CN114478603B

CN114478603B - Organic boron condensed ring compound containing branch molecular structure and organic electroluminescent device

Info

Publication number: CN114478603B
Application number: CN202210176670.3A
Authority: CN
Inventors: 王利祥; 邵世洋; 王兴东; 赵磊; 李伟利; 吕剑虹; 王淑萌
Original assignee: Changchun Institute of Applied Chemistry of CAS
Current assignee: Changchun Institute of Applied Chemistry of CAS
Priority date: 2022-02-24
Filing date: 2022-02-24
Publication date: 2024-05-31
Anticipated expiration: 2042-02-24
Also published as: CN114478603A

Abstract

The invention provides an organoboron fused ring compound containing a branch molecular structure, which is shown as a formula (I). On one hand, the rigid framework structure of the condensed ring compound can be utilized to reduce the relaxation degree of the excited state structure, so that the narrower half-peak width is realized; on the other hand, the heavy atomic effect of selenium atoms or tellurium atoms is utilized to promote the cross-over between opposite systems, thereby obtaining the delayed fluorescence effect and realizing high luminous efficiency. Meanwhile, by changing the kind of the aromatic ring or the heteroaromatic ring contained in the condensed-cyclic compound, further adjustment of the delayed fluorescence lifetime and half-width can be achieved. Experimental results show that the luminescent compound disclosed by the invention is used as a luminescent layer of an electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized under the condition of no optical filter and microcavity structure, but also the high external quantum efficiency of the device can be realized. Experimental results show that the fused ring compound provided by the invention has the characteristics of TADF effect, high luminous efficiency and narrow luminous spectrum.

Description

Organic boron condensed ring compound containing branch molecular structure and organic electroluminescent device

Technical Field

The invention relates to the technical field of materials, in particular to an organic boron fused ring compound containing a branch molecular structure and an organic electroluminescent device.

Background

Organic Light Emitting Devices (OLEDs) have the characteristics of rich color, thin thickness, wide viewing angle, rapid response, and the like, and can be manufactured into flexible devices, which are considered to be the next generation flat panel display and solid lighting technologies that have the most promising development. In general, an OLED is composed of an 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, 1 to 2 organic layers may be omitted as needed, and an Exciton (Exciton) is formed by combining holes (Hole) injected from a positive electrode and a negative electrode on an organic thin film with electrons (electrons) and releases energy in a luminescence form when the Exciton returns to a stable ground state from an excited state to emit light. For OLED materials, the current commercial OLED display screens mostly adopt organic small molecule luminescent materials based on a vacuum evaporation process, and the devices of the materials have the defects of higher efficiency, low utilization rate, higher cost and the like. In contrast, organic electroluminescent materials that are solution processable (e.g., inkjet printing and roll-to-roll printing processes) have the advantages of reduced production costs and energy consumption, easy manufacture of large-sized displays, etc., but suffer from lower device efficiency.

Currently, the OLED luminescent materials used in the solution processing technology mainly include two kinds of polymer luminescent materials and dendritic luminescent materials. Among them, the polymer luminescent material has excellent solution processability, but has the disadvantages of difficult purification, poor batch stability, and the like. Compared with a high molecular luminescent material, the dendritic luminescent material is a luminescent material with a definite chemical structure, and the molecular size and the topological structure of the dendritic luminescent material can be precisely controlled in synthesis; meanwhile, the dendritic luminescent material also has good film forming performance and solution processing performance, and luminescent materials with different luminescent wavelengths can be obtained by selecting different central cores, different branch building units and different peripheral modification groups, so that the dendritic luminescent material is one of OLED material systems with development prospects.

On the other hand, the Thermal Activation Delayed Fluorescence (TADF) material is a new generation of organic luminescent material subsequent to the traditional fluorescent and phosphorescent materials, and the material generally has a small singlet-triplet energy level difference (Δe _ST), and the triplet excited state is transferred to the singlet excited state to emit fluorescence by using a thermal activation reverse intersystem crossing (RISC) process, so that the full utilization of the singlet and triplet excitons is realized, the internal quantum efficiency of 100% is realized, and the defect that the traditional fluorescent material can only realize the internal quantum efficiency of 25% is overcome.

At present, most dendritic thermal activation delay fluorescent materials adopt non-condensed ring units such as triphenyltriazine, diphenyl sulfone, benzophenone and the like as a central core, and the excited state structure of the dendritic thermal activation delay fluorescent materials is relatively strong in relaxation, so that the problems of relatively wide luminescence spectrum (half-peak width is generally 70-100nm, mater.chem.front.,2018,2,1097; J.Mater.chem.C,2016,4,2442; dye.Pigm.2016,133, 380386) and low color purity are caused.

Therefore, how to develop dendritic compounds with both TADF effect and high luminous efficiency and narrow luminous spectrum through reasonable chemical structural design, and solve the defects faced by the above materials has become one of the problems to be solved in the field of many prospective researchers.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide an organoboron fused ring compound having a dendron structure and an organic electroluminescent device. The fused ring compound provided by the invention has the characteristics of TADF effect, high luminous efficiency and narrow luminous spectrum.

The invention provides an organoboron fused ring compound containing a branch molecular structure, which is shown as a formula (I):

Wherein, X ₁、X₂、X₃ and X ₄ are independently selected from NR _a, O, S, se or Te; wherein R _a is selected from a substituted or unsubstituted C1-C30 straight chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 cycloalkyl group, an aromatic group having 6 to 60 carbon atoms, or a heteroaromatic group having 5 to 60 carbon atoms, the heteroatoms of the heteroaromatic group being independently selected from Si, ge, N, P, O, S or Se; or R _a is a single bond, -O-, -S- And/>Any one or more of which are linked to form a ring;

L ₁～L₄ is independently selected from H, D, F, cl, br, I, -CN, -O-R¹、-S-R¹、/>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 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; r ¹、R² and R ³ are each independently selected from H, D, F, cl, br, I, -OH, -SH, -NH ₂, substituted or unsubstituted C1-C30 straight-chain hydrocarbyl, substituted or unsubstituted C1-C30 branched-chain hydrocarbyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group; the hetero atoms in the heteroaromatic group are selected from one or more of Si, ge, N, P, O, S and Se; or R ¹、R² and R ³ are each independently selected from the group consisting of a single bond, -O-, -S-, and, And/>Is linked to form a ring;

a ₁ and a ₂ are integers of 1 to 4;

Representing a first generation of initial priming core units;

Representing an intermediate iteration unit;

representing the last generation of iteration units; wherein x corresponds to algebra of the iterative unit, and x is an integer of 2-3;

R _x is a substituent on the corresponding iteration unit, each independently selected from H, D, F, cl, br, I, -CN, -O-R¹、-S-R¹、/> 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 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; r ¹、R² and R ³ are each independently selected from H, D, F, cl, br, I, -OH, -SH, -NH ₂, substituted or unsubstituted C1-C30 straight-chain hydrocarbyl, substituted or unsubstituted C1-C30 branched-chain hydrocarbyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group; the hetero atoms in the heteroaromatic group are selected from one or more of Si, ge, N, P, O, S and Se; or R ¹、R² and R ³ are linked to each other by a single bond, -O-, -S-,/>And/>Is linked to form a ring;

n _x is the number of R _x, selected from integers from 1 to 6;

And/> Each independently selected from structures of formulae D-1 to D-43:

selected from a carbon-carbon single bond, a C1-C30 straight chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, or having the structure of formula SP-1-SP-21:

The invention provides an organoboron fused ring compound containing a branch molecular structure, which can utilize the rigid framework structure of the fused ring compound to reduce the relaxation degree of an excited state structure so as to realize narrower half-peak width; on the other hand, the heavy atomic effect of selenium atoms or tellurium atoms is utilized to promote the cross-over between opposite systems, thereby obtaining the delayed fluorescence effect and realizing high luminous efficiency. Meanwhile, by changing the kind of the aromatic ring or the heteroaromatic ring contained in the condensed-cyclic compound, further adjustment of the delayed fluorescence lifetime and half-width can be achieved. Experimental results show that the luminescent compound disclosed by the invention is used as a luminescent layer of an electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized under the condition of no optical filter and microcavity structure, but also the high external quantum efficiency of the device can be realized. Experimental results show that the condensed-cyclic compound provided by the invention has the characteristics of TADF effect, high luminous efficiency and narrow luminous spectrum.

Detailed Description

In one embodiment, R _a is selected from substituted or unsubstituted C1-C20 straight chain hydrocarbyl, substituted or unsubstituted C1-C20 branched hydrocarbyl, substituted or unsubstituted C1-C20 cycloalkyl, an aromatic group having 6 to 30 carbon atoms, or a heteroaromatic group having 5 to 30 carbon atoms, the heteroatoms of the heteroaromatic group being independently selected from Si, ge, N, P, O, S or Se; or R _a is selected from the group consisting of a single bond, -O-, -S-, a single bond, a ring attached to N, and a ring attached to N, And/>Any one or more of which are linked to form a ring;

In one embodiment, R _a is selected from a substituted or unsubstituted C1-C10 straight chain hydrocarbon group, a substituted or unsubstituted C1-C10 branched hydrocarbon group, a substituted or unsubstituted C1-C10 cycloalkyl group, an aromatic group having 6 to 10 carbon atoms, or a heteroaromatic group having 5 to 10 carbon atoms, the heteroatoms of the heteroaromatic group being independently selected from Si, ge, N, P, O, S or Se; or R _a is connected with N where it is located and benzene ring connected with N through single bond, -O-, And/>Any one or more of which are linked to form a ring.

In one embodiment, L ₁～L₄ is each independently selected from H, D, F, cl, br, I, -CN, -O-R¹、-S-R¹、/> 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 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; r ¹、R² and R ³ are each independently selected from H, D, F, cl, br, I, -OH, -SH, -NH ₂, substituted or unsubstituted C1-C30 straight-chain hydrocarbyl, substituted or unsubstituted C1-C30 branched-chain hydrocarbyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C5-C60 heteroaromatic group; the hetero atoms in the heteroaromatic group are selected from one or more of Si, ge, N, P, O, S and Se; or R ¹、R² and R ³ are linked to each other by a single bond, -O-, -S-,/> And/>Is linked to form a ring;

In one embodiment, L ₁～L₄ is independently selected from H, D, substituted or unsubstituted C1-C20 straight chain hydrocarbyl, substituted or unsubstituted C1-C20 branched hydrocarbyl, substituted or unsubstituted C1-C20 haloalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aromatic, substituted or unsubstituted C5-C60 heteroaromatic; each of R ¹、R² and R ³ is independently selected from H, a substituted or unsubstituted C1-C20 straight chain hydrocarbyl group, a substituted or unsubstituted C1-C20 branched chain hydrocarbyl group, a substituted or unsubstituted C1-C20 haloalkyl group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted C6-C30 aromatic group, a substituted or unsubstituted C5-C30 heteroaromatic group; or R ¹、R² and R ³ are each independently selected from the group consisting of a single bond, -O-, -S-, and, And/>Is linked to form a ring;

In one embodiment, L ₁～L₄ is independently selected from H, substituted or unsubstituted C1-C10 straight chain hydrocarbyl, substituted or unsubstituted C1-C10 branched hydrocarbyl, substituted or unsubstituted C1-C10 haloalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C10 aromatic, substituted or unsubstituted C5-C10 heteroaromatic; each of R ¹、R² and R ³ is independently selected from H substituted or unsubstituted C1-C10 straight chain hydrocarbyl, substituted or unsubstituted C1-C10 branched chain hydrocarbyl, substituted or unsubstituted C1-C30 haloalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C10 aromatic group, substituted or unsubstituted C5-C10 heteroaromatic group; or R ¹、R² and R ³ are each independently selected from the group consisting of a single bond, -O-, And/>Is linked in a ring.

In one embodiment, a ₁ and a ₂ are integers from 1 to 4; in one embodiment and, a ₁ and a ₂ are 1or 2.

Representing a first generation of initial priming core units;

Representing an intermediate iteration unit;

In one embodiment, R _x is selected from H, substituted or unsubstituted C1-C20 straight chain hydrocarbyl, substituted or unsubstituted C1-C20 branched chain hydrocarbyl, substituted or unsubstituted C1-C20 haloalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aromatic, substituted or unsubstituted C5-C30 heteroaromatic; each of R ¹、R² and R ³ is independently selected from H, a substituted or unsubstituted C1-C20 straight chain hydrocarbyl group, a substituted or unsubstituted C1-C20 branched chain hydrocarbyl group, a substituted or unsubstituted C1-C20 haloalkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C6-C30 aromatic group, a substituted or unsubstituted C5-C30 heteroaromatic group; or R ¹、R² and R ³ are each independently selected from the group consisting of a single bond, -O-, And/>Is linked in a ring.

In one embodiment, n _x is the number of R _x, selected from integers from 1 to 6; in one embodiment, n _x is selected from integers from 1 to 4.

In one embodiment of the present invention, in one embodiment,And/>Each independently selected from structures of formulae D-1 to D-43:

In one embodiment of the present invention, in one embodiment, Selected from a carbon-carbon single bond, a C1-C30 straight chain hydrocarbon group, a substituted or unsubstituted C1-C30 branched hydrocarbon group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, or having the structure of formula SP-1-SP-21:

In one embodiment, the Has the structure of the formula R-1 to the formula R-44:

/>

In one embodiment, the X ₁ is selected from N, S or Se; the X ₂ is selected from N, S, te or Se; the X ₃ is selected from N or S; the X ₄ is selected from N or S.

In one embodiment, the X ₁ is selected from N, S or Se; the X ₂ is selected from N, S, te or Se; the X ₃ and X ₄ are selected from N; or the X ₁ is selected from N, S or Se; the X ₂ is selected from N, S, te or Se; the X ₃ and X ₄ are selected from N.

In one embodiment, theHas the structure of formula R-3 or formula R-20.

Specifically, the dendritic fused ring compound has the structure of the formulas I-1 to I-43:

/>

The invention provides an organoboron condensed-cyclic compound containing a branch molecular structure, which can utilize the rigid framework structure of the condensed-cyclic compound to reduce the relaxation degree of an excited state structure so as to realize narrower half-peak width; on the other hand, the heavy atomic effect of selenium atoms or tellurium atoms is utilized to promote the cross-over between opposite systems, thereby obtaining the delayed fluorescence effect and realizing high luminous efficiency. Meanwhile, by changing the kind of the aromatic ring or the heteroaromatic ring contained in the condensed-cyclic compound, further adjustment of the delayed fluorescence lifetime and half-width can be achieved. Experimental results show that the luminescent compound disclosed by the invention is used as a luminescent layer of an electroluminescent device, so that not only can the narrow electroluminescent half-peak width be realized under the condition of no optical filter and microcavity structure, but also the high external quantum efficiency of the device can be realized. Experimental results show that the condensed-cyclic compound provided by the invention has the characteristics of TADF effect, high luminous efficiency and narrow luminous spectrum.

The preparation method of the fused ring compound is not particularly limited, and a typical preparation process is as follows:

and (3) reacting the compound shown in the formula (II) with the compound shown in the formula (III) in a solvent to obtain the condensed-cyclic compound shown in the formula (I).

Wherein Lu ₁、Lu₂、Lu₃ is each independently selected from hydrogen, halogen, hydroxy, mercapto, amino,/>

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

The structure of the organic electroluminescent device is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the application situation, quality requirements and product requirements by using a conventional organic electroluminescent device well known to the person skilled in the art, and the structure of the organic electroluminescent device preferably comprises: 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 to 0.7mm, more preferably 0.4 to 0.6mm; the choice of the substrate is not particularly limited and may be any substrate known to those skilled in the art for conventional organic electroluminescent devices, and may be chosen and adjusted by those skilled in the art according to the application, quality requirements and product requirements, and in the present invention, the substrate is preferably glass or plastic.

According to the present invention, the anode is preferably a material that facilitates hole injection, more preferably a conductive metal or conductive metal oxide, and still more preferably indium tin oxide.

The organic film layer can be one layer or a plurality of 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 comprises a condensed ring compound shown in the formula (I); the condensed-cyclic 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, 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 process of preparing 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 preferably, the present invention is prepared by using processes of vacuum evaporation, solution spin coating, solution doctor blading, inkjet printing, offset printing and three-dimensional printing.

In one embodiment, the organic thin film layer includes: the hole transport layer, the exciton blocking layer, the light emitting layer and the electron transport layer are sequentially laminated.

In one embodiment, the hole transport layer is formed of TAPC; the exciton blocking layer is formed of TCTA; the light-emitting layer is formed by a fused ring compound and SiMCP with the mass ratio of 1-2:8-9; the electron transport layer is formed of TmPyPB.

In one embodiment, the organic thin film layer includes: the hole transport layer, the light emitting layer, the hole blocking layer and the electron transport layer are sequentially stacked.

In one embodiment, the hole transport layer is formed by PEDOT: PSS, and the light emitting layer is formed by a fused ring compound and SiMCP < 2 > in a mass ratio of 1-2:8-9; the hole blocking layer is formed of TSPO 1; the electron transport layer is formed of TmPyPB.

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 on the anode, including a light emitting layer; 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 the materials of the organic electroluminescent device and the corresponding preferred principles of the preparation method of the invention can correspond to the corresponding materials and structures of the organic electroluminescent device and the corresponding preferred principles, and are not described in detail herein.

The present invention is not particularly limited in the manner of forming the anode on the substrate at first, and may be carried out according to methods well known to those skilled in the art. The present invention is not particularly limited in the manner of forming the light emitting layer and the organic thin film layers below and above the light emitting layer, and may be formed on the anode by vacuum evaporation, solution spin coating, solution knife coating, inkjet printing, offset printing, or three-dimensional printing. The present invention is not particularly limited as to the manner of forming the cathode after the organic layer is formed, and is preferably a method known to those skilled in the art, including but not limited to vacuum deposition, to prepare the cathode on the surface thereof.

In order to further illustrate the present invention, the following examples are provided to describe in detail an organoboron fused ring compound containing a dendron structure and an organic electroluminescent device.

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

Example 1

The chemical structure and synthetic route of I-1 are as follows:

1-1 ((3, 5-dichlorophenyl) -diphenylamine) (6.91 g,22 mmol) was added to a 50mL Schlenk flask under argon atmosphere, and N, N' -diphenyl-m-phenylenediamine (2.6g,10mmol),Pd₂(dba)₃(0.46g,0.5mmol),t-Bu₃PHBF₄(0.58g,2mmol),t-BuONa(3.84g,40mmol), was then injected with 20mL toluene and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to100 mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 1-2 (4.5 g, yield: 55%). Elemental analysis: theoretical value C,79.50; h,4.94; n,6.87; test value C,79.47; h,4.91; n,6.89. Matrix assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF (m/z)): theoretical value 814.3; experimental value 814.3 (M ⁺).

1-2 (0.82 G,1 mmol), boron triiodide (1.57 g,4 mmol) and dried o-dichlorobenzene (20 mL) were weighed out in a 100mL two-necked flask under argon atmosphere, and heated to 90℃for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (0.52 g,4 mmol) was added dropwise to the reaction system, after the completion of the addition, methylene chloride and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent and separated by column to give the product 1-3 (0.18 g, yield: 22%). Elemental analysis: theoretical value C,78.01; h,4.12; n,6.74; test value C,78.02; h,4.10; n,6.75.MALDI-TOF (m/z): theory 830.2; experimental 830.2 (m+).

Under argon atmosphere, 1-4 (1-4 was prepared according to the synthetic route described in Adv.Funct. Mater.2014,24,3413-3421, then 20mL of toluene was injected, reacted at 110℃for 24 hours, cooled to room temperature, extracted with deionized water and 100mL of methylene chloride, washed with deionized water several times, the organic phase was separated, and the dendrimer compound I-1 (1.03 g, yield: 26%) was obtained by column separation, desolvation, elemental analysis: theory C,86.46; H,6.65; N,6.35 test values C,86.47; H,6.61; N,6.39.MALDI-TOF (M/z): theory 3970.1; experimental 3970.1 (M+).

The photophysical properties of the condensed-cyclic compound prepared in example 1 of the present invention were examined, and the results are shown in Table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 1 of the present invention.

Example 2

The chemical structure and synthetic route of I-2 are as follows:

2-1 ((5-chloro-3-fluorophenyl) -diphenylamine) (2.98 g,10 mmol) m-bromophenol (1.73 g,10 mmol) and K ₂CO₃ (2.76 g,20 mmol) were weighed into a 500mL three-necked flask under argon atmosphere, 40mL DMF was added to the flask, the temperature was raised to 90℃and stirred under argon for reaction for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate and the organic phase obtained by filtration was freed from the solvent, and the crude product was isolated as a column to give the product 2-2 (2.9 g, yield: 65%). Elemental analysis: theoretical value C,63.95; h,3.80; n,3.11; test value C,63.91; h,3.77; n,3.14. Electrospray ionization mass spectrometry (ESI-MS): theoretical value 449.0; experimental value 449.0 (m+).

1-1 (3.1 G,10 mmol), aniline (1.0 g,11 mmol), pd ₂(dba)₃ (0.46 g,0.5 mmol), S-phos (0.58 g,2 mmol), t-Buona (1.92 g,20 mmol) were added to a 50mL Schlenk flask under argon, then 20mL toluene was injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 2-3 (3.2 g, yield: 45%). Elemental analysis: theoretical C,77.72; h,5.16; n,7.55; test value C,77.71; h,5.12; n,7.58.ESI-MS theoretical value 370.1; experimental value 370.1 (M ⁺).

2-2(4.5g,10mmol),2-3(3.7g,10mmol),Pd₂(dba)₃(0.46g,0.5mmol),S-phos(0.58g,2mmol),t-BuONa(1.92g,20mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated and the solvent was removed by column separation to give the product 2-4 (3.7 g, yield: 50%). Elemental analysis: theoretical C,77.83; h,4.76; n,5.67; test value C,77.80; h,4.72; n,5.69.MALDI-TOF (m/z): theory 739.2; experimental value 739.2 (M ⁺).

2-4 (0.74 G,1 mmol), boron triiodide (1.57 g,4 mmol) and dried o-dichlorobenzene (20 mL) were weighed out in a 100mL two-necked flask under argon atmosphere, and heated to 90℃for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (0.52 g,4 mmol) was added dropwise to the reaction system, after the completion of the addition, methylene chloride and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent and separated by column to give the product 2-5 (0.18 g, yield: 24%). Elemental analysis: theoretical value C,76.23; h,3.86; n,5.56; test value C,76.21; h,3.82; n,5.59.MALDI-TOF (m/z): theory 755.2; experimental value 755.2 (M ⁺).

1-4(1.77g,1.1mmol),2-5(0.76g,1mmol),Pd₂(dba)₃(46mg,0.05mmol),t-Bu₃PHBF₄(58mg,0.2mmol),t-BuONa(0.19g,2mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-2 (1.32 g, yield: 34%). Elemental analysis: theoretical value C,86.28; h,6.65; n,6.11; test value C,86.24; h,6.62; n,6.13.MALDI-TOF (m/z): theory 3895.1; experimental value 3895.1 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 2 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 2 of the present invention.

Example 3

The chemical structure and synthetic route of I-8 are as follows:

1-1 (3.1 g,10 mmol), N, N' -diphenyl-m-phenylenediamine (2.6 g,10 mmol), pd ₂(dba)₃ (0.46 g,0.5 mmol), S-phos (0.58 g,2 mmol), t-Buona (1.92 g,20 mmol) were added to a 50mL Schlenk flask under argon, then 20mL toluene was injected and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 3-1 (2.2 g, yield: 40%). Elemental analysis: theoretical value C,80.36; h,5.24; n,7.81; test value C,80.32; h,5.21; n,7.83.ESI-MS: theoretical value 537.2; experimental value 537.2 (M ⁺).

3-2 (1-Bromo-3-chloro-5-fluorobenzene) (2.98 g,10 mmol) was weighed in a 500mL three-necked flask under argon atmosphere, diphenyl ditelluride (1.73 g,10 mmol) and sodium borohydride (2.76 g,20 mmol) were slowly added dropwise into the flask, 40mL DMF was warmed to 90℃and stirred under argon for reaction for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate and the organic phase obtained by filtration was desolventized, and the crude product was isolated as 3-3 (2.4 g, 60% yield). Elemental analysis: theoretical value C,36.47; h,2.04; ; test value C,36.49; h,2.05; . ESI-MS: theoretical value 395.9; experimental value 395.9 (m+).

3-1(5.4g,10mmol),3-3(4.0g,10mmol),Pd₂(dba)₃(0.46g,0.5mmol),S-phos(0.58g,2mmol),t-BuONa(1.92g,20mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give 3-4 (4.3 g, yield: 51%). Elemental analysis: theoretical value C,67.64; h,4.14; n,4.93; test value C,67.62; h,4.12; n,4.95.MALDI-TOF (m/z): theory 853.1; experimental value 853.1 (M ⁺).

3-4 (0.85 G,1 mmol), boron triiodide (1.57 g,4 mmol) and dried o-dichlorobenzene (20 mL) were weighed out under argon atmosphere in a 100mL two-necked flask and heated to 90℃for reaction for 24 hours. The reaction was cooled to 0℃and N, N-diisopropylethylamine (0.52 g,4 mmol) was added dropwise to the reaction system, after the completion of the addition, methylene chloride and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the organic phase obtained by filtration was freed from the solvent and separated by column to give the product 3-5 (0.19 g, yield: 22%). Elemental analysis: theoretical value C,66.43; h,3.37; n,4.84; test value C,66.41; h,3.34; n,4.87.MALDI-TOF (m/z): theory 869.1; experimental value 869.1 (M ⁺).

1-4(1.77g,1.1mmol),3-5(0.87g,1mmol),Pd₂(dba)₃(46mg,0.05mmol),t-Bu₃PHBF₄(58mg,0.2mmol),t-BuONa(0.19g,2mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-8 (1.24 g, yield: 31%). Elemental analysis: theoretical value C,83.88; h,6.46; n,5.94; test value C,83.84; h,6.42; n,5.95.MALDI-TOF (m/z): theory 4009.0; experimental value 4009.0 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 3 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 3 of the present invention.

Example 4

The chemical structure and synthetic route of I-11 are as follows:

4-1 (2, 3-dibromo-5-chloro-1-fluorobenzene) (28.8 g,0.1 mol), diphenyl diselenide (15.7 g,0.05 mol) and sodium borohydride (3.8 g,0.10 mol) were weighed in a 500mL three-necked flask under argon atmosphere, 80mL DMF was slowly added dropwise to a bottle, heated to 90℃and reacted under argon atmosphere for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to obtain 4-2 (17.0 g, yield: 40%). Elemental analysis: theoretical value C,33.88; h,1.66; test value C,33.89; h,1.68.ESI-MS: theoretical value 423.8; experimental value 423.8 (m+).

4-2 (9.35 G,22 mmol) was added to a 50mL Schlenk flask under argon, N, N' -diphenyl-m-phenylenediamine (2.6g,10mmol),Pd₂(dba)₃(0.46g,0.5mmol),t-Bu₃PHBF₄(0.58g,2mmol),t-BuONa(3.84g,40mmol), was then injected with 20mL toluene and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give 4-3 (3.3 g, yield: 35%). Elemental analysis: theoretical value C,53.14; h,2.97; n,2.95; test value C,53.11; h,2.94; n,2.98.MALDI-TOF (m/z): theory 947.8; experimental value 947.8 (M ⁺).

4-3 (0.93 G,1 mmol) and dried o-xylene (20 mL) were weighed into a 250mL two-neck flask under argon atmosphere, butyl lithium solution (0.8 mL,2.5M,2 mmol) was added dropwise at-30℃and stirred for 2 hours at-30℃and boron tribromide (0.56 g,2.2 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (0.52 g,4 mmol) into the reaction system, and heating to 125 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 4-4 (0.16 g, yield: 20%) was obtained by column separation. Elemental analysis: theoretical value C,62.50; h,3.00; n,3.47; test value C,62.47; h,2.96; n,3.48.MALDI-TOF (m/z): theory 808.0; experimental value 808.0 (m+).

1-4(1.77g,1.1mmol),4-4(0.81g,1mmol),Pd₂(dba)₃(46mg,0.05mmol),t-Bu₃PHBF₄(58mg,0.2mmol),t-BuONa(0.19g,2mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-11 (1.18 g, yield: 30%). Elemental analysis: theoretical value C,83.34; h,6.43; n,5.68; test value C,83.31; h,6.42; n,5.69.MALDI-TOF (m/z): theory 3947.9; experimental value 3947.9 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 4 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 4 of the present invention.

Example 5

The chemical structure and synthetic route of I-13 are as follows:

5-1 (2-bromo-5-chloro-1, 3-difluorobenzene) (2.3 g,10 mmol), 3, 6-dimethylcarbazole (2.3 g,12 mmol), and Cs2CO3 (6.52 g,20 mol) were added to a 50mL Schlenk flask under argon atmosphere, 80mL DMF was taken and reacted at 120℃for 8 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 5-2 (2.1 g, yield: 45%). Elemental analysis: theoretical value C,59.65; h,3.50; n,3.48; test value C,59.62; h,3.48; n,3.47.ESI-MS: theoretical value 401.0; experimental value 401.0 (m+).

5-2 (8.8 G,22 mol), 3-hydroxy thiophenol (1.26 g,10 mol) and K2CO3 (5.53 g,40 mol) were weighed into a 500mL three-neck flask under argon atmosphere, 80mL DMF was added into the flask, the temperature was raised to 120℃and the reaction was stirred under argon protection for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated by column separation to give the product 5-3 (2.7 g, yield: 30%). Elemental analysis: theoretical value C,61.97; h,3.62; n,3.14; s,3.60; test value C,61.93; h,3.60; n,3.13; s,3.64.MALDI-TOF (m/z): theoretical value 888.0; experimental value 888.0 (m+).

5-3 (0.89 G,1 mmol) and dried o-xylene (20 mL) were weighed into a 250mL two-neck flask under argon atmosphere, a butyllithium solution (0.8 mL,2.5M,2 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃and then boron tribromide (0.56 g,2.2 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (0.52 g,4 mmol) into the reaction system, and heating to 125 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 5-4 (0.17 g, yield: 23%) was obtained by column separation. Elemental analysis: theoretical value C,73.73; h,3.77; n,3.74; s,4.28; test value C,73.71; h,3.73; n,3.75; s,4.29.MALDI-TOF (m/z): theory 748.1; experimental value 748.1 (m+).

1-4(1.77g,1.1mmol),5-4(0.75g,1mmol),Pd2(dba)3(46mg,0.05mmol),t-Bu3PHBF4(58mg,0.2mmol),t-BuONa(0.19g,2mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-13 (1.32 g, yield: 34%). Elemental analysis: theoretical value C,85.82; h,6.63; n,5.76; s,0.82; test value C,85.79; h,6.60; n,5.77; s,0.85.MALDI-TOF (m/z): theory 3888.0; experimental value 3888.0 (m+).

The photophysical properties of the condensed-cyclic compound prepared in example 5 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 5 of the present invention.

Example 6

The chemical structure and synthetic route of I-14 are as follows:

4-1 (2.9 g,10 mmol), acridine (2.5 g,12 mmol), pd2 (dba) 3 (92 mg,0.1 mmol), S-phos (164 mg,0.4 mmol), t-Buona (0.38 g,4 mmol) were added to a 50mL Schlenk flask under argon, then 20mL toluene was injected and reacted at 110℃for 8 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 6-1 (1.9 g, yield: 45%). Elemental analysis: theoretical value C,60.53; h,3.87; n,3.36; test value C,60.51; h,3.83; n,3.37.ESI-MS: theoretical value 415.0; experimental value 415.0 (m+).

Under argon atmosphere, 6-1 (9.1 g,22 mol), resorcinol (1.1 g,10 mol) and K ₂CO₃ (5.53 g,40 mol) were weighed into a 500mL three-necked flask, 80mL DMF was added into the flask, the temperature was raised to 90℃and the reaction was stirred for 8 hours under the protection of argon, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as a column to obtain the product 6-2 (3.4 g, yield: 38%). Elemental analysis: theoretical value C,63.81; h,4.02; n,3.10; test value C,63.80; h,4.03; n,3.11.MALDI-TOF (m/z): theoretical 900.0; experimental value 900.0 (M ⁺).

6-2 (0.9 G,1 mmol) and dried o-xylene (20 mL) were weighed into a 250mL two-neck flask under argon atmosphere, a butyllithium solution (0.8 mL,2.5M,2 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃and then boron tribromide (0.56 g,2.2 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (0.52 g,4 mmol) into the reaction system, and heating to 125 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 6-3 (0.16 g, yield: 21%) was obtained by column separation. Elemental analysis: theoretical value C,75.73; h,4.24; n,3.68; test value C,75.71; h,4.22; n,3.67.MALDI-TOF (m/z): theory 760.2; experimental value 760.2 (M ⁺).

1-4(1.77g,1.1mmol),6-3(0.76g,1mmol),Pd2(dba)3(46mg,0.05mmol),t-Bu3PHBF4(58mg,0.2mmol),t-BuONa(0.19g,2mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-14 (1.29 g, yield: 33%). Elemental analysis: theoretical value C,86.17; h,6.71; n,5.74; test value C,86.14; h,6.70; n,5.76.MALDI-TOF (m/z): theory 3900.1; experimental value 3900.1 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 6 of the present invention were examined, and the results are shown in Table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 6 of the present invention.

Example 7

The chemical structure and synthetic route of I-17 are as follows:

7-1 ((2-bromo-5-chloro-3-fluorophenyl) -diphenylamine) (8.3 g,22 mol), m-xylylene disulfide (1.4 g,10 mol) and K ₂CO₃ (5.53 g,40 mol) were weighed into a 500mL three-necked flask under argon atmosphere, 80mL DMF was added into the flask, the temperature was raised to 90℃and stirred under argon for reaction for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as 7-2 (3.4 g, yield: 40%). Elemental analysis: theoretical value C,58.96; h,3.30; n,3.27; s,7.50; test value C,58.92; h,3.27; n,3.29; s,7.52.MALDI-TOF (m/z): theoretical value 851.9; experimental value 851.9 (M ⁺).

7-2 (0.86 G,1 mmol) and dried o-xylene (20 mL) were weighed into a 250mL two-neck flask under argon atmosphere, a butyllithium solution (0.8 mL,2.5M,2 mmol) was dropwise added at-30℃and stirred for 2 hours at-30℃and then boron tribromide (0.56 g,2.2 mmol) was dropwise added to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (0.52 g,4 mmol) into the reaction system, and heating to 125 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 7-3 (0.14 g, yield: 20%) was obtained by column separation. Elemental analysis: theoretical value C,70.72; h,3.39; n,3.93; s,8.99; test value C,70.70; h,3.37; n,3.95; s,8.95.MALDI-TOF (m/z): theory 712.1; experimental value 712.1 (M ⁺).

1-4(1.77g,1.1mmol),7-3(0.71g,1mmol),Pd₂(dba)₃(46mg,0.05mmol),t-Bu₃PHBF₄(58mg,0.2mmol),t-BuONa(0.19g,2mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-17 (1.29 g, yield: 33%). Elemental analysis: theoretical value C,85.37; h,6.59; n,5.81; s,1.66; test value C,85.32; h,6.56; n,5.83; s,1.69.MALDI-TOF (m/z): theory 3852.0; experimental value 3852.0 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 7 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 7 of the present invention.

Example 8

The chemical structure and synthetic route of I-22 are as follows:

8-1 (2-bromo-5-chloro-3-fluoro-diphenyl sulfide) (7.0 g,22 mol) and K ₂CO₃ (5.53 g,40 mol) were weighed into a 500mL three-necked flask under argon atmosphere, 80mL DMF was added into the flask, the temperature was raised to 90℃and stirred under argon for reaction for 8 hours, then cooled to room temperature, the reaction solution was diluted with toluene and poured into water, the organic phase was separated, dried over anhydrous sodium sulfate, the solvent was removed from the organic phase obtained by filtration, and the crude product was isolated as 8-2 (2.9 g, yield: 40%). Elemental analysis: theoretical value C,48.86; h,2.46; s,17.39; test value C,48.84; h,2.41; s,17.37.MALDI-TOF (m/z): theoretical value 733.8; experimental value 733.8 (M ⁺).

8-2 (0.74 G,1 mmol) and dried o-xylene (20 mL) were weighed into a 250mL two-neck flask under argon atmosphere, a butyllithium solution (0.8 mL,2.5M,2 mmol) was added dropwise at-30℃and stirred for 2 hours at-30℃and then boron tribromide (0.56 g,2.2 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (0.52 g,4 mmol) into the reaction system, and heating to 125 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 8-3 (0.12 g, yield: 20%) was obtained by column separation. Elemental analysis: theoretical value C,60.54; h,2.37; s,21.55; test value C,60.54; h,2.37; s,21.55.MALDI-TOF (m/z): theory 593.9; experimental value 593.9 (M ⁺).

1-4(1.77g,1.1mmol),8-3(0.6g,1mmol),Pd₂(dba)₃(46mg,0.05mmol),t-Bu₃PHBF₄(58mg,0.2mmol),t-BuONa(0.19g,2mmol), Was added to a 50mL Schlenk flask and then 20mL toluene was injected under argon atmosphere and reacted at 110℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give fused ring compound I-22 (1.12 g, yield: 30%). Elemental analysis: theoretical value C,85.37; h,6.59; n,5.81; s,1.66; test value C,85.32; h,6.56; n,5.83; s,1.69.MALDI-TOF (m/z): theory 3852.0; experimental value 3852.0 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 8 of the present invention were examined, and the results are shown in Table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 8 of the present invention.

Example 9

The chemical structure and synthetic route of I-31 are as follows:

9-1 (N-phenylcarbazole-3-boronic acid) (5.7 g,21 mmol), 3, 6-dibromocarbazole (7.6 g,10 mmol), catalyst Pd ₂(dba)₃ (0.47 g,0.5 mmol) and ligand S-phos (0.82 g,2 mmol) were added to a 250mL three-necked flask under argon atmosphere, 80mL toluene was taken into a bottle, potassium carbonate (5.53 g,40 mmol) was dissolved in 20mL water, an aqueous solution of potassium carbonate was introduced into the bottle, the temperature was raised to 110℃under argon, the reaction was stirred for 16 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as 9-2 (2.6 g, yield: 40%). Elemental analysis: theoretical C,88.72; h,4.81; n,6.47; test value C,88.70; h,4.79; n,6.49.ESI-MS: theoretical value 649.2; experimental value 649.2 (M ⁺)

9-2 (2.6 G,4 mmol) was charged into a 100mL three-necked flask under argon atmosphere, and 1,3, 5-tribromobenzene (0.63g,2mmol),Pd₂(dba)₃(91mg,0.1mmol),t-Bu₃PHBF₄(116mg,0.4mmol),t-BuONa(0.38g,4mmol), was then injected into 50mL toluene for reaction at 110℃for 24 hours. Cooled to room temperature, deionized water and 100mL of methylene chloride were added to extract and separate the organic phase. Column separation and desolventizing gave the product 9-3 (1.1 g, yield: 38%). Elemental analysis: theoretical value C,84.34; h,4.37; n,5.79; test value C,84.32; h,4.36; n,5.78.MALDI-TOF (m/z): theoretical value 1450.4; experimental value 1450.4 (M ⁺)

1-3 (2.5 G,3 mmol) and the boronate ester (1.5 g,6 mmol) were weighed into a 100mL two-necked flask under argon atmosphere, pdCl ₂ (dppf) (0.11 g,0.15 mmol), potassium acetate (0.6 g,6 mmol) was added to the flask, 40mL DMF was taken and the temperature was raised to 85℃and stirred for 10 hours. Then cooled to room temperature, the reaction solution was washed with deionized water, extracted with methylene chloride solution to give an organic phase which was concentrated and dried, and the crude product was separated by column to give a product 9-4 (1.4 g, yield: 46%). Elemental analysis: theoretical value C,78.14; h,5.76; n,5.52; test value C,78.12; h,5.71; n,5.54.MALDI-TOF (m/z): theoretical 1014.5; experimental value 1014.5 (M ⁺)

9-3 (1.6 G,1.1 mmol), 9-4 (0.51 g,0.5 mmol), and the ligand Pd ₂(dba)₃ (46 mg,0.05 mmol) and the ligand S-phos (82 mg,0.2 mmol) were added to a 50mL Schlenk flask under an argon atmosphere, 20mL toluene was taken and dissolved in 1mL water, an aqueous potassium carbonate solution was introduced into the flask, the temperature was raised to 110℃and the reaction was stirred under argon for 24 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give dendrimer compound I-31 (0.61 g, yield: 35%). Elemental analysis: theoretical C,88.39; h,4.60; n,6.39; test value C,88.33; h,4.61; n,6.36.MALDI-TOF (m/z): theoretical value 3503.3; experimental value 3503.3 (M ⁺)

The photophysical properties of the condensed-cyclic compound prepared in example 9 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 9 of the present invention.

Example 10

The chemical structure and synthetic route of I-32 are as follows:

10-1 (1, 3-dibromo-2, 4-xylene) (2.64 g,10 mmol) aniline (2.0 g,22 mmol), pd2 (dba) 3 (0.46 g,0.5 mmol), BINAP (0.47 g,0.75 mmol), t-Buona (3.84 g,40 mmol) were added to a 50mL Schlenk flask under an argon atmosphere, followed by 20mL toluene and reaction at 110℃for 8 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 10-2 (1.6 g, yield: 56%). Elemental analysis: theoretical value C,83.30; h,6.99; n,9.71; test value C,83.29; h,6.93; n,9.72.MALDI-TOF (m/z): theory 288.2; experimental value 288.2 (m+).

10-2 (4.9 G,10 mmol), 2, 3-dibromo-5-chloro-4' -tert-butylthiophenyl benzene (9.6 g,22 mmol), pd2 (dba) 3 (0.46 g,0.5 mmol), S-phos (0.58 g,2 mmol), t-Buona (3.84 g,40 mmol) were added to a 50mL Schlenk flask under argon, then 20mL toluene was injected and reacted at 110℃for 8 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated, and the solvent was removed by column separation to give the product 10-3 (3.5 g, yield: 35%). Elemental analysis: theoretical value C,62.72; h,4.86; n,2.81; s,6.44; test value C,62.70; h,4.81; n,2.83; s,6.45.MALDI-TOF (m/z): theory 992.1; experimental 992.1 (m+).

10-3 (1.0 G,1 mmol) and dried o-xylene (20 mL) were weighed into a 250mL two-neck flask under argon atmosphere, a butyllithium solution (0.8 mL,2.5M,2 mmol) was added dropwise at-30℃and stirred for 2 hours at-30℃and then boron tribromide (0.56 g,2.2 mmol) was added dropwise to the system and stirred for 1 hour at room temperature after 20 minutes. Cooling to 0 ℃ again, dropwise adding N, N-diisopropylethylamine (0.52 g,4 mmol) into the reaction system, and heating to 125 ℃ for reaction for 20 hours after the dropwise addition is finished. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, the organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase obtained by filtration, and the product 10-4 (0.17 g, yield: 20%) was obtained by column separation. Elemental analysis: theoretical value C,73.17; h,5.20; n,3.28; s,7.51; test value C,73.15; h,5.19; n,3.27; s,7.52.MALDI-TOF (m/z): theory 852.2; experimental value 852.2 (M ⁺).

10-4 (2.5 G,3 mmol) and the boronate ester (1.5 g,6 mmol) were weighed into a 100mL two-necked flask under argon atmosphere, pdCl ₂ (dppf) (0.11 g,0.15 mmol), potassium acetate (0.6 g,6 mmol) was added to the flask, 40mL DMF was taken and the temperature was raised to 85℃and stirred for 10 hours. Then cooled to room temperature, the reaction solution was washed with deionized water, extracted with methylene chloride solution to give an organic phase which was concentrated and dried, and the crude product was separated by column to give a product 10-5 (1.6 g, yield: 51%). Elemental analysis: theoretical value C,74.15; h,6.61; n,2.70; s,6.19; test value C,74.12; h,6.60; n,2.72; s,6.16.MALDI-TOF (m/z): theoretical value 1036.5; experimental value 1036.5 (M ⁺)

10-6 (10-6 Prepared according to the synthetic route disclosed in Org. Lett.2018,20, 7864-7868) (1.3 g,1.1 mmol), 10-5 (0.52 g,0.5 mmol), the reagent Pd ₂(dba)₃ (46 mg,0.05 mmol) and the ligand S-phos (82 mg,0.2 mmol) were added to a 50mL Schlenk flask under an argon atmosphere, 20mL toluene was taken, potassium carbonate (0.27 g,2 mmol) was dissolved in 1mL water, an aqueous potassium carbonate solution was introduced into the flask, the temperature was raised to 110℃and stirred under argon for 24 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give dendrimer compound I-32 (0.54 g, yield: 35%). Elemental analysis: theoretical value C,90.84; h,5.45; n,0.91; s,2.09; test value C,90.83; h,5.41; n,0.92; s,2.07.MALDI-TOF (m/z): theoretical value 3065.3; experimental value 3065.3 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 10 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 10 of the present invention.

Example 11

The chemical structure and synthetic route of I-35 are as follows:

11-1 was prepared according to the synthetic route disclosed in literature polym.chem.,2015,6,1180-1191.

11-1 (2.64 G,1.1 mmol), 9-4 (0.51 g,0.5 mmol), the reagent Pd ₂(dba)₃ (46 mg,0.05 mmol) and the ligand S-phos (82 mg,0.2 mmol) were added to a 50mL Schlenk flask under an argon atmosphere, 20mL toluene was taken and dissolved in 1mL water, an aqueous potassium carbonate solution was introduced into the flask, the temperature was raised to 110℃and the reaction was stirred under argon for 24 hours, then cooled to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column separation to give dendrimer compound I-32 (1.02 g, yield: 38%). Elemental analysis: theoretical C,84.99; h,6.39; n,4.67; test value C,84.95; h,6.34; n,4.69.MALDI-TOF (m/z): theoretical value 5394.7; experimental value 5394.7 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 11 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 11 of the present invention.

Example 12

The chemical structure and synthetic route of I-36 are as follows:

1-3 (4.2 g,5 mmol) and sodium tert-butoxide (0.54 g,10 mmol) were weighed into a 50mL two-necked flask under argon atmosphere, 20mL DMF was taken and added to the flask, and the temperature was raised to 120℃for 16 hours. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated by column to give the product 12-1 (2.06 g, yield: 50%). Elemental analysis: theoretical C,81.77; h,4.90; n,6.81; test value C,81.75; h,4.89; n,6.83.MALDI-TOF (m/z): theoretical value 822.3; experimental value 822.3 ([ M ⁺ ]).

12-1 (1.64 G,2 mmol) and dried methylene chloride (30 mL) were weighed into a 50mL two-necked flask under argon atmosphere, boron tribromide (1.5 g,6 mmol) was added dropwise at 0℃and reacted at room temperature for 5 hours after the addition was completed. Pouring into water, separating out an organic phase, adding anhydrous sodium sulfate for drying, removing solvent from the organic phase obtained by filtration, and separating the crude product by a column to obtain a product 12-2 (0.95 g, yield: 60%). Elemental analysis: theoretical value C,81.63; h,4.57; n,7.05; test value C,81.61; h,4.53; n,7.06.MALDI-TOF (m/z): theoretical value 794.3; experimental value 794.3 ([ M ⁺ ]).

1-4 (3.2 G,2 mmol), dibromobutane (0.87 g,4 mmol) and anhydrous potassium carbonate (0.6 g,4 mmol) were added to a 100mL three-necked flask under argon atmosphere, 20mL DMF was taken and added to the flask, and the temperature was raised to 120℃for 16 hours. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as 12-3 (2.4 g, yield: 70%). Elemental analysis: theoretical value C,82.73; h,7.06; n,5.63 test value C,82.63; h,7.11; n,5.69.MALDI-TOF (m/z): theoretical value 1739.9; experimental value 1739.9 (M ⁺).

12-2 (0.4 G,0.5 mmol), 12-3 (1.74 g,1 mmol) and anhydrous potassium carbonate (0.28 g,2 mmol) were added to a 50mL two-necked flask under argon atmosphere, 10mL DMF was taken and added to the flask, and the temperature was raised to 120℃for 16 hours. The temperature was lowered to room temperature, the reaction solution was poured into water and the organic phase was separated by extraction with methylene chloride. The organic phase obtained by filtration was freed from the solvent by drying with the addition of anhydrous sodium sulfate, and the crude product was isolated as a column to give the product I-36 (0.93 g, yield: 45%). Elemental analysis: theoretical C,85.77; h,6.81; n,6.12; test value C,85.73; h,6.80; n,6.14.MALDI-TOF (m/z): theoretical value 4114.2; experimental value 4114.2 (M ⁺).

The photophysical properties of the condensed-cyclic compound prepared in example 12 of the present invention were examined, and the results are shown in table 1. Table 1 shows the photophysical properties of the condensed-cyclic compound prepared in example 12 of the present invention.

TABLE 1 photophysical Properties of fused Ring Compounds prepared according to the examples of the invention

Examples	Condensed ring compound	ΔE_ST(eV)	Delayed fluorescence lifetime (μs)
				1	I-1	0.18	70
2	I-2	0.16	72
				3	I-8	0.17	75
4	I-11	0.17	61
				5	I-13	0.15	57
6	I-14	0.13	56
				7	I-17	0.14	70
8	I-22	0.18	76
				9	I-31	0.16	47
10	I-32	0.18	53
				11	I-35	0.14	58
12	I-36	0.15	42

In Table 1, ΔE _ST is the difference between the singlet energy level and the triplet energy level, a sample to be measured was prepared by dissolving a compound in toluene solution at a concentration of 10: 10 ^-4 mol/L, and the difference between the initial (onset) values of the fluorescence spectrum and the phosphorescence spectrum was measured, and the test instrument was HORIBA FluoroMax spectrofluorometer (Japan); the delayed fluorescence lifetime was measured by doping a compound at a concentration of 1wt% in polystyrene to prepare a sample to be tested using a time resolved fluorescence spectrometer, test instrument Edinburgh fluorescence spectrometer (FLS-980, uk).

As can be seen from Table 1, the fused ring compounds in the examples provided herein have a small ΔE _ST (< 0.2 eV), exhibit a thermally activated delayed fluorescence effect, and have a delayed fluorescence lifetime of 42 to 76 μs.

Device instance

As device examples, the present invention provides two types of device structures (device structure a and device structure B) to prepare an organic electroluminescent device:

The device structure A is ITO/PEDOT, PSS (40 nm)/the dendritic fused ring compound (30 nm)/TSPO 1 (8 nm)/TmPyPB (30 nm)/LiF (0.8 nm)/Al (100 nm).

The steps for preparing the device by adopting the device structure A are as follows: poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT: PSS) was spin-coated on Indium Tin Oxide (ITO) supported on a glass substrate, annealed at 120 ℃ for 30 minutes, followed by spin-coating a toluene solution of the invented dendrimer compound at 1500rpm for 1 minute, and annealed at 80 ℃ for 30 minutes, and then sequentially depositing TSPO1, tmPyPB, and LiF/Al cathodes under a vacuum of 4×10 ^-4 Pa, to obtain an organic electroluminescent device, wherein TSPO1, tmPyPB serve as a hole blocking layer and an electron transport layer, respectively, and the structural formulae thereof are as follows:

the device structure B is ITO/PEDOT, PSS (40 nm)/a blend of the dendritic fused ring compound and a main material SiMCP (mass ratio is 1:9) (30 nm)/TSPO 1 (8 nm)/TmPyPB (42 nm)/LiF (1 nm)/Al (100 nm).

The steps for preparing the device by adopting the device structure B are 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, followed by spin-coating the inventive dendritic fused ring compound with SiMCP2 at a spin speed of 1500rpm in a mass ratio of 1:9, and annealing at 80 ℃ for 30 minutes, and then sequentially depositing TSPO1, tmPyPB and LiF/Al cathodes under a vacuum of 4×10 ^-4 Pa to obtain an organic electroluminescent device, wherein the structural formula of the host material SiMCP is as follows:

Examples 13 to 14

The fused ring compound was directly used as an organic light emitting layer, and an organic electroluminescent device was prepared using the structure described as "device structure a", and the obtained device was tested, with reference to table 2, and the performance parameters of the electroluminescent device prepared according to the present invention are provided in table 2, using I-1 in example 1 and I-17 in example 7, respectively, as an implementation object.

Examples 15 to 26

The fused ring compound and SiMCP2 are respectively taken as implementation targets of I-1 in example 1, I-2 in example 2, I-8 in example 3, I-11 in example 4, I-13 in example 5, I-14 in example 6, I-17 in example 7, I-22 in example 8, I-31 in example 9, I-32 in example 10, I-35 in example 11 and I-36 in example 12 according to a mass ratio of 1:9, mixing the materials to be used as an organic light-emitting layer, preparing an organic electroluminescent device by using the structure of the device structure B, and testing the obtained device.

Referring to table 2, table 2 provides the performance parameters of the electroluminescent devices prepared according to the present invention.

Comparative example 1

Taking a compound 2BNN without a dendritic structure as an implementation object, taking the 2BNN directly as an organic light-emitting layer, preparing an organic electroluminescent device by using the structure of a device structure A, testing the obtained device, and providing the performance parameters of the electroluminescent device prepared by the invention in the table 2 with reference to the results of the table 2.

Wherein, the chemical structure of 2BNN is as follows:

The synthesis method comprises the following steps: 1-3 (0.83 g,1 mmol), pd ₂(dba)₃ (92 mg,0.1 mmol), triphenyl phosphite (62 mg,0.2 mmol), t-Buona (0.19 g,4 mmol) were added to a 50mL Schlenk flask under argon, then 20mL isopropyl alcohol was injected and reacted at 80℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated and the product 2BNN was obtained by column separation (0.4 g, yield: 53%). Elemental analysis: theoretical value C,85.06; h,4.76; n,7.35; test value C,85.04; h,4.72; n,7.36.MALDI-TOF (m/z): theory 762.3; experimental value 762.3 (M ⁺).

Comparative example 2

Taking a compound 2BNS without a dendritic structure as an implementation object, taking the 2BNS directly as an organic light-emitting layer, preparing an organic electroluminescent device by using the structure of a device structure A, testing the obtained device, and providing the performance parameters of the electroluminescent device prepared by the invention in the table 2 with reference to the results of the table 2.

The chemical structure of 2BNS is:

The synthesis method comprises the following steps: 7-3 (0.71 g,1 mmol), pd ₂(dba)₃ (92 mg,0.1 mmol), triphenyl phosphite (62 mg,0.2 mmol), t-Buona (0.19 g,4 mmol) were added to a 50mL Schlenk flask under argon, then 20mL isopropyl alcohol was injected and reacted at 80℃for 24 hours. Cooling to room temperature, adding deionized water and dichloromethane to 100mL for extraction, and washing with deionized water for multiple times. The organic phase was separated and the product 2BNS (0.33 g, yield: 52%) was obtained by column separation. Elemental analysis: theoretical value C,78.28; h,4.07; n,4.35; s,9.95; test value C,78.25; h,4.05; n,4.37; s,9.92.MALDI-TOF (m/z): theory 644.2; experimental value 644.2 (M ⁺).

Comparative example 3

Taking a compound 2BNN which does not contain a dendritic structure as an implementation object, mixing 2BNN with SiMCP2 according to a mass ratio of 1:9 as an organic light emitting layer, an organic electroluminescent device was prepared using the structure described as "device structure B", and the resulting device was tested, and the results are shown in table 2, and the performance parameters of the electroluminescent device prepared according to the present invention are provided in table 2.

Comparative example 4

Taking compound 2BNS without dendritic structure as an implementation object, mixing 2BNS and SiMCP2 according to a mass ratio of 1:9 as an organic light emitting layer, an organic electroluminescent device was prepared using the structure described as "device structure B", and the resulting device was tested, and the results are shown in table 2, and the performance parameters of the electroluminescent device prepared according to the present invention are provided in table 2.

TABLE 2 Performance parameters of electroluminescent devices prepared according to the invention

In table 2, the turn-on voltage is the driving voltage of the device when the luminance is 1cd m ^-2; the maximum external quantum efficiency is obtained according to the current-voltage curve and the electroluminescence spectrum of the device and the calculation method described in the literature (Jpn.J.appl.Phys.2001, 40, L783); the half-width is the width of the peak at half the peak height of the electroluminescent spectrum at room temperature, i.e. the midpoint of the peak height is taken as a straight line parallel to the bottom of the peak, which straight line intersects the distance between the two points on both sides of the peak.

As can be seen from Table 2, the device prepared from the condensed-ring compound containing the dendron structure provided by the invention has very narrow electroluminescent spectrum, the half-peak width is smaller than 40nm, and the problem that the electroluminescent spectrum of the TADF compound with the traditional D-A structure is wider (70-100 nm) is solved; meanwhile, the maximum external quantum efficiency of the device is 16.2-23.9%, which is higher than that of a comparative compound (3.8-6.0%) without branch molecular structure.

The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims

1. An organoboron fused ring compound containing a dendron structure, as shown in formula (I):

Wherein, X ₁、X₂、X₃ and X ₄ are independently selected from NR _a, O, S, se or Te; wherein R _a is selected from aromatic groups having 6 to 10 carbon atoms; or R _a is connected with N and benzene ring of N through single bond, -O-and Any one or more of which are linked to form a ring;

L ₁～L₄ is independently selected from H, D, F, cl, br, I, -O-R ¹, C1-C10 straight-chain alkyl, C1-C10 branched-chain alkyl, C1-C10 halogenated alkyl; r ¹ is selected from C1-C10 straight-chain hydrocarbon groups;

a ₁ and a ₂ are integers of 1 to 4;

The said Has the structure of the formula R-1 to the formula R-44:

2. The dendritic fused ring compound of claim 1 wherein X ₁ is selected from N, S or Se; the X ₂ is selected from N, S, te or Se; the X ₃ is selected from N or S; the X ₄ is selected from N or S.

3. The dendritic fused ring compound of claim 2 wherein X ₁ is selected from N, S or Se; the X ₂ is selected from N, S, te or Se; the X ₃ and X ₄ are selected from N;

Or the X ₁ is selected from N, S or Se; the X ₂ is selected from N, S, te or Se; the X ₃ and X ₄ are selected from N.

4. The dendritic fused ring compound of claim 3 wherein the compound isHas the structure of formula R-3 or formula R-20.

5. The dendritic fused ring compound of claim 1, wherein the dendritic fused ring compound has the structure of formula I-1 to formula I-43:

6. 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 comprising the condensed cyclic compound according to any one of claims 1 to 5.

7. The organic electroluminescent device according to claim 6, wherein the organic thin film layer comprises a light emitting layer; the light-emitting layer comprising the condensed cyclic compound according to any one of claims 1 to 5.

8. The organic electroluminescent device according to claim 7, wherein the organic thin film layer comprises: the hole transport layer, the exciton blocking layer, the light emitting layer and the electron transport layer are sequentially laminated.

9. The organic electroluminescent device of claim 8, wherein the hole transport layer is formed of TAPC having the following structure:

the exciton blocking layer is formed of TCTA having the following structure:

The light-emitting layer is formed by a fused ring compound and SiMCP-9 parts by mass ratio of 1-2:8-9, and SiMCP is provided with the following structure:

the electron transport layer is formed from TmPyPB having the structure:

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