Organoboron compound containing benzoheterocycle functional unit and two boron atoms and application thereof

Abstract

The invention relates to the technical field of organic light-emitting materials, in particular to an organoboron compound containing a benzoheterocycle functional unit and two boron atoms and application of the organoboron compound. The organic boron compound has a structure as shown in a formula I or a formula II. A double-boron structure of a fused benzoheterocycle is adopted as a light emitting unit, on one hand, shearing vibration of molecules can be inhibited through the steric hindrance effect of benzoheterocycle, smaller half-peak width is obtained, HOMO and LUMO separation is achieved through the resonance effect of boron atoms and heteroatoms, and efficient TADF emission is obtained; on the other hand, the emission spectrum can be accurately adjusted by using the electron effect of the benzoheterocycle, the conjugation is expanded, the luminous efficiency is improved, and the organic electroluminescent device with narrower half-peak width and higher color purity is obtained. In addition, heavy atoms can be introduced by introducing benzoheterocycles, spin-orbit coupling is improved, and therefore the reverse intersystem crossing rate is increased, and efficiency roll-off is reduced. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of organic light-emitting materials, and particularly to an organoboron compound containing a benzheterocyclic functional unit and two boron atoms and its application. Background Art

[0002] Organic light-emitting devices (OLEDs) are generally composed of a cathode, an anode, and an organic layer inserted between the cathode and the anode. The mechanism is that a voltage is formed between the two electrodes, electrons are injected from the cathode, and holes are injected from the anode at the same time. The electrons and holes combine in the light-emitting layer to form an excited state, and the excited state radiates back to the ground state, thereby realizing device luminescence. Due to characteristics such as rich colors, fast response, and the ability to prepare flexible devices, organic electroluminescent materials are considered to be the most promising next-generation flat panel display and solid lighting materials.

[0003] Due to the limitation of the spin quantum statistical law, traditional fluorescent materials can only utilize singlet excitons accounting for 25% of all excitons during electroluminescence. The remaining 75% of triplet excitons are deactivated by non-radiative transitions, and the theoretical limit value of the internal quantum efficiency (IQE) of the device is 25%. In order to improve the exciton utilization rate, it is necessary to realize the utilization of triplet excitons. For example, phosphorescent metal complexes can convert triplet excitons into photons by using the spin-orbit coupling effect of heavy metal atoms to achieve 100% internal quantum efficiency, but this approach faces the problem of the high price of phosphorescent metal complexes. Another way to utilize triplet excitons is to develop luminescent materials with thermally activated delayed fluorescence (TADF) properties, and use the thermally activated reverse intersystem crossing (RISC) process to transfer triplet excited states to singlet excited states to emit fluorescence, thereby realizing the full utilization of singlet and triplet excitons. Molecules with TADF properties generally need to meet two conditions: a small singlet-triplet energy level difference (ΔE ST ) and a high fluorescence quantum efficiency (PLQY). On the one hand, a small ΔE ST (<0.3 eV) is conducive to the occurrence of thermally activated reverse intersystem crossing, thereby facilitating the improvement of the utilization efficiency of triplet excitons; on the other hand, the material must have a high PLQY to promote the decay of singlet excitons in the form of light and improve the device efficiency.

[0004] Currently, the main way to develop TADF molecules is to introduce donor (D) and acceptor (A) groups to effectively separate the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in space, thereby achieving a small ΔE STHowever, due to the vibrational relaxation of its excited state, this D-A structure exhibits a large Stokes shift, and its emission spectrum is relatively broad, with a full width at half maximum (FWHM) generally in the range of 70 - 100 nm. In practical applications, it is often necessary to use a filter or construct an optical microcavity to improve the color purity, but this will lead to a reduction in the external quantum efficiency of the device or a complication of the device structure.

[0005] Therefore, how to develop a fluorescent material that not only has the TADF effect but also has narrow spectral characteristics through appropriate chemical structure design to solve the defect of the relatively broad full width at half maximum of the above materials has become one of the urgent problems to be solved by researchers in this field. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide an organoboron compound containing a benzheterocyclic functional unit and two boron atoms and its application, and the prepared electroluminescent device has a narrow full width at half maximum and high color purity.

[0007] The present invention provides an organoboron compound containing a benzheterocyclic functional unit and two boron atoms, having the structure shown in Formula I or Formula II:

[0008]

[0009] Wherein, any one of Y1 and Y2 is selected from a single bond, and the other is selected from O, S, Se, Te, N(R a ), C(R a )2 or Si(R a )2;

[0010] Any one of Y1' and Y2' is selected from a single bond, and the other is selected from O, S, Se, Te, N(R a ), C(R a )2 or Si(R a )2;

[0011] The R a is selected from H, a substituted or unsubstituted straight-chain or branched alkyl group with 1 - C 30 , a substituted or unsubstituted cycloalkyl group with 3 - 30 carbon atoms, a substituted or unsubstituted aromatic group with 6 - C 60 , and a substituted or unsubstituted heteroaromatic group with 3 - C 60 ;

[0012] Wherein Ar1 - Ar8, Ar'1 - Ar'7 are independently selected from a substituted or unsubstituted aromatic ring group with 6 - C 60 , and a substituted or unsubstituted aromatic heterocyclic group with 3 - C 60 ;

[0013] Q1, Q2, Q1', Q2', R1 to R6, and R'1 to R'6 are each independently selected from H, deuterium, halogen, cyano, hydroxy, nitro, amino, substituted or unsubstituted C1-C 30 linear or branched hydrocarbon group, substituted or unsubstituted C3-C 30 cycloalkyl group, substituted or unsubstituted C6-C 60 aromatic group, substituted or unsubstituted C3-C 60 heteroaromatic group, or any one of the following groups:

[0014]

[0015] R 1 , R 2 and R 3 are each independently selected from H, substituted or unsubstituted C1-C 30 linear or branched hydrocarbon group, substituted or unsubstituted C3-C 30 cycloalkyl group, substituted or unsubstituted C6-C 60 aromatic group, substituted or unsubstituted C3-C 60 heteroaromatic group;

[0016] The heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, Se, and Te;

[0017] represents the connection position.

[0018] In the present invention, any one of Y1 and Y2 is selected from a single bond, and the other is selected from O, S, Se, Te, N(R a ), C(R a )2, or Si(R a )2. Preferably, any one of Y1 and Y2 is selected from a single bond, and the other is selected from O, S, Se, or Te. When Y1 or Y2 is a single bond, it means that Ar1 and Ar3, and Ar2 and Ar4 are connected by a single bond at the corresponding positions of Y1 or Y2.

[0019] When Y1 is a single bond, the organoboron compound has the structure shown in Formula II-1:

[0020]

[0021] When Y2 is a single bond, the organoboron compound has the structure shown in Formula II-2:

[0022]

[0023] In the present invention, any one of Y1' and Y2' is selected from a single bond, and the other is selected from O, S, Se, Te, N(R a)、C(R a )2 or Si(R a )2. Preferably, any one of Y1' and Y2' is selected from a single bond, and the other is selected from O, S, Se or Te. When Y1' or Y2' is a single bond, it means that Ar'1 and Ar'3 are connected by a single bond at the corresponding position of Y1' or Y2'.

[0024] When Y1' is a single bond, the organoboron compound has the structure shown in Formula I-1:

[0025]

[0026]

[0027] When Y2' is a single bond, the organoboron compound has the structure shown in Formula I-2:

[0028]

[0029] Preferably, the R a is selected from H, a straight-chain or branched-chain hydrocarbon group of substituted or unsubstituted C1-C 10 , a cycloalkyl group of substituted or unsubstituted C3-C6, an aromatic group of substituted or unsubstituted C6-C 14 , and a heteroaromatic group of substituted or unsubstituted C3-C 14 .

[0030] More preferably, the R a is selected from H, a straight-chain or branched-chain hydrocarbon group of substituted or unsubstituted C1-C6, a cycloalkyl group of substituted or unsubstituted C3-C6, an aromatic group of substituted or unsubstituted C6-C 10 , and a heteroaromatic group of substituted or unsubstituted C3-C 10 .

[0031] In the present invention, the hydrocarbon group includes an alkyl group, an alkenyl group, and an alkynyl group.

[0032] In some specific embodiments, the R a is selected from H, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, pyrrolyl, pyridyl, pyrimidinyl, etc.

[0033] The substitution is preferably substituted by any one or more of deuterium, halogen, nitro, hydroxyl, cyano, and amino.

[0034] The Ar1-Ar8, Ar'1-Ar'7 are independently selected from substituted or unsubstituted aromatic ring groups of C6-C 60 , substituted or unsubstituted C3-C 60aromatic heterocyclic group; preferably a substituted or unsubstituted C6-C 14 aromatic ring group, substituted or unsubstituted C3-C 14 aromatic heterocyclic group; more preferably a substituted or unsubstituted C6-C 10 aromatic ring group, substituted or unsubstituted C3-C 10 aromatic heterocyclic group.

[0035] In some specific embodiments, Ar1-Ar8, Ar'1-Ar'7 are independently selected from substituted or unsubstituted phenyl groups.

[0036] The substitution is by one or more of deuterium, halogen, cyano, hydroxy, nitro, amino, substituted or unsubstituted C1-C 10 linear or branched hydrocarbon group.

[0037] The hydrocarbon group includes alkyl, alkenyl and alkynyl.

[0038] Q1, Q2, Q1', Q2', R1-R6, R'1-R'6 are independently selected from H, deuterium, halogen, cyano, hydroxy, nitro, amino, substituted or unsubstituted C1-C 30 linear or branched hydrocarbon group, substituted or unsubstituted C3-C 30 cycloalkyl group, substituted or unsubstituted C6-C 60 aromatic group, substituted or unsubstituted C3-C 60 heteroaromatic group or any of the following groups:

[0039]

[0040] Preferably, the R 1 , R 2 and R 3 are each independently selected from H, substituted or unsubstituted C1-C 30 linear or branched hydrocarbon group, substituted or unsubstituted C3-C 30 cycloalkyl group, substituted or unsubstituted C6-C 60 aromatic group, substituted or unsubstituted C3-C 60 heteroaromatic group; more preferably, the R 1 , R 2 and R 3 are each independently selected from H, substituted or unsubstituted C1-C 10 linear or branched hydrocarbon group, substituted or unsubstituted C3-C6 cycloalkyl group, substituted or unsubstituted C6-C 14 aromatic group, substituted or unsubstituted C3-C 14 heteroaromatic group; further preferably, the R 1 , R2 and R 3 are each independently selected from H, a substituted or unsubstituted linear or branched C1-C6 hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C 10 aromatic group, a substituted or unsubstituted C3-C 10 heteroaromatic group; in some specific embodiments, the R 1 , R 2 and R 3 are each independently selected from H, a substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, pyrrolyl, pyridyl, pyrimidinyl, etc.

[0041] The substitution is preferably substituted by any one or more of deuterium, halogen, nitro, hydroxyl, cyano, and amino.

[0042] Preferably, the R1-R6, R'1-R'6 are independently selected from H, deuterium, halogen, cyano, hydroxyl, nitro, amino, a substituted or unsubstituted C1-C 10 linear or branched hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C 14 aromatic group. More preferably, the R1-R6, R'1-R'6 are independently selected from H, deuterium, halogen, cyano, hydroxyl, nitro, amino, a substituted or unsubstituted C1-C 10 linear or branched hydrocarbon group. Even more preferably, the R1-R6, R'1-R'6 are independently selected from H, deuterium, halogen, cyano, hydroxyl, nitro, amino, a substituted or unsubstituted C1-C6 linear or branched hydrocarbon group.

[0043] The hydrocarbon group includes alkyl, alkenyl, and alkynyl.

[0044] In some specific embodiments, the R1-R6, R'1-R'6 are independently selected from H, deuterium, halogen, cyano, hydroxyl, nitro, amino, a substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, etc.

[0045] The substitution is preferably substituted by any one or more of deuterium, halogen, nitro, hydroxyl, cyano, and amino.

[0046] In some specific embodiments, the organoboron compound has any one of the structures shown in formula (1-1) to formula (1-4), formula (2-1) to formula (2-4):

[0047]

[0048] The definitions of Y1, Y2, Q1, and Q2 are the same as those described above.

[0049] Preferably, Q1, Q2, Q1', and Q2' are independently selected from H, deuterium, halogen, cyano, hydroxy, nitro, amino, substituted or unsubstituted C1-C 10 linear or branched hydrocarbon groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C 14 aromatic groups, substituted or unsubstituted C5-C 14 heteroaromatic groups.

[0050] Preferably, the heteroaromatic group structure contains at least one N atom, and the N atom is connected to the parent nucleus.

[0051] Preferably, the heteroaromatic group is selected from any of the following structures:

[0052]

[0053] wherein, L1-L2 are each independently selected from H, deuterium, cyano, halogen, nitro, hydroxy, amino, substituted or unsubstituted C1-C 30 linear or branched hydrocarbon groups, substituted or unsubstituted C3-C 30 cycloalkyl groups, substituted or unsubstituted C6-C 60 aromatic groups, substituted or unsubstituted C3-C 60 heteroaromatic groups; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, Se, and Te.

[0054] Preferably, L1-L2 are each independently selected from H, deuterium, cyano, halogen, nitro, hydroxy, amino, substituted or unsubstituted C1-C 10 linear or branched hydrocarbon groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C 14 aromatic groups, substituted or unsubstituted C3-C 14 heteroaromatic groups; more preferably, L1-L2 are each independently selected from H, deuterium, cyano, halogen, nitro, hydroxy, amino, substituted or unsubstituted C1-C6 linear or branched hydrocarbon groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C 12 aromatic groups, substituted or unsubstituted C3-C 12 heteroaromatic groups.

[0055] In some specific embodiments, each of L1 to L2 is independently selected from H, deuterium, cyano, F, Cl, Br, I, nitro, hydroxy, amino, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, pyrrolyl, pyridyl, pyrimidinyl, carbazolyl, etc.

[0056] The substitution is preferably substituted by any one or more of deuterium, halogen, nitro, hydroxy, cyano, amino, carbazolyl, and tert-butyl-substituted carbazolyl.

[0057] In some specific embodiments, the organoboron compound has any of the following structures:

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] The present invention provides the application of the above-mentioned organoboron compound as an organic electroluminescent material.

[0079] The present invention also provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprises the above-mentioned organoboron compound.

[0080] The present invention does not particularly limit the structure of the organic electroluminescent device, and a conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to application scenarios, quality requirements, and product requirements. The structure of the organic electroluminescent device according to the present invention preferably comprises: a substrate; an anode provided on the substrate; an organic thin film layer provided on the anode; and a cathode provided on the organic thin film layer.

[0081] The thickness of the substrate is preferably 0.3 - 0.7 mm, more preferably 0.4 - 0.6 mm; the present invention does not particularly limit the selection of the substrate, and a substrate of a conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to application scenarios, quality requirements, and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0082] According to the present invention, the anode is preferably a material easy for hole injection, more preferably a conductive metal or a conductive metal oxide, and still more preferably indium tin oxide.

[0083] 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 comprises a light-emitting layer; the light-emitting layer comprises the above-mentioned organoboron compound; preferably, the organoboron compound provided by the present invention directly constitutes an organic electroluminescent layer as a light-emitting material.

[0084] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum, and silver, and preferably aluminum.

[0085] 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 present invention does not particularly limit 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, and they can be selected and adjusted according to the materials and thicknesses well-known to those skilled in the art. The present invention does not particularly limit 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 preferably vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography processes are used for preparation.

[0086] The present invention does not particularly limit the preparation method of the organic electroluminescent device, and it 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;

[0087] The light-emitting layer includes one or more of the above-mentioned organic boron compounds.

[0088] The present invention can correspond the structure and materials of the organic electroluminescent device in the above preparation method, as well as the corresponding preferred principles, to the corresponding materials and structures, and the corresponding preferred principles in the foregoing organic electroluminescent device, and will not be elaborated herein one by one.

[0089] The present invention first forms an anode on the substrate. The present invention does not particularly limit the formation method of the anode, and it can be carried out according to the method well-known to those skilled in the art. The present invention does not particularly limit the formation methods of the light-emitting layer and the organic thin film layers below and above the light-emitting layer, and they can be formed on the anode by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. After the organic layer is formed, a cathode is prepared on its surface. The present invention does not particularly limit the formation method of the cathode, and preferably it is the method well-known to those skilled in the art, including but not limited to vacuum deposition.

[0090] Compared with the prior art, the present invention uses a diboron structure of condensed benzheterocycle as the light-emitting unit. On the one hand, through the steric hindrance effect of the benzheterocycle, the shear vibration of the molecule can be inhibited, a smaller full width at half maximum can be obtained, and the separation of HOMO and LUMO can be achieved through the resonance effect between boron atoms and heteroatoms, obtaining efficient TADF emission; on the other hand, the emission spectrum can be precisely adjusted by using the electronic effect of the benzheterocycle, the conjugation can be expanded to improve the luminescence efficiency, and an organic electroluminescent device with a narrower full width at half maximum and higher color purity can be obtained. In addition, heavy atoms can be introduced by introducing benzheterocycles to enhance the spin-orbit coupling, thereby increasing the reverse intersystem crossing rate and reducing the efficiency roll-off. Detailed implementation mode

[0091] To further illustrate the present invention, it will be described in detail below in conjunction with embodiments. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the invention.

[0092] There are no special restrictions on the sources of all raw materials of the present invention, and they can be purchased on the market or prepared according to the conventional methods well-known to those skilled in the art.

[0093] Example 1

[0094] The reaction formula is as follows:

[0095]

[0096] Under an argon atmosphere, m-dibromobenzene (50.0 g, 212 mmol), 2,4,6-trimethylaniline (27.2 g, 423 mmol), tris(dibenzylideneacetone)dipalladium (1.94 g, 2.1 mmol), BINAP (1.98 g, 3.2 mmol), and sodium tert-butoxide (61.1 g, 636 mmol) were added to a 500 mL three-necked flask. 500 mL of toluene was added to the flask, and the temperature was raised to 100 °C and stirred for 5 hours. After cooling to room temperature, it was extracted with 500 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, anhydrous sodium sulfate was added for drying, and after the solvent was removed by vacuum distillation of the organic phase, the product 1-1 (63.4 g, yield: 87%) was obtained by silica gel column separation.

[0097] Elemental analysis structure (C24H28N2): theoretical value C, 83.68; H, 8.19; N, 8.13; measured value C, 83.69; H, 8.15; N, 8.11.

[0098] MALDI-TOF mass spectrometry: theoretical value 344.2; experimental value 344.2 (M + )

[0099] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), diphenylamine (12.8 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), and sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. Then, 200 mL of toluene was added to the flask, and the temperature was raised to 100 °C. The mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 1-2 (20.5 g, yield: 94%) was obtained by silica gel column chromatography.

[0100] Elemental Analysis: C, 60.28; H, 3.65; Br, 22.28; Cl, 9.88; N, 3.91

[0101] Elemental analysis of the structure (C18H13BrClN): Theoretical values: C, 60.28; H, 3.65; Br, 22.28; Cl, 9.88; N, 3.91. Measured values: C, 60.38; H, 3.62; N, 3.96.

[0102] MALDI-TOF mass spectrometry: Theoretical value 357.0; Experimental value 358.0 (M+1 + )

[0103] Under an argon atmosphere, 4-bromodibenzoselenophene (20.0 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), and sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask. Then, 100 mL of toluene was added to the flask, and the temperature was raised to 100 °C. The mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 100 mL of dichloromethane and washed three times with saturated brine (100 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 1-3 (21.7 g, yield: 92%) was obtained by silica gel column chromatography.

[0104] Elemental analysis of the structure (C21H19NSe): Theoretical values: C, 69.23; H, 5.26; N, 3.84; Se, 21.67. Measured values: C, 69.26; H, 5.21; N, 3.89.

[0105] MALDI-TOF mass spectrometry: Theoretical value 365.1; Experimental value 365.1 (M + )

[0106] Under argon atmosphere, 1-3 (20.0 g, 54.7 mmol), 1-2 (19.7 g, 54.7 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 1-4 (33.1 g, yield: 94%).

[0107] Elemental analysis structure (C39H31ClN2Se): theoretical value C, 72.95; H, 4.87; Cl, ​​5.52; N, 4.36; Se, 12.30 tested value C, 72.95; H, 4.90; Cl, ​​5.59; N, 4.32.

[0108] MALDI-TOF mass spectrum: theoretical value 642.1; experimental value 642.1 (M + )

[0109] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 54.7 mmol), 1-2 (19.7 g, 54.7 mmol), tri(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by vacuum distillation. The resulting solid was separated by silica gel column to obtain product 1-5 (25.5 g, yield: 95%).

[0110] Elemental analysis structure (C33H29ClN2): theoretical value C, 81.05; H, 5.98; Cl, ​​7.25; N, 5.73 tested value C, 81.02; H, 5.88; N, 5.93.

[0111] MALDI-TOF mass spectrum: theoretical value 488.2; experimental value 488.2 (M + )

[0112] Under an argon atmosphere, 1-5 (20.0 g, 41.0 mmol), 1-1 (16.9 g, 49.2 mmol), tris(dibenzylideneacetone)dipalladium (1.88 g, 2.0 mmol), SPhos (1.68 g, 4.1 mmol) and sodium tert-butoxide (5.9 g, 61.5 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 1-6 (23.8 g, yield: 73%).

[0113] Elemental analysis of structure (C57H56N4): Theoretical values C, 85.89; H, 7.08; N, 7.03. Measured values C, 85.81; H, 7.12; N, 7.09.

[0114] MALDI-TOF mass spectrum: Theoretical value 796.5; Experimental value 796.5 (M + )

[0115] Under an argon atmosphere, 1-6 (10.0 g, 12.5 mmol), 1-4 (9.7 g, 15.1 mmol), tris(dibenzylideneacetone)dipalladium (0.57 g, 0.6 mmol), SPhos (0.51 g, 4.1 mmol) and sodium tert-butoxide (1.8 g, 18.8 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 1-7 (12.0 g, yield: 68%).

[0116] Elemental analysis of structure (C96H86N6Se): Theoretical values C, 82.20; H, 6.18; N, 5.99; Se, 5.63. Measured values C, 82.15; H, 6.12; N, 6.03.

[0117] MALDI-TOF mass spectrum: Theoretical value 1402.6; Experimental value 1403.6 (M+1 + )

[0118] Under an argon atmosphere, 1-7 (5.0 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain product A1-3 (1.2 g, yield: 23%).

[0119] Elemental analysis of the structure (C96H80B2N6Se): Theoretical values: C, 81.30; H, 5.69; B, 1.52; N, 5.93; Se, 5.57. Measured values: C, 81.33; H, 5.62; N, 5.99.

[0120] MALDI-TOF mass spectrometry: Theoretical value 1418.6; Experimental value 1418.6 (M + )

[0121] The photophysical properties of the polycyclic compound prepared in Example 1 of the present invention were detected.

[0122] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0123] Example 2

[0124] The reaction formula is as follows:

[0125]

[0126] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), 3,6-di-tert-butylcarbazole (21.2 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. 200 mL of toluene was added to the flask, and the temperature was raised to 100 °C. The mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, anhydrous sodium sulfate was added for drying. After the solvent was removed from the organic phase by distillation under reduced pressure, product 2-1 (24.0 g, yield: 81%) was obtained by silica gel column chromatography.

[0127] Elemental analysis of the structure (C26H27BrClN): Theoretical values: C, 66.60; H, 5.80; Br, 17.04; Cl, 7.56; N, 2.99. Measured values: C, 66.53; H, 5.72; N, 2.93.

[0128] MALDI-TOF mass spectrometry: Theoretical value 467.1; Experimental value 467.1 (M+ ).

[0129] Under argon atmosphere, 4-bromodibenzothiophene (17.0 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask, 100 mL of toluene was added to the flask, the temperature was raised to 100 ° C, the reaction was stirred for 5 hours, and after cooling to room temperature, 100 mL of dichloromethane was used for extraction, and the mixture was washed three times with saturated brine (100 mL×3). The organic phase was separated and dried over anhydrous sodium sulfate. The organic phase was distilled under reduced pressure to remove the solvent, and the product 2-2 (19.0 g, yield: 93%) was obtained by silica gel column separation.

[0130] Elemental analysis structure (C21H19NS): theoretical value C, 79.46; H, 6.03; N, 4.41; S, 10.10 tested value C, 79.48; H, 6.01; N, 4.45; S, 10.13.

[0131] MALDI-TOF mass spectrum: theoretical value 317.1; experimental value 317.1 (M + )

[0132] Under argon atmosphere, 2-2 (20.0 g, 63.1 mmol), 2-1 (29.6 g, 63.1 mmol), tris(dibenzylideneacetone)dipalladium (0.58 g, 0.6 mmol), tri-tert-butylphosphine tetrafluoroborate (0.75 g, 2.5 mmol) and sodium tert-butoxide (9.1 g, 94.6 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 2-3 (42.3 g, yield: 95%).

[0133] Elemental analysis structure (C47H45ClN2S): theoretical value C, 80.03; H, 6.43; Cl, ​​5.03; N, 3.97; S, 4.54 tested value C, 80.13; H, 6.48; N, 3.91; S, 4.52.

[0134] MALDI-TOF mass spectrum: theoretical value 704.3; experimental value 705.3 (M+1 + )

[0135] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 54.7 mmol), 2-1 (25.8 g, 54.7 mmol), tri(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 2-4 (30.3 g, yield: 92%).

[0136] Elemental analysis structure (C41H43ClN2): Theoretical value C, 82.18; H, 7.23; Cl, ​​5.92; N, 4.67 Measured value C, 82.11; H, 7.28; N, 4.62.

[0137] MALDI-TOF mass spectrum: theoretical value 598.3; experimental value 598.3 (M + )

[0138] Under argon atmosphere, 2-4 (10.0 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butylate (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 2-5 (11.2 g, yield: 74%).

[0139] Elemental analysis structure (C66H71N3): Theoretical value C, 87.47; H, 7.90; N, 4.64 Test value C, 87.41; H, 7.92; N, 4.68.

[0140] MALDI-TOF mass spectrum: theoretical value 905.6; experimental value 905.6 (M + )

[0141] Under an argon atmosphere, 2-5 (11.3 g, 12.5 mmol), 2-3 (10.6 g, 15.1 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.57 g, 0.6 mmol), SPhos (0.51 g, 1.2 mmol) and sodium tert-butoxide (1.8 g, 18.8 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by vacuum distillation, the obtained solid was separated by silica gel column chromatography to obtain product 2-6 (12.4 g, yield: 63%).

[0142] Elemental analysis of structure (C112H114N6S): Theoretical values: C, 85.34; H, 7.29; N, 5.33; S, 2.03. Measured values: C, 85.30; H, 7.35; N, 5.31; S, 2.01.

[0143] MALDI-TOF mass spectrum: Theoretical value 1574.9; Experimental value 1574.9 (M + )

[0144] Under an argon atmosphere, 2-6 (5.6 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The obtained solid was separated by silica gel column chromatography to obtain product A4-2 (1.0 g, yield: 19%).

[0145] Elemental analysis of structure (C112H108B2N6S): Theoretical values: C, 84.51; H, 6.84; N, 5.28; S, 2.01. Measured values: C, 84.54; H, 6.81; N, 5.26; S, 2.01.

[0146] MALDI-TOF mass spectrum: Theoretical value 1590.9; Experimental value 1590.9 (M + )

[0147] The photophysical properties of the polycyclic compound prepared in Example 2 of the present invention were detected.

[0148] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0149] Example 3

[0150] The reaction formula is as follows:

[0151]

[0152] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), phenothiazine (15.1 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), and sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. Then, 200 mL of toluene was added to the flask. The temperature was raised to 100 °C and the mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 3-1 (22.2 g, yield: 90%) was obtained by silica column chromatography.

[0153] Elemental analysis of structure (C18H11BrClNS): Theoretical values: C, 55.62; H, 2.85; Br, 20.56; Cl, 9.12; N, 3.60; S, 8.25. Measured values: C, 55.55; H, 2.75; N, 3.66; S, 8.20.

[0154] MALDI-TOF mass spectrum: Theoretical value 386.9; Experimental value 386.9 (M + )

[0155] Under an argon atmosphere, 4-bromodibenzotellurophene (23.2 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), and sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask. Then, 100 mL of toluene was added to the flask. The temperature was raised to 100 °C and the mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 100 mL of dichloromethane and washed three times with saturated brine (100 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 3-2 (20.2 g, yield: 76%) was obtained by silica column chromatography.

[0156] Elemental analysis of structure (C21H19NTe): Theoretical values: C, 61.07; H, 4.64; N, 3.39; Te, 30.90. Measured values: C, 61.01; H, 4.69; N, 3.31.

[0157] MALDI-TOF mass spectrum: Theoretical value 415.1; Experimental value 415.1 (M + )

[0158] Under argon atmosphere, 3-2 (20.0 g, 48.4 mmol), 3-1 (18.8 g, 48.4 mmol), tris(dibenzylideneacetone)dipalladium (0.44 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.28 g, 1.9 mmol) and sodium tert-butoxide (7.0 g, 72.6 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain the product 3-3 (33.9 g, yield: 97%).

[0159] Elemental analysis structure (C39H29ClN2STe): theoretical value C, 64.99; H, 4.06; Cl, ​​4.92; N, 3.89; S, 4.45; Te, 17.70 tested value C, 64.92; H, 4.01; N, 3.84; S, 4.41.

[0160] MALDI-TOF mass spectrum: theoretical value 722.1; experimental value 722.1 (M)

[0161] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 54.7 mmol), 3-1 (21.4 g, 54.7 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by vacuum distillation. The resulting solid was separated by silica gel column to obtain product 3-4 (25.7 g, yield: 90%).

[0162] Elemental analysis structure (C41H43ClN2): Theoretical value C, 82.18; H, 7.23; Cl, ​​5.92; N, 4.67 Measured value C, 82.11; H, 7.28; N, 4.62.

[0163] MALDI-TOF mass spectrum: theoretical value 598.3; experimental value 598.3 (M + )

[0164] Under an argon atmosphere, 3-4 (8.7 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butoxide (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 3-5 (10.8 g, yield: 78%).

[0165] Elemental analysis of structure (C57H54N4S): theoretical values C, 82.77; H, 6.58; N, 6.77; S, 3.88; measured values C, 82.74; H, 6.55; N, 6.79; S, 3.91.

[0166] MALDI-TOF mass spectrometry: theoretical value 826.4; experimental value 827.4 (M+1 + )

[0167] Under an argon atmosphere, 3-5 (10.0 g, 12.1 mmol), 3-3 (10.5 g, 14.5 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.55 g, 0.6 mmol), SPhos (0.50 g, 1.2 mmol) and sodium tert-butoxide (1.7 g, 18.8 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 3-6 (10.0 g, yield: 55%).

[0168] Elemental analysis of structure (C96H82N6S2Te): theoretical values C, 76.29; H, 5.47; N, 5.56; S, 4.24; Te, 8.44; measured values C, 76.26; H, 5.45; N, 5.52; S, 4.28.

[0169] MALDI-TOF mass spectrometry: theoretical value 1512.5; experimental value 1512.5 (M + )

[0170] Under an argon atmosphere, 3-6 (5.4 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column chromatography to obtain product A10-4 (0.6 g, yield: 12%).

[0171] Elemental analysis of the structure (C96H76B2N6S2Te): theoretical values C, 75.51; H, 5.02; B, 1.42; N, 5.50; S, 4.20; Te, 8.36; measured values C, 75.53; H, 5.01; N, 5.54; S, 4.26.

[0172] MALDI-TOF mass spectrometry: theoretical value 1528.5; experimental value 1528.5 (M + )

[0173] The photophysical properties of the polycyclic compound prepared in Example 3 of the present invention were detected.

[0174] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0175] Example 4

[0176] The reaction formula is as follows:

[0177]

[0178] Under an argon atmosphere, 1-bromodibenzofuran (15.9 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask. 100 mL of toluene was added to the flask. The temperature was raised to 100 °C and the reaction was stirred for 5 hours. After cooling to room temperature, it was extracted with 100 mL of dichloromethane and washed three times with saturated brine (100 mL × 3). The organic phase was separated, anhydrous sodium sulfate was added for drying. After the solvent was removed from the organic phase by distillation under reduced pressure, product 4-1 (17.1 g, yield: 88%) was obtained by silica gel column chromatography.

[0179] Elemental analysis of the structure (C21H19NO): theoretical values C, 83.69; H, 6.35; N, 4.65; O, 5.31; measured values C, 83.62; H, 6.31; N, 4.75; O, 5.32.

[0180] MALDI-TOF mass spectrum: theoretical value 301.1; experimental value 301.1 (M + )

[0181] Under argon atmosphere, 4-1 (20.0 g, 66.4 mmol), 1-2 (23.9 g, 66.4 mmol), tris(dibenzylideneacetone)dipalladium (0.61 g, 0.7 mmol), tri-tert-butylphosphine tetrafluoroborate (0.79 g, 2.7 mmol) and sodium tert-butoxide (9.6 g, 99.7 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 4-2 (36.9 g, yield: 96%).

[0182] Elemental analysis structure (C39H31ClN2O): theoretical value C, 80.88; H, 5.40; Cl, ​​6.12; N, 4.84; O, 2.76 tested value C, 80.82; H, 5.42; N, 4.88; O, 2.75.

[0183] MALDI-TOF mass spectrum: theoretical value 578.2; experimental value 578.2 (M)

[0184] Under argon atmosphere, 4-2 (10.0 g, 17.3 mmol), 1-6 (16.5 g, 20.8 mmol), tris(dibenzylideneacetone)dipalladium (0.79 g, 0.9 mmol), SPhos (0.71 g, 17.3 mmol) and sodium tert-butylate (2.5 g, 26.0 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of ether and washed three times with saturated brine (100 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 4-3 (13.2 g, yield: 59%).

[0185] Elemental analysis structure (C96H86N6O): theoretical value C, 86.06; H, 6.47; N, 6.27; O, 1.19 tested value C, 86.01; H, 6.52; N, 6.21; O, 1.12.

[0186] MALDI-TOF mass spectrum: theoretical value 1338.7; experimental value 1339.7 (M+1 + )

[0187] Under an argon atmosphere, 4-3 (4.8 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 170 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain product B1-1 (1.3 g, yield: 25%).

[0188] Elemental analysis of the structure (C96H80B2N6O): Theoretical values: C, 85.07; H, 5.95; B, 1.60; N, 6.20; O, 1.18. Measured values: C, 85.09; H, 5.90; N, 6.25; O, 1.12.

[0189] MALDI-TOF mass spectrometry: Theoretical value 1354.7; Experimental value 1354.7 (M + ).

[0190] The photophysical properties of the polycyclic compound prepared in Example 4 of the present invention were detected.

[0191] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0192] Example 5

[0193] The reaction formula is as follows:

[0194]

[0195] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), 9,9-dimethyl-9,10-dihydroacridine (15.9 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. 200 mL of toluene was added to the flask. The temperature was raised to 100 °C and the mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, anhydrous sodium sulfate was added for drying. After the solvent was removed from the organic phase by distillation under reduced pressure, the product 5-1 (23.0 g, yield: 91%) was obtained by silica gel column chromatography.

[0196] Elemental analysis of the structure (C21H17BrClN): Theoretical values: C, 63.26; H, 4.30; Br, 20.04; Cl, 8.89; N, 3.51. Measured values: C, 63.36; H, 4.33; N, 3.59.

[0197] MALDI-TOF mass spectrum: theoretical value 397.0; experimental value 397.0 (M + ).

[0198] Under argon atmosphere, 1-bromodibenzothiophene (17.0 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask, 100 mL of toluene was added to the flask, the temperature was raised to 100 ° C, the reaction was stirred for 5 hours, and after cooling to room temperature, 100 mL of dichloromethane was used for extraction, and the mixture was washed three times with saturated brine (100 mL×3), the organic phase was separated, and anhydrous sodium sulfate was added to dry the organic phase. After the solvent was removed by distillation under reduced pressure, the product 5-2 (17.2 g, yield: 84%) was obtained by silica gel column separation.

[0199] Elemental analysis structure (C21H19NS): theoretical value C, 79.46; H, 6.03; N, 4.41; S, 10.10 tested value C, 79.41; H, 6.02; N, 4.23; S, 10.54.

[0200] MALDI-TOF mass spectrum: theoretical value 317.1; experimental value 317.1 (M + )

[0201] Under argon atmosphere, 5-2 (20.0 g, 63.0 mmol), 5-1 (25.1 g, 63.0 mmol), tris(dibenzylideneacetone)dipalladium (0.58 g, 0.6 mmol), tri-tert-butylphosphine tetrafluoroborate (0.75 g, 2.5 mmol) and sodium tert-butoxide (9.1 g, 94.5 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 5-3 (37.2 g, yield: 93%).

[0202] Elemental analysis structure (C42H35ClN2S): theoretical value C, 79.41; H, 5.55; Cl, ​​5.58; N, 4.41; S, 5.05 tested value C, 79.38; H, 5.51; N, 4.31; S, 5.25.

[0203] MALDI-TOF mass spectrum: theoretical value 634.2; experimental value 634.2 (M)

[0204] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 54.7 mmol), 5-1 (21.9 g, 54.7 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by vacuum distillation. The resulting solid was separated by silica gel column to obtain product 5-4 (25.7 g, yield: 90%).

[0205] Elemental analysis structure (C41H43ClN2): Theoretical value C, 82.18; H, 7.23; Cl, ​​5.92; N, 4.67 Measured value C, 82.11; H, 7.28; N, 4.62.

[0206] MALDI-TOF mass spectrum: theoretical value 598.3; experimental value 598.3 (M + )

[0207] Under argon atmosphere, 5-4 (8.8 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butylate (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 5-5 (10.0 g, yield: 72%).

[0208] Elemental analysis structure (C60H60N4): Theoretical value C, 86.08; H, 7.22; N, 6.69 Test value C, 86.18; H, 7.28; N, 6.61.

[0209] MALDI-TOF mass spectrum: theoretical value 836.5; experimental value 836.5 (M + )

[0210] Under an argon atmosphere, 5-3 (10.0 g, 15.7 mmol), 5-5 (15.8 g, 18.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.72 g, 0.8 mmol), SPhos (0.64 g, 1.6 mmol) and sodium tert-butoxide (2.3 g, 23.6 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain the product 5-6 (14.7 g, yield: 65%).

[0211] Elemental analysis of the structure (C102H94N6S): theoretical values C, 85.32; H, 6.60; N, 5.85; S, 2.23; measured values C, 85.30; H, 6.66; N, 5.82; S, 2.25.

[0212] MALDI-TOF mass spectrum: theoretical value 1434.7; experimental value 1434.7 (M + )

[0213] Under an argon atmosphere, 5-6 (5.1 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 170 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain the product B7-2 (1.4 g, yield: 28%).

[0214] Elemental analysis of the structure (C102H88B2N6S): theoretical values C, 84.40; H, 6.11; B, 1.49; N, 5.79; S, 2.21; measured values C, 84.32; H, 6.15; N, 5.71; S, 2.25.

[0215] MALDI-TOF mass spectrum: theoretical value 1450.7; experimental value 1450.7 (M + )

[0216] The photophysical properties of the polycyclic compound prepared in Example 5 of the present invention were detected.

[0217] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0218] Example 6

[0219] The reaction formula is as follows:

[0220]

[0221] Under argon atmosphere, 4-1 (20.0 g, 66.4 mmol), 3-chloro-5-bromotoluene (13.6 g, 66.4 mmol), tri(dibenzylideneacetone)dipalladium (0.58 g, 0.6 mmol), tri-tert-butylphosphine tetrafluoroborate (0.75 g, 2.5 mmol) and sodium tert-butoxide (9.1 g, 94.5 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 6-2 (26.9 g, yield: 95%).

[0222] Elemental analysis structure (C28H24ClNO): theoretical value C, 78.95; H, 5.68; Cl, ​​8.32; N, 3.29; O, 3.76 tested value C, 78.91; H, 5.88; Cl, ​​8.12; N, 3.45; O, 3.71.

[0223] MALDI-TOF mass spectrum: theoretical value 425.2; experimental value 425.2 (M + )

[0224] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 54.7 mmol), 3-chloro-5-bromotoluene (11.3 g, 54.7 mmol), tri(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 6-3 (16.6 g, yield: 90%).

[0225] Elemental analysis structure (C41H43ClN2): Theoretical value C, 82.18; H, 7.23; Cl, ​​5.92; N, 4.67 Measured value C, 82.11; H, 7.28; N, 4.62.

[0226] MALDI-TOF mass spectrum: theoretical value 598.3; experimental value 598.3 (M + )

[0227] Under an argon atmosphere, 6-3 (5.6 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butoxide (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the resulting solid was separated by silica gel column chromatography to obtain the product 6-4 (8.7 g, yield: 81%).

[0228] Elemental analysis of the structure (C46H49N3): theoretical values C, 85.80; H, 7.67; N, 6.53; measured values C, 85.81; H, 7.37; N, 6.76.

[0229] MALDI-TOF mass spectrum: theoretical value 643.4; experimental value 643.4 (M + )

[0230] Under an argon atmosphere, 6-4 (10.0 g, 15.5 mmol), 6-2 (7.7 g, 18.6 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.71 g, 0.8 mmol), SPhos (0.64 g, 1.6 mmol) and sodium tert-butoxide (2.2 g, 23.3 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the resulting solid was separated by silica gel column chromatography to obtain the product 6-5 (12.2 g, yield: 76%).

[0231] Elemental analysis of the structure (C74H72N4O): theoretical values C, 86.01; H, 7.02; N, 5.42; O, 1.55; measured values C, 86.06; H, 7.08; N, 5.45; O, 1.51.

[0232] MALDI-TOF mass spectrum: theoretical value 1032.6; experimental value 1032.6 (M + )

[0233] Under an argon atmosphere, 6-5 (3.7 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain product B13-1 (1.2 g, yield: 31%).

[0234] Elemental analysis of structure (C74H66B2N4O): Theoretical values: C, 84.73; H, 6.34; B, 2.06; N, 5.34; O, 1.53. Measured values: C, 84.73; H, 6.34; N, 5.34; O, 1.53.

[0235] MALDI-TOF mass spectrum: Theoretical value 1048.5; Experimental value 1048.5 (M + )

[0236] The photophysical properties of the polycyclic compound prepared in Example 6 of the present invention were detected.

[0237] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0238] Example 7

[0239] The reaction formula is as follows:

[0240]

[0241] Under an argon atmosphere, 2-bromodibenzothiophene (17.0 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask. 100 mL of toluene was added to the flask, and the temperature was raised to 100 °C and stirred for 5 hours. After cooling to room temperature, it was extracted with 100 mL of dichloromethane and washed three times with saturated brine (100 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the organic phase by distillation under reduced pressure. The product 7-1 (17.4 g, yield: 85%) was obtained by silica gel column chromatography.

[0242] Elemental analysis of structure (C21H19NS): Theoretical values: C, 79.46; H, 6.03; N, 4.41; S, 10.10. Measured values: C, 79.91; H, 6.62; N, 4.21; S, 10.58.

[0243] MALDI-TOF mass spectrum: Theoretical value 317.1; Experimental value 317.1 (M+ )

[0244] Under argon atmosphere, 7-1 (20.0 g, 63.1 mmol), 1-2 (22.6 g, 63.1 mmol), tris(dibenzylideneacetone)dipalladium (0.61 g, 0.7 mmol), tri-tert-butylphosphine tetrafluoroborate (0.79 g, 2.7 mmol) and sodium tert-butoxide (9.6 g, 99.7 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 7-2 (36.4 g, yield: 97).

[0245] Elemental analysis structure (C39H31ClN2S): theoretical value C, 78.70; H, 5.25; Cl, ​​5.96; N, 4.71; S, 5.39 tested value C, 78.60; H, 5.37; N, 4.77; S, 5.32.

[0246] MALDI-TOF mass spectrum: theoretical value 594.2; experimental value 595.2 (M+1 + )

[0247] Under argon atmosphere, 7-2 (10.0 g, 15.5 mmol), 1-6 (14.9 g, 18.6 mmol), tris(dibenzylideneacetone)dipalladium (0.71 g, 0.8 mmol), SPhos (0.64 g, 23.3 mmol) and sodium tert-butylate (2.2 g, 23.3 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of ether and washed three times with saturated brine (100 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 7-3 (16.8 g, yield: 80%).

[0248] Elemental analysis structure (C96H86N6S): theoretical value C, 85.04; H, 6.39; N, 6.20; S, 2.36 tested value C, 85.00; H, 6.35; N, 6.50; S, 2.31.

[0249] MALDI-TOF mass spectrum: theoretical value 1354.7; experimental value 1354.7 (M + )

[0250] Under an argon atmosphere, 7-3 (4.8 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain product C1-2 (1.4 g, yield: 28%).

[0251] Elemental analysis of structure (C96H80B2N6S): Theoretical values: C, 84.08; H, 5.88; B, 1.58; N, 6.13; S, 2.34. Measured values: C, 84.00; H, 5.28; N, 6.43; S, 2.31.

[0252] MALDI-TOF mass spectrometry: Theoretical value 1370.6; Experimental value 1370.6 (M + ).

[0253] The photophysical properties of the polycyclic compound prepared in Example 7 of the present invention were detected.

[0254] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0255] Example 8

[0256] The reaction formula is as follows:

[0257]

[0258] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), 1,3,6,8-tetramethylcarbazole (16.9 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. 200 mL of toluene was added to the flask, and the temperature was raised to 100 °C. The mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent was removed from the organic phase by distillation under reduced pressure. The product 8-1 (21.7 g, yield: 83%) was obtained by silica gel column chromatography.

[0259] Elemental analysis of structure (C22H19BrClN): Theoretical values: C, 64.02; H, 4.64; Br, 19.36; Cl, 8.59; N, 3.39. Measured values: C, 64.04; H, 4.61; N, 3.39.

[0260] MALDI-TOF mass spectrum: theoretical value 411.0; experimental value 411.0 (M + ).

[0261] Under argon atmosphere, 2-bromodibenzotellurphene (27.3 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask, 100 mL of toluene was added to the flask, the temperature was raised to 100 ° C, the reaction was stirred for 5 hours, and after cooling to room temperature, 100 mL of dichloromethane was used for extraction, and the mixture was washed three times with saturated brine (100 mL×3), the organic phase was separated, and anhydrous sodium sulfate was added to dry the organic phase. After the solvent was removed by distillation under reduced pressure, the product 8-2 (19.7 g, yield: 74%) was obtained by silica gel column separation.

[0262] Elemental analysis structure (C21H19NTe): theoretical value C, 61.07; H, 4.64; N, 3.39; Te, 30.90 tested value C, 61.06; H, 4.68; N, 3.32.

[0263] MALDI-TOF mass spectrum: theoretical value 415.1; experimental value 415.1 (M + )

[0264] Under argon atmosphere, 8-2 (20.0 g, 48.2 mmol), 8-1 (20.0 g, 48.2 mmol), tris(dibenzylideneacetone)dipalladium (0.44 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.57 g, 1.9 mmol) and sodium tert-butoxide (6.9 g, 72.3 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 8-3 (29.8 g, yield: 83%).

[0265] Elemental analysis structure (C43H37ClN2Te): theoretical value C, 69.34; H, 5.01; Cl, ​​4.76; N, 3.76; Te, 17.13 tested value C, 69.36; H, 5.07; N, 3.71.

[0266] MALDI-TOF mass spectrum: theoretical value 746.2; experimental value 746.2 (M)

[0267] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 54.7 mmol), 8-1 (22.7 g, 54.7 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 8-4 (24.7 g, yield: 83%).

[0268] Elemental analysis structure (C37H35ClN2): Theoretical value C, 81.82; H, 6.50; Cl, ​​6.53; N, 5.16 Measured value C, 81.86; H, 6.53; N, 5.11.

[0269] MALDI-TOF mass spectrum: theoretical value 542.2; experimental value 542.2 (M + )

[0270] Under argon atmosphere, 8-4 (9.0 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butylate (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 8-5 (10.0 g, yield: 72%).

[0271] Elemental analysis structure (C60H60N4): Theoretical value C, 86.08; H, 7.22; N, 6.69 Test value C, 86.18; H, 7.28; N, 6.61.

[0272] MALDI-TOF mass spectrum: theoretical value 836.5; experimental value 836.5 (M + )

[0273] Under an argon atmosphere, 8-3 (10.0 g, 15.7 mmol), 8-5 (10.5 g, 18.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.54 g, 0.6 mmol), SPhos (0.48 g, 1.2 mmol) and sodium tert-butoxide (1.7 g, 17.6 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added for drying. After removing the solvent by vacuum distillation, the obtained solid was separated by silica gel column chromatography to obtain the product 8-6 (7.5 g, yield: 41%).

[0274] Elemental analysis of the structure (C104H98N6Te): Theoretical values: C, 80.10; H, 6.33; N, 5.39; Te, 8.18. Measured values: C, 80.17; H, 6.37; N, 5.33.

[0275] MALDI-TOF mass spectrometry: Theoretical value 1560.7; Experimental value 1561.7 (M + 1 + )

[0276] Under an argon atmosphere, 8-6 (5.6 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation, and the obtained solid was separated by silica gel column chromatography to obtain the product C5-4 (0.6 g, yield: 11%).

[0277] Elemental analysis of the structure (C104H92B2N6Te): Theoretical values: C, 79.30; H, 5.89; B, 1.37; N, 5.34; Te, 8.10. Measured values: C, 79.56; H, 5.82; N, 5.37.

[0278] MALDI-TOF mass spectrometry: Theoretical value 1576.7; Experimental value 1576.7 (M + )

[0279] The photophysical properties of the polycyclic compounds prepared in Example 8 of the present invention were detected.

[0280] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0281] Example 9

[0282] The reaction formula is as follows:

[0283]

[0284] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), phenoselenazine (18.7 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), and sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. Then 200 mL of toluene was added to the flask. The temperature was raised to 100 °C and the mixture was stirred and reacted for 5 hours. After cooling to room temperature, the mixture was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 9-1 (20.1 g, yield: 87%) was obtained by silica gel column chromatography.

[0285] Elemental analysis of structure (C18H11BrClNSe): Theoretical values: C, 49.63; H, 2.55; Br, 18.34; Cl, 8.14; N, 3.22; Se, 18.13. Measured values: C, 49.61; H, 2.53; N, 3.27.

[0286] MALDI-TOF mass spectrum: Theoretical value 434.9; Experimental value 434.9 (M + )

[0287] Under an argon atmosphere, 2-bromodibenzoselenophene (23.0 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), and sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask. Then 100 mL of toluene was added to the flask. The temperature was raised to 100 °C and the mixture was stirred and reacted for 5 hours. After cooling to room temperature, the mixture was extracted with 100 mL of dichloromethane and washed three times with saturated brine (100 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 9-2 (20.7 g, yield: 88%) was obtained by silica gel column chromatography.

[0288] Elemental analysis of structure (C39H29ClN2Se2): Theoretical values: C, 65.14; H, 4.07; Cl, 4.93; N, 3.90; Se, 21.96. Measured values: C, 64.99; H, 4.01; N, 3.95.

[0289] MALDI-TOF mass spectrum: Theoretical value 720.0; Experimental value 720.0 (M + )

[0290] Under argon atmosphere, 9-2 (20.0 g, 45.8 mmol), 9-1 (20.0 g, 45.8 mmol), tris(dibenzylideneacetone)dipalladium (0.42 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.55 g, 1.9 mmol) and sodium tert-butoxide (6.6 g, 68.9 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 9-3 (30.0 g, yield: 83%).

[0291] Elemental analysis structure (C39H29ClN2Se2): theoretical value C, 65.14; H, 4.07; Cl, ​​4.93; N, 3.90; Se, 21.96 tested value C, 65.10; H, 4.32; N, 3.66.

[0292] MALDI-TOF mass spectrum: theoretical value 720.0; experimental value 720.0 (M)

[0293] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 54.7 mmol), 9-1 (22.7 g, 54.7 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 9-4 (27.1 g, yield: 87%).

[0294] Elemental analysis structure (C33H27ClN2Se): theoretical value C, 70.03; H, 4.81; Cl, ​​6.26; N, 4.95; Se, 13.95 tested value C, 70.08; H, 4.73; N, 4.91.

[0295] MALDI-TOF mass spectrum: theoretical value 566.1; experimental value 567.1 (M+1 + )

[0296] Under an argon atmosphere, 9-4 (9.4 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butoxide (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 9-5 (10.7 g, yield: 73%).

[0297] Elemental analysis of structure (C57H54N4Se): Theoretical values C, 78.33; H, 6.23; N, 6.41; Se, 9.03. Measured values C, 78.31; H, 6.25; N, 6.44.

[0298] MALDI-TOF mass spectrometry: Theoretical value 874.4; Experimental value 874.4 (M + )

[0299] Under an argon atmosphere, 9-3 (10.0 g, 13.9 mmol), 9-5 (14.6 g, 16.7 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.64 g, 0.7 mmol), SPhos (0.57 g, 1.4 mmol) and sodium tert-butoxide (2.0 g, 20.9 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 9-6 (12.4 g, yield: 57%).

[0300] Elemental analysis of structure (C96H82N6Se3): Theoretical values C, 74.07; H, 5.31; N, 5.40; Se, 15.22. Measured values C, 74.01; H, 5.38; N, 5.24.

[0301] MALDI-TOF mass spectrometry: Theoretical value 1558.4; Experimental value 1558.4 (M + )

[0302] Under an argon atmosphere, 9-6 (5.5 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the resulting solid was separated by silica gel column chromatography to obtain product C11-3 (0.9 g, yield: 16%).

[0303] Elemental analysis of the structure (C96H76B2N6Se3): Theoretical values: C, 73.34; H, 4.87; B, 1.38; N, 5.35; Se, 15.07. Measured values: C, 73.38; H, 4.83; N, 5.31;

[0304] MALDI-TOF mass spectrometry: Theoretical value 1574.4; Experimental value 1574.4 (M + ).

[0305] The photophysical properties of the polycyclic compound prepared in Example 9 of the present invention were detected.

[0306] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0307] Example 10

[0308] The reaction formula is as follows:

[0309]

[0310] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), 3,3',5,5'-tetramethyldiphenylamine (17.1 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. 200 mL of toluene was added to the flask, and the temperature was raised to 100 °C and stirred for 5 hours. After cooling to room temperature, it was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure from the organic phase. The product 10-1 (23.9 g, yield: 91%) was obtained by silica gel column chromatography.

[0311] Elemental analysis of the structure (C22H21BrClN): Theoretical values: C, 63.71; H, 5.10; Br, 19.26; Cl, 8.55; N, 3.38. Measured values: C, 63.64; H, 5.11; N, 3.39.

[0312] MALDI-TOF mass spectrum: theoretical value 413.1; experimental value 413.1 (M + ).

[0313] Under argon atmosphere, 3-bromodibenzofuran (15.9 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask, 100 mL of toluene was added to the flask, the temperature was raised to 100 ° C, the reaction was stirred for 5 hours, and after cooling to room temperature, 100 mL of dichloromethane was used for extraction, and the mixture was washed three times with saturated brine (100 mL×3). The organic phase was separated and dried over anhydrous sodium sulfate. The organic phase was distilled under reduced pressure to remove the solvent, and the product 10-2 (17.1 g, yield: 88%) was obtained by silica gel column separation.

[0314] Elemental analysis structure (C21H19NO): theoretical value C, 83.69; H, 6.35; N, 4.65; O, 5.31 tested value C, 83.60; H, 6.27; N, 4.72; O, 5.37.

[0315] MALDI-TOF mass spectrum: theoretical value 301.1; experimental value 301.1 (M + )

[0316] Under argon atmosphere, 10-2 (20.0 g, 54.9 mmol), 10-1 (20.0 g, 54.9 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.4 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain the product 10-3 (32.4 g, yield: 93%).

[0317] Elemental analysis structure (C43H39ClN2O): theoretical value C, 81.30; H, 6.19; Cl, ​​5.58; N, 4.41; O, 2.52 tested value C, 81.35; H, 6.12; N, 4.41; O, 2.51.

[0318] MALDI-TOF mass spectrum: theoretical value 634.3; experimental value 634.3 (M)

[0319] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 55.0 mmol), 10-1 (22.8 g, 55.0 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain the product 10-4 (25.4 g, yield: 85%).

[0320] Elemental analysis structure (C37H37ClN2): theoretical value C, 81.52; H, 6.84; Cl, ​​6.50; N, 5.14 tested value C, 81.51; H, 6.86; N, 5.10.

[0321] MALDI-TOF mass spectrum: theoretical value 544.3; experimental value 544.3 (M+ + )

[0322] Under argon atmosphere, 10-4 (9.1 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butylate (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain the product 10-5 (11.4 g, yield: 80%).

[0323] Elemental analysis structure (C61H64N4): Theoretical value C, 85.87; H, 7.56; N, 6.57 Test value C, 85.89; H, 7.51; N, 6.55.

[0324] MALDI-TOF mass spectrum: theoretical value 852.5; experimental value 852.5 (M + )

[0325] Under an argon atmosphere, 10-3 (10.0 g, 15.7 mmol), 10-5 (16.1 g, 18.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.72 g, 0.8 mmol), SPhos (0.64 g, 1.6 mmol) and sodium tert-butoxide (2.3 g, 23.6 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added for drying. After the solvent was removed by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 10-6 (14.2 g, yield: 62%).

[0326] Elemental analysis of structure (C104H102N6O): theoretical values C, 86.03; H, 7.08; N, 5.79; O, 1.10; measured values C, 86.06; H, 7.01; N, 5.83; O, 1.16.

[0327] MALDI-TOF mass spectrometry: theoretical value 1450.8; experimental value 1450.8 (M + )

[0328] Under an argon atmosphere, 10-6 (5.2 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain product D2-1 (1.1 g, yield: 21%).

[0329] Elemental analysis of structure (C104H96B2N6O): theoretical values C, 85.12; H, 6.59; B, 1.47; N, 5.73; O, 1.09; measured values C, 85.03; H, 6.66; N, 5.71; O, 1.03.

[0330] MALDI-TOF mass spectrometry: theoretical value 1466.8; experimental value 1466.8 (M + )

[0331] The photophysical properties of the polycyclic compound prepared in Example 10 of the present invention were detected.

[0332] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0333] Example 11

[0334] The reaction formula is as follows:

[0335]

[0336] Under an argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), 9,9-diphenyl-9,10-dihydroacridine (25.3 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), and sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask. 200 mL of toluene was added to the flask, and the temperature was raised to 100 °C. The mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 200 mL of dichloromethane and washed three times with saturated brine (500 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 11-1 (31.1 g, yield: 94%) was obtained by silica gel column chromatography.

[0337] Elemental analysis of the structure (C31H21BrClN): theoretical values C, 71.21; H, 4.05; Br, 15.28; Cl, 6.78; N, 2.68; measured values C, 71.12; H, 4.25; N, 2.61.

[0338] MALDI-TOF mass spectrometry: theoretical value 521.1; experimental value 521.1 (M + )

[0339] Under an argon atmosphere, 3-bromodibenzoselenophene (20.0 g, 64.5 mmol), 2,4,6-trimethylaniline (8.7 g, 64.5 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.59 g, 0.65 mmol), BINAP (0.63 g, 0.97 mmol), and sodium tert-butoxide (9.3 g, 96.8 mmol) were added to a 500 mL three-necked flask. 100 mL of toluene was added to the flask, and the temperature was raised to 100 °C. The mixture was stirred and reacted for 5 hours. After cooling to room temperature, it was extracted with 100 mL of dichloromethane and washed three times with saturated brine (100 mL × 3). The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The product 11-2 (20.9 g, yield: 89%) was obtained by silica gel column chromatography.

[0340] Elemental analysis of the structure (C21H19NSe): theoretical values C, 69.23; H, 5.26; N, 3.84; Se, 21.67; measured values C, 69.21; H, 5.28; N, 3.83.

[0341] MALDI-TOF mass spectrometry: theoretical value 365.1; experimental value 365.1 (M + )

[0342] Under argon atmosphere, 11-2 (20.0 g, 54.9 mmol), 11-1 (28.7 g, 54.9 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.4 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain the product 11-3 (40.7 g, yield: 93%).

[0343] Elemental analysis structure (C52H39ClN2Se): theoretical value C, 77.46; H, 4.88; Cl, ​​4.40; N, 3.47; Se, 9.79 tested value C, 77.48; H, 4.89; N, 3.41.

[0344] MALDI-TOF mass spectrum: theoretical value 806.2; experimental value 806.2 (M + )

[0345] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 55.0 mmol), 11-1 (28.8 g, 55.0 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain the product 11-4 (32.3 g, yield: 90%).

[0346] Elemental analysis structure (C46H37ClN2): Theoretical value C, 84.58; H, 5.71; Cl, ​​5.43; N, 4.29 Measured value C, 84.55; H, 5.73; N, 4.27.

[0347] MALDI-TOF mass spectrum: theoretical value 652.3; experimental value 652.3 (M + )

[0348] Under an argon atmosphere, 11-4 (10.9 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butoxide (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 11-5 (12.8 g, yield: 80%).

[0349] Elemental analysis of structure (C70H64N4): Theoretical values C, 87.46; H, 6.71; N, 5.83. Measured values C, 87.42; H, 6.68; N, 5.81.

[0350] MALDI-TOF mass spectrum: Theoretical value 960.5; Experimental value 960.5 (M + )

[0351] Under an argon atmosphere, 11-3 (10.0 g, 12.4 mmol), 11-5 (14.3 g, 14.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.57 g, 0.6 mmol), SPhos (0.51 g, 1.2 mmol) and sodium tert-butoxide (1.8 g, 18.6 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 11-6 (12.2 g, yield: 57%).

[0352] Elemental analysis of structure (C122H102N6Se): Theoretical values C, 84.64; H, 5.94; N, 4.85; Se, 4.56. Measured values C, 84.61; H, 5.98; N, 4.87.

[0353] MALDI-TOF mass spectrum: Theoretical value 1730.7; Experimental value 1730.7 (M + )

[0354] Under argon atmosphere, 11-6 (6.2 g, 3.6 mmol), o-dichlorobenzene (100 mL), and boron tribromide (8.9 g, 35.6 mmol) were added to a 500 mL two-necked flask, and the temperature was raised to 180°C for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column to obtain product D8-3 (1.6 g, yield: 31%).

[0355] Elemental analysis structure (C122H96B2N6Se): theoretical value C, 83.89; H, 5.54; B, 1.24; N, 4.81; Se, 4.52 tested value C, 83.82; H, 5.51; N, 4.85.

[0356] MALDI-TOF mass spectrum: theoretical value 1746.7; experimental value 1746.7 (M + ).

[0357] The photophysical properties of the fused ring compound prepared in Example 11 of the present invention were tested.

[0358] See Table 1, which shows the photophysical properties of the condensed ring compounds prepared in the examples of the present invention.

[0359] Example 12

[0360] The reaction formula is as follows:

[0361]

[0362] Under argon atmosphere, 11-2 (20.0 g, 54.9 mmol), 3-chlorobromotoluene (10.5 g, 54.9 mmol), tri(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.4 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain the product 12-1 (45.3 g, yield: 97%).

[0363] Elemental analysis structure (C27H22ClNSe): theoretical value C, 68.29; H, 4.67; Cl, ​​7.46; N, 2.95; Se, 16.63 tested value C, 68.26; H, 4.69; N, 2.92.

[0364] MALDI-TOF mass spectrum: theoretical value 475.1; experimental value 475.1 (M+ )

[0365] Under argon atmosphere, 2,4,6-trimethyl-N-phenylamine (11.6 g, 55.0 mmol), 3-chlorobromobenzene (7.4 g, 55.0 mmol), tris(dibenzylideneacetone)dipalladium (0.50 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.65 g, 2.2 mmol) and sodium tert-butoxide (7.9 g, 82.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 12-2 (15.9 g, yield: 90%).

[0366] Elemental analysis structure (C21H20ClN): theoretical value C, 78.37; H, 6.26; Cl, ​​11.01; N, 4.35 tested value C, 78.31; H, 6.23; N, 4.39.

[0367] MALDI-TOF mass spectrum: theoretical value 321.1; experimental value 321.1 (M + )

[0368] Under argon atmosphere, 12-2 (5.4 g, 16.7 mmol), 1-1 (6.9 g, 23.0 mmol), tris(dibenzylideneacetone)dipalladium (0.76 g, 0.8 mmol), SPhos (0.68 g, 1.7 mmol) and sodium tert-butylate (2.4 g, 25.0 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain the product 12-3 (8.9 g, yield: 85%).

[0369] Elemental analysis structure (C45H47N3): Theoretical value C, 85.81; H, 7.52; N, 6.67. Measured value C, 85.83; H, 7.55; N, 6.62.

[0370] MALDI-TOF mass spectrum: theoretical value 629.4; experimental value 630.4 (M+1 + )

[0371] Under an argon atmosphere, 12-1 (10.0 g, 21.1 mmol), 12-3 (15.9 g, 25.3 mmol), tris(dibenzylideneacetone)dipalladium(0) (0.96 g, 1.1 mmol), SPhos (0.86 g, 2.1 mmol) and sodium tert-butoxide (3.0 g, 31.5 mmol) were added to a 500 mL three-necked flask, and 100 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 100 mL of diethyl ether and washed three times with saturated brine (100 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 12-4 (16.9 g, yield: 84%).

[0372] Elemental analysis of the structure (C72H62B2N4Se): Theoretical values: C, 79.78; H, 5.77; B, 1.99; N, 5.17; Se, 7.29. Measured values: C, 79.78; H, 5.77; B, 1.99; N, 5.17; Se, 7.29.

[0373] MALDI-TOF mass spectrometry: Theoretical value 1084.4; Experimental value 1084.4 (M + )

[0374] Under an argon atmosphere, 12-4 (3.9 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain product D12-3 (1.1 g, yield: 27%).

[0375] Elemental analysis of the structure (C72H62B2N4Se): Theoretical values: C, 79.78; H, 5.77; B, 1.99; N, 5.17; Se, 7.29. Measured values: C, 79.76; H, 5.79; N, 5.12.

[0376] MALDI-TOF mass spectrometry: Theoretical value 1084.4; Experimental value 1084.4 (M + )

[0377] The photophysical properties of the polycyclic compounds prepared in Example 12 of the present invention were detected.

[0378] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0379] Example 13

[0380] The reaction formula is as follows:

[0381]

[0382] Under an argon atmosphere, 1-4 (10.8 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain the product 13-1 (8.9 g, yield: 63%).

[0383] Elemental analysis structure (C102H88N6Se2): Theoretical value C, 78.74; H, 5.70; N, 5.40; Se, 10.15. Measured value C, 78.77; H, 5.78; N, 5.32.

[0384] MALDI-TOF mass spectrometry: Theoretical value 1556.5; Experimental value 1556.5 (M + )

[0385] Under an argon atmosphere, 13-1 (5.5 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain the product E1-3 (1.2 g, yield: 22%).

[0386] Elemental analysis structure (C102H82B2N6Se2): Theoretical value C, 77.96; H, 5.26; B, 1.38; N, 5.35; Se, 10.05. Measured value C, 77.93; H, 5.22; N, 5.31.

[0387] MALDI-TOF mass spectrometry: Theoretical value 1572.5; Experimental value 1572.5 (M + )

[0388] The photophysical properties of the polycyclic compound prepared in Example 13 of the present invention were detected.

[0389] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0390] Example 14

[0391] The reaction formula is as follows:

[0392]

[0393] Under argon atmosphere, 2-2 (20.0 g, 63.1 mmol), 10-1 (26.2 g, 63.1 mmol), tris(dibenzylideneacetone)dipalladium (0.58 g, 0.6 mmol), tri-tert-butylphosphine tetrafluoroborate (0.75 g, 2.5 mmol) and sodium tert-butoxide (9.1 g, 94.6 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 14-1 (38.6 g, yield: 94%).

[0394] Elemental analysis structure (C43H39ClN2S): theoretical value C, 79.30; H, 6.04; Cl, ​​5.44; N, 4.30; S, 4.92 tested value C, 79.33; H, 6.01; N, 4.34; S, 4.97.

[0395] MALDI-TOF mass spectrum: theoretical value 650.3; experimental value 650.3 (M + )

[0396] Under argon atmosphere, 14-1 (21.7 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butylate (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain product 14-2 (12.2 g, yield: 58%).

[0397] Elemental analysis structure (C110H104N6S2): Theoretical value C, 83.93; H, 6.66; N, 5.34; S, 4.07 Test value C, 83.91; H, 6.68; N, 5.37; S, 4.02.

[0398] MALDI-TOF mass spectrum: theoretical value 1572.8; experimental value 1572.8 (M + )

[0399] Under argon atmosphere, 14-2 (3.9 g, 3.6 mmol), o-dichlorobenzene (100 mL), and boron tribromide (8.9 g, 35.6 mmol) were added to a 500 mL two-necked flask, and the temperature was raised to 180°C for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column to obtain product E2-2 (2.1 g, yield: 37%).

[0400] Elemental analysis structure (C110H98B2N6S2): Theoretical value C, 83.11; H, 6.21; B, 1.36; N, 5.29; S, 4.03 Test value C, 83.18; H, 6.27; N, 5.22; S, 4.08.

[0401] MALDI-TOF mass spectrum: theoretical value 1588.7; experimental value 1588.7 (M + ).

[0402] The photophysical properties of the fused ring compound prepared in Example 14 of the present invention were tested.

[0403] See Table 1, which shows the photophysical properties of the condensed ring compounds prepared in the examples of the present invention.

[0404] Embodiment 15

[0405] The reaction formula is as follows:

[0406]

[0407] Under argon atmosphere, 3-2 (20.0 g, 48.4 mmol), 10-1 (20.1 g, 48.4 mmol), tris(dibenzylideneacetone)dipalladium (0.58 g, 0.6 mmol), tri-tert-butylphosphine tetrafluoroborate (0.75 g, 2.5 mmol) and sodium tert-butoxide (9.1 g, 94.6 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 15-1 (34.3 g, yield: 95%).

[0408] Elemental analysis structure (C43H39ClN2Te): theoretical value C, 69.15; H, 5.26; Cl, ​​4.75; N, 3.75; Te, 17.09 tested value C, 69.19; H, 5.22; N, 3.71.

[0409] MALDI-TOF mass spectrometry: theoretical value 748.2; experimental value 748.2 (M + )

[0410] Under an argon atmosphere, 15-1 (24.9 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 15-2 (10.1 g, yield: 43%).

[0411] Elemental analysis of structure (C110H104N6Te2): theoretical values C, 74.84; H, 5.94; N, 4.76; Te, 14.46; measured values C, 74.81; H, 5.96; N, 4.64.

[0412] MALDI-TOF mass spectrometry: theoretical value 1768.6; experimental value 1768.6 (M + )

[0413] Under an argon atmosphere, 15-2 (6.3 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain product E2-4 (0.6 g, yield: 10%).

[0414] Elemental analysis of structure (C110H98B2N6Te2): theoretical values C, 74.19; H, 5.55; B, 1.21; N, 4.72; Te, 14.33; measured values C, 74.19; H, 5.55; N, 4.72.

[0415] MALDI-TOF mass spectrometry: theoretical value 1784.6; experimental value 1784.6 (M + )

[0416] The photophysical properties of the polycyclic compounds prepared in Example 15 of the present invention were detected.

[0417] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0418] Example 16

[0419] The reaction formula is as follows:

[0420]

[0421] Under argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), di-tert-butylcarbazole (54.8 g, 75.9 mmol), tris(dibenzylideneacetone)dipalladium (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask, 200 mL of toluene was added to the flask, the temperature was raised to 100 ° C, the reaction was stirred for 5 hours, and after cooling to room temperature, 200 mL of dichloromethane was used for extraction, and the mixture was washed three times with saturated brine (500 mL×3), the organic phase was separated, and anhydrous sodium sulfate was added to dry the organic phase. After the solvent was removed by distillation under reduced pressure, the product 16-1 (52.5 g, yield: 91%) was obtained by silica gel column separation.

[0422] Elemental analysis structure (C58H57BrClN3): theoretical value C, 76.43; H, 6.30; Br, 8.77; Cl, ​​3.89; N, 4.61 tested value C, 76.41; H, 6.34; N, 4.68.

[0423] MALDI-TOF mass spectrum: theoretical value 909.3; experimental value 909.3 (M + ).

[0424] Under argon atmosphere, 16-1 (20.0 g, 21.9 mmol), 5-2 (7.0 g, 21.9 mmol), tris(dibenzylideneacetone)dipalladium (0.20 g, 0.2 mmol), tri-tert-butylphosphine tetrafluoroborate (0.26 g, 0.9 mmol) and sodium tert-butoxide (3.2 g, 32.9 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain the product 16-2 (21.1 g, yield: 84%).

[0425] Elemental analysis structure (C79H75ClN4S): Theoretical value C, 82.65; H, 6.59; Cl, ​​3.09; N, 4.88; S, 2.79 Measured value C, 82.65; H, 6.59; N, 4.82; S, 2.71.

[0426] MALDI-TOF mass spectrometry: theoretical value 1146.5; experimental value 1147.5 (M+1 + )

[0427] Under an argon atmosphere, 16-1 (38.3 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 16-3 (15.8 g, yield: 46%).

[0428] Elemental analysis of the structure (C182H176N10S2): theoretical values C, 85.14; H, 6.91; N, 5.46; S, 2.50; measured values C, 85.11; H, 6.95; N, 5.42; S, 2.53.

[0429] MALDI-TOF mass spectrometry: theoretical value 2565.4; experimental value 2565.5 (M + )

[0430] Under an argon atmosphere, 16-3 (9.2 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain product F6-2 (3.4 g, yield: 36%).

[0431] Elemental analysis of the structure (C182H170B2N10S2): theoretical values C, 84.62; H, 6.63; B, 0.84; N, 5.42; S, 2.48; measured values C, 84.63; H, 6.61; N, 5.47; S, 2.42.

[0432] MALDI-TOF mass spectrometry: theoretical value 2581.3; experimental value 2581.3 (M + )

[0433] The photophysical properties of the polycyclic compounds prepared in Example 16 of the present invention were detected.

[0434] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0435] Embodiment 17

[0436] The reaction formula is as follows:

[0437]

[0438] Under argon atmosphere, 1-bromo-3-chloro-5-iodobenzene (20.0 g, 63.3 mmol), phenoxazine (13.9 g, 75.9 mmol), tri(dibenzylideneacetone)dipalladium (1.16 g, 1.3 mmol), dppf (1.40 g, 2.5 mmol), sodium tert-butoxide (9.1 g, 95.0 mmol) were added to a 500 mL three-necked flask, 200 mL of toluene was added to the flask, the temperature was raised to 100 ° C, the reaction was stirred for 5 hours, and after cooling to room temperature, 200 mL of dichloromethane was used for extraction, and the mixture was washed three times with saturated brine (500 mL×3). The organic phase was separated and dried over anhydrous sodium sulfate. The organic phase was distilled under reduced pressure to remove the solvent, and the product 17-1 (21.0 g, yield: 89%) was obtained by silica gel column separation.

[0439] Elemental analysis structure (C18H11BrClNO): theoretical value C, 58.02; H, 2.98; Br, 21.44; Cl, ​​9.51; N, 3.76; O, 4.29 tested value C, 58.06; H, 2.92; N, 3.71; O, 4.34.

[0440] MALDI-TOF mass spectrum: theoretical value 371.0; experimental value 371.0 (M + ).

[0441] Under argon atmosphere, 17-1 (20.0 g, 53.6 mmol), 4-1 (16.1 g, 53.6 mmol), tris(dibenzylideneacetone)dipalladium (0.49 g, 0.5 mmol), tri-tert-butylphosphine tetrafluoroborate (0.64 g, 0.2 mmol) and sodium tert-butoxide (7.7 g, 80.4 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 17-2 (26.1 g, yield: 82%).

[0442] Elemental analysis structure (C39H29ClN2O2): theoretical value C, 78.98; H, 4.93; Cl, ​​5.98; N, 4.72; O, 5.39 tested value C, 78.92; H, 4.91; N, 4.76; O, 5.32.

[0443] MALDI-TOF mass spectrometry: theoretical value 592.2; experimental value 592.2 (M + )

[0444] Under an argon atmosphere, 17-2 (19.8 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by vacuum distillation, the obtained solid was separated by silica gel column chromatography to obtain product 17-3 (8.4 g, yield: 43%).

[0445] Elemental analysis of structure (C102H84N6O4): theoretical values C, 84.04; H, 5.81; N, 5.76; O, 4.39; measured values C, 84.01; H, 5.85; N, 5.71; O, 4.33.

[0446] MALDI-TOF mass spectrometry: theoretical value 1456.7; experimental value 1456.7 (M + )

[0447] Under an argon atmosphere, 17-3 (5.2 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by vacuum distillation. The obtained solid was separated by silica gel column chromatography to obtain product F9-1 (3.2 g, yield: 33%).

[0448] Elemental analysis of structure (C102H78B2N6O4): theoretical values C, 83.15; H, 5.34; B, 1.47; N, 5.70; O, 4.34; measured values C, 83.11; H, 5.32; N, 5.74; O, 4.31.

[0449] MALDI-TOF mass spectrometry: theoretical value 1472.6; experimental value 1472.6 (M + )

[0450] The photophysical properties of the polycyclic compounds prepared in Example 17 of the present invention were detected.

[0451] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0452] Embodiment 18

[0453] The reaction formula is as follows:

[0454]

[0455] Under argon atmosphere, 3-chloro-5-bromotrifluoromethylbenzene (20.0 g, 77.2 mmol), 4-1 (23.2 g, 77.2 mmol), tris(dibenzylideneacetone)dipalladium (0.71 g, 0.8 mmol), tri-tert-butylphosphine tetrafluoroborate (0.92 g, 0.3 mmol) and sodium tert-butoxide (11.1 g, 115.8 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 18-2 (34.1 g, yield: 82%).

[0456] Elemental analysis structure (C28H21ClF3NO): theoretical value C, 70.07; H, 4.41; Cl, ​​7.39; F, 11.88; N, 2.92; O, 3.33 tested value C, 70.02; H, 4.45; N, 2.98; O, 3.37.

[0457] MALDI-TOF mass spectrum: theoretical value 479.1; experimental value 479.1 (M + )

[0458] Under argon atmosphere, 18-2 (16.0 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butylate (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 18-3 (7.6 g, yield: 46%).

[0459] Elemental analysis structure (C80H68F6N4O2): theoretical value C, 78.03; H, 5.57; F, 9.26; N, 4.55; O, 2.60 tested value C, 78.06; H, 5.51; N, 4.53; O, 2.66.

[0460] MALDI-TOF mass spectrometry: theoretical value 1230.5; experimental value 1230.5 (M + )

[0461] Under an argon atmosphere, 18-3 (4.4 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column chromatography to obtain product F16-1 (1.5 g, yield: 34%).

[0462] Elemental analysis of the structure (C80H62B2F6N4O2): theoretical values C, 77.05; H, 5.01; B, 1.73; F, 9.14; N, 4.49; O, 2.57; measured values C, 77.01; H, 5.04; N, 4.42; O, 2.54.

[0463] MALDI-TOF mass spectrometry: theoretical value 1246.5; experimental value 1246.5 (M + )

[0464] The photophysical properties of the polycyclic compounds prepared in Example 18 of the present invention were detected.

[0465] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0466] Example 19

[0467] The reaction formula is as follows:

[0468]

[0469] Under an argon atmosphere, 7-2 (20.0 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added for drying. After the solvent was removed by distillation under reduced pressure, the resulting solid was separated by silica gel column chromatography to obtain product 19-1 (7.6 g, yield: 39%).

[0470] Elemental analysis structure (C102H88N6S2): Theoretical values: C, 83.80; H, 6.07; N, 5.75; S, 4.39. Test values: C, 83.85; H, 6.03; N, 5.72; S, 4.34.

[0471] MALDI-TOF mass spectrometry: Theoretical value 1460.7; Experimental value 1460.7 (M + )

[0472] Under an argon atmosphere, 19-1 (5.2 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain product G1-2 (0.7 g, yield: 16%).

[0473] Elemental analysis structure (C102H82B2N6S2): Theoretical values: C, 82.92; H, 5.59; B, 1.46; N, 5.69; S, 4.34. Test values: C, 82.98; H, 5.54; N, 5.65; S, 4.38.

[0474] MALDI-TOF mass spectrometry: Theoretical value 1476.6; Experimental value 1476.6 (M + )

[0475] The photophysical properties of the polycyclic compounds prepared in Example 19 of the present invention were detected.

[0476] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0477] Example 20

[0478] The reaction formula is as follows:

[0479]

[0480] Under an argon atmosphere, 8-3 (24.9 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of diethyl ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain the product 20-1 (6.6 g, yield: 28%).

[0481] Elemental analysis of structure (C110H100N6Te2): theoretical values C, 75.02; H, 5.72; N, 4.77; Te, 14.49; measured values C, 75.07; H, 5.76; N, 4.74.

[0482] MALDI-TOF mass spectrometry: theoretical value 1764.6; experimental value 1764.6 (M + )

[0483] Under an argon atmosphere, 20-1 (5.2 g, 3.6 mmol) and o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column chromatography to obtain the product G5-4 (0.8 g, yield: 11%).

[0484] Elemental analysis of structure (C110H94B2N6Te2): theoretical values C, 74.36; H, 5.33; B, 1.22; N, 4.73; Te, 14.36; measured values C, 74.32; H, 5.36; N, 4.71.

[0485] MALDI-TOF mass spectrometry: theoretical value 1780.6; experimental value 1780.6 (M + )

[0486] The photophysical properties of the polycyclic compounds prepared in Example 20 of the present invention were detected.

[0487] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0488] Example 21

[0489] The reaction formula is as follows:

[0490]

[0491] Under argon atmosphere, 3-chloro-5-bromobenzonitrile (20.0 g, 92.2 mmol), 4-1 (27.7 g, 92.2 mmol), tris(dibenzylideneacetone)dipalladium (0.84 g, 0.9 mmol), tri-tert-butylphosphine tetrafluoroborate (1.10 g, 0.4 mmol) and sodium tert-butoxide (13.3 g, 138.2 mmol) were added to a 500 mL three-necked flask, and 250 mL of toluene was added. The temperature was raised to 100 ° C and stirred for 3 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column to obtain product 21-1 (38.3 g, yield: 95%).

[0492] Elemental analysis structure (C28H21ClN2O): Theoretical value C, 76.97; H, 4.84; Cl, ​​8.11; N, 6.41; O, 3.66 Measured value C, 76.94; H, 4.82; N, 6.45; O, 3.61.

[0493] MALDI-TOF mass spectrum: theoretical value 436.1; experimental value 436.1 (M + )

[0494] Under argon atmosphere, 21-1 (14.6 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butylate (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 ° C and stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After the organic phases were combined, anhydrous sodium sulfate was added to dry, and the solvent was removed by distillation under reduced pressure. The obtained solid was separated by silica gel column to obtain the product 21-2 (5.2 g, yield: 34%).

[0495] Elemental analysis structure (C80H68N6O2): theoretical value C, 83.89; H, 5.98; N, 7.34; O, 2.79 tested value C, 83.82; H, 5.93; N, 7.34; O, 2.73.

[0496] MALDI-TOF mass spectrum: theoretical value 1144.5; experimental value 1144.5 (M + )

[0497] Under an argon atmosphere, 21-2 (4.1 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain product G14-1 (0.5 g, yield: 13%).

[0498] Elemental analysis of structure (C80H62B2N6O2): Theoretical values: C, 82.76; H, 5.38; B, 1.86; N, 7.24; O, 2.76. Measured values: C, 82.76; H, 5.38; N, 7.24; O, 2.76.

[0499] MALDI-TOF mass spectrometry: Theoretical value 1160.5; Experimental value 1160.5 (M + )

[0500] The photophysical properties of the polycyclic compound prepared in Example 21 of the present invention were detected.

[0501] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0502] Example 22

[0503] The reaction formula is as follows:

[0504]

[0505] Under an argon atmosphere, 10-3 (21.2 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the obtained solid was separated by silica gel column chromatography to obtain product 22-1 (7.8 g, yield: 38%).

[0506] Elemental analysis of structure (C110H104N6O2): Theoretical values: C, 85.68; H, 6.80; N, 5.45; O, 2.07. Measured values: C, 85.63; H, 6.83; N, 5.41; O, 2.04.

[0507] MALDI-TOF mass spectrometry: Theoretical value 1540.8; Experimental value 1540.8 (M+ )

[0508] Under an argon atmosphere, 22-1 (5.2 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column chromatography to obtain the product H2-1 (1.2 g, yield: 21%).

[0509] Elemental analysis of the structure (C110H98B2N6O2): Theoretical values: C, 84.82; H, 6.34; B, 1.39; N, 5.40; O, 2.05. Measured values: C, 84.84; H, 6.36; N, 5.47; O, 2.08.

[0510] MALDI-TOF mass spectrometry: Theoretical value 1556.8; Experimental value 1556.8 (M + )

[0511] The photophysical properties of the polycyclic compound prepared in Example 22 of the present invention were detected.

[0512] See Table 1. Table 1 shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0513] Example 23

[0514] The reaction formula is as follows:

[0515]

[0516] Under an argon atmosphere, 11-3 (26.9 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). The combined organic phases were dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The resulting solid was separated by silica gel column chromatography to obtain the product 23-1 (10.3 g, yield: 41%).

[0517] Elemental analysis of the structure (C128H104N6Se2): Theoretical values: C, 81.59; H, 5.56; N, 4.46; Se, 8.38. Measured values: C, 81.52; H, 5.51; N, 4.43.

[0518] MALDI-TOF mass spectrometry: theoretical value 1884.7; experimental value 1884.7 (M + )

[0519] Under an argon atmosphere, 23-1 (6.7 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the resulting solid was separated by silica gel column chromatography to obtain the product H8-3 (1.3 g, yield: 24%).

[0520] Elemental analysis of the structure (C128H98B2N6Se2): theoretical values C, 80.92; H, 5.20; B, 1.14; N, 4.42; Se, 8.31; measured values C, 80.98; H, 5.24; N, 4.46

[0521] MALDI-TOF mass spectrometry: theoretical value 1900.6; experimental value 1900.6 (M + )

[0522] The photophysical properties of the polycyclic compounds prepared in Example 23 of the present invention were detected.

[0523] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0524] Example 24

[0525] The reaction formula is as follows:[[]]

[0526]

[0527] Under an argon atmosphere, 12-2 (15.9 g, 33.4 mmol), 1-1 (4.6 g, 13.4 mmol), tris(dibenzylideneacetone)dipalladium (1.53 g, 1.7 mmol), SPhos (1.37 g, 3.3 mmol) and sodium tert-butoxide (4.8 g, 50.1 mmol) were added to a 500 mL three-necked flask, and 250 mL of tert-butylbenzene was added. The temperature was raised to 170 °C and the reaction was stirred for 24 hours. After cooling to room temperature, the reaction solution was extracted with 200 mL of ether and washed three times with saturated brine (200 mL × 3). After combining the organic phases, anhydrous sodium sulfate was added for drying. After removing the solvent by distillation under reduced pressure, the resulting solid was separated by silica gel column chromatography to obtain the product 24-1 (5.7 g, yield: 35%).

[0528] Elemental analysis of the structure (C78H70N4Se2): theoretical values C, 76.70; H, 5.78; N, 4.59; Se, 12.93; measured values C, 76.74; H, 5.72; N, 4.60

[0529] MALDI-TOF mass spectrometry: theoretical value 1222.4; experimental value 1223.4 (M+1 + )

[0530] Under an argon atmosphere, 24-1 (4.4 g, 3.6 mmol), o-dichlorobenzene (100 mL) were added to a 500 mL two-necked flask, and boron tribromide (8.9 g, 35.6 mmol) was added. The temperature was raised to 180 °C and the reaction was carried out for 24 hours. After cooling to room temperature, the solvent was removed by distillation under reduced pressure, and the obtained solid was separated by silica gel column chromatography to obtain product H12-3 (1.3 g, yield: 23%).

[0531] Elemental analysis of structure (C78H64B2N4Se2): theoretical values C, 75.74; H, 5.22; B, 1.75; N, 4.53; Se, 12.77; measured values C, 75.70; H, 5.21; N, 4.60.

[0532] MALDI-TOF mass spectrometry: theoretical value 1238.4; experimental value 1238.4 (M + )

[0533] The photophysical properties of the polycyclic compounds prepared in Example 24 of the present invention were detected.

[0534] See Table 1, which shows the photophysical properties of the polycyclic compounds prepared in the examples of the present invention.

[0535] Table 1 Photophysical properties of the polycyclic compounds prepared in the examples of the present invention

[0536]

[0537]

[0538] Note: The delayed fluorescence lifetime in the table was obtained by doping the compound in polystyrene at a concentration of 1 wt% to make a test sample and measuring it with a time-resolved fluorescence spectrometer. The test instrument was Edinburgh fluorescencespectrometer (FLS-980, UK); the full width at half maximum was the peak width at half of the peak height of the fluorescence spectrum at room temperature, that is, a straight line parallel to the peak base was drawn through the midpoint of the peak height, and the distance between the two intersection points of this straight line and the two sides of the peak. The fluorescence spectrum was obtained by dissolving the compound in toluene solution at a concentration of 10 -5 mol / L to make a test sample and measuring it with a fluorescence spectrometer (HORIBA FluoroMax spectrofluorometer (Japan)).

[0539] As can be seen from Table 1, the polycyclic compounds in the embodiments provided by the present invention exhibit thermally activated delayed fluorescence effect, and their delayed fluorescence lifetimes are in the range of 1 to 20 μs. At the same time, the luminescent compounds provided by the present invention also exhibit an extremely narrow full width at half maximum (<20 nm), overcoming the defect of the relatively wide full width at half maximum (50 - 100 nm) of traditional TADF luminescent materials.

[0540] Device Embodiment

[0541] As a device embodiment, the present invention provides a device structure: ITO / PEDOT:PSS(40 nm) / PVK(15 nm) / EML(30 nm) / nm) / mSiTRZ(12 nm) / TmPPPyTz(55 nm) / LiF(1 nm) / Al(150 nm), wherein the light-emitting layer (EML) includes a host material selected from any one of mCP, mCBP, SiCzCz, and SiCzTrz, a sensitizing material 5CzTRZ, and the polycyclic compound of the present invention.

[0542] The steps for preparing a device using the device structure are as follows: Spin-coat poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) on indium tin oxide loaded on a glass substrate and anneal at 120 °C for 30 minutes; subsequently, spin-coat a 1,2-dichlorobenzene solution of PVK onto the PEDOT:PSS layer and anneal at 100 °C for 10 minutes; then spin-coat a toluene solution containing the polycyclic compound of the present invention onto the PVK layer and anneal at 100 °C for 10 minutes; finally, deposit mSiTRZ, TmPPPPyTz, and LiF / Al cathode successively under a vacuum of 6 x 10 -7 Torr to obtain an organic light-emitting device.

[0543] Some material structures in this device embodiment are as follows:

[0544]

[0545] Example 25

[0546] Taking A1-3 in Example 1 as the implementation object, doping A1-3 into the organic light-emitting layer. Using the device structure to prepare an organic light-emitting device and testing the obtained device.

[0547] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with A1-3 provided by the present invention.

[0548] Example 26

[0549] Taking A4-2 in Example 2 as the implementation object, doping A4-2 into the organic light-emitting layer. Using the device structure to prepare an organic light-emitting device and testing the obtained device.

[0550] Refer to Table 2, which provides the performance parameters of the electroluminescent device prepared with A4-2 provided by the present invention.

[0551] Example 27

[0552] Taking A10-4 in Example 3 as the implementation object, A10-4 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0553] Refer to Table 2, which provides the performance parameters of the electroluminescent device prepared with A10-4 provided by the present invention.

[0554] Example 28

[0555] Taking B1-1 in Example 4 as the implementation object, B1-1 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0556] Refer to Table 2, which provides the performance parameters of the electroluminescent device prepared with B1-1 provided by the present invention.

[0557] Example 29

[0558] Taking B7-2 in Example 5 as the implementation object, B7-2 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0559] Refer to Table 2, which provides the performance parameters of the electroluminescent device prepared with B7-2 provided by the present invention.

[0560] Example 30

[0561] Taking B13-1 in Example 6 as the implementation object, B12-1 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0562] Refer to Table 2, which provides the performance parameters of the electroluminescent device prepared with B12-1 provided by the present invention.

[0563] Example 31

[0564] Taking C1-2 in Example 7 as the implementation object, C1-2 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0565] Refer to Table 2, which provides the performance parameters of the electroluminescent device prepared with C1-2 provided by the present invention.

[0566] Example 32

[0567] Taking C5-4 in Example 8 as the implementation object, C5-4 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0568] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with C5-4 provided by the present invention.

[0569] Example 33

[0570] Taking C11-3 in Example 9 as the implementation object, C11-3 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0571] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with C11-3 provided by the present invention.

[0572] Example 34

[0573] Taking D2-1 in Example 10 as the implementation object, D2-1 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0574] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with D2-1 provided by the present invention.

[0575] Example 35

[0576] Taking D8-3 in Example 11 as the implementation object, D8-3 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0577] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with D8-3 provided by the present invention.

[0578] Example 36

[0579] Taking D12-3 in Example 12 as the implementation object, D12-3 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0580] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with D12-3 provided by the present invention.

[0581] Example 37

[0582] Taking E1-3 in Example 13 as the implementation object, E1-3 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0583] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with E1-3 provided by the present invention.

[0584] Example 38

[0585] Taking E2-2 in Example 14 as the implementation object, E2-2 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0586] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with E2-2 provided by the present invention.

[0587] Example 39

[0588] Taking E2-4 in Example 15 as the implementation object, E2-4 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0589] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with E2-4 provided by the present invention.

[0590] Example 40

[0591] Taking F6-2 in Example 16 as the implementation object, F6-2 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0592] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with F6-2 provided by the present invention.

[0593] Example 41

[0594] Taking F9-1 in Example 17 as the implementation object, F9-1 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0595] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with F9-1 provided by the present invention.

[0596] Example 42

[0597] Taking F16-1 in Example 18 as the implementation object, F16-1 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0598] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with F16-1 provided by the present invention.

[0599] Example 43

[0600] Taking G1-2 in Example 19 as the object of implementation, G1-2 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0601] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with G1-2 provided by the present invention.

[0602] Example 44

[0603] Taking G5-4 in Example 20 as the object of implementation, G5-4 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0604] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with G5-4 provided by the present invention.

[0605] Example 45

[0606] Taking G14-1 in Example 21 as the object of implementation, G14-1 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0607] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with G14-1 provided by the present invention.

[0608] Example 46

[0609] Taking H2-1 in Example 22 as the object of implementation, H2-1 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0610] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with H2-1 provided by the present invention.

[0611] Example 47

[0612] Taking H8-3 in Example 23 as the object of implementation, H8-3 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0613] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with H8-3 provided by the present invention.

[0614] Example 48

[0615] Taking H12-3 in Example 24 as the implementation object, H12-3 was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0616] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared with H12-3 provided by the present invention.

[0617] Comparative Example 1

[0618] Taking υ-DABNA as the implementation object, it was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0619] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared in Comparative Example 1.

[0620] Comparative Example 2

[0621] Taking t-BuCz-DABNA as the implementation object, it was doped into the organic light-emitting layer. An organic electroluminescent device was prepared using the device structure, and the obtained device was tested.

[0622] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent device prepared in Comparative Example 2.

[0623] Chemical structures of υ-DABNA and t-BuCz-DABNA:

[0624]

[0625] Table 2 Performance parameters of the electroluminescent device prepared with the polycyclic compound provided by the present invention

[0626]

[0627]

[0628] The description of the above embodiments is only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. An organic boron compound containing a benzheterocyclic functional unit and two boron atoms, having the structure shown in Formula I or Formula II: Among them, Any one of Y1 and Y2 is selected from a single bond, and the other is selected from O, S, Se, Te, N(R a ), C(R a )2 or Si(R a ); Any one of Y1’ and Y2’ is selected from a single bond, and the other is selected from O, S, Se, Te, N(R a ), C(R a )2 or Si(R a ); Said R a is selected from H, a straight-chain or branched C1-C 30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C 60 aryl group, a substituted or unsubstituted C3-C 60 heteroaryl group; Among them, Ar1 to Ar8 and Ar'1 to Ar'7 are independently selected from substituted or unsubstituted C6 to C 60 aromatic ring groups, and substituted or unsubstituted C3 to C 60 aromatic heterocyclic groups; Q1, Q2, Q1', Q2', R1 to R6, and R'1 to R'6 are independently selected from H, deuterium, halogen, cyano, hydroxyl, nitro, amino, substituted or unsubstituted C1-C 30 linear or branched hydrocarbon group, substituted or unsubstituted C3-C 30 cycloalkyl group, substituted or unsubstituted C6-C 60 aromatic group, substituted or unsubstituted C3-C 60 heteroaromatic group or any of the following groups: The R 1 , R 2 and R 3 are each independently selected from H, a substituted or unsubstituted linear or branched C1-C 30 hydrocarbyl group, a substituted or unsubstituted C3-C 30 cycloalkyl group, a substituted or unsubstituted C6-C 60 aryl group, or a substituted or unsubstituted C3-C 60 heteroaryl group; The heteroatom in the heteroaromatic group is selected from one or more of Si, Ge, N, P, O, S, Se, and Te; Indicates the connection position.

2. The organic boron compound according to claim 1, wherein Having any of the following structures:

3. The organic boron compound according to claim 1, wherein The R1 to R6 and R'1 to R'6 are independently selected from H, deuterium, halogen, cyano, hydroxy, nitro, amino, substituted or unsubstituted C1-C 10 linear or branched hydrocarbon groups.

4. The organoboron compound according to claim 1, wherein The Ar1-Ar8 and Ar'1-Ar'7 are independently selected from substituted or unsubstituted phenyl groups; The substitution is replaced by one or more of deuterium, halogen, cyano, hydroxyl, nitro, amino, substituted or unsubstituted C1-C 10 substituted in a straight-chain or branched hydrocarbon group.

5. The organoboron compound according to any one of claims 1, characterized in that, The organic boron compound has any of the structures shown in Formula (1-1)-(1-4) and Formula (2-1)-(2-4); The definitions of Y1, Y2, Q1, and Q2 are the same as those in claim 1.

6. The organic boron compound according to any one of claims 1 to 5, characterized in that, Q1, Q2, Q1', and Q2' are independently selected from H, deuterium, halogen, cyano, hydroxy, nitro, amino, substituted or unsubstituted C1-C 10 linear or branched hydrocarbon groups, substituted or unsubstituted C3-C6 cycloalkyl groups, substituted or unsubstituted C6-C 14 aromatic groups, substituted or unsubstituted C5-C 14 heteroaromatic groups.

7. The organoboron compound according to claim 6, wherein The heteroaromatic group structure contains at least one N atom, and the N atom is connected to the parent nucleus.

8. The organic boron compound according to claim 7, wherein The heteroaromatic group is selected from any of the following structures: L1 to L2 are each independently selected from H, deuterium, cyano, halogen, nitro, hydroxy, amino, a substituted or unsubstituted C1-C 30 linear or branched hydrocarbon group, a substituted or unsubstituted C3-C 30 cycloalkyl group, a substituted or unsubstituted C6-C 60 aromatic group, a substituted or unsubstituted C3-C 60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, Se and Te.

9. The organoboron compound according to any one of claims 1 to 8, characterized in that, Having any of the following structures:

10. Use of the organic boron compound according to any one of claims 1-9 as an organic electroluminescent material.

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