A fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle and an organic electroluminescence device

Abstract

The application provides a fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle, as shown in formula (I). Compared with the prior art, the application uses the fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle as a light-emitting material, which can realize the separation of HOMO and LUMO by using the resonance effect between boron atoms, nitrogen atoms and sulfur atoms, thereby realizing smaller ΔE ST and TADF effect, and meanwhile, the hybrid fused ring unit has a rigid skeleton structure, can reduce the relaxation degree of the excited state structure, thereby realizing a narrower half peak width; on the other hand, the five-membered aromatic heterocycle and different substituents can be introduced into the skeleton of the boron / nitrogen / sulfur hybrid fused ring unit, so that the lifetime and half peak width of the delayed fluorescence can be further adjusted.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic light-emitting materials, and particularly relates to a fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle and an organic electroluminescent device. BACKGROUND

[0002] An organic light-emitting device (OLED) is generally composed of a cathode, an anode and an organic layer interposed between the cathode and the anode, i.e., the device is composed of a transparent ITO anode, a hole injection layer (TIL), a hole transport layer (HTL), an emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL) and a cathode, and 1-2 organic layers can be omitted or an exciton blocking layer (EBL) can be added as needed, the mechanism of action is that a voltage is formed between the two electrodes, electrons are injected from the cathode and holes are injected from the anode at the same time, the electrons and holes combine in the emitting layer to form an excited state, the excited state radiates back to the ground state, thereby realizing light emission of the device. Due to the rich color, fast response and the characteristics of being able to prepare flexible devices, organic electroluminescent materials are considered to be the most promising next-generation flat panel display and solid-state lighting materials.

[0003] Due to the limitation of spin quantum statistics, only 25% of singlet excitons can be utilized in the electroluminescent process of traditional fluorescent materials, and 75% of triplet excitons are lost in the form of non-radiative transition, and the theoretical limit of internal quantum efficiency (IQE) is 25%, so making full use of triplet excitons is one of the effective ways to improve quantum efficiency. For example, phosphorescent metal complexes can convert triplet excitons into photons by using the spin-orbit coupling of heavy metal atoms, achieving 100% internal quantum efficiency, but this approach faces the problem of expensive phosphorescent metal complexes. Another way to utilize triplet excitons is to develop luminescent materials with thermally activated delayed fluorescence (TADF) properties, which can convert triplet excitons into singlets through a thermally activated reverse intersystem crossing (RISC) process, and then emit fluorescence by radiative decay to the ground state, thereby achieving full utilization of singlet and triplet excitons without the need for noble metals.

[0004] The main way to design TADF materials at present is to introduce donor (D) and acceptor (A) groups to effectively separate the highest occupied orbital (HOMO) and the lowest unoccupied orbital (LUMO) in space, thereby realizing a small singlet-triplet energy level difference (ΔEST) and efficient reverse intersystem crossing (RISC) from the triplet state to the singlet state. ST), thereby promoting the reverse intersystem crossing process. However, due to the strong vibration relaxation of the excited state of such D-A structure, the luminescence spectrum is wide, and the full width at half maximum (FWHM) is generally 70-100 nm, resulting in poor color purity. In practical applications, a filter or an optical microcavity is often used to improve the color purity, but this will result in a decrease in the external quantum efficiency of the device or a complex device structure.

[0005] Therefore, how to solve the defect of wide half peak width of the above-mentioned material by suitable chemical structure design, and develop a TADF fluorescent material with narrow spectral characteristics has become one of the problems to be solved by many researchers in the field. SUMMARY

[0006] Therefore, the technical problem to be solved by the present application is to provide a fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle, and an organic electroluminescent device. The fused ring compound has both TADF effect and narrow half peak width spectral characteristics.

[0007] The present application provides a fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle, as shown in formula (I):

[0008]

[0009] wherein m, n and p are each independently an integer from 0 to 20;

[0010] each independently selected from a substituted or unsubstituted six-membered aromatic ring, a substituted or unsubstituted six-membered heteroaromatic ring, a substituted or unsubstituted five-membered aromatic heterocycle, and a substituted or unsubstituted aromatic fused ring unit; the aromatic fused ring unit contains one or more of a six-membered aromatic ring, a six-membered heteroaromatic ring and a five-membered aromatic heterocycle, and the aromatic fused ring unit is connected to B, N or S through a six-membered aromatic ring, a six-membered heteroaromatic ring or a five-membered aromatic heterocycle; and at least one is a substituted or unsubstituted five-membered aromatic heterocycle, or an aromatic fused ring unit containing a five-membered aromatic heterocycle, and the aromatic fused ring unit is connected to B, N or S through a five-membered aromatic heterocycle;

[0011] R a , R b , R c and R d are each independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -O-R 1 , -S-R 1 , -Se-R 1 , -Te-R 1 substituted or unsubstituted C1-C30 linear hydrocarbyl, substituted or unsubstituted C1-C30 branched hydrocarbyl, substituted or unsubstituted C1-C30 halogenated hydrocarbyl, substituted or unsubstituted C3-C30 cyclic hydrocarbyl, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group;

[0012] said R 1 , R 2 and R 3 are each independently selected from the group consisting of H, D, F, Cl, Br, I, -OH, -SH, -NH2, substituted or unsubstituted C1-C30 linear hydrocarbyl, substituted or unsubstituted C1-C30 branched hydrocarbyl, substituted or unsubstituted C1-C30 halogenated hydrocarbyl, substituted or unsubstituted C3-C30 cyclic hydrocarbyl, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group;

[0013] the heteroatoms in said heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se;

[0014] or R a , R b and R c are each connected to each other, or R 1 , R 2 and R 3 are connected to each other by one or more of a single bond, -C-C-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te, ;

[0015] or R d and are connected by one or more of a single bond, -C-C-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te, ;

[0016] or when R a or R b is adjacent to N, R d and R a or R b are connected by one or more of a single bond, -C-C-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te, ;

[0017] L1' to L 12 each independently is selected from H, D, F, Cl, Br, I, -CN, -NO2, a substituted or unsubstituted C1-C30 linear alkyl group, a substituted or unsubstituted C1-C30 branched alkyl group, a substituted or unsubstituted C1-C30 halogenated alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group.

[0018] The present application provides a fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle, as shown in formula (I). Compared with the prior art, the present application uses a fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle as a light-emitting material, which can realize the separation of HOMO and LUMO by the resonance effect between boron atoms and nitrogen atoms and sulfur atoms, thereby realizing a smaller ΔE ST and TADF effect. At the same time, such hybrid fused ring units have a rigid backbone structure, which can reduce the relaxation degree of the excited state structure, thereby realizing a narrower half peak width. On the other hand, by introducing a five-membered aromatic heterocycle and different substituents into the backbone of the boron / nitrogen / sulfur hybrid fused ring unit, the lifetime and half peak width of the delayed fluorescence can be further adjusted.

[0019] Experimental results show that the light-emitting compound of the present application used as the light-emitting layer of the electroluminescent device can realize narrow electroluminescent half peak width without the need for optical filters and microcavity structures, and can also realize high device efficiency. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0021] The present application provides a fused ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle, as shown in formula (I):

[0022]

[0023] each independently is a substituted or unsubstituted six-membered aromatic ring, a substituted or unsubstituted six-membered heteroaromatic ring, a substituted or unsubstituted five-membered aromatic heterocycle, or a substituted or unsubstituted aromatic fused ring unit; the aromatic fused ring unit contains one or more of a six-membered aromatic ring, a six-membered aromatic heterocycle and a five-membered aromatic heterocycle, and the aromatic fused ring unit is connected to B, N or S through a six-membered aromatic ring, a six-membered aromatic heterocycle or a five-membered aromatic heterocycle; and at least one is a substituted or unsubstituted five-membered aromatic heterocycle, or an aromatic fused ring unit containing a five-membered aromatic heterocycle, and the aromatic fused ring unit is connected through the five-membered aromatic heterocycle to B and N or S; that is, the fused compound has a structure shown in formula (II) to formula (VIII):

[0024]

[0025] each independently is a substituted or unsubstituted five-membered aromatic heterocycle, a substituted or unsubstituted aromatic fused ring unit containing a five-membered aromatic heterocycle, and the fused ring unit is connected through the five-membered aromatic heterocycle to B and N or S;

[0026] each independently is a substituted or unsubstituted six-membered aromatic ring or a six-membered aromatic heterocycle, a substituted or unsubstituted aromatic fused ring unit containing a six-membered aromatic ring or a six-membered aromatic heterocycle, and the fused ring unit is connected through the six-membered aromatic ring or the six-membered aromatic heterocycle to B and X or Y;

[0027] In the present application, the each independently is preferably a substituted or unsubstituted C6-C60 six-membered aromatic ring, a substituted or unsubstituted C3-C60 six-membered heteroaromatic ring, a substituted or unsubstituted C3-C60 five-membered heteroaromatic ring, a substituted or unsubstituted C4-C80 aromatic fused ring unit; more preferably a substituted or unsubstituted C6-C40 six-membered aromatic ring, a substituted or unsubstituted C3-C40 six-membered heteroaromatic ring, a substituted or unsubstituted C3-C40 five-membered heteroaromatic ring, a substituted or unsubstituted C4-C60 aromatic fused ring unit; still more preferably a substituted or unsubstituted C6-C30 six-membered aromatic ring, a substituted or unsubstituted C3-C30 six-membered heteroaromatic ring, a substituted or unsubstituted C3-C30 five-membered heteroaromatic ring, a substituted or unsubstituted C4-C50 aromatic fused ring unit; still more preferably a substituted or unsubstituted C6-C15 six-membered aromatic ring, a substituted or unsubstituted C3-C15 six-membered heteroaromatic ring, a substituted or unsubstituted C3-C15 five-membered heteroaromatic ring, a substituted or unsubstituted C4-C40 aromatic fused ring unit; most preferably a substituted or unsubstituted C6-C10 six-membered aromatic ring, a substituted or unsubstituted C3-C10 six-membered heteroaromatic ring, a substituted or unsubstituted C3-C10 five-membered heteroaromatic ring, a substituted or unsubstituted C4-C30 aromatic fused ring unit; the aromatic fused ring unit contains one or more of a six-membered aromatic ring, a six-membered aromatic heterocycle and a five-membered aromatic heterocycle; the heteroatoms in the six-membered aromatic heterocycle and the five-membered aromatic heterocycle are each independently one or more of Si, Ge, N, P, O, S and Se.

[0028] The substituents in the substituted six-membered aromatic ring, substituted six-membered aromatic heterocycle, substituted five-membered aromatic heterocycle, and substituted aromatic fused ring unit are each preferably D, substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, substituted or unsubstituted C1-C30 branched hydrocarbon group, substituted or unsubstituted C1-C30 haloalkane group, substituted or unsubstituted C3-C30 cycloalkyl group, or substituted or unsubstituted C6-C60... One or more of the following: aromatic groups, substituted or unsubstituted C5-C60 heteroaromatic groups; more preferably, D, substituted or unsubstituted C1-C20 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C20 branched hydrocarbon groups, substituted or unsubstituted C1-C20 haloalkane groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C6-C40 aromatic groups, and substituted or unsubstituted C5-C40 heteroaromatic groups; even more preferably, D, substituted or unsubstituted C1-C10 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C60... The heteroatom in the heteroaromatic group is selected from one or more of the following: branched hydrocarbon group, substituted or unsubstituted C1-C10 haloalkane group, substituted or unsubstituted C3-C10 cycloalkyl group, substituted or unsubstituted C6-C30 aromatic group, and substituted or unsubstituted C5-C30 heteroaromatic group; most preferably, it is selected from one or more of the following: D, substituted or unsubstituted C1-C5 straight-chain hydrocarbon group, substituted or unsubstituted C1-C5 branched hydrocarbon group, substituted or unsubstituted C1-C5 haloalkane group, substituted or unsubstituted C3-C8 cycloalkyl group, substituted or unsubstituted C6-C20 aromatic group, and substituted or unsubstituted C5-C20 heteroaromatic group; wherein the heteroatom in the heteroaromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

[0029] In this invention, more preferably, the... Each is independently selected from one of the groups shown in Ar1-Ar27 and Ar1-Ar33, and At least one is selected from Ar1 to Ar27, and at the same time Through B, S and Forming a six-membered ring, Through B, N and Forming a six-membered ring:

[0030]

[0031]

[0032] L1, L2and L3are each independently preferably H, D, a substituted or unsubstituted C1-C30 linear hydrocarbyl, a substituted or unsubstituted C1-C30 branched hydrocarbyl, a substituted or unsubstituted C1-C30 halogenated hydrocarbyl, a substituted or unsubstituted C3-C30 cyclic hydrocarbyl, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; more preferably H, D, a substituted or unsubstituted C1-C20 linear hydrocarbyl, a substituted or unsubstituted C1-C20 branched hydrocarbyl, a substituted or unsubstituted C1-C20 halogenated hydrocarbyl, a substituted or unsubstituted C3-C20 cyclic hydrocarbyl, a substituted or unsubstituted C6-C40 aromatic group, a substituted or unsubstituted C5-C40 heteroaromatic group; again preferably H, D, a substituted or unsubstituted C1-C10 linear hydrocarbyl, a substituted or unsubstituted C1-C10 branched hydrocarbyl, a substituted or unsubstituted C1-C10 halogenated hydrocarbyl, a substituted or unsubstituted C3-C10 cyclic hydrocarbyl, a substituted or unsubstituted C6-C30 aromatic group, a substituted or unsubstituted C5-C30 heteroaromatic group; most preferably H, D, a substituted or unsubstituted C1-C5 linear hydrocarbyl, a substituted or unsubstituted C1-C5 branched hydrocarbyl, a substituted or unsubstituted C1-C5 halogenated hydrocarbyl, a substituted or unsubstituted C3-C8 cyclic hydrocarbyl, a substituted or unsubstituted C6-C20 aromatic group, a substituted or unsubstituted C5-C20 heteroaromatic group; the heteroatom(s) in the heteroaromatic group being selected from one or more of Si, Ge, N, P, O, S and Se.

[0033] m, n and p are each independently the number of R a , R b and R c , each independently an integer from 0 to 20, preferably an integer from 0 to 15, more preferably an integer from 0 to 10, again preferably an integer from 0 to 5, most preferably an integer from 0 to 4, i.e. m, n and p are each independently 0, 1, 2, 3 or 4.

[0034] R a , R b , R c and R d are each independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -O-R 1 , -S-R1, -Se-R 1 , -Te-R 1 , The following are possible meanings: substituted or unsubstituted C1-C30 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C30 branched hydrocarbon groups, substituted or unsubstituted C1-C30 haloalkane groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C6-C60 aromatic groups, and substituted or unsubstituted C5-C60 heteroaromatic groups; preferably D, F, Cl, Br, I, -CN, or -NO2. -OR 1 -SR 1 , -Se-R 1 , -Te-R 1 The following are substituted or unsubstituted C1-C20 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C20 branched hydrocarbon groups, substituted or unsubstituted C1-C20 haloalkane groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C6-C40 aromatic groups, and substituted or unsubstituted C5-C40 heteroaromatic groups; more preferably D, F, Cl, Br, I, -CN, or -NO2. -OR 1 -SR 1 , -Se-R 1 , -Te-R 1 , The following are possible substituted or unsubstituted C1-C10 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C10 branched hydrocarbon groups, substituted or unsubstituted C1-C10 haloalkane groups, substituted or unsubstituted C3-C15 cycloalkyl groups, substituted or unsubstituted C6-C30 aromatic groups, and substituted or unsubstituted C5-C30 heteroaromatic groups; preferably D, F, Cl, Br, I, -CN, or -NO2. -OR 1 -SR 1 , -Se-R 1 , -Te-R 1 , Substituted or unsubstituted C1-C5 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C5 branched hydrocarbon groups, substituted or unsubstituted C1-C5 haloalkane groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C6-C20 aromatic groups, and substituted or unsubstituted C5-C20 heteroaromatic groups.

[0035] The R 1R 2 and R 3 Each can be independently H, D, F, Cl, Br, I, -OH, -SH, -NH2, substituted or unsubstituted C1 to C30. The following are possible meanings: a straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkane group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, or a substituted or unsubstituted C5-C60 heteroaromatic group; preferably H, D, F, Cl, Br, I, -OH, -SH, -NH2, a substituted or unsubstituted C1-C20 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C20 branched hydrocarbon group, a substituted or unsubstituted C1-C20 haloalkane group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C40 aromatic group, or a substituted or unsubstituted C5-C40 heteroaromatic group; more preferably H, D, F, ... Cl, Br, I, -OH, -SH, -NH2, substituted or unsubstituted C1-C10 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C10 branched hydrocarbon groups, substituted or unsubstituted C1-C10 haloalkane groups, substituted or unsubstituted C3-C15 cycloalkyl groups, substituted or unsubstituted C6-C30 aromatic groups, substituted or unsubstituted C5-C30 heteroaromatic groups; preferably H, D, F, Cl, Br, I, -OH, -SH, -NH2, substituted or unsubstituted C1-C5 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C5 branched hydrocarbon groups, substituted or unsubstituted C1-C5 haloalkane groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C6-C15 aromatic groups, substituted or unsubstituted C5-C15 heteroaromatic groups; wherein the heteroatom in the heteroaromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

[0036] Or R a R b and R c Between each other (i.e., R) a In its own groups, R b In its own group or R c (in its own group), or R 1 R 2 and R 3 They are interconnected via single bonds, -CC-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te-, One or more connections in the process.

[0037] Or R d and Through single bonds, -CC-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te-, One or more connections in;

[0038] Or when R a Or R b When adjacent to N, R d With R a Or R b Through single bonds, -CC-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te-, One or more connections in the process.

[0039] The L1′~L 12Each of the following is independently H, D, F, Cl, Br, I, -CN, -NO2, substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, substituted or unsubstituted C1-C30 branched hydrocarbon group, substituted or unsubstituted C1-C30 haloalkane group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C6-C60 aromatic group, or substituted or unsubstituted C5-C60 heteroaromatic group, preferably H, D, F, Cl, Br, I, -CN, -NO2, substituted or unsubstituted C1-C20 straight-chain hydrocarbon group, or substituted or unsubstituted C1-C20 branched hydrocarbon group. Branched hydrocarbon groups, substituted or unsubstituted C1-C20 haloalkane groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C6-C40 aromatic groups, substituted or unsubstituted C5-C40 heteroaromatic groups; more preferably H, D, F, Cl, Br, I, -CN, -NO2, substituted or unsubstituted C1-C10 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C10 branched hydrocarbon groups, substituted or unsubstituted C1-C10 haloalkane groups, substituted or unsubstituted C3-C15 cycloalkyl groups, substituted or unsubstituted C6-C30 aromatic groups, substituted or unsubstituted C5-C30 heteroaromatic groups; more preferably H, D, F, Cl, Br, I, -CN, -NO2, substituted or unsubstituted C1-C5 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C5 branched hydrocarbon groups, substituted or unsubstituted C1-C5... The group may contain: a haloalkane group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C6-C20 aromatic group, or a substituted or unsubstituted C5-C20 heteroaromatic group; most preferably, H, D, F, Cl, Br, I, -CN, -NO2, a substituted or unsubstituted C1-C4 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C4 branched hydrocarbon group, a substituted or unsubstituted C1-C4 haloalkane group, a substituted or unsubstituted C5-C8 cycloalkyl group, a substituted or unsubstituted C6-C15 aromatic group, or a substituted or unsubstituted C5-C15 heteroaromatic group.

[0040] According to the present invention, and more preferably, the fused ring compound has the structures shown in formulas A1-1-1 to A27-1-4:

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056] Among them, R1 to R9 are independently H, D, F, Cl, Br, I, -CN, -NO2, -OR 1 -SR 1 , -Se-R 1 , -Te-R 1 , The following are possible meanings: substituted or unsubstituted C1-C30 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C30 branched hydrocarbon groups, substituted or unsubstituted C1-C30 haloalkane groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C6-C60 aromatic groups, and substituted or unsubstituted C5-C60 heteroaromatic groups; preferably H, D, F, Cl, Br, I, -CN, or -NO2. -OR 1 -SR 1 , -Se-R 1 , -Te-R 1 , The following are substituted or unsubstituted C1-C20 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C20 branched hydrocarbon groups, substituted or unsubstituted C1-C20 haloalkane groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C6-C40 aromatic groups, and substituted or unsubstituted C5-C40 heteroaromatic groups; more preferably H, D, F, Cl, Br, I, -CN, or -NO2. -OR 1 -SR 1 , -Se-R 1 -Te-R 1 The following are possible substituted or unsubstituted C1-C10 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C10 branched hydrocarbon groups, substituted or unsubstituted C1-C10 haloalkane groups, substituted or unsubstituted C3-C15 cycloalkyl groups, substituted or unsubstituted C6-C30 aromatic groups, and substituted or unsubstituted C5-C30 heteroaromatic groups; preferably H, D, F, Cl, Br, I, -CN, or -NO2. -OR 1 -SR 1 , -Se-R 1 , -Te-R 1 , The following are possible meanings: substituted or unsubstituted C1-C5 straight-chain hydrocarbon groups, substituted or unsubstituted C1-C5 branched hydrocarbon groups, substituted or unsubstituted C1-C5 haloalkane groups, substituted or unsubstituted C3-C8 cycloalkyl groups, substituted or unsubstituted C6-C20 aromatic groups, and substituted or unsubstituted C5-C20 heteroaromatic groups. The R... 1 R 2 and R 3 As mentioned above, there will be no further explanation here.

[0057] L1 to L6 are each preferably independently H, D, substituted or unsubstituted C1 to C30 straight-chain hydrocarbon groups, substituted or unsubstituted C1 to C30 branched-chain hydrocarbon groups, substituted or unsubstituted C1 to C30 haloalkane groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6 to C60 aromatic groups, or substituted or unsubstituted C5 to C60 heteroaromatic groups; more preferably H, D, substituted or unsubstituted C1 to C20 The following are preferred: a straight-chain hydrocarbon group, a substituted or unsubstituted C1-C20 branched hydrocarbon group, a substituted or unsubstituted C1-C20 haloalkane group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C40 aromatic group, or a substituted or unsubstituted C5-C40 heteroaromatic group; more preferably, H, D, a substituted or unsubstituted C1-C10 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C10 branched hydrocarbon group, a substituted or unsubstituted C1-C10 haloalkane group, a substituted or unsubstituted C3-C10 cycloalkyl group, or a substituted or unsubstituted... The aromatic group is a substituted C6-C30 aromatic group or a substituted or unsubstituted C5-C30 heteroaromatic group; most preferably, it is a H, D, a substituted or unsubstituted C1-C5 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C5 branched hydrocarbon group, a substituted or unsubstituted C1-C5 haloalkane group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C6-C20 aromatic group, or a substituted or unsubstituted C5-C20 heteroaromatic group; the heteroatom in the heteroaromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

[0058] Alternatively, in formulas A1-1-1 to A27-1-4, the substituent L1 on the N atom can be bonded to adjacent substituents via single bonds, -CC-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te-, One or more connections in;

[0059] Alternatively, in formulas A1-1-1 to A27-1-4, the substituent L1 on the N atom is bonded to one of the adjacent aromatic rings connected to the N atom via a single bond, -CC-, -C=C-, -C=N-, -C=P-, -C≡C-, -O-, -S-, -Se-, -Te-, One or more connections in the process.

[0060] According to the present invention, most preferably, the fused ring compound has the structures shown in formulas a1-1-1 to b3-11-55:

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086] This invention uses a fused-ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle as a luminescent material. On the one hand, the resonance effect between boron, nitrogen and sulfur atoms can be used to achieve separation of HOMO and LUMO, thereby achieving a smaller ΔE. ST In addition to the TADF effect, these hybrid fused ring units have a rigid framework structure, which can reduce the relaxation degree of the excited state structure, thereby achieving a narrower half-width at half-maximum. On the other hand, by introducing five-membered aromatic heterocycles and different substituents into the framework of the boron / nitrogen / sulfur hybrid fused ring unit, it is possible to further adjust the delayed fluorescence lifetime and half-width at half-maximum.

[0087] The present invention also provides a method for preparing the above-mentioned fused-ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle, comprising: reacting the compound shown in formula (IX) with alkyllithium, and then reacting it with boron trihalide and an organic amine to obtain the fused-ring compound shown in formula (I); wherein the alkyllithium is preferably one or more of butyllithium, sec-butyllithium, tert-butyllithium, methyllithium and ethyllithium; wherein the boron trihalide is preferably one or more of boron trifluoride, boron trichloride, boron tribromide and boron triiodide; and wherein the organic amine is preferably one or more of N,N-diisopropylethylamine, triethylamine and tri-n-butylamine.

[0088]

[0089] Wherein, Lu represents hydrogen or halogen; the other codes are the same as those mentioned above and will not be repeated here.

[0090] Alternatively: Combine the compound shown in formula (X) with a compound containing -R a -R b and -R c The material with the structure reacts in a solvent to obtain the fused ring compound shown in formula (I).

[0091]

[0092] Among them, at least one of Lu1, Lu2, and Lu3 is hydrogen, halogen, The rest are R a R b Or R c .

[0093] The present invention also provides the application of the fused ring compound represented by formula (I) above as a luminescent material.

[0094] The present invention also provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprising a fused ring compound represented by formula (I) above.

[0095] The present invention does not impose any particular limitation on the structure of the organic electroluminescent device, and any conventional organic electroluminescent device known to those skilled in the art can be used. Those skilled in the art can select and adjust the structure according to the application, quality requirements and product requirements. The preferred structure of the organic electroluminescent device of the present invention includes: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.

[0096] The thickness of the substrate is preferably 0.3-0.7 mm, more preferably 0.4-0.6 mm. The present invention does not impose any special restrictions on the selection of the substrate, and any substrate of conventional organic electroluminescent devices known to those skilled in the art can be used. Those skilled in the art can select and adjust the substrate according to the application, quality requirements and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0097] According to the present invention, the anode is preferably a material that is easy to inject holes, more preferably a conductive metal or a conductive metal oxide, and even more preferably an indium tin oxide.

[0098] The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; in this invention, the organic thin film layer preferably includes a light-emitting layer; the light-emitting layer includes the fused ring compound shown in formula (I) above; the fused ring compound shown in formula (I) provided by this invention directly constitutes the organic electroluminescent layer as a light-emitting material.

[0099] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum and silver, with aluminum being the most preferred.

[0100] To improve the performance and efficiency of the device, the organic thin film layer between the anode and the light-emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light-emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. This invention does not impose particular limitations on the materials and thicknesses of the hole injection layer, hole transport layer, electron blocking layer, organic electroluminescent layer, hole blocking layer, electron injection layer, and electron transport layer; materials and thicknesses well known to those skilled in the art can be selected and adjusted. This invention does not impose particular limitations on the fabrication processes of the electrodes, hole injection layer, hole transport layer, electron blocking layer, organic electroluminescent layer, hole blocking layer, electron injection layer, and electron transport layer; vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography are preferred fabrication processes.

[0101] The present invention does not impose any particular limitation on the preparation method of the organic electroluminescent device, and can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers on the anode, including a light-emitting layer; forming a cathode on the organic thin film layer;

[0102] The light-emitting layer comprises one or more compounds represented by formula (I).

[0103] The structure and materials of the organic electroluminescent device in the above preparation method, as well as the corresponding preferred principles, can be compared with the materials and structures and the corresponding preferred principles in the aforementioned organic electroluminescent device, and will not be repeated here.

[0104] This invention first forms an anode on a substrate. The method of forming the anode is not particularly limited; any method well-known to those skilled in the art can be used. The method of forming the light-emitting layer and the organic thin film layers below and above the light-emitting layer is not particularly limited; the anode can be formed by vacuum evaporation, solution spin coating, solution scraping, inkjet printing, offset printing, or stereolithography. After the organic layer is formed, a cathode is fabricated on its surface. The method of forming the cathode is not particularly limited; preferred methods are those well-known to those skilled in the art, including but not limited to vacuum deposition.

[0105] To further illustrate the present invention, the following describes in detail, with reference to embodiments, a fused-ring compound containing boron atoms, oxalate atoms, and a five-membered aromatic heterocycle and an organic electroluminescent device provided by the present invention.

[0106] All reagents used in the following examples are commercially available.

[0107] Example 1

[0108] The reaction equation is as follows:

[0109]

[0110] Under an argon atmosphere, 1-1 (19.9 g, 0.1 mol), diphenylamine (16.9 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 200 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to give product 1-2 (25.9 g, yield: 90%).

[0111] Elemental analysis structure (C16 H 11 ClFNO): Theoretical values: C, 66.79; H, 3.85; N, 4.87; Test values: C, 66.81; H, 3.84; N, 4.86.

[0112] Electrospray ionization mass spectrometry (ESI-MS) analysis: Theoretical value 287.0; Experimental value 287.1 (M + ).

[0113] Under an argon atmosphere, 1-2 (23.1 g, 0.08 mol), thiophenol (8.8 g, 0.08 mol), potassium carbonate (22.1 g, 0.16 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 1-3 (21.2 g, yield: 70%).

[0114] Elemental analysis structure (C 22 H 16 ClNOS): Theoretical values: C, 69.93; H, 4.27; N, 3.71; S, 8.48; Test values: C, 69.91; H, 4.28; N, 3.73; S, 8.50.

[0115] ESI-MS analysis: Theoretical value 377.1; Experimental value 378.0 ([M+H]) + ).

[0116] Under an argon atmosphere, 1-3 (18.9 g, 50.0 mmol) and dry o-xylene (80 mL) were added to a 250 mL two-necked flask. A 2.5 M, 52.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.1 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a1-1-1 (5.2 g, yield: 30%).

[0117] Elemental analysis structure (C 22 H 14BNOS): Theoretical values: C, 75.23; H, 4.02; N, 3.99; S, 9.13; Test values: C, 75.20; H, 4.03; N, 4.00; S, 9.11.

[0118] ESI-MS analysis: Theoretical value 351.1; Experimental value 351.0 (M + ).

[0119] The photophysical properties of the fused ring compound prepared in Example 1 of this invention were tested, and the results are shown in Table 1.

[0120] Example 2

[0121] The reaction equation is as follows:

[0122]

[0123] Under an argon atmosphere, 2-1 (19.3 g, 0.1 mol), 2-2 (15.0 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 70 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 2-3 (22.0 g, yield: 68%).

[0124] Elemental analysis structure (C 14 H8BrFOS): Theoretical values: C, 52.03; H, 2.50; S, 9.92; Test values: C, 52.01; H, 2.50; S, 9.90.

[0125] ESI-MS analysis: Theoretical value 322.0; Experimental value 322.1 (M + ).

[0126] Under an argon atmosphere, 2-3 (19.4 g, 0.06 mol), 3,6-di-tert-butylcarbazole (16.8 g, 0.06 mol), cesium carbonate (39.1 g, 0.12 mol), and anhydrous DMF (100 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 2-4 (31.7 g, yield: 90%).

[0127] Elemental analysis structure (C 34 H 32BrNOS): Theoretical values: C, 70.10; H, 5.54; N, 2.40; S, 5.50; Test values: C, 70.13; H, 5.53; N, 2.41; S, 5.49.

[0128] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: Theoretical value 581.1; Experimental value 581.2 (M + ).

[0129] Under an argon atmosphere, 2-4 (23.3 g, 40.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a7-1-2 (7.0 g, yield: 34%).

[0130] Elemental analysis structure (C 34 H 30 BNOS): Theoretical values: C, 79.84; H, 5.91; N, 2.74; S, 6.27; Test values: C, 79.83; H, 5.90; N, 2.77; S, 6.24.

[0131] MALDI-TOF analysis: Theoretical value 511.2; Experimental value 512.2 ([M+H]) + ).

[0132] The photophysical properties of the fused ring compound prepared in Example 2 of this invention were tested, and the results are shown in Table 1.

[0133] Example 3

[0134] The reaction equation is as follows:

[0135]

[0136] Under an argon atmosphere, 2-1 (19.3 g, 0.1 mol), 3-1 (15.1 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 2-3 (21.4 g, yield: 66%).

[0137] Elemental analysis structure (C 13 H7BrFNOS): Theoretical values: C, 48.17; H, 2.18; N, 4.32; S, 9.89; Test values: C, 48.11; H, 2.17; N, 4.33; S, 9.91.

[0138] ESI-MS analysis: Theoretical value 322.9; Experimental value 322.8 (M + ).

[0139] Under an argon atmosphere, 3-2 (19.5 g, 0.06 mol), 3,6-di-tert-butylcarbazole (16.8 g, 0.06 mol), cesium carbonate (39.1 g, 0.12 mol), and anhydrous DMF (110 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 3-3 (30.5 g, yield: 87%).

[0140] Elemental analysis structure (C 33 H 31 BrN2OS): Theoretical values: C, 67.92; H, 5.35; N, 4.80; S, 5.49; Test values: C, 67.95; H, 5.35; N, 4.82; S, 5.51.

[0141] MALDI-TOF analysis: Theoretical value 582.1; Experimental value 582.1 (M + ).

[0142] Under an argon atmosphere, 3-3 (23.3 g, 40.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a11-1-1 (6.4 g, yield: 31%).

[0143] Elemental analysis structure (C 33 H 29 BN2OS): Theoretical values: C, 77.34; H, 5.70; N, 5.47; S, 6.26; Test values: C, 77.30; H, 5.72; N, 5.48; S, 6.24.

[0144] MALDI-TOF analysis: Theoretical value 512.2; Experimental value 513.1 ([M+H]) + ).

[0145] The photophysical properties of the fused ring compound prepared in Example 3 of this invention were tested, and the results are shown in Table 1.

[0146] Example 4

[0147] The reaction equation is as follows:

[0148]

[0149] Under an argon atmosphere, 2-1 (19.3 g, 0.1 mol), 4-1 (15.2 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 70 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 4-2 (22.4 g, yield: 69%).

[0150] Elemental analysis structure (C 12H6BrFN2OS): Theoretical values: C, 44.33; H, 1.86; N, 8.62; S, 9.86; Test values: C, 44.31; H, 1.87; N, 8.63; S, 9.91.

[0151] ESI-MS analysis: Theoretical value 323.9; Experimental value 323.9 (M + ).

[0152] Under an argon atmosphere, 4-2 (19.5 g, 0.06 mol), 3,6-di-tert-butylcarbazole (16.8 g, 0.06 mol), cesium carbonate (39.1 g, 0.12 mol), and anhydrous DMF (110 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered out, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 4-3 (29.8 g, yield: 85%).

[0153] Elemental analysis structure (C 32 H 30 BrN3OS): Theoretical values: C, 65.75; H, 5.17; N, 7.19; S, 5.48; Test values: C, 65.71; H, 5.15; N, 7.19; S, 5.43.

[0154] MALDI-TOF analysis: Theoretical value 583.1; Experimental value 584.0 ([M+H]) + ).

[0155] Under an argon atmosphere, 4-3 (23.4 g, 40.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a12-1-1 (8.7 g, yield: 42%).

[0156] Elemental analysis structure (C 32 H 28BN3OS): Theoretical values: C, 74.85; H, 5.50; N, 8.18; S, 6.24; Test values: C, 74.83; H, 5.51; N, 8.16; S, 6.27.

[0157] MALDI-TOF analysis: Theoretical value 513.2; Experimental value 513.3 (M + ).

[0158] The photophysical properties of the fused ring compound prepared in Example 4 of this invention were tested, and the results are shown in Table 1.

[0159] Example 5

[0160] The reaction equation is as follows:

[0161]

[0162] Under an argon atmosphere, 2-1 (19.3 g, 0.1 mol), 5-1 (16.6 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 5-2 (24.4 g, yield: 72%).

[0163] Elemental analysis structure (C 14 H8BrFS2): Theoretical values: C, 49.57; H, 2.38; S, 18.90; Test values: C, 49.55; H, 2.34; S, 18.93.

[0164] ESI-MS analysis: Theoretical value 337.9; Experimental value 337.8 (M + ).

[0165] Under an argon atmosphere, 5-2 (17.0 g, 0.05 mol), 3,6-di-tert-butylcarbazole (14.0 g, 0.05 mol), cesium carbonate (32.6 g, 0.10 mol), and anhydrous DMF (90 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 5-3 (25.8 g, yield: 86%).

[0166] Elemental analysis structure (C 34 H 32BrNS2): Theoretical values: C, 68.21; H, 5.39; N, 2.34; S, 10.71; Test values: C, 68.23; H, 5.38; N, 2.33; S, 10.69.

[0167] MALDI-TOF analysis: Theoretical value 597.1; Experimental value 597.0 (M + ).

[0168] Under an argon atmosphere, 23.4 g (40.0 mmol) of 5-3 and 90 mL of dried o-xylene were added to a 250 mL two-necked flask. A 16.8 mL (2.5 M, 42.0 mmol) solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a14-1-2 (10.5 g, yield: 50%).

[0169] Elemental analysis structure (C 34 H 30 BNS2): Theoretical values ​​C, 77.41; H, 5.73; N, 2.66; S, 12.15; Test values ​​C, 77.40; H, 5.71; N, 2.70; S, 12.11.

[0170] MALDI-TOF analysis: Theoretical value 527.2; Experimental value 528.2 ([M+H]) + ).

[0171] The photophysical properties of the fused ring compound prepared in Example 5 of this invention were tested, and the results are shown in Table 1.

[0172] Example 6

[0173] The reaction equation is as follows:

[0174]

[0175] Under an argon atmosphere, 6-1 (32.0 g, 0.15 mol), aniline (14.0 g, 0.15 mol), tris(dibenzylacetone)palladium (2.1 g, 2.3 mmol), tri-tert-butylphosphide tetrafluoroborate (2.6 g, 9.0 mmol), sodium tert-butoxide (21.6 g, 0.23 mol), and 300 mL of anhydrous toluene were added to a 1000 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 6-2 (23.7 g, yield: 70%).

[0176] Elemental analysis structure (C 14 H 11 NS): Theoretical values ​​C, 74.63; H, 4.92; N, 6.22; S, 14.23; Test values ​​C, 74.56; H, 4.91; N, 6.24; S, 14.25.

[0177] ESI-MS analysis: Theoretical value 225.1; Experimental value 226.1 ([M+H]) + ).

[0178] Under an argon atmosphere, 6-2 (22.5 g, 0.1 mol), 6-3 (20.9 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 200 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 6-4 (29.7 g, yield: 84%).

[0179] Elemental analysis structure (C 20 H 13 ClFNS): Theoretical values: C, 67.89; H, 3.70; N, 3.96; S, 9.06; Test values: C, 67.91; H, 3.69; N, 3.94; S, 9.10.

[0180] ESI-MS analysis: Theoretical value 353.0; Experimental value 353.1 (M + ).

[0181] Under an argon atmosphere, 6-4 (28.3 g, 0.08 mol), 1-naphthiophenol (12.8 g, 0.08 mol), potassium carbonate (22.1 g, 0.16 mol), and 90 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 6-5 (25.7 g, yield: 65%).

[0182] Elemental analysis structure (C 30 H 20 ClNS2): Theoretical values: C, 72.93; H, 4.08; N, 2.84; S, 12.98; Test values: C, 72.91; H, 4.04; N, 2.86; S, 13.00.

[0183] ESI-MS analysis: Theoretical value 493.1; Experimental value 493.1.

[0184] Under an argon atmosphere, 6-5 (19.8 g, 40.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 80.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a14-2-1 (7.2 g, yield: 38%).

[0185] Elemental analysis structure (C 30 H 18 BNS2): Theoretical values: C, 77.09; H, 3.88; N, 3.00; S, 13.72; Test values: C, 77.11; H, 3.92; N, 3.00; S, 13.70.

[0186] ESI-MS analysis: Theoretical value 467.1; Experimental value 467.0 (M + ).

[0187] The photophysical properties of the fused ring compound prepared in Example 6 of this invention were tested, and the results are shown in Table 1.

[0188] Example 7

[0189] The reaction equation is as follows:

[0190]

[0191] Under an argon atmosphere, 6-4 (17.7 g, 50.0 mmol), 7-1 (11.3 g, 50.0 mmol), potassium carbonate (13.8 g, 0.10 mol), and 70 mL NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After cooling to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 7-2 (18.8 g, yield: 67%).

[0192] Elemental analysis structure (C 35 H 26 ClNS2): Theoretical values: C, 75.05; H, 4.68; N, 2.50; S, 11.45; Test values: C, 75.07; H, 4.63; N, 2.52; S, 11.47.

[0193] MALDI-TOF analysis: Theoretical value 559.1; Experimental value 560.1 ([M+H]) + ).

[0194] Under an argon atmosphere, 7-2 (16.8 g, 30.0 mmol) and dry o-xylene (50 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (12.6 mL, 2.5 M, 31.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (7.6 g, 9.9 mL, 60.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a14-3-1 (6.8 g, yield: 42%).

[0195] Elemental analysis structure (C 35 H 24 BNS2): Theoretical values ​​C, 78.80; H, 4.53; N, 2.63; S, 12.02; Test values ​​C, 78.79; H, 4.51; N, 2.64; S, 12.00.

[0196] ESI-MS analysis: Theoretical value 533.1; Experimental value 533.2 (M + ).

[0197] The photophysical properties of the fused ring compound prepared in Example 7 of this invention were tested, and the results are shown in Table 1.

[0198] Example 8

[0199] The reaction equation is as follows:

[0200]

[0201] Under an argon atmosphere, 2-1 (19.3 g, 0.1 mol), 8-1 (16.7 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 100 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 8-2 (24.2 g, yield: 71%).

[0202] Elemental analysis structure (C 13 H7BrFNS2): Theoretical values: C, 45.89; H, 2.07; N, 4.12; S, 18.85; Test values: C, 45.94; H, 2.05; N, 4.11; S, 18.83.

[0203] ESI-MS analysis: Theoretical value 338.9; Experimental value 339.9 ([M+H]) + ).

[0204] Under an argon atmosphere, 8-2 (13.6 g, 40.0 mmol), 3,6-di-tert-butylcarbazole (11.2 g, 40.0 mmol), cesium carbonate (26.1 g, 80.0 mmol), and anhydrous DMF (90 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered off, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 8-3 (19.9 g, yield: 83%).

[0205] Elemental analysis structure (C 33 H 31 BrN2S2): Theoretical values: C, 66.10; H, 5.21; N, 4.67; S, 10.69; Test values: C, 66.13; H, 5.25; N, 4.64; S, 10.66.

[0206] MALDI-TOF analysis: Theoretical value 598.1; Experimental value 598.2 (M + ).

[0207] Under an argon atmosphere, 8-3 (18.0 g, 30.0 mmol) and dry o-xylene (60 mL) were added to a 250 mL two-necked flask. A 12.6 mL, 2.5 M, 31.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (7.6 g, 9.9 mL, 60.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a17-1-1 (6.9 g, yield: 44%).

[0208] Elemental analysis structure (C 33 H 29 BN2S2): Theoretical values: C, 74.99; H, 5.53; N, 5.30; S, 12.13; Test values: C, 77.90; H, 5.51; N, 5.33; S, 12.15.

[0209] MALDI-TOF analysis: Theoretical value 528.2; Experimental value 528.1 (M + ).

[0210] The photophysical properties of the fused ring compound prepared in Example 8 of this invention were tested, and the results are shown in Table 1.

[0211] Example 9

[0212] The reaction equation is as follows:

[0213]

[0214] Under an argon atmosphere, 2-1 (19.3 g, 0.1 mol), 9-1 (16.8 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 100 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 9-2 (25.2 g, yield: 74%).

[0215] Elemental analysis structure (C 12H6BrFN2S2): Theoretical values: C, 42.24; H, 1.77; N, 8.21; S, 18.79; Test values: C, 42.27; H, 1.76; N, 8.22; S, 18.77.

[0216] ESI-MS analysis: Theoretical value 339.9; Experimental value 335.0 ([M+H]) + ).

[0217] Under an argon atmosphere, 9-2 (11.9 g, 35.0 mmol), 3,6-di-tert-butylcarbazole (9.8 g, 35.0 mmol), cesium carbonate (22.8 g, 70.0 mmol), and anhydrous DMF (80 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered off, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 9-3 (18.5 g, yield: 88%).

[0218] Elemental analysis structure (C 32 H 30 BrN3S2): Theoretical values: C, 63.99; H, 5.03; N, 7.00; S, 10.68; Test values: C, 63.97; H, 5.00; N, 7.03; S, 10.64.

[0219] MALDI-TOF analysis: Theoretical value 599.1; Experimental value 599.1 (M + ).

[0220] Under an argon atmosphere, 9-3 (18.0 g, 30.0 mmol) and dry o-xylene (60 mL) were added to a 250 mL two-necked flask. A 12.6 mL, 2.5 M, 31.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (7.6 g, 9.9 mL, 60.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a19-1-1 (5.0 g, yield: 32%).

[0221] Elemental analysis structure (C 32 H 28BN3S2): Theoretical values: C, 72.58; H, 5.33; N, 7.94; S, 12.11; Test values: C, 72.56; H, 5.34; N, 7.93; S, 12.10.

[0222] MALDI-TOF analysis: Theoretical value 529.2; Experimental value 530.2 ([M+H]) + ).

[0223] The photophysical properties of the fused ring compound prepared in Example 9 of this invention were tested, and the results are shown in Table 1.

[0224] Example 10

[0225] The reaction equation is as follows:

[0226]

[0227] Under an argon atmosphere, 2⁻¹ (19.3 g, 0.1 mol), 10⁻¹ (16.3 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 100 mL NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 10⁻² (25.9 g, yield: 77%).

[0228] Elemental analysis structure (C 15 H 11 BrFNS): Theoretical values: C, 53.59; H, 3.30; N, 4.17; S, 9.54; Test values: C, 53.61; H, 3.28; N, 4.15; S, 9.57.

[0229] ESI-MS analysis: Theoretical value 335.0; Experimental value 335.1 (M + ).

[0230] Under an argon atmosphere, 10⁻² (13.4 g, 40.0 mmol), 3,6-di-tert-butylcarbazole (11.2 g, 40.0 mmol), cesium carbonate (26.1 g, 80.0 mmol), and anhydrous DMF (70 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 10⁻³ (20.3 g, yield: 85%).

[0231] Elemental analysis structure (C 35 H 35BrN2S): Theoretical values: C, 70.58; H, 5.92; N, 4.70; S, 5.38; Test values: C, 70.63; H, 5.90; N, 4.71; S, 5.35.

[0232] MALDI-TOF analysis: Theoretical value 594.2; Experimental value 595.1 ([M+H]) + ).

[0233] Under an argon atmosphere, 10⁻³ (17.9 g, 30.0 mmol) and dry o-xylene (60 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (12.6 mL, 2.5 M, 31.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (7.6 g, 9.9 mL, 60.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a20-1-2 (8.5 g, yield: 54%).

[0234] Elemental analysis structure (C 35 H 33 BN2S): Theoretical values: C, 80.14; H, 6.34; N, 5.34; S, 6.11; Test values: C, 80.20; H, 6.33; N, 5.31; S, 6.07.

[0235] MALDI-TOF analysis: Theoretical value 524.3; Experimental value 524.2 (M + ).

[0236] The photophysical properties of the fused ring compound prepared in Example 10 of this invention were tested, and the results are shown in Table 1.

[0237] Example 11

[0238] The reaction equation is as follows:

[0239]

[0240] Under an argon atmosphere, 2-1 (19.3 g, 0.1 mol), 11-1 (16.4 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 90 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 11-2 (26.6 g, yield: 79%).

[0241] Elemental analysis structure (C 14 H 10 BrFN2S): Theoretical values: C, 49.87; H, 2.99; N, 8.31; S, 9.51; Test values: C, 49.89; H, 3.00; N, 8.28; S, 9.47.

[0242] ESI-MS analysis: Theoretical value 336.0; Experimental value 336.1 (M + ).

[0243] Under an argon atmosphere, 11-2 (11.8 g, 35.0 mmol), 3,6-di-tert-butylcarbazole (9.8 g, 35.0 mmol), cesium carbonate (22.8 g, 70.0 mmol), and anhydrous DMF (80 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered out, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 11-3 (18.8 g, yield: 90%).

[0244] Elemental analysis structure (C 34 H 34 BrN3S): Theoretical values: C, 68.45; H, 5.74; N, 7.04; S, 5.37; Test values: C, 68.50; H, 5.73; N, 7.07; S, 5.38.

[0245] MALDI-TOF analysis: Theoretical value 595.2; Experimental value 596.2 ([M+H]) + ).

[0246] Under an argon atmosphere, 11-3 (18.5 g, 31.0 mmol) and dry o-xylene (70 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (13.0 mL, 2.5 M, 32.6 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.3 g, 3.6 mL, 37.2 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (8.0 g, 10.3 mL, 62.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a24-1-1 (6.6 g, yield: 41%).

[0247] Elemental analysis structure (C 34 H 32 BN3S): Theoretical values: C, 77.71; H, 6.14; N, 8.00; S, 6.10; Test values: C, 77.68; H, 6.16; N, 7.98; S, 6.14.

[0248] MALDI-TOF analysis: Theoretical value 525.2; Experimental value 526.2 ([M+H]) + ).

[0249] The photophysical properties of the fused ring compound prepared in Example 11 of this invention were tested, and the results are shown in Table 1.

[0250] Example 12

[0251] The reaction equation is as follows:

[0252]

[0253] Under an argon atmosphere, 2-1 (23.2 g, 0.12 mol), 12-1 (19.8 g, 0.12 mol), potassium carbonate (33.2 g, 0.24 mol), and 100 mL NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 12-2 (32.5 g, yield: 80%).

[0254] Elemental analysis structure (C 13H9BrFN3S): Theoretical values: C, 46.17; H, 2.68; N, 12.42; S, 9.48; Test values: C, 46.21; H, 2.69; N, 12.40; S, 9.51.

[0255] ESI-MS analysis: Theoretical value 337.0; Experimental value 337.1 (M + ).

[0256] Under an argon atmosphere, 12-2 (23.7 g, 70.0 mmol), 3,6-di-tert-butylcarbazole (19.6 g, 70.0 mmol), cesium carbonate (45.6 g, 160.0 mmol), and anhydrous DMF (120 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered off, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 12-3 (36.0 g, yield: 86%).

[0257] Elemental analysis structure (C 33 H 33 BrN4S): Theoretical values: C, 66.32; H, 5.57; N, 9.38; S, 5.36; Test values: C, 66.41; H, 5.55; N, 9.34; S, 5.35.

[0258] MALDI-TOF analysis: Theoretical value 596.2; Experimental value 596.1 (M + ).

[0259] Under an argon atmosphere, 12-3 (29.9 g, 50.0 mmol) and dry o-xylene (110 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product a26-1-1 (13.7 g, yield: 52%).

[0260] Elemental analysis structure (C 33 H 31BN4S): Theoretical values: C, 75.28; H, 5.93; N, 10.64; S, 6.09; Test values: C, 75.31; H, 5.94; N, 10.66; S, 6.11.

[0261] MALDI-TOF analysis: Theoretical value 526.2; Experimental value 527.3 ([M+H]) + ).

[0262] The photophysical properties of the fused ring compound prepared in Example 12 of this invention were tested, and the results are shown in Table 1.

[0263] Example 13

[0264] The reaction equation is as follows:

[0265]

[0266] Under an argon atmosphere, 13-1 (27.2 g, 0.1 mol), 5-1 (16.6 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 100 mL NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 13-2 (34.7 g, yield: 83%).

[0267] Elemental analysis structure (C 14 H7Br2FS2): Theoretical values: C, 40.22; H, 1.69; S, 15.33; Test values: C, 40.20; H, 1.68; S, 15.37.

[0268] ESI-MS analysis: Theoretical value 415.8; Experimental value 415.7 (M + ).

[0269] Under an argon atmosphere, 13-2 (20.9 g, 0.05 mol), 3,6-di-tert-butylcarbazole (14.0 g, 0.05 mol), cesium carbonate (32.6 g, 0.10 mol), and anhydrous DMF (100 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 13-3 (29.5 g, yield: 87%).

[0270] Elemental analysis structure (C 34 H 31Br2NS2): Theoretical values: C, 60.27; H, 4.61; N, 2.07; S, 9.46; Test values: C, 60.25; H, 4.60; N, 2.09; S, 9.47.

[0271] MALDI-TOF analysis: Theoretical value 675.0; Experimental value 675.1 (M + ).

[0272] Under an argon atmosphere, 13-3 (27.1 g, 40.0 mmol) and dry o-xylene (90 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b2-1-2 (10.9 g, yield: 45%).

[0273] Elemental analysis structure (C 34 H 29 BBrNS2): Theoretical values: C, 67.34; H, 4.82; N, 2.31; S, 10.57; Test values: C, 67.33; H, 4.84; N, 2.30; S, 10.59.

[0274] MALDI-TOF analysis: Theoretical value 605.1; Experimental value 605.0 (M + ).

[0275] The photophysical properties of the fused ring compound prepared in Example 13 of this invention were tested, and the results are shown in Table 1.

[0276] Example 14

[0277] The reaction equation is as follows:

[0278]

[0279] Under an argon atmosphere, 14-1 (24.1 g, 0.15 mol), aniline (14.0 g, 0.15 mol), tris(dibenzylacetone)palladium (2.1 g, 2.3 mmol), tri-tert-butylphosphide tetrafluoroborate (2.6 g, 9.0 mmol), sodium tert-butoxide (21.6 g, 0.23 mol), and 200 mL of anhydrous toluene were added to a 1000 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 14-2 (18.4 g, yield: 71%).

[0280] Elemental analysis structure (C 11 H 11 NO): Theoretical values ​​C, 76.28; H, 6.40; N, 8.09; Test values ​​C, 76.23; H, 6.44; N, 8.12.

[0281] ESI-MS analysis: Theoretical value 173.1; Experimental value 174.2 ([M+H]) + ).

[0282] Under an argon atmosphere, 14-2 (17.3 g, 0.1 mol), 6-3 (20.9 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 200 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 14-3 (24.4 g, yield: 81%).

[0283] Elemental analysis structure (C 17 H 13 ClFNO): Theoretical values: C, 67.67; H, 4.34; N, 4.64; Test values: C, 67.71; H, 4.33; N, 4.61.

[0284] ESI-MS analysis: Theoretical value 301.1; Experimental value 301.0 (M + ).

[0285] Under an argon atmosphere, 14-3 (24.1 g, 0.08 mol), 14-4 (9.1 g, 0.08 mol), potassium carbonate (22.1 g, 0.16 mol), and 70 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 14-5 (25.3 g, yield: 80%).

[0286] Elemental analysis structure (C 22 H 18 ClNO2S): Theoretical values: C, 66.74; H, 4.58; N, 3.54; S, 8.10; Test values: C, 66.70; H, 4.59; N, 3.56; S, 8.09.

[0287] ESI-MS analysis: Theoretical value 395.1; Experimental value 395.0 (M + ).

[0288] Under an argon atmosphere, 14-5 (19.8 g, 50.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. A 2.5 M, 52.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-1-2 (8.5 g, yield: 46%).

[0289] Elemental analysis structure (C 22 H 16 BNO2S): Theoretical values: C, 71.56; H, 4.37; N, 3.79; S, 8.68; Test values: C, 71.51; H, 4.34; N, 3.76; S, 8.71.

[0290] ESI-MS analysis: Theoretical value 369.1; Experimental value 370.0 ([M+H]) + ).

[0291] The photophysical properties of the fused ring compound prepared in Example 14 of this invention were tested, and the results are shown in Table 1.

[0292] Example 15

[0293] The reaction equation is as follows:

[0294]

[0295] Under an argon atmosphere, 14-2 (17.3 g, 0.1 mol), 15-1 (19.9 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 200 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 15-2 (24.5 g, yield: 84%).

[0296] Elemental analysis structure (C 17 H 13 ClFNO): Theoretical values: C, 61.76; H, 3.80; N, 4.80; Test values: C, 61.70; H, 3.81; N, 4.83.

[0297] ESI-MS analysis: Theoretical value 291.1; Experimental value 291.1 (M + ).

[0298] Under an argon atmosphere, 15-2 (20.4 g, 0.07 mol), 15-3 (8.0 g, 0.08 mol), potassium carbonate (19.3 g, 0.14 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 15-4 (23.8 g, yield: 88%).

[0299] Elemental analysis structure (C 20 H 16 ClNO3S): Theoretical values: C, 62.26; H, 4.18; N, 3.63; S, 8.31; Test values: C, 62.22; H, 4.17; N, 3.61; S, 8.27.

[0300] ESI-MS analysis: Theoretical value 385.1; Experimental value 386.0 ([M+H]) + ).

[0301] Under an argon atmosphere, 15-4 (19.3 g, 50.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-1-3 (7.7 g, yield: 43%).

[0302] Elemental analysis structure (C 20 H 14 BNO3S): Theoretical values: C, 66.88; H, 3.93; N, 3.90; S, 8.93; Test values: C, 66.84; H, 3.94; N, 3.93; S, 8.97.

[0303] ESI-MS analysis: Theoretical value 359.1; Experimental value 360.1 ([M+H]) + ).

[0304] The photophysical properties of the fused ring compound prepared in Example 15 of this invention were tested, and the results are shown in Table 1.

[0305] Example 16

[0306] The reaction equation is as follows:

[0307]

[0308] Under an argon atmosphere, 16-1 (23.0 g, 0.13 mol), aniline (12.1 g, 0.13 mol), tris(dibenzylacetone)palladium (1.8 g, 2.0 mmol), tri-tert-butylphosphide tetrafluoroborate (2.3 g, 7.8 mmol), sodium tert-butoxide (18.7 g, 0.20 mol), and 250 mL of anhydrous toluene were added to a 1000 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 16-2 (19.4 g, yield: 79%).

[0309] Elemental analysis structure (C 11 H11 NS): Theoretical values ​​C, 69.80; H, 5.86; N, 7.40; S, 16.94; Test values ​​C, 69.77; H, 5.89; N, 7.37; S, 16.99.

[0310] ESI-MS analysis: Theoretical value 189.1; Experimental value 189.1 (M + ).

[0311] Under an argon atmosphere, 16-2 (18.9 g, 0.1 mol), 6-3 (20.9 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 200 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 16-3 (27.0 g, yield: 85%).

[0312] Elemental analysis structure (C 17 H 13 ClFNS): Theoretical values: C, 64.25; H, 4.12; N, 4.41; S, 10.09; Test values: C, 64.29; H, 4.14; N, 4.39; S, 10.11.

[0313] ESI-MS analysis: Theoretical value 317.0; Experimental value 318.1 ([M+H]) + ).

[0314] Under an argon atmosphere, 16-3 (25.4 g, 0.08 mol), thiophenol (8.8 g, 0.08 mol), potassium carbonate (22.1 g, 0.16 mol), and 60 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 16-4 (26.8 g, yield: 82%).

[0315] Elemental analysis structure (C 23 H 18 ClNS2): Theoretical values: C, 67.71; H, 4.45; N, 3.43; S, 15.72; Test values: C, 67.68; H, 4.47; N, 3.44; S, 15.77.

[0316] ESI-MS analysis: Theoretical value 407.1; Experimental value 407.2 (M + ).

[0317] Under an argon atmosphere, 16-4 (20.4 g, 50.0 mmol) and dried o-xylene (100 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-1-4 (7.2 g, yield: 37%).

[0318] Elemental analysis structure (C 23 H 16 BNS2): Theoretical values: C, 72.45; H, 4.23; N, 3.67; S, 16.82; Test values: C, 72.49; H, 4.21; N, 3.66; S, 16.88.

[0319] ESI-MS analysis: Theoretical value 381.1; Experimental value 382.2 ([M+H]) + ).

[0320] The photophysical properties of the fused ring compound prepared in Example 16 of this invention were tested, and the results are shown in Table 1.

[0321] Example 17

[0322] The reaction equation is as follows:

[0323]

[0324] Under an argon atmosphere, 16-2 (20.8 g, 0.11 mol), 17-1 (23.7 g, 0.11 mol), tris(dibenzylacetone)dipalladium (1.5 g, 1.7 mmol), tri-tert-butylphosphide tetrafluoroborate (1.9 g, 6.6 mmol), sodium tert-butoxide (16.5 g, 0.16 mol), and 180 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 17-2 (27.1 g, yield: 76%).

[0325] Elemental analysis structure (C 15 H 11 ClFNS2): Theoretical values: C, 55.64; H, 3.42; N, 4.33; S, 19.80; Test values: C, 55.71; H, 3.41; N, 4.32; S, 19.77.

[0326] ESI-MS analysis: Theoretical value 323.0; Experimental value 323.1 (M + ).

[0327] Under an argon atmosphere, 17-2 (22.6 g, 0.07 mol), thiophenol (7.7 g, 0.07 mol), potassium carbonate (19.3 g, 0.14 mol), and 60 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 17-3 (21.2 g, yield: 73%).

[0328] Elemental analysis structure (C 21 H 18 ClNS3): Theoretical values: C, 60.63; H, 4.36; N, 3.37; S, 23.12; Test values: C, 60.70; H, 4.35; N, 3.35; S, 23.10.

[0329] ESI-MS analysis: Theoretical value 415.0; Experimental value 416.1 ([M+H]) + ).

[0330] Under an argon atmosphere, 17-3 (16.6 g, 40.0 mmol) and dry o-xylene (70 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 80.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-1-5 (6.5 g, yield: 42%).

[0331] Elemental analysis structure (C 21 H 16 BNS3): Theoretical values: C, 64.78; H, 4.14; N, 3.60; S, 24.70; Test values: C, 64.82; H, 4.12; N, 3.58; S, 24.77.

[0332] ESI-MS analysis: Theoretical value 389.1; Experimental value 389.0 (M + ).

[0333] The photophysical properties of the fused ring compound prepared in Example 17 of this invention were tested, and the results are shown in Table 1.

[0334] Example 18

[0335] The reaction equation is as follows:

[0336]

[0337] Under an argon atmosphere, 6-3 (20.9 g, 0.1 mol), diphenylamine (16.9 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 150 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to give product 18-1 (27.0 g, yield: 91%).

[0338] Elemental analysis structure (C 18 H 13ClFN): Theoretical values: C, 72.61; H, 4.40; N, 4.70; Test values: C, 72.58; H, 4.41; N, 4.72.

[0339] ESI-MS analysis: Theoretical value 297.1; Experimental value 297.0 (M + ).

[0340] Under an argon atmosphere, 18-1 (23.8 g, 0.08 mol), 18-2 (9.1 g, 0.08 mol), potassium carbonate (22.1 g, 0.16 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 18-3 (26.6 g, yield: 82%).

[0341] Elemental analysis structure (C 24 H 21 ClN2S): Theoretical values: C, 71.18; H, 5.23; N, 6.92; S, 7.92; Test values: C, 71.11; H, 5.25; N, 6.95; S, 7.90.

[0342] ESI-MS analysis: Theoretical value 404.1; Experimental value 405.0 ([M+H]) + ).

[0343] Under an argon atmosphere, 18-3 (20.3 g, 50.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. A 2.5 M, 52.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.1 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-1-6 (9.5 g, yield: 50%).

[0344] Elemental analysis structure (C 24 H 19BN2S): Theoretical values: C, 76.20; H, 5.06; N, 7.41; S, 8.47; Test values: C, 76.16; H, 5.07; N, 7.39; S, 8.51.

[0345] ESI-MS analysis: Theoretical value 378.1; Experimental value 378.0 (M + ).

[0346] The photophysical properties of the fused ring compound prepared in Example 18 of this invention were tested, and the results are shown in Table 1.

[0347] Example 19

[0348] The reaction equation is as follows:

[0349]

[0350] Under an argon atmosphere, 19-1 (21.3 g, 0.1 mol), 9,9-dimethylacridine (20.9 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 100 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 19-2 (28.3 g, yield: 83%).

[0351] Elemental analysis structure (C 20 H 18 ClFN2): Theoretical values: C, 70.48; H, 5.32; N, 8.22; Test values: C, 70.51; H, 5.30; N, 8.19.

[0352] ESI-MS analysis: Theoretical value 340.1; Experimental value 340.1 (M + ).

[0353] Under an argon atmosphere, 19-2 (23.8 g, 0.07 mol), 19-3 (7.9 g, 0.07 mol), potassium carbonate (19.3 g, 0.14 mol), and 70 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 19-4 (26.7 g, yield: 85%).

[0354] Elemental analysis structure (C26 H 26 ClN3S): Theoretical values: C, 69.70; H, 5.85; N, 9.38; S, 7.16; Test values: C, 69.61; H, 5.83; N, 9.44; S, 7.21.

[0355] ESI-MS analysis: Theoretical value 447.2; Experimental value 448.2 ([M+H]) + ).

[0356] Under an argon atmosphere, 19-4 (22.4 g, 50.0 mmol) and dried o-xylene (100 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.1 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-1-7 (8.6 g, yield: 41%).

[0357] Elemental analysis structure (C 26 H 24 BN3S): Theoretical values: C, 74.11; H, 5.74; N, 9.97; S, 7.61; Test values: C, 74.17; H, 5.76; N, 9.95; S, 7.64.

[0358] ESI-MS analysis: Theoretical value 421.2; Experimental value 421.3 (M + ).

[0359] The photophysical properties of the fused ring compound prepared in Example 19 of this invention were tested, and the results are shown in Table 1.

[0360] Example 20

[0361] The reaction equation is as follows:

[0362]

[0363] Under an argon atmosphere, 2⁻¹ (19.3 g, 0.1 mol), 2⁰⁻¹ (13.1 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 2⁰⁻² (26.2 g, yield: 86%).

[0364] Elemental analysis structure (C 10 H7BrFNS2): Theoretical values: C, 39.48; H, 2.32; N, 4.60; S, 21.08; Test values: C, 39.55; H, 2.31; N, 4.63; S, 21.01.

[0365] ESI-MS analysis: Theoretical value 302.9; Experimental value 303.8 ([M+H]) + ).

[0366] Under an argon atmosphere, 20-2 (21.3 g, 0.07 mol), 3,6-di-tert-butylcarbazole (19.6 g, 0.07 mol), cesium carbonate (45.6 g, 0.14 mol), and anhydrous DMF (120 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 20-3 (33.5 g, yield: 85%).

[0367] Elemental analysis structure (C 30 H 31 BrN2S2): Theoretical values: C, 63.93; H, 5.54; N, 4.97; S, 11.38; Test values: C, 63.88; H, 5.55; N, 4.99; S, 11.41.

[0368] MALDI-TOF analysis: Theoretical value 562.1; Experimental value 562.0 (M + ).

[0369] Under an argon atmosphere, 20-3 (22.5 g, 40.0 mmol) and dry o-xylene (70 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-1-10 (7.8 g, yield: 40%).

[0370] Elemental analysis structure (C 30 H 29 BN2S2): Theoretical values: C, 73.16; H, 5.94; N, 5.69; S, 13.02; Test values: C, 73.21; H, 5.93; N, 5.66; S, 12.99.

[0371] MALDI-TOF analysis: Theoretical value 492.2; Experimental value 493.2 ([M+H]) + ).

[0372] The photophysical properties of the fused ring compound prepared in Example 20 of this invention were tested, and the results are shown in Table 1.

[0373] Example 21

[0374] The reaction equation is as follows:

[0375]

[0376] Under an argon atmosphere, 21-1 (26.8 g, 0.12 mol), 5-1 (20.0 g, 0.12 mol), potassium carbonate (33.2 g, 0.24 mol), and 100 mL NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 21-2 (33.2 g, yield: 75%).

[0377] Elemental analysis structure (C 15 H 10BrFOS2): Theoretical values: C, 48.79; H, 2.73; S, 17.36; Test values: C, 48.83; H, 2.74; S, 17.41.

[0378] ESI-MS analysis: Theoretical value 367.9; Experimental value 368.0 (M + ).

[0379] Under an argon atmosphere, 21-2 (29.5 g, 0.08 mol), 3,6-di-tert-butylcarbazole (22.4 g, 0.08 mol), cesium carbonate (52.1 g, 0.16 mol), and anhydrous DMF (150 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered out, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 21-3 (43.8 g, yield: 87%).

[0380] Elemental analysis structure (C 35 H 34 BrNOS2): Theoretical values: C, 66.87; H, 5.45; N, 2.23; S, 10.20; Test values: C, 66.90; H, 5.48; N, 2.25; S, 10.17.

[0381] MALDI-TOF analysis: Theoretical value 627.1; Experimental value 628.0 ([M+H]) + ).

[0382] Under an argon atmosphere, 21-3 (37.7 g, 60.0 mmol) and dry o-xylene (120 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (25.2 mL, 2.5 M, 63.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (18.0 g, 6.9 mL, 72.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (15.5 g, 19.9 mL, 0.12 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-2-9 (12.0 g, yield: 36%).

[0383] Elemental analysis structure (C 35 H 32BNOS2): Theoretical values: C, 75.39; H, 5.79; N, 2.51; S, 11.50; Test values: C, 75.41; H, 5.80; N, 2.49; S, 11.55.

[0384] MALDI-TOF analysis: Theoretical value 557.2; Experimental value 558.3 ​​([M+H]) + ).

[0385] The photophysical properties of the fused ring compound prepared in Example 21 of this invention were tested, and the results are shown in Table 1.

[0386] Example 22

[0387] The reaction equation is as follows:

[0388]

[0389] Under an argon atmosphere, 13-1 (27.2 g, 0.1 mol), 22-1 (15.0 g, 0.1 mol), potassium carbonate (27.6 g, 0.2 mol), and 100 mL NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 13-2 (35.0 g, yield: 87%).

[0390] Elemental analysis structure (C 14 H7Br2FOS): Theoretical values: C, 41.82; H, 1.75; S, 7.97; Test values: C, 41.80; H, 1.75; S, 7.99.

[0391] ESI-MS analysis: Theoretical value 400.0; Experimental value 401.0 ([M+H]) + ).

[0392] Under an argon atmosphere, 22-2 (20.1 g, 0.05 mol), 3,6-di-tert-butylcarbazole (14.0 g, 0.05 mol), cesium carbonate (32.6 g, 0.10 mol), and anhydrous DMF (100 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 22-3 (28.1 g, yield: 85%).

[0393] Elemental analysis structure (C 34 H 31Br2NOS): Theoretical values: C, 61.73; H, 4.72; N, 2.12; S, 4.85; Test values: C, 61.75; H, 4.73; N, 2.10; S, 4.84.

[0394] MALDI-TOF analysis: Theoretical value 659.1; Experimental value 660.1 ([M+H]) + ).

[0395] Under an argon atmosphere, 22-3 (26.5 g, 40.0 mmol) and dry o-xylene (90 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product 22-4 (9.4 g, yield: 40%).

[0396] Elemental analysis structure (C 34 H 29 BBrNOS): Theoretical values: C, 69.17; H, 4.95; N, 2.37; S, 5.43; Test values: C, 69.19; H, 4.97; N, 2.36; S, 5.44.

[0397] MALDI-TOF analysis: Theoretical value 589.1; Experimental value 589.2 (M + ).

[0398] Under an argon atmosphere, 22-4 (5.9 g, 10.0 mmol), Pd(OAc)2 (33.7 mg, 0.15 mmol), xPhos (143.0 mg, 0.3 mmol), potassium ferrocyanide trihydrate (1.06 g, 2.5 mmol), potassium carbonate (1.4 mg, 10.0 mmol), and 20 mL of 1,4-dioxane / water (1:1) solution were added to a 100 mL pressure tube. The pressure tube was sealed, and the mixture was stirred at 120 °C for 12 hours. After cooling to room temperature, the mixture was diluted with diethyl ether and washed three times with saturated sodium chloride aqueous solution. The organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product b3-3-7 (2.9 g, yield: 60%).

[0399] Elemental analysis structure (C 35 H 29 BN2OS): Theoretical values: C, 78.36; H, 5.45; N, 5.22; S, 5.98; Test values: C, 78.40; H, 5.44; N, 5.24; S, 6.01.

[0400] MALDI-TOF analysis: Theoretical value 536.2; Experimental value 536.1 (M + ).

[0401] The photophysical properties of the fused ring compound prepared in Example 22 of this invention were tested, and the results are shown in Table 1.

[0402] Example 23

[0403] The reaction equation is as follows:

[0404]

[0405] Under an argon atmosphere, 23-1 (35.9 g, 0.15 mol), aniline (14.0 g, 0.15 mol), tris(dibenzylacetone)palladium (2.1 g, 2.3 mmol), tri-tert-butylphosphide tetrafluoroborate (2.6 g, 9.0 mmol), sodium tert-butoxide (21.6 g, 0.23 mol), and 300 mL of anhydrous toluene were added to a 1000 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 23-2 (28.9 g, yield: 82%).

[0406] Elemental analysis structure (C 16 H 13 NO): Theoretical values ​​C, 81.68; H, 5.57; N, 5.95; Test values ​​C, 81.70; H, 5.60; N, 5.91.

[0407] ESI-MS analysis: Theoretical value 235.1; Experimental value 235.0 (M + ).

[0408] Under an argon atmosphere, 23-2 (23.5 g, 0.1 mol), 15-1 (20.0 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 200 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 23-3 (30.8 g, yield: 89%).

[0409] Elemental analysis structure (C 20 H 13 ClFNO2): Theoretical values: C, 67.90; H, 3.70; N, 3.96; Measured values: C, 67.92; H, 3.74; N, 3.95.

[0410] ESI-MS analysis: Theoretical value 353.1; Experimental value 354.2 ([M+H]) + ).

[0411] Under an argon atmosphere, 23-3 (28.3 g, 0.08 mol), 23-4 (14.1 g, 0.08 mol), potassium carbonate (22.1 g, 0.16 mol), and 70 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 23-5 (32.2 g, yield: 79%).

[0412] Elemental analysis structure (C 30 H 20 ClNO3S): Theoretical values: C, 70.65; H, 3.95; N, 2.75; S, 6.29; Test values: C, 70.61; H, 3.93; N, 2.74; S, 6.33.

[0413] MALDI-TOF analysis: Theoretical value 509.1; Experimental value 509.0 (M + ).

[0414] Under an argon atmosphere, 23-5 (20.4 g, 40.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 80.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-4-1 (9.9 g, yield: 51%).

[0415] Elemental analysis structure (C 30 H 18 BNO3S): Theoretical values: C, 74.55; H, 3.75; N, 2.90; S, 6.63; Test values: C, 74.51; H, 3.76; N, 2.88; S, 6.64.

[0416] ESI-MS analysis: Theoretical value 483.1; Experimental value 484.0 ([M+H]) + ).

[0417] The photophysical properties of the fused ring compound prepared in Example 23 of this invention were tested, and the results are shown in Table 1.

[0418] Example 24

[0419] The reaction equation is as follows:

[0420]

[0421] Under an argon atmosphere, 24-1 (32.3 g, 0.12 mol), 5-1 (20.0 g, 0.12 mol), potassium carbonate (33.2 g, 0.24 mol), and 120 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 24-2 (39.9 g, yield: 80%).

[0422] Elemental analysis structure (C 20 H 12BrFS2): Theoretical values ​​C, 57.84; H, 2.91; S, 15.44; Test values ​​C, 57.88; H, 2.92; S, 15.40.

[0423] ESI-MS analysis: Theoretical value 414.0; Experimental value 414.1 (M + ).

[0424] Under an argon atmosphere, 24-2 (33.2 g, 0.08 mol), 3,6-di-tert-butylcarbazole (22.4 g, 0.08 mol), cesium carbonate (52.1 g, 0.16 mol), and anhydrous DMF (150 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered out, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 24-3 (43.7 g, yield: 81%).

[0425] Elemental analysis structure (C 40 H 36 BrNS2): Theoretical values: C, 71.20; H, 5.38; N, 2.08; S, 9.50; Test values: C, 71.22; H, 5.41; N, 2.07; S, 9.49.

[0426] MALDI-TOF analysis: Theoretical value 673.2; Experimental value 673.1 (M + ).

[0427] Under an argon atmosphere, 24-3 (33.7 g, 50.0 mmol) and dry o-xylene (120 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 0.10 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-4-2 (6.6 g, yield: 22%).

[0428] Elemental analysis structure (C 40 H 34BNS2): Theoretical values: C, 79.59; H, 5.68; N, 2.32; S, 10.62; Test values: C, 79.66; H, 5.69; N, 2.31; S, 10.66.

[0429] MALDI-TOF analysis: Theoretical value 603.2; Experimental value 604.3 ([M+H]) + ).

[0430] The photophysical properties of the fused ring compound prepared in Example 24 of this invention were tested, and the results are shown in Table 1.

[0431] Example 25

[0432] The reaction equation is as follows:

[0433]

[0434] Under an argon atmosphere, 19-3 (16.0 g, 50.0 mmol), 25-1 (16.0 g, 50.0 mmol), tris(dibenzylacetone)dipalladium (0.7 g, 0.75 mmol), tri-tert-butylphosphide tetrafluoroborate (0.9 g, 3.0 mmol), sodium tert-butoxide (7.2 g, 75.0 mmol), and 100 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 25-2 (25.2 g, yield: 90%).

[0435] Elemental analysis structure (C 35 H 30 ClN3S): Theoretical values: C, 75.05; H, 5.40; N, 7.50; S, 5.72; Test values: C, 75.07; H, 5.42; N, 7.47; S, 5.69.

[0436] MALDI-TOF analysis: Theoretical value 559.2; Experimental value 560.1 ([M+H]) + ).

[0437] Under an argon atmosphere, 25-2 (22.4 g, 40.0 mmol) and dry o-xylene (90 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 80.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-4-3 (5.1 g, yield: 24%).

[0438] Elemental analysis structure (C 35 H 28 BN3S): Theoretical values: C, 78.80; H, 5.29; N, 7.88; S, 6.01; Test values: C, 78.77; H, 5.30; N, 7.89; S, 5.99.

[0439] MALDI-TOF analysis: Theoretical value 533.2; Experimental value 533.1 (M + ).

[0440] The photophysical properties of the fused ring compound prepared in Example 25 of this invention were tested, and the results are shown in Table 1.

[0441] Example 26

[0442] The reaction equation is as follows:

[0443]

[0444] Under an argon atmosphere, 17-2 (22.7 g, 70.0 mmol), 4-chlorothiophenol (10.1 g, 70.0 mmol), potassium carbonate (19.3 g, 0.14 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 26-1 (27.1 g, yield: 82%).

[0445] Elemental analysis structure (C 21 H 17Cl2NS3): Theoretical values: C, 55.99; H, 3.80; N, 3.11; S, 21.35; Test values: C, 56.01; H, 3.79; N, 3.10; S, 21.33.

[0446] ESI-MS analysis: Theoretical value 449.0; Experimental value 449.1 ([M+H]) + ).

[0447] Under an argon atmosphere, 26-1 (22.5 g, 50.0 mmol) and dried o-xylene (100 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 0.10 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product 26-2 (9.2 g, yield: 43%).

[0448] Elemental analysis structure (C 21 H 15 BClNS3): Theoretical values: C, 59.52; H, 3.57; N, 3.31; S, 22.69; Test values: C, 59.50; H, 3.58; N, 3.30; S, 22.71.

[0449] ESI-MS analysis: Theoretical value 423.0; Experimental value 422.9 (M + ).

[0450] Under an argon atmosphere, 26-2 (4.2 g, 10.0 mmol), 26-3 (5.4 g, 15.0 mmol), tris(dibenzylacetone)palladium (0.4 g, 0.4 mmol), 2-dicyclohexylphosphine-2′,6′-dimethoxybiphenyl (0.5 g, 1.2 mmol), potassium carbonate (2.8 g, 20.0 mmol), deionized water (12.5 mL), and 1,4-dioxane (50 mL) were added to a 100 mL three-necked flask. The mixture was heated to 110 °C and stirred for 16 hours under argon protection. The mixture was then cooled to room temperature, and the reaction solution was precipitated in saturated brine. The solid was filtered out, washed with deionized water, and dried under reduced pressure at 80 °C. The crude product was separated by column chromatography to obtain product b3-4-4 (5.6 g, yield: 80%).

[0451] Elemental analysis structure (C 46 H 30 BNS3): Theoretical values: C, 78.51; H, 4.30; N, 1.99; S, 13.67; Test values: C, 78.47; H, 4.35; N, 1.97; S, 13.70.

[0452] MALDI-TOF analysis: Theoretical value 703.2; Experimental value 704.2 ([M+H]) + ).

[0453] The photophysical properties of the luminescent compound prepared in Example 26 of this invention were tested, and the results are shown in Table 1.

[0454] Example 27

[0455] The reaction equation is as follows:

[0456]

[0457] Under an argon atmosphere, 27-1 (27.5 g, 0.13 mol), 27-2 (18.6 g, 0.13 mol), tris(dibenzylacetone)palladium (1.8 g, 2.0 mmol), tri-tert-butylphosphide tetrafluoroborate (2.3 g, 7.8 mmol), sodium tert-butoxide (18.7 g, 0.20 mol), and 200 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 27-3 (30.1 g, yield: 84%).

[0458] Elemental analysis structure (C 18 H 13 NS): Theoretical values ​​C, 78.51; H, 4.76; N, 5.09; S, 11.64; Test values ​​C, 78.55; H, 4.74; N, 5.07; S, 11.65.

[0459] ESI-MS analysis: Theoretical value 275.1; Experimental value 275.0 (M + ).

[0460] Under an argon atmosphere, 27-3 (27.5 g, 0.1 mol), 6-3 (20.9 g, 0.1 mol), tris(dibenzylacetone)palladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 180 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 27-4 (31.1 g, yield: 77%).

[0461] Elemental analysis structure (C 24 H 15 ClFNS): Theoretical values: C, 71.37; H, 3.74; N, 3.47; S, 7.94; Test values: C, 71.40; H, 3.73; N, 3.45; S, 7.99.

[0462] ESI-MS analysis: Theoretical value 403.1; Experimental value 404.2 ([M+H]) + ).

[0463] Under an argon atmosphere, 27-4 (28.3 g, 70.0 mmol), 27-5 (15.1 g, 70.0 mmol), potassium carbonate (19.3 g, 0.14 mol), and 90 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After cooling to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 27-6 (34.0 g, yield: 81%).

[0464] Elemental analysis structure (C 36 H 22 ClNS3): Theoretical values: C, 72.04; H, 3.69; N, 2.33; S, 16.02; Test values: C, 72.11; H, 3.72; N, 2.31; S, 16.00.

[0465] MALDI-TOF analysis: Theoretical value 599.1; Experimental value 599.0 (M + ).

[0466] Under an argon atmosphere, 27-6 (30.0 g, 50.0 mmol) and dry o-xylene (110 mL) were added to a 250 mL two-necked flask. A 2.5 M, 52.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-4-5 (9.7 g, yield: 34%).

[0467] Elemental analysis structure (C 36 H 20 BNS3): Theoretical values ​​C, 75.39; H, 3.51; N, 2.44; S, 16.77; Test values ​​C, 75.41; H, 3.49; N, 2.43; S, 16.83.

[0468] MALDI-TOF analysis: Theoretical value 573.1; Experimental value 574.1 ([M+H]) + ).

[0469] The photophysical properties of the fused ring compound prepared in Example 27 of this invention were tested, and the results are shown in Table 1.

[0470] Example 28

[0471] The reaction equation is as follows:

[0472]

[0473] Under an argon atmosphere, 2-3 (16.2 g, 0.05 mol), 7H-dibenzocarbazole (13.4 g, 0.05 mol), cesium carbonate (32.6 g, 0.10 mol), and anhydrous DMF (80 mL) were added to a 250 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 28-1 (24.2 g, yield: 85%).

[0474] Elemental analysis structure (C 34 H 20BrNOS): Theoretical values: C, 71.58; H, 3.53; N, 2.46; S, 5.62; Test values: C, 71.60; H, 3.56; N, 2.45; S, 5.59.

[0475] MALDI-TOF analysis: Theoretical value 569.0; Experimental value 569.1 (M + ).

[0476] Under an argon atmosphere, 28-1 (17.1 g, 30.0 mmol) and dried o-xylene (60 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (12.6 mL, 2.5 M, 31.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (9.0 g, 3.5 mL, 36.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (7.8 g, 9.9 mL, 60.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-4-6 (5.3 g, yield: 36%).

[0477] Elemental analysis structure (C 34 H 18 BNOS): Theoretical values: C, 81.77; H, 3.63; N, 2.80; S, 6.42; Test values: C, 81.80; H, 3.62; N, 2.81; S, 6.40.

[0478] MALDI-TOF analysis: Theoretical value 499.1; Experimental value 499.0 (M + ).

[0479] The photophysical properties of the fused ring compound prepared in Example 28 of this invention were tested, and the results are shown in Table 1.

[0480] Example 29

[0481] The reaction equation is as follows:

[0482]

[0483] Under an argon atmosphere, 1-2 (28.8 g, 0.10 mol), 2-chlorothiophenol (14.5 g, 0.10 mol), potassium carbonate (27.6 g, 0.20 mol), and 100 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 29-1 (35.5 g, yield: 86%).

[0484] Elemental analysis structure (C 22 H 15 Cl2NOS): Theoretical values: C, 64.09; H, 3.67; N, 3.40; S, 7.78; Test values: C, 64.02; H, 3.64; N, 3.42; S, 7.80.

[0485] ESI-MS analysis: Theoretical value 411.0; Experimental value 412.0 ([M+H]) + ).

[0486] Under an argon atmosphere, 29-1 (20.6 g, 50.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 0.10 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product 29-2 (5.6 g, yield: 29%).

[0487] Elemental analysis structure (C 22 H 13 BClNOS): Theoretical values: C, 68.51; H, 3.40; N, 3.63; S, 8.31; Test values: C, 68.49; H, 3.39; N, 3.62; S, 8.29.

[0488] ESI-MS analysis: Theoretical value 385.1; Experimental value 385.0 (M + ).

[0489] Under an argon atmosphere, 29-2 (3.9 g, 10.0 mmol), carbazole (1.7 g, 10.0 mmol), tris(dibenzylacetone)palladium (0.14 g, 0.15 mmol), tri-tert-butylphosphide tetrafluoroborate (0.17 g, 0.6 mmol), sodium tert-butoxide (1.4 g, 15.0 mmol), and 30 mL of anhydrous toluene were added to a 100 mL two-necked flask. The mixture was heated to 100 °C and stirred for 14 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product b3-5-5 (3.6 g, yield: 70%).

[0490] Elemental analysis structure (C 34 H 21 BN2OS): Theoretical values: C, 79.08; H, 4.10; N, 5.42; S, 6.21; Test values: C, 79.05; H, 4.11; N, 5.41; S, 6.20.

[0491] MALDI-TOF analysis: Theoretical value 516.2; Experimental value 516.1 (M + ).

[0492] The photophysical properties of the luminescent compound prepared in Example 29 of this invention were tested, and the results are shown in Table 1.

[0493] Example 30

[0494] The reaction equation is as follows:

[0495]

[0496] Under an argon atmosphere, 6-2 (22.5 g, 0.1 mol), 30-1 (24.4 g, 0.1 mol), tris(dibenzylacetone)dipalladium (1.4 g, 1.5 mmol), tri-tert-butylphosphide tetrafluoroborate (1.7 g, 6.0 mmol), sodium tert-butoxide (14.4 g, 0.15 mol), and 100 mL of anhydrous toluene were added to a 500 mL two-necked flask. The mixture was heated to 100 °C and stirred for 12 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product 30-2 (30.7 g, yield: 79%).

[0497] Elemental analysis structure (C 20 H 12Cl2FNS): Theoretical values: C, 61.87; H, 3.12; N, 3.61; S, 8.26; Test values: C, 61.85; H, 3.13; N, 3.60; S, 8.27.

[0498] ESI-MS analysis: Theoretical value 387.0; Experimental value 388.1 ([M+H]) + ).

[0499] Under an argon atmosphere, 30-2 (27.1 g, 70.0 mmol), 30-3 (15.8 g, 70.0 mmol), potassium carbonate (19.3 g, 0.14 mol), and 80 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 30-4 (34.5 g, yield: 83%).

[0500] Elemental analysis structure (C 35 H 25 Cl2NS2): Theoretical values: C, 70.70; H, 4.24; N, 2.36; S, 10.78; Test values: C, 70.71; H, 4.26; N, 2.34; S, 10.77.

[0501] MALDI-TOF analysis: Theoretical value 593.1; Experimental value 594.2 (M + ).

[0502] Under an argon atmosphere, 30-4 (29.7 g, 50.0 mmol) and dry o-xylene (130 mL) were added to a 250 mL two-necked flask. A 2.5 M, 52.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 100.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product 30-5 (9.9 g, yield: 35%).

[0503] Elemental analysis structure (C 35 H 23BClNS2): Theoretical values: C, 74.02; H, 4.08; B, 1.90; N, 2.47; S, 11.29; Test values: C, 74.00; H, 4.04; B, 1.91; N, 2.48; S, 11.31.

[0504] MALDI-TOF analysis: Theoretical value 567.1; Experimental value 567.0 (M + ).

[0505] Under an argon atmosphere, 30-5 (2.8 g, 5.0 mmol), diphenylamine (0.85 g, 5.0 mmol), tris(dibenzylacetone)dipalladium (0.07 g, 0.08 mmol), tri-tert-butylphosphide tetrafluoroborate (0.09 g, 0.3 mmol), sodium tert-butoxide (0.7 g, 7.5 mmol), and 20 mL of anhydrous toluene were added to a 100 mL two-necked flask. The mixture was heated to 100 °C and stirred for 12 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product b3-5-7 (2.5 g, yield: 71%).

[0506] Elemental analysis structure (C 47 H 33 BN2S2): Theoretical values: C, 80.56; H, 4.75; N, 4.00; S, 9.15; Test values: C, 80.59; H, 4.77; N, 4.01; S, 9.11.

[0507] MALDI-TOF analysis: Theoretical value 700.2; Experimental value 701.1 ([M+H]) + ).

[0508] The photophysical properties of the fused ring compound prepared in Example 30 of this invention were tested, and the results are shown in Table 1.

[0509] Example 31

[0510] The reaction equation is as follows:

[0511]

[0512] Under an argon atmosphere, 30-2 (38.8 g, 0.10 mol), 31-1 (13.4 g, 0.10 mol), potassium carbonate (27.6 g, 0.20 mol), and 140 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 31-2 (38.4 g, yield: 74%).

[0513] Elemental analysis structure (C 28 H 17 Cl2NOS2): Theoretical values: C, 64.87; H, 3.31; N, 2.70; S, 12.37; Test values: C, 64.90; H, 3.30; N, 2.66; S, 12.39.

[0514] MALDI-TOF analysis: Theoretical value 517.0; Experimental value 516.9 (M + ).

[0515] Under an argon atmosphere, 31-2 (25.9 g, 50.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. A 2.5 M, 52.5 mmol solution of n-butyllithium was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 0.10 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product 31-3 (9.8 g, yield: 40%).

[0516] Elemental analysis structure (C 28 H 15 BClNOS2): Theoretical values: C, 68.38; H, 3.07; N, 2.85; S, 13.04; Test values: C, 68.44; H, 3.06; N, 2.82; S, 13.01.

[0517] ESI-MS analysis: Theoretical value 491.0; Experimental value 492.0 ([M+H]) + ).

[0518] Under an argon atmosphere, 31-3 (1.5 g, 3.0 mmol), cesium carbonate (1.5 g, 4.5 mol), diphenylphosphine oxide (0.9 g, 4.5 mol), palladium acetate (6.7 mg, 0.03 mmol), 1,1'-bis(diphenylphosphine)ferrocene (33.2 mg, 0.06 mmol), and dry DMF (30 mL) were added to a 100 mL two-necked flask. The mixture was stirred at 120 °C for 10 hours. After cooling to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered off, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product b3-7-5 (1.1 g, yield: 54%).

[0519] Elemental analysis structure (C 40 H 25 BNO2PS2): Theoretical values: C, 73.07; H, 3.83; N, 2.13; S, 9.75; Test values: C, 73.01; H, 3.84; N, 2.14; S, 9.79.

[0520] MALDI-TOF analysis: Theoretical value 657.1; Experimental value 657.0 (M + ).

[0521] The photophysical properties of the fused ring compound prepared in Example 31 of this invention were tested, and the results are shown in Table 1.

[0522] Example 32

[0523] The reaction equation is as follows:

[0524]

[0525] Under an argon atmosphere, 32-1 (27.1 g, 0.10 mol), 32-2 (23.5 g, 0.10 mol), potassium carbonate (27.6 g, 0.20 mol), and 180 mL of NMP were added to a 500 mL two-necked flask. The mixture was heated to 120 °C and stirred for 6 hours. After the reaction mixture cooled to room temperature, the reaction solution was precipitated in saturated brine, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 32-3 (36.5 g, yield: 75%).

[0526] Elemental analysis structure (C 18 H 18 Br2FNSSi): Theoretical values: C, 44.37; H, 3.72; N, 2.87; S, 6.58; Test values: C, 44.41; H, 3.71; N, 2.85; S, 6.61.

[0527] MALDI-TOF analysis: Theoretical value 484.9; Experimental value 484.8 (M + ).

[0528] Under an argon atmosphere, 32-3 (29.3 g, 60.0 mmol), 3,6-di-tert-butylcarbazole (16.0 g, 60.0 mmol), cesium carbonate (39.1 g, 0.12 mol), and anhydrous DMF (130 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered off, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 32-4 (36.3 g, yield: 81%).

[0529] Elemental analysis structure (C 38 H 42 Br2N2SSi): Theoretical values: C, 61.12; H, 5.67; N, 3.75; S, 4.29; Test values: C, 61.10; H, 5.68; N, 3.74; S, 4.33.

[0530] MALDI-TOF analysis: Theoretical value 744.1; Experimental value 745.0 ([M+H]) + ).

[0531] Under an argon atmosphere, 32-3 (29.9 g, 0.04 mol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.4 g, 13.2 mL, 80.0 mmol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product 32-5 (11.6 g, yield: 43%).

[0532] Elemental analysis structure (C 38 H 40 BBrN2SSi): Theoretical values: C, 67.56; H, 5.97; N, 4.15; S, 4.75; Measured values: C, 67.53; H, 5.99; N, 4.16; S, 4.77.

[0533] MALDI-TOF analysis: Theoretical value 674.2; Experimental value 674.1 (M + ).

[0534] Under an argon atmosphere, 32-5 (5.4 g, 8.0 mmol) and dry tetrahydrofuran (30 mL) were added to a 250 mL two-necked flask. A solution of n-butyllithium (3.4 mL, 2.5 M, 8.4 mmol) was added dropwise at 0 °C. After stirring for 30 minutes following the addition, a tetrahydrofuran solution of boron bis(trimethyl)fluoride (2.4 g, 8.8 mmol) was added dropwise. The reaction mixture was then allowed to return to room temperature and stirred overnight. The reaction mixture was quenched with a small amount of methanol, diluted with diethyl ether, washed three times with saturated sodium chloride aqueous solution, and the organic phase was collected and dried over MgSO4. The crude product was separated by column chromatography to obtain product 32-6 (3.7 g, yield: 55%).

[0535] Elemental analysis structure (C 56 H 62 B2N2SSi): Theoretical values: C, 79.61; H, 7.40; N, 3.32; S, 3.79; Test values: C, 79.59; H, 7.41; N, 3.30; S, 3.81.

[0536] MALDI-TOF analysis: Theoretical value 844.5; Experimental value 844.4 (M + ).

[0537] Under an argon atmosphere, 32-6 (3.4 g, 4.0 mmol) and dry THF (15 mL) were added to a 100 mL two-necked flask. Iodine monochloride (1.9 g, 0.6 mL, 12.0 mmol) was added dropwise at room temperature, and the reaction was stirred for 5 hours. The reaction solution was settled in 100 mL of saturated sodium sulfite solution, filtered to obtain the solid, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 32-7 (3.4 g, yield: 94%).

[0538] Elemental analysis structure (C 53 H 53 B2IN2S): Theoretical values: C, 70.84; H, 5.95; N, 3.12; S, 3.57; Test values: C, 70.89; H, 5.93; N, 3.14; S, 3.55.

[0539] MALDI-TOF analysis: Theoretical value 898.3; Experimental value 898.2 (M + ).

[0540] Under an argon atmosphere, 32-7 (2.7 g, 3.0 mmol), diphenylamine (0.5 g, 3.0 mmol), tris(dibenzylacetone)dipalladium (41.2 mg, 0.05 mmol), tri-tert-butylphosphide tetrafluoroborate (52.2 g, 0.2 mmol), sodium tert-butoxide (0.4 g, 4.5 mmol), and 20 mL of anhydrous toluene were added to a 100 mL two-necked flask. The mixture was heated to 110 °C and stirred for 12 hours. After cooling to room temperature, the mixture was diluted with diethyl ether, washed three times with saturated ammonium chloride aqueous solution, and the organic phase was collected. The phase was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the crude product was separated by column chromatography to obtain product b3-8-5 (2.3 g, yield: 80%).

[0541] Elemental analysis structure (C 65 H 63 B2N3S): Theoretical values: C, 83.06; H, 6.76; N, 4.47; S, 3.41; Test values: C, 83.11; H, 6.75; N, 4.46; S, 3.40.

[0542] MALDI-TOF analysis: Theoretical value 939.5; Experimental value 939.5 (M + ).

[0543] The photophysical properties of the fused ring compound prepared in Example 32 of this invention were tested, and the results are shown in Table 1.

[0544] Example 33

[0545] The reaction equation is as follows:

[0546]

[0547] Under an argon atmosphere, 5-2 (33.2 g, 0.08 mol), trimeric indole (39.8 g, 0.08 mol), cesium carbonate (52.1 g, 0.16 mol), and anhydrous DMF (200 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered out, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 33-1 (43.1 g, yield: 66%).

[0548] Elemental analysis structure (C 50 H 30 BrN3S2): Theoretical values: C, 73.52; H, 3.70; N, 5.14; S, 7.85; Test values: C, 73.54; H, 3.75; N, 5.13; S, 7.81.

[0549] MALDI-TOF analysis: Theoretical value 815.1; Experimental value 815.1 (M + ).

[0550] Under an argon atmosphere, 33-1 (40.8 g, 50.0 mmol) and dry o-xylene (180 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (21.0 mL, 2.5 M, 52.5 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (15.0 g, 5.8 mL, 60.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (12.9 g, 16.6 mL, 0.10 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-11-1 (12.0 g, yield: 32%).

[0551] Elemental analysis structure (C 50 H 28 BN3S2): Theoretical values: C, 80.53; H, 3.78; N, 5.63; S, 8.60; Test values: C, 80.57; H, 3.77; N, 5.59; S, 8.63.

[0552] MALDI-TOF analysis: Theoretical value 745.2; Experimental value 746.2 ([M+H]) + ).

[0553] The photophysical properties of the fused ring compound prepared in Example 33 of this invention were tested, and the results are shown in Table 1.

[0554] Example 34

[0555] The reaction equation is as follows:

[0556]

[0557] Under an argon atmosphere, 2-3 (19.4 g, 0.06 mol), 34-1 (15.4 g, 0.06 mol), cesium carbonate (39.1 g, 0.12 mol), and anhydrous DMF (100 mL) were added to a 250 mL two-necked flask, and the mixture was heated to 120 °C and stirred for 6 hours. After the reaction was cooled to room temperature, the reaction solution was precipitated in saturated brine, the solid was filtered out, washed with deionized water, dried under reduced pressure at 80 °C, and the crude product was separated by column chromatography to obtain product 34-2 (26.9 g, yield: 80%).

[0558] Elemental analysis structure (C32 H 18 BrNO2S): Theoretical values: C, 68.58; H, 3.24; N, 2.50; S, 5.72; Test values: C, 68.63; H, 3.22; N, 2.48; S, 5.71.

[0559] Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF) analysis: Theoretical value 559.0; Experimental value 558.9 (M + ).

[0560] Under an argon atmosphere, 34-2 (23.3 g, 40.0 mmol) and dry o-xylene (100 mL) were added to a 250 mL two-necked flask. Then, n-butyllithium solution (16.8 mL, 2.5 M, 42.0 mmol) was added dropwise at -30 °C. After the addition was complete, the mixture was stirred at -30 °C for 10 minutes, then brought to room temperature and stirred for 2 hours. The temperature was then lowered to -30 °C, and boron tribromide (12.0 g, 4.6 mL, 48.0 mmol) was added dropwise. After the addition was complete, the mixture was stirred at room temperature for 1 hour. The temperature was then lowered again to 0 °C, and N,N-diisopropylethylamine (10.3 g, 13.3 mL, 0.08 mol) was added dropwise to the reaction system. After the addition was complete, the temperature was raised to 120 °C and the reaction was carried out for 12 hours. After the reaction was cooled to room temperature, a solid was precipitated in the filtration system and washed with methanol. The crude product was separated by column chromatography to obtain product b3-11-10 (10.4 g, yield: 46%).

[0561] Elemental analysis structure (C 32 H 16 BNO2S): Theoretical values: C, 78.54; H, 3.30; N, 2.86; S, 6.55; Test values: C, 78.55; H, 3.32; N, 2.83; S, 6.54.

[0562] MALDI-TOF analysis: Theoretical value 489.1; Experimental value 490.1 ([M+H]) + ).

[0563] The photophysical properties of the fused ring compound prepared in Example 34 of this invention were tested, and the results are shown in Table 1.

[0564] Table 1. Photophysical properties of the fused-ring compounds prepared in the embodiments of the present invention.

[0565]

[0566]

[0567] Note: ΔE in the table ST The difference between the singlet and triplet energy levels is represented by the compound being 10... -4The test sample was prepared by dissolving the compound in toluene at a concentration of mol / L. The difference between the onset values ​​of the fluorescence spectrum and the phosphorescence spectrum was measured using a HORIBA FluoroMax spectrofluorometer (Japan). The delayed fluorescence lifetime was obtained by doping the compound in polystyrene at a concentration of 1 wt% and measuring the sample using a time-resolved fluorescence spectrometer (Edinburgh fluorescence spectrometer, FLS-980, UK). The half-width at half-maximum (HWHM) is the peak width at half the peak height of the fluorescence spectrum at room temperature, calculated as the distance between the two points where a straight line parallel to the peak base intersects the peak. The fluorescence spectrum was obtained by dissolving the compound in toluene at a concentration of 10 mol / L. -5 The sample was prepared by dissolving it in toluene solution at a concentration of mol / L and then measured using a fluorescence spectrometer (HORIBA FluoroMax spectrofluorometer (Japan)).

[0568] As can be seen from Table 1, the fused-ring compounds in the embodiments provided by the present invention all have small ΔE values. ST (<0.2eV), exhibiting thermally activated delayed fluorescence effect, with a delayed fluorescence lifetime of 25-70μs; at the same time, the luminescent compound provided by the present invention also exhibits a narrow half-width (<50nm), overcoming the defect of the wide half-width (70-100nm) of traditional TADF luminescent materials.

[0569] Device Examples

[0570] The process of fabricating the device using the organic light-emitting layer via vacuum evaporation is as follows: On indium tin oxide supported on a glass substrate, 4×10 -4 Under a vacuum of Pa, TAPC, TCTA, EML (the invented luminescent compound and SiMCP2 are deposited sequentially at a mass ratio of 1:9), TmPyPB, and a LiF / Al cathode to obtain an organic electroluminescent device. TAPC and TmPyPB serve as the hole transport layer and electron transport layer, respectively, and TCTA is the exciton blocking layer. Its structural formula is shown below:

[0571]

[0572] The specific device structure (device structure A) is as follows:

[0573] ITO / TAPC(50nm) / TCTA(5nm) / EML(30nm) / TmPyPB(30nm) / LiF(0.8nm) / Al(100nm).

[0574] The process of fabricating the organic light-emitting layer using solution processing is as follows: Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) is spin-coated onto indium tin oxide supported on a glass substrate, annealed at 120°C for 30 minutes, followed by spin-coating at 1500 rpm with a toluene solution of the invented light-emitting compound and SiMCP2 mixed at a mass ratio of 1:9 for 1 minute, annealed at 80°C for 30 minutes, and then... -4 Organic electroluminescent devices were obtained by sequentially depositing TSPO1, TmPyPB, and LiF / Al cathodes under a vacuum of Pa, where TSPO1 and TmPyPB served as the hole blocking layer, electron transport layer, and host material, respectively. Their structural formulas are shown below:

[0575]

[0576] The specific device structure (device structure B) is as follows:

[0577] ITO / PEDOT:PSS(40nm) / EML(30nm) / TSPO1(8nm) / TmPyPB(42nm) / LiF(1nm) / Al(100nm).

[0578] Example 35

[0579] Using a1-1-1 from Example 1 as the implementation object, a1-1-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0580] See Table 2, which provides the performance parameters of the electroluminescent device prepared according to a1-1-1 provided by the present invention.

[0581] Example 36

[0582] Using a7-1-2 from Example 2 as the implementation object, a7-1-2 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0583] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a7-1-2 provided by the present invention.

[0584] Example 37

[0585] Using a11-1-1 from Example 3 as the implementation object, a11-1-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0586] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a11-1-1 method provided by this invention.

[0587] Example 38

[0588] Using a12-1-1 from Example 4 as the implementation object, a12-1-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0589] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a12-1-1 method provided by this invention.

[0590] Example 39

[0591] Using a14-1-2 from Example 5 as the implementation object, a14-1-2 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0592] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a14-1-2 provided by the present invention.

[0593] Example 40

[0594] Using a14-2-1 from Example 6 as the implementation object, a14-2-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0595] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a14-2-1 method provided by this invention.

[0596] Example 41

[0597] Using a14-3-1 from Example 7 as the implementation object, a14-3-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0598] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a14-3-1 method provided by this invention.

[0599] Example 42

[0600] Using a17-1-1 from Example 8 as the implementation object, a17-1-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0601] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a17-1-1 method provided by this invention.

[0602] Example 43

[0603] Using a19-1-1 from Example 9 as the implementation object, a19-1-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0604] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a19-1-1 method provided by this invention.

[0605] Example 44

[0606] Using a20-1-2 from Example 10 as the implementation object, a20-1-2 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0607] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a20-1-2 provided by the present invention.

[0608] Example 45

[0609] Using a24-1-1 from Example 11 as the implementation object, a24-1-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0610] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a24-1-1 method provided by this invention.

[0611] Example 46

[0612] Using a26-1-1 from Example 12 as the implementation object, a26-1-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0613] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the a26-1-1 method provided by this invention.

[0614] Example 47

[0615] Using b2-1-2 from Example 13 as the implementation object, b2-1-2 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0616] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b2-1-2 method provided in this invention.

[0617] Example 48

[0618] Using b3-1-2 from Example 14 as the implementation object, b3-1-2 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0619] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-1-2 method provided in this invention.

[0620] Example 49

[0621] Using b3-1-3 from Example 15 as the implementation object, b3-1-3 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0622] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-1-3 method provided in this invention.

[0623] Example 50

[0624] Using b3-1-4 from Example 16 as the implementation object, b3-1-4 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0625] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-1-4 method provided in this invention.

[0626] Example 51

[0627] Using b3-1-5 from Example 17 as the implementation object, b3-1-5 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0628] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-1-5 provided in this invention.

[0629] Example 52

[0630] Using b3-1-6 from Example 18 as the implementation object, b3-1-6 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0631] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-1-6 provided in this invention.

[0632] Example 53

[0633] Using b3-1-7 from Example 19 as the implementation object, b3-1-7 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0634] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-1-7 provided in this invention.

[0635] Example 54

[0636] Using b3-1-10 from Example 20 as the implementation object, b3-1-10 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0637] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-1-10 provided in this invention.

[0638] Example 55

[0639] Using b3-2-9 from Example 21 as the implementation object, b3-2-9 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0640] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-2-9 provided in this invention.

[0641] Example 56

[0642] Using b3-3-7 from Example 22 as the implementation object, b3-3-7 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0643] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-3-7 provided in this invention.

[0644] Example 57

[0645] Using b3-4-1 from Example 23 as the implementation object, b3-4-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0646] See Table 2, which provides the performance parameters of the electroluminescent device prepared according to b3-4-1 provided by the present invention.

[0647] Example 58

[0648] Using b3-4-2 from Example 24 as the implementation object, b3-4-2 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0649] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-4-2 method provided in this invention.

[0650] Example 59

[0651] Using b3-4-3 from Example 25 as the implementation object, b3-4-3 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0652] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-4-3 method provided in this invention.

[0653] Example 60

[0654] Using b3-4-4 from Example 26 as the implementation object, b3-4-4 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0655] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-4-4 method provided in this invention.

[0656] Example 61

[0657] Using b3-4-5 from Example 27 as the implementation object, b3-4-5 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0658] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-4-5 provided in this invention.

[0659] Example 62

[0660] Using b3-4-6 from Example 28 as the implementation object, b3-4-6 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0661] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-4-6 provided in this invention.

[0662] Example 63

[0663] Using b3-5-5 from Example 29 as the implementation object, b3-5-5 was mixed with SiMCP2 at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technology, and an organic electroluminescent device was prepared using the structure described in "Device Structure B". The resulting device was then tested.

[0664] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-5-5 provided in this invention.

[0665] Example 64

[0666] Using b3-5-7 from Example 30 as the implementation object, b3-5-7 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0667] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-5-7 provided in this invention.

[0668] Example 65

[0669] Using b3-7-5 from Example 31 as the implementation object, b3-7-5 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0670] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-7-5 provided in this invention.

[0671] Example 66

[0672] Using b3-8-5 from Example 32 as the implementation object, b3-8-5 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0673] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-8-5 provided in this invention.

[0674] Example 67

[0675] Taking b3-11-1 from Example 33 as the implementation object, b3-11-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0676] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-11-1 method provided by this invention.

[0677] Example 68

[0678] Using b3-11-10 from Example 34 as the implementation object, b3-11-10 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a vacuum evaporation process, and an organic electroluminescent device was prepared using the structure described in "Device Structure A". The resulting device was then tested.

[0679] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the b3-11-10 provided in this invention.

[0680] Comparative Example 1

[0681] Using BSN-1, a fused-ring compound containing boron, sulfur, nitrogen atoms, and a six-membered aromatic ring, as a comparative example, BSN-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was deposited using a vacuum evaporation process, and an organic electroluminescent device was fabricated using the structure described in "Device Structure A." The resulting device was then tested.

[0682]

[0683] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the BSN-1 provided by this invention.

[0684] Comparative Example 2

[0685] Using BSN-1, a fused-ring compound containing boron, sulfur, nitrogen atoms, and a six-membered aromatic ring, as a comparative example, BSN-1 and SiMCP2 were mixed at a mass ratio of 1:9 to form an organic light-emitting layer. The organic light-emitting layer was fabricated using a solution processing technique, and an organic electroluminescent device was prepared using the structure described in "Device Structure B." The resulting device was then tested.

[0686] See Table 2, which provides the performance parameters of the electroluminescent device prepared using the BSN-1 provided by this invention.

[0687] Table 2 Performance parameters of electroluminescent devices prepared from the compounds provided in this invention

[0688]

[0689]

[0690] Note: The start-up voltage in the table is for a brightness of 1 cd / m². -2The driving voltage of the device; the maximum external quantum efficiency is obtained from the current-voltage curve and electroluminescence spectrum of the device according to the calculation method described in the literature (Jpn.J.Appl.Phys.2001,40,L783); the half-width at half-maximum (WHM) is the peak width at half the peak height of the electroluminescence spectrum at room temperature, that is, the distance between the two points where the straight line parallel to the bottom of the peak is drawn through the midpoint of the peak height and intersects the two sides of the peak.

[0691] As shown in Table 2, the devices prepared from the compounds provided by this invention exhibit a very narrow electroluminescence spectrum, with a full width at half maximum (FWHM) of less than 50 nm, overcoming the problem of the broad electroluminescence spectrum (70–100 nm) of traditional DA-structured TADF compounds. Furthermore, compared to the comparative compounds (Comparative Examples 1 and 2) containing boron, sulfur, nitrogen atoms, and a six-membered aromatic ring, the devices prepared from the fused-ring compounds containing boron, nitrogen, sulfur atoms, and a five-membered aromatic heterocycle provided by this invention all exhibit higher device efficiencies, with a maximum external quantum efficiency reaching 26.1%.

Claims

1. A fused-ring compound containing boron, nitrogen, sulfur atoms and a five-membered aromatic heterocycle, The fused-ring compound has the following structure:

2. An organic electroluminescent device, characterized in that, It includes an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer includes the fused ring compound of claim 1.

3. The organic electroluminescent device according to claim 2, characterized in that, The organic thin film layer includes a light-emitting layer; the light-emitting layer includes the fused ring compound of claim 1.

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