A chiral indolocarbazole light-emitting material, an organic electroluminescent device and application

Abstract

The application belongs to the technical field of organic electroluminescence, and particularly relates to a chiral indolocarbazole light-emitting material, an organic electroluminescent device and application. The chiral indolocarbazole light-emitting material introduces [2.2] paracyclophane into a traditional indolocarbazole skeleton in a central fused conjugated form, and the spatial conjugation effect of the molecular center can effectively adjust the indolocarbazole molecular energy level and the excited state, so that the electron delocalization can be realized without increasing the traditional planar conjugated length, the emission spectrum is red-shifted, and the chiral indolocarbazole light-emitting material can be used as a light-emitting layer in a circularly polarized organic light-emitting diode.

Description

Technical Field

[0001] This invention belongs to the field of organic electroluminescence technology, specifically relating to a chiral indolocarbazole luminescent material, an organic electroluminescent device, and its applications. Background Technology

[0002] Organic light-emitting diodes (OLEDs), as the core of next-generation display technology, place higher demands on the efficiency, color purity, and stability of luminescent materials. In recent years, organic light-emitting materials with multiple resonance (MR) effects have demonstrated narrow-band emission characteristics (typically less than 40 nm half-width at half-maximum) due to their highly localized excited states and extremely small structural relaxation, exhibiting significant advantages in achieving high color purity luminescence. The indole-carbazole framework, due to the electronegativity difference between its nitrogen and carbon atoms, can form an electronic structure similar to the boron-nitrogen multiple resonance system, possessing inherent multiple resonance characteristics and excellent thermo / electrochemical stability, making it a highly promising MR-type luminescent core.

[0003] However, due to the limitations of its conjugated system, the intrinsic luminescence of unmodified indolocarbazole backbones is typically located in the ultraviolet to deep blue light region, which is insufficient to meet the requirements of pure blue light or even longer wavelengths in practical display applications. Generally, the emission wavelengths of blue light materials required for OLED displays are concentrated in the 460–480 nm range, so there is a need to develop molecular design strategies that can effectively redshift the emission wavelength of indolocarbazole molecules. Existing molecular modification strategies generally increase intramolecular charge transfer characteristics by introducing strong electron donor or acceptor units, but this often leads to a decrease in luminous efficiency or spectral broadening. Another approach is to expand the molecular backbone and increase planar conjugation, but large planar conjugation easily induces aggregation quenching, affecting device performance.

[0004] It is evident that existing technologies still need improvement and enhancement. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a chiral indolocarbazole luminescent material, an organic electroluminescent device and its application, with the aim of forming a luminescent material with better performance based on the indolocarbazole framework.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: The first aspect of this invention provides a chiral indolocarbazole-based luminescent material having the formula ( R / S The chemical structure shown is )-M, where, R / S -M represents the chiral configuration of compound M. R -type or S -type,( R )-M and ( S )-M exhibits chiral enantiomeric structural features;

[0007] Among them, ring A and ring B may have the same or different structures, and are independently selected from C6 to C6. 18 Aromatic rings, 5- to 20-membered heterocyclic rings; m and k are independently selected from integers from 0 to 3, n and l are independently selected from integers from 0 to 4, and when there are multiple R1 to R4, they are independently selected from the same or different structures; R1 to R4 are independently selected from H, D (deuterium), CN, and C1 to C. 12 Alkyl, C1-C 12 Alkoxy, C3~C 10 cycloalkyl, C6-C 18 Aryl, 5- to 20-membered heteroaryl, , by at least one R c Replacement of C6~C 18 aryl, with at least one R c Substituted 5- to 20-membered heteroaryl groups, or two adjacent R1 to R4 groups bonded together with the ring attached to them to form substituted or unsubstituted aryl or heteroaryl groups; R a and R b Independently selected from C1 to C 12 Alkyl, C3-C 10 cycloalkyl, C6-C 18 aryl, 5- to 20-membered heteroaryl, with at least one R c Replacement of C6~C 18 aryl, or with at least one R c Substituted 5- to 20-membered heteroaryl groups; R c Independently selected from D (deuterium), CN, C1~C 12 Alkyl, C1-C 12 Alkoxy, C3~C 10 cycloalkyl, C6-C 18 aryl, 5- to 20-membered heteroaryl, diphenylamino, with at least one R d Replacement of C6~C 18 aryl, with at least one R d Substituted 5- to 20-membered heteroaryl, or with at least one R d Substituted diphenylamine group; R d Independently selected from D (deuterium), CN, C1-C6 alkyl, C1-C6 alkyl groups. 12 Alkoxy, C3~C 10 cycloalkyl, C6-C 18 Aryl, 5- to 20-membered heteroaryl, diphenylamino or triphenylamino.

[0008] A second aspect of the present invention provides a light-emitting layer material, which includes the chiral indolocarbazole-based light-emitting material as described above.

[0009] A third aspect of the present invention provides an organic electroluminescent device comprising a light-emitting layer comprising the light-emitting layer material as described above.

[0010] A fourth aspect of the present invention provides an electronic device comprising the organic electroluminescent device as described above.

[0011] Beneficial effects: This invention provides a novel organic light-emitting material, a chiral indolocarbazole-based light-emitting material. The chiral indolocarbazole-based light-emitting material is an indolocarbazole derivative based on the [2,2] p-cycloarane structure. By introducing the [2,2] p-cycloarane into the traditional indolocarbazole skeleton in a fused conjugated form, electron delocalization can be achieved without increasing the traditional planar conjugation length, effectively controlling the molecular energy level and excited state, causing the emission wavelength to redshift, and obtaining compounds with blue light and above wavelengths. It can be used as the light-emitting layer in circularly polarized organic light-emitting diodes. Attached Figure Description

[0012] Figure 1 This is a synthetic route diagram for a chiral indolocarbazole-based luminescent material in one embodiment.

[0013] Figure 2 This is a synthetic route diagram for chiral indolocarbazole luminescent materials in another embodiment.

[0014] Figure 3 For compounds ( R / S Synthesis route of )-M-1.

[0015] Figure 4 For compounds ( R / S Synthesis route of )-M-4.

[0016] Figure 5 For compounds ( R / S Synthesis route map of )-M-11.

[0017] Figure 6 For compounds ( R / S Synthesis route map of )-M-22.

[0018] Figure 7 For compounds ( R / S Synthesis roadmap for M-25.

[0019] Figure 8 For compounds ( R / S Synthesis route map of )-M-38.

[0020] Figure 9For compounds ( R / S Synthesis route map of )-M-60.

[0021] Figure 10 For compounds ( R / S Synthesis route of )-M-78.

[0022] Figure 11 This is the structure of an organic electroluminescent device. Detailed Implementation

[0023] This invention provides a chiral indolocarbazole-based luminescent material, an organic electroluminescent device, and its applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the following embodiments are provided to further illustrate the invention in detail. It should be understood that the specific embodiments described herein are only for explaining the invention and are not intended to limit the invention.

[0024] The first aspect of this invention provides a chiral indolocarbazole-based luminescent material having the formula ( R / S The chemical structure shown is )-M, where, R / S -M represents the chiral configuration of compound M. R -type or S -type,( R )-M and ( S )-M exhibits chiral enantiomeric structural features;

[0025] Among them, ring A and ring B may have the same or different structures, and are independently selected from C6 to C6. 18 Aromatic rings, 5- to 20-membered heterocyclic rings; m and k are independently selected from integers from 0 to 3, n and l are independently selected from integers from 0 to 4, and when there are multiple R1 to R4, they are independently selected from the same or different structures; R1 to R4 are independently selected from H, D (deuterium), CN, and C1 to C. 12 Alkyl, C1-C 12 Alkoxy, C3~C 10 cycloalkyl, C6-C 18 Aryl, 5- to 20-membered heteroaryl, , by at least one R c Replacement of C6~C 18 aryl, with at least one R c Substituted 5- to 20-membered heteroaryl groups, or two adjacent R1 to R4 groups bonded together with the ring attached to them to form substituted or unsubstituted aryl or heteroaryl groups; R a and R b Independently selected from C1 to C 12 Alkyl, C3-C 10cycloalkyl, C6-C 18 aryl, 5- to 20-membered heteroaryl, with at least one R c Replacement of C6~C 18 aryl, or with at least one R c Substituted 5- to 20-membered heteroaryl groups; R c Independently selected from D (deuterium), CN, C1~C 12 Alkyl, C1-C 12 Alkoxy, C3~C 10 cycloalkyl, C6-C 18 aryl, 5- to 20-membered heteroaryl, diphenylamino, with at least one R d Replacement of C6~C 18 aryl, with at least one R d Substituted 5- to 20-membered heteroaryl, or with at least one R d Substituted diphenylamine group; R d Independently selected from D (deuterium), CN, C1-C6 alkyl, C1-C6 alkyl groups. 12 Alkoxy, C3~C 10 cycloalkyl, C6-C 18 Aryl, 5- to 20-membered heteroaryl, diphenylamino or triphenylamino.

[0026] Specifically, in the formation of substituted or unsubstituted aryl or heteroaryl groups by bonding between two adjacent R1 to R4 and their connected rings, the connected ring for R2 is ring A, the connected ring for R4 is ring B, and the connected rings for R1 and R3 are benzene rings. For example, when n is 3, the three R2 groups are each connected to ring A, and two adjacent R2 groups are grouped together with their connected ring A to form substituted or unsubstituted aryl or heteroaryl groups.

[0027] Preferably, ring A and ring B are independently selected from benzene rings or five-membered heterocycles.

[0028] Preferably, the chiral indolocarbazole luminescent material has the following formula ( R / S )-Mm1 to ( R / S The chemical structures shown for any of the following are: )-Mm6

[0029] Among them, R 11 ~R 13 R 21 ~R 24 R 31 ~R 33 R 41~R 44 X is selected independently from the same structure as R1 to R4, and X is selected from O, S or Se.

[0030] Preferably, the R 11 ~R 13 R 21 ~R 24 R 31 ~R 33 R 41 ~R 44 Independently selected from H, D (deuterium), CN, C1~C 12 Alkyl, C1-C 12 Alkoxy, C3~C 10 cycloalkyl, C6-C 18 aryl, 5- to 20-membered heteroaryl, with at least one C1-C 12 Alkyl or C1-C 12 Alkoxy-substituted C6-C 18 Aryl group, with at least one C1-C 12 Alkyl-substituted 5- to 20-membered heteroaryl, diphenylamino, or alkyl-substituted with at least one C1 to C2 group 12 Alkyl or C3-C 10 Cycloalkyl-substituted diphenylamino group, triphenylamino group, or group with at least one C1-C2 substituted group 12 Alkyl-substituted triphenylamine, 5- to 20-membered heteroarylamine, with at least one C1-C 12 Alkyl or phenyl-substituted 5- to 20-membered heteroarylamine, or adjacent R 11 ~R 13 R 21 ~R 24 R 31 ~R 33 R 41 ~R 44 The rings attached to it bond together to synthesize substituted or unsubstituted aryl or heteroaryl groups.

[0031] Specifically, the aforementioned adjacent R 11 ~R 13 R 21 ~R 24 R 31 ~R 33 R 41 ~R 44 The formation of substituted or unsubstituted aryl or heteroaryl groups by bonding with the rings attached to them refers to the formation of substituted or unsubstituted aryl or heteroaryl groups on the rings adjacent to each other. 11 With R 12 R 12 With R 13 R 21 With R 22 R22 With R 23 R 23 With R 24 R 31 With R 32 R 32 With R 33 R 41 With R 42 R 42 With R 43 R 43 With R 44 Among them, at least one group of rings connected to it bonds together to synthesize substituted or unsubstituted aryl or heteroaryl groups.

[0032] Preferably, the chiral indolocarbazole luminescent material is selected from the following compounds:

[0033]

[0034]

[0035] .

[0036] In one embodiment, when preparing ( R / S )-M1 to ( R / S When using any of the compounds described in )-M59, the following methods may be employed: Figure 1 The synthetic method shown uses diiodo[2.2]-p-cycloarane as the starting material. When the starting materials a and b are different, steps I and II are performed separately, i.e., the precursor is obtained through a stepwise Ullmann reaction. When the starting materials a and b are the same, the precursor is obtained through a one-step Ullmann reaction. The precursor is then subjected to a ring-closure reaction in step III to obtain the final target compound. The target product obtained at this point is a pair of racemic compounds (…). R / S ), separated into chiral liquid chromatography column R Configuration and S Configuration.

[0037] When preparing ( R / S) -M60 to ( R / SWhen synthesizing any of the compounds described in M93, first obtain the product with methoxy substitution at the corresponding position (starting material c) by referring to the above synthetic method. Then, utilize the electron-donating effect of the methoxy group to perform a series of transformations: first, starting material c undergoes hydrolysis to obtain a hydroxyl-substituted product, then is converted to an OTf functional group-substituted product under the action of Tf₂O, and finally carbon-nitrogen coupled with starting material d (such as an aromatic amine or heteroaromatic amine) to form the target product. The target product obtained at this time is a pair of racemates, which are separated by chiral liquid chromatography column chromatography into... R Configuration and S Configuration. Figure 2 This is one of the synthetic routes corresponding to the above.

[0038] The chemical structure of the raw material c can be selected from: or ; The chemical structure of the raw material d can be selected from: Or carbazoyl group.

[0039] Specifically, in the above embodiments, raw material a and raw material b can be independently selected from the following structures:

[0040]

[0041]

[0042] .

[0043] Raw material d can be selected from the following structures:

[0044] .

[0045] Compounds ( R / S )-M-1 to ( R / S The raw materials a, b, and d corresponding to )-M-93, as well as the overall reaction yield, are shown in Table 1.

[0046] Table 1

[0047] The present invention further proposes a light-emitting layer material, comprising the chiral light-emitting compound as described above.

[0048] The present invention further proposes an organic electroluminescent device, including a light-emitting layer, wherein the light-emitting layer comprises the light-emitting layer material as described above.

[0049] The present invention further proposes an electronic device, which includes the organic electroluminescent device described above.

[0050] The following specific examples provide further illustration.

[0051] Example 1 Combination Figure 3 As shown, the compound ( R / S )-M-1, its synthesis method is as follows: In the first step, under a nitrogen atmosphere, diiodo[2.2]-p-cycloarane (1.0 equivalent), 1-bromo-9H-carbazole (2.5 equivalent), cuprous iodide (0.5 equivalent), 1,10-phenanthroline (0.5 equivalent), and cesium carbonate (3.0 equivalent) were dissolved in o-dichlorobenzene solvent in a reaction vessel and heated and stirred at 180°C for 24 hours. The mixture was then cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was extracted with dichloromethane and washed with deionized water. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a white solid precursor-1 (yield 82%).

[0052] In the second step, under an argon atmosphere, in a reaction vessel, precursor-1 (1.0 equivalent), benzyltriethylammonium chloride (BTEAc) (2.0 equivalent), potassium carbonate (10.0 equivalent), triphenylphosphine (PPh3) (4.0 equivalent), and palladium(II) acetate (Pd(OAc)2) (0.3 equivalent) were mixed and dissolved in N,N-dimethylacetamide (DMAC) solvent, stirred, and heated under reflux for 10 hours. The mixture was then cooled to room temperature and poured into ice water. The resulting precipitate was filtered to obtain a dark green solid crude product, which was then washed with deionized water and ethanol. The residue was purified by silica gel column chromatography to obtain a light yellow solid product. R / S )-M-1 (yield 38%). Mass spectrometry: 534.14, elemental analysis: C, 89.89; H, 4.85; N, 5.26. The product obtained at this point is a pair of racemic compounds, which were further separated by chiral high-performance liquid chromatography to obtain two single enantiomers. R -M-1 and S -M-1.

[0053] Example 2 Combination Figure 4 As shown, the compound ( R / S)-M-4, its synthesis method is as follows: In the first step, under a nitrogen atmosphere, diiodo[2.2]-p-cycloarane (1.0 equivalent), 1-bromo-3,6-di-tert-butyl-9H-carbazole (2.5 equivalent), cuprous iodide (0.5 equivalent), 1,10-phenanthroline (0.5 equivalent), and cesium carbonate (3.0 equivalent) were dissolved in o-dichlorobenzene solvent in a reaction vessel and the mixture was heated and stirred at 180°C for 24 hours. The mixture was then cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was extracted with dichloromethane and washed with deionized water. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a white solid precursor-4 (yield 86%).

[0054] In the second step, under an argon atmosphere, in a reaction vessel, precursor-4 (1.0 equivalent), benzyltriethylammonium chloride (BTEAc) (2.0 equivalent), potassium carbonate (10.0 equivalent), triphenylphosphine (PPh3) (4.0 equivalent), and palladium(II) acetate (Pd(OAc)2) (0.3 equivalent) were mixed and dissolved in N,N-dimethylacetamide (DMAC) solvent, stirred, and heated under reflux for 10 hours. The mixture was then cooled to room temperature and poured into ice water. The resulting precipitate was filtered to obtain a dark green solid crude product, which was then washed with deionized water and ethanol. The residue was purified by silica gel column chromatography to obtain a yellow solid product (…). R / S )-M-4 (yield 47%). Mass spectrometry: 758.55, elemental analysis: C, 88.58; H, 7.69; N, 3.73. This is a pair of racemic compounds, which were further separated into two single enantiomers by chiral high-performance liquid chromatography. R -M-4 and S -M-4.

[0055] Example 3 Combination Figure 5 As shown, the compound ( R / S )-M-11, its synthesis method is as follows: In the first step, under a nitrogen atmosphere, diiodine[2.2]-p-cycloarane (1.0 equivalent), 1-bromo-4-methoxy-9H-carbazole (2.5 equivalent), cuprous iodide (0.5 equivalent), 1,10-phenanthroline (0.5 equivalent), and cesium carbonate (3.0 equivalent) were dissolved in o-dichlorobenzene solvent in a reaction vessel and reacted at 180°C with stirring for 24 hours. The mixture was then cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was extracted with dichloromethane and washed with deionized water. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to obtain a white solid precursor-11 (78% yield).

[0056] In the second step, under an argon atmosphere, in a reaction vessel, precursor-11 (1.0 equivalent), benzyltriethylammonium chloride (BTEAc) (2.0 equivalent), potassium carbonate (10.0 equivalent), triphenylphosphine (PPh3) (4.0 equivalent), and palladium(II) acetate (Pd(OAc)2) (0.3 equivalent) were mixed in N,N-dimethylacetamide (DMAC) solvent, stirred, and heated under reflux for 10 hours. The mixture was then cooled to room temperature and poured into ice water. The resulting precipitate was filtered to obtain a dark green solid crude product, which was then washed with deionized water and ethanol. The residue was purified by silica gel column chromatography to obtain a yellow solid product (…). R / S )-M-11 (yield 41%). Mass spectrometry: 594.31, elemental analysis: C, 84.78; H, 5.12; N, 4.67; O, 5.43. This is a pair of racemic compounds, which were further separated into two single enantiomers by chiral high-performance liquid chromatography. R -M-11 and S -M-11.

[0057] Example 4 Combination Figure 6 As shown, the compound ( R / S )-M-22, its synthesis method is as follows: In the first step, under a nitrogen atmosphere, diiodo[2.2]-p-cycloarane (1.0 equivalent), 1-bromo-9H-carbazole (1.0 equivalent), cuprous iodide (0.25 equivalent), 1,10-phenanthroline (0.25 equivalent), and cesium carbonate (1.5 equivalent) were dissolved in o-dichlorobenzene solvent in a reaction vessel and heated and stirred at 180°C for 12 hours. The mixture was then cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was extracted with dichloromethane and washed with deionized water. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a white solid intermediate -22 (69% yield).

[0058] In the second step, under a nitrogen atmosphere, intermediate-22 (1.0 equivalent), 1-bromo-3,6-di-tert-butyl-9H-carbazole (1.2 equivalent), cuprous iodide (0.3 equivalent), 1,10-phenanthroline (0.3 equivalent), and cesium carbonate (2.0 equivalent) were dissolved in o-dichlorobenzene solvent in a reaction vessel and reacted at 180°C with stirring for 12 hours. The mixture was then cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was extracted with dichloromethane and washed with deionized water. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a white solid precursor-22 (73% yield).

[0059] In the third step, under an argon atmosphere, in a reaction vessel, precursor-22 (1.0 equivalent), benzyltriethylammonium chloride (BTEAc) (2.0 equivalent), potassium carbonate (10.0 equivalent), triphenylphosphine (PPh3) (4.0 equivalent), and palladium(II) acetate (Pd(OAc)2) (0.3 equivalent) were mixed in N,N-dimethylacetamide (DMAC) solvent, stirred, and heated under reflux for 10 hours. The mixture was then cooled to room temperature and poured into ice water. The resulting precipitate was filtered to obtain the crude product, which was then washed with deionized water and ethanol. The residue was purified by silica gel column chromatography to obtain a yellow solid product (…). R / S )-M-22 (yield 38%). Mass spectrometry: 646.25, elemental analysis: C, 89.17; H, 6.50; N, 4.32. This is a pair of racemic compounds, which were then separated into two single enantiomers by chiral high-performance liquid chromatography. R -M-22 and S -M-22.

[0060] Example 5 Combination Figure 7 As shown, the compound ( R / S M-25, its synthesis method is as follows: In the first step, under a nitrogen atmosphere, diiodine[2.2]-p-cycloarane (1.0 equivalent), 8-bromo-7H-benzocarbazole (2.5 equivalent), cuprous iodide (0.5 equivalent), 1,10-phenanthroline (0.5 equivalent), and cesium carbonate (3.0 equivalent) were dissolved in o-dichlorobenzene solvent in a reaction vessel and heated and stirred at 180°C for 24 hours. The mixture was then cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was extracted with dichloromethane and washed with deionized water. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a white solid precursor-25 (79% yield).

[0061] In the second step, under an argon atmosphere, in a reaction vessel, precursor-25 (1.0 equivalent), benzyltriethylammonium chloride (BTEAc) (2.0 equivalent), potassium carbonate (10.0 equivalent), triphenylphosphine (PPh3) (4.0 equivalent), and palladium(II) acetate (Pd(OAc)2) (0.3 equivalent) were mixed and dissolved in N,N-dimethylacetamide (DMAC) solvent, stirred, and heated under reflux for 10 hours. The mixture was then cooled to room temperature and poured into ice water. The resulting precipitate was filtered to obtain a dark green solid crude product, which was then washed with deionized water and ethanol. The residue was purified by silica gel column chromatography to obtain a yellow solid product (…). R / S)-M-25 (yield 35%). Mass spectrometry: 634.36, elemental analysis: C, 90.80; H, 4.75; N, 4.45. The product obtained at this point is a pair of racemic compounds, which were further separated by chiral high-performance liquid chromatography to obtain two single enantiomers. R -M-25 and S -M-25.

[0062] Example 6 Combination Figure 8 As shown, the compound ( R / S )-M-38, its synthesis method is as follows: In the first step, under a nitrogen atmosphere, diiodine[2.2]-p-cycloarane (1.0 equivalent), 1-bromo-10H-benzothiopheneindole (2.5 equivalent), cuprous iodide (0.5 equivalent), 1,10-phenanthroline (0.5 equivalent), and cesium carbonate (3.0 equivalent) were dissolved in o-dichlorobenzene solvent in a reaction vessel and reacted at 180°C with stirring for 24 hours. The mixture was then cooled to room temperature, and the solvent was removed under vacuum. The resulting residue was extracted with dichloromethane and washed with deionized water. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a white solid precursor-38 (72% yield).

[0063] In the second step, under an argon atmosphere, in a reaction vessel, precursor-38 (1.0 equivalent), benzyltriethylammonium chloride (BTEAc) (2.0 equivalent), potassium carbonate (10.0 equivalent), triphenylphosphine (PPh3) (4.0 equivalent), and palladium(II) acetate (Pd(OAc)2) (0.3 equivalent) were mixed and dissolved in N,N-dimethylacetamide (DMAC) solvent. The mixture was stirred and heated under reflux for 10 hours. It was then cooled to room temperature and poured into ice water. The resulting precipitate was filtered to obtain a dark green solid crude product, which was then washed with deionized water and ethanol. The residue was purified by silica gel column chromatography to obtain a yellow solid product (…). R / S )-M-38 (yield 35%). Mass spectrometry: 646.34, elemental analysis: C, 81.67; H, 4.10; N, 4.36; S, 9.87. The product obtained at this point is a pair of racemic compounds, which were further separated by chiral high-performance liquid chromatography to obtain two single enantiomers. R -M-38 and S -M-38.

[0064] Example 7 Combination Figure 9 As shown, the compound ( R / S )-M-60, its synthesis method is as follows: With compounds ( R / SUsing M-11 as a raw material, under a nitrogen atmosphere, in a reaction vessel, compound ( R / S) -M-11 (1.0 equivalent) was dissolved in dichloromethane solution, and then 1M boron tribromide (BBr3) in dichloromethane solution (5.0 equivalent) was added. The mixture was heated under reflux for 8 hours. After the reaction was completed, the mixture was cooled and poured into ice water. The precipitate was filtered, washed with methanol, and dried to give intermediate -60-1 (yield 85%). Intermediate-60-1 (1.0 equivalent) was dissolved in a mixture of dichloromethane and pyridine, and trifluoromethanesulfonic anhydride (Tf2O) (7.0 equivalent) was added. After stirring at room temperature for 8 hours, water was added, and the resulting precipitate was filtered and washed with methanol and ethyl acetate to obtain intermediate-60-2 (yield 72%). Under an argon atmosphere, in a reaction vessel, intermediate 60-2 (1.0 equivalent), diphenylamine (2.5 equivalent), tris(dibenzylacetone)dipalladium (Pd2(dba)3) (0.02 equivalent), and (1-methyl-2,2-diphenylcyclopropyl)di-tert-butylphosphine (cBRIDP) (0.15 equivalent) were dissolved in xylene solution. A 1M toluene solution (2.5 equivalent) of lithium bis(trimethylsilyl)amide (LiHMDS) was added dropwise with stirring. This mixture was heated under reflux for 12 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture. The reaction solution was extracted three times with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a yellow solid ( R / S M-60 (yield 56%). Mass spectrometry: 868.64, elemental analysis: C, 88.48; H, 5.13; N, 6.39. This is a pair of racemic compounds, which were then separated into two single enantiomers by chiral high-performance liquid chromatography. R -M-60 and S -M-60.

[0065] Example 8 Compounds ( R / S )-M-76, its synthesis method is as follows: Compounds ( R / S Reference for the synthesis of M-76 R / SThe synthesis of M-60, with the final step replacing the diphenylamine feedstock with carbazole: Under an argon atmosphere, in a reaction vessel, intermediate M-60-2 (1.0 equivalent), carbazole (2.5 equivalent), tris(dibenzylacetone)dipalladium (Pd2(dba)3) (0.02 equivalent), and (1-methyl-2,2-diphenylcyclopropyl)di-tert-butylphosphine (cBRIDP) (0.15 equivalent) were dissolved in xylene solution, and a 1M toluene solution of lithium bis(trimethylsilyl)amide (LiHMDS) (2.5 equivalent) was added dropwise with stirring. This mixture was heated under reflux for 12 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture. The reaction solution was extracted three times with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a yellow solid. R / S M-76 (yield 52%). Mass spectrometry: 864.54, elemental analysis: C, 88.91; H, 4.63; N, 6.46. The obtained product was then separated into two single enantiomers by chiral high-performance liquid chromatography. R -M-76 and S -M-76.

[0066] Example 9 Combination Figure 10 As shown, the compound ( R / S )-M-78, its synthesis method is as follows: With compounds ( R / S Using M-12 as a raw material, under a nitrogen atmosphere, in a reaction vessel, compound ( R / S )-M-12 (1.0 equivalent) was dissolved in dichloromethane solution, and then 1M boron tribromide (BBr3) in dichloromethane solution (5.0 equivalent) was added. The mixture was heated under reflux for 8 hours. After the reaction was completed, the mixture was cooled and poured into ice water. The precipitate was filtered, washed with methanol, and dried to give intermediate -78-1 (yield 80%). Intermediate-78-1 (1.0 equivalent) was dissolved in a mixture of dichloromethane and pyridine, and trifluoromethanesulfonic anhydride (Tf2O) (7.0 equivalent) was added. After stirring at room temperature for 8 hours, water was added, and the resulting precipitate was filtered and washed with methanol and ethyl acetate to obtain intermediate-78-2 (yield 66%). Under an argon atmosphere, in a reaction vessel, intermediate-78-2 (1.0 equivalent), diphenylamine (2.5 equivalent), tris(dibenzylacetone)dipalladium (Pd2(dba)3) (0.02 equivalent), and (1-methyl-2,2-diphenylcyclopropyl)di-tert-butylphosphine (cBRIDP) (0.15 equivalent) were dissolved in xylene solution. A 1M toluene solution (2.5 equivalent) of lithium bis(trimethylsilyl)amide (LiHMDS) was added dropwise with stirring. This mixture was heated under reflux for 12 hours. After cooling to room temperature, water and ethyl acetate were added to the reaction mixture. The reaction solution was extracted three times with ethyl acetate, and the organic layer was washed with saturated brine. The organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by silica gel column chromatography to give a yellow solid ( R / S )-M-78 (yield 51%). Mass spectrometry: 868.18, elemental analysis: C, 88.41; H, 5.07; N, 6.52. This is a pair of racemic compounds, which were then separated into two single enantiomers by chiral high-performance liquid chromatography. R -M-78 and S -M-78.

[0067] Example 10 The compound obtained in this invention is used as a guest dopant material for the luminescent layer in the fabrication of organic light-emitting diode (OLED) devices. The structure of the organic electroluminescent device, such as... Figure 11 As shown, from bottom to top, it includes: an anode 1, a hole injection layer 2, a hole transport layer 3, an electron blocking layer 4, a light-emitting layer 5, a hole blocking layer 6, an electron transport layer 7, an electron injection layer 8, and a cathode 9. The anode is made of ITO material; the hole injection layer is formed by doping HATCN and BPBPA materials, with HATCN doping ratio of 3wt% and a thickness of 75nm; the hole transport layer is made of BPBPA material with a thickness of 50nm; the electron blocking layer is made of BCzPh material with a thickness of 5nm; the light-emitting layer is formed by co-doping a host material and a guest material, with the host material being BH and the guest material being the material of this invention. R / S The compound is a 1 wt% guest doping layer with a thickness of 20 nm; the hole blocking layer is a TRZ-pDBF material with a thickness of 5 nm; the electron transport layer is formed by Liq and Im-An-Na materials, with Liq doping of 50 wt% and a thickness of 25 nm; the electron injection layer is a Liq material with a thickness of 2 nm; and the cathode is metallic Al with a thickness of 100 nm.

[0068] Comparative Example 1: It differs from Example 10 in that the luminescent guest material used is compound D1.

[0069] Comparative Example 2: It differs from Example 10 in that the luminescent guest material used is compound D2.

[0070] The chemical structures of the materials involved in the above-mentioned electroluminescent device structure are as follows:

[0071] .

[0072] Table 2 shows the maximum external quantum efficiency of electroluminescence, electroluminescence asymmetry factor, and electroluminescence spectrum peak positions of the device. Table 2. Maximum external quantum efficiency, electroluminescence spectral peak position, and electroluminescence asymmetry factor of electroluminescent devices.

[0073]

[0074] It can be seen that the circularly polarized electroluminescence spectra of organic light-emitting diode devices prepared using the single enantiomeric material of the luminescent compound prepared in this invention all exhibit chiral signals, with electroluminescence asymmetry factors ranging from 1.0 to 2.5 × 10⁻⁶. -3 Between these two examples, the comparative molecule showed no chiral signal. Meanwhile, compared to the comparative molecule, the organic electroluminescent device using the compound of this invention, while maintaining a comparable level of device efficiency, exhibits a significant redshift of the emission wavelength peak to the blue light and above region due to the introduction of the central cycloarylene.

[0075] It is understood that those skilled in the art can make equivalent substitutions or modifications to the technical solution and inventive concept of the present invention, and all such substitutions or modifications should fall within the protection scope of the appended claims.

Claims

1. A chiral indolocarbazole-based luminescent material, characterized in that, It has the formula ( R / S The chemical structure shown is )-M, where, R / S -M represents the chiral configuration of compound M. R -type or S -type,( R )-M and ( S )-M exhibits chiral enantiomeric structural features; Among them, the structures of ring A and ring B may be the same or different, and they are independently selected from benzene rings or five-membered heterocycles; m and k are independently selected from integers from 0 to 3, n and l are independently selected from integers from 0 to 4, and when there are multiple R1 to R4, they are independently selected from the same or different structures; R1 to R4 are independently selected from H, D, C1 to C 12 Alkyl, C1-C 12 Alkoxy, phenyl , by at least one C1~C 12 Alkyl-substituted phenyl groups, with at least one C1-C2 bond 12 Benzenes are synthesized by alkoxy-substituted phenyl groups or by two adjacent R1 to R4 groups bonded together with the ring they are attached to. R a and R b Independently selected from phenyl, and surrounded by at least one C1-C2. 12 Alkyl-substituted phenyl groups.

2. A chiral indolocarbazole-based luminescent material, characterized in that, It has the formula ( R / S The chemical structure shown is )-M, where, R / S -M represents the chiral configuration of compound M. R -type or S -type,( R )-M and ( S )-M exhibits chiral enantiomeric structural features; ； The chiral indolocarbazole luminescent material is selected from the following compounds: 。 3. A method for preparing a chiral indolocarbazole-based luminescent material, characterized in that, Used to prepare the (in claim 2) R / S )-M-1 to ( R / S The preparation method of any one of the compounds described in (M-58) comprises the following steps: Diiodine [2.2] for cycloaromatics Using raw materials a and b as starting materials, when raw materials a and b are different, the precursor is obtained through a stepwise Ullman reaction; when raw materials a and b are the same, the precursor is obtained through a one-step Ullman reaction. Under an argon atmosphere, in a reaction vessel, a mixture of precursor, benzyltriethylammonium chloride (BTEAc), potassium carbonate, triphenylphosphine (PPh3), and palladium(II) acetate (Pd(OAc)2) in a molar ratio of 1:2:10:4:0.3 was dissolved in N,N-dimethylacetamide (DMAC) solvent, stirred, and heated under reflux for 10 hours. The mixture was then cooled to room temperature and poured into ice water. The resulting precipitate was filtered to obtain a crude product, which was then washed with deionized water and ethanol. The residue was purified by silica gel column chromatography to obtain a racemic mixture of a chiral indolocarbazole luminescent material, which was then separated by chiral liquid chromatography to obtain... R Configuration and S Configurational single enantiomer; The chemical structure of raw material a is as follows: ； The chemical structure of raw material b is as follows: ； The chemical structure of the precursor is as follows: 。 4. A method for preparing a chiral indolocarbazole-based luminescent material, characterized in that, Used to prepare the (in claim 2) R / S) -M-60 to ( R / S The compound according to any one of M-93 includes the following steps: The methoxy group of raw material c is hydrolyzed to obtain a hydroxy-substituted product, which is then converted into an OTf functional group substituted product under the action of Tf2O. Finally, it is coupled with raw material d to form a chiral indolocarbazole luminescent material. The chemical structure of raw material c is as follows: or The raw material d is selected from one of the following structures: 。 5. A light-emitting layer material, characterized in that, Includes the chiral indolocarbazole luminescent material as described in any one of claims 1-2.

6. An organic electroluminescent device, characterized in that, It includes a light-emitting layer, the light-emitting layer comprising the light-emitting layer material as described in claim 5.

7. An electronic device, characterized in that, Including the organic electroluminescent device as described in claim 6.

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