A light-emitting material, applications thereof, and an organic electroluminescent device comprising the same

Abstract

This invention relates to the field of organic electroluminescence technology, and particularly to a general formula compound and its applications, as well as an organic electroluminescent device comprising the compound. The general formula compound of this invention has the structure shown in formula (1), where Y represents O or S, and R... a The compounds are selected from one of the following: substituted or unsubstituted C6-C60 aryl groups, substituted or unsubstituted C6-C60 aryloxy groups, substituted or unsubstituted C5-C60 heteroaryl groups, substituted or unsubstituted C6-C30 arylamino groups, and C3-C30 heteroarylamino groups. Organic electroluminescent devices using the compounds of this invention exhibit excellent luminous efficiency and lifetime.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescence technology, and particularly to an organic compound and its applications, as well as an organic electroluminescent device containing the compound. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a type of device with a sandwich-like structure, consisting of positive and negative electrode layers and an organic functional material layer sandwiched between them. When a voltage is applied to the electrodes of an OLED device, positive charges are injected from the positive electrode and negative charges from the negative electrode. Under the influence of an electric field, the positive and negative charges migrate, meet, and recombine within the organic layer to emit light. Due to their advantages such as high brightness, fast response, wide viewing angle, simple manufacturing process, and flexibility, OLED devices have attracted significant attention in the fields of new display technology and new lighting technology. Currently, this technology is widely used in display panels for new lighting fixtures, smartphones, and tablets, and its application is expected to expand further into large-size display products such as televisions. It is a rapidly developing and technologically demanding new display technology.

[0003] As OLED technology continues to advance in both lighting and display fields, research into its core materials is receiving increasing attention. This is because a high-efficiency, long-life OLED device is typically the result of an optimized combination of device structure and various organic materials. This presents chemists with both significant opportunities and challenges in designing and developing functionalized materials with diverse structures. Common functionalized organic materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as luminescent host materials and luminescent guest materials (dyes), etc.

[0004] To fabricate OLED devices with lower driving voltages, better luminous efficiency, and longer lifespans, and to continuously improve the performance of OLED devices, it is necessary not only to innovate the structure and fabrication process of OLED devices, but also to continuously research and innovate the optoelectronic functional materials in OLED devices to prepare functional materials with higher performance. Based on this, the OLED materials community has been committed to developing new organic electroluminescent materials to achieve devices with low start-up voltages, high luminous efficiency, and better lifespans.

[0005] TADF materials can theoretically achieve 100% internal quantum efficiency by utilizing the upconversion process from triplet to singlet states, thus enabling highly efficient light emission. However, traditional TADF molecules have a highly twisted electron donor-acceptor structure, which cannot simultaneously achieve high reverse intersystem crossing rates and high radiative transition rates, limiting further efficiency improvements and restricting the further application of this type of material in the display field. Summary of the Invention

[0006] To solve the above-mentioned technical problems, the present invention provides an organic compound with the structure shown below:

[0007]

[0008] In equation (1), Y represents O or S;

[0009] R a It is selected from one of the following: substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C30 arylamino, and C3-C30 heteroarylamino.

[0010] R 1 R 2 R represents substituents from a single substituent to the maximum permissible number of substituents. 1 R 2 Each group is independently selected from hydrogen, deuterium, halogen, or substituted or unsubstituted groups from the following: C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, and C5-C60 heteroaryl;

[0011] When the above R a R 1 R 2 When substituents are present, the substituents are each independently selected from one of cyano, C1-C10 chain alkyl, C3-C30 cycloalkyl, C1-C6 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl.

[0012] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents, they can be selected from different substituents. In this invention, when the same expression is used, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0013] In this specification, the expression Ca-Cb indicates that the group has a number of carbon atoms of ab. Unless otherwise specified, this number of carbon atoms generally does not include the number of carbon atoms of the substituents.

[0014] In this specification, the way a ring structure is represented by "—" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0015] In this specification, "each independently" means that when there are multiple subjects, they may be the same or different from each other.

[0016] In this invention, unless otherwise specified, the description of chemical elements generally includes the concept of their isotopes. For example, the description of "hydrogen (H)" includes its isotopes. 1 H (protium or H), 2 The concept of H (deuterium or D); carbon (C) includes... 12 C 13 C, etc., will not be elaborated further.

[0017] In this invention, heteroatoms generally refer to atoms or groups of atoms selected from N, O, S, P, Si and Se, preferably selected from N, O and S.

[0018] Examples of halogens in this specification include fluorine, chlorine, bromine, and iodine.

[0019] In this invention, unless otherwise specified, aryl and heteroaryl groups include both monocyclic and fused-ring types.

[0020] In this invention, the substituted or unsubstituted C6-C60 aryl groups include monocyclic aryl groups and fused-ring aryl groups, preferably C6-C30 aryl groups, and more preferably C6-C20 aryl groups. A monocyclic aryl group refers to a molecule containing at least one phenyl group. When a molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, exemplarily such as phenyl, biphenyl, and terphenyl. Specifically, the biphenyl group includes 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, meta-terphenyl-4-yl, meta-terphenyl-3-yl, and meta-terphenyl-2-yl. A fused-ring aryl group refers to a molecule containing at least two aromatic rings, where the aromatic rings are not independent of each other but share two adjacent carbon atoms fused together. Examples include: naphthyl, anthracene, phenanthrene, indene, fluorenyl, fluoranthyl, triphenylene, pyrene, perylene, etc. Naphthyl, 2-naphthyl, and their derivative groups, etc. The naphthyl includes 1-naphthyl or 2-naphthyl; the anthraceneyl is selected from 1-anthrayl, 2-anthrayl, and 9-anthrayl; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrene is selected from 1-pyrene, 2-pyrene, and 4-pyrene; the 2-tetraphenyl is selected from 1-2 ... The fluorene derivative group is selected from 9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, 9,9'-spirodifluorenyl, and benzo[a]fluorenyl.

[0021] The C3-C60 heteroaryl groups mentioned in this invention include monocyclic heteroaryl groups and fused-ring heteroaryl groups, preferably C3-C30 heteroaryl groups, more preferably C4-C20 heteroaryl groups, and even more preferably C5-C12 heteroaryl groups. A monocyclic heteroaryl group refers to a molecule containing at least one heteroaryl group. When a molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and the other groups are independent of each other and connected by a single bond. Examples of monocyclic heteroaryl groups include furanyl, thiophene, pyrrole, and pyridinyl. A fused-ring heteroaryl group refers to a molecule containing at least one aromatic heterocycle and an aromatic ring (aromatic heterocycle or aromatic ring), and the two are not independent of each other but share a group consisting of two adjacent atoms fused together. Examples of fused-ring heteroaryl groups include: benzofuranyl, benzothiophenyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazoyl, acridineyl, isobenzofuranyl, isobenzothiophenyl, benzocarbazoyl, azircarbazoyl, phenothiazinyl, phenothiazinyl, 9-phenylcarbazoyl, 9-naphthylcarbazoyl, dibenzocarbazoyl, indolocarbazoyl, etc.

[0022] Specific examples of arylene groups in this invention can be exemplified by removing one hydrogen atom from the aforementioned aryl examples to obtain a divalent group. The number of carbon atoms in arylene groups includes, but is not limited to, C6, C8, C10, C12, C14, C16, C18, C20, C22, C24, C26, and C28. Specific examples of heteroarylene groups in this invention can be exemplified by removing one hydrogen atom from the aforementioned heteroaryl examples to obtain a divalent group.

[0023] The aryl group in this invention can be exemplified by the monovalent group composed of the above-mentioned aryl and heteroaryl groups and oxygen.

[0024] In this invention, arylamino represents a group formed by replacing the hydrogen on an amino group with one or two aryl groups, wherein the linking site of the arylamino can be linked to the aryl group in the arylamino or to the N group in the arylamino, and the exemplary number of carbons and specific groups of the aryl group in the arylamino are the same as described above.

[0025] Examples of C6-C30 arylamino groups mentioned in this invention include phenylamino, methylphenylamino, naphthylamino, anthraceneylamino, phenanthreneamino, biphenylamino, etc.

[0026] Examples of C3-C30 heteroaryl amino groups mentioned in this invention include pyridinylamino, pyrimidinylamino, and dibenzofuranylamino.

[0027] Unless otherwise specified, the chain alkyl groups mentioned in this invention include straight-chain alkyl groups and branched-chain alkyl groups. Specifically, substituted or unsubstituted C1-C30 chain alkyl groups are preferably substituted or unsubstituted C1-C16 chain alkyl groups, and more preferably substituted or unsubstituted C1-C10 chain alkyl groups. Examples of substituted or unsubstituted C1-C10 chain alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, etc.

[0028] In this invention, the cycloalkyl group includes monocycloalkyl and polycycloalkyl; wherein, monocycloalkyl refers to an alkyl group containing a single ring structure; polycycloalkyl refers to a structure composed of two or more cycloalkyl groups sharing one or more carbon atoms on a ring; examples of C3-C20 cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0029] In this specification, the substituted or unsubstituted C1-C20 alkoxy group is preferably a substituted or unsubstituted C1-C10 alkoxy group. Examples of C1-C10 alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentooxy, isopentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, etc., among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentoxy, and isopentoxy are preferred, and methoxy is more preferred.

[0030] It should be noted that while the possible effects of each group / feature have been described separately for ease of explanation in this application, this does not mean that these groups / features act in isolation. In fact, the reason for achieving good performance is essentially the optimized combination of the entire molecule, the result of the synergistic effect between various groups, rather than the effect of a single group.

[0031] Furthermore, the general formula compounds of the present invention have the structures shown in formulas (2) and (3) as follows:

[0032]

[0033] In equations (2) and (3), Y and R 1 R 2 R a The definition is the same as that in equation (1), R a The definition of ' and R a same;

[0034] R bSelected from hydrogen, deuterium, halogen, or substituted or unsubstituted groups of the following: C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, C5-C60 heteroaryl;

[0035] When the above R b When substituents are present, the substituents are each independently selected from one of cyano, C1-C10 chain alkyl, C3-C30 cycloalkyl, C1-C6 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl.

[0036] Furthermore, in the above equations (1), (2), and (3), the R... 1 R 2 Each group is independently selected from hydrogen, deuterium, halogen, or substituted or unsubstituted groups of the following: C1-C10 chain alkyl, C3-C10 cycloalkyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, or C5-C60 heteroaryl.

[0037] When R 1 R 2 When substituents are present independently, the substituents are each independently selected from one of cyano, C1-C10 chain alkyl, C3-C30 cycloalkyl, C1-C6 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl.

[0038] Preferably, the R 1 R 2 Each group is independently selected from hydrogen or from one of the following groups, substituted or unsubstituted: C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, or C5-C60 heteroaryl, when R 2 When substituents are present, the substituents are each independently selected from one of cyano, C1-C10 chain alkyl, C3-C30 cycloalkyl, C1-C6 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl.

[0039] Furthermore, in the above general formula, R b Selected from hydrogen, deuterium, halogen, or substituted or unsubstituted groups of the following: C1-C10 chain alkyl, C3-C10 cycloalkyl, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, or C5-C60 heteroaryl.

[0040] When R b When substituents are present, the substituents are each independently selected from one of cyano, C1-C10 chain alkyl, C3-C30 cycloalkyl, C1-C6 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl;

[0041] Preferably, the R b Selected from hydrogen or a substituted or unsubstituted group of the following: C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C6-C60 aryloxy, or C5-C60 heteroaryl, when R b When substituents are present, the substituents are each independently selected from one of cyano, C1-C10 chain alkyl, C3-C30 cycloalkyl, C1-C6 alkoxy, C6-C30 aryl, and C3-C30 heteroaryl.

[0042] Furthermore, in the above general formula, R a Choose one of the following structural formulas:

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050] Furthermore, in the above general formula, R a With R a 'Same or different, R' a With R a Each is independently selected from one of the following structural formulas:

[0051]

[0052]

[0053]

[0054] Furthermore, in the above general formula, R2 and R... b Each group is independently selected from hydrogen or from any of the following groups:

[0055]

[0056]

[0057] Furthermore, the general formula compounds of the present invention are preferably compounds with the following specific structures, but are not limited to the following structures:

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073] The present invention also provides an organic electroluminescent device, including a substrate, including a first electrode, a second electrode, and one or more organic layers inserted between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by the above general formula (1).

[0074] Specifically, an embodiment of the present invention provides an organic electroluminescent device, including a substrate, and an anode layer, a plurality of light-emitting functional layers and a cathode layer sequentially formed on the substrate; the light-emitting functional layers include a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is located between the hole transport layer and the electron transport layer; wherein, preferably, the light-emitting layer contains a compound of the general formula of the present invention shown in formula (1) above.

[0075] OLED devices prepared using the compounds of this invention have low start-up voltage, high luminous efficiency, and better lifespan, which can meet the current requirements of panel manufacturers for high-performance materials.

[0076] The general formula compounds of the present invention introduce a group having a π-electron conjugated plane at the 1-position of ketones and their derivatives, R a The group representing aromatic or heteroaromatic hydrocarbons forms an effective steric n-π* (TSnp) transition between the carbonyl group and the 1-substituent, thus exhibiting both high radiative transition rates and reverse intersystem crossing rates, significantly improving the luminescence efficiency of this type of compound and enhancing device lifetime. In the general formula of this invention, R a Similar to the definition of Ra, its introduction expands the molecular frontier orbital distribution, reduces the singlet-triplet energy difference, and improves the delayed thermal activation characteristics of the molecule. R b The group representing aromatic hydrocarbons, when introduced, shields the luminescent core, increases the distance between adjacent molecules, and avoids concentration quenching, thus helping to improve the luminescence efficiency of this type of compound. Y represents O or S. O and S atoms belong to the same Group 6 element, with similar electronegativity (affecting the electron acceptor ability of the ketone parent nucleus) and atomic radius (affecting the ground state configuration of the molecule). Therefore, regardless of whether Y is O or S, the compound has excellent performance. However, due to the heavy atom effect, when Y is S, the molecular spin-orbit coupling constant is larger, which can further increase the reverse intersystem crossing rate and improve the luminescence efficiency.

[0077] In addition, the preparation process of the compounds of the present invention is simple and easy to implement, the raw materials are readily available, and it is suitable for mass production scale-up. Detailed Implementation

[0078] The specific preparation methods of the above-mentioned new compounds of the present invention will be described in detail below using several synthetic examples, but the preparation methods of the present invention are not limited to these synthetic examples.

[0079] All the chemical reagents used in this invention, such as petroleum ether, ethyl acetate, sodium sulfate, toluene, dichloromethane, o-dichlorobenzene, potassium carbonate, 9H-carbazole, cesium carbonate, and reaction intermediates, were purchased from Shanghai Titan Technology Co., Ltd. and Anhui Zesheng Technology Co., Ltd. The mass spectrometer used to determine the following compounds was a ZAB-HS type mass spectrometer (manufactured by Micromass, UK).

[0080] The following is a brief description of the synthesis method of the compounds of this invention: Due to the small steric hindrance of the carbonyl group, the reactivity of the bromine atom is almost the same in the Suzuki-Miyaura reaction and the Ullmann reaction. However, isomers can be separated by liquid chromatography, and the reaction site can be identified by the fluorescence color of the intermediate product. Step (I): If it is a carbon-carbon coupling reaction, the Suzuki-Miyaura reaction is selected: using a zero-valent palladium complex as a catalyst, potassium carbonate as a base, toluene and deionized water as solvents, and R-based boric acid or borate esters cross-coupled with bromo9H-oxanthracene-9-one under a nitrogen atmosphere; if it is a carbon-nitrogen coupling reaction, the Ullmann reaction is selected: using cuprous iodide as a catalyst, 1,10-bisphenanthrene-6 or 18-crown ether-6 as a ligand, potassium carbonate as a base, o-dichlorobenzene as a solvent, and R-based R-based R-based R-based R-coupled with bromo9H-oxanthracene-9-one under a nitrogen atmosphere. The second step (II) is similar to the first step, but due to steric hindrance, if the second step is a carbon-nitrogen coupling, the Ullmann reaction requires cuprous iodide as a catalyst, 18-crown ether-6 as a ligand, potassium carbonate as a base, o-dichlorobenzene as a solvent, and the group to be cross-coupled with bromo-9H-oxanthracene-9-one under a nitrogen atmosphere at 180°C.

[0081]

[0082] In the above formula, R represents 0-5 substituents at different positions, independently selected from hydrogen, deuterium, or one of the following groups, substituted or unsubstituted: halogen, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C1-C10 thioalkoxy, carbonyl, carboxyl, nitro, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused-ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl, or C5-C60 fused-ring heteroaryl. Two adjacent groups in R1-R5 can bond to each other to form one of the following groups, substituted or unsubstituted: C3-C10 cycloalkanes, C6-C30 aromatics, or C5-C30 heteroaromatics.

[0083] More specifically, the following provides methods for synthesizing representative compounds of the present invention:

[0084] Synthesis Examples

[0085] Synthesis Example 1: Synthesis of Compound B-1

[0086] 2.55 g (9.27 mmol) of 1-bromo-9H-oxanthracene-9-one, 1.55 g (9.27 mmol) of 9H-carbazole, 0.36 g (1.86 mmol) of cuprous iodide, 0.54 g (1.86 mmol) of 18-crown-6-ether, and 2.56 g (18.6 mmol) of anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 150 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product B-1 (2.11 g, 62.98% yield, HPLC purity 98.9%), which was a green solid. MALDI-TOF-MS results: Molecular ion peak: 361.11; Elemental analysis results: Theoretical values: C, 83.09; H, 4.18; N, 3.88; O, 8.85; Actual values: C, 83.10; H, 4.16; N, 3.87; O, 8.87.

[0087] Synthesis Example 2: Synthesis of Compound B-31

[0088] Synthesis of intermediate Z-1:

[0089]

[0090] 5 g (11.30 mmol) of 3-boronate pinacol-9,9'-spirodifluorene, 4.00 g (11.30 mmol) of 1,6-dibromo-9H-oxanthracene-9-one, and 1.31 g (1.13 mmol) of tetrakis(triphenylphosphine)palladium were added to 100 ml of toluene, and 3.12 g (22.61 mmol) of potassium carbonate was dissolved in 20 ml of deionized water. The mixture was reacted at 80 °C for 12 h under a nitrogen atmosphere. The mixture was separated, the solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:1) to obtain intermediate Z-1.

[0091] Synthesis of compound B-31:

[0092] 5.46 g (9.27 mmol) Z-1, 2.60 g (9.27 mmol) 9-H-3,6-bis-tert-butylcarbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene. The mixture was reacted at 150 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure. The product was then passed through a silica gel column (eluent: petroleum ether: dichloromethane = 4:1) to obtain the target product B-31 (6.17 g, 84.46% yield, HPLC purity 99.6%), a bright yellow solid. MALDI-TOF-MS results: Molecular ion peak: 787.35; Elemental analysis results: Theoretical values: C, 88.41; H, 5.76; N, 1.78; O, 4.06; Actual values: C, 88.41; H, 5.76; N, 1.76; O, 4.07.

[0093] Synthesis Example 3: Synthesis of Compound B-35

[0094] 5.46 g (9.27 mmol) Z-1, 2.72 g (9.27 mmol) 3H-3-purine diphenyl[G,IJ]nayl[2,1,8-CDE]chamomile, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:2) to obtain the target product B-35 (5.08 g, 68.51% yield, HPLC purity 99.1%), which was an orange solid. MALDI-TOF-MS results: Molecular ion peak: 799.25; Elemental analysis results: Theoretical values: C, 90.09; H, 4.16; N, 1.75; O, 4.00; Actual values: C, 90.08; H, 4.17; N, 1.72; O, 4.03.

[0095] Synthesis Example 4: Synthesis of Compound B-41

[0096] 5.46 g (9.27 mmol) Z-1, 3.10 g (9.27 mmol) 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:2) to obtain the target product B-41 (6.66 g, 85.43% yield, HPLC purity 98.8%), which was a bright yellow solid. MALDI-TOF-MS results: Molecular ion peak: 840.28; Elemental analysis results: Theoretical values: C, 88.55; H, 4.31; N, 3.33; O, 3.80; Actual values: C, 88.54; H, 4.32; N, 3.31; O, 3.83.

[0097] Synthesis Example 5: Synthesis of Compound B-51

[0098] Synthesis of intermediate Z-2:

[0099]

[0100] 5 g (11.30 mmol) of 3-boronate pinacol-9,9'-spirodifluorene, 4.00 g (11.30 mmol) of 1,3-dibromo-9H-oxanthracene-9-one, and 1.31 g (1.13 mmol) of tetrakis(triphenylphosphine)palladium were added to 100 ml of toluene, and 3.12 g (22.61 mmol) of potassium carbonate was dissolved in 20 ml of deionized water. The mixture was reacted at 80 °C for 12 h under a nitrogen atmosphere. The mixture was separated, the solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:1) to obtain intermediate Z-2.

[0101] Synthesis of compound B-51:

[0102] 5.46 g (9.27 mmol) Z-2, 2.72 g (9.27 mmol) 3H-3-purine diphenyl[G,IJ]nayl[2,1,8-CDE]chamomile, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:2) to obtain the target product B-51 (5.08 g, 68.51% yield, HPLC purity 99.3%), which was an orange solid. MALDI-TOF-MS results: Molecular ion peak: 799.25; Elemental analysis results: Theoretical values: C, 90.09; H, 4.16; N, 1.75; O, 4.00; Actual values: C, 90.10; H, 4.15; N, 1.73; O, 4.02.

[0103] Synthesis Example 6: Synthesis of Compound B-58

[0104] 5.46 g (9.27 mmol) Z-2, 3.10 g (9.27 mmol) 5-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:2) to obtain the target product B-58 (6.66 g, 85.43% yield, HPLC purity 98.8%), a bright yellow solid. MALDI-TOF-MS results: Molecular ion peak: 840.28; Elemental analysis results: Theoretical values: C, 88.55; H, 4.31; N, 3.33; O, 3.80; Actual values: C, 88.53; H, 4.33; N, 3.32; O, 3.82.

[0105] Synthesis Example 7: Synthesis of Compound B-67

[0106] Synthesis of intermediate Z-3:

[0107]

[0108] 4.00 g (11.30 mmol) of 1,6-bromo-9H-oxanthracene-9-one, 3.75 g (11.30 mmol) of 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.43 g (2.26 mmol) of cuprous iodide, 0.41 g (2.26 mmol) of 1,10-bisphenanthreneline, and 3.12 g (22.60 mmol) of potassium carbonate were added to 150 mL of ultra-dry o-dichlorobenzene and reacted at 180 °C for 18 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 2:1) to give intermediate Z-3, a golden yellow solid.

[0109] Synthesis of compound B-67

[0110] 5.61 g (9.27 mmol) Z-3, 2.72 g (9.27 mmol) 3H-3-purine diphenyl[G,IJ]nayl[2,1,8-CDE]chamomile, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:2) to obtain the target product B-67 (6.18 g, 81.71% yield, HPLC purity 98.2%), which was an orange-yellow solid. MALDI-TOF-MS results: Molecular ion peak: 815.26; Elemental analysis results: Theoretical values: C, 86.85; H, 4.08; N, 5.15; O, 3.92; Actual values: C, 86.87; H, 4.06; N, 5.17; O, 3.90.

[0111] Synthesis Example 8: Synthesis of Compound B-69

[0112] 5.61 g (9.27 mmol) Z-3, 1.70 g (9.27 mmol) 10H-phenoxazine, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 140 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product B-69 (3.75 g, 57.15% yield, HPLC purity 97.9%), which was a red solid. MALDI-TOF-MS results: Molecular ion peak: 707.22; Elemental analysis results: Theoretical values: C, 83.15; H, 4.13; N, 5.94; O, 6.78; Actual values: C, 83.13; H, 4.15; N, 5.93; O, 6.79.

[0113] Synthesis Example 9: Synthesis of Compound B-73

[0114] 5.61 g (9.27 mmol) Z-3, 3.10 g (9.27 mmol) 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product B-73 (7.11 g, 89.56% yield, HPLC purity 99.2%), which was a golden yellow solid. MALDI-TOF-MS results: Molecular ion peak: 856.28; Elemental analysis results: Theoretical values: C, 85.49; H, 4.23; N, 6.54; O, 3.73; Actual values: C, 85.52; H, 4.21; N, 6.55; O, 3.72.

[0115] Synthesis Example 10: Synthesis of Compound B-74:

[0116] 5.61 g (9.27 mmol) Z-3, 3.10 g (9.27 mmol) 5-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product B-74 (6.49 g, 81.69% yield, HPLC purity 99.1%), which was a golden yellow solid. MALDI-TOF-MS results: Molecular ion peak: 856.28; Elemental analysis results: Theoretical values: C, 85.49; H, 4.23; N, 6.54; O, 3.73; Actual values: C, 85.50; H, 4.24; N, 6.55; O, 3.71.

[0117] Synthesis Example 11: Synthesis of Compound B-119

[0118] Synthesis of intermediate Z-4:

[0119]

[0120] 4.02 g (9.27 mmol) of 1,3,6-bromo-9H-oxanthracene-9-one, 5.20 g (18.54 mmol) of 9-H-3,6-bis-tert-butylcarbazole, 0.36 g (1.86 mmol) of cuprous iodide, 0.54 g (1.86 mmol) of 18-crown-6-ether, and 2.56 g (18.54 mmol) of anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 150 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the mixture was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 5:1) to give intermediate Z-4.

[0121] 7.69 g (9.27 mmol) Z-4, 2.07 g (9.27 mmol) 9-H-1,3,6,8-tetramethylcarbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 160 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:1) to obtain the target product B-119 (7.62 g, 84.54% yield, HPLC purity 98.8%), a bright yellow solid. MALDI-TOF-MS results: Molecular ion peak: 971.54; Elemental analysis results: Theoretical values: C, 85.23; H, 7.15; N, 4.32; O, 3.29; Actual values: C, 85.22; H, 7.16; N, 4.31; O, 3.31.

[0122] Synthesis Example 12: Synthesis of Compound B-121

[0123] 7.69 g (9.27 mmol) Z-4, 3.10 g (9.27 mmol) 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 2:1) to obtain the target product B-121 (9.00 g, 89.78% yield, HPLC purity 99.1%), which was a golden yellow solid. MALDI-TOF-MS results: Molecular ion peak: 1080.53; Elemental analysis results: Theoretical values: C, 85.52; H, 6.34; N, 5.18; O, 2.96; Actual values: C, 85.52; H, 6.33; N, 5.16; O, 2.99.

[0124] Synthesis Example 13: Synthesis of Compound B-123

[0125] 7.69 g (9.27 mmol) Z-4, 3.10 g (9.27 mmol) 5-phenyl-5,7-dihydroindole[2,3-b]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 2:1) to obtain the target product B-123 (9.00 g, 89.78% yield, HPLC purity 99.1%), which was an orange-yellow solid. MALDI-TOF-MS results: Molecular ion peak: 1080.53; Elemental analysis results: Theoretical values: C, 85.52; H, 6.34; N, 5.18; O, 2.96; Actual values: C, 85.55; H, 6.31; N, 5.15; O, 2.99.

[0126] Synthesis Example 14: Synthesis of Compound C-1

[0127] 2.68 g (9.27 mmol) of 1-bromo-9H-thioxanthracene-9-one, 1.55 g (9.27 mmol) of 9H-carbazole, 0.36 g (1.86 mmol) of cuprous iodide, 0.54 g (1.86 mmol) of 18-crown-6-ether, and 2.56 g (18.6 mmol) of anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 150 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product C-1 (2.16 g, 61.73% yield, HPLC purity 98.2%), which was a yellow-green solid. MALDI-TOF-MS results: Molecular ion peak: 377.09; Elemental analysis results: Theoretical values: C, 79.55; H, 4.01; N, 3.71; O, 4.24; S, 8.49; Actual values: C, 79.58; H, 4.01; N, 3.73; O, 4.22; S, 8.47.

[0128] Synthesis Example 15: Synthesis of Compound C-31

[0129] Synthesis of intermediate Z-5:

[0130]

[0131] 5 g (11.30 mmol) of 3-boronate pinacol-9,9'-spirodifluorene, 4.18 g (11.30 mmol) of 1,6-dibromo-9H-thioxanthracene-9-one, and 1.31 g (1.13 mmol) of tetrakis(triphenylphosphine)palladium were added to 100 ml of toluene, and 3.12 g (22.61 mmol) of potassium carbonate was dissolved in 20 ml of deionized water. The mixture was reacted at 80 °C for 12 h under a nitrogen atmosphere. The mixture was separated, the solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:1) to obtain intermediate Z-5.

[0132] Synthesis of compound C-31:

[0133] 5.61 g (9.27 mmol) Z-5, 2.60 g (9.27 mmol) 9-H-3,6-bis-tert-butylcarbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene. The mixture was reacted at 150 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure. The product was then passed through a silica gel column (eluent: petroleum ether: dichloromethane = 4:1) to obtain the target product C-31 (6.21 g, 83.32% yield, HPLC purity 99.1%), which was an orange-yellow solid. MALDI-TOF-MS results: Molecular ion peak: 803.32; Elemental analysis results: Theoretical values: C, 86.64; H, 5.64; N, 1.74; O, 1.99; S, 3.99; Actual values: C, 86.62; H, 5.62; N, 1.75; O, 1.98; S, 4.03.

[0134] Synthesis Example 16: Synthesis of Compound C-35

[0135] 5.61 g (9.27 mmol) Z-5, 2.72 g (9.27 mmol) 3H-3-purine diphenyl[G,IJ]nayl[2,1,8-CDE]chamomile, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:2) to obtain the target product C-35 (5.22 g, 69.01% yield, HPLC purity 99.5%), which was an orange-red solid. MALDI-TOF-MS results: Molecular ion peak: 815.23; Elemental analysis results: Theoretical values: C, 88.32; H, 4.08; N, 1.72; O, 1.96; S, 3.93; Actual values: C, 88.34; H, 4.07; N, 1.71; O, 1.97; S, 3.91.

[0136] Synthesis Example 17: Synthesis of Compound C-41

[0137] 5.61 g (9.27 mmol) Z-5, 3.10 g (9.27 mmol) 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:2) to obtain the target product C-41 (6.78 g, 85.34% yield, HPLC purity 98.1%), which was an orange-yellow solid. MALDI-TOF-MS results: Molecular ion peak: 856.25; Elemental analysis results: Theoretical values: C, 86.89; H, 4.23; N, 3.27; O, 1.87; S, 3.74; Actual values: C, 86.90; H, 4.25; N, 3.24; O, 1.89; S, 3.72.

[0138] Synthesis Example 18: Synthesis of Compound C-51

[0139] Synthesis of intermediate Z-6:

[0140]

[0141] 5 g (11.30 mmol) of pinacol-9,9'-spirodifluorene, 4.18 g (11.30 mmol) of 1,3-dibromo-9H-thioxanthracene-9-one, and 1.31 g (1.13 mmol) of tetrakis(triphenylphosphine)palladium were added to 100 ml of toluene, and 3.12 g (22.61 mmol) of potassium carbonate was dissolved in 20 ml of deionized water. The mixture was reacted at 80 °C for 12 h under a nitrogen atmosphere. The mixture was separated, the solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:1) to obtain intermediate Z-6.

[0142] Synthesis of compound C-51:

[0143] 5.61 g (9.27 mmol) Z-6, 2.72 g (9.27 mmol) 3H-3-purine diphenyl[G,IJ]nayl[2,1,8-CDE]chamomile, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:2) to obtain the target product C-51 (6.11 g, 80.78% yield, HPLC purity 99.5%), which was an orange-red solid. MALDI-TOF-MS results: Molecular ion peak: 815.23; Elemental analysis results: Theoretical values: C, 88.32; H, 4.08; N, 1.72; O, 1.96; S, 3.93; Actual values: C, 88.32; H, 4.07; N, 1.71; O, 1.95; S, 3.95.

[0144] Synthesis Example 19: Synthesis of Compound C-58

[0145] 5.61 g (9.27 mmol) Z-6, 3.10 g (9.27 mmol) 5-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:2) to obtain the target product C-58 (6.58 g, 82.82% yield, HPLC purity 98.4%), which was an orange-red solid. MALDI-TOF-MS results: Molecular ion peak: 856.25; Elemental analysis results: Theoretical values: C, 86.89; H, 4.23; N, 3.27; O, 1.87; S, 3.74; Actual values: C, 86.90; H, 4.20; N, 3.29; O, 1.85; S, 3.76.

[0146] Synthesis Example 20: Synthesis of Compound C-67

[0147] Synthesis of intermediate Z-7:

[0148]

[0149] 4.18 g (11.30 mmol) of 1,6-bromo-9H-thioxanthracene-9-one, 3.75 g (11.30 mmol) of 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.43 g (2.26 mmol) of cuprous iodide, 0.41 g (2.26 mmol) of 1,10-bisphenanthreneline, and 3.12 g (22.60 mmol) of potassium carbonate were added to 150 mL of ultra-dry o-dichlorobenzene and reacted at 180 °C for 18 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 2:1) to give intermediate Z-7, a golden yellow solid.

[0150] Synthesis of compound C-67

[0151] 5.76 g (9.27 mmol) Z-7, 2.72 g (9.27 mmol) 3H-3-purine diphenyl[G,IJ]nayl[2,1,8-CDE]chamomile, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (electrolyte: petroleum ether: dichloromethane = 1:2) to obtain the target product C-67 (5.83 g, 75.59% yield, HPLC purity 98.9%), which was an orange-red solid. MALDI-TOF-MS results: Molecular ion peak: 831.23; Elemental analysis results: Theoretical values: C, 85.17; H, 4.00; N, 5.05; O, 1.92; S, 3.85; Actual values: C, 85.17; H, 4.01; N, 5.03; O, 1.95; S, 3.84.

[0152] Synthesis Example 21: Synthesis of Compound C-69

[0153] 5.76 g (9.27 mmol) Z-7, 1.70 g (9.27 mmol) 10H-phenoxazine, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 140 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product C-69 (4.83 g, 71.98% yield, HPLC purity 97.6%), which was a red solid. MALDI-TOF-MS results: Molecular ion peak: 723.20; Elemental analysis results: Theoretical values: C, 81.31; H, 4.04; N, 5.81; O, 4.42; S, 4.43; Actual values: C, 81.30; H, 4.02; N, 5.84; O, 4.43; S, 4.41.

[0154] Synthesis Example 22: Synthesis of Compound C-73

[0155] 5.76 g (9.27 mmol) Z-7, 3.10 g (9.27 mmol) 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product C-73 (7.17 g, 88.59% yield, HPLC purity 99.4%), which was a golden yellow solid. MALDI-TOF-MS results: Molecular ion peak: 872.26; Elemental analysis results: Theoretical values: C, 83.92; H, 4.16; N, 6.42; O, 1.83; S, 3.67; Actual values: C, 83.93; H, 4.15; N, 6.44; O, 1.82; S, 3.66.

[0156] Synthesis Example 23: Synthesis of Compound C-74:

[0157] 5.76 g (9.27 mmol) Z-7, 3.10 g (9.27 mmol) 5-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 1:1) to obtain the target product C-74 (6.49 g, 80.19% yield, HPLC purity 99.4%), which was a golden yellow solid. MALDI-TOF-MS results: Molecular ion peak: 872.26; Elemental analysis results: Theoretical values: C, 83.92; H, 4.16; N, 6.42; O, 1.83; S, 3.67; Actual values: C, 83.91; H, 4.18; N, 6.41; O, 1.82; S, 3.68.

[0158] Synthesis Example 24: Synthesis of Compound C-119

[0159] Synthesis of intermediate Z-8:

[0160]

[0161] 4.17 g (9.27 mmol) of 1,3,6-bromo-9H-thioxanthracene-9-one, 5.20 g (18.54 mmol) of 9-H-3,6-bis-tert-butylcarbazole, 0.36 g (1.86 mmol) of cuprous iodide, 0.54 g (1.86 mmol) of 18-crown-6-ether, and 2.56 g (18.54 mmol) of anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 150 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the mixture was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 5:1) to give intermediate Z-8.

[0162] 7.84 g (9.27 mmol) Z-8, 2.07 g (9.27 mmol) 9-H-1,3,6,8-tetramethylcarbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 160 °C for 12 h under a nitrogen atmosphere. The solvent was removed by vacuum distillation, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 3:1) to obtain the target product C-119 (7.77 g, 84.90% yield, HPLC purity 99.0%), a bright yellow solid. MALDI-TOF-MS results: Molecular ion peak: 987.52; Elemental analysis results: Theoretical values: C, 83.85; H, 7.04; N, 4.25; O, 1.62; S, 3.24; Actual values: C, 83.85; H, 7.05; N, 4.28; O, 1.60; S, 3.22.

[0163] Synthesis Example 25: Synthesis of Compound C-121

[0164] 7.84 g (9.27 mmol) Z-8, 3.10 g (9.27 mmol) 12-phenyl-5,12-dihydroindole[3,2-a]carbazole, 0.36 g (1.86 mmol) cuprous iodide, 0.54 g (1.86 mmol) 18-crown-6-ether, and 2.56 g (18.6 mmol) anhydrous potassium carbonate were added to 100 mL of o-dichlorobenzene and reacted at 180 °C for 12 h under a nitrogen atmosphere. The solvent was removed by heating under reduced pressure, and the product was passed through a silica gel column (eluent: petroleum ether: dichloromethane = 2:1) to obtain the target product C-121 (8.77 g, 86.20% yield, HPLC purity 99.3%), which was a golden yellow solid. MALDI-TOF-MS results: Molecular ion peak: 1096.51; Elemental analysis results: Theoretical values: C, 84.27; H, 6.25; N, 5.11; O, 1.46; S, 2.92; Actual values: C, 84.26; H, 6.23; N, 5.10; O, 1.45; S, 2.96.

[0165] The photophysical properties of some representative compounds in this invention are detailed in Table 1 below.

[0166] Table 1:

[0167]

[0168]

[0169] The organic electroluminescent device of the present invention will be further described below through specific compound application examples.

[0170] Example 1

[0171] The device structure of this embodiment is shown below:

[0172] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-1(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0173] In this embodiment, the anode is ITO; the hole injection layer is made of HI, with a total thickness of 5-30 nm, and 10 nm in this embodiment; the hole transport layer is made of HI, with a total thickness of 5-500 nm, and 30 nm in this embodiment; the host is the main material of the wide bandgap organic light-emitting layer, B-1 is a dye with a doping concentration of 20 wt%, and the thickness of the organic light-emitting layer is generally 1-200 nm, and 30 nm in this embodiment; the electron transport layer is made of ET, with a thickness of 5-300 nm, and 30 nm in this embodiment; the electron injection layer and cathode materials are LiF (0.5 nm) and aluminum (150 nm).

[0174] Example 2

[0175] The preparation method is the same as in Example 1, except that the dye is replaced with B-2 instead of B-1. The specific synthesis method of compound B-2 can be found in Synthesis Example 1. The device structure is as follows:

[0176] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-2(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0177] Example 3

[0178] The preparation method is the same as in Example 1, except that the dye is replaced with B-7 instead of B-1. The specific synthesis method for compound B-7 can be found in Example 1. The device structure is as follows:

[0179] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-7(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0180] Example 4

[0181] The preparation method is the same as in Example 1, except that the dye is replaced with B-8 instead of B-1. The specific synthesis method of compound B-8 can be found in Synthesis Example 1. The device structure is as follows:

[0182] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-8(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0183] Example 5

[0184] The preparation method is the same as in Example 1, except that the dye is replaced with B-9 instead of B-1. The specific synthesis method of compound B-9 can be found in Synthesis Example 1. The device structure is as follows:

[0185] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-9(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0186] Example 6

[0187] The preparation method is the same as in Example 1, except that the dye is replaced with B-25 instead of B-1. The specific synthesis method of compound B-25 can be found in Synthesis Example 4. The device structure is as follows:

[0188] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-25(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0189] Example 7

[0190] The preparation method is the same as in Example 1, except that the dye is replaced with B-36 instead of B-1. The specific synthesis method of compound B-36 can be found in Synthesis Example 4. The device structure is as follows:

[0191] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-36(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0192] Example 8

[0193] The preparation method is the same as in Example 1, except that the dye is replaced with B-37 instead of B-1. The specific synthesis method of compound B-37 can be found in Synthesis Example 4. The device structure is as follows:

[0194] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-37(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0195] Example 9

[0196] The preparation method is the same as in Example 1, except that the dye is replaced with B-46 instead of B-1. The specific synthesis method for compound B-46 can be found in Synthesis Example 4. The device structure is as follows:

[0197] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-46(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0198] Example 10

[0199] The preparation method is the same as in Example 1, except that the dye is replaced with B-52 instead of B-1. The specific synthesis method of compound B-52 can be found in Synthesis Example 4. The device structure is as follows:

[0200] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-52(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0201] Example 11

[0202] The preparation method is the same as in Example 1, except that the dye is replaced with B-61 instead of B-1. The specific synthesis method of compound B-61 can be found in Synthesis Example 7. The device structure is as follows:

[0203] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-61(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0204] Example 12

[0205] The preparation method is the same as in Example 1, except that the dye is replaced with B-73 instead of B-1. The device structure is as follows: ITO / HI (10nm) / HT (30nm) / Host: 20wt% B-73 (30nm) / ET (30nm) / LiF (0.5nm) / Al (150nm)

[0206] Example 13

[0207] The preparation method is the same as in Example 1, except that the dye is replaced with B-85 instead of B-1. The specific synthesis method of compound B-85 can be found in Synthesis Example 7. The device structure is as follows:

[0208] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-85(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0209] Example 14

[0210] The preparation method is the same as in Example 1, except that the dye is replaced with B-93 instead of B-1. The specific synthesis method of compound B-93 can be found in Synthesis Example 7. The device structure is as follows:

[0211] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-93(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0212] Example 15

[0213] The preparation method is the same as in Example 1, except that the dye is replaced with B-115. The specific synthesis method of compound B-115 can be found in Synthesis Example 11. The device structure is as follows:

[0214] ITO / HI(10nm) / HT(30nm) / Host:20wt%B-115(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0215] Example 16

[0216] The preparation method is the same as in Example 1, except that the dye is replaced with C-1 instead of B-1. The device structure is as follows:

[0217] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-1(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0218] Example 17

[0219] The preparation method is the same as in Example 1, except that the dye is replaced by C-2 instead of B-1. The specific synthesis method of compound C-2 can be found in Synthesis Example 14. The device structure is as follows:

[0220] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-2(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0221] Example 18

[0222] The preparation method is the same as in Example 1, except that the dye is replaced by C-7 instead of B-1. The specific synthesis method of compound C-7 can be found in Synthesis Example 14. The device structure is as follows:

[0223] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-7(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0224] Example 19

[0225] The preparation method is the same as in Example 1, except that the dye is replaced by C-8 instead of B-1. The specific synthesis method of compound C-8 can be found in Synthesis Example 14. The device structure is as follows:

[0226] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-8(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0227] Example 20

[0228] The preparation method is the same as in Example 1, except that the dye is replaced with C-9 instead of B-1. The specific synthesis method of compound C-9 can be found in Synthesis Example 14. The device structure is as follows:

[0229] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-9(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0230] Example 21

[0231] The preparation method is the same as in Example 1, except that the dye is replaced by C-25 instead of B-1. The specific synthesis method of compound C-25 can be found in Synthesis Example 17. The device structure is as follows:

[0232] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-25(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0233] Example 22

[0234] The preparation method is the same as in Example 1, except that the dye is replaced by C-36 instead of B-1. The specific synthesis method of compound C-36 can be found in Synthesis Example 17. The device structure is as follows:

[0235] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-36(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0236] Example 23

[0237] The preparation method is the same as in Example 1, except that the dye is replaced with C-37 instead of B-1. The specific synthesis method of compound C-37 can be found in Synthesis Example 17. The device structure is as follows:

[0238] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-37(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0239] Example 24

[0240] The preparation method is the same as in Example 1, except that the dye is replaced with C-46 instead of B-1. The specific synthesis method of compound C-46 can be found in Synthesis Example 17. The device structure is as follows:

[0241] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-46(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0242] Example 25

[0243] The preparation method is the same as in Example 1, except that the dye is replaced with C-52 instead of B-1. The specific synthesis method of compound C-52 can be found in Synthesis Example 17. The device structure is as follows:

[0244] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-52(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0245] Example 26

[0246] The preparation method is the same as in Example 1, except that the dye is replaced with C-61 instead of B-1. The specific synthesis method of compound C-61 can be found in Synthesis Example 20. The device structure is as follows:

[0247] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-61(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0248] Example 27

[0249] The preparation method is the same as in Example 1, except that the dye is replaced with C-73 instead of B-1. The specific synthesis method of compound C-73 can be found in Synthesis Example 20. The device structure is as follows:

[0250] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-73(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0251] Example 28

[0252] The preparation method is the same as in Example 1, except that the dye is replaced with C-85 instead of B-1. The specific synthesis method of compound C-85 can be found in Synthesis Example 20. The device structure is as follows:

[0253] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-85(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0254] Example 29

[0255] The preparation method is the same as in Example 1, except that the dye is replaced with C-93 instead of B-1. The specific synthesis method of compound C-93 can be found in Synthesis Example 20. The device structure is as follows:

[0256] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-93(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0257] Example 30

[0258] The preparation method is the same as in Example 1, except that the dye is replaced by C-115 instead of B-1. The specific synthesis method of compound C-115 can be found in Synthesis Example 24. The device structure is as follows:

[0259] ITO / HI(10nm) / HT(30nm) / Host:20wt%C-115(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0260] Comparative Device Example 1

[0261] The preparation method is the same as that of device example 1, except that the compound B-1 of the present invention used in the light-emitting layer is replaced with compound P1 in the prior art. The specific device structure is as follows:

[0262] ITO / HI(10nm) / HT(30nm) / Host:20wt%P1(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0263] Comparative Device Example 2

[0264] The preparation method is the same as that of device example 1, except that the compound B-1 of the present invention used in the light-emitting layer is replaced with compound P2 in the prior art. The specific device structure is as follows:

[0265] ITO / HI(10nm) / HT(30nm) / Host:20wt%P2(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0266] Comparative Device Example 3

[0267] The preparation method is the same as that of device example 1, except that the compound B-1 of the present invention used in the light-emitting layer is replaced with compound P3 in the prior art. The specific device structure is as follows:

[0268] ITO / HI(10nm) / HT(30nm) / Host:20wt%P3(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0269] Comparative Device Example 4

[0270] The preparation method is the same as that of device example 1, except that the compound B-1 of the present invention used in the light-emitting layer is replaced with compound P4 in the prior art. The specific device structure is as follows:

[0271] ITO / HI(10nm) / HT(30nm) / Host:20wt%P4(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0272] Comparative Device Example 5

[0273] The preparation method is the same as that of device example 1, except that the compound B-1 of the present invention used in the light-emitting layer is replaced with compound P5 in the prior art. The specific device structure is as follows:

[0274] ITO / HI(10nm) / HT(30nm) / Host:20wt%P5(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0275] The structural formulas of the various organic materials used in the above embodiments are as follows:

[0276]

[0277]

[0278] The specific performance data of the organic electroluminescent devices D1 to D30 and devices R1 to R5 prepared in the above-described device embodiments are detailed in Table 2 below:

[0279] Table 2:

[0280]

[0281]

[0282] As shown in Table 2, when the material schemes and fabrication processes of other functional layers in the organic electroluminescent device structure are exactly the same, compared with the comparative examples, the organic electroluminescent devices prepared in Device Examples 1-30 of the present invention have significant improvements in light color, efficiency, roll-off and device lifetime compared with the organic electroluminescent devices prepared in Comparative Examples 1-5.

[0283] From the perspective of light color, the introduction of n orbitals into the compound of this invention reduces the emission band gap and has a certain degree of red shift compared to the comparative compounds P1-P5 which do not have n orbitals. Subsequently, D1-D30 achieved full-color emission in the visible light region from blue to red by adjusting the intensity of the dye electron donor, breaking through the bottleneck of difficult light color adjustment of this type of material.

[0284] From an efficiency perspective, spatial n-π*(TSnp) transitions significantly increase the spin-orbit coupling constant of molecules, thereby improving the utilization rate of triplet excitons. Additionally, R... b It protects the luminescent core and reduces exciton quenching, thus significantly improving device efficiency. In terms of roll-off, the spatial n-π*(TSnp) transition increases the reverse intersystem crossing rate, reduces the triplet exciton lifetime, and suppresses exciton quenching. Therefore, compared to R1-R5, devices D1-D30 still have higher external quantum efficiency and smaller roll-off at high brightness.

[0285] From a lifetime perspective, the carbonyl group of the compound of this invention has strong chemical reactivity, which can form hydrogen bonds with adjacent molecules and damage device lifetime. The addition of a protecting group at the ortho position can effectively inhibit the formation of intermolecular hydrogen bonds. In addition, the spatial n-π*(TSnp) transition increases the reverse intersystem crossing rate and reduces the triplet exciton lifetime, which can effectively inhibit the annihilation of triplet excitons to generate high-energy intermediates and reduce chemical bond breaking. Therefore, compared with R1-R5, the lifetime of D1-D30 devices is significantly improved.

[0286] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be implemented. Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above embodiments. It should be understood that, guided by the concept of the present invention, those skilled in the art can make various modifications and improvements. The appended claims summarize the scope of the present invention. Equivalent substitutions of various raw materials in the product of the present invention, the addition of auxiliary components, and the selection of specific methods all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A compound selected from the following specific structures: 。 2. The application of the compound of claim 1 as a light-emitting layer material in organic electroluminescent devices.

3. An organic electroluminescent device, comprising a first electrode, a second electrode, and one or more organic layers inserted between the first electrode and the second electrode, characterized in that, The organic layer includes at least one compound as described in claim 1.

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