chloroform-d) δ 8.36 (dd, J = 7.9, 1.0 Hz, 1H), 8.20 (s, 1H), 7.70 (d, J = 8.5 Hz, 1H), 7.54 (ddd, J = 8.2, 7.0, 1.2 Hz, 1H), 7.47 (dt, J = 8.2, 1.0 Hz, 1H), 7.36 - 7.34 (m, 1H), 7.34 - 7.32 (m, 1H).

[0088] (4) Compound 12 (1.2 g, 4.3 mmol), m-bromophenylboronic acid (673.4 mg, 4.3 mmol), and tetrakis(triphenylphosphine)palladium (250 mg, 0.2 mmol) were added to a 100 mL round-bottom flask, and then toluene (26 mL), ethanol (9 mL), and 2 M aqueous potassium carbonate solution (9 mL) were sequentially injected, vacuumed and filled with argon three times. The reaction was performed at 85°C for 12 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain 1.2 g of a white powder, which was compound 13, at a yield of 85%.1 H NMR (400 MHz, Chloroform-d) δ 8.56 (d, J = 7.8 Hz, 1H), 8.20 (t, J = 1.8 Hz, 1H), 8.03 (dt, J = 7.7, 1.4 Hz, 1H), 7.76 (s, 2H), 7.65 (t, J = 7.7 Hz, 2H), 7.60 - 7.55 (m, 2H), 7.54 - 7.50 (m, 2H), 7.48 (d, J = 8.2 Hz, 1H), 7.46 - 7.41 (m, 1H), 7.38 (tt, J = 8.0, 1.4 Hz, 2H).

[0089] (5) Compound 13 (1.5 g, 4.2 mmol), 3,5-di-tert-butylaniline (432 g, 2.1 mmol), tris(dibenzylideneacetone)dipalladium (311 mg, 0.34 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxy-biphenyl (317 mg, 0.68 mmol), sodium tert-butoxide (979 mg, 10.2 mmol) were added to a 100 mL round bottom flask, and after vacuum-pumping and argon bubbling were repeated three times, toluene (60 mL) was added. After reacting at 110°C for 12 hours, the crude product was extracted with ethyl acetate and water after cooling to room temperature, and the organic layer was collected. The organic layer was washed with water three times, and the organic layer was collected, and the organic solvent was removed by distillation under reduced pressure. The crude product was separated and purified by column chromatography to obtain 1.4 g of a yellow solid product, which was compound 14, with a yield of 77.9%. 1 H NMR (400 MHz, Chloroform-d) δ 8.47 (d, J = 7.8 Hz, 2H), 7.94 (t, J = 2.0 Hz, 2H), 7.84 (dt, J = 7.8, 1.2 Hz, 2H), 7.69 - 7.64 (m, 4H), 7.6 - 7.58 (m, 4H), 7.56 - 7.53 (m, 4H), 7.47 (tt, J = 6.9, 1.5 Hz, 6H), 7.41 (t, J = 7.9 Hz, 2H), 7.33 (ddd, J = 8.0, 6.4, 1.7 Hz, 2H), 7.19 (ddd, J = 8.0, 2.3, 1.0 Hz, 2H), 7.15 - 7.12 (m, 3H), 1.28 (s, 18H).

[0090] (6) Compound 14 (1 g, 1.4 mmol), potassium chloroplatinate (664 mg, 1.6 mmol), and acetic acid (40 mL) were added to a 100 mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was performed at 135°C for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated and purified by column chromatography to obtain 840 mg of a red solid, which was the circularly polarized luminescent complex material 1-12, with a yield of 68%. 1H NMR (400 MHz, Chloroform-d) δ 8.03 (d, J = 8.8 Hz, 2H), 7.84 (d, J = 7.9 Hz, 2H), 7.74 (d, J = 8.6 Hz, 2H), 7.61 (t, J = 7.8 Hz, 4H), 7.55 (t, J = 1.8 Hz, 1H), 7.51 - 7.46 (m, 2H), 7.43 (d, J = 7.4 Hz, 2H), 7.37 - 7.32 (m, 4H), 7.30 (d, J = 1.8 Hz, 2H), 7.09 (dd, J = 8.4, 7.4 Hz, 2H), 7.03 (ddd, J = 8.4, 7.1, 1.3 Hz, 2H), 6.86 (d, J = 8.3 Hz, 2H), 6.36 - 6.29 (m, 4H), 1.38 (s, 18H).

[0091] Example 4

[0092] The present example provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0093]

[0094] (1) Compound 15 (2.5 g, 12 mmol), compound 16 (2.4 g, 12 mmol) and tetraphenylphosphonium palladium (300 mg, 0.26 mmol) were added to a 500 mL round-bottom two-neck flask, vacuumed and filled with argon for three times, and then toluene (72 mL), ethanol (24 mL) and 2M potassium carbonate aqueous solution (24 mL) were sequentially injected. The reaction was carried out at 85°C for 12 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected. The solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain 2.0 g of white powder product, i.e. compound 17, with a yield of 84%. 1 H NMR (500 MHz, Chloroform-d) δ 8.36 (t, J = 1.9 Hz, 1H), 8.25 (d, J = 8.6 Hz, 1H), 8.17 (d, J = 8.5 Hz, 1H), 8.08 (dt, J = 7.7, 1.3 Hz, 1H), 7.85 (d, J = 3.3 Hz, 1H), 7.84 (d, J = 1.6 Hz, 1H), 7.75 (ddd, J = 8.4, 6.8, 1.5 Hz, 1H), 7.59 (ddd, J = 7.9, 2.1, 1.0 Hz, 1H), 7.55 (ddd, J = 8.1, 6.9, 1.2 Hz, 1H), 7.40 (t, J = 7.9 Hz, 1H).

[0095] (2) Compound 17 (1.5 g, 5.3 mmol), 3,5-di-tert-butylaniline (1.1 g, 5.3 mmol), palladium acetate (120 mg, 0.53 mmol), tri-tert-butylphosphine tetrafluoroborate (307.4 mg, 1.0 mmol), potassium tert-butoxide (1.5 g, 16 mmol) were added to a 100 mL round bottom flask, which was vacuumed and purged with argon three times, and then toluene (60 mL) was added. The reaction was carried out at 110°C for 12 hours, and after cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water three times, and the organic layer was collected, and the organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography to obtain 2.0 g of yellow-brown solid product, which was compound 18, with a yield of 92%. 1 H NMR (600 MHz, Chloroform-d) δ 8.20 (d, J = 8.6 Hz, 1H), 8.14 (d, J = 8.5 Hz, 1H), 7.98 (s, 1H), 7.84 (dd, J = 19.5, 8.3 Hz, 2H), 7.73 - 7.69 (m, 1H), 7.63 (d, J = 7.3 Hz, 1H), 7.52 (t, J = 7.4 Hz, 1H), 7.40 (t, J = 7.8 Hz, 1H), 7.14 (dd, J = 8.0, 2.5 Hz, 1H), 7.07 (s, 3H), 5.90 (s, 1H), 1.35 (s, 18H).

[0096] (3) Compound 19 (1.2 g, 3.4 mmol), compound 18 (1.4 g, 3.4 mmol), tris(dibenzylideneacetone)dipalladium (311 mg, 0.34 mmol), 2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl (317 mg, 0.68 mmol), sodium tert-butoxide (979 mg, 10.2 mmol) were added to a 100 mL round bottom flask, which was vacuumed and purged with argon three times, and then toluene (60 mL) was added. The reaction was carried out at 110°C for 12 hours, and after cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water three times, and the organic layer was collected, and the organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography to obtain 1.9 g of yellow solid product, which was compound 20, with a yield of 77.7%. 1H NMR (400 MHz, Chloroform-d) δ 8.47 (d, J = 7.9 Hz, 1H), 8.16 (d, J = 8.7 Hz, 1H), 7.97 (t, J = 2.0 Hz, 1H), 7.91 (t, J = 2.0 Hz, 1H), 7.86 (d, J = 7.8 Hz, 1H), 7.82 (d, J = 8.4 Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.76 (d, J = 8.7 Hz, 1H), 7.71 (d, J = 5.7 Hz, 1H), 7.68 (s, 1H), 7.65 (s, 1H), 7.63 (s, 1H), 7.61 (s, 1H), 7.59 (s, 1H), 7.56 (d, J = 1.5 Hz, 1H), 7.55 - 7.53 (m, 1H), 7.50 - 7.49 (m, 1H), 7.47 (d, J = 4.3 Hz, 2H), 7.41 (t, J = 7.9 Hz, 3H), 7.33 (ddd, J = 8.0, 6.6, 1.4 Hz, 1H), 7.25 - 7.23 (m, 1H), 7.21 - 7.17 (m, 1H), 7.14 - 7.11 (m, 4H), 1.27 (s,

[0097] (4) Compound 20 (1.4 g, 1.6 mmol), potassium chloroplatinate (664 mg, 1.6 mmol) and acetic acid (40 mL) were added into a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 24 hours. After cooling to room temperature, filtration was carried out, and the solid was collected. The crude product was separated by column chromatography to obtain 729 mg of red solid, which was a circularly polarized luminescent complex material 1-13, with a yield of 39%. 1 H NMR (500 MHz, Methylene Chloride-d2) δ 8.35 (d, J = 8.7 Hz, 1H), 8.23 (d, J = 8.7 Hz, 1H), 8.12 (d, J = 8.8 Hz, 1H), 8.02 (dd, J = 8.8, 6.9 Hz, 2H), 7.95 (d, J = 8.0 Hz, 1H), 7.72 (t, J = 7.1 Hz, 2H), 7.68 - 7.57 (m, 6H), 7.47 (d, J = 7.4 Hz, 1H), 7.26 - 7.14 (m, 4H), 7.11 - 7.04 (m, 3H), 6.77 (ddd, J = 8.5, 6.9, 1.5 Hz, 1H), 6.34 (ddd, J = 25.4, 17.8, 8.2 Hz, 3H), 1.39 (s, 18H).

[0098] Example 5

[0099] The present embodiment provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0100]

[0101] (1) Into a 100 mL round bottom flask was placed compound 21 (1.2 g, 5.3 mmol), 3,5-di-tert-butylaniline (1.1 g, 5.3 mmol), palladium acetate (120 mg, 0.53 mmol), tri-tert-butylphosphonium tetrafluoroborate (307.4 mg, 1.0 mmol), potassium tert-butoxide (1.5 g, 16 mmol). The flask was evacuated and backfilled with argon three times, then toluene (60 mL) was added. The reaction was heated at 110 °C for 12 h. After cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water three times, and the organic layer was collected. The organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography to give 1.8 g of yellow-brown solid product, compound 22, in 90% yield. 1 H NMR (500 MHz, Chloroform-d) δ 8.66 (d, J = 4.5 Hz, 1H), 7.76 - 7.67 (m, 3H), 7.48 (d, J = 7.7 Hz, 1H), 7.35 (t, J = 7.8 Hz, 1H), 7.21 (t, J = 6.0 Hz, 1H), 7.13 - 7.10 (m, 1H), 7.04 (dd, J = 15.1, 1.7 Hz, 4H), 1.33 (s, 18H).

[0102] (2) Into a 100 mL round bottom flask was placed compound 19 (1.2 g, 3.4 mmol), compound 22 (1.2 g, 3.4 mmol), tris(dibenzylideneacetone)dipalladium (311 mg, 0.34 mmol), 2-dicyclohexylphosphino-2',6'-diisopropoxy-1,1'-biphenyl (317 mg, 0.68 mmol), sodium tert-butoxide (979 mg, 10.2 mmol). The flask was evacuated and backfilled with argon three times, then toluene (60 mL) was added. The reaction was heated at 110 °C for 12 h. After cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water three times, and the organic layer was collected. The organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography to give 1.6 g of yellow solid product, compound 23, in 72% yield. 1H NMR (500 MHz, Chloroform-d) δ 8.67 - 8.64 (m, 1H), 7.93 - 7.89 (m, 1H), 7.86 (dd, J = 8.5, 1.5 Hz, 2H), 7.72 - 7.67 (m, 3H), 7.66 - 7.62 (m, 4H), 7.58 (dd, J = 8.4, 1.5 Hz, 2H), 7.52 - 7.47 (m, 3H), 7.42 (t, J = 7.8 Hz, 1H), 7.40 - 7.35 (m, 2H), 7.24 - 7.17 (m, 3H), 7.13 (t, J = 1.7 Hz, 1H), 7.11 (d, J = 1.7 Hz, 2H), 1.28 (s, 18H).

[0103] (3) Compound 23 (1.0 g, 1.5 mmol), potassium chloroplatinate (830 mg, 2 mmol) and acetic acid (40 mL) were added into a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 min, the reaction was carried out at 135 °C for 24 h. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography to obtain 600 mg of red solid, which was circularly polarized luminescent complex material 1-14, with a yield of 46%. 1 H NMR (600 MHz, Methylene Chloride-d2) δ 8.66 (d, J = 8.1 Hz, 1H), 8.45 (d, J = 5.1 Hz, 1H), 7.99 (d, J = 8.7 Hz, 1H), 7.89 (dd, J = 16.4, 8.3 Hz, 2H), 7.74 - 7.62 (m, 4H), 7.60 - 7.53 (m, 2H), 7.47 - 7.40 (m, 2H), 7.37 (d, J = 7.3 Hz, 1H), 7.31 (d, J = 7.3 Hz, 1H), 7.19 (d, J = 1.8 Hz, 2H), 7.04 (t, J = 7.9 Hz, 1H), 6.98 (t, J = 7.9 Hz, 1H), 6.94 (ddd, J = 7.9, 6.3, 1.5 Hz, 1H), 6.72 (t, J = 6.5 Hz, 1H), 6.29 (dd, J = 35.0, 8.3 Hz, 3H), 1.55 (s, 18H)

[0104] Example 6

[0105] This example provides a preparation method of a circularly polarized luminescent complex material, and the preparation flow is as follows:

[0106]

[0107] (1) Compound 24 (2.5 g, 12 mmol), compound 16 (2.4 g, 12 mmol) and tetrakis(triphenylphosphine)palladium (300 mg, 0.26 mmol) were added to a 500 mL round-bottom flask, vacuumed and filled with argon three times, and then toluene (72 mL), ethanol (24 mL) and 2 M aqueous potassium carbonate solution (24 mL) were sequentially injected. The reaction was performed at 85°C for 12 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected and distilled under reduced pressure to remove the solvent. The crude product was purified by column chromatography to obtain 2.5 g of white powder, which was compound 25, at a yield of 74%. 1 HNMR (600 MHz, Chloroform-d) δ 9.33 (s, 1H), 8.31 (t, J = 1.8 Hz, 1H), 8.08-8.03 (m, 2H), 8.03-7.99 (m, 1H), 7.91-7.87 (m, 1H), 7.72 (ddd, J = 8.2, 6.8, 1.3 Hz, 1H), 7.62 (ddd, J = 8.1, 6.8, 1.2 Hz, 1H), 7.54 (ddd, J = 8.0, 2.0, 1.0 Hz, 1H), 7.38 (t, J = 7.9 Hz, 1H).

[0108] (2) Compound 25 (1.5 g, 5.3 mmol), 3,5-di-tert-butylaniline (1.1 g, 5.3 mmol), palladium acetate (120 mg, 0.53 mmol), tri-tert-butylphosphine tetrafluoroborate (307.4 mg, 1.0 mmol), potassium tert-butoxide (1.5 g, 16 mmol) were added to a 100 mL round-bottom flask, vacuumed and filled with argon three times, and then toluene (60 mL) was added. The reaction was performed at 110°C for 12 hours, and after cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water three times, and the organic layer was collected and distilled under reduced pressure to remove the organic solvent. The crude product was purified by column chromatography to obtain 1.8 g of yellow-brown solid, which was compound 26, at a yield of 83%. 1 HNMR (500 MHz, Chloroform-d) δ 9.31 (s, 1H), 8.05 (s, 1H), 7.99 (d, J = 8.1 Hz, 1H), 7.90 (d, J = 2.2 Hz, 1H), 7.83 (d, J = 8.1 Hz, 1H), 7.71-7.67 (m, 1H), 7.66-7.63 (m, 1H), 7.58 (ddd, J = 8.0, 6.8, 1.1 Hz, 1H), 7.39 (t, J = 7.8 Hz, 1H), 7.11 (dd, J = 7.9, 2.1 Hz, 1H), 7.06 (d, J = 1.3 Hz, 3H), 5.94-5.82 (m, 1H), 1.35 (d, J = 1.1 Hz, 18H).

[0109] (3) Compound 19 (1 g, 2.8 mmol), compound 26 (1.2 g, 2.8 mmol), tris(dibenzylideneacetone)dipalladium (3280 mg), 2-dicyclohexylphospho-2',6'-diisopropoxy-1,1'-biphenyl (317 mg, 0.68 mmol), sodium tert-butoxide (979 mg, 10.2 mmol) were added to a 100 mL round bottom flask, which was vacuumed and purged with argon for 3 times. Toluene (60 mL) was added. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, the crude product was extracted with ethyl acetate and water. The organic layer was collected. The organic layer was washed with water for 3 times. The organic layer was collected and the organic solvent was removed by distillation under reduced pressure. The crude product was purified by column chromatography to obtain the yellow solid product 1.7 g, which was compound 27, with a yield of 85%. 1 H NMR (500 MHz, Chloroform-d) δ 9.28 (s, 1H), 8.46 (d, J = 7.8 Hz, 1H), 7.98 (t, J = 2.0 Hz, 1H), 7.95 (d, J = 8.1 Hz, 2H), 7.91 (t, J = 2.0 Hz, 1H), 7.85 (dt, J = 7.7, 1.3 Hz, 1H), 7.82 - 7.77 (m, 2H), 7.69 - 7.65 (m, 2H), 7.65 - 7.62 (m, 2H), 7.60 (d, J = 7.6 Hz, 2H), 7.56 - 7.53 (m, 3H), 7.49 - 7.46 (m, 3H), 7.40 (dt, J = 10.6, 7.9 Hz, 2H), 7.35 - 7.31 (m, 1H), 7.22 - 7.17 (m, 2H), 7.12 (s, 2H), 1.27 (s, 18H).

[0110] (4) Compound 27 (1.5 g, 2.1 mmol), potassium chloroplatinate (1000 mg, 2.5 mmol) and acetic acid (40 mL) were added to a 100 mL two-necked round bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography to obtain the red solid 925 mg, which was the circularly polarized luminescent complex material 1-15, with a yield of 48%. 1H NMR (500 MHz, Chloroform-d) δ 9.27 (s, 1H), 8.79 (d, J = 8.0 Hz, 1H), 8.19 (s, 1H), 8.04 (d, J = 8.7 Hz, 1H), 7.95 (d, J = 8.6 Hz, 1H), 7.84 (d, J = 8.2 Hz, 1H), 7.73 (d, J = 7.1 Hz, 4H), 7.67 - 7.63 (m, 1H), 7.61 (td, J = 8.7, 8.3, 2.0 Hz, 1H), 7.56 (t, J = 1.8 Hz, 1H), 7.53 (d, J = 7.4 Hz, 1H), 7.49 (d, J = 8.3 Hz, 1H), 7.37 (d, J = 7.4 Hz, 1H), 7.36 - 7.32 (m, 1H), 7.30 (d, J = 1.8 Hz, 3H), 7.17 - 7.11 (m, 1H), 7.10 - 7.07 (m, 1H), 7.05 (d, J = 7.9 Hz, 1H), 6.73 (t, J = 7.5 Hz, 1H), 6.40 (d, J = 8.3 Hz, 1H), 6.37 (d, J = 8.3 Hz, 1H), 1.40 (s, 18H).

[0111] Example 7

[0112] The present example provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0113]

[0114] (1) Compound 28 (5 g, 18.3 mmol), 3,5-di-tert-butylaniline (3.7 g, 18.3 mmol), palladium acetate (120 mg, 0.53 mmol), tri-tert-butylphosphine tetrafluoroborate (1 g, 3.7 mmol), potassium tert-butoxide (10 g, 91 mmol) were added to a 2500 mL round-bottom flask, and vacuum was applied and argon was introduced repeatedly for 3 times, and then toluene (100 mL) was added. The reaction was carried out at 110°C for 12 hours, and then cooled to room temperature. The crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water repeatedly for 3 times, and the organic layer was collected, and the organic solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain 6.2 g of yellow-brown solid product, i.e. compound 29, with a yield of 85%. 1H NMR (500 MHz, Chloroform-d) δ 8.10 (s, 1H), 7.88-7.83 (m, 1H), 7.62-7.58 (m, 1H), 7.40 (t, J = 8.0 Hz, 1H), 7.35-7.28 (m, 2H), 7.12 (dd, J = 4.6, 2.0 Hz, 2H), 7.07-7.03 (m, 3H), 6.96 (ddd, J = 7.8, 2.0, 0.9 Hz, 1H), 5.91 (s, 1H), 1.33 (s, 18H).

[0115] (2) Compound 29 (2 g, 5 mmol), compound 19 (1.8 g, 5 mmol), palladium acetate (17 mg, 0.1 mmol), tri-tert-butylphosphine tetrafluoroborate (0.29 g, 1 mmol), potassium tert-butoxide (2.8 g, 25 mmol) were added to a 2500 mL round bottom flask, vacuumed and argon was introduced for 3 times, then toluene (100 mL) was added. The reaction was carried out at 110 °C for 12 hours, after cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water for 3 times, the organic layer was collected, and the organic solvent was removed by reduced pressure distillation. The crude product was purified by column chromatography to obtain 2.6 g of yellow-brown solid product, compound 30, with a yield of 72%. 1 H NMR (600 MHz, Chloroform-d) δ 8.49 (d, J = 7.8 Hz, 1H), 8.13 (t, J = 2.0 Hz, 1H), 7.89-7.85 (m, 2H), 7.79 (d, J = 8.6 Hz, 1H), 7.74 (d, J = 8.6 Hz, 1H), 7.68 (dd, J = 8.3, 7.3 Hz, 2H), 7.63-7.60 (m, 2H), 7.58-7.51 (m, 4H), 7.47 (t, J = 7.8 Hz, 1H), 7.43 (t, J = 8.0 Hz, 1H), 7.38 (ddd, J = 7.9, 6.6, 1.3 Hz, 1H), 7.30-7.27 (m, 2H), 7.26 (dq, J = 5.3, 1.8, 1.4 Hz, 2H), 7.22-7.19 (m, 1H), 7.18 (d, J = 1.8 Hz, 2H), 7.14 (ddd, J = 8.2, 7.2, 1.1 Hz, 1H), 7.10-7.06 (m, 1H), 1.34 (s, 18H).

[0116] (3) Compound 30 (2 g, 2.8 mmol) was added to a 250 mL two-necked flask, which was vacuumed and filled with argon for 3 times, then tetrahydrofuran 100 mL was added, followed by injection of iodomethane (4 g, 28 mmol). The reaction was carried out at 70 °C for 48 hours. After cooling to room temperature, the solvent and the remaining iodomethane were removed by distillation under reduced pressure to obtain the yellow solid product 2.4 g, which was compound 31, with a yield of 90%.

[0117] (4) Compound 31 (1 g, 1.2 mmol), potassium chloroplatinate (581 mg, 1.4 mmol) and acetic acid (30 mL) were added to a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography to obtain the red solid 454 mg, which was the circularly polarized luminescent complex material 1-36, with a yield of 41%.[M] + :923.1.

[0118] Example 8

[0119] This example provides a method for preparing a circularly polarized luminescent complex material, and the preparation process is as follows:

[0120]

[0121] (1) Compound 32 (2.0 g, 7.8 mmol), compound 33 (1.1 g, 7.8 mmol), palladium tetra-triphenylphosphine (180 mg) and potassium carbonate (4.3 g) were placed in a 250 mL two-necked round-bottom flask, followed by injection of 50 mL of toluene, 20 mL of ethanol and 16 mL of water in sequence. The reaction was carried out by stirring and heating to 85 °C for 24 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected. The solvent was removed by distillation under reduced pressure. The crude product was separated and purified by column chromatography to obtain the white powder product 1.1 g, which was compound 34, with a yield of 52%. 1 HNMR (500 MHz, Chloroform-d) δ 9.35 (s, 1H), 8.70 (d, J = 8.6 Hz, 1H), 8.27-8.15 (m, 2H), 7.97 (d, J = 8.3 Hz, 1H), 7.94-7.88 (m, 1H), 7.84-7.66 (m, 4H), 7.52-7.41 (m, 2H).

[0122] (2) Compound 34 (1 g, 3.7 mmol), compound 35 (1.1 g, 3.7 mmol) and potassium carbonate (2.1 g, 14.8 mmol) were added to a 100 mL round bottom flask, which was vacuumed and filled with argon for 3 times, and then 60 mL of N-methylpyrrolidone was injected. Stirring and heating to 180°C for 72 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected. The solvent was removed under reduced pressure. The crude product was separated and purified by column chromatography to obtain 0.73 g of white powder product, i.e. compound 36, with a yield of 60%. 1 HNMR (500 MHz, Chloroform-d) δ 8.58 (d, J = 8.6 Hz, 2H), 8.25-8.12 (m, 4H), 8.03 (d, J = 8.3 Hz, 2H), 7.94-7.88 (m, 2H), 7.84 (m, 6H), 7.52-7.41 (m, 2H) 7.35 (m, 6H).

[0123] (3) Compound 36 (500 mg, 0.95 mmol), potassium chloroplatinate (498 mg, 1.2 mmol) and acetic acid (30 mL) were added to a 100 mL two-necked round bottom flask. After bubbling with argon for 30 minutes, it was reacted at 135°C for 24 hours. After cooling to room temperature, it was filtered and the solid was collected. The crude product was separated by column chromatography to obtain 327 mg of product, i.e. circularly polarized luminescent complex material 2-1, with a yield of 48%. 1 HNMR (500 MHz, Chloroform-d) δ 8.35 (d, J = 8.6 Hz, 2H), 8.20-8.12 (m, 4H), 8.13 (d, J = 8.3 Hz, 2H), 7.94-7.86 (m, 2H), 7.66 (m, 6H), 7.52-7.41 (m, 2H) 7.33 (m, 4H).

[0124] Example 9

[0125] This example provides a method for preparing a circularly polarized luminescent complex material, and the preparation process is as follows:

[0126]

[0127] (1) Compound 37 (2 g, 5.8 mmol), Pd(dppf)2Cl2 (85 mg) and potassium acetate (2.8 g, 29 mmol) were added to a 250 mL two-necked round bottom flask, which was vacuumed and filled with argon for 3 times, and then 100 mL of 1,4-dioxane was injected. Stirring and heating to 135°C for 48 hours. After cooling to room temperature, it was filtered and the solid was collected. The crude product was separated by column chromatography to obtain 1.8 g of product, i.e. compound 38, with a yield of 72%. 1H NMR (500 MHz, Chloroform-d) δ 7.35 (d, J = 4.8, 2H), 7.17 (m, 4H), 7.52 - 7.41 (m, 2H) 7.08 (m, 2H), 6.68 (d, J = 6.8, 2H), 1.35 (s, 24H)

[0128] (2) Compound 38 (1.5 g, 3.4 mmol), compound 39 (2.2 g, 8.5 mmol), tetrakis triphenylphosphine palladium (180 mg) and potassium carbonate (3.7 g) were placed in a 250 mL two-necked round-bottom flask, and then 50 mL of toluene, 20 mL of ethanol and 16 mL of water were sequentially injected. The reaction was stirred and heated to 85°C for 24 hours. After cooling, the reaction solution was extracted with dichloromethane and water, and the lower layer was collected and the solvent was removed under reduced pressure. The crude product was separated and purified by column chromatography to obtain 899 mg of product 40, a white powder, which was compound 40, with a yield of 49%. 1 H NMR (500 MHz, Chloroform-d) δ 8.66 (d, J = 8.6 Hz, 2H), 8.38 - 8.25 (m, 4H), 8.12 (d, J = 8.3 Hz, 2H), 7.80 - 7.35 (m, 2H), 7.84 (m, 6H), 7.24 - 7.10 (m, 2H) 6.88 (m, 6H).

[0129] (3) Compound 40 (500 mg, 0.91 mmol), potassium chloroplatinate (498 mg, 1.2 mmol) and acetic acid (30 mL) were added to a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135°C for 24 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated and purified by column chromatography to obtain 327 mg of product, which was a circularly polarized luminescent complex material 3-1, with a yield of 45%. 1 H NMR (500 MHz, Chloroform-d) δ 8.42 (d, J = 8.6 Hz, 2H), 8.28 - 8.18 (m, 4H), 8.15 (d, J = 8.3 Hz, 2H), 7.88 - 7.72 (m, 2H), 7.66 (m, 6H), 7.52 - 7.32 (m, 2H) 7.13 (m, 4H).

[0130] Example 10

[0131] This example provides a method for preparing a circularly polarized luminescent complex material, and the preparation process is as follows:

[0132]

[0133] (1) In a 250 mL three-necked flask, compound 41 (2 g, 6 mmol), magnesium turnings (10 g, 416 mmol), iodine (5.3 g, 416 mmol) and 100 mL of HPLC grade tetrahydrofuran solvent were added. The reaction was stirred at 50 °C for 4 hours and ready for use.

[0134] (2) In a 500 mL two-necked flask, compound 42 (786 mg, 3 mmol) and 150 mL of HPLC grade tetrahydrofuran solvent were added at -78 °C. The reaction vessel was vacuumed and purged with argon for 3 times. 2.5 M n-butyllithium solution (5 mL) was added slowly into the reaction vessel. After 1 hour, the above reaction solution was added dropwise. The reaction was continued overnight after warming to room temperature. The reaction was quenched by adding 10 mL of water. The reaction solution was extracted with dichloromethane and water. The lower layer was collected and the solvent was removed under reduced pressure. The crude product was purified by column chromatography to obtain 212 mg of product, compound 43, with a yield of 10%. 1 H NMR (400 MHz, Chloroform-d) δ 9.32 - 9.27 (m, 2H), 8.22 - 8.10 (m, 4H), 8.05 (dt, J = 7.7, 1.3 Hz, 2H), 7.95 (s, 2H), 7.89 - 7.83 (m, 2H), 7.66 (t, J = 8.8 Hz, 2H), 7.60 - 7.50 (m, 6H), 7.27 (t, J = 7.9 Hz, 2H), 7.15 - 6.98 (m, 2H), 6.88 (dd, J = 15.6, 1.8 Hz, 3H), 7.52 (s, 1H), 1.30 (s, 18H).

[0135] (2) In a 25 mL two-necked round-bottom flask, compound 43 (150 mg, 0.21 mmol), potassium chloroplatinate (124 mg, 0.3 mmol) and acetic acid (10 mL) were added. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 72 hours. After cooling to room temperature, the solid was collected by filtration. The crude product was separated by column chromatography to obtain 56 mg of product, circularly polarized luminescent complex material 4-1, with a yield of 30%. 1H NMR (400 MHz, Chloroform-d) δ 9.33 (d, J = 4.8 Hz, 2H), 8.15 (d, J = 4.8 Hz, 2H), 8.04 (d, J = 8.3 Hz, 2H), 7.62 (t, J = 2.0 Hz, 1H), 7.54 (d, J = 7.4 Hz, 2H), 7.42 - 7.31 (m, 4H), 7.24 (s, 2H), 7.19 (dd, J = 8.3, 7.4 Hz, 2H), 7.12 (d, J = 8.7 Hz, 2H), 7.05 (ddd, J = 8.0, 6.9, 1.2 Hz, 2H), 6.54 (ddd, J = 8.3, 7.0, 1.3 Hz, 2H), 6.42 (d, J = 8.3 Hz, 2H), 1.40 (s, 18H).

[0136] Example 11

[0137] The present embodiment provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0138]

[0139] (1) Compound 44 (2 g, 4 mmol), Pd(dppf)2Cl2(85 mg) and potassium acetate (1.6 g, 16 mmol) were added to a 250 mL two-port round-bottom flask, which was vacuumed and filled with argon for three times, and then 100 mL of 1,4-dioxane was injected. Stirring was performed, and heating was performed to 135°C for 48 hours. After cooling to room temperature, filtration was performed, and the solid was collected. The crude product was separated by column chromatography to obtain 1.9 g of product 45, i.e., compound 45, with a yield of 81%. 1 HNMR (500 MHz, Chloroform-d) δ 7.66 (s, 2H), 7.38 - 7.25 (m, 8H), 7.12 (d, J = 8.3 Hz, 2H), 7.80 - 7.35 (m, 2H), 7.84 (m, 2H), 7.24 - 7.10 (m, 2H), 1.35 (s, 24H).

[0140] (2) Compound 45 (1.5 g, 2.6 mmol), compound 46 (1.2 g, 5.7 mmol), tetrakis(triphenylphosphine)palladium (80 mg) and potassium carbonate (2.7 g) were placed in a 250 mL two-port round-bottom flask, and then 50 mL of toluene, 15 mL of ethanol and 10 mL of water were sequentially injected. Stirring was performed, and heating was performed to 85°C for 24 hours. Cooling was performed, the reaction solution was extracted with dichloromethane and water, the lower layer was collected, and the solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain 771 mg of white powder product 47, i.e., compound 47, with a yield of 43%. 1H NMR (500 MHz, Chloroform-d) δ 9.68 (d, J = 8.1 Hz, 2H), 8.44 (d, J = 8.5 Hz, 2H), 8.31 (d, J = 8.4 Hz, 2H), 7.78 (t, J = 1.8 Hz, 2H), 7.76 - 7.61 (m, 2H), 7.49 - 7.43 (m, 2H), 7.33 (d, J = 8.7 Hz, 2H), 7.29-7.20 (m, 8H), 7.17-7.06 (m, 8H), 6.64 (ddd, J = 8.2, 6.8, 1.3 Hz, 2H), 6.35 (dd, J = 8.3, 0.9 Hz, 2H).

[0141] (3) Compound 47 (500 mg, 0.721 mmol), potassium chloroplatinate (361 m, 87 mmol) and acetic acid (35 mL) were added to a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 72 hours. After cooling to room temperature, filtration was carried out, and the solid was collected. The crude product was separated by column chromatography to obtain 248 mg of product, i.e., circularly polarized luminescent complex material 5-1, with a yield of 39%. 1 H NMR (500 MHz, Chloroform-d) δ 9.48 (d, J = 8.1 Hz, 2H), 8.42 (d, J = 8.5 Hz, 2H), 7.76 (t, J = 1.8 Hz, 2H), 7.70 - 7.61 (m, 2H), 7.52 - 7.43 (m, 2H), 7.31 (d, J = 8.7 Hz, 2H), 7.29-7.20 (m, 8H), 7.15-7.06 (m, 8H), 6.62 (ddd, J = 8.2, 6.8, 1.3 Hz, 2H), 6.38 (dd, J = 8.3, 0.9 Hz, 2H).

[0142] Example 12

[0143] The present embodiment provides a preparation method of a circularly polarized luminescent complex material, and the preparation flow is as follows:

[0144]

[0145] (1) Compound 4 (1 g, 1.4 mmol) obtained in Example 1, palladium acetate (232 mg, 1.4 mmol) and acetic acid (40 mL) were added to a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 24 hours. After cooling to room temperature, filtration was carried out, and the solid was collected. The crude product was separated by column chromatography to obtain 114 mg of red solid, i.e., circularly polarized luminescent complex material 11-1, with a yield of 10%. 1H NMR (500 MHz, Acetone-d6) δ 9.48 (d, J = 8.1 Hz, 2H), 8.40 (d, J = 8.5 Hz, 2H), 8.29 (d, J = 8.4 Hz, 2H), 7.73 (t, J = 1.8 Hz, 1H), 7.66 - 7.61 (m, 2H), 7.49 - 7.43 (m, 2H), 7.35 (d, J = 8.7 Hz, 2H), 7.32 - 7.26 (m, 4H), 7.17 - 7.06 (m, 4H), 6.64 (ddd, J = 8.2, 6.8, 1.3 Hz, 2H), 6.35 (dd, J = 8.3, 0.9 Hz, 2H)

[0146] Example 13

[0147] The present embodiment provides a preparation method of a circularly polarized luminescent complex material, and the preparation process is as follows:

[0148]

[0149] (1) Compound 48 (2 g, 7 mmol), 3,5-di-tert-butylaniline (717 mg, 3.5 mmol), palladium acetate (23 mg, 0.1 mmol), tri-tert-butylphosphonium tetrafluoroborate (290 mg, 1 mmol), potassium tert-butoxide (4 g, 35 mmol) were added into a 250 mL round-bottom flask, and then the flask was vacuumed and filled with argon for 3 times. Then, toluene (100 mL) was added. The reaction was carried out at 110°C for 12 hours. After cooling to room temperature, the crude product was extracted with ethyl acetate and water, and the organic layer was collected. The organic layer was washed with water for 3 times, and the organic layer was collected. The organic solvent was removed by reduced pressure distillation. The crude product was separated and purified by column chromatography to obtain 1.7 g of yellow-brown solid product, which was compound 49, and the yield was 84%. 1 H NMR (600 MHz, Chloroform-d) δ 8.14 (dd, J = 20.9, 8.5 Hz, 4H), 7.96 (t, J = 2.0 Hz, 2H), 7.84 - 7.77 (m, 4H), 7.75 (d, J = 8.6 Hz, 2H), 7.69 (t, J = 7.4 Hz, 2H), 7.50 (t, J = 7.5 Hz, 2H), 7.41 (t, J = 7.9 Hz, 2H), 7.23 (ddd, J = 8.1, 2.4, 1.0 Hz, 2H), 7.13 (t, J = 1.7 Hz, 1H), 7.10 (d, J = 1.7 Hz, 2H), 1.26 (s, 18H).

[0150] (2) Compound 49 (1 g, 1.6 mmol), palladium acetate (366 mg, 1.6 mmol) and acetic acid (40 mL) were added to a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 24 hours. After cooling to room temperature, filtration was carried out, and the solid was collected. The crude product was separated by column chromatography to obtain 114 mg of red solid, which was a circularly polarized luminescent complex material 11-7, with a yield of 10%. 1 H NMR (500 MHz, Chloroform-d) δ 8.30 (d, J = 8.6 Hz, 2H), 8.17 (d, J = 8.7 Hz, 2H), 7.77 (dd, J = 8.1, 1.4 Hz, 2H), 7.67 (d, J = 8.6 Hz, 2H), 7.62 - 7.58 (m, 2H), 7.53 (t, J = 1.8 Hz, 1H), 7.30 - 7.26 (m, 2H), 7.21 (d, J = 1.8 Hz, 2H), 7.10 (dd, J = 8.3, 7.4 Hz, 2H), 6.85 (ddd, J = 8.5, 6.9, 1.4 Hz, 2H), 6.40 (dd, J = 8.3, 0.9 Hz, 2H), 1.35 (s, 18H).

[0151] Example 14

[0152] This example provides a preparation method of a circularly polarized luminescent complex material, and the preparation flow is as follows:

[0153]

[0154] (1) Compound 7 (1 g, 1.4 mmol) obtained in Example 2, palladium acetate (232 mg, 1.4 mmol) and acetic acid (40 mL) were added to a 100 mL two-necked round-bottom flask. After bubbling with argon for 30 minutes, the reaction was carried out at 135 °C for 24 hours. After cooling to room temperature, filtration was carried out, and the solid was collected. The crude product was separated by column chromatography to obtain 230 mg of red solid, which was a circularly polarized luminescent complex material 11-8, with a yield of 20%. 1 H NMR (500 MHz, DMSO-d6) δ 8.63 (d, J = 8.7 Hz, 2H), 8.53 (d, J = 8.9 Hz, 2H), 8.03 (dd, J = 8.1, 1.4 Hz, 2H), 7.74 (d, J = 1.7 Hz, 2H), 7.59 - 7.50 (m, 3H), 7.41 (ddd, J = 8.1, 6.9, 1.1 Hz, 2H), 7.09 (d, J = 1.8 Hz, 2H), 6.96 (ddd, J = 8.4, 6.8, 1.5 Hz, 2H), 6.38 (d, J = 1.7 Hz, 2H), 1.35 (s, 18H), 1.17 (s, 18H).

[0155] Test Example 1

[0156] The HPLC separation effect of the chiral preparation column of Examples 1, 3, 4 and 12 was determined. Test conditions: Column size: 0.46 cm I.D. x 25 cm L; Injection: 0.5 ul; Mobile phase: DCM = 100%; Flow rate: 1.0 ml / min; Wave length: UV 254 nm; Temperature: 35°C; HPLC equipment: Shimadzu LC-20AT CP-HPLC-09. The results are shown in Table 1 and Figures 1-4 :

[0157] Table 1 Chiral separation data of each example

[0158] Example Peak 1 retention time (min) Peak 2 retention time (min) 1 4.54 5.03 3 4.58 5.11 4 4.69 6.52 12 5.75 7.80

[0159] As can be seen from the data in Table 1 and Figures 1-4 Table 2, each example has good separation degree and can be prepared in large quantities.

[0160] Test Example 2

[0161] The ultraviolet absorption spectrum, photoluminescence spectrum and circularly polarized photoluminescence spectrum of each example in dichloromethane solution were determined, and the results are shown in Table 2:

[0162] Table 2 Physical property data of each example

[0163] Example Absorption peak wavelength [nm] Emission peak wavelength [nm] Decomposition temperature [°C] 1 400 / 550 690 358 2 380 / 450 / 600 735 356 3 364 / 433 / 578 664 402 4 368 / 430 / 588 709 393 5 348 / 437 / 556 645 415 6 345 / 434 / 555 641 399 7 339 / 431 / 540 635 420 8 310 / 450 525 398 9 325 / 455 545 400 10 330 / 448 585 399 11 332 / 452 568 420 12 292 / 345 / 501 602 341 13 277 / 358 / 521 635 337 14 279 / 365 / 540 640 330

[0164] As can be seen from the data in Table 2, each example complex is suitable for red to near-infrared dopant, and the decomposition temperature at 5wt% is higher than 330°C, indicating that the example complex has good thermal stability.

[0165] Test Example 3

[0166] The large-scale chiral preparation of Example 1 was carried out, and the effects before and after preparation are shown in Figures 5-7 The results show that at the level of hundreds of milligrams, the sample of Example 1 can effectively carry out chiral separation, and two groups of components with ee value of about 97% are obtained, which are enantiomers.

[0167] Table 3. ee value data of Example 1 after chiral preparation

[0168] Sample name Sample state ee value Product mass / g Before preparation Black powder -- 0.2801 Peak 1 Brown solid ＞96.5％ 0.1157 Peak 2 Brown solid >97.5％ 0.1121

[0169] Test Example 4

[0170] Circular polarization absorption and emission tests were performed on Example 1 in dichloromethane solution and thin film state, respectively, with an excitation wavelength of 450 nm. The results are shown in Figure 6, which shows that Example 1 has strong circular polarization absorption and emission signals in both dichloromethane and thin film states, with a g factor of 2 x 10 Figures 8-12 -3 This shows that the present application achieves the purpose of circular polarization luminescence and can achieve a good CPL signal effect.

[0171] Test Example 5

[0172] The electroluminescent performance of electroluminescent devices based on Examples 1, 2, 3, 4, 5, 6, 7, 12, 13 and 14 was determined to show the application of the complexes of the present application in electroluminescent devices. The structure of the electroluminescent device was: ITO / HATCN (5 nm) / TPD15 (30 nm) / TCTA (15 nm) / DMIC-CZ + DMIC-TRZ + chiral complex of the present application (3 compounds in a ratio of 100:100:6) (50 nm) / ANT-BIZ (30 nm) / Liq (2 nm) / Al (100 nm). The structural formula of the structure except for the chiral complex of the present application is as follows, and the results are shown in Table 4 below.

[0173]

[0174] Table 4 shows the results of the characterization of the devices of each example

[0175]

[0176]

[0177] Note: T90 is the time consumed for the device to run to 90% of the initial luminance value.

[0178] The results show that the electroluminescent devices of the examples of the present application have good electroluminescent red and near-infrared light emission performance, and the device has good running stability.

[0179] Obviously, the above examples are merely examples for clarity and do not limit the embodiments. Based on the above description, other different forms of changes or variations can be made by those of ordinary skill in the art. Here, it is not necessary and impossible to exhaust all embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.​

Claims

1. A circularly polarized luminescent complex material, characterized in that, The circularly polarized luminescent complex material is selected from compounds of the following structure: 。 2. Use of the circularly polarized luminescent complex material according to claim 1, characterized in that, Use in the preparation of chiral liquid crystal materials, chiral conductive polymer materials and chiral electroluminescent materials.

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