An organic compound, application thereof, and an organic electroluminescence device comprising the same

Abstract

The present application relates to a kind of compound and its application, and the organic electroluminescent device comprising the compound, the compound has the structure of the following formula, wherein, X 1 And X 2 Respectively independently N or B;Ring A, ring B, ring C are benzene ring;Ring d 1 , ring d 2 Respectively independently benzene ring or naphthalene ring;Ring E and ring F each independently represents C4-C30 aromatic ring.The compound of the present application as the luminescent material in OLED device, it shows excellent device performance and stability.The present application simultaneously protects the organic electroluminescent device using the compound of the above general formula.

Description

Technical Field

[0001] This invention relates to an organic compound and its applications, as well as an organic electroluminescent device containing the compound, belonging to the field of organic electroluminescence technology. 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. Due to their advantages such as high brightness, fast response, wide viewing angle, simple fabrication, and flexibility, OLEDs have attracted significant attention in the fields of new display and lighting technologies. Currently, this technology is widely used in display panels for new lighting fixtures, smartphones, and tablets, and its application is further expanding to large-size display products such as televisions. It is a rapidly developing and technologically demanding new display technology. To fabricate OLEDs with lower driving voltages, better luminous efficiency, and longer lifespans, and to continuously improve the performance of OLEDs, it is necessary not only to optimize the OLED device structure and fabrication process but also to conduct in-depth research on the optoelectronic functional materials within OLED devices to develop higher-performance functional materials.

[0003] In 2012, to promote the development of the ultra-high-definition display field, the International Telecommunication Union Radiocommunication Sector (ITU-R) issued the BT.2020 standard, whose color gamut area is much larger than BT.709, posing new challenges to the construction of OLEDs. Therefore, improving the color purity of OLEDs to meet the BT.2020 standard has become an important research direction in this field.

[0004] Studies have shown that the multiple resonance (MR) effect can effectively suppress molecular structural relaxation and vibrational coupling, significantly narrowing the fluorescence spectrum of dyes and thus greatly improving the color purity of devices. Currently, the multiple resonance effect is mainly induced by alternating nitrogen and boron atoms or carbonyl groups. However, boron atoms and carbonyl groups have high chemical reactivity, which, while improving the color purity of devices, also introduces stability issues, limiting the application of such materials. Therefore, preparing multiple resonance materials with good stability remains a significant challenge. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention provides a novel multi-resonance fluorescent dye. The specific technical solution is as follows.

[0006] An organic compound having a structure as shown in any of the following formulas (1), (2), (3), or (4):

[0007]

[0008] Among them, X 1 and X 2 Each can be N or B independently;

[0009] Rings A, B, and C are all benzene rings; ring d 1 , ring d 2 Each ring can be a benzene ring or a naphthalene ring; ring E and ring F can each independently represent a C4 to C30 aromatic ring.

[0010] The R A R B R C R D R E and R F Each substituent group can be independently represented from a single substituent group to the maximum permissible number of substitutions. R A R B R C R D R E and R F Each is independently selected from one of the following: hydrogen, deuterium, halogen, cyano, amino, substituted or unsubstituted C1-C36 chain alkyl, substituted or unsubstituted C3-C36 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C1-C10 thioalkoxy, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C60 monocyclic aryl or fused-ring aryl, substituted or unsubstituted C6-C60 aryloxy, and substituted or unsubstituted C5-C60 heteroaryl.

[0011] The R A R B R C R D R E and R F Each of them is connected to rings A, B, C, D, E, and F via a single bond, or R. A R B R C R D R E and R F Each of them is fused with and connected to rings A, B, C, D, E, and F, wherein R A R B R C R D R E and R F Two adjacent elements can be connected to form a loop or not;

[0012] When the above R A R B R C R D R E and R F When substituents are present, the substituents are independently selected from one of deuterium, halogen, cyano, amino, C1-C30 chain alkyl, C3-C30 cycloalkyl, C1-C10 alkoxy, C6-C60 aryl, and C5-C60 heteroaryl.

[0013] The organic compounds of this invention differ from traditional boron-nitrogen and carbonyl-nitrogen structures. The compounds of this invention utilize the electronegativity difference between nitrogen or boron atoms and carbon atoms to regulate the molecular frontier orbitals, achieving a significant multiple resonance effect. Specifically, these compounds of this invention adopt the core structure shown in formula (I), where rings A, B, and C are all aromatic rings such as benzene or naphthalene rings, ring D is a fused aromatic hydrocarbon, and rings E and F are fused to form a fused aromatic hydrocarbon. X 1 and X 2 They are each independently selected from B or N. Among them, heteroatom X 1 and X 2 The para position of ring A enhances the electronic cooperation effect and reduces the energy level of the molecule. Rings A, B, and C, and heteroatom X... 1 and X 2 The structure forms an indole-carbazole-like skeleton, a unique type of skeleton that facilitates the localized distribution of LUMO orbital spacing across atoms, resulting in multiple resonance effects. Ring D is fused to the aforementioned indole-carbazole-like skeleton via a six-membered ring, reducing bond strain and improving chemical stability. Ring E is fused to the aforementioned indole-carbazole-like skeleton via a five-membered ring, enhancing the rigidity of the molecular structure, suppressing structural relaxation in excited states, and narrowing the spectrum. Although rings D and E have different connection sites with the parent nucleus, these connection sites do not alter the indole-carbazole-like skeleton of the parent nucleus. The fusion modes of rings D and E with the parent nucleus remain six-membered and five-membered rings, respectively, both enhancing the chemical stability and structural rigidity of the molecule and achieving a stable, narrow emission spectrum. In summary, thanks to the above structural characteristics, the molecular structure of this invention possesses a large rigid conjugated plane, an indole-carbazole-like parent nucleus structure, and moderate bond strain, enabling a balance between multiple resonance effects and excited-state regulation, resulting in high color purity and highly efficient and stable performance. Therefore, when these compounds of the present invention are used as luminescent dyes, they are expected to be used to prepare efficient and stable narrow-spectrum organic light-emitting diodes, which have great application value in the fields of display and lighting.

[0014] In this specification, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents, they can be selected from different substituents. When the same expression is used in this invention, they all have the same meaning, and the selection range of substituents is as shown above and will not be repeated one by one.

[0015] In this specification, the expression Ca to Cb represents that the group has a to b carbon atoms. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms of the substituents.

[0016] 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.

[0017] In this specification, "each independently" means that when there are multiple subjects, they may be the same or different from each other.

[0018] In this specification, unless otherwise specified, the description of chemical elements usually 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.

[0019] The heteroatoms in heteroaryl groups in this specification generally refer to atoms or groups of atoms selected from B, N, O, S, P, Si and Se, preferably selected from N, O and S.

[0020] Examples of halogens in this specification include fluorine, chlorine, bromine, and iodine.

[0021] In this specification, the substituted or unsubstituted C6-C60 aryl groups include monocyclic aryl groups and fused-ring aryl groups, with C6-C30 aryl groups being more preferred. 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 including 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.

[0022] In this specification, the substituted or unsubstituted C5-C60 heteroaryl groups include monocyclic heteroaryl groups and fused-ring heteroaryl groups, more preferably C5-C30 heteroaryl groups, and even more preferably C5-C15 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.

[0023] For ease of further explanation, the ring D in equation (I) can be derived from the ring d. 1 and ring d 2 It is formed by fusion. Among them, the ring d 1 and ring d 2 Each of the C6-C30 aromatic rings and the C4-C30 heteroaromatic rings can be represented independently.

[0024] The organic compounds of the present invention are further preferably those having a structure shown in any one of formulas (5), (6), (7), or (8):

[0025]

[0026] In equations (5)-(8), X 1 X 2 R A R B R CR D R E R F , ring d 1 and ring d 2 The definitions are the same as those in equations (1), (2), (3), or (4).

[0027] The organic compounds of the present invention are further preferably those having a structure shown in any of the following formulas (9), (10), (11), or (12):

[0028]

[0029] In equations (9)-(12), X 1 X 2 R A R B R C R D R E and R F The definitions are all the same as those in equations (1), (2), (3), or (4); the R B R C R D R E and R F Each ring structure is connected to the others via single bonds or fused connections.

[0030] In the above-described general formulas of the present invention, preferably, the X 1 and X 2 Simultaneously, it is an N atom, or, the X 1 and X 2 It is also a B atom; more preferably, the X 1 and X 2 It is also an N atom.

[0031] The organic compounds of the present invention are further preferably those having the structure shown in formula (13), formula (14), formula (15) or formula (16):

[0032]

[0033] In the above-described general formulas of the present invention, preferably, the R A R B R C R D R E and R FEach of the following is independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, phenyl, naphthyl, anthracene, benzo[a]anthrayl, phenanthrene, benzo[a]phenanthrene, pyrene, pyryl, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, amphylphenyl, terphenyl, triphenyl, tetraphenyl, fluorene, spirodifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans The following are listed: indoxorphinyl, trimerinyl, isotrimerininyl, spirotrimerininyl, spiroisotrimerininyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thiopheneyl, benzothiopheneyl, isobenzothiopheneyl, dibenzothiopheneyl, pyrroleyl, isoindolyl, carbazoyl, indoxorphinyl, pyridinyl, quinolinyl, isoquinolinyl, acridineyl, phenanthridineyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, pyrazolyl, indazoleyl, imidazoyl, benzimidazoleyl, naphthiazoleyl, phenanthridineimidazoleyl, pyridinimidazoleyl, pyrazinimidazoleyl, quinoxorphinimidazoleyl, oxazolyl, benzooxazolyl, naphthiazoleyl, anthracene Benzoxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazathanel, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenthiazinyl, naphridinyl, azacarbazolyl, benzocarbazolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5 The substituted group is selected from one of the following: _endiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridyl, indazyl, benzothiadiazolyl, 9,9-dimethylacridyl, diarylamine, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silyl, or a combination of the two substituents listed above;

[0034] Preferably, the R A R B R C R D R E and R FEach of the following groups is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, adamantyl, fluorine, trifluoromethyl, phenyl, tricrylyl, naphthyl, anthraceneyl, furanyl, tetrahydrofuranyl, pyrroleyl, tetrahydropyrroleyl, thiophene, carbazoyl, triazineyl, pyridyl, quinolinyl, acridineyl, cyano, methoxy, silyl, dimethylamino, triarylamino, fluorenyl, dibenzofuranyl, dibenzothiophene, or a combination of the two substituent groups mentioned above.

[0035] Furthermore, the compounds of general formula (I) of the present invention can preferably be the following specific structural compounds: X-1 to X-375. These compounds are merely representative:

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048] The present invention also provides an organic electroluminescent device, comprising 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 any of the above general formulas (I), (1) to (12).

[0049] 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 present invention represented by any one of the above general formulas (I), (1) to (12).

[0050] In addition, the present invention also protects organic electroluminescent devices containing any of the organic compounds shown in general formula (I), general formula (1) to formula (12) for use in display and lighting devices.

[0051] The organic compounds provided by this invention, suitable for use in organic electroluminescent devices, possess a large-planar indole-carbazole-like structure. The electronegativity difference between heteroatoms and carbon atoms enhances the multiple resonance effect of the molecule, resulting in excellent luminous efficiency and high color purity. The higher bond energy also contributes to better chemical stability and water / oxygen resistance. When these compounds are applied as doping materials in the emitting layer of organic electroluminescent devices, the OLED devices exhibit narrower spectral half-width, superior device performance, and longer lifespan. The organic compounds of this invention meet the current requirements of panel manufacturers for high-performance materials and demonstrate promising application prospects. Detailed Implementation

[0052] 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.

[0053] All the chemical reagents used in this invention, such as petroleum ether, hydroiodic acid, acetonitrile, sodium chloride, dichloromethane, N,N-dimethylformamide, ethyl acetate, palladium acetate, tetra(triphenylphosphine)palladium, tri-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide, cuprous iodide, tetra-n-butylammonium chloride, toluene, boron tribromide, n-butyllithium, tetrahydrofuran, and other reaction intermediates, and other basic chemical raw materials, were purchased from Shanghai Titan Technology Co., Ltd. and Shanghai Bid Pharmaceutical Technology Co., Ltd. The mass spectrometer used to determine the following compounds was a ZAB-HS type mass spectrometer (manufactured by Micromass, UK).

[0054] The synthesis method of the compounds of this invention is briefly described below. For X 1 and X 2The molecules, all containing nitrogen atoms, are first subjected to a Ullmann reaction at 120°C using cuprous iodide as a catalyst, tetrabutylammonium hydroxide as a base, and N,N-dimethylformamide as a solvent to achieve ring closure, thus yielding the target compound. For X... 1 and X 2 When the nitrogen and boron atoms are different atoms, a Ullmann reaction catalyzed by cuprous iodide is first used to clasp the intermediate, yielding a lithium-halogen exchange reaction. Next, lithium-boron exchange is performed by adding boron tribromide, followed by the addition of a Lewis base such as N,N-diisopropylethylamine, to initiate a tandem boro-Friedel-Crafts reaction, yielding the target compound. For X... 1 and X 2 All molecules are boron atoms. The synthesis process is similar to the boron truncation process described above. After the intermediates undergo lithium halide exchange and lithium boron exchange reactions, a boron-Faker reaction occurs in the presence of N,N-diisopropylethylamine to obtain the target compound.

[0055] More specifically, the following provides methods for synthesizing representative specific compounds of the present invention.

[0056] Synthesis Examples

[0057] Synthesis Example 1:

[0058]

[0059] (1) Synthesis of compound X-1-1

[0060]

[0061] In a 250 mL two-necked flask, 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole (4.12 g, 10.00 mmol), (3-chloronaphthyl-2-yl)boronic acid (2.27 g, 11.00 mmol), tetrakis(triphenylphosphine)palladium (35 mg, 0.30 mmol), and potassium carbonate (2.76 g, 20.00 mmol) were added sequentially. Under a nitrogen atmosphere, 60 mL of toluene, 20 mL of ethanol, and 10 mL of water were added, and the reaction was stopped after 12 hours at 90 °C. After cooling to room temperature, 200 mL of dichloromethane was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:1) as eluent to obtain a yellow powder X-1-1 (3.77 g).

[0062] (2) Synthesis of compound X-1-2

[0063]

[0064] In a 100 mL double-necked flask, X-1-1 (2.69 g, 5.00 mmol), (8-chloronaphthyl-1-yl)boric acid (1.13 g, 5.50 mmol), tetrakis(triphenylphosphine)palladium (35 mg, 0.30 mmol), and potassium carbonate (1.38 g, 10.00 mmol) were added sequentially. Under a nitrogen atmosphere, 30 mL of toluene, 10 mL of ethanol, and 50 mL of water were added, and the reaction was stopped after 12 hours at 90 °C. After cooling to room temperature, 200 mL of dichloromethane was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain a yellow powder, X-1-2 (1.2 g).

[0065] (3) Synthesis of compound X-1

[0066]

[0067] Intermediate X-1-1 (0.43 g, 0.75 mmol) and cuprous iodide (0.29 g, 1.50 mmol) were added to a 100 mL two-necked round-bottom flask, respectively. Under a nitrogen atmosphere, 25 mL of N,N-dimethylformamide and 2.5 mL of tetra-n-butylammonium chloride were added sequentially. The mixture was then heated to 120 °C and reacted for 24 h. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic phase was collected and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure and separated by column chromatography to obtain the target compound X-1 (0.31 g, 82% yield, HPLC purity 95%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 504.15 Elemental analysis results: Theoretical values: C, 90.45; H, 4.00; N, 5.55 (%); Experimental values: C, 90.42; H, 3.38; N, 5.60 (%).

[0068] Synthesis Example 2:

[0069]

[0070] (1) Synthesis of compound X-2-1

[0071]

[0072] In a 250 mL two-necked flask, 6-iodo-10-bromo-5,11-dihydroindole[3,2-b]carbazole (4.60 g, 10.00 mmol), (3-chloronaphthyl-2-yl)boronic acid (2.27 g, 11.00 mmol), tetrakis(triphenylphosphine)palladium (35 mg, 0.30 mmol), and potassium carbonate (2.76 g, 20.00 mmol) were added sequentially. Under a nitrogen atmosphere, 60 mL of toluene, 20 mL of ethanol, and 10 mL of water were added, and the reaction was stopped after 12 hours at 90 °C. After cooling to room temperature, 200 mL of dichloromethane was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:1) as eluent to obtain a yellow powder X-2-1 (2.95 g).

[0073] (2) Synthesis of compound X-2-2

[0074]

[0075] In a 100 mL double-necked flask, X-2-1 (2.69 g, 5.00 mmol), (8-chloronaphth-1-yl)boric acid (1.13 g, 5.50 mmol), tetrakis(triphenylphosphine)palladium (35 mg, 0.30 mmol), and potassium carbonate (1.38 g, 10.00 mmol) were added sequentially. Under a nitrogen atmosphere, 30 mL of toluene, 10 mL of ethanol, and 50 mL of water were added, and the reaction was stopped after 12 hours at 90 °C. After cooling to room temperature, 200 mL of dichloromethane was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to obtain a yellow powder, X-2-2 (0.9 g).

[0076] (3) Synthesis of compound X-2

[0077]

[0078] Intermediate X-2-2 (0.57 g, 1.00 mmol) and cuprous iodide (0.40 g, 2.00 mmol) were added to a 100 mL two-necked round-bottom flask, respectively. Under a nitrogen atmosphere, 33 mL of N,N-dimethylformamide and 3.3 mL of tetrabutylammonium chloride were added sequentially. The mixture was then heated to 120 °C and reacted for 24 h. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic phase was collected and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure and separated by column chromatography to obtain the target compound X-2 (0.44 g, 87% yield, HPLC purity 92%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 504.15 Elemental analysis results: Theoretical values: C, 90.45; H, 4.00; N, 5.55 (%); Experimental values: C, 90.46; H, 4.02; N, 5.52 (%).

[0079] Synthesis Example 3:

[0080]

[0081] (1) Synthesis of compound X-3-1

[0082]

[0083] In a 250 mL two-necked flask, 4,10-dibromo-5,11-dihydroindole[3,2-b]carbazole (4.12 g, 10.00 mmol), (3-chloronaphthyl-2-yl)boronic acid (2.27 g, 11.00 mmol), tetrakis(triphenylphosphine)palladium (35 mg, 0.30 mmol), and potassium carbonate (2.76 g, 20.00 mmol) were added sequentially. Under a nitrogen atmosphere, 60 mL of toluene, 20 mL of ethanol, and 10 mL of water were added, and the reaction was stopped after 12 hours at 90 °C. After cooling to room temperature, 200 mL of dichloromethane was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:1) as eluent to obtain a yellow powder X-3-1 (3.64 g).

[0084] (2) Synthesis of compound X-3-2

[0085]

[0086] X-3-1 (2.69 g, 5.00 mmol), (8-chloronaphth-1-yl)boric acid (1.13 g, 5.50 mmol), tetrakis(triphenylphosphine)palladium (35 mg, 0.30 mmol), and potassium carbonate (1.38 g, 10.00 mmol) were added sequentially to a 100 mL double-necked flask. Under a nitrogen atmosphere, 30 mL of toluene, 10 mL of ethanol, and 50 mL of water were added, and the reaction was stopped after 12 hours at 90 °C. After cooling to room temperature, 200 mL of dichloromethane was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain a yellow powder, X-3-2 (1.1 g).

[0087] (3) Synthesis of compound X-3

[0088]

[0089] Intermediate X-3-2 (0.57 g, 1.00 mmol) and cuprous iodide (0.40 g, 2.00 mmol) were added to a 100 mL two-necked round-bottom flask, respectively. Under a nitrogen atmosphere, 33 mL of N,N-dimethylformamide and 3.3 mL of tetrabutylammonium chloride were added sequentially. The mixture was then heated to 120 °C and reacted for 24 h. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic phase was collected and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure and separated by column chromatography to obtain the target compound X-3 (0.36 g, 71% yield, HPLC purity 96%) as a yellow-orange solid. MALDI-TOF-MS results: Molecular ion peak: 504.12 Elemental analysis results: Theoretical values: C, 90.45; H, 4.00; N, 5.55 (%); Experimental values: C, 90.41; H, 4.03; N, 5.56 (%).

[0090] Synthesis Example 4:

[0091]

[0092] (1) Synthesis of compound X-16-1

[0093]

[0094] This embodiment is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole needs to be replaced with 6,12-dibromo-2,8-di-tert-butyl-5,11-dihydroindole[3,2-b]carbazole. The target compound X-16-1 (2.67 g) was obtained as a pale yellow powder.

[0095] (2) Synthesis of compound X-16-2

[0096]

[0097] This embodiment is basically the same as the synthesis of compound X-1-2, except that X-1-1 needs to be replaced with X-16-1 in this example. The target compound X-16-2 (1.04 g) was obtained as a yellow powder.

[0098] (3) Synthesis of compound X-16

[0099]

[0100] This example is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced with X-16-2. The target compound X-16 (0.28 g, 75% yield, HPLC purity 98%) is a red solid. MALDI-TOF-MS results: Molecular ion peak: 616.27. Elemental analysis results: Theoretical values: C, 89.58; H, 5.88; N, 4.54 (%); Experimental values: C, 89.57; H, 5.85; N, 4.58 (%).

[0101] Synthesis Example 5:

[0102]

[0103] (1) Synthesis of compound X-18-1

[0104]

[0105] This embodiment is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole needs to be replaced with 4,10-dibromo-2,8-di-tert-butyl-5,11-dihydroindole[3,2-b]carbazole. The target compound X-18-1 (2.73 g) was obtained as a pale yellow powder.

[0106] (2) Synthesis of compound X-18-2

[0107]

[0108] This embodiment is basically the same as the synthesis of compound X-1-2, except that X-1-1 needs to be replaced with X-18-1 in this example. The target compound X-18-2 (1.21 g) was obtained as a yellow powder.

[0109] (3) Synthesis of compound X-18

[0110]

[0111] This example is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced with X-18-2. The target compound X-18 (0.35 g, 83% yield, HPLC purity 96%) is a yellow-orange solid. MALDI-TOF-MS results: Molecular ion peak: 616.32. Elemental analysis results: Theoretical values: C, 89.58; H, 5.88; N, 4.54 (%); Experimental values: C, 89.65; H, 5.86; N, 4.49 (%).

[0112] Synthesis Example 6:

[0113]

[0114] (1) Synthesis of compound X-57-1

[0115]

[0116] This embodiment is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole needs to be replaced with 6-iodo-10-bromo-2,8-adamantane-5,11-dihydroindole[3,2-b]carbazole. The target compound X-57-1 (3.14 g) was obtained as a pale yellow powder.

[0117] (2) Synthesis of compound X-57-2

[0118]

[0119] This embodiment is basically the same as the synthesis of compound X-1-2, except that X-1-1 needs to be replaced with X-57-1. The target compound X-57-2 (1.36 g) was obtained as a yellow powder.

[0120] (3) Synthesis of compound X-57

[0121]

[0122] This example is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced with X-57-2. The target compound X-57 (0.29 g, 80% yield, HPLC purity 95%) is an orange solid. MALDI-TOF-MS results: Molecular ion peak: 772.31. Elemental analysis results: Theoretical values: C, 90.12; H, 6.26; N, 3.62 (%); Experimental values: C, 90.15; H, 6.27; N, 3.58 (%).

[0123] Synthesis Example 7:

[0124]

[0125] (1) Synthesis of compound X-81-1

[0126]

[0127] In a 100 mL double-necked flask, X-1 (1.02 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain a red powder, X-81-1 (0.79 g).

[0128] (2) Synthesis of compound X-81

[0129]

[0130] X-81-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-81 (0.25 g, 80% yield, HPLC purity 99%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 740.33 Elemental analysis results: Theoretical values: C, 90.78; H, 5.44; N, 3.78 (%); Experimental values: C, 90.71; H, 5.48; N, 3.81 (%).

[0131] Synthesis Example 8:

[0132]

[0133] (1) Synthesis of compound X-83-1

[0134]

[0135] In a 100 mL double-necked flask, X-3 (1.02 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain a yellow-orange powder, X-83-1 (0.84 g).

[0136] (2) Synthesis of compound X-83

[0137]

[0138] X-83-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-83 (0.28 g, 87% yield, HPLC purity 97%) as a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 740.38 Elemental analysis results: Theoretical values: C, 90.78; H, 5.44; N, 3.78 (%); Experimental values: C, 90.83; H, 5.42; N, 3.75 (%).

[0139] Synthesis Example 9:

[0140]

[0141] (1) Synthesis of compound X-134-1

[0142]

[0143] In a 100 mL double-necked flask, X-57 (1.56 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain an orange powder, X-134-1 (1.37 g).

[0144] (2) Synthesis of compound X-134

[0145]

[0146] X-134-1 (0.85 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-134 (0.66 g, 87% yield, HPLC purity 97%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 890.48 Elemental analysis results: Theoretical values: C, 90.30; H, 6.56; N, 3.14 (%); Experimental values: C, 90.24; H, 6.60; N, 3.12 (%).

[0147] Synthesis Example 10:

[0148]

[0149] (1) Synthesis of compound X-141

[0150]

[0151] In a 25 mL two-necked flask, X-81-1 (0.66 g, 1.00 mmol), carbazole (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol), and sodium tert-butoxide (192 mg, 2 mmol) were added sequentially. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added, and the reaction was stopped after 24 hours at 110 °C. After cooling to room temperature, 200 mL of dichloromethane was added, and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to give the target compound X-141 (0.42 g, 50% yield, HPLC purity 93%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 834.32. Elemental analysis results: Theoretical values: C, 89.19; H, 4.10; N, 6.71 (%); Experimental values: C, 89.22; H, 4.05; N, 6.73 (%).

[0152] Synthesis Example 11:

[0153]

[0154] (1) Synthesis of compound X-148

[0155]

[0156] X-83-1 (0.36 g, 0.50 mmol), triphenylamine boric acid (0.32 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to give the target compound X-148 (0.28 g, 80% yield, HPLC purity 95%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 990.38 Elemental analysis results: Theoretical values: C, 89.67; H, 4.68; N, 5.65 (%); Experimental values: C, 89.70; H, 4.66; N, 5.64 (%).

[0157] Synthesis Example 12:

[0158]

[0159] (1) Synthesis of compound X-156

[0160]

[0161] X-81-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-3-fluorenboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-156 (0.31 g, 86% yield, HPLC purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 888.33 Elemental analysis results: Theoretical values: C, 91.86; H, 4.99; N, 3.15 (%); Experimental values: C, 91.87; H, 5.00; N, 3.13 (%).

[0162] Synthesis Example 13:

[0163]

[0164] (1) Synthesis of compound X-156

[0165]

[0166] X-81-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluorenboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-171 (0.28 g, 77% yield, HPLC purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 888.31 Elemental analysis results: Theoretical values: C, 91.86; H, 4.99; N, 3.15 (%); Experimental values: C, 91.84; H, 5.00; N, 3.16 (%).

[0167] Synthesis Example 14:

[0168]

[0169] (1) Synthesis of compound X-195-1

[0170]

[0171] In a 100 mL double-necked flask, X-2 (1.01 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to obtain an orange powder, X-195-1 (1.37 g).

[0172] (2) Synthesis of compound X-195-2

[0173]

[0174] X-195-1 (0.62 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give an orange solid X-195-2 (0.68 g).

[0175] (3) Synthesis of compound X-195-3

[0176]

[0177] In a 100 mL double-necked flask, X-195-2 (0.63 g, 1.01 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain an orange powder, X-195-3 (0.70 g).

[0178] (4) Synthesis of compound X-195

[0179]

[0180] X-195-3 (0.39 g, 0.50 mmol), 9-phenyl-9H-carbazole-4-ylboronic acid (0.32 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to give the target compound X-195 (0.34 g, 81% yield, HPLC purity 98%) as a deep red solid. MALDI-TOF-MS results: Molecular ion peak: 1104.2 Elemental analysis results: Theoretical values: C, 90.19; H, 4.74; N, 5.07 (%); Experimental values: C, 90.18; H, 4.75; 5.07 (%).

[0181] Synthesis Example 15:

[0182]

[0183] (1) Synthesis of compound X-204-1

[0184]

[0185] In a 100 mL double-necked flask, X-3 (1.02 g, 2.02 mmol) was dissolved in 25 mL of N,N-dimethylformamide. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain a yellow-orange powder, X-204-1 (0.92 g).

[0186] (2) Synthesis of compound X-204

[0187]

[0188] X-204-1 (1.65 g, 2.50 mmol), 2,4,6-trimethylphenylboronic acid (0.90 g, 5.50 mmol), tetrakis(triphenylphosphine)palladium (85 mg, 0.075 mmol), and potassium carbonate (0.85 g, 6.25 mmol) were added sequentially to a 100 mL double-necked flask. Under a nitrogen atmosphere, 20 mL of tetrahydrofuran and 5 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give X-204-2 (1.28 g), a yellow-orange solid.

[0189] (3) Synthesis of compound X-204-3

[0190]

[0191] In a 100 mL double-necked flask, X-204-2 (1.48 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to obtain a yellow-orange powder, X-204-3 (1.22 g).

[0192] (4) Synthesis of compound X-204

[0193]

[0194] X-204-3 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluorenboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-204 (0.23 g, 87% yield, HPLC purity 97%) as a yellow solid. MALDI-TOF-MS results: Molecular ion peak: 1125.42 Elemental analysis results: Theoretical values: C, 91.78; H, 5.73 N, 2.49 (%); Experimental values: C, 91.79; H, 5.71 N, 2.50 (%).

[0195] Synthesis Example 16:

[0196]

[0197] (1) Synthesis of compound X-206-1

[0198]

[0199] This embodiment is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole needs to be replaced with 6,12-dibromo-2,8-dicyano-5,11-dihydroindole[3,2-b]carbazole. The target compound X-206-1 (2.25 g) was obtained as a pale yellow powder.

[0200] (2) Synthesis of compound X-206-2

[0201]

[0202] This embodiment is basically the same as the synthesis of compound X-1-2, except that X-1-1 needs to be replaced with X-206-1. The target compound X-206-2 (0.87 g) was obtained as a yellow powder.

[0203] (3) Synthesis of compound X-206

[0204]

[0205] This example is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced with X-206-2. The target compound X-206 (0.20 g, 75% yield, HPLC purity 98%) is a deep red solid. MALDI-TOF-MS results: Molecular ion peak: 554.13. Elemental analysis results: Theoretical values: C, 86.63; H, 3.27; N, 10.10 (%); Experimental values: C, 86.60; H, 3.29; N, 10.11 (%).

[0206] Synthesis Example 17:

[0207]

[0208] (1) Synthesis of compound X-211-1

[0209]

[0210] This embodiment is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole needs to be replaced with 6,12-dibromo-3,7-dicyano-5,11-dihydroindole[3,2-b]carbazole. The target compound X-211-1 (1.52 g) was obtained as a pale yellow powder.

[0211] (2) Synthesis of compound X-211-2

[0212]

[0213] This embodiment is basically the same as the synthesis of compound X-1-2, except that X-1-1 needs to be replaced with X-211-1 in this example. The target compound X-211-2 (0.92 g) was obtained as a yellow powder.

[0214] (3) Synthesis of compound X-211

[0215]

[0216] This embodiment is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced with X-211-2. The target compound X-211 (0.32 g, 82% yield, HPLC purity 97%) is a deep red solid. MALDI-TOF-MS results: Molecular ion peak: 554.15. Elemental analysis results: Theoretical values: C, 86.63; H, 3.27; N, 10.10 (%); Experimental values: C, 86.61; H, 3.28; N, 10.11 (%).

[0217] Synthesis Example 18:

[0218]

[0219] (1) Synthesis of compound X-228-1

[0220]

[0221] This embodiment is basically the same as the synthesis of compound X-1-1, except that 6,12-dibromo-5,11-dihydroindole[3,2-b]carbazole needs to be replaced with 4,10-dibromo-2,8-dicyano-5,11-dihydroindole[3,2-b]carbazole. The target compound X-228-1 (1.97 g) was obtained as a pale yellow powder.

[0222] (2) Synthesis of compound X-228-2

[0223]

[0224] This embodiment is basically the same as the synthesis of compound X-1-2, except that X-1-1 needs to be replaced with X-228-1. The target compound X-228-2 (1.03 g) was obtained as a yellow powder.

[0225] (3) Synthesis of compound X-228-3

[0226]

[0227] This embodiment is basically the same as the synthesis of compound X-1, except that X-1-2 needs to be replaced with X-228-2. The target compound X-228-3 (0.35 g) is a yellow-orange solid.

[0228] (4) Synthesis of compound X-228-4

[0229]

[0230] In a 100 mL double-necked flask, X-228-3 (1.11 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain a yellow-orange powder, X-228-4 (0.74 g).

[0231] (5) Synthesis of compound X-228

[0232]

[0233] In a 25 mL two-necked flask, X-228-1 (0.37 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added, and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluents to obtain a yellow-orange solid X-228-2 (0.47 g, 79% yield, HPLC purity 96%). MALDI-TOF-MS results: Molecular ion peak: 672.23. Elemental analysis results: Theoretical values: C, 87.48; H, 4.20; N, 8.33 (%); Experimental values: C, 87.50; H, 4.21; N, 8.30 (%).

[0234] Synthesis Example 19:

[0235]

[0236] (1) Synthesis of compound X-230

[0237]

[0238] X-228-4 (0.63 g, 1.00 mmol), diphenylamine (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol), and sodium tert-butoxide (192 mg, 2 mmol) were added sequentially to a 25 mL two-necked flask. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added, and the reaction was stopped after 24 hours at 110 °C. The mixture was cooled to room temperature, and 200 mL of dichloromethane was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to give the target compound X-230 (0.44 g, 77% yield, HPLC purity 95%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 721.24 Elemental analysis results: Theoretical values: C, 86.53; H, 3.77; N, 9.70 (%); Experimental values: C, 86.56; H, 3.78; N, 9.66 (%).

[0239] Synthesis Example 20:

[0240]

[0241] (1) Synthesis of compound X-246-1

[0242]

[0243] In a 100 mL double-necked flask, X-195 (0.87 g, 1.50 mmol) and cuprous cyanide (0.40 g, 4.4 mmol) were dissolved in 25 mL of 1-methylpyrrolidone. The reaction was carried out under nitrogen protection at 150 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, and 200 mL of dichloromethane was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain an orange-red powder, X-246-1 (0.69 g).

[0244] (2) Synthesis of compound X-246-2

[0245]

[0246] In a 100 mL double-necked flask, X-246-1 (1.07 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain a red powder, X-246-1 (0.85 g).

[0247] (3) Synthesis of compound X-246

[0248]

[0249] X-246-2 (0.34 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to give the target compound X-246 (0.30 g, 86% yield, HPLC purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 765.33 Elemental analysis results: Theoretical values: C, 89.38; H, 5.13; N, 5.49 (%); Experimental values: C, 89.40; H, 5.14; N, 5.46 (%).

[0250] Synthesis Example 21:

[0251]

[0252] (1) Synthesis of compound X-251-1

[0253]

[0254] X-228-4 (0.66 g, 1.00 mmol), diphenylamine (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol), and sodium tert-butoxide (192 mg, 2 mmol) were added sequentially to a 25 mL two-necked flask. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added, and the reaction was stopped after 24 hours at 110 °C. The mixture was cooled to room temperature, and 200 mL of dichloromethane was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to give an orange solid, X-251 (0.54 g).

[0255] (2) Synthesis of compound X-251-2

[0256]

[0257] In a 100 mL double-necked flask, X-251-1 (0.84 g, 1.01 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain an orange powder, X-251-2 (0.61 g).

[0258] (3) Synthesis of compound X-251

[0259]

[0260] X-251-2 (0.50 g, 0.50 mmol) and cuprous cyanide (0.40 g, 4.4 mmol) were dissolved in 25 mL of 1-methylpyrrolidone in a 25 mL double-necked flask. The reaction was carried out under nitrogen protection at 150 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, and 200 mL of dichloromethane was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to obtain the target compound X-251 (0.19 g, 77% yield, HPLC purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 888.31. Elemental analysis results: Theoretical values: C, 86.47; H, 4.08; N, 9.45 (%); Experimental values: C, 86.49; H, 4.07; N, 9.44 (%).

[0261] Synthesis Example 22:

[0262]

[0263] (1) Synthesis of compound X-255

[0264]

[0265] X-246-2 (0.34 g, 0.50 mmol), 9,9-dimethyl-4-fluorenboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-255 (0.35 g, 87% yield, HPLC purity 96%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 913.33 Elemental analysis results: Theoretical values: C, 90.66; H, 4.74; N, 4.60 (%); Experimental values: C, 90.67; H, 4.73; N, 4.60 (%).

[0266] Synthesis Example 23:

[0267]

[0268] (1) Synthesis of compound X-260-1

[0269]

[0270] X-83-1 (0.33 g, 0.50 mmol), (2-(9H-carbazole-9-yl)phenyl)boronic acid (0.33 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give a yellow solid X-260-1 (0.40 g).

[0271] (2) Synthesis of compound X-260-2

[0272]

[0273] In a 100 mL double-necked flask, X-260-1 (0.99 g, 1.01 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain an orange powder, X-260-2 (0.76 g).

[0274] (3) Synthesis of compound X-260

[0275]

[0276] X-260-2 (0.57 g, 0.50 mmol) and cuprous cyanide (0.40 g, 4.4 mmol) were dissolved in 25 mL of 1-methylpyrrolidone in a 25 mL double-necked flask. The reaction was carried out under nitrogen protection at 150 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, and 200 mL of dichloromethane was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to obtain the target compound X-260 (0.39 g, 62% yield, HPLC purity 97%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 1036.35 Elemental analysis results: Theoretical values: C, 88.01; H, 3.89; N, 8.10 (%); Experimental values: C, 88.00; H, 3.90; N, 8.10 (%).

[0277] Synthesis Example 24:

[0278]

[0279] (1) Synthesis of compound X-261-1

[0280]

[0281] In a 25 mL two-necked flask, X-195-1 (0.58 g, 1.00 mmol), diphenylamine (167 mg, 1.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol), and sodium tert-butoxide (192 mg, 2 mmol) were added sequentially. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added, and the reaction was stopped after 24 hours at 110 °C. After cooling to room temperature, 200 mL of dichloromethane was added, and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to give a red solid X-261-1 (0.47 g).

[0282] (2) Synthesis of compound X-261-2

[0283]

[0284] In a 100 mL double-necked flask, X-261-1 (0.67 g, 1.01 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain a red powder, X-261-2 (0.60 g).

[0285] (3) Synthesis of compound X-261

[0286]

[0287] X-261-2 (0.34 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-261 (0.39 g, 90% yield, HPLC purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 907.36 Elemental analysis results: Theoretical values: C, 89.93; H, 5.44; N, 4.63 (%); Experimental values: C, 89.95; H, 5.45; N, 4.60 (%).

[0288] Synthesis Example 25:

[0289]

[0290] (1) Synthesis of compound X-265-1

[0291]

[0292] In a 100 mL double-necked flask, X-83 (1.48 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to obtain a yellow-orange powder, X-265-1 (0.73 g).

[0293] (2) Synthesis of compound X-265

[0294]

[0295] X-265-1 (0.90 g, 1.00 mmol), carbazole (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol), and sodium tert-butoxide (192 mg, 2 mmol) were added sequentially to a 25 mL two-necked flask. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added, and the reaction was stopped after 24 hours at 110 °C. After cooling to room temperature, 200 mL of dichloromethane was added, and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to give the target compound X-265 (0.62 g, 79% yield, HPLC purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 1071.44 Elemental analysis results: Theoretical values: C, 89.69; H, 5.08; N, 5.23 (%); Experimental values: C, 89.70; H, 5.09; N, 5.21.

[0296] Synthesis Example 26:

[0297]

[0298] (1) Synthesis of compound X-271-1

[0299]

[0300] X-195-1 (0.58 g, 1.00 mmol), (4-(9H-carbazole-9-yl)phenyl)boronic acid (0.33 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give an orange solid, X-271-1 (0.37 g).

[0301] (2) Synthesis of compound X-271-2

[0302]

[0303] In a 100 mL double-necked flask, X-271-1 (0.75 g, 1.01 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain an orange powder, X-271-2 (0.58 g).

[0304] (3) Synthesis of compound X-271

[0305]

[0306] X-271-2 (0.45 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to give the target compound X-271 (0.32 g, 75% yield, HPLC purity 98%) as an orange solid. MALDI-TOF-MS results: Molecular ion peak: 903.06. Elemental analysis results: Theoretical values: C, 74.43; H, 3.23; N, 4.65 (%); Experimental values: C, 74.45; H, 3.24; N, 4.62 (%).

[0307] Synthesis Example 27:

[0308]

[0309] (1) Synthesis of compound X-276

[0310]

[0311] X-81-1 (0.36 g, 0.50 mmol), 1-naphthoboric acid (0.18 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-276 (0.22 g, 78% yield, HPLC purity 99%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 756.24 Elemental analysis results: Theoretical values: C, 92.04; H, 4.26; N, 3.70 (%); Experimental values: C, 92.07; H, 4.27; N, 3.66 (%).

[0312] Synthesis Example 28:

[0313]

[0314] (1) Synthesis of compound X-283

[0315]

[0316] X-83-1 (0.36 g, 0.50 mmol), anthracene-9-ylboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-283 (0.21 g, 83% yield, HPLC purity 98%) as a yellow-orange solid. MALDI-TOF-MS results: Molecular ion peak: 856.26 Elemental analysis results: Theoretical values: C, 92.50; H, 4.23; N, 3.27 (%); Experimental values: C, 92.49; H, 4.24; N, 3.27 (%).

[0317] Synthesis Example 29:

[0318]

[0319] (1) Synthesis of compound X-293-1

[0320]

[0321] X-195-1 (0.58 g, 1.00 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give an orange solid X-293-1 (0.51 g).

[0322] (2) Synthesis of compound X-293-2

[0323]

[0324] In a 100 mL double-necked flask, X-293-1 (0.75 g, 1.01 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.36 g, 2.02 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to obtain an orange powder, X-293-2 (0.55 g).

[0325] (3) Synthesis of compound X-293

[0326]

[0327] X-293-2 (0.39 g, 0.50 mmol), anthracene-9-ylboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:3) as eluent to give the target compound X-293 (0.23 g, 45% yield, HPLC purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 1097.38 Elemental analysis results: Theoretical values: C, 91.86; H, 4.31; N, 3.83 (%); Experimental values: C, 91.88; H, 4.33; N, 3.79 (%).

[0328] Synthesis Example 30:

[0329]

[0330] (1) Synthesis of compound X-316-1

[0331]

[0332] 2-Naphthylboryl ester (2.54 g, 10.00 mmol), 2',3',5',6'-tetrabromo-1,1',4,1”-bitriphenyl (5.42 g, 10.00 mmol), tetraphenylphosphine palladium (0.35 g, 0.30 mmol), and potassium carbonate (3.45 g, 25.00 mmol) were added sequentially to a 100 mL double-necked flask. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 100 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 5:1) as eluent to obtain a white powder X-316-1 (3.6 g).

[0333] (2) Synthesis of compound X-316-2

[0334]

[0335] In a 100 mL double-necked flask, 1-naphthylboryl ester (1.27 g, 5.00 mmol), X-316-1 (2.70 g, 5.00 mmol), tetraphenylphosphine palladium (0.35 g, 0.30 mmol), and potassium carbonate (3.45 g, 25.00 mmol) were added sequentially. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 100 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:1) as eluent to obtain a pale yellow powder, X-316-2 (3.6 g).

[0336] (2) Synthesis of compound X-316

[0337]

[0338] A solution of n-butyllithium (10 mL, 2.50 M, 25.00 mmol) was slowly added to a solution of X-316-2 (3.19 g, 5.00 mmol) in 80 mL of tert-butylbenzene at 0 °C, and the mixture was then heated to 60 °C for 3 hours each time. After the reaction was complete, the temperature was lowered to -30 °C, and boron tribromide (6.26 g, 25.00 mmol) was slowly added. The mixture was stirred at room temperature for 0.5 hours. N,N-diisopropylethylamine (4.83 g, 37.5 mmol) was added at room temperature, and the reaction was continued at 145 °C for 5 hours before being stopped. The reaction was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected and dried over anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was performed using petroleum ether and dichloromethane (petroleum ether: dichloromethane = 1:1) as eluents to obtain the target compound X-316 (0.38 g, 25% yield, HPLC purity 97%), as a red solid. MALDI-TOF-MS results: Molecular ion peak: 498.18. Elemental analysis results: Theoretical values: C, 91.61; H, 4.05 (%); Experimental values: C, 91.55; H, 4.07 (%).

[0339] Synthesis Example 30:

[0340]

[0341] (1) Synthesis of compound X-316-1

[0342]

[0343] 2-Naphthylboryl ester (2.54 g, 10.00 mmol), 2',3',5',6'-tetrabromo-1,1',4,1”-bitriphenyl (5.42 g, 10.00 mmol), tetraphenylphosphine palladium (0.35 g, 0.30 mmol), and potassium carbonate (3.45 g, 25.00 mmol) were added sequentially to a 100 mL double-necked flask. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 100 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 5:1) as eluent to obtain a white powder X-316-1 (3.6 g).

[0344] (2) Synthesis of compound X-316-2

[0345]

[0346] In a 100 mL double-necked flask, 1-naphthylboryl ester (1.27 g, 5.00 mmol), X-316-1 (2.70 g, 5.00 mmol), tetraphenylphosphine palladium (0.35 g, 0.30 mmol), and potassium carbonate (3.45 g, 25.00 mmol) were added sequentially. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 100 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:1) as eluent to obtain a pale yellow powder, X-316-2 (3.6 g).

[0347] (2) Synthesis of compound X-316

[0348]

[0349] A solution of n-butyllithium (10 mL, 2.50 M, 25.00 mmol) was slowly added to a solution of X-316-2 (3.19 g, 5.00 mmol) in 80 mL of tert-butylbenzene at 0 °C, and the mixture was then heated to 60 °C for 3 hours each time. After the reaction was complete, the temperature was lowered to -30 °C, and boron tribromide (6.26 g, 25.00 mmol) was slowly added. The mixture was stirred at room temperature for 0.5 hours. N,N-diisopropylethylamine (4.83 g, 37.5 mmol) was added at room temperature, and the reaction was continued at 145 °C for 5 hours before being stopped. The reaction was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected and dried over anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was performed using petroleum ether and dichloromethane (petroleum ether: dichloromethane = 1:1) as eluents to obtain the target compound X-316 (0.38 g, 25% yield, HPLC purity 97%), as a red solid. MALDI-TOF-MS results: Molecular ion peak: 498.18. Elemental analysis results: Theoretical values: C, 91.61; H, 4.05 (%); Experimental values: C, 91.55; H, 4.07 (%).

[0350] Synthesis Example 31:

[0351]

[0352] (1) Synthesis of compound X-323-1

[0353]

[0354] This embodiment is basically the same as the synthesis of compound X-316-1, except that an equal amount of the halogenated product needs to be replaced in this example. The target compound X-323-1 (4.5 g) is a pale yellow solid.

[0355] (2) Synthesis of compound X-323-2

[0356]

[0357] This embodiment is basically the same as the synthesis of compound X-316-2, except that X-316-1 needs to be replaced with X-323-1 in this example. The target compound X-323-2 (4.5 g) is a pale yellow solid.

[0358] (3) Synthesis of compound X-323

[0359]

[0360] This example is basically the same as the synthesis of compound X-316, except that X-316-2 needs to be replaced with X-323-2. The target compound X-323 (0.37 g, 25% yield, HPLC purity 97%) is an orange solid. MALDI-TOF-MS results: Molecular ion peak: 610.23. Elemental analysis results: Theoretical values: C, 90.51; H, 5.94 (%); Experimental values: C, 90.56; H, 5.96 (%).

[0361] Synthesis Example 32:

[0362]

[0363] (1) Synthesis of compound X-331-1

[0364]

[0365] In a 100 mL double-necked flask, X-316 (1.02 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain a red powder, X-331-1 (0.80 g).

[0366] (2) Synthesis of compound X-331

[0367]

[0368] X-331-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-331 (0.23 g, 49% yield, HPLC purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 734.31 Elemental analysis results: Theoretical values: C, 91.57; H, 5.49 (%); Experimental values: C, 91.62; H, 5.46 (%).

[0369] Synthesis Example 33:

[0370]

[0371] (1) Synthesis of compound X-251-1

[0372]

[0373] X-331-1 (0.66 g, 1.00 mmol), carbazole (334 mg, 2.00 mmol), palladium acetate (22 mg, 0.10 mmol), tri-tert-butylphosphine tetrafluoroborate (87 mg, 0.30 mmol), and sodium tert-butoxide (192 mg, 2 mmol) were added sequentially to a 25 mL two-necked flask. Under a nitrogen atmosphere, 5 mL of anhydrous toluene was added, and the reaction was stopped after 24 hours at 110 °C. After cooling to room temperature, 200 mL of dichloromethane was added, and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 3:2) as eluent to give the target compound X-335 (0.58 g, 68% yield, HPLC purity 96%) as a deep red solid. MALDI-TOF-MS results: Molecular ion peak: 828.28. Elemental analysis results: Theoretical values: C, 89.87; H, 4.14; N, 3.38 (%); Experimental values: C, 89.94; H, 4.13; N, 3.34 (%).

[0374] Synthesis Example 34:

[0375]

[0376] (1) Synthesis of compound X-336

[0377]

[0378] X-331-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluorenboronic acid (0.26 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-336 (0.25 g, 46% yield, HPLC purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 882.33 Elemental analysis results: Theoretical values: C, 92.53; H, 5.02 (%); Experimental values: C, 92.52; H, 5.01 (%).

[0379] Synthesis Example 35:

[0380]

[0381] (1) Synthesis of compound X-341

[0382]

[0383] X-331-1 (0.36 g, 0.50 mmol), anthracene-9-ylboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-341 (0.27 g, 43% yield, HPLC purity 98%) as a deep red solid. MALDI-TOF-MS results: Molecular ion peak: 850.33 Elemental analysis results: Theoretical values: C, 93.19; H, 4.27 (%); Experimental values: C, 93.22; H, 4.25 (%).

[0384] Synthesis Example 36:

[0385]

[0386] (1) Synthesis of compound X-346-1

[0387]

[0388] 2,3-Dibromonaphthalene (2.84 g, 10.00 mmol), 2-phenyl-1,4-diboron-9-hydrocarbazole (4.95 g, 10.00 mmol), tetraphenylphosphine palladium (0.35 g, 0.30 mmol), and potassium carbonate (3.45 g, 25.00 mmol) were added sequentially to a 250 mL double-necked flask. Under a nitrogen atmosphere, 100 mL of tetrahydrofuran and 25 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 2:1) as eluent to give a pale yellow solid X-346-1 (3.6 g).

[0389] (2) Synthesis of compound X-346-2

[0390]

[0391] In a 100 mL two-necked flask, 1,8-dibromonaphthalene (1.42 g, 5.00 mmol), 2-phenyl-1,4-diboron-9-hydrocarbazole (2.87 g, 5.00 mmol), tetraphenylphosphine palladium (0.18 g, 0.15 mmol), and potassium carbonate (1.73 g, 12.50 mmol) were added sequentially. Under a nitrogen atmosphere, 50 mL of tetrahydrofuran and 12 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 100 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give a yellow solid X-346-2 (1.9 g).

[0392] (3) Synthesis of compound X-346-3

[0393]

[0394] Intermediate X-346-2 (3.25 g, 5.00 mmol) and cuprous iodide (1.00 g, 5.00 mmol) were added to a 250 mL two-necked round-bottom flask, respectively. Under a nitrogen atmosphere, 60 mL of N,N-dimethylformamide and 6 mL of tetra-n-butylammonium chloride were added sequentially. The mixture was then heated to 120 °C and reacted for 12 h. After the reaction was complete, the mixture was cooled to room temperature and extracted with dichloromethane and water. The organic phase was collected and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure and then separated by column chromatography to obtain an orange solid X-346-3 (1.3 g).

[0395] (4) Synthesis of compound X-346

[0396]

[0397] A solution of n-butyllithium (0.8 mL, 2.50 M, 2.00 mmol) was slowly added to a solution of X-346-3 (1.14 g, 2.00 mmol) in 20 mL of tert-butylbenzene at 0 °C, and the mixture was then heated to 60 °C for 3 hours at each temperature. After the reaction was complete, the temperature was lowered to -30 °C, and boron tribromide (0.52 g, 2.00 mmol) was slowly added. The mixture was stirred at room temperature for 0.5 hours. N,N-diisopropylethylamine (0.50 g, 4.00 mmol) was added at room temperature, and the reaction was continued at 145 °C for 5 hours before being stopped. The reaction was cooled to room temperature, extracted with dichloromethane and water, and the organic phase was collected and dried over anhydrous sodium sulfate. After the organic phase was concentrated under reduced pressure, column chromatography was performed using petroleum ether and dichloromethane (petroleum ether: dichloromethane = 1:1) as eluents to obtain the target compound X-346 (0.21 g, 19% yield, HPLC purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 501.18. Elemental analysis results: Theoretical values: C, 91.03; H, 4.02; N, 2.79 (%); Experimental values: C, 90.97; H, 4.06; N, 2.80 (%).

[0398] Synthesis Example 37:

[0399]

[0400] (1) Synthesis of compound X-356-1

[0401]

[0402] This example is basically the same as the synthesis of compound X-346-1, except that an equal amount of boron ester and bromide are replaced in this example. The target compound X-356-1 (2.8 g) is a white solid.

[0403] (2) Synthesis of compound X-356-2

[0404]

[0405] This embodiment is basically the same as the synthesis of compound X-346-2, except that 2-phenyl-1,4-diboronate-9-hydrocarbazole needs to be replaced with an equal amount of X-356-1. The target compound X-356-2 (1.7 g) is a pale yellow solid.

[0406] (3) Synthesis of compound X-356-3

[0407]

[0408] This embodiment is basically the same as the synthesis of compound X-346-3, except that X-346-2 needs to be replaced with an equal amount of X-356-2. The target compound X-356-3 (1.2 g) is a yellow solid.

[0409] (4) Synthesis of compound X-356

[0410]

[0411] This example is essentially the same as the synthesis of compound X-346, except that X-346-3 needs to be replaced with X-356-3. The target compound X-356 (0.29 g, 25% yield, HPLC purity 97%) is a red solid. MALDI-TOF-MS results: Molecular ion peak: 769.75. Elemental analysis results: Theoretical values: C, 90.49; H, 6.28; N, 1.82 (%); Experimental values: C, 90.52; H, 6.26; N, 1.83 (%).

[0412] Synthesis Example 38:

[0413]

[0414] (1) Synthesis of compound X-361-1

[0415]

[0416] In a 100 mL double-necked flask, X-346 (1.02 g, 2.02 mmol) was dissolved in 25 mL of dichloromethane. The solution was cooled to 0 °C, and N-bromosuccinimide (0.72 g, 4.04 mmol) was added in portions. The reaction was carried out in the dark for 24 hours, followed by extraction with 200 mL of dichloromethane and water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The solution was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:2) as eluent to obtain a red powder, X-361-1 (0.63 g).

[0417] (2) Synthesis of compound X-361

[0418]

[0419] X-361-1 (0.36 g, 0.50 mmol), 2,4,6-trimethylphenylboronic acid (0.18 g, 1.10 mmol), tetratetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-361 (0.22 g, 53% yield, HPLC purity 98%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 737.35 Elemental analysis results: Theoretical values: C, 91.17; H, 5.47; N, 1.90 (%); Experimental values: C, 91.18; H, 5.48; N, 1.89 (%).

[0420] Synthesis Example 39:

[0421]

[0422] (1) Synthesis of compound X-366

[0423]

[0424] X-361-1 (0.36 g, 0.50 mmol), 9,9-dimethyl-4-fluorenboronic acid (0.26 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. The mixture was cooled to room temperature, and 200 mL of ethyl acetate was added, followed by extraction with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-366 (0.29 g, 42% yield, HPLC purity 97%) as a red solid. MALDI-TOF-MS results: Molecular ion peak: 885.37 Elemental analysis results: Theoretical values: C, 92.19; H, 5.01; N, 1.58 (%); Experimental values: C, 92.17; H, 5.02; N, 1.59 (%).

[0425] Synthesis Example 40:

[0426]

[0427] (1) Synthesis of compound X-371

[0428]

[0429] X-361-1 (0.36 g, 0.50 mmol), anthracene-9-ylboronic acid (0.24 g, 1.10 mmol), tetraphenylphosphine palladium (17 mg, 0.015 mmol), and potassium carbonate (0.17 g, 1.25 mmol) were added sequentially to a 25 mL double-necked flask. Under a nitrogen atmosphere, 4 mL of tetrahydrofuran and 1 mL of water were added, and the reaction was stopped after 24 hours at 85 °C. After cooling to room temperature, 200 mL of ethyl acetate was added and the mixture was extracted with water. The organic phase was collected, dried over anhydrous sodium sulfate, and the organic solvent was removed under reduced pressure. The mixture was purified by column chromatography using petroleum ether and dichloromethane (v / v = 1:1) as eluent to give the target compound X-371 (0.15 g, 39% yield, HPLC purity 96%) as a deep red solid. MALDI-TOF-MS results: Molecular ion peak: 853.33 Elemental analysis results: Theoretical values: C, 92.84; H, 4.27; N, 1.64 (%); Experimental values: C, 92.85; H, 4.26; N, 1.64 (%).

[0430] The technical effects and advantages of the present invention are demonstrated and verified by specifically applying the compounds of the present invention to organic electroluminescent devices and testing their actual performance.

[0431] Specifically, the method for fabricating the organic electroluminescent device in this embodiment of the invention includes the following steps:

[0432] 1. The glass plate coated with the anodic material is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a mixture of acetone and ethanol, baked in a clean environment until all moisture is removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0433] 2. Place the glass plate with the anode inside the vacuum chamber and evacuate to a vacuum level of 1×10⁻⁶. -5 ~9×10 -3 Pa, a hole injection layer is formed by vacuum evaporation of hole injection material on the above-mentioned anolyte film, with an evaporation rate of 0.1-0.5 nm / s;

[0434] 3. A hole transport layer is formed by vacuum evaporation of a hole transport material on top of the hole injection layer, with an evaporation rate of 0.1-0.5 nm / s.

[0435] 4. An electron blocking layer is vacuum-deposited on top of the hole transport layer at a deposition rate of 0.1-0.5 nm / s;

[0436] 5. An organic light-emitting layer for the device is vacuum-deposited on top of an electron blocking layer. The organic light-emitting layer material can be single-component or multi-component. Multi-component materials may include a host material, a sensitizer, or a dye, or any combination thereof. A multi-source co-evaporation method is used to adjust the evaporation rate of the host material, the evaporation rate of the sensitizer material, and the evaporation rate of the dye to achieve a preset doping ratio.

[0437] 6. A hole blocking layer is vacuum-deposited on the organic light-emitting layer at a deposition rate of 0.1-0.5 nm / s;

[0438] 7. An electron transport layer is formed by vacuum evaporating the electron transport material of the device on top of the hole blocking layer, with an evaporation rate of 0.1-0.5 nm / s;

[0439] 8. A LiF layer is vacuum-deposited at 0.1-0.5 nm / s as the electron injection layer on the electron transport layer, and an Al layer is vacuum-deposited at 0.5-1 nm / s as the cathode of the device.

[0440] The organic electroluminescent device of the present invention will be further described below through specific embodiments.

[0441] Device Example 1

[0442] The structure of the organic electroluminescent device prepared in this embodiment is shown below:

[0443] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-1(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0444] The anode material is ITO; the hole injection layer material is HI, with a total thickness of 5-30 nm, and 10 nm in this embodiment; the hole transport layer material is HT, 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, and the compound X-1 of this invention is a dye with a doping concentration of 2 wt%, with a thickness of 1-200 nm, and 30 nm in this embodiment; the electron transport layer material is ET, with a thickness of 5-300 nm, and 30 nm in this embodiment; the electron injection layer and cathode materials are selected as LiF (0.5 nm) and metallic aluminum (150 nm).

[0445] A DC voltage was applied to the organic electroluminescent device D1 prepared in this embodiment, and the 10 cd / m² voltage was measured.2 The emission characteristics yielded an orange emission with a wavelength of 561 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.42, 0.54), and an external quantum efficiency (EQE) of 4.2% (driving voltage of 2.7 V).

[0446] Device Example 2

[0447] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material used in the light-emitting layer is replaced with a TADF-type host TD1. The specific device structure is as follows:

[0448] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD1:2wt%X-1(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0449] The performance results of the organic electroluminescent device D2 prepared in this embodiment are as follows: A DC voltage was applied, and the D2 was measured at 10 cd / m². 2 The emission characteristics yielded an orange emission with a wavelength of 564 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.44, 0.52), and an external quantum efficiency (EQE) of 18.1% (driving voltage of 2.7 V).

[0450] Device Example 3

[0451] The preparation method is the same as that of device embodiment 1, except that the dye used in the light-emitting layer is replaced by X-2 instead of X-1.

[0452] The device structure is as follows:

[0453] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-2(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0454] The performance results of the organic electroluminescent device D3 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 535 nm, a full width at half maximum (FWHM) of 20 nm, CIE color coordinates (x, y) = (0.25, 0.62), and an external quantum efficiency (EQE) of 4.4% (driving voltage of 2.8 V).

[0455] Device Example 4

[0456] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-2 instead of X-1. The device structure is as follows:

[0457] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-2(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0458] The performance results of the organic electroluminescent device D4 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 536 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.25, 0.60), and an external quantum efficiency (EQE) of 19.3% (driving voltage of 2.8 V).

[0459] Device Example 5

[0460] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-3 instead of X-1. The device structure is as follows:

[0461] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-3(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0462] The performance results of the organic electroluminescent device D5 prepared in this embodiment are as follows: A DC voltage was applied, and the D5 value was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 505 nm, a full width at half maximum (FWHM) of 18 nm, CIE color coordinates (x, y) = (0.15, 0.60), and an external quantum efficiency (EQE) of 4.6% (driving voltage of 3.0 V).

[0463] Device Example 6

[0464] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-3 instead of X-1. The device structure is as follows:

[0465] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-3(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0466] The performance results of the organic electroluminescent device D6 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 505 nm, a full width at half maximum (FWHM) of 18 nm, CIE color coordinates (x, y) = (0.15, 0.60), and an external quantum efficiency (EQE) of 24.1% (driving voltage of 3.0 V).

[0467] Device Example 7

[0468] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-16 instead of X-11. The device structure is as follows:

[0469] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-16(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0470] The performance results of the organic electroluminescent device D7 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded an orange emission with a wavelength of 575 nm, a full width at half maximum (FWHM) of 25 nm, CIE color coordinates (x, y) = (0.50, 0.42), and an external quantum efficiency (EQE) of 3.9% (driving voltage of 2.7 V).

[0471] Device Example 8

[0472] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-16 instead of X-16. The device structure is as follows:

[0473] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-16(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0474] The performance results of the organic electroluminescent device D8 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded an orange emission with a wavelength of 576 nm, a full width at half maximum (FWHM) of 26 nm, CIE color coordinates (x, y) = (0.50, 0.42), and an external quantum efficiency (EQE) of 21.7% (driving voltage of 2.7 V).

[0475] Device Example 9

[0476] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-18 instead of X-11. The device structure is as follows:

[0477] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-18(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0478] The performance results of the organic electroluminescent device D9 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 516 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.19, 0.70), and an external quantum efficiency (EQE) of 4.6% (driving voltage of 3.0 V).

[0479] Device Example 10

[0480] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-18 instead of X-18. The device structure is as follows:

[0481] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-18(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0482] The performance results of the organic electroluminescent device D10 prepared in this embodiment are as follows: A DC voltage was applied, and the D10 was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 516 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.20, 0.69), and an external quantum efficiency (EQE) of 18.4% (driving voltage of 3.0 V).

[0483] Device Example 11

[0484] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-57 instead of X-1. The device structure is as follows:

[0485] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-57(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0486] The performance results of the organic electroluminescent device D11 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded a yellow emission with a wavelength of 541 nm, a full width at half maximum (FWHM) of 25 nm, CIE color coordinates (x, y) = (0.33, 0.56), and an external quantum efficiency (EQE) of 3.8% (driving voltage of 2.8 V).

[0487] Device Example 12

[0488] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-57 instead of X-1. The device structure is as follows:

[0489] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-57(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0490] The performance results of the organic electroluminescent device D12 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded a yellow emission with a wavelength of 541 nm, a full width at half maximum (FWHM) of 27 nm, CIE color coordinates (x, y) = (0.33, 0.56), and an external quantum efficiency (EQE) of 20.4% (driving voltage of 2.8 V).

[0491] Device Example 13

[0492] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-81 instead of X-1. The device structure is as follows:

[0493] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-81(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0494] The performance results of the organic electroluminescent device D13 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded orange emission with a wavelength of 578 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.51, 0.39), and an external quantum efficiency (EQE) of 3.6% (driving voltage of 2.6 V).

[0495] Device Example 14

[0496] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-81 instead of X-1. The device structure is as follows:

[0497] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-81(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0498] The performance results of the organic electroluminescent device D14 prepared in this embodiment were measured as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded an orange emission with a wavelength of 578 nm, a full width at half maximum (FWHM) of 23 nm, CIE color coordinates (x, y) = (0.50, 0.40), and an external quantum efficiency (EQE) of 18.4% (driving voltage of 2.6 V).

[0499] Device Example 15

[0500] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-83 instead of X-1. The device structure is as follows:

[0501] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-83(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0502] The performance results of the organic electroluminescent device D15 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded a yellow emission with a wavelength of 552 nm, a full width at half maximum (FWHM) of 20 nm, CIE color coordinates (x, y) = (0.35, 0.58), and an external quantum efficiency (EQE) of 3.6% (driving voltage of 2.7 V).

[0503] Device Example 16

[0504] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-83 instead of X-1. The device structure is as follows:

[0505] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-83(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0506] The performance results of the organic electroluminescent device D16 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded a yellow emission with a wavelength of 553 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.35, 0.59), and an external quantum efficiency (EQE) of 23.1% (driving voltage of 2.7 V).

[0507] Device Example 17

[0508] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-171 instead of X-1. The device structure is as follows:

[0509] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-171(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0510] The performance results of the organic electroluminescent device D17 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded orange emission with a wavelength of 576 nm, a full width at half maximum (FWHM) of 22 nm, CIE color coordinates (x, y) = (0.45, 0.50), and an external quantum efficiency (EQE) of 4.5% (driving voltage of 2.7 V).

[0511] Device Example 18

[0512] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-171 instead of X-1. The device structure is as follows:

[0513] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-171(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0514] The performance results of the organic electroluminescent device D18 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2The emission characteristics yielded an orange emission with a wavelength of 576 nm, a full width at half maximum (FWHM) of 24 nm, CIE color coordinates (x, y) = (0.50, 0.45), and an external quantum efficiency (EQE) of 23.1% (driving voltage of 2.7 V).

[0515] Device Example 19

[0516] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-195 instead of X-1. The device structure is as follows:

[0517] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-195(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0518] The performance results of the organic electroluminescent device D19 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded a yellow emission with a wavelength of 544 nm, a full width at half maximum (FWHM) of 20 nm, CIE color coordinates (x, y) = (0.40, 0.52), and an external quantum efficiency (EQE) of 3.3% (driving voltage of 2.8 V).

[0519] Device Example 20

[0520] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-195. The device structure is as follows:

[0521] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-195(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0522] The performance results of the organic electroluminescent device D20 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded a yellow emission with a wavelength of 545 nm, a full width at half maximum (FWHM) of 21 nm, CIE color coordinates (x, y) = (0.39, 0.51), and an external quantum efficiency (EQE) of 18.8% (driving voltage of 2.8 V).

[0523] Device Example 21

[0524] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-204 instead of X-1. The device structure is as follows:

[0525] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-204(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0526] The performance results of the organic electroluminescent device D25 prepared in this embodiment were measured as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green light with a wavelength of 512 nm, a full width at half maximum (FWHM) of 18 nm, CIE color coordinates (x, y) = (0.22, 0.69), and an external quantum efficiency (EQE) of 4.8% (driving voltage of 3.0 V).

[0527] Device Example 22

[0528] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-204 instead of X-1. The device structure is as follows:

[0529] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-204(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0530] The performance results of the organic electroluminescent device D26 prepared in this embodiment were measured as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green light with a wavelength of 512 nm, a full width at half maximum (FWHM) of 18 nm, CIE color coordinates (x, y) = (0.21, 0.69), and an external quantum efficiency (EQE) of 23.1% (driving voltage of 3.0 V).

[0531] Device Example 23

[0532] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-246 instead of X-1. The device structure is as follows:

[0533] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-246(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0534] The performance results of the organic electroluminescent device D27 prepared in this embodiment were measured as follows: A DC voltage was applied, and the performance was measured at 10 cd / m².2 The emission characteristics yielded a yellow emission with a wavelength of 558 nm, a full width at half maximum (FWHM) of 24 nm, CIE color coordinates (x, y) = (0.39, 0.55), and an external quantum efficiency (EQE) of 3.4% (driving voltage of 2.8 V).

[0535] Device Example 24

[0536] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-246 instead of X-1. The device structure is as follows:

[0537] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-246(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0538] The performance results of the organic electroluminescent device D28 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded a yellow emission with a wavelength of 558 nm, a full width at half maximum (FWHM) of 24 nm, CIE color coordinates (x, y) = (0.38, 0.55), and an external quantum efficiency (EQE) of 21.3% (driving voltage of 2.8 V).

[0539] Device Example 25

[0540] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-260 instead of X-1. The device structure is as follows:

[0541] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-260(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0542] The performance results of the organic electroluminescent device D29 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded an orange emission with a wavelength of 566 nm, a full width at half maximum (FWHM) of 32 nm, CIE color coordinates (x, y) = (0.42, 0.52), and an external quantum efficiency (EQE) of 3.3% (driving voltage of 2.8 V).

[0543] Device Example 26

[0544] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-260 instead of X-1. The device structure is as follows:

[0545] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-260(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0546] The performance results of the organic electroluminescent device D30 prepared in this embodiment were measured as follows: A DC voltage was applied, and the D30 was measured at 10 cd / m². 2 The emission characteristics yielded orange emission with a wavelength of 568 nm, a full width at half maximum (FWHM) of 33 nm, CIE color coordinates (x, y) = (0.42, 0.50), and an external quantum efficiency (EQE) of 19.0% (driving voltage of 2.8 V).

[0547] Device Example 27

[0548] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced with X-276 instead of X-1. The device structure is as follows:

[0549] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-276(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0550] The performance results of the organic electroluminescent device D23 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded orange emission with a wavelength of 585 nm, a full width at half maximum (FWHM) of 24 nm, CIE color coordinates (x, y) = (0.53, 0.40), and an external quantum efficiency (EQE) of 4.3% (driving voltage of 2.6 V).

[0551] Device Example 28

[0552] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-276 instead of X-1. The device structure is as follows:

[0553] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-276(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0554] The performance results of the organic electroluminescent device D24 prepared in this embodiment were measured as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded orange emission with a wavelength of 588 nm, a full width at half maximum (FWHM) of 24 nm, CIE color coordinates (x, y) = (0.53, 0.38), and an external quantum efficiency (EQE) of 23.4% (driving voltage of 2.6 V).

[0555] Device Example 29

[0556] The fabrication method is the same as that of Device Example 1, except that the dye in the light-emitting layer is replaced by X-283 with X-1. The device structure is as follows:

[0557] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / Host:2wt%X-283(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0558] The performance results of the organic electroluminescent device D21 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 513 nm, a full width at half maximum (FWHM) of 21 nm, CIE color coordinates (x, y) = (0.18, 0.70), and an external quantum efficiency (EQE) of 4.2% (driving voltage of 3.0 V).

[0559] Device Example 30

[0560] The fabrication method is the same as that in Device Example 1, except that the wide-bandgap host material in the light-emitting layer is replaced with a TADF-type host TD, and the dye is replaced with X-283 instead of X-1. The device structure is as follows:

[0561] ITO / HI(10nm) / HT(30nm) / EBL(10nm) / TD:2wt%X-283(30nm) / HBL(10nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0562] The performance results of the organic electroluminescent device D22 prepared in this embodiment were measured as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green light with a wavelength of 513 nm, a full width at half maximum (FWHM) of 21 nm, CIE color coordinates (x, y) = (0.18, 0.70), and an external quantum efficiency (EQE) of 25.5% (driving voltage of 3.0 V).

[0563] Comparative Device Example 1

[0564] The preparation method is the same as that of device example 1, except that the compound X-1 of the present invention used in the light-emitting layer is replaced with the prior art compound TTPA. The specific device structure is as follows:

[0565] ITO / HI(10nm) / HT(40nm) / Host:2wt%TTPA(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0566] The performance results of the organic electroluminescent device DD1 prepared in this embodiment are as follows: When a DC voltage is applied, the characteristics of emitting light at 10 cd / m2 are measured, and green light emission with a wavelength of 529 nm, a half-width of 54 nm, CIE color coordinates (x,y)=(0.29,0.59), and an external quantum efficiency (EQE) of 3.5% is obtained (driving voltage of 2.7V).

[0567] Comparative Device Example 2

[0568] The preparation method is the same as that of device example 2, except that the compound X-1 of the present invention used in the light-emitting layer is replaced with the prior art compound TTPA. The specific device structure is as follows:

[0569] ITO / HI(10nm) / HT(40nm) / TD:2wt%TTPA(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0570] The performance results of the organic electroluminescent device DD2 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green light with a wavelength of 530 nm, a full width at half maximum (FWHM) of 52 nm, CIE color coordinates (x, y) = (0.30, 0.59), and an external quantum efficiency (EQE) of 15.7% (driving voltage of 2.7 V).

[0571] Comparative Device Example 3

[0572] The preparation method is the same as that of device example 1, except that the compound X-1 of the present invention used in the light-emitting layer is replaced with the prior art compound 2F-BN. The specific device structure is as follows:

[0573] ITO / HI(10nm) / HT(40nm) / Host:2wt%2F-BN(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0574] The performance results of the organic electroluminescent device DD3 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m³. 2 The emission characteristics show that green light emission with a wavelength of 501 nm, a full width at half maximum (FWHM) of 40 nm, CIE color coordinates (x, y) = (0.16, 0.60), and an external quantum efficiency (EQE) of 13.7% can be obtained (driving voltage of 3.0 V).

[0575] Comparative Device Example 4

[0576] The preparation method is the same as that of device example 2, except that the compound X-1 of the present invention used in the light-emitting layer is replaced with the prior art compound 2F-BN. The specific device structure is as follows:

[0577] ITO / HI(10nm) / HT(40nm) / TD1:2wt%2F-BN(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0578] The performance results of the organic electroluminescent device DD4 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded green emission with a wavelength of 502 nm, a full width at half maximum (FWHM) of 40 nm, CIE color coordinates (x, y) = (0.16, 0.60), and an external quantum efficiency (EQE) of 17.6% (driving voltage of 3.0 V).

[0579] Comparative Device Example 5

[0580] The preparation method is the same as that of device example 1, except that the compound X-1 of the present invention used in the light-emitting layer is replaced with compound DM1 in the prior art. The specific device structure is as follows:

[0581] ITO / HI(10nm) / HT(40nm) / Host:2wt%DM1(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0582] The performance results of the organic electroluminescent device DD5 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded blue emission with a wavelength of 480 nm, a full width at half maximum (FWHM) of 35 nm, CIE color coordinates (x, y) = (0.15, 0.20), and an external quantum efficiency (EQE) of 3.1% (driving voltage of 3.2 V).

[0583] Comparative Device Example 6

[0584] The preparation method is the same as that of device example 2, except that the compound X-1 of the present invention used in the light-emitting layer is replaced with compound DM1 in the prior art. The specific device structure is as follows:

[0585] ITO / HI(10nm) / HT(40nm) / TD1:2wt%DM1(30nm) / ET(30nm) / LiF(0.5nm) / Al(150nm)

[0586] The performance results of the organic electroluminescent device DD6 prepared in this embodiment are as follows: A DC voltage was applied, and the performance was measured at 10 cd / m². 2 The emission characteristics yielded blue emission with a wavelength of 482 nm, a full width at half maximum (FWHM) of 35 nm, CIE color coordinates (x, y) = (0.15, 0.21), and an external quantum efficiency (EQE) of 14.4% (driving voltage of 3.2 V).

[0587] The structural formulas of the various organic materials used in the above embodiments are as follows:

[0588]

[0589]

[0590]

[0591] The specific performance data of the organic electroluminescent devices D1 to D30 and devices DD1, DD2, DD3, DD4, DD5 and DD6 prepared in the above device embodiments are detailed in Tables 1 and 2 below.

[0592] Table 1:

[0593]

[0594]

[0595] Table 2:

[0596]

[0597]

[0598] As can be seen from the data in Tables 1 and 2, compared with the existing compounds TTPA, 2F-BN, and DM1, the compounds of this invention have a narrower fluorescence spectrum half-width at half-maximum, belonging to a new type of stable MR-type narrow-spectrum fluorescent dye. Although the classic green fluorescent dye TTPA has a high fluorescence quantum yield, its broad fluorescence emission spectrum makes it difficult to meet the color purity requirements of BT2020. In contrast, 2F-BN utilizes the electronegativity difference between boron and nitrogen atoms to achieve a multiple resonance effect, obtaining a narrow emission fluorescence spectrum. However, the chemical stability of boron atoms is poor, and the small single triplet energy level difference in the molecule slows down the exciton dynamics process. Compound DM1, as a traditional fluorescent dye, also has a narrow fluorescence spectrum and a short fluorescence lifetime, but the electron cloud distribution of this type of material is limited in delocalization, and the energy band is large, often requiring a high driving voltage, thus also facing stability issues. In this invention, we have invented a novel multiple resonance fluorescent dye system. Unlike the traditional boron-nitrogen and carbonyl-nitrogen structures, this invention utilizes the electronegativity difference between heteroatoms and carbon atoms to achieve a multiple resonance effect. The introduction of the six-membered fused ring effectively expands the molecular conjugation area, widens the energy difference between the single and triplet states, further accelerates the exciton dynamics process, and improves device stability. Therefore, the fusion of a five-membered ring and a six-membered ring achieves a balance between narrow-spectrum, high-efficiency luminescence and high stability. The results show that the electroemission spectrum of the examples has a small full width at half maximum (FWHM), confirming its effective multiple resonance effect. Simultaneously, the molecules exhibit excellent luminescence efficiency, with PLQY both exceeding 90%. Utilizing the sensitization effect of the thermally activated delayed fluorescence host, the examples also demonstrate excellent device stability, significantly improved compared to the comparative example DD4, proving the significant advantages of the molecular structure in improving device efficiency and stability. Given its excellent efficiency, color purity, and stability, the above compounds should have promising application prospects.

[0599] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of the above embodiments are only for the purpose of helping to understand the method and core ideas of the present invention. For those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of the present invention. The content of this specification should not be construed as a limitation of the present invention.

Claims

1. An organic compound having a structure as shown in any of formula (5), (6), (7) or (8): in, X 1 and X 2 Each is independently represented by N; Ring d 1 , ring d 2 Each ring can be a benzene ring or a naphthalene ring, and they can be separated independently. The R A R B R C R D R E and R F Each substituent group can be independently represented from a single substituent group to the maximum allowed number of substitutions; R A R B R C R D R E and R F Each is independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-Trifluoroethyl, phenyl, naphthyl, anthracene, benzo[a]anthrayl, phenanthrene, benzo[a]phenanthrene, pyrene, pyroxyl, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, terphenyl, tetraphenyl, fluorenyl, spirodifluorenyl, furanyl, benzo[a]furanyl, dibenzo[a]furanyl, thiophene, benzo[a]thiophene, pyrrole, carbazole, indoxacarbazole, pyridyl, quinolinyl, acridineyl, Pyrazolyl, indazole, imidazole, benzimidazole, naphthizimidazole, phenanthrenezimidazole, pyridinium-imidazolyl, benzoxoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthidinyl, azacarbazolyl, benzocarbazolyl, phenanthrene-rhazolyl, 1,2, 3-Triazolyl, 1,2,4-Triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, benzothiadiazolyl, 9,9-dimethylacridinyl, diarylamine, triarylamine, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, methoxy, silyl, or a combination of the two substituents listed above; The R A R B R C R D R E and R F Each of them is connected to rings A, B, C, D, E, and F via single bonds.

2. The organic compound according to claim 1, having a structure shown in any one of formula (9), (10), (11), or (12): In equations (9)-(12), X 1 X 2 R A R B R C R D R E and R F The definitions are all the same as those in equations (5), (6), (7) or (8); In equation (9), R B R C Each is independently not selected from fluorenyl, 9,9-dimethylfluorenyl, or naphthyl; R D R E and R F Not selected from hydrogen; In equation (10), R A Not selected from cyano, trimethylphenyl, R B R C Each of the following is independently not selected from a combination of trimethylphenyl, phenyl, and carbazole groups; R D R E and R F All are hydrogen; In equation (12), R A Not selected from hydrogen, cyano, phenyl, or trimethylphenyl; R B R C Each and every one of the following is independently not selected from fluorenyl, 9,9-dimethylfluorenyl, combinations of phenyl and carbazole, or anthracene; R D R E and R F Both are hydrogen.

3. The organic compound according to claim 1 or 2, wherein R A R B R C R D R E and R F Each of the following groups is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclohexyl, adamantyl, fluorine, trifluoromethyl, phenyl, tricrylyl, naphthyl, anthraceneyl, furanyl, tetrahydrofuranyl, pyrroleyl, tetrahydropyrroleyl, thiophene, carbazoyl, triazineyl, pyridyl, quinolinyl, acridineyl, cyano, methoxy, silyl, dimethylamino, triarylamino, fluorenyl, dibenzofuranyl, dibenzothiophene, or a combination of the two substituent groups mentioned above.

4. An organic compound selected from the following compounds: 。 5. The use of the compound according to any one of claims 1-4, wherein the use is as a functional material in organic electronic devices, said organic electronic devices including organic electroluminescent devices, optical sensors, solar cells, lighting elements, information tags, electronic artificial skin sheets, sheet-type scanners, or electronic paper.

6. The compound according to claim 5 is used as a light-emitting layer material in organic electroluminescent devices.

7. An organic electroluminescent device, comprising a first electrode, a second electrode, and one or more light-emitting functional layers inserted between the first electrode and the second electrode, wherein the light-emitting functional layer comprises a hole transport region, a light-emitting layer, and an electron transport region, wherein the hole transport region is formed on an anode layer, a cathode layer is formed on the electron transport region, and the light-emitting layer is located between the hole transport region and the electron transport region, wherein the light-emitting layer contains a compound according to any one of claims 1-4.

Images