CN112851700A

CN112851700A - Condensed ring compound containing boron atom, oxygen atom and five-membered aromatic heterocycle and organic electroluminescent device

Info

Publication number: CN112851700A
Application number: CN202011521509.2A
Authority: CN
Inventors: 王利祥; 邵世洋; 杜宝云; 赵磊; 王兴东; 王淑萌; 吕剑虹; 田洪坤
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2020-12-21
Filing date: 2020-12-21
Publication date: 2021-05-28

Abstract

The invention provides a condensed ring compound containing boron atoms, oxygen atoms and five-membered aromatic heterocyclic rings, which is shown as a formula (I). Compared with the prior art, the invention adopts the alloy containing boron atoms, oxygen atoms and five-membered atomsThe aromatic heterocyclic fused ring compound is used as a luminescent material, and on one hand, the resonance effect between boron atoms and oxygen atoms (oxygen, sulfur, selenium and tellurium) can be utilized to realize the separation of HOMO and LUMO, thereby realizing smaller Delta E_STAnd TADF effect, meanwhile, the boron/oxygen (sulfur, selenium and tellurium) hybrid fused ring unit has a rigid skeleton structure, and the relaxation degree of an excited state structure can be reduced, so that narrower half-peak width is realized; on the other hand, five-membered aromatic heterocycle and different substituent groups can be introduced into the framework of the boron/oxygen (sulfur, selenium and tellurium) hybrid fused ring unit, so that the further adjustment of the delayed fluorescence lifetime and the half-peak width can be realized.

Description

Condensed ring compound containing boron atom, oxygen atom and five-membered aromatic heterocycle and organic electroluminescent device

Technical Field

The invention belongs to the technical field of organic luminescent materials, and particularly relates to a fused ring compound containing boron atoms, oxygen atoms and five-membered aromatic heterocycle and an organic electroluminescent device.

Background

Organic Light Emitting Devices (OLEDs) are generally composed of a cathode, an anode, and organic layers interposed between the cathode and the anode, that is, the device is composed of a transparent ITO anode, a hole injection layer (TIL), a Hole Transport Layer (HTL), an Emission Layer (EL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a cathode, and 1 to 2 organic layers may be omitted as needed, or an Exciton Blocking Layer (EBL) is added, and an action mechanism thereof is that a voltage is formed between two electrodes, electrons are injected from the anode while electrons are injected from the cathode, the electrons and holes are combined in the emission layer to form an excited state, and the excited state is radiated to a ground state, thereby realizing light emission of the device. Due to the characteristics of rich colors, fast response, and the ability to produce flexible devices, organic electroluminescent materials are considered to be the most promising next-generation flat panel display and solid lighting materials.

Due to the limitation of the statistical law of spin quantum, the traditional fluorescent material can only utilize 25% of singlet excitons in the electroluminescent process, 75% of triplet excitons are lost in the form of non-radiative transition, and the theoretical limit value of quantum efficiency (IQE) in the device is 25%, so that the full utilization of triplet excitons is one of effective ways for improving the quantum efficiency. For example, the phosphorescent metal complex can convert triplet excitons into photons by utilizing the spin-orbit coupling action of heavy metal atoms, achieving 100% internal quantum efficiency, but this approach faces the problem that the phosphorescent metal complex is expensive. Another approach to utilize triplet excitons is to develop TADF-based light emitting materials that can convert triplet excitons into singlet states using thermally activated delayed fluorescence (RISC) process and emit fluorescence by radiative decay to the ground state, thereby achieving full utilization of singlet and triplet excitons without the need for noble metals.

The main approach for designing TADF materials at present is to introduce donor (D) and acceptor (a) groups so that the highest occupied orbital (HOMO) and lowest unoccupied orbital (LUMO) can be effectively separated spatially, thereby achieving a smaller singlet-triplet energy level difference (Δ E)_ST) Thereby facilitating the inter-system cross-over process. However, the excited state of the D-a structure shows strong vibration relaxation, so that the emission spectrum is wide, the full width at half maximum (FWHM) is generally 70-100 nm, and the color purity is poor, and in practical application, a filter or an optical microcavity is often required to be adopted to improve the color purity, but the external quantum efficiency of the device is reduced or the structure of the device becomes complex.

Therefore, it is one of the problems to be solved by many researchers in the field that how to develop a TADF fluorescent material with narrow spectral characteristics by solving the above-mentioned drawback of wide half-peak width through a suitable chemical structure design.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a fused ring compound containing a boron atom, an oxygen atom and a five-membered aromatic heterocycle, which has both TADF effect and narrow half-peak broad spectrum characteristics, and an organic electroluminescent device.

The invention provides a condensed ring compound containing boron atoms, oxygen atoms and five-membered aromatic heterocyclic rings, which is shown as a formula (I):

wherein m, n and p are each independently an integer of 0 to 20;

x and Y are each independently selected from O, S, Se or Te;

and

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 heterocyclic ring, a substituted or unsubstituted aromatic fused ring unit; the aromatic condensed ring monomer contains one or more of six-membered aromatic ring, six-membered aromatic heterocycle and five-membered aromatic heterocycle, and the aromatic condensed ring unit is connected with B and X or Y through the six-membered aromatic ring, the six-membered aromatic heterocycle or the five-membered aromatic heterocycle; and is

And

at least one is substituted or unsubstituted five-membered aromatic heterocycle, or contain aromatic condensed ring unit of five-membered aromatic heterocycle, and the aromatic condensed ring unit is connected with B and X or Y through five-membered aromatic heterocycle;

R_a、R_band R_cEach independently selected from D, F, Cl, Br, I, -CN, -NO₂、

Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group;

the R is¹、R²And R³Each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH₂Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group;

the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se;

or R_a、R_bAnd R_cEach of them is independently, or R¹、R²And R³Are linked to each other by a single bond, -C-C-, -C-N-, -C-P-, -C-C-, -O-, -S-),

And

one or more of the above;

said L₁′～L₁₂' independently from each other are selected from H, D, F, Cl, Br, I, -CN, -NO₂Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 halogenated alkyl, substituted or unsubstituted C3-C30 naphthenic base, substituted or unsubstituted C6-C60 aromatic hydrocarbonAromatic group, substituted or unsubstituted C5-C60 heteroaromatic group.

The invention provides a condensed ring compound containing boron atoms, oxygen atoms and five-membered aromatic heterocyclic rings, which is shown as a formula (I). Compared with the prior art, the invention adopts the condensed ring compound containing boron atoms, oxygen atoms and five-membered aromatic heterocyclic rings as the luminescent material, and on one hand, the separation of HOMO and LUMO can be realized by utilizing the resonance effect between the boron atoms and the oxygen atoms (oxygen, sulfur, selenium and tellurium), thereby realizing smaller Delta E_STAnd TADF effect, meanwhile, the boron/oxygen (sulfur, selenium and tellurium) hybrid fused ring unit has a rigid skeleton structure, and the relaxation degree of an excited state structure can be reduced, so that narrower half-peak width is realized; on the other hand, five-membered aromatic heterocycle and different substituent groups can be introduced into the framework of the boron/oxygen (sulfur, selenium and tellurium) hybrid fused ring unit, so that the further adjustment of the delayed fluorescence lifetime and the half-peak width can be realized.

Experimental results show that the luminescent compound provided by the invention is used as a luminescent layer of an electroluminescent device, so that the narrow electroluminescent half-peak width can be realized without an optical filter or a microcavity structure, and the high external quantum efficiency of the device can be realized.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

x and Y are each independently selected from O, S, Se or Te.

And

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 heterocyclic ring, a substituted or unsubstituted aromatic fused ring unit; the aromatic condensed ring monomer contains one or more of six-membered aromatic ring, six-membered aromatic heterocycle and five-membered aromatic heterocycle, and the aromatic condensed ring unit is connected with B and X or Y through the six-membered aromatic ring, the six-membered aromatic heterocycle or the five-membered aromatic heterocycle; and is

And

at least one is substituted or unsubstituted five-membered aromatic heterocycle, or contain aromatic condensed ring unit of five-membered aromatic heterocycle, and the aromatic condensed ring unit is connected with B and X or Y through five-membered aromatic heterocycle; i.e. the thickening compound has the structure represented by formulae (II) to (VI):

and

each independently is a substituted or unsubstituted five-membered aromatic heterocycle, a substituted or unsubstituted aromatic fused ring unit containing the five-membered aromatic heterocycle, and the fused ring unit is connected with B, X or Y through the five-membered aromatic heterocycle;

and

each independently is a substituted or unsubstituted six-membered aromatic ring or six-membered aromatic heterocyclic ring, a substituted or unsubstituted aromatic condensed ring unit containing the six-membered aromatic ring or the aromatic heterocyclic ring, and the condensed ring unit is connected with B, X or Y through the six-membered aromatic ring or the aromatic heterocyclic ring;

in the present invention, the

And

independently of each other, the aromatic fused ring unit 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, or a substituted or unsubstituted C4-C80; 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; further preferably substituted or unsubstituted C6-C30 six-membered aromatic ring, substituted or unsubstituted C3-C30 six-membered heteroaromatic ring, substituted or unsubstituted C3-C30 five-membered heteroaromatic ring, and substituted or unsubstituted C4-C50 aromatic fused ring unit; further preferably substituted or unsubstituted C6-C15 six-membered aromatic ring, substituted or unsubstituted C3-C15 six-membered heteroaromatic ring, substituted or unsubstituted C3-C15 five-membered heteroaromatic ring, and substituted or unsubstituted C4-C40 aromatic fused ring unit; most preferably substituted or unsubstituted C6-C10 six-membered aromatic ring, substituted or unsubstituted C3-C10 six-membered heteroaromatic ring, substituted or unsubstituted C3-C10 five-membered heteroaromatic ring, and substituted or unsubstituted C4-C30 aromatic fused ring unit; the aromatic condensed ring unit contains one or more of six-membered aromatic ring, six-membered aromatic heterocycle and five-membered aromatic heterocycle; the heteroatoms in the six-membered aromatic heterocyclic ring and the five-membered aromatic heterocyclic ring are respectively and independently one or more of Si, Ge, N, P, O, S and Se.

The substituent in the substituted six-membered aromatic ring, the substituted six-membered aromatic heterocyclic ring and the substituted five-membered aromatic heterocyclic ring is preferably D, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 halogenated alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group independently; more preferably D, a substituted or unsubstituted linear hydrocarbon group of C1-C20, a substituted or unsubstituted branched hydrocarbon group of C1-C20, a substituted or unsubstituted haloalkane group of C1-C20, a substituted or unsubstituted cycloalkyl group of C3-C20, a substituted or unsubstituted aromatic group of C6-C40, a substituted or unsubstituted heteroaromatic group of C5-C40; further preferably D, substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C1-C10 branched chain alkyl, substituted or unsubstituted C1-C10 alkyl halide, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group; most preferably D, substituted or unsubstituted C1-C5 straight chain alkyl, substituted or unsubstituted C1-C5 branched chain alkyl, substituted or unsubstituted C1-C5 alkyl halide, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C20 aromatic group, and substituted or unsubstituted C5-C20 heteroaromatic group; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

In the present invention, it is further preferable that the

And

each independently selected from one of the groups represented by Ar 1-Ar 27 and Ar 1-Ar 32, and

and

at least one selected from Ar 1-Ar 27:

L₁、L₂and L₃Each independently preferably represents H, D, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, and substituted or unsubstituted C5-C60 heteroaromatic group; more preferably H, D, a substituted or unsubstituted C1-C20 linear 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, a substituted or unsubstituted C5-C40 heteroaromatic group; h, D, substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C1-C10 branched chain alkyl, substituted or unsubstituted C1-C10 alkyl halide, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group are further preferable; most preferably H, D, a substituted or unsubstituted C1-C5 linear 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, a substituted or unsubstituted C5-C20 heteroaromatic group; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

m, n and p are each R_a、R_bAnd R_cIs an integer of 0 to 20, preferably an integer of 0 to 15, more preferably 0 to E10, more preferably 0 to 5, and most preferably 0 to 4, i.e., m, n, and p are each independently 0, 1, 2, 3, or 4.

Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group; preferably D, F, Cl, Br, I, -CN, -NO₂、

Substituted or unsubstituted C1-C20 straight-chain alkyl, substituted or unsubstituted C1-C20 branched-chain alkyl, substituted or unsubstituted C1-C20 haloalkane, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C40 aromatic group and substituted or unsubstituted C5-C40 heteroaromatic group; more preferably D, F, Cl, Br, I, -CN, -NO₂、

Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C1-C10 haloalkane, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group; further preferred are D, F, Cl, Br, I, -CN, -NO₂、

Substituted or unsubstituted C1-C5 straight-chain alkyl, substituted or unsubstituted C1-C5 branched-chain alkyl, substituted or unsubstituted C1-C5 haloalkane, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C20 aromatic group and substituted or unsubstituted C5-C20 heteroaromatic group.

The R is¹、R²And R³Each independently is H, D, F, Cl, Br, I, -OH, -SH, -NH₂Substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group; preferably H, D, F, Cl, Br, I, -OH, -SH, -NH₂Substituted or unsubstituted C1-C20 straight-chain alkyl, substituted or unsubstituted C1-C20 branched-chain alkyl, substituted or unsubstituted C1-C20 haloalkane, substituted or unsubstituted C3-C20 naphthenic base, substituted or unsubstituted C6-C40 aromatic group and substituted or unsubstituted C5-C40 heteroaromatic group; more preferably H, D, F, Cl, Br, I, -OH, -SH, -NH₂A substituted or unsubstituted C1-C10 linear hydrocarbon group,Substituted or unsubstituted C1-C10 branched chain alkyl, substituted or unsubstituted C1-C10 halogenated alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group; further preferred are H, D, F, Cl, Br, I, -OH, -SH, -NH₂Substituted or unsubstituted C1-C5 straight-chain alkyl, substituted or unsubstituted C1-C5 branched-chain alkyl, substituted or unsubstituted C1-C5 haloalkane, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C15 aromatic group and substituted or unsubstituted C5-C15 heteroaromatic group; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

Or R_a、R_bAnd R_cEach between (i.e. R)_aIn the radical of itself, R_bIn a radical of itself or R_cIn a radical of itself), or R¹、R²And R³Are linked to each other by a single bond, -C-C-, -C-N-, -C-P-, -C-C-, -O-, -S-),

Is connected.

Said L₁′～L₁₂' independently of one another are H, D, F, Cl, Br, I, -CN, -NO₂Substituted or unsubstituted C1-C30 straight chain hydrocarbon group, substituted or unsubstituted C1-C30 branched chain hydrocarbon group, substituted or unsubstituted C1-C30 alkyl halide group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C6-C60 aromatic group and substituted or unsubstituted C5-C60 heteroaromatic group, preferably H, D, F, Cl, Br, I, -CN, -NO₂Substituted or unsubstituted C1-C20 straight-chain alkyl, substituted or unsubstituted C1-C20 branched-chain alkyl, substituted or unsubstituted C1-C20 halogenated alkyl, substituted or unsubstituted C3-C20 naphthenic base, substituted or unsubstituted C6-C40 aromatic hydrocarbonA substituted or unsubstituted C5-C40 heteroaromatic group; more preferably H, D, F, Cl, Br, I, -CN, -NO₂Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C1-C10 haloalkane, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group; further preferred are H, D, F, Cl, Br, I, -CN and-NO₂Substituted or unsubstituted C1-C5 straight-chain alkyl, substituted or unsubstituted C1-C5 branched-chain alkyl, substituted or unsubstituted C1-C5 haloalkane, substituted or unsubstituted C3-C8 cycloalkyl, substituted or unsubstituted C6-C20 aromatic group and substituted or unsubstituted C5-C20 heteroaromatic group; most preferably H, D, F, Cl, Br, I, -CN, -NO₂The aromatic hydrocarbon compound comprises a substituted or unsubstituted C1-C4 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C4 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C4 halogenated alkyl group, a substituted or unsubstituted C5-C8 naphthenic group, a substituted or unsubstituted C6-C15 aromatic group and a substituted or unsubstituted C5-C15 heteroaromatic group.

Further preferably, according to the present invention, the condensed ring compound has a structure represented by formula A1-1-1 to formula J4-4-1:

wherein R is₁～R₉Each independently is D, F, Cl, Br, I, -CN, -NO₂、

L₁～L₆Each independently is preferably H, D, substituted or unsubstituted C1-C30 straight-chain alkyl, substituted or unsubstituted C1-C30 branched-chain alkyl, substituted or unsubstituted C1-C30 haloalkane, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, and substituted or unsubstituted C5-C60 heteroaromatic group; more preferably H, D, a substituted or unsubstituted C1-C20 linear 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, a substituted or unsubstituted C5-C40 heteroaromatic group; h, D, substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C1-C10 branched chain alkyl, substituted or unsubstituted C1-C10 alkyl halide, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group are further preferable; most preferably H, D, a substituted or unsubstituted C1-C5 linear 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, a substituted or unsubstituted C5-C20 heteroaromatic group; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

Most preferably, according to the present invention, the fused ring compound has a structure represented by formula a1-1-1 to formula n 3-10-2:

the invention adopts the condensed ring compound containing boron atoms, oxygen atoms and five-membered aromatic heterocyclic rings as the luminescent material, on one hand, the separation of HOMO and LUMO can be realized by utilizing the resonance effect between the boron atoms and the oxygen atoms (oxygen, sulfur, selenium and tellurium), thereby realizing smaller Delta E_STAnd TADF effect, meanwhile, the boron/oxygen (sulfur, selenium and tellurium) hybrid fused ring unit has a rigid skeleton structure, and the relaxation degree of an excited state structure can be reduced, so that narrower half-peak width is realized; on the other hand, five-membered aromatic heterocycle and different substituent groups can be introduced into the framework of the boron/oxygen (sulfur, selenium and tellurium) hybrid fused ring unit, so that the further adjustment of the delayed fluorescence lifetime and the half-peak width can be realized.

The invention also provides a preparation method of the fused ring compound containing the boron atom, the oxygen atom and the five-membered aromatic heterocycle, which comprises the following steps: reacting a compound shown as a formula (VII) with alkyl lithium, and then reacting with boron trihalide and organic amine to obtain a fused ring compound shown as a formula (I); the alkyl lithium is preferably one or more of butyl lithium, sec-butyl lithium, tert-butyl lithium, methyl lithium and ethyl lithium; the boron trihalide is preferably one or more of boron trifluoride, boron trichloride, boron tribromide and boron triiodide; the organic amine is preferably one or more of N, N-diisopropylethylamine, triethylamine and tri-N-butylamine.

Wherein Lu is hydrogen or halogen; other codes are the same as those described above, and are not described herein again.

Or: reacting a compound represented by the formula (VIII) with a compound containing-R_a、-R_band-R_cReacting the materials with the structure in a solvent to obtain the fused ring compound shown in the formula (I).

Wherein Lu₁、Lu₂、Lu₃At least one is hydrogen, halogen,

The remainder being R_a、R_bOr R_c。

The invention also provides application of the fused ring compound shown in the formula (I) as a luminescent material.

The invention also provides an organic electroluminescent device, which comprises an anode, a cathode and an organic thin film layer positioned between the anode and the cathode; the organic thin film layer includes a condensed ring compound represented by the above formula (I).

The structure of the organic electroluminescent device is not particularly limited in the present invention, and may be a conventional organic electroluminescent device well known to those skilled in the art, and those skilled in the art may select and adjust the structure according to the application, quality requirements and product requirements, and the structure of the organic electroluminescent device of the present invention preferably 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.

The thickness of the substrate is preferably 0.3-0.7 mm, and more preferably 0.4-0.6 mm; the choice of the substrate is not particularly limited by the present invention, and may be a substrate of a conventional organic electroluminescent device well known to those skilled in the art, which may be selected and adjusted according to the application, quality requirements and product requirements, and in the present invention, the substrate is preferably glass or plastic.

According to the invention, the anode is preferably a material susceptible to hole injection, more preferably a conductive metal or conductive metal oxide, and even more preferably indium tin oxide.

The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light emitting layer; the light-emitting layer includes a condensed ring compound represented by the above formula (I); the condensed ring compound shown in the formula (I) provided by the invention is used as a luminescent material to directly form an organic electroluminescent layer.

The cathode is preferably a metal including, but not limited to, calcium, magnesium, barium, aluminum, and silver, preferably aluminum.

In order 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 and an electron injection layer and an electron transport layer. The materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer are not particularly limited in the present invention, and may be selected and adjusted according to materials and thicknesses well known to those skilled in the art. The present invention is not particularly limited in the preparation processes of the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer and the electron transport layer, and is preferably prepared by processes of vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing and stereolithography.

The preparation method of the organic electroluminescent device is not particularly limited, and can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers including a light emitting layer on the anode; forming a cathode on the organic thin film layer;

the light-emitting layer includes one or more compounds represented by formula (I).

The structure and material of the organic electroluminescent device in the preparation method, and the corresponding preferred principle, and the corresponding material and structure in the organic electroluminescent device, and the corresponding preferred principle may be corresponding, and are not described in detail herein.

The present invention first forms an anode on a substrate, and the present invention does not specifically limit the manner of forming the anode, and may be performed according to a method known to those skilled in the art. The present invention is not particularly limited in the form of the light-emitting layer and the organic thin film layer below and above the light-emitting layer, and the organic thin film layer may be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or three-dimensional printing. After the organic layer is formed, a cathode is prepared on the surface thereof, and the cathode is formed by a method known to those skilled in the art, including but not limited to vacuum deposition.

In order to further illustrate the present invention, the following will describe in detail a fused ring compound containing a boron atom, an oxygen atom and a five-membered aromatic heterocycle and an organic electroluminescent device provided by the present invention with reference to examples.

The reagents used in the following examples are all commercially available.

Example 1

The reaction formula is as follows:

1-1(40.0g, 210.0mmol) and sodium thiophenolate (26.4g,200.0mmol) were charged into a 250mL three-necked flask under an argon atmosphere, 100mL of N-methylpyrrolidone (NMP) was charged into the flask, the flask was heated to 100 ℃ and stirred for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, methylene chloride was used for extraction to separate an organic phase, anhydrous sodium sulfate was added for drying, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 1-2(37.2g, yield: 66%).

Elemental analysis of its Structure (C)₁₂H₈BrFS) theoretical value C, 50.90; h, 2.85; s, 11.32; test value C, 50.77; h, 2.73; s, 11.44.

Electrospray ionization mass spectrometry (ESI-MS) analysis: theoretical value 282.0; experimental value 282.1 (M)⁺)。

1-2(5.6g, 20.0mmol), 3-mercapto-1-benzofuran (3.6g,24.0 mmol) and potassium carbonate (4.2g,30.0mmol) were added to a 100mL three-necked flask under an argon atmosphere, 30mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred for 12 hours, and then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 1-3(3.7g, yield: 45%).

Elemental analysis of its Structure (C)₂₀H₁₃BrOS₂) Theoretical C, 58.12; h, 3.15; n, 3.87; s, 15.51; test value C, 58.24; h, 3.23; n, 3.78; and S, 15.40.

ESI-MS analysis: theoretical value 412.0; experimental value 412.0 (M)⁺)。

Under argon atmosphere, 1-3(1.6g,4.0mmol) and o-xylene (70mL) are added into a 250mL double-neck flask, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) is dropwise added at-30 ℃, stirring is completed for 2 hours after the dropwise addition, then stirring is performed for 1 hour at room temperature, cooling is performed again to-30 ℃, boron tribromide (1.2g,0.5mL,4.8mmol) is dropwise added into the system, and stirring is performed for 1 hour at room temperature after the dropwise addition is completed for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. Then the reaction was cooled to room temperature, the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give product a7-1-1(280.0mg, yield: 21%).

Elemental analysis of its Structure (C)₂₀H₁₁BOS₂) Theoretical value C,70.16; h, 3.24; s, 18.74; test value C, 70.24; h, 3.32; and S, 18.90.

ESI-MS analysis: theoretical value 342.0; experimental value 343.1([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 1 of the present invention were examined.

Referring to table 1, table 1 shows photophysical properties of the luminescent compounds prepared in the examples of the present invention.

Example 2

The reaction formula is as follows:

under argon atmosphere, 1-1(40.0g, 210mmol), 1-naphthylthiophenol (32.0g,200mmol) and potassium carbonate (41.5g,300.0mmol) are added into a 250mL three-neck flask, 100mL of N-methylpyrrolidone (NMP) is added into the flask, the temperature is raised to 100 ℃, the reaction solution is stirred for 12 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is poured into water and stirred for 1 hour, dichloromethane is used for extraction to separate out an organic phase, anhydrous sodium sulfate is added for drying, the solvent of the organic phase obtained by filtration is removed, and the crude product is subjected to column separation to obtain a product 2-2(40.0g, yield: 60%).

Elemental analysis of its Structure (C)₁₆H₁₀BrFS) theoretical value C, 57.67; h, 3.03; s, 9.61; test value C, 57.88; h, 2.92; and S, 9.42.

ESI-MS analysis: theoretical value 332.0; experimental value 332.1 (M)⁺)。

Under argon atmosphere, 2-2(10.0g, 30.2mmol), 3-mercapto-1-benzofuran (4.7g,28.0 mmol) and potassium carbonate (6.3g,45.0mmol) were added to a 100mL three-necked flask, 30mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 2-3(9.4g, yield: 70%).

Elemental analysis of the junctionStructure (C)₂₄H₁₅BrS₃) Theoretical C, 60.12; h, 3.15; s, 20.06; test value C, 60.23; h, 3.37; and S, 20.13.

ESI-MS analysis: theoretical value 478.0; experimental value 477.9 (M)⁺)。

Under argon atmosphere, 2-3(1.9g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. Then, the reaction system was cooled to room temperature, and the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give product a14-2-1(500mg, yield: 31%).

Elemental analysis of its Structure (C)₂₄H₁₃BS₃) Theoretical C, 70.59; h, 3.21; s, 23.55; test value C, 70.48; h, 3.35; and S, 23.62.

ESI-MS analysis: theoretical value 408.0; experimental value 409.0([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 2 of the present invention were examined.

Example 3

The reaction formula is as follows:

under argon atmosphere, 1-1(9.6g, 50.0mmol), 3-mercapto-1-benzofuran (16.6g,110.0 mmol) and potassium carbonate (20.7g,150.0mmol) were added to a 250mL three-necked flask, 120mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product 3-1(18.0g, yield: 80%).

Elemental analysis of its Structure (C)₂₂H₁₃BrO₂S₂) Theoretical C, 58.28; h, 2.89; s, 14.14; test value C, 58.36; h, 2.79; s, 14.42.

ESI-MS analysis: theoretical value 452.0; experimental value 452.1 (M)⁺)。

Under argon atmosphere, 3-1(3.6g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. Then, the reaction system was cooled to room temperature, and the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give product a7-1-3(1.5g, yield: 51%).

Elemental analysis of its Structure (C)₂₂H₁₁BO₂S₂) Theoretical C, 69.13; h, 2.90; s, 16.77; test value C, 69.31; h, 2.98; s, 16.85.

ESI-MS analysis: theoretical value 382.0; experimental value 382.9([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 3 of the present invention were examined.

Example 4

The reaction formula is as follows:

under argon atmosphere, 4-1(40.8g, 150mmol), 3-mercaptobenzofuran (21.0g,140 mmol) and potassium carbonate (30.4g,220mmol) are added to a 250mL three-necked flask, 100mL of N-methylpyrrolidone (NMP) is added to the flask, the temperature is raised to 100 ℃, the reaction is stirred under argon protection for 12 hours, then the reaction solution is cooled to room temperature, poured into water and stirred for 1 hour, the organic phase is separated by extraction with dichloromethane, anhydrous sodium sulfate is added for drying, the solvent is removed from the filtered organic phase, and the crude product is subjected to column separation to obtain the product 4-2(24.0g, yield: 43%).

Elemental analysis of its Structure (C)₁₄H₇Br₂FOS) theoretical value C, 41.82; h, 1.75; s, 7.97; test value C, 41.70; h, 1.48; s,7.85

ESI-MS analysis: theoretical value 400.0; experimental value 400.1 (M)⁺)。

Under argon atmosphere, 4-2(15.0g, 37.5mmol), 3-mercapto-1-benzothiophene (5.8g,35.0 mmol) and potassium carbonate (6.3g,45.0mmol) were added to a 100mL three-necked flask, 30mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 4-3(10.1g, yield: 53%).

Elemental analysis of its Structure (C)₂₂H₁₂Br₂OS₃) Theoretical C, 48.19; h, 2.21; s, 17.54; test value C, 48.32; h, 2.40; s, 17.72.

Matrix-assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF MS) analysis: theoretical value 545.9; experimental value 546.0 (M)⁺)。

Under argon atmosphere, 4-3(2.2g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 20 minutes and then at room temperature for 1 hour. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give product k2-1-8(500.0mg, yield: 31%).

Elemental analysis of its Structure (C)₂₂H₁₀BBrOS₃) Theoretical C, 55.37; h, 2.11; s, 20.15; test value C, 55.45; h, 2.37; s, 20.29.

ESI-MS analysis: theoretical value 476.0; experimental value 477.1([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 4 of the present invention were examined.

Example 5

The reaction formula is as follows:

under argon atmosphere, a7-1-3(764.0mg, 2.0mmol) and 5mL Tetrahydrofuran (THF) are added into a 50mL three-neck flask, N-bromosuccinimide (NBS,783.2mg,4.4mmol) is dissolved in 10mL THF, then NBS is dropwise added into the flask by using a constant-pressure titration funnel under the condition of a lightproof ice-water bath, the flask is kept away from light for 12 hours at room temperature after the completion of dropping, after the reaction is finished, the reaction solution is treated by deionized water, dichloromethane is extracted and separated to obtain an organic phase, anhydrous sodium sulfate is added for drying, the obtained organic phase is filtered to remove a solvent, and a crude product is subjected to column separation to obtain a product k1-1-22(441.1mg, the yield: 41%).

Elemental analysis of its Structure (C)₂₂H₉BBr₂O₂S₂) Theoretical value C, 48.93; h, 1.68; s, 11.87; test value C, 48.75; h, 1.45; s, 11.62.

MALDI-TOF MS analysis: theoretical value 537.9; experimental value 537.8 (M)⁺)。

Example 6

The reaction formula is as follows:

under argon atmosphere, 4-1(13.6g, 50.0mmol), 3-mercapto-5-bromo-1-benzothiophene (27.0 g,110.0mmol) and potassium carbonate (20.7g,150.0mmol) were added to a 250mL three-necked flask, 100mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column chromatography to give 6-1(10.0g, yield: 28%).

Elemental analysis of its Structure (C)₂₂H₁₀Br₄S₄) Theoretical value C, 36.59; h, 1.40; s, 17.76; test value C, 36.48; h, 1.31; s, 17.39.

MALDI-TOF MS analysis: theoretical value 717.7; experimental value 717.6 (M)⁺)。

Under argon atmosphere, 6-1(5.7g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give product k2-1-28(1.14g, yield: 22%).

Elemental analysis of its Structure (C)₂₂H₈BBr₃S₄) Theoretical value C, 40.59; h, 1.24; s, 19.70; test value C, 40.47; h, 1.02; s, 19.58.

MALDI-TOF MS analysis: theoretical value 647.7; experimental value 648.6([ M + H ]]⁺)。

The photophysical properties of the luminescent compound prepared in example 6 of the present invention were examined.

Example 7

The reaction formula is as follows:

under argon atmosphere, 4-1(27.2g,100.0mmol), phenol (8.5g,90.0mmol) and potassium carbonate (18.6g,135.0mmol) were added to a 500mL three-necked flask, 150mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column chromatography to give product 7-1(29.2g, yield: 85%).

Elemental analysis of its Structure (C)₁₂H₇Br₂FO) theoretical value C, 41.66; h, 2.04; test value C, 41.53; h, 2.22.

ESI-MS analysis: theoretical value 343.9; experimental value 343.8 (M)⁺)。

Under argon atmosphere, 7-1(6.9g, 20.0mmol), 3-hydroxybenzothiophene (2.7g,18.0 mmol) and potassium carbonate (3.8g,27.0mmol) are added into a 100mL three-neck flask, 40mL of N-methylpyrrolidone (NMP) is added into the flask, the temperature is raised to 100 ℃, the reaction solution is stirred for 12 hours under the protection of argon, then the reaction solution is cooled to room temperature, the reaction solution is poured into water and stirred for 1 hour, dichloromethane is used for extraction to separate out an organic phase, anhydrous sodium sulfate is added for drying, the solvent is removed from the organic phase obtained by filtration, and the crude product is subjected to column separation to obtain the product 7-2(6.6g, yield: 70%).

Elemental analysis of its Structure (C)₂₀H₁₂Br₂O₂S) theoretical value C, 50.45; h, 2.54; s, 6.73; test value C, 50.31; h, 2.31; and S, 6.59.

ESI-MS analysis: theoretical value 473.9; experimental value 474.0 (M)⁺)。

7-2(1.9g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after completion of dropping for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give product n1-1-1(967.2mg, yield: 60%).

Elemental analysis of its Structure (C)₂₀H₁₀BBrO₂S) theoretical value C, 59.30; h, 2.49; s, 7.91; test value C, 59.03; h, 2.25; s, 7.71.

ESI-MS analysis: theoretical value 404.0; experimental value 405.0([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 7 of the present invention were examined.

Example 8

The reaction formula is as follows:

under argon atmosphere, 1-1(19.3g,100.0mmol), m-trimethylsilylphenylselenol (20.6g, 90.0mmol) and potassium carbonate (18.6g,135.0mmol) were added to a 500mL three-necked flask, 150mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction mixture was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction mixture was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain product 8-1(14.2 g, yield: 48%).

Elemental analysis of its Structure (C)₁₅H₁₆BrFSeSi) theoretical value C, 44.79; h, 4.01; test value C, 44.40; h, 4.35.

ESI-MS analysis: theoretical value 402.0; experimental value 402.1 (M)⁺)。

Under argon atmosphere, 8-1(8.0g, 20.0mmol), benzothiophene-3-selenol (3.6g,18.0 mmol) and potassium carbonate (3.8g,27.0mmol) were added to a 100mL three-necked flask, 40mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product 8-2(3.3g, yield: 32%).

Elemental analysis of its Structure (C)₂₃H₂₁BrOSe₂Si) theoretical value C, 47.68; h, 3.65; test value C, 47.98; h, 3.32.

MALDI-TOF MS analysis: theoretical value 579.3; experimental value 579.2 (M)⁺)。

Under argon atmosphere, 8-2(2.3g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 20 minutes and then at room temperature for 1 hour. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give product 8-3(315.2mg, yield: 18%).

Elemental analysis of its Structure (C)₂₃H₁₉BOSe₂Si) theoretical value C, 54.36; h, 3.77; test value C, 54.17; h, 3.89.

MALDI-TOF MS analysis: theoretical value 510.0; experimental value 509.9 (M)⁺)。

8-3(306.0mg, 0.6mmol) and N-iodosuccinimide (NIS) (540.0mg,2.4mmol) were charged in a 25mL three-necked flask under an argon atmosphere, 8mL of acetonitrile was taken and added to the flask, and stirred at room temperature overnight, then cooled to 0 ℃, deionized water was added to the reaction system, extraction was performed with methylene chloride, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-isolated to give the product m 1-2-2-2 (73.0mg, yield: 32%).

Elemental analysis of its Structure (C)₂₀H₁₀BIOSe₂) Theoretical value C, 42.75; h, 1.79; test value C, 42.50; h, 1.64.

ESI-MS analysis: theoretical value 563.8; experimental value 564.9([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 8 of the present invention were examined.

Example 9

The reaction formula is as follows:

under argon atmosphere, 1-1(15.5g,80.0mmol), 3-hydroxybenzofuran (21.5g,160.0 mmol) and potassium carbonate (33.2g,240.0mmol) were charged into a 500mL three-necked flask, 200mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain product 9-1(16.8g, yield: 50%).

Elemental analysis of its Structure (C)₂₂H₁₃BrO₄) Theoretical C, 62.73; h, 3.11; test value C, 62.60; h, 3.16.

ESI-MS analysis: theoretical value 420.0; experimental value 421.0([ M + H)]⁺)。

9-1(6.7g,16.0mmol) and o-xylene (240mL) were added to a 500mL two-necked flask under an argon atmosphere, an n-butyllithium solution (6.8mL,2.5M,16.8mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (4.8g,2.0mL,19.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 20 minutes and then at room temperature for 1 hour. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (4.4g,5.2mL,32.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 16 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give product b7-1-3(3.9g, yield: 70%).

Elemental analysis of its Structure (C)₂₂H₁₁BO₄) Theoretical C, 75.47; h, 3.17; test value C, 75.55; h, 3.49.

ESI-MS analysis: theoretical value 350.1; experimental value 351.1([ M + H)]⁺)。

B7-1-3(1.2g, 3.4mmol) and N-bromosuccinimide (NBS) (544.7mg,3.1mmol) were charged in a 50mL three-necked flask under argon atmosphere, 20mL Tetrahydrofuran (THF) was charged in the flask, and the reaction was stirred at room temperature for 3 hours, then cooled to 0 ℃ and deionized water was added to the reaction system, followed by extraction with dichloromethane, drying the resulting organic phase over anhydrous sodium sulfate, filtration, concentration to remove the solvent, and column separation of the crude product to give product l 1-1-9(464.3mg, yield: 35%).

Elemental analysis of its Structure (C)₂₂H₁₀BBrO₄) Theoretical C, 61.59; h, 2.35; test value C, 61.34; h, 2.50.

ESI-MS analysis: theoretical value 428.0; experimental value 428.1 (M)⁺)。

Under argon atmosphere, magnesium chips (28.8mg, 1.2mmol) were added to a 50mL two-necked flask, l 1-1-9(428.0mg, 1.0mmol) was dissolved in 20mL of dried THF solution, and then dropwise added to the two-necked flask containing the magnesium chips, the resulting Grignard reagent was filtered and slowly added dropwise to a THF solution of trimethyl borate (114.4mg, 1.1mmol) at-70 ℃, after completion of the reaction, the reaction solution was slowly poured into a rapidly stirred ice-water bath, hydrochloric acid was added and stirred for 30min, the mixture was extracted with diethyl ether to obtain an organic phase, which was washed with deionized water, dried over anhydrous sodium sulfate to obtain an organic phase, which was concentrated and drained, and the crude product was recrystallized with hot n-hexane to obtain product l 1-3-7(212.7mg, yield: 45%).

Elemental analysis of its Structure (C)₂₂H₁₂B₂O₆) Theoretical value C, 67.07; h, 3.07; test value C, 67.14; h, 3.12.

ESI-MS analysis: theoretical value 394.1; experimental value 394.0 (M)⁺)。

Example 10

The reaction formula is as follows:

1-1(9.6g, 50.0mmol), 3-mercapto-5-bromo-1-benzofuran (10.3g, 45.0mmol) and potassium carbonate (9.3g,67.5mmol) were added to a 250mL three-necked flask under an argon atmosphere, 80mL of N-methylpyrrolidone (NMP) was taken and added to the flask, the temperature was raised to 100 ℃ and the reaction was stirred under an argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column chromatography to give product 10-1(15.8g, yield: 88%).

Elemental analysis of its Structure (C)₁₄H₇Br₂FOS) theoretical value C, 41.82; h, 1.75; s, 7.97; test value C, 41.61; h, 1.62; and S, 7.76.

ESI-MS analysis: theoretical value 399.9; experimental value 400.9([ M + H)]⁺)。

In a 100mL three-necked flask, 10-1(12.0g, 30.0mmol), 3-mercapto-5-bromo-1-benzothiophene (6.7g, 27.0mmol) and potassium carbonate (5.6g,40.5mmol) were charged under argon atmosphere, 50mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 100 ℃ and the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column chromatography to give product 10-2(16.8g, yield: 56%).

Elemental analysis ofStructure (C)₂₂H₁₁Br₃OS₃) Theoretical value C, 42.13; h, 1.77; s, 15.33; test value C, 41.99; h, 1.64; s, 15.28.

MALDI-TOF MS analysis: theoretical value 623.8; experimental value 623.9 (M)⁺)。

10-2(5.0g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after completion of dropping for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give product k1-1-24(1.28g, yield: 29%).

Elemental analysis of its Structure (C)₂₂H₉BBr₂OS₃) Theoretical value C, 47.52; h, 1.63; s, 17.30; test value C, 47.32; h, 1.81; s, 17.22.

MALDI-TOF MS analysis: theoretical value 553.8; experimental value 553.8 (M)⁺)。

In a 50mL two-necked flask, under an argon atmosphere, k1-1-24 (554.0mg,1.0mmol) and diboronic acid ester (514.3mg,2.0 mmol), Pd were added₂(dppf) (74.3mg, 0.1mmol), potassium acetate (400.0mg, 4.0mmol), 15mL of DMF was taken and added to the flask, and the reaction was stirred at 85 ℃ for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized water, extracted with methylene chloride solution, and the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product k 2-4-12 (455.0mg, yield: 70%).

Elemental analysis of its Structure (C)₃₄H₃₃B₃O₅S₃) Theoretical value C, 62.80; h, 5.12; s, 14.79; test value C, 62.98; h, 5.01; s, 14.67.

MALDI-TOF MS analysis: theoretical value 650.2; experimental value 650.1(M⁺)。

Example 11

The reaction formula is as follows:

under argon atmosphere, k2-1-28 (648.0mg, 1.0mmol) and tetrahydrofuran (10mL) were added to a 50mL two-necked flask, a butyllithium solution (0.42mL,2.5M,1.05mmol) was added dropwise at-78 deg.C, and after the addition was completed, stirring was performed at-78 deg.C for 30 minutes, a tetrahydrofuran solution of tributyltin chloride (457.2mg,1.2mmol) was added dropwise to the system, and after the addition was completed for 20 minutes, the mixture was returned to room temperature and stirred for 3 hours. Deionized water was added to the system, extraction was performed with diethyl ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give product k2-5-15(770.0mg, yield: 60%).

Elemental analysis of its Structure (C)₅₈H₈₉BS₄Sn₃) Theoretical value C, 54.36; h, 7.00; s, 10.01; test value C, 54.53; h, 7.07; s, 10.32.

MALDI-TOF MS analysis: theoretical value 1284.3; experimental value 1284.2 (M)⁺)。

Example 12

The reaction formula is as follows:

under argon atmosphere, 1-1(23.2g,100.0mmol), p-bromothiophenol (17.1g,90.0mmol) and potassium carbonate (18.7g,135.0mmol) were added to a 500mL three-necked flask, 200mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product 12-1(28.2g, yield: 87%).

Elemental analysis of its Structure (C)₁₂H₇Br₂FS) theoretical value C, 39.81; h, 1.95; s, 8.86; test value C, 39.68; h, 1.80; and S, 8.89.

ESI-MS analysis: theoretical 360.0; experimental value 361.0([ M + H)]⁺)。

Under argon atmosphere, 12-1(18.0g,50.0mmol), benzofuran-3-selenol (8.9g,45.0 mmol) and potassium carbonate (9.4g,67.5mmol) were added to a 500mL three-necked flask, 100mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product 12-2(15.7g, yield: 65%).

Elemental analysis of its Structure (C)₂₀H₁₂Br₂OSSe) theoretical value C, 44.56; h, 2.24; s, 5.95; test value C, 44.33; h, 2.65; and S, 5.90.

MALDI-TOF MS analysis: theoretical value 537.8; experimental value 537.8 (M)⁺)。

12-2(8.6g,16.0mmol) and o-xylene (240mL) were added to a 500mL two-necked flask under an argon atmosphere, an n-butyllithium solution (6.8mL,2.5M,16.8mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (4.8g,2.0mL,19.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 20 minutes and then at room temperature for 1 hour. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (4.4g,5.2mL,32.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 16 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was separated by column to give a product n 1-1-6(2.5g, yield: 34%).

Elemental analysis of its Structure (C)₂₀H₁₀BBrOSSe), theoretical value C, 51.33; h, 2.15; s, 6.85; test value C, 51.10; h, 2.35; and S, 6.80.

ESI-MS analysis: theoretical value 467.9; experimental value 468.0 (M)⁺)。

Under argon atmosphere, n 1-1-6(468.0mg, 1.0mmol) and tetrahydrofuran (10mL) were added to a 50mL two-necked flask, a butyl lithium solution (0.42mL,2.5M,1.05mmol) was added dropwise at-78 deg.C, and after the addition was completed, stirring was performed at-78 deg.C for 30 minutes, a tetrahydrofuran solution of tributyltin chloride (457.2mg,1.2mmol) was added dropwise to the system, and after the addition was completed for 20 minutes, the mixture was returned to room temperature and stirred for 3 hours. Deionized water was added to the system, extraction was performed with diethyl ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give the product n 1-4-3(258.4mg, yield: 38%).

Elemental analysis of its Structure (C)₃₂H₃₇Bosssesn) theoretical value C, 56.67; h, 5.50; s, 4.73; test value C, 56.44; h, 5.56; and S, 4.88.

MALDI-TOF MS analysis: theoretical value 680.1; experimental value 680.0 (M)⁺)。

Example 13

The reaction formula is as follows:

13-1(23.8g, 0.10mol), sodium thiophenolate (26.4g,0.20mol), N, N-diisopropylethylamine (39.0g,50mL,0.30mol), catalyst Pd, were added to a 250mL three-necked flask under an argon atmosphere₂(dba)₃(4.6g,5.0mmol) and ligand Xantphos (5.8g,10.0mmol), 100mL of 1,4-dioxane (1,4-dioxane) is added into a bottle, the temperature is raised to 125 ℃, the reaction solution is stirred under the protection of argon for 15 hours, then the reaction solution is cooled to room temperature, the reaction solution is poured into water, solid is separated out, the stirring is carried out for 1 hour, the crude product is obtained after filtration, and the crude product is subjected to column separation to obtain the product 13-2(14.2g, the yield is 48%).

Elemental analysis of its Structure (C)₁₇H₁₄OS₂) Theoretical value C, 68.42; h, 4.73; s, 21.49; test value C, 68.49; h, 4.58; and S, 21.58.

ESI-MS analysis: theoretical value 298.1; experimental value 298.0 (M)⁺)。

13-2(1.2g,4mmol) and tert-butyl benzene (70mL) are added dropwise to a 100mL two-necked flask under an argon atmosphere, a tert-butyl lithium solution (3.3mL,1.3M,4.2mmol) is added dropwise at-30 ℃, stirring is carried out for 2 hours at-30 ℃ after the dropwise addition, stirring is carried out for 1 hour at 0 ℃, then boron tribromide (1.2g,0.5mL,4.8mmol) is added dropwise to the system at-30 ℃, and stirring is carried out for 2 hours at room temperature after 20 minutes of the dropwise addition. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, a solid was precipitated from the filtration system and washed with methanol, and the crude product was isolated by column to give product k 3-1-1(120mg, yield: 10%).

Elemental analysis of its Structure (C)₁₇H₁₁BOS₂) Theoretical value C, 66.68; h, 3.62; s, 20.94; test value C, 66.72; h, 3.53; and S, 20.80.

ESI-MS analysis: theoretical value 306.1; experimental value 307.2([ M + H ]]⁺)。

The photophysical properties of the luminescent compound prepared in example 13 of the present invention were examined.

Example 14

The reaction formula is as follows:

13-1(23.8g, 100.0mmol), 3-hydroxybenzofuran (13.5g, 100.0mmol), N, N-diisopropylethylamine (39.0g,50mL,300.0mmol), and a catalyst Pd were added to a 250mL three-necked flask under an argon atmosphere₂(dba)₃(4.6g,5.0mmol) and ligand Xantphos (5.8g,10.0mmol), 100mL of 1,4-dioxane (1,4-dioxane) is added into a bottle, the temperature is raised to 125 ℃, the reaction solution is stirred under the protection of argon for 15 hours, then the reaction solution is cooled to room temperature, the reaction solution is poured into water, solid is separated out, the stirring is carried out for 1 hour, the crude product is obtained after filtration, and the crude product is subjected to column separation to obtain the product 14-1(14.0g, the yield is 48%).

Elemental analysis of its Structure (C)₁₃H₉BrO₃) Theoretical value C, 53.27; h, 3.10; test value C, 53.24; h, 3.43.

ESI-MS analysis: theoretical 292.0; experimental value 292.0 (M)⁺)。

In a 50mL three-necked flask, 14-1(2.92g, 10.0mmol), 3-tert-butylphenol (3.1g,20.0 mmol), N, N-diisopropylethylamine (3.9g,5.0mL,30.0mmol) and a catalyst Pd were added under an argon atmosphere₂(dba)₃(460.0mg,0.5mmol) and ligand Xantphos (580.0mg,1.0mmol), 20mL of 1,4-dioxane (1,4-dioxane) is added into a bottle, the temperature is raised to 125 ℃, the reaction solution is stirred under the protection of argon for 15 hours, then the reaction solution is cooled to room temperature, the reaction solution is poured into water, solid is separated out, the stirring is carried out for 1 hour, the crude product is obtained by filtration, and the product 14-2(1.4g, yield: 40%) is obtained by column separation of the crude product.

Elemental analysis of its Structure (C)₂₃H₂₂O₄) Theoretical value C, 76.22; h, 6.12; test value C, 76.39; h, 6.04.

ESI-MS analysis: theoretical 362.1; experimental value 362.2 (M)⁺)。

Under argon atmosphere, 14-2(1.4g,4.0mmol) and tert-butyl benzene (70mL) were added dropwise to a 100mL two-necked flask, a tert-butyl lithium solution (3.3mL,1.3M,4.2mmol) was added dropwise at-30 ℃, stirring was performed at-30 ℃ for 2 hours after the dropwise addition was completed, stirring was performed at 0 ℃ for 1 hour again, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system at-30 ℃, and stirring was performed at room temperature for 2 hours after 20 minutes of the dropwise addition was completed. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, a solid precipitated from the filtration system and washed with methanol, and the crude product was isolated by column to give the product l 3-1-5(176.0mg, yield: 12%).

Elemental analysis of its Structure (C)₂₃H₁₉BO₄) Theoretical C, 74.62; h, 5.17; test value C, 74.54; h, 5.25.

ESI-MS analysis: theoretical value 370.0; experimental value 371.0([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 14 of the present invention were examined.

Example 15

The reaction formula is as follows:

1-2(5.6g, 20.0mmol), 2-methyl-4-hydroxythiazole (3.2g,24.0 mmol) and potassium carbonate (4.2g,30.0mmol) were added to a 100mL three-necked flask under an argon atmosphere, 30mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under an argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 15-1(3.9g, yield: 50%).

Elemental analysis of its Structure (C)₁₆H₁₂BrNS₂O) theoretical value C, 48.73; h, 3.07; n, 3.55; s, 16.26; test value C, 48.55; h, 3.22; n, 3.46; s, 16.45.

ESI-MS analysis: theoretical value 376.9; experimental value 376.8 (M)⁺)。

15-1(1.56g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give the product n 3-1-1(320.0mg, yield: 25%).

Elemental analysis of its Structure (C)₁₆H₁₀BNS₂O) theoretical value C, 59.45; h, 3.12; n, 4.33; s, 21.63; test value C, 59.54; h, 3.09; n, 4.02; s, 21.55.

ESI-MS analysis: theoretical value 307.0; experimental value 307.0 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 15 of the present invention were examined.

Example 16

The reaction formula is as follows:

under argon atmosphere, 4-1(81.6g, 300mmol) and sodium thiophenolate (37g,280mmol) are added into a 500mL three-neck flask, 200mL of N-methylpyrrolidone (NMP) is added into the flask, the temperature is raised to 100 ℃, stirring is carried out under argon protection for reaction for 12 hours, then the mixture is cooled to room temperature, the reaction liquid is poured into water and stirred for 1 hour, dichloromethane is used for extraction to separate out an organic phase, anhydrous sodium sulfate is added for drying, the solvent is removed from the organic phase obtained by filtration, and the crude product is subjected to column separation to obtain the product 16-1(70.6g, yield: 75%).

Elemental analysis of its Structure (C)₁₂H₇Br₂FS) theoretical value C, 39.81; h, 1.95; s, 8.86; test value C, 39.90; h, 1.78; s, 8.67.

ESI-MS analysis: theoretical 360.0; experimental value 360.1 (M)⁺)。

Under argon atmosphere, 16-1(14.4g, 40.0mol), 3-mercapto-1-benzothiophene (6.1g,36.0 mmol) and potassium carbonate (7.6g,54.0mmol) were added to a 100mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 16-2(6.2g, yield: 34%).

Elemental analysis of its Structure (C)₂₀H₁₂Br₂S₃) Theoretical C, 47.26; h, 2.38; s, 18.92; test value C, 47.39; h, 2.20; (S) the first step of the method,18.80。

MALDI-TOF MS analysis: theoretical value 505.8; experimental value 506.7([ M + H)]⁺)。

Under argon atmosphere, 16-2(4.06g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give product k2-1-2 (1.5g, yield: 43%).

Elemental analysis of its Structure (C)₂₀H₁₀BBrS₃) Theoretical value C, 54.95; h, 2.31; s, 22.00; test value C, 54.81; h, 2.43; s, 22.14.

ESI-MS analysis: theoretical value 436.0; experimental value 437.0([ M + H)]⁺)。

In a 100mL two-necked flask, k2-1-2 (1.0g, 2.3mmol) and sodium thiomethoxide (324.2mg,4.6 mmol), Pd were added under an argon atmosphere₂(dba)₃(52.6mg, 0.057mmol), Xantphos ligand (65.8mg, 0.114mmol), i-Pr₂20mL of 1,4-dioxane was taken from NEt (620.0 mg,4.6 mmol) and added into a bottle, the temperature was raised to 110 ℃, and the reaction was stirred under argon protection for 10 hours. Then, the reaction mixture was cooled to room temperature, washed with deionized water, extracted with methylene chloride to separate an organic phase, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product k3-2-5 (357.0mg, yield: 40%).

Elemental analysis of its Structure (C)₂₁H₁₃BOS₃) Theoretical value C, 64.95; h, 3.37; s, 24.77; test value C, 64.72; h, 3.25; and S, 24.55.

ESI-MS analysis: theoretical value 388.0; experimental value 388.0 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 16 of the present invention were examined.

Example 17

The reaction formula is as follows:

under argon atmosphere, 1-1(15.0g, 80.0mmol), 1-methyl-2-fluoro-4-thiolpyrrole (26.2 g,200.0mmol) and potassium carbonate (33.1g,240.0mol) were added to a 250mL three-necked flask, 100mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 17-1 (13.5g, yield: 41%).

Elemental analysis of its Structure (C)₁₆H₁₃BrF₂N₂S₂) Theoretical C, 46.27; h, 3.16; n, 6.75; s, 15.44; test value C, 46.02; h, 3.01; n, 6.51; and S, 15.30.

ESI-MS analysis: theoretical value 414.0; experimental value 414.1 (M)⁺)。

17-1(1.66g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after completion of dropping for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give the product k3-3-2 (250.0mg, yield: 18%).

Elemental analysis of its Structure (C)₁₆H₁₁BF₂N₂S₂) Theoretical value C, 55.83; h, 3.22; n, 8.14; s, 18.63; test value C, 55.71; h, 3.33; n, 8.09; and S, 18.46.

ESI-MS analysis: theoretical value 344.0; experimental value 343.9 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 17 of the present invention were examined.

Example 18

The reaction formula is as follows:

under argon atmosphere, 4-1(13.6g, 50.0mmol), 9, 9-dimethyl-9H-fluorene-2-thiophenol (10.2g,45.0mmol) and potassium carbonate (9.4g,67.5mol) were added to a 100mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column chromatography to give the product 18-1(9.2g, yield: 43%).

Elemental analysis of its Structure (C)₂₁H₁₅Br₂FS) theoretical value C, 52.74; h, 3.16; s, 6.70; test value C, 52.51; h, 3.32; and S, 6.84.

ESI-MS analysis: theoretical value 475.9; experimental value 476.8([ M + H ]]⁺)。

Under argon atmosphere, 18-1(8.0g, 16.8mmol), 3-mercapto-1-benzothiophene (2.7g,16.0 mmol) and potassium carbonate (3.4g,24.0mmol) were added to a 100mL three-necked flask, 30mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 18-2(5.2g, yield: 52%).

Elemental analysis of its Structure (C)₂₉H₂₀Br₂S₃) Theoretical C, 55.78; h, 3.23; s, 15.40; test value C, 55.67; h, 3.30; s, 15.36.

MALDI-TOF MS analysis: theoretical value 621.9; experimental value 621.8 (M)⁺)。

18-2(5.0g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after completion of dropping for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give 18-3(800.0mg, yield: 18%).

Elemental analysis of its Structure (C)₂₉H₁₈BBrS₃) Theoretical C, 62.95; h, 3.28; s, 17.38; test value C, 62.81; h, 3.32; s, 17.58.

MALDI-TOF MS analysis: theoretical value 552.0; experimental value 552.1 (M)⁺)。

18-3(552.0mg, 1.0mmol), potassium ferricyanide (K) were added to a 50mL three-necked flask under an argon atmosphere₃[Fe(CN)₆]2mL, 0.25mmol), catalyst Pd (OAc)₂(5.6mg,0.15mmol) and ligand X-phos (14.0mg,0.03mmol), 10mL of 1,4-dioxane was charged into a flask, potassium carbonate (35.0mg,0.25mmol) was dissolved in 8mL of water, an aqueous solution of potassium carbonate was introduced into the flask, the temperature was raised to 120 ℃ and the reaction was stirred under argon atmosphere for 16 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the crude product was subjected to column separation to give product k 3-3-8(140.0mg, yield: 28%).

Elemental analysisIts structure (C)₃₀H₁₈BNS₃) Theoretical value C, 72.14; h, 3.63; n, 2.80; s, 19.26; test value C, 72.00; h, 3.73; n, 2.63; s, 19.18.

ESI-MS analysis: theoretical value 499.0; experimental value 499.9([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 18 of the present invention were examined.

Example 19

The reaction formula is as follows:

under argon atmosphere, k2-1-2 (2.2g, 5.0mmol) and dry tetrahydrofuran (40mL) were added to a 100mL two-necked flask, a butyl lithium solution (2.1mL,2.5M,5.24mmol) was added dropwise at-78 deg.C, and after the addition was completed, stirring was performed at-78 deg.C for 30 minutes, a tetrahydrofuran solution of triphenylsilicon chloride (1.8g,6.0mmol) was added dropwise to the system, and after the addition was completed for 20 minutes, the system was returned to room temperature and stirred for 3 hours. Deionized water was added to the system, extraction was performed with diethyl ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give product k 3-3-38(1.4g, yield: 47%).

Elemental analysis of its Structure (C)₃₈H₂₅BS₃Si) theoretical value C, 74.01; h, 4.09; s, 15.60; test value C, 74.20; h, 4.26; s, 15.52.

MALDI-TOF MS analysis: theoretical value 616.0; experimental value 617.0([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 19 of the present invention were examined.

Example 20

The reaction formula is as follows:

in a 50mL three-necked flask, k2-1-2 (305.0mg, 0.7mmol), phenylboronic acid (128.1mg, 1.05mmol) and a catalyst Pd were added under an argon atmosphere₂(dba)₃(25.7mg, 0.028mmol) and ligand S-phos (34.5mg, 0.084mmol), 15mL of 1,4-dioxane was charged into a flask, potassium carbonate (35.0mg,0.14mmol) was dissolved in 8mL of water, an aqueous solution of potassium carbonate was introduced into the flask, the temperature was raised to 110 ℃ and the reaction was stirred under argon atmosphere for 16 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the crude product was isolated on a column to give product k 3-4-1(76.0mg, yield: 25%).

Elemental analysis of its Structure (C)₂₆H₁₅BS₃) Theoretical value C, 71.89; h, 3.48; s, 22.14; test value C, 71.68; h, 3.56; s, 22.28.

ESI-MS analysis: theoretical value 434.0; experimental value 434.0 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 20 of the present invention were examined.

Example 21

The reaction formula is as follows:

under argon atmosphere, 1-2(10.0g, 35.5mmol), 2-phenyl-4-thiothiophene (6.2g, 32.0mmol) and potassium carbonate (6.7g,48.0mmol) were added to a 100mL three-necked flask, 30mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain product 21-1(5.0g, yield: 34%).

Elemental analysis of its Structure (C)₂₂H₁₅BrS₃) Theoretical C, 58.02; h, 3.32; s, 21.12; test value C, 58.18; h, 3.19; s, 21.00.

ESI-MS analysis: theoretical value 454.0; experimental value 454.1 (M)⁺)。

21-1(1.8g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give the product k 3-4-2(600.0mg, yield: 40%).

Elemental analysis of its Structure (C)₂₂H₁₃BS₃) Theoretical value C, 68.75; h, 3.41; s, 25.02; test value C, 68.67; h, 3.30; s, 25.18.

ESI-MS analysis: theoretical value 384.0; experimental value 385.1([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 21 of the present invention were examined.

Example 22

The reaction formula is as follows:

6-1(17.3g, 50.0mmol), N-methylbenzopyrrole-3-tellurium (27.2g, 105.0mmol) and potassium carbonate (20.8g,150.0mmol) were charged into a 250mL three-necked flask under an argon atmosphere, 100mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 100 ℃ and the reaction was stirred under an argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to give 22-1(8.7g, yield: 30%).

Elemental analysis of its Structure (C)₂₁H₁₅Br₂NOTE) theoretical value C, 43.13; h, 2.59; n, 2.40; test value C, 43.01; h, 2.68; and N, 2.29.

MALDI-TOF MS analysis: theoretical value 584.9; experimental value 584.9 (M)⁺)。

Under argon atmosphere, 22-1(4.68g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give 22-2(1.1g, yield: 25%).

Elemental analysis of its Structure (C)₂₁H₁₃BBrNOTE) theoretical value C, 49.11; h, 2.55; n, 2.73; test value C, 49.30; h, 2.42; and N, 2.60.

MALDI-TOF MS analysis: theoretical value 515.0; experimental value 516.0([ M + H)]⁺)。

In a 50mL three-necked flask, under an argon atmosphere, 22-2(360.5mg, 0.7mmol), dibenzofuran-2-boronic acid (378.2 mg,1.05mmol) and Pd as a catalyst were placed₂(dba)₃(25.7mg, 0.028mmol) and ligand S-phos (34.5mg, 0.084mmol), 15mL of 1,4-dioxane was added to the flask, potassium carbonate (35.0mg,0.14mmol) was dissolved in 8mL of water, the aqueous potassium carbonate solution was introduced to the flask, the temperature was raised to 110 deg.C, the reaction was stirred under argon for 16 hours, then cooled to room temperature, the reaction was poured into water and stirred for 1 hour, extracted with dichloromethaneThe organic phase was separated, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the crude product was column-separated to give the product n 3-4-4(176.5mg, yield: 42%).

Elemental analysis of its Structure (C)₃₃H₂₀BNO₂Te) theoretical value C, 65.96; h, 3.35; n, 2.33; test values C, 65.74; h, 3.41; and N, 2.22.

MALDI-TOF MS analysis: theoretical value 601.0; experimental value 601.1 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 22 of the present invention were examined.

Example 23

The reaction formula is as follows:

under argon atmosphere, 1-1(9.6g, 50.0mmol), 4-mercapto-dibenzothiophene (9.8g,45.0 mmol) and potassium carbonate (9.4g,67.5mol) were added to a 100mL three-necked flask, 50mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product 23-1(12.2g, yield: 70%).

Elemental analysis of its Structure (C)₁₈H₁₀BrFS₂) Theoretical value C, 55.54; h, 2.59; s, 16.47; test value C, 55.66; h, 2.43; s, 16.65.

ESI-MS analysis: theoretical value 387.9; experimental value 387.8 (M)⁺)。

Under argon atmosphere, 23-1(6.5g, 16.8mmol), benzofuran-3-thiophenol (3.6g,16.0 mmol) and potassium carbonate (3.4g,24.0mmol) were added to a 100mL three-necked flask, 30mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 23-2(4.6g, yield: 46%).

Elemental analysis of its Structure (C)₂₆H₁₄Br₂OS₃) Theoretical C, 52.19; h, 2.36; s, 16.07; test value C, 52.24; h, 2.56; s, 16.11.

MALDI-TOF MS analysis: theoretical value 595.9; experimental value 595.9 (M)⁺)。

23-2(4.8g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after completion of dropping for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give 23-3(2.8g, yield: 66%).

Elemental analysis of its Structure (C)₂₆H₁₂BBrOS₃) Theoretical value C, 59.23; h, 2.29; s, 18.24; test value C, 59.56; h, 2.41; and S, 18.14.

MALDI-TOF MS analysis: theoretical value 526.0; experimental value 527.1([ M + H)]⁺)。

23-3(2.1g, 4.0mmol) and diboronic acid ester (2.1g,8.0mmol), Pd2(dppf) (297.2mg, 0.4mmol), potassium acetate (1.6g, 16.0mmol) were added to a 50mL two-necked flask under an argon atmosphere, 20mL of DMF was taken and added to the flask, and the reaction was stirred at 85 ℃ for 10 hours. Then, the reaction solution was cooled to room temperature, washed with deionized water, extracted with dichloromethane solution, and the organic phase was separated, dried with anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 23-4(1.6g, yield: 70%).

Elemental analysis of its Structure (C)₃₂H₂₄B₂O₃S₃) Theoretical C, 66.92; h, 4.21; s, 16.75; test value C, 66.76; h, 4.32; s, 16.59.

MALDI-TOF MS analysis: theoretical value 574.1; experimental value 574.0 (M)⁺)。

23-4(311.5mg, 0.5mmol), diphenylchlorotriazine (160.2mg, 0.6mmol) and Pd as a catalyst were placed in a 50mL three-necked flask under an argon atmosphere₂(dba)₃(18.4mg, 0.02mmol) and ligand S-phos (24.7mg, 0.06mmol), 15mL of 1,4-dioxane was taken and added to a bottle, potassium carbonate (25mg,0.1mmol) was dissolved in 8mL of water, an aqueous solution of potassium carbonate was introduced into the bottle, the temperature was raised to 110 ℃ and the reaction was stirred under argon atmosphere for 16 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the crude product was subjected to column separation to obtain product k3-5-2(170.0mg, yield: 50%).

Elemental analysis of its Structure (C)₄₁H₂₂BN₃OS₃) Theoretical value C, 72.46; h, 3.26; n, 6.18; s, 14.15; test value C, 72.37; h, 3.35; n, 6.35; s, 14.30.

MALDI-TOF MS analysis: theoretical value 679.1; experimental value 679.1 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 23 of the present invention were examined.

Example 24

The reaction formula is as follows:

under argon atmosphere, 4-1(13.6g, 50.0mmol), benzothiophene-3-selenol (22.4g,105.0 mmol) and potassium carbonate (20.8g,150.0mmol) were added to a 250mL three-necked flask, 100mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain the product 24-1(15.1g, yield: 46%).

Elemental analysis of its Structure (C)₂₂H₁₂Br₂S2Se₂) Theoretical value C, 40.15; h, 1.84; s, 9.74; test value C, 40.28; h, 1.68; and S, 9.89.

MALDI-TOF MS analysis: theoretical value 657.8; experimental value 657.7 (M)⁺)。

Under argon atmosphere, 24-1(5.26g,8.0mmol) and o-xylene (120mL) were added to a 250mL two-necked flask, an n-butyllithium solution (3.4mL,2.5M,8.4mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (2.4g,1.0mL,9.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (2.2g,2.6mL,16.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give a product m 2-1-8(3.2g, yield: 68%).

Elemental analysis of its Structure (C)₂₂H₁₀BBrS₂Se₂) Theoretical C, 45.01; h, 1.72; s, 10.92; test value C, 44.81; h, 1.60; s, 10.78.

MALDI-TOF MS analysis: theoretical value 587.8; experimental value 588.7([ M + H)]⁺)。

In a 50mL three-necked flask, m 2-1-8(411.6mg, 0.7mmol),9,9' -spirobifluorene-3-boronic acid (378.2 mg,1.05mmol) and a catalyst Pd were added under an argon atmosphere₂(dba)₃(25.7mg, 0.028mmol) and ligand S-phos (34.5mg, 0.084mmol), 15mL of 1,4-dioxane was added to the flask, potassium carbonate (35mg,0.14mmol) was dissolved in 8mL of water, the aqueous potassium carbonate solution was introduced to the flask, the temperature was raised to 110 ℃, the reaction was stirred under argon for 16 hours, then cooled to room temperature, the reaction was poured into water and stirred for 1 hour,the organic phase was separated by extraction with methylene chloride, dried by adding anhydrous sodium sulfate, the solvent was removed from the filtered organic phase, and the crude product was column-separated to give the product m 3-4-8(317.2mg, yield: 55%).

Elemental analysis of its Structure (C)₄₇H₂₅BS₂Se₂) Theoretical C, 68.63; h, 3.06; s, 7.80; test value C, 68.50; h, 3.22; and S, 7.75.

MALDI-TOF MS analysis: theoretical 824.0; experimental value 824.1 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 24 of the present invention were examined.

Example 25

The reaction formula is as follows:

under argon atmosphere, 4-1(27.2g,100.0mmol), benzothiophene-3-tellurium phenol (23.8g,90.0 mmol) and potassium carbonate (18.6g,135.0mmol) were charged into a 500mL three-necked flask, 150mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 25-1(33.4g, yield: 65%).

Elemental analysis of its Structure (C)₁₄H₇Br₂FSTe) theoretical value C, 32.74; h, 1.37; s, 6.24; test value C, 32.89; h, 1.57; and S, 6.40.

ESI-MS analysis: theoretical value 513.8; experimental value 513.9 (M)⁺)。

Under argon atmosphere, 25-1(10.3g, 20.0mmol),9, 9-dimethyl-9H-fluorene-2-thiophenol (4.1g,18.0mmol) and potassium carbonate (3.8g,27.0mmol) were added to a 100mL three-necked flask, 40mL of N-methylpyrrolidone (NMP) was added to the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column chromatography to give 25-2(4.9g, yield: 34%).

Elemental analysis of its structure C₂₉H₂₀Br₂S₂Te) theoretical value C, 48.38; h, 2.80; s, 8.91; test value C, 48.47; h, 2.94; s, 8.80; .

MALDI-TOF MS analysis: theoretical value 719.9; experimental value 719.8 (M)⁺)。

Under argon atmosphere, 25-2(2.9g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give 25-3(598.0mg, yield: 23%).

Elemental analysis of its Structure (C)₂₉H₁₈BBrS₂Te) theoretical value C, 53.68; h, 2.80; s, 9.88; test value C, 53.79; h, 2.62; s, 9.69; .

MALDI-TOF MS analysis: theoretical value 650.0; experimental value 651.0([ M + H)]⁺)。

25-3(240.5mg, 0.37mmol), diphenylamine (94.7mg,0.56 mmol) and Pd as a catalyst were added to a 25mL three-necked flask under an argon atmosphere₂(dba)₃(13.8mg, 0.015mmol), ligand t-Bu₃P·BF₄(17.4mg, 0.06mmol) and sodium tert-butoxide (115.2mg,1.2mmol), 10mL of toluene is added into a bottle, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 12 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction solution is poured into water and stirred for 1 hour, dichloromethane is used for extraction and separation of an organic phase, and the organic phase is addedDried over anhydrous sodium sulfate, the organic phase obtained by filtration was freed of the solvent, and the crude product was column-separated to give the product n3-4-5(95.7mg, yield: 35%).

Elemental analysis of its Structure (C)₄₁H₂₈BNS₂Te) theoretical value C, 66.80; h, 3.83; n, 1.90; s, 8.70; test value C, 66.98; h, 3.76; n, 1.75; s, 8.61.

MALDI-TOF MS analysis: theoretical value 739.1; experimental value 739.0 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 25 of the present invention were examined.

Example 26

The reaction formula is as follows:

under argon atmosphere, 4-1(27.2g,100.0mmol), 4-hydroxypyridine (8.6g,90.0mmol) and potassium carbonate (18.6g,135.0mmol) were charged into a 500mL three-necked flask, 150mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 26-1(18.6g, yield: 60%).

Elemental analysis of its Structure (C)₁₁H₆Br₂FNO) theoretical value C, 38.08; h, 1.74; n, 4.04; test value C, 38.20; h, 1.99; and N, 4.28.

ESI-MS analysis: theoretical value 344.9; experimental value 345.0 (M)⁺)。

26-1(6.9g, 20.0mmol), 3-hydroxybenzothiophene (2.7g,18.0 mmol) and potassium carbonate (3.8g,27.0mmol) are added to a 100mL three-necked flask under an argon atmosphere, 40mL of N-methylpyrrolidone (NMP) is added to the flask, the temperature is raised to 100 ℃, the reaction solution is stirred for 12 hours under an argon protection, then the reaction solution is cooled to room temperature, the reaction solution is poured into water and stirred for 1 hour, the organic phase is extracted and separated by dichloromethane, anhydrous sodium sulfate is added for drying, the solvent is removed from the organic phase obtained by filtration, and the crude product is subjected to column separation to obtain the product 26-2(3.4g, yield: 40%).

Elemental analysis of its Structure (C)₁₉H₁₁Br₂NO₂S) theoretical value C, 47.83; h, 2.32; n, 2.94; s, 6.72; test value C, 47.79; h, 2.20; n, 2.79; and S, 6.66.

ESI-MS analysis: theoretical value 474.9; experimental value 474.8 (M)⁺)。

26-2(1.9g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after completion of dropping for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give 26-3(324mg, yield: 20%).

Elemental analysis of its Structure (C)₁₉H₉BBrNO₂S) theoretical value C, 56.20; h, 2.23; n, 3.45; s, 7.90; test value C, 56.36; h, 2.18; n, 3.29; and S, 7.70.

ESI-MS analysis: theoretical value 405.0; experimental value 406.0([ M + H ]]⁺)。

26-3(162.0mg, 0.4mmol), 9-H-carbazole (102.0mg,0.61 mmol) and a catalyst Pd were added to a 25mL three-neck flask under an argon atmosphere₂(dba)₃(15.0mg, 0.017mmol), ligand t-Bu₃P·BF₄(18.8mg, 0.065mmol) and sodium tert-butoxide (124.6mg,1.3mmol), 10mL of toluene is taken and added into a bottle, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 12 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into water and stirred for 1 hour, dichloromethane is used for extraction and separation of an organic phase, anhydrous sodium sulfate is added for drying, and the organic phase obtained by filtration is extracted and driedThe solvent was removed from the organic phase, and the crude product was column-separated to give the product l 3-5-1(130.0mg, yield: 66%).

Elemental analysis of its Structure (C)₃₁H₁₇BN₂O₂S) theoretical value C, 75.62; h, 3.48; n, 5.69; s, 6.51; test value C, 75.48; h, 3.29; n, 5.64; and S, 6.40.

ESI-MS analysis: theoretical value 492.1; experimental value 493.0([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 26 of the present invention were examined.

Example 27

The reaction formula is as follows:

under argon atmosphere, 25-1(8.4g, 20.0mmol), phenylselenophenol (2.82g,18.0mmol) and potassium carbonate (3.8g,27.0mmol) are added to a 100mL three-necked flask, 40mL of N-methylpyrrolidone (NMP) is added to the flask, the temperature is raised to 100 ℃, the reaction solution is stirred under argon protection for 12 hours, then the reaction solution is cooled to room temperature, the reaction solution is poured into water and stirred for 1 hour, dichloromethane is used for extraction to separate out an organic phase, anhydrous sodium sulfate is added for drying, the solvent is removed from the organic phase obtained by filtration, and the crude product is subjected to column separation to obtain the product 27-1(2.8g, yield: 28%).

Elemental analysis of its Structure (C)₂₀H₁₂Br₂S₂Se) theoretical value C, 43.27; h, 2.18; s, 11.55; test value C, 43.39; h, 2.36; s, 11.23.

MALDI-TOF MS analysis: theoretical value 553.8; experimental value 553.7 (M)⁺)。

27-1(2.2g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after completion of dropping for 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give the product n 2-1-1(774.2mg, yield: 40%).

Elemental analysis of its Structure (C)₂₀H₁₀BBrS₂Se) theoretical value C, 49.62; h, 2.08; s, 13.25; test value C, 49.36; h, 2.19; and S, 13.11.

ESI-MS analysis: theoretical value 483.9; experimental value 483.8 (M)⁺)。

In a 25mL three-necked flask, n 2-1-1(180.0mg, 0.37mmol),9, 9-dimethyl-9, 10-2H-acridine (117.1mg,0.56mmol) and a catalyst Pd were added under an argon atmosphere₂(dba)₃(13.8mg, 0.015mmol), ligand t-Bu₃P·BF₄(17.4mg, 0.06mmol) and sodium tert-butoxide (115.2mg,1.2mmol), 10mL of toluene are taken and added to a bottle, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 12 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into water and stirred for 1 hour, the organic phase is separated by extraction with dichloromethane, anhydrous sodium sulfate is added for drying, the solvent is removed from the organic phase obtained by filtration, and the crude product is subjected to column separation to obtain the product n 3-5-3(72.6mg, yield: 32%).

Elemental analysis of its Structure (C)₃₅H₂₄BNS₂Se) theoretical value C, 68.64; h, 3.95; n, 2.29; s, 10.47; test value C, 68.42; h, 3.76; n, 2.14; s, 10.33.

MALDI-TOF MS analysis: theoretical value 613.1; experimental value 614.1([ M + H)]⁺)。

The photophysical properties of the luminescent compound prepared in example 27 of the present invention were examined.

Example 28

The reaction formula is as follows:

under argon atmosphere, 25-1(8.4g, 20.0mmol), 1-hydroxy-9, 9-dimethyl-N-phenylacridine (5.4g,18.0mmol) and potassium carbonate (3.8g,27.0mmol) were charged in a 100mL three-necked flask, 40mL of N-methylpyrrolidone (NMP) was charged in the flask, the temperature was raised to 100 ℃ and the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column chromatography to give product 28-1(2.8g, yield: 20%).

Elemental analysis of its Structure (C)₃₅H₂₅Br₂NOS₂) Theoretical value C, 60.10; h, 3.60; n, 2.00; s, 9.17; test value C, 60.17; h, 3.70; n, 2.23; and S, 9.10.

MALDI-TOF MS analysis: theoretical value 697.0; experimental value 698.0 (M)⁺)。

28-1(2.8g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 20 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give product 28-2(376.2mg, yield: 15%).

Elemental analysis of its Structure (C)₃₅H₂₃BBrNOS₂) Theoretical value C, 66.90; h, 3.69; n, 2.23; s, 10.20; test value C, 66.94; h, 3.51; n, 2.20; s, 10.34.

MALDI-TOF MS analysis: theoretical value 627.0; experimental value 627.1 (M)⁺)。

28-2(232.0mg, 0.37mmol), pyridine [3,2-b ] was added to a 25mL three-necked flask under an argon atmosphere]Indole (94.1mg, 0.56mmol), catalyst Pd₂(dba)₃(13.8mg, 0.015mmol), ligand t-Bu₃P·BF₄(17.4mg, 0.06mmol) and sodium tert-butoxide (115.2mg,1.2mmol), 10mL of toluene are taken and added to a bottle, the temperature is raised to 110 ℃, the mixture is stirred and reacted for 12 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into water and stirred for 1 hour, the organic phase is extracted and separated by dichloromethane, anhydrous sodium sulfate is added for drying, the solvent is removed from the organic phase obtained by filtration, and the crude product is subjected to column separation to obtain the product n 3-5-6(211.2mg, yield: 80%).

Elemental analysis of its Structure (C)₄₆H₃₀BN₃OS₂) Theoretical C, 77.20; h, 4.23; n, 5.87; s, 8.96; test value C, 77.29; h, 4.10; n, 5.72; and S, 8.89.

MALDI-TOF MS analysis: theoretical value 715.2; experimental value 715.3 (M)⁺)。

The photophysical properties of the luminescent compound prepared in example 28 of the present invention were examined.

Example 29

The reaction formula is as follows:

under argon atmosphere, n 2-1-1(936.0mg,2.0mmol) and tetrahydrofuran (25mL) were added to a 50mL two-necked flask, a butyllithium solution (0.84mL,2.5M,2.12mmol) was added dropwise at-78 deg.C, and after the addition was completed, stirring was performed at-78 deg.C for 30 minutes, a tetrahydrofuran solution of triminylboron (643.2mg,2.4mmol) was added dropwise to the system, and after the addition was completed for 20 minutes, the system was returned to room temperature and stirred for 3 hours. Deionized water was added to the system, extraction was performed with diethyl ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give the product n 3-6-1(893.2mg, yield: 70%).

Elemental analysis of its Structure (C)₃₈H₃₂B₂OSSe) theoretical value C, 71.62; h, 5.06; s, 5.03; test value C,71.39；H,5.00；S,5.18。

MALDI-TOF MS analysis: theoretical value 638.2; experimental value 637.1([ M + H)]⁺)。

The photophysical properties of the fused ring compound prepared in example 29 of the present invention were examined.

Referring to table 1, table 1 shows the photophysical properties of the fused ring compounds prepared in the examples of the present invention.

Example 30

The reaction formula is as follows:

16-1(15.0g,41.5mmol), 3-mercaptothieno [3,2-C ] pyridine (6.3g, 37.4mmol) and potassium carbonate (7.8g,56.3mmol) were charged in a 250mL three-necked flask under an argon atmosphere, 80mL of N-methylpyrrolidone (NMP) was taken and charged in a bottle, the temperature was raised to 100 ℃ and the reaction was stirred under an argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to give 30-1(9.8g, yield: 52%).

Elemental analysis of its Structure (C)₁₉H₁₁Br₂NS₃) Theoretical value C, 44.81; h, 2.18; n, 2.75; s, 18.89; test value C, 44.76; h, 2.03; n, 2.67; and S, 18.98.

MALDI-TOF MS analysis: theoretical value 506.8; experimental value 506.9 (M)⁺)。

30-1(2.03g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask under an argon atmosphere, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 16 hours. The reaction system was cooled to room temperature, the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give 30-2(664.0mg, yield: 38%).

Elemental analysis of its Structure (C)₁₉H₉BBrNS₃) Theoretical value C, 52.08; h, 2.07; n, 3.20; s, 21.95; test value C, 52.20; h, 2.14; n, 3.11; s, 21.74.

ESI-MS analysis: theoretical value 436.9; experimental value 436.8 (M)⁺)。

In a 50mL two-necked flask, 30-2(437.0mg, 1.0mmol) and Cs were added under an argon atmosphere₂CO₃(500mg,1.5mmol), diphenylphosphine oxide (308.0mg,1.5mol) was dissolved in 10ml of DMF and added to a two-necked flask. Adding Pd (OAc) into the reaction system₂(2.4mg, 0.01mmol) and dppf (11.2mg, 0.02mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction product was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated to remove the solvent, and the crude product was column-separated to give product k 3-7-2(167.6mg, yield: 30%).

Elemental analysis of its Structure (C)₃₁H₁₉BNOPS₃) Theoretical value C, 66.55; h, 3.42; n, 2.50; s, 17.19; test value C, 66.39; h, 3.30; n, 2.41; s, 17.30.

MALDI-TOF MS analysis: theoretical value 559.1; experimental value 560.1([ M + H)]⁺)。

The photophysical properties of the fused ring compound prepared in example 30 of the present invention were examined.

Referring to table 1, table 3 shows the photophysical properties of the fused ring compounds prepared in the examples of the present invention.

Example 31

The reaction formula is as follows:

31-1(31.8g, 100.0mmol), 3- (9, 9-dimethylacridine) thiophenol (31.4g,100.0mmol), N, N-bis (N-methylacridine) were placed in a 500mL three-necked flask under an argon atmosphereIsopropyl ethylamine (39.0g,50mL,300.0mmol), Pd as catalyst₂(dba)₃(4.6g,5.0mmol) and ligand Xantphos (5.8g,10.0mmol), 200mL of 1,4-dioxane (1,4-dioxane) is added into a bottle, the temperature is raised to 125 ℃, the mixture is stirred and reacted for 15 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into water, solid is separated out, the mixture is stirred for 1 hour, a crude product is obtained after filtration, and the product 31-2(24.8g, yield: 45%) is obtained after column separation of the crude product.

Elemental analysis of its Structure (C)₃₁H₂₄BrNS₂) Theoretical C, 67.14; h, 4.36; n, 2.53; s, 11.56; test value C, 67.32; h, 4.52; n, 2.88; and S, 11.70.

MALDI-TOF MS analysis: theoretical value 553.1; experimental value 553.2 (M)⁺)。

31-2(16.6g, 30.0mmol), benzofuran-3-tellurium phenol (7.3g,30.0 mmol), N, N-diisopropylethylamine (11.7g,15mL,90.0mmol), and Pd as a catalyst were added to a 250mL three-necked flask under an argon atmosphere₂(dba)₃(1.38g,1.5mmol) and ligand Xantphos (1.74g,3.0mmol), 100mL of 1,4-dioxane (1,4-dioxane) is added into a bottle, the temperature is increased to 125 ℃, the mixture is stirred and reacted for 15 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into water, solid is separated out, the mixture is stirred for 1 hour, a crude product is obtained after filtration, and the product 31-3(8.6g, yield: 40%) is obtained after column separation of the crude product.

Elemental analysis of its Structure (C)₃₉H₂₉NOS₂Te) theoretical value C, 65.12; h, 4.06; n, 1.95; s, 8.91; test value C, 65.27; h, 4.09; n, 1.80; and S, 8.96.

MALDI-TOF MS analysis: theoretical value 721.1; experimental value 721.0 (M)⁺)。

Under argon atmosphere, 31-3(2.6g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 16 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was separated by column to give a product n 3-5-7(1.6g, yield: 64%).

Elemental analysis of its Structure (C)₃₉H₂₆BNOS₂Te) theoretical value C, 64.42; h, 3.60; n, 1.93; s, 8.82; test value C, 64.30; h, 3.48; n, 1.80; and S, 8.89.

MALDI-TOF MS analysis: theoretical value 729.0; experimental value 729.1 (M)⁺)。

The photophysical properties of the fused ring compound prepared in example 31 of the present invention were examined.

Example 32

The reaction formula is as follows:

under argon atmosphere, 4-1(21.7g,80.0mmol), 3-mercapto-5-chlorobenzofuran (29.6g, 160.0mmol) and potassium carbonate (33.2g,240.0mmol) were charged into a 500mL three-necked flask, 200mL of N-methylpyrrolidone (NMP) was charged into the flask, the temperature was raised to 100 ℃, the reaction was stirred under argon atmosphere for 12 hours, then cooled to room temperature, the reaction solution was poured into water and stirred for 1 hour, the organic phase was separated by extraction with dichloromethane, dried by adding anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was subjected to column separation to obtain 32-1 (26.3g, yield: 55%).

Elemental analysis of its Structure (C)₂₂H₁₀Br₂Cl₂O₂S₂) Theoretical value C, 43.96; h, 1.68; s, 10.67; test value C, 43.69; h, 1.63; s, 10.55.

MALDI-TOF MS analysis: theoretical value 597.8; experimental value 597.7 (M)⁺)。

32-1(9.6g,16.0mmol) and o-xylene (240mL) were added to a 500mL two-necked flask under an argon atmosphere, an n-butyllithium solution (6.8mL,2.5M,16.8mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (4.8g,2.0mL,19.6mmol) was added dropwise to the system, and stirring was continued at room temperature for 20 minutes and then at room temperature for 1 hour. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (4.4g,5.2mL,32.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 16 hours. The reaction system was cooled to room temperature, the solid precipitated in the system was filtered and washed with methanol, and the crude product was isolated by column to give 32-2(2.1g, yield: 25%).

Elemental analysis of its Structure (C)₂₂H₈BBrCl₂O₂S₂) Theoretical value C, 49.85; h, 1.52; s, 12.10; test value C, 49.60; h, 1.54; and S, 12.01.

MALDI-TOF MS analysis: theoretical value 527.9; experimental value 528.8([ M + H ]]⁺)。

32-2(1.05g, 2.0mmol) and Cs were added to a 50mL two-necked flask under an argon atmosphere₂CO₃(1.0g,3.0mmol), diphenylphosphine oxide (606.0mg,3.0mol) was dissolved in 20mL of DMF and added to a two-necked flask. Adding Pd (OAc) into the reaction system₂(4.8mg, 0.02mmol) and dppf (22.4mg, 0.04mmol), the reaction was stirred at 120 ℃ for 10 hours. After cooling to room temperature, the reaction was poured into an excess of saturated brine, extracted with dichloromethane, the resulting organic phase was dried over anhydrous sodium sulfate, filtered, concentrated to remove the solvent, and the crude product was column-separated to give the product 32-3(390.0mg, yield: 30%).

Elemental analysis of its Structure (C)₃₄H₁₈BCl₂O₃PS₂) Theoretical value C, 62.70; h, 2.79; s, 9.84; test value C, 62.52; h, 2.61; s, 9.77.

32-3(325.0mg,0.5mmol) and tetrahydrofuran (8mL) were added dropwise to a 25mL two-necked flask under an argon atmosphere, a butyllithium solution (0.21mL,2.5M,0.53mmol) was added dropwise at-78 deg.C, and after completion of the addition, stirring was carried out at-78 deg.C for 30 minutes, a tetrahydrofuran solution of trimidoboron fluoride (162.0mg,0.6mmol) was added dropwise to the system, and after completion of the addition for 20 minutes, the mixture was returned to room temperature and stirred for 3 hours. Deionized water was added to the system, extraction was performed with diethyl ether, the resulting organic phase was dried over anhydrous sodium sulfate, and the crude product was separated by column to give product k 3-8-5 (366.5mg, yield: 68%).

Elemental analysis of its Structure (C)₇₀H₆₂B₃O₃PS₂) Theoretical value C, 79.11; h, 5.88; s, 6.03; test value C, 79.00; h, 5.73; and S, 6.11.

MALDI-TOF MS analysis: theoretical value 1078.4; experimental value 1078.5 (M)⁺)。

The photophysical properties of the fused ring compound prepared in example 32 of the present invention were examined.

Example 33

The reaction formula is as follows:

33-1(30.2g, 0.10mol), benzofuran-3-mercapto-5-tert-butyl (51.5g,0.25mol), N, N-diisopropylethylamine (39.0g,50mL,0.30mol), catalyst Pd, were added to a 500mL three-necked flask under an argon atmosphere₂(dba)₃(4.6g,5.0mmol) and ligand Xantphos (5.8g,10.0mmol), 200mL of 1,4-dioxane (1,4-dioxane) is added into a bottle, the temperature is raised to 125 ℃, the mixture is stirred and reacted for 15 hours under the protection of argon, then the mixture is cooled to room temperature, the reaction liquid is poured into water, solid is separated out, the mixture is stirred for 1 hour, the crude product is obtained after filtration, and the product 33-2(28.7g, yield: 52%) is obtained after column separation of the crude product.

Elemental analysis of its Structure (C)₃₄H₃₂O₃S₂) Theoretical C, 73.88; h, 5.84; s, 11.60; test value C, 73.67; h, 5.75; s, 11.75.

MALDI-TOF MS analysis: theoretical value 552.2; experimental value 552.3 (M)⁺)。

Under argon atmosphere, 33-2(2.2g,4.0mmol) and o-xylene (70mL) were added to a 250mL two-necked flask, an n-butyllithium solution (1.7mL,2.5M,4.2mmol) was added dropwise at-30 deg.C, stirring was completed for 2 hours, then stirring was continued at room temperature for 1 hour, cooling was again conducted to-30 deg.C, boron tribromide (1.2g,0.5mL,4.8mmol) was added dropwise to the system, and stirring was continued at room temperature for 1 hour after 20 minutes. The temperature is reduced to 0 ℃ again, N-diisopropylethylamine (1.1g,1.3mL,8.0mmol) is dropwise added into the reaction system, and the temperature is raised to 125 ℃ after the dropwise addition is finished to react for 16 hours. The reaction system was cooled to room temperature, the precipitated solid in the system was filtered and washed with methanol, and the crude product was isolated by column to give a product k 3-4-25(0.76g, yield: 54%).

Elemental analysis of its Structure (C)₃₄H₂₉BO₃S₂) Theoretical C, 72.85; h, 5.22; s, 11.44; test value C, 72.63; h, 5.01; s, 11.49.

MALDI-TOF MS analysis: a theoretical value of 560.2; experimental value 560.1 (M)⁺)。

The photophysical properties of the fused ring compound prepared in example 33 of the present invention were examined.

TABLE 1 photophysical properties of fused ring compounds prepared in the examples of the present invention

Note that in the table,. DELTA.E_STIs the difference between the singlet level and the triplet level, obtained by reacting the compound with 10^-4A test sample was prepared by dissolving the concentration of mol/L in a toluene solution, and the difference between the initial (onset) value of the fluorescence spectrum and the phosphorescence spectrum was measured with a HORIBA FluoroMax spectrophotometer (Japan); the delayed fluorescence lifetime is obtained by doping 1 wt% of compound into polystyrene to obtain sample, and time-resolved fluorescence is usedThe spectrometer test is carried out, and the test instrument is an Edinburgh fluorescence spectrometer (FLS-980, UK); half-peak width is the peak width at half of the peak height of the fluorescence spectrum at room temperature, i.e. a straight line parallel to the bottom of the peak is drawn through the midpoint of the peak height and the straight line intersects with the two points on both sides of the peak at a distance of 10 deg.C^-5The concentration of mol/L was dissolved in a toluene solution to prepare a sample to be measured, and the sample was measured by a fluorescence spectrometer (HORIBA FluoroMax spectrophotometer (Japan)).

As can be seen from Table 1, the fused ring compound containing a boron atom, an oxygen atom and a five-membered aromatic heterocycle in the examples provided by the present invention has a small Δ E_ST(<0.25eV), the delayed fluorescence effect of thermal activation is shown, and the delayed fluorescence life is 10-89 mu s; meanwhile, the luminescent compound provided by the invention also shows narrower half-peak width (<50nm) and overcomes the defect that the half-peak width of the traditional TADF luminescent material is wider (70-100 nm).

Device examples

The process of preparing the device by the organic light-emitting layer by adopting a vacuum evaporation process is as follows: on indium tin oxide supported on a glass substrate, 4X 10^-4Sequentially depositing TAPC, TCTA, EML (the luminescent compound is mixed with SIMCP2 according to the mass ratio of 1: 9), TmPyPB and a LiF/Al cathode under the vacuum degree of Pa to obtain the organic electroluminescent device, wherein the TAPC and the TmPyPB are respectively used as a hole transport layer and an electron transport layer, the TCTA is an exciton blocking layer, and the structural formula is shown as follows:

the specific device structure (device structure a) is:

ITO/TAPC(50nm)/TCTA(5nm)/EML(30nm)/TmPyPB(30nm)/LiF(0.8nm)/Al(100nm)。

the process of preparing the device by adopting the solution processing technology for the organic light-emitting layer is as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated onto indium tin oxide supported on a glass substrate, annealed at 120 ℃ for 30 minutes, and subsequently spin-coated at 1500rpmThe mass ratio of the luminescent compound to SIMCP2 is 1: 9 the mixed toluene solution was annealed at 80 ℃ for 30 minutes and then at 4X 10^-4Sequentially depositing TSPO1, TmPyPB and a LiF/Al cathode under Pa vacuum degree to obtain the organic electroluminescent device, wherein TSPO1 and TmPyPB are respectively used as a hole blocking layer, an electron transport layer and a main material, and the structural formula is as follows:

the specific device structure (device structure B) is:

ITO/PEDOT:PSS(40nm)/EML(30nm)/TSPO1(8nm)/TmPyPB(42nm)/LiF(1nm)/Al(100nm)。

example 34

A7-1-1 in example 1 is used as a subject, and a7-1-1 and SIMCP2 are mixed according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with a7-1-1 provided by the present invention.

Example 35

A14-2-1 in example 2 is used as a subject, and a14-2-1 and SIMCP2 are mixed according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with a14-2-1 provided by the present invention.

Example 36

A7-1-3 in example 3 is used as a subject, and a7-1-3 and SIMCP2 are mixed according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with a7-1-3 provided by the present invention.

Example 37

Taking k2-1-8 in example 4 as a subject, mixing k2-1-8 with SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k2-1-8 provided by the present invention.

Example 38

Taking k1-1-22 in example 5 as a subject, mixing k1-1-22 with SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k1-1-22 provided by the present invention.

Example 39

Taking k2-1-28 in example 6 as a subject, mixing k2-1-28 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k2-1-28 provided by the present invention.

Example 40

Taking n1-1-1 in example 7 as an implementation object, mixing n1-1-1 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with n1-1-1 provided by the present invention.

EXAMPLE 41

Taking m1-2-2 in example 8 as an implementation object, mixing m1-2-2 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with m1-2-2 provided by the present invention.

Example 42

Taking l 1-3-7 in example 9 as an implementation object, mixing l 1-3-7 with SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with l 1-3-7 provided by the present invention.

Example 43

Taking k 2-4-12 in example 10 as an implementation object, mixing the k 2-4-12 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k 2-4-12 provided by the present invention.

Example 44

Taking k2-5-15 in example 11 as an implementation object, mixing the k2-5-15 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k2-5-15 provided by the present invention.

Example 45

Taking n 1-4-3 in example 12 as an implementation object, mixing n 1-4-3 with SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with n 1-4-3 provided by the present invention.

Example 46

With k 3-1-1 in example 13 as an object of implementation, the mass ratio of k 3-1-1 to SIMCP2 was 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with k 3-1-1 provided by the present invention.

Example 47

Taking l 3-1-5 in example 14 as an implementation object, mixing l 3-1-5 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with l 3-1-5 provided by the present invention.

Example 48

With n 3-1-1 in example 15 as an object of implementation, the mass ratio of n 3-1-1 to SIMCP2 was 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with n 3-1-1 provided by the present invention.

Example 49

Taking k3-2-5 in example 16 as a subject, mixing k3-2-5 with SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k3-2-5 provided by the present invention.

Example 50

Taking k3-3-2 in example 17 as a subject, mixing k3-3-2 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k3-3-2 provided by the present invention.

Example 51

Taking k 3-3-8 in example 18 as a subject, mixing k 3-3-8 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k 3-3-8 provided by the present invention.

Example 52

Taking k 3-3-38 in example 19 as a subject, mixing k 3-3-38 with SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k 3-3-38 provided by the present invention.

Example 53

With k 3-4-1 in example 20 as an object of implementation, the mass ratio of k 3-4-1 to SIMCP2 is 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with k 3-4-1 provided by the present invention.

Example 54

Taking k 3-4-2 in example 21 as an implementation object, mixing the k 3-4-2 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k 3-4-2 provided by the present invention.

Example 55

Taking n 3-4-4 in example 22 as a subject, mixing n 3-4-4 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with n 3-4-4 provided by the present invention.

Example 56

Taking k3-5-2 in example 23 as an implementation object, mixing the k3-5-2 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k3-5-2 provided by the present invention.

Example 57

Taking m 3-4-8 in example 24 as an implementation object, mixing m 3-4-8 with SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with m 3-4-8 provided by the present invention.

Example 58

With n3-4-5 in example 25 as an object of implementation, the mass ratio of n3-4-5 to SIMCP2 was 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with n3-4-5 provided by the present invention.

Example 59

L 3-5-1 in example 26 was used as a subject, and l 3-5-1 was mixed with SIMCP2 at a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to Table 2, Table 2 provides performance parameters for electroluminescent devices prepared with l 3-5-1 provided by the present invention.

Example 60

With n 3-5-3 in example 27 as an object of implementation, the mass ratio of n 3-5-3 to SIMCP2 was 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with n 3-5-3 provided by the present invention.

Example 61

Taking n 3-5-6 in example 28 as a subject, mixing n 3-5-6 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with n 3-5-6 provided by the present invention.

Example 62

With n 3-6-1 in example 29 as an object of implementation, the mass ratio of n 3-6-1 to SIMCP2 was 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to Table 2, Table 2 provides the performance parameters of electroluminescent devices prepared with n 3-6-1 provided by the present invention.

Example 63

Taking k 3-7-2 in example 30 as an implementation object, mixing the k 3-7-2 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k 3-7-2 provided by the present invention.

Example 64

Taking n 3-5-7 in example 31 as a subject, mixing n 3-5-7 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with n 3-5-7 provided by the present invention.

Example 65

Taking k 3-8-5 in example 32 as an implementation object, mixing the k 3-8-5 and SIMCP2 according to the mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k 3-8-5 provided by the present invention.

Example 66

Taking k 3-4-25 in example 33 as a subject, mixing k 3-4-25 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with k 3-4-25 provided by the present invention.

Comparative example 1

Taking a compound Ctrl-1 in which boron and oxygen atoms are connected through a six-membered aromatic ring as an object of implementation, and mixing the Ctrl-1 and the SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with Ctrl-1 provided by the present invention.

Comparative example 2

Taking a compound Ctrl-1 in which boron and oxygen atoms are connected through a six-membered aromatic ring as an object of implementation, and mixing the Ctrl-1 and the SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Comparative example 3

Taking a compound Ctrl-2 in which boron and oxygen atoms are connected through a six-membered aromatic ring as an object of implementation, and mixing the Ctrl-2 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a vacuum evaporation process, an organic electroluminescent device is prepared by utilizing the structure of the device structure A, and the obtained device is tested.

Referring to table 2, table 2 provides the performance parameters of electroluminescent devices prepared with Ctrl-2 provided by the present invention.

Comparative example 4

Taking a compound Ctrl-2 in which boron and oxygen atoms are connected through a six-membered aromatic ring as an object of implementation, and mixing the Ctrl-2 with SIMCP2 according to a mass ratio of 1: 9 as an organic light emitting layer. The organic light-emitting layer adopts a solution processing technology, an organic electroluminescent device is prepared by utilizing the structure of the device structure B, and the obtained device is tested.

Table 2 performance parameters of electroluminescent devices prepared from fused ring compounds provided by the present invention

Note: the on-voltage in the table is 1cd m in luminance^-2The driving voltage of the time device; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device by the calculation method described in the literature (Jpn.J.appl.Phys.2001,40, L783); the half-peak width is the peak width at half of the height of the peak of the electroluminescence spectrum at room temperature, i.e. a straight line parallel to the bottom of the peak is drawn through the midpoint of the peak height, and the straight line is the distance between two intersecting points on two sides of the peak.

As can be seen from Table 2, the device prepared by the compound provided by the invention has a narrow electroluminescent spectrum, the half-peak width of the device is less than 50nm, and the problem that the electroluminescent spectrum of the TADF compound with the traditional D-A structure is wide (70-100 nm) is solved. Meanwhile, compared with a compound (comparative examples 1-4) in which boron and oxygen atoms are connected through a six-membered aromatic ring, the device prepared from the condensed ring compound containing the five-membered aromatic heterocycle has higher device efficiency, and the maximum external quantum efficiency reaches 27.9%.

Claims

1. A fused ring compound containing a boron atom, an oxygen atom and a five-membered aromatic heterocycle is represented by the formula (I):

wherein m, n and p are each independently an integer of 0 to 20;

x and Y are each independently selected from O, S, Se or Te;

and

And

Substituted or unsubstituted C1-C30 straight chain alkyl, substituted or unsubstituted C1-C30 branched chain alkyl, substituted or unsubstituted C1-C30 halogenAlkyl substituted group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group;

And

one or more of the above;

said L₁′～L₁₂' independently from each other are selected from H, D, F, Cl, Br, I, -CN, -NO₂The aromatic hydrocarbon compound comprises a substituted or unsubstituted C1-C30 straight-chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched-chain hydrocarbon group, a substituted or unsubstituted C1-C30 halogenated alkyl group, a substituted or unsubstituted C3-C30 naphthenic group, a substituted or unsubstituted C6-C60 aromatic group and a substituted or unsubstituted C5-C60 heteroaromatic group.

2. The fused ring compound of claim 1, wherein the fused ring compound is a cyclic compound of formula i

And

each independently selected from substituted or unsubstituted C6-C15 six-membered aromatic ring, substituted or unsubstituted C3-C15 six-membered heteroaromatic ring, substituted or unsubstituted C3-C15 five-membered aromatic heterocyclic ring and substituted or unsubstituted C4-C40 aromatic fused ring unit.

3. The fused-ring compound of claim 1, wherein the substituents in the substituted six-membered aromatic ring, substituted six-membered heteroaromatic ring, substituted five-membered aromatic heterocyclic ring and substituted aromatic fused ring unit are selected from the group consisting of D, substituted or unsubstituted C1-C30 linear 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, substituted or unsubstituted C5-C60 heteroaromatic groups; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

4. The fused ring compound of claim 1, wherein the fused ring compound is a cyclic compound of formula i

And

and

at least one selected from Ar 1-Ar 27:

L₁、L₂and L₃Each independently selected from H, D, substituted or unsubstituted C1-C30 straight chain alkyl, substituted or unsubstituted C1-C30 branched chain alkyl, substituted or unsubstituted C1-C30 alkyl halide, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, and substituted or unsubstituted C5-C60 heteroaromatic group; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

5. The fused ring compound of claim 1, wherein m, n, and p are each independently integers from 0 to 4.

6. The fused ring compound of claim 1, wherein the fused ring compound has a structure represented by formula a1-1-1 to formula J4-4-1:

wherein R is₁～R₉Each independently selected from D, F, Cl, Br, I, -CN, -NO₂、

L₁～L₆each independently selected from H, D, substituted or unsubstituted C1-C30 straight chain alkyl, substituted or unsubstituted C1-C30 branched chain alkyl, substituted or unsubstituted C1-C30 alkyl halide, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, and substituted or unsubstituted C5-C60 heteroaromatic group; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

7. The fused ring compound of claim 6, wherein R is₁～R₉Each independently selected from D, F, Cl, Br, I, -CN, -NO₂、

Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C1-C10 haloalkane, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group;

the R is¹、R²And R³Each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH₂Substituted or unsubstituted C1-C10 straight-chain alkyl, substituted or unsubstituted C1-C10 branched-chain alkyl, substituted or unsubstituted C1-C10 haloalkane, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group and substituted or unsubstituted C5-C30 heteroaromatic group;

or R¹、R²And R³Are linked to each other by a single bond, -C-C-, -C-N-, -C-P-, -C-C-, -O-, -S-),

And

one or more of the above;

L₁～L₆each independently selected from H, D, substituted or unsubstituted C1-C10 straight chain alkyl, substituted or unsubstituted C1-C10 branched chain alkyl, substituted or unsubstituted C1-C10 alkyl halide, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aromatic group, substituted or unsubstituted C5-C30 heteroAn aromatic group; the hetero atom in the hetero aromatic group is selected from one or more of Si, Ge, N, P, O, S and Se.

8. The fused ring compound of claim 1, wherein the fused ring compound has a structure represented by formula a1-1-1 to formula n 3-10-2:

9. an organic electroluminescent device comprising an anode, a cathode, and an organic thin film layer between the anode and the cathode; the organic thin film layer includes the condensed ring compound according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, wherein the organic thin film layer comprises a light emitting layer; the light-emitting layer includes the condensed ring compound according to any one of claims 1 to 8.