Double-carbon positive ion type compound, preparation method and application

Abstract

The invention relates to a double-carbon positive ion type compound as well as a preparation method and application thereof, and belongs to the technical field of organic light-emitting materials. According to the double-carbon positive ion type compound disclosed by the invention, on one hand, the relaxation degree of an excited state structure can be reduced by utilizing a rigid skeleton structure of a fused ring compound, so that relatively narrow half-peak width is realized; on the other hand, separation of HOMO and LUMO is achieved through the resonance effect between carbocations and heteroatoms, and therefore small delta EST and TADF effects are achieved, and high luminous efficiency is achieved. Meanwhile, by changing the types of aromatic rings, heteroaromatic rings or counter anions contained in the fused ring compound, the further adjustment of the light-emitting wavelength, the delayed fluorescence lifetime and the half-peak width can be realized. When the dual-carbon positive ion type compound is used as a light-emitting layer of the electroluminescent device, narrow electroluminescent half-peak width can be realized under the condition that an optical filter and a micro-cavity structure are not needed, and high device external quantum efficiency can also be realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic light-emitting materials, and particularly relates to a dicationic compound, a preparation method and uses thereof. Background Art

[0002] The display technology based on organic light-emitting diodes (OLEDs) has characteristics such as flexibility, ultra-light weight, ultra-thinness, low energy consumption, wide viewing angle, active light emission, and vivid colors, and occupies a pivotal position in the current and future display technology fields. OLEDs are a type of electroluminescent device, and their light-emitting principle is to use an ITO transparent electrode and a metal electrode as the anode and cathode of the device respectively. Under the drive of a certain voltage, electrons and holes are respectively injected from the cathode and anode, migrate to the light-emitting layer, and meet in the light-emitting layer to form a light-emitting phenomenon. OLEDs are mainly composed of a light-emitting layer, an electron / hole injection layer, an electron / hole transport layer, a hole blocking layer and other layered structures. The core is the light-emitting layer, and color light emission is achieved by selecting different light-emitting materials.

[0003] Thermally activated delayed fluorescence (TADF) materials are called the third-generation OLED light-emitting materials. Such materials can effectively obtain triplet excitons through reverse intersystem crossing (RISC), and theoretically can achieve 100% internal quantum efficiency. It can not only effectively improve the device efficiency, but also reduce the triplet exciton concentration, thereby suppressing the device efficiency roll-off, and has received extensive attention from global scientific researchers. At present, the main implementation approach of TADF molecules is to introduce electron donor (D) and electron acceptor (A) units, so that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are separated, thereby achieving a small ΔE ST . However, due to the obvious vibrational relaxation of its excited state, this D-A structure exhibits a large Stokes shift, and the emission spectrum is relatively wide, with the full width at half maximum (FWHM) generally being 70-100 nm. In practical applications, it is usually necessary to use a filter or construct an optical microcavity to improve the color purity, but this will lead to a decrease in the external quantum efficiency of the device or the device structure becoming complex.

[0004] Currently, multiple resonance TADF (MR-TADF) materials based on heteroatom-doped polycyclic aromatic hydrocarbons have attracted remarkable attention due to their significantly narrow-band emission (FWHM < 70 nm). However, most reported MR-TADF materials mostly adopt organic boron / nitrogen resonance structures or carbonyl / nitrogen resonance structures, and their emissions are mostly located in the blue / green region.

[0005] Therefore, how to develop long-wavelength (λ em > 550 nm) light-emitting materials that have both TADF effects and narrow full width at half maximum spectral characteristics through reasonable chemical structure design has become one of the problems that many forward-looking researchers in the field urgently need to solve. Summary of the Invention

[0006] The present invention aims to solve the technical problems in the prior art and provides a dicationic compound, a preparation method and uses thereof. The dicationic compound of the present invention has both long-wavelength emission (λ em >550 nm), and also has TADF effect and narrow full-width at half-maximum spectral characteristics.

[0007] To solve the above technical problems, the technical solution of the present invention is as follows:

[0008] A dicationic compound, the structural formula of which is shown in formula (I):

[0009]

[0010]

[0011] Wherein, X 1 , X 2 are independently selected from O, S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), or Si(R 1 R 2 );

[0012] Y 1 ~Y 4 are independently selected from N(R 1 ), O, S, Se or Te;

[0013] Ar 1 ~Ar 4 are independently selected from a substituted or unsubstituted aryl ring of C6-C60, or a substituted or unsubstituted heteroaryl ring of C3-C60; wherein the heteroatoms of the heteroaryl ring are independently selected from Si, Ge, N, P, O, S or Se;

[0014] R 1 ~R 4 are each independently selected from H, D, F, Cl, Br, I, -CN, -NO 2 , -CF 3 , -OH, -SH, -NH 2 , a straight-chain alkyl of C1-C30, a branched-chain alkyl of C3-C30, a cycloalkyl of C3-C30, an alkoxy of C1-C30, an alkylthio of C1-C30, an alkylamino of C1-C30, an aryl of C6-C60, an aryl ether of C6-C60, a heteroaryl of C3-C60 or a heteroaryl ether of C3-C60; wherein the heteroatoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se;

[0015] The R 1 and R 2 are each independently selected from H, D, a linear alkyl group having 1 to 30 carbon atoms, a branched alkyl group having 3 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 60 carbon atoms, or a heteroaryl group having 5 to 60 carbon atoms; wherein the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S, or Se;

[0016] wherein, a, b, c, and d are each independently an integer from 0 to 3;

[0017] A 1 - and A 2 - are monovalent anions, each independently selected from, but not limited to, F - , Cl - , Br - , I - , ClO 4 - , BF 4 - , FeCl 4 - , GaCl 4 - , PF 6 - , SbCl 6 - or selected from one of the following monovalent anions:

[0018]

[0019] In the above technical solution, preferably, the X 1 and X 2 are independently selected from O, S, or N(R 1 ).

[0020] In the above technical solution, preferably, the Y 1 ~Y 4 are independently selected from O, S, or N(R 1 ).

[0021] In the above technical solution, preferably, the Ar 1 ~Ar 4 are each independently selected from one of the groups shown in A1 to A19:

[0022]

[0023]

[0024] wherein, L1 , L 2 , L 3 Each independently selected from H, D, a substituted or unsubstituted linear C1-C30 alkyl group, a substituted or unsubstituted branched C1-C30 alkyl group, a substituted or unsubstituted C1-C30 haloalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0025] In the above technical solution, preferably, the dicationic compound is selected from any one of the following structures:

[0026]

[0027]

[0028]

[0029]

[0030] A method for preparing a dicationic compound, comprising the following steps:

[0031] When X 1 ~X 2 , Y 1 ~Y 4 are both O or both S, or X 1 ~X 2 is S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), or Si(R 1 R 2 ), and Y 1 ~Y 4 are both O, the preparation method comprises the following steps:

[0032] Under an argon atmosphere, put intermediate A-1, A-2 or A-3, LiI and N-methylpyrrolidone into a reaction flask, then add 2,4,6-trimethylpyridine. After the reaction is completed, cool the reaction mixture, extract with dichloromethane, dry and filter the organic phase with anhydrous sodium sulfate, and separate the crude product by silica gel column chromatography and recrystallize to obtain the dicationic compound shown in B-1, B-2 or B-4;

[0033] When X 1 ~X 2 , Y 1 ~Y4 All are N(R 1 ), and when R 1 is an alkyl group, or when X 1 ~X 2 is S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), or Si(R 1 R 2 ), and Y 1 ~Y 4 are all N(R 1 ), and when R 1 is an alkyl group, the preparation method includes the following steps:

[0034] Under an argon atmosphere, add intermediate A-1 or A-3, alkylamine, benzoic acid, and N-methylpyrrolidone to a two-necked flask, heat and stir, add alkylamine twice during the reaction, after the reaction is completed, cool to room temperature, pour the reaction mixture into deionized water, filter and collect the formed precipitate, wash with water and dry under vacuum, dissolve the crude product in dichloromethane and precipitate in ether for further purification, and recrystallize from acetonitrile after filtration to obtain the dicationic compound shown as B-3-1 or B-5-1;

[0035] When X 1 ~X 2 , Y 1 ~Y 4 are all N(R 1 ), and when R 1 is an aryl group, or when X 1 ~X 2 is S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), or Si(R 1 R 2 ), and Y 1 ~Y 4 are all N(R 1 ), and when R 1 is an aryl group, the preparation method includes the following steps:

[0036] Under an argon atmosphere, intermediate A-1 or A-3 and an aromatic amine were added to a two-necked flask, and then sodium hydride was added and the temperature was heated from room temperature to the reflux temperature. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction was quenched by adding deionized water, and extracted with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and filtered, then the dichloromethane was removed by rotary evaporation, and a solid precipitate was precipitated and filtered by adding diethyl ether. The precipitated solid was separated by column chromatography with ethanol and dichloromethane, and recrystallized by evaporating dichloromethane in dichloromethane and toluene to obtain the dicationic compounds shown as B-3-2 or B-5-2;

[0037]

[0038] wherein, Ar 1 ~Ar 4 , (R 1 ) a ~(R 4 ) d , R 1 ~R 2 are all as defined above.

[0039] In the above technical solution, preferably, a specific implementation manner of the preparation method of the dicationic compound of the present invention is as follows:

[0040] When X 1 ~X 2 , Y 1 ~Y 4 are both O or both S, or X 1 ~X 2 is S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), Si(R 1 R 2 ), and Y 1 ~Y 4 are both O, the preparation method includes the following steps:

[0041] Under an argon atmosphere, intermediate A-1, A-2 or A-3, LiI, N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 250 mL two-necked flask, and then the temperature was raised to 140 °C and reacted for 3 h. After the reaction was completed, the reaction mixture was cooled, extracted with dichloromethane three times, the organic phase was dried over anhydrous sodium sulfate and filtered, and after concentration, the crude product was separated by column chromatography with methanol / dichloromethane, and recrystallized in ethyl acetate to obtain the dicationic fused-ring compounds B-1, B-2 or B-4;

[0042] When X 1 ~X 2, Y 1 ~Y 4 are all N(R 1 ), and when R 1 is an alkyl group, or when X 1 ~X 2 is S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), Si(R 1 R 2 ), Y 1 ~Y 4 are all N(R 1 ), and when R 1 is an alkyl group, the preparation method includes the following steps:

[0043] Under an argon atmosphere, add A-1 or A-3, alkylamine, benzoic acid and N-methylpyrrolidone to a 250 mL two-necked flask, heat under reflux for 20 h, add alkylamine twice during the reaction, after the reaction is completed, cool to room temperature, pour the reaction mixture into water, filter and collect the formed precipitate, wash with water and dry under vacuum, dissolve the crude product in dichloromethane and precipitate in ether for further purification, and recrystallize from acetonitrile after filtration to obtain the dicationic polycyclic compound B-3-1 or B-5-1;

[0044] When X 1 ~X 2 , Y 1 ~Y 4 are all N(R 1 ), and when R 1 is an aryl group, or when X 1 ~X 2 is S, Se, Te, N(R 1 ), B(R 1 ), C(R 1 R 2 ), Si(R 1 R 2 ), Y 1 ~Y 4 are all N(R 1 ), and when R 1 is an aryl group, the preparation method includes the following steps:

[0045] Under an argon atmosphere, add A-1 or A-3 and aromatic amine to a 500 mL two-necked flask, then add sodium hydride (60% w / w), and place the round-bottom flask in an oil bath and heat it from room temperature to the reflux temperature within 20 min. During the reaction, observe the color change. After the reaction is completed, cool the reaction mixture to room temperature, quench the reaction by slowly adding deionized water, and extract twice with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and filtered, then the dichloromethane is removed by rotary evaporation, and a solid precipitate is precipitated by adding ether and filtered. After the precipitated solid is separated by ethanol / dichloromethane column chromatography, the dicationic polycyclic compound B-3-2 or B-5-2 is obtained by recrystallization by slowly evaporating dichloromethane in dichloromethane / toluene;

[0046]

[0047] wherein, Ar 1 ~Ar 4 , (R 1 ) a ~(R 4 ) d , R 1 ~R 2 The codes are all defined as above and will not be elaborated here.

[0048] Application of a dicationic polycyclic compound as a luminescent material, especially in an organic electroluminescent device.

[0049] 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 select and adjust according to the application situation, quality requirements and product requirements. For example, the organic electroluminescent device described in the present invention includes an anode, a cathode and an organic thin film layer located between the anode and the cathode; the organic thin film layer includes the dicationic compound shown in formula (I) of the present invention. Further, the organic thin film layer includes a light-emitting layer; the light-emitting layer includes the dicationic compound shown in formula (I) of the present invention. The structure of the organic electroluminescent device described in the present invention preferably specifically includes: 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.

[0050] 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 select and adjust according to the application situation, quality requirements and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0051] According to the present invention, the anode is preferably a material that is easy for hole injection, more preferably a conductive metal or a conductive metal oxide, and still more preferably indium tin oxide.

[0052] The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; in the present invention, the organic thin film layer preferably includes a light-emitting layer; the light-emitting layer includes the dicationic compound shown in the above formula (I); the dicationic compound shown in formula (I) provided by the present invention directly constitutes an organic electroluminescent layer as a light-emitting material.

[0053] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum, and silver, and preferably aluminum.

[0054] In order to improve the performance and efficiency of the device, the organic thin film layer between the anode and the light-emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light-emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. The 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 electrodes, 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.

[0055] 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; and forming a cathode on the organic thin film layer. The light-emitting layer includes the dicationic compound shown in formula (I).

[0056] The present invention can correspond the structures 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 aforementioned organic electroluminescent device, and will not be elaborated herein one by one.

[0057] The present invention first forms an anode on a substrate. There are no special restrictions on the formation method of the anode in the present invention, and it can be carried out according to methods well-known to those skilled in the art. There are no special restrictions on 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. There are no special restrictions on the formation method of the cathode in the present invention, and it is preferably a method well-known to those skilled in the art, including but not limited to vacuum deposition.

[0058] In the present invention, in order to improve the light-emitting performance of the device, an auxiliary ionic compound can also be added to the light-emitting layer, and the mass ratio of the compound in the light-emitting layer is 0.5 wt% - 80 wt%. The compound is preferably selected from the following structures:

[0059]

[0060]

[0061] The beneficial effects of the present invention are:

[0062] For the dicationic compound of the present invention, on the one hand, the rigid backbone structure of the polycyclic compound can be used to reduce the degree of excited-state structural relaxation, thereby achieving a narrow full width at half maximum; on the other hand, the resonance effect between the carbocation and the heteroatom is also used to achieve the separation of HOMO and LUMO, thereby achieving a small ΔE ST and TADF effect, thereby achieving high luminous efficiency. At the same time, by changing the types of aromatic rings, heteroaromatic rings or counter anions contained in the polycyclic compound, further adjustment of the emission wavelength, delayed fluorescence lifetime and full width at half maximum can also be achieved.

[0063] Experimental results show that using the dicationic compound of the present invention as the light-emitting layer of the electroluminescent device can achieve a narrow electroluminescence full width at half maximum without a filter and a microcavity structure, and can also achieve a high external quantum efficiency of the device.

[0064] The preparation method of the dicationic compound of the present invention has simple steps and mild conditions. Detailed implementation manners

[0065] The following will combine the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the present invention.

[0066] The reagents used in the following examples are all commercially available.

[0067] Example 1

[0068]

[0069] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous diethyl ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous diethyl ether was slowly added dropwise. After stirring until the lithium was completely dissolved, a mixed solution of 1-1 (49.5 mL, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 days. 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, and slowly added to the reaction system, and the reaction was refluxed under condensation at 65 °C for 3 days. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with diethyl ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HBF 4 (24 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous diethyl ether. The crude product was separated by silica gel column chromatography to obtain product 1-3 (55.4 g, yield: 70%).

[0070] Elemental analysis of structure (C 44 H 48 B 2 F 8 O 12 ): Theoretical values: C, 56.07; H, 5.13; B, 2.29; F, 16.13; O, 20.37; Measured values: C, 56.09; H, 5.10; B, 2.31; F, 16.16; O, 20.41.

[0071] MALDI-TOF-MS: Theoretical value: 942.3237; Experimental value: 942.3740.

[0072] Under an argon atmosphere, 1-3 (491.7 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, extracted with dichloromethane 3 times (150 mL × 3), the organic phase was dried over anhydrous sodium sulfate and filtered, and after concentration, the crude product was separated by methanol / dichloromethane column and recrystallized from ethyl acetate (50 mL) to obtain product M6 (166.2 mg, yield: 39%).

[0073] Elemental analysis of structure (C 32 H 12 B2 F 8 O 6 ):Theoretical values: C, 57.71; H, 1.82; B, 3.25; F, 22.82; O, 14.41; Measured values: C, 57.75; H, 1.80; B, 3.21; F, 22.87; O, 14.43.

[0074] MALDI-TOF-MS: Theoretical value: 666.0692; Experimental value: 666.1359.

[0075] Example 2

[0076]

[0077] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous diethyl ether were added to a 1 L two-necked flask. Under an ice bath condition, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous diethyl ether was slowly added dropwise. After stirring until the lithium was completely dissolved, a mixed solution of 1-1 (49.5 mL, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 days. 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, and it was slowly added to the reaction system, and the reaction was refluxed under condensation at 65 °C for 3 days. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with diethyl ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HPF 6 (30 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous diethyl ether. The crude product was separated by silica gel column chromatography to obtain product 1-4 (64.9 g, yield: 73%).

[0078] Elemental analysis structure (C 44 H 48 F 12 O 12 P 2 ):Theoretical values: C, 49.91; H, 4.57; F, 21.53; O, 18.13; P, 5.85; Measured values: C, 49.94; H, 4.51; F, 21.50; O, 18.15; P, 5.81.

[0079] MALDI-TOF-MS: Theoretical value: 1058.2484; Experimental value: 1058.4539.

[0080] Under an argon atmosphere, 1-4 (677.3 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, and extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and then recrystallized from ethyl acetate (50 mL) to obtain product M9 (220.2 mg, yield: 44%).

[0081] Elemental analysis for (C 32 H 12 F 12 O 6 P 2 ): Theoretical: C, 49.12; H, 1.55; F, 29.14; O, 12.27; P, 7.92; Found: C, 49.14; H, 1.54; F, 29.16; O, 12.25; P, 7.95.

[0082] MALDI-TOF-MS: Theoretical: 781.9972; Observed: 781.8483.

[0083] Example 3

[0084]

[0085] Under an argon atmosphere, 1-3 (4.9 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask. The mixture was heated under reflux for 20 h, and isopropylamine was added twice during the reaction (1.0 mL × 2). After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried in vacuo. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M22 (1.9 g, yield: 33%).

[0086] Elemental analysis for (C 50 H 54 B 2 F 8 N 6 ): Theoretical: C, 65.80; H, 5.96; B, 2.37; F, 16.65; O, 9.21; Found: C, 65.83; H, 5.99; B, 2.34; F, 16.63; O, 9.25.

[0087] MALDI-TOF-MS: Theoretical value: 912.4468; Experimental value: 912.4831.

[0088] Example 4

[0089]

[0090] Under an argon atmosphere, 1-4 (6.7 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and the mixture was heated under reflux for 20 h. During the reaction, isopropylamine was added twice (1.0 mL × 2). After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M23 (2.30 g, yield: 35%).

[0091] Elemental analysis of structure (C 50 H 54 B 2 F 12 N 6 P 2 ): Theoretical value: C, 58.37; H, 5.29; F, 22.16; N, 8.17; P, 6.02; Test value: C, 58.39; H, 5.24; F, 22.20; N, 8.19; P, 6.06.

[0092] MALDI-TOF-MS: Theoretical value: 1028.3748; Experimental value: 1028.4391.

[0093] Example 5

[0094]

[0095] Sodium tetraphenylborate (9.79 g, 28.6 mmol) was dissolved in 4 mL of acetonitrile, and M23 (586.1 mg, 0.57 mmol) was quickly added. After the solvent evaporated, the crude product was separated by methanol / dichloromethane column chromatography. After dissolution, filtration and vacuum drying, solid M25 (549.3 mg, yield 70%) was obtained.

[0096] Elemental analysis of structure (C 98 H 94 B 2 N 6 ): Theoretical value: C, 85.45; H, 6.88; B, 1.57; N, 6.10; Test value: C, 85.49; H, 6.85; B, 1.59; N, 6.15.

[0097] MALDI-TOF-MS: Theoretical value: 1376.7726; Experimental value: 1376.5926.

[0098] Example 6

[0099]

[0100] Under an argon atmosphere, 2-1 (3.3 g, 9.2 mmol) and 100 mL of ultradry diethyl ether were added to a 500 mL two-necked flask. At -78 °C, 13.7 mL of an n-BuLi solution (1.55 M, 21.2 mmol) dissolved in n-hexane was added dropwise over 10 min. After the addition, the mixture was stirred for 1 h, 2-2 (5.8 g, 21.2 mmol) was added, and the temperature was raised to 23 °C. The resulting solution was stirred at 23 °C for 1 h, diluted with deionized water, and the precipitate was collected by filtration, washed three times with water (100 mL × 3) and three times with methanol (100 mL × 3). The crude product was dissolved in chloroform and heated at 60 °C for 5 min. After cooling to 23 °C, the filtrate was removed by filtration, and the yellow solid intermediate was obtained by vacuum drying. Then the intermediate was dissolved in 130 mL of trifluoroacetic anhydride, and 42% HBF 4 solution (13.4 mL, 88.8 mmol) was added under an ice bath. The reaction solution turned dark red and was stirred at 23 °C for 2 h. The addition of ultradry diethyl ether caused the precipitation of the ionic salt. The precipitate was filtered, washed three times with diethyl ether (15 mL × 3), and vacuum dried to obtain red powder 2-3 (3.73 g, yield: 46%).

[0101] Elemental analysis structure (C 40 H 36 B 2 F 8 O 8 S 2 ): Theoretical value: C, 54.44; H, 4.11; B, 2.45; F, 17.22; O, 14.50; S, 7.27; Test value: C, 54.48; H, 4.15; B, 2.41; F, 17.28; O, 14.53; S, 7.29.

[0102] MALDI-TOF-MS: Theoretical value: 882.1910; Experimental value: 882.4073.

[0103] Under an argon atmosphere, 2-3 (564.6 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone, and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, and extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and recrystallized from ethyl acetate (50 mL) to obtain product M43 (187.6 mg, yield: 42%).

[0104] Elemental analysis of structure (C 32 H 12 B 2 F 8 O 4 S 2 ): Theoretical values: C, 55.05; H, 1.73; B, 3.10; F, 21.77; O, 9.17; S, 9.18; Measured values: C, 55.09; H, 1.70; B, 3.15; F, 21.75; O, 9.16; S, 9.19.

[0105] MALDI-TOF-MS: Theoretical value: 698.0235; Experimental value: 698.1597.

[0106] Example 7

[0107]

[0108] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous diethyl ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous diethyl ether was slowly added dropwise, stirred until the lithium was completely dissolved, and a mixed solution of 3-1 (63.4 g, 373 mmol) and 150 mL of anhydrous benzene was added. The reaction was refluxed at 35 °C for 3 d. 3-2 (32.8 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, slowly added to the reaction system, and the reaction was refluxed under condensation at 65 °C for 3 d. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with diethyl ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and an aqueous solution of HBF 4 (24 mL, 200 mmol) was added to the filtrate, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous diethyl ether. The crude product was separated by silica gel column chromatography to obtain product 3-3 (62.9 g, yield: 66%).

[0109] Elemental analysis of structure (C 44 H 48 B2 F 8 S 12 ):Theoretical values: C, 46.55; H, 4.26; B, 1.90; F, 13.39; S 33.89; Measured values: C, 46.58; H, 4.22; B, 1.95; F, 13.36; S 33.88.

[0110] MALDI-TOF-MS: Theoretical value: 1134.0463; Experimental value: 1134.2951.

[0111] Under an argon atmosphere, 3-3 (725.7 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone, and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, and extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography, and then recrystallized from ethyl acetate (50 mL) to obtain product M44 (234.1 mg, yield: 48%).

[0112] Elemental analysis of structure (C 32 H 12 B 2 F 8 S 6 ):Theoretical values: C, 50.41; H, 1.59; B, 2.84; F, 19.93; S, 25.23; Measured values: C, 50.46; H, 1.62; B, 2.80; F, 19.97; S, 25.27.

[0113] MALDI-TOF-MS: Theoretical value: 761.9322; Experimental value: 761.5185.

[0114] Example 8

[0115]

[0116] Under an argon atmosphere, 2-3 (5.6 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol), and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and heated under reflux for 20 h. Isopropylamine was added twice during the reaction (1.0 mL × 2). After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water, and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M45 (2.04 g, yield: 33%).

[0117] Elemental analysis structure (C 44 H 40 B 2 F 8 N 4 S 2 ): Theoretical values: C, 61.72; H, 4.67; B, 2.51; F, 17.62; N, 6.50; S, 7.43; Test values: C, 61.76; H, 4.63; B, 2.55; F, 17.66; N, 6.53; S, 7.40.

[0118] MALDI-TOF-MS: Theoretical value: 862.2753; Experimental value: 862.5295.

[0119] Example 9

[0120]

[0121] Under an argon atmosphere, 2-1 (3.3 g, 9.2 mmol) and 100 mL of ultra-dry diethyl ether were added to a 500 mL two-necked flask. At -78 °C, 13.7 mL of an n-BuLi solution (1.55 M, 21.2 mmol) dissolved in n-hexane was added dropwise over 10 min. After the addition was complete, the mixture was stirred at -20 °C for 1 h, 4-1 (6.8 g, 21.2 mmol) was added, and the temperature was raised to 23 °C. The resulting solution was stirred at 23 °C for 1 h, diluted with deionized water, and the precipitate was collected by filtration, washed three times with water (100 mL × 3) and three times with methanol (100 mL × 3). The crude product was dissolved in CHCl 3 and heated at 60 °C for 5 min. After cooling to 23 °C, the filtrate was removed by filtration, and the yellow solid intermediate was obtained by vacuum drying. Then the intermediate was dissolved in 130 mL of trifluoroacetic anhydride, and 42% HBF 4 solution (13.4 mL, 88.8 mmol) was added under an ice bath, and the mixture was stirred at 23 °C for 2 h. The addition of ultra-dry diethyl ether caused the precipitation of the ionic salt. The precipitate was filtered, washed three times with diethyl ether (15 mL × 3), and dried under vacuum to obtain product 4-2 (4.50 g, yield: 50%).

[0122] Elemental analysis structure (C 40 H 36 B 2 F 8 O 8 Se 2):Theoretical values: C, 49.21; H, 3.72; B, 2.21; F, 15.57; O, 13.11; Se, 16.18; Measured values: C, 49.25; H, 3.77; B, 2.24; F, 15.52; O, 13.15; Se, 16.16.

[0123] MALDI-TOF-MS: Theoretical value: 978.0799; Experimental value: 978.2708.

[0124] Under an argon atmosphere, 4-2 (625.9 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, extracted with dichloromethane three times (150 mL × 3), the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and then recrystallized from ethyl acetate (50 mL) to obtain product M53 (254.1 mg, yield: 50%).

[0125] Elemental analysis structure (C 32 H 12 B 2 F 8 O 4 Se 2 ):Theoretical values: C, 48.53; H, 1.53; B, 2.73; F, 19.19; O, 8.08; Se, 19.94; Measured values: C, 48.57; H, 1.56; B, 2.75; F, 19.15; O, 8.04; Se, 19.96.

[0126] MALDI-TOF-MS: Theoretical value: 793.9124; Experimental value: 793.8984.

[0127] Example 10

[0128]

[0129] Under an argon atmosphere, 4-2 (6.3 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and the mixture was heated under reflux for 20 h. During the reaction, isopropylamine (1.0 mL × 2) was added twice. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of diethyl ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M54 (2.45 g, yield: 40%).

[0130] Elemental analysis structure (C 44 H 40 B 2 F 8 N 4 Se 2 ): Theoretical values: C, 55.26; H, 4.22; B, 2.26; F, 15.89; N, 5.86; Se, 16.51; Measured values: C, 55.29; H, 4.25; B, 2.29; F, 15.85; N, 5.82; Se, 16.54.

[0131] MALDI-TOF-MS: Theoretical value: 958.1642; Experimental value: 957.8324.

[0132] Example 11

[0133]

[0134] Under an argon atmosphere, 2-1 (3.3 g, 9.2 mmol) and 100 mL of ultra-dry diethyl ether were added to a 500 mL two-necked flask. Under the condition of -78 °C, 13.7 mL of n-BuLi solution (1.55 M, 21.2 mmol) dissolved in n-hexane was added dropwise over 10 min. After the addition was complete, the mixture was stirred at -20 °C for 1 h, 5-1 (5.9 g, 21.2 mmol) was added, and the temperature was raised to 23 °C. The resulting solution was stirred at 23 °C for 1 h, diluted with deionized water, and the precipitate was collected by filtration, washed with water 3 times (100 mL × 3) and washed with methanol 3 times (100 mL × 3). The crude product was dissolved in CHCl 3 and heated at 60 °C for 5 min. After cooling to 23 °C, the filtrate was removed by filtration, and the yellow solid intermediate was obtained by drying under vacuum. Then the intermediate was dissolved in 130 mL of trifluoroacetic anhydride, and 42% HBF was added under ice bath conditions 4The solution (13.4 mL, 88.8 mmol) was stirred at 23 °C for 2 h. The addition of ultradry diethyl ether resulted in the precipitation of the ionic salt. The precipitate was filtered, washed three times with diethyl ether (15 mL × 3), and dried in vacuo to give the product 5-2 (4.43 g, yield: 52%).

[0135] Elemental analysis for (C 46 H 50 B 4 F 8 O 8 ): calculated: C, 59.66; H, 5.44; B, 4.67; F, 16.41; O, 13.82; found: C, 59.69; H, 5.40; B, 4.62; F, 16.46; O, 13.86.

[0136] MALDI-TOF-MS: calculated: 926.3750; found: 926.1252.

[0137] Under an argon atmosphere, 5-2 (592.9 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-collidine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled and extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by column chromatography on methanol / dichloromethane and recrystallized from ethyl acetate (50 mL) to give the product M55 (190.0 mg, yield: 40%).

[0138] Elemental analysis for (C 38 H 26 B 4 F 8 O 4 ): calculated: C, 61.52; H, 3.53; B, 5.83; F, 20.49; O, 8.63; found: C, 61.55; H, 3.56; B, 5.80; F, 20.51; O, 8.60.

[0139] MALDI-TOF-MS: calculated: 742.2076; found: 742.8492.

[0140] Example 12

[0141]

[0142] Under an argon atmosphere, 5-2 (5.9 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and the mixture was heated under reflux for 20 h. During the reaction, isopropylamine (1.0 mL × 2) was added twice. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M56 (1.74 g, yield: 30%).

[0143] Elemental analysis of structure (C 50 H 54 B 4 F 8 N 4 ): Theoretical values: C, 66.27; H, 6.01; B, 4.77; F, 16.77; N, 6.18; Measured values: C, 66.22; H, 6.05; B, 4.74; F, 16.73; N, 6.20.

[0144] MALDI-TOF-MS: Theoretical value: 906.4593; Experimental value: 906.2372.

[0145] Example 13

[0146]

[0147] Under an argon atmosphere, 2-1 (3.3 g, 9.2 mmol) and 100 mL of ultra-dry ether were added to a 500 mL two-necked flask. Under the condition of -78 °C, 13.7 mL of n-BuLi solution (1.55 M, 21.2 mmol) dissolved in n-hexane was added dropwise over 10 min. After the addition was complete, the mixture was stirred at -20 °C for 1 h, 6-1 (6.5 g, 21.2 mmol) was added, and the temperature was raised to 23 °C. The resulting solution was stirred at 23 °C for 1 h, diluted with deionized water, and the precipitate was collected by filtration, washed with water 3 times (100 mL × 3) and washed with methanol 3 times (100 mL × 3). The crude product was dissolved in CHCl 3 and heated at 60 °C for 5 min. After cooling to 23 °C, the filtrate was removed by filtration, and the yellow solid intermediate was obtained by drying under vacuum. Then the intermediate was dissolved in 130 mL of trifluoroacetic anhydride, and 42% HBF 4 solution (13.4 mL, 88.8 mmol) was added under ice bath conditions, and the mixture was stirred at 23 °C for 2 h. The addition of ultra-dry ether caused the precipitation of the ionic salt. The precipitate was filtered, washed with ether 3 times (15 mL × 3), and dried under vacuum to obtain product 6-2 (3.61 g, yield: 42%).

[0148] Elemental analysis structure (C 44 H 48 B 2 F 8 O 8 Si 2 ): Theoretical values: C, 56.54; H, 5.18; B, 2.31; F, 16.26; O, 13.69; Si, 6.01; Measured values: C, 56.57; H, 5.18; B, 2.35; F, 16.29; O, 13.64; Si, 6.04.

[0149] MALDI-TOF-MS: Theoretical value: 934.2946; Experimental value: 934.6372.

[0150] Under an argon atmosphere, 6-2 (598.0 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, extracted three times with dichloromethane (150 mL × 3), the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and then recrystallized from ethyl acetate (50 mL) to obtain product M57 (249.6 mg, yield: 52%).

[0151] Elemental analysis structure (C 36 H 24 B 2 F 8 O 4 Si 2 ): Theoretical values: C, 57.63; H, 3.22; B, 2.88; F, 20.26; O, 8.53; Si, 7.49; Measured values: C, 57.66; H, 3.25; B, 2.85; F, 20.22; O, 8.58; Si, 7.46.

[0152] MALDI-TOF-MS: Theoretical value: 750.1271; Experimental value: 750.3612.

[0153] Example 14

[0154]

[0155] Under an argon atmosphere, 6-2 (6.0 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and the mixture was heated under reflux for 20 h. During the reaction, isopropylamine (1.0 mL × 2) was added twice. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M58 (2.11 g, yield: 36%).

[0156] Elemental analysis of structure (C 48 H 52 B 2 F 8 N 4 Si 2 ): Theoretical values: C, 63.03; H, 5.73; B, 2.36; F, 16.62; N, 6.12; Si, 6.14; Measured values: C, 63.07; H, 5.77; B, 2.31; F, 16.65; N, 6.15; Si, 6.18.

[0157] MALDI-TOF-MS: Theoretical value: 914.3789; Experimental value: 914.7492.

[0158] Example 15

[0159]

[0160] Under an argon atmosphere, 2-1 (3.3 g, 9.2 mmol) and 100 mL of ultra-dry ether were added to a 500 mL two-necked flask. At -78 °C, 13.7 mL of an n-BuLi solution (1.55 M, 21.2 mmol) dissolved in n-hexane was added dropwise over 10 min. After the addition was complete, the mixture was stirred at -20 °C for 1 h, 7-1 (6.0 g, 21.2 mmol) was added, and the temperature was raised to 23 °C. The resulting solution was stirred at 23 °C for 1 h, diluted with deionized water, and the precipitate was collected by filtration, washed with water 3 times (100 mL × 3) and washed with methanol 3 times (100 mL × 3). The crude product was dissolved in CHCl 3 and heated at 60 °C for 5 min. After cooling to 23 °C, the filtrate was removed by filtration and dried under vacuum to obtain a yellow solid intermediate. Then the intermediate was dissolved in 130 mL of trifluoroacetic anhydride, and 42% HBF was added under ice bath conditions 4The solution (13.4 mL, 88.8 mmol) was stirred at 23 °C for 2 h. The addition of ultra-dry diethyl ether resulted in the precipitation of the ionic salt. The precipitate was filtered, washed three times with diethyl ether (15 mL × 3), and dried under vacuum to obtain product 7-2 (4.57 g, yield: 55%).

[0161] Elemental analysis of the structure (C 46 H 48 B 2 F 8 O 8 ): Theoretical values: C, 61.22; H, 5.36; B, 2.40; F, 16.84; O, 14.18; Measured values: C, 61.25; H, 5.39; B, 2.45; F, 16.80; O, 14.16.

[0162] MALDI-TOF-MS: Theoretical value: 902.3408; Experimental value: 902.5829.

[0163] Under an argon atmosphere, 7-2 (577.3 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone, and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, extracted three times with dichloromethane (150 mL × 3), the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by column chromatography with methanol / dichloromethane and then recrystallized from ethyl acetate (50 mL) to obtain product M59 (206.8 mg, yield: 45%).

[0164] Elemental analysis of the structure (C 38 H 24 B 2 F 8 O 4 ): Theoretical values: C, 63.55; H, 3.37; B, 3.01; F, 21.16; O, 8.91; Measured values: C, 63.59; H, 3.32; B, 3.05; F, 21.10; O, 8.95.

[0165] MALDI-TOF-MS: Theoretical value: 718.1733; Experimental value: 718.3212.

[0166] Example 16

[0167]

[0168] Under an argon atmosphere, 7-2 (5.8 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask. The mixture was heated under reflux for 20 h, and isopropylamine (1.0 mL × 2) was added twice during the reaction. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M60 (1.8 g, yield: 33%).

[0169] Elemental analysis of structure (C 50 H 52 B 2 F 8 N 4 ): Theoretical values: C, 68.04; H, 5.94; B, 2.45; F, 17.22; N, 6.35; Measured values: C, 68.07; H, 5.97; B, 2.40; F, 17.26; N, 6.38.

[0170] MALDI-TOF-MS: Theoretical value: 882.4250; Experimental value: 882.6012.

[0171] Example 17

[0172]

[0173] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous ether was slowly added dropwise, and the mixture was stirred until the lithium was completely dissolved. A mixed solution of 8-1 (51.8 g, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 d. 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, and it was slowly added to the reaction system, and the reaction was condensed and refluxed at 65 °C for 3 d. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HBF 4 (24 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous ether. The crude product was separated by silica gel column chromatography to obtain product 8-2 (55.6 g, yield: 70%).

[0174] Elemental analysis of structure (C 40 H 44 N4 B 2 F 8 O 12 ):Theoretical values: C, 50.76; H, 4.69; B, 2.28; F, 16.06; N, 5.92; O, 20.29; Measured values: C, 50.72; H, 4.72; B, 2.31; F, 16.10; N, 5.96; O, 20.34.

[0175] MALDI-TOF-MS: Theoretical value: 946.3014; Experimental value: 946.3852.

[0176] Under an argon atmosphere, 8-2 (494.1 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone, and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, extracted three times with dichloromethane (150 mL × 3), the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and then recrystallized from ethyl acetate (50 mL) to obtain product M61 (197.3 mg, yield: 46%).

[0177] Elemental analysis structure (C 28 H 8 N 4 B 2 F 8 O 6 ):Theoretical values: C, 50.20; H, 1.20; B, 3.23; F, 22.68; N, 8.36; O, 14.33; Measured values: C, 50.16; H, 1.19; B, 3.27; F, 22.71; N, 8.42; O, 14.36.

[0178] MALDI-TOF-MS: Theoretical value: 670.0502; Experimental value: 670.1541.

[0179] Example 18

[0180]

[0181] Under an argon atmosphere, 8-2 (4.94 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask. The mixture was heated under reflux for 20 h, and isopropylamine (1.0 mL × 2) was added twice during the reaction. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried in vacuo. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M62 (2.64 g, yield: 45%).

[0182] Elemental analysis of structure (C 44 H 40 B 2 F 8 N 4 S 2 ): Theoretical values: C, 60.28; H, 5.50; B, 2.36; F, 16.58; N, 15.28; Measured values: C, 60.16; H, 5.36; B, 2.51; F, 16.32; N, 15.39.

[0183] MALDI-TOF-MS: Theoretical value: 916.4267; Experimental value: 916.3249.

[0184] Example 19

[0185]

[0186] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous ether was slowly added dropwise, and the mixture was stirred until the lithium was completely dissolved. A mixed solution of 9-1 (64.4 mL, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 d. 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, and it was slowly added to the reaction system, and the reaction was refluxed under condensation at 65 °C for 3 d. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HBF 4 (24 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous ether. The crude product was separated by silica gel column chromatography to obtain product 9-2 (59.5 g, yield: 62%).

[0187] Elemental analysis of structure (C 60 H56 B 2 F 8 O 12 ):Theoretical values: C, 63.07; H, 4.94; B, 1.89; F, 13.30; O, 16.80; Measured values: C, 63.11; H, 4.96; B, 1.84; F, 13.37; O, 16.75.

[0188] MALDI-TOF-MS: Theoretical value: 1142.3830; Experimental value: 1142.4258.

[0189] Under an argon atmosphere, 9-2 (619.5 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and then recrystallized from ethyl acetate (50 mL) to obtain product M65 (133.9 mg, yield: 30%).

[0190] Elemental analysis structure (C 48 H 20 B 2 F 8 O 6 ):Theoretical values: C, 66.55; H, 2.33; B, 2.50; F, 17.54; O, 11.08; Measured values: C, 66.51; H, 2.30; B, 2.45; F, 17.51; O, 11.12.

[0191] MALDI-TOF-MS: Theoretical value: 866.1318; Experimental value: 866.2019.

[0192] Example 20

[0193]

[0194] Under an argon atmosphere, 9-2 (6.20 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and the mixture was heated under reflux for 20 h. During the reaction, isopropylamine (1.0 mL × 2) was added twice. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M66 (2.42 g, yield: 34%).

[0195] Elemental analysis of structure (C 44 H 40 B 2 F 8 N 4 S 2 ): Theoretical values: C, 71.23; H, 5.62; B, 1.94; F, 13.66; N, 7.55; Measured values: C, 71.26; H, 5.68; B, 1.97; F, 13.62; N, 7.59.

[0196] MALDI-TOF-MS: Theoretical value: 1112.5083; Experimental value: 1112.5867.

[0197] Example 21

[0198]

[0199] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous ether was slowly added dropwise, and the mixture was stirred until the lithium was completely dissolved. A mixed solution of 10-1 (66.4 g, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 d. 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, and it was slowly added to the reaction system, and the mixture was condensed and refluxed at 65 °C for 3 d. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HBF 4 (24 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous ether. The crude product was separated by silica gel column chromatography to obtain product 10-2 (73.0 g, yield: 75%).

[0200] Elemental analysis of structure (C 53H 48 B 2 F 8 O 16 ):Theoretical values: C, 58.05; H, 4.87; B, 1.87; F, 13.12; O, 23.09; Measured values: C, 58.07; H, 4.90; B, 1.85; F, 13.15; O, 23.06.

[0201] MALDI-TOF-MS: Theoretical value: 1158.3616; Experimental value: 1158.4752.

[0202] Under an argon atmosphere, 10-2 (741.4 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and reacted for 3 h. The reaction mixture was cooled, extracted with dichloromethane three times (150 mL × 3), the organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and then recrystallized from ethyl acetate (50 mL) to obtain product M73 (197.6 mg, yield: 35%).

[0203] Elemental analysis structure (C 40 H 12 B 2 F 8 O 10 ):Theoretical values: C, 59.90; H, 2.29; B, 2.45; F, 17.23; O, 18.13; Measured values: C, 59.69; H, 2.42; B, 2.34; F, 17.45; O, 18.34.

[0204] MALDI-TOF-MS: Theoretical value: 882.1104; Experimental value: 882.1233.

[0205] Example 22

[0206]

[0207] Under an argon atmosphere, 10-2 (7.1 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and the mixture was heated under reflux for 20 h. During the reaction, isopropylamine (1.0 mL × 2) was added twice. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M74 (2.61 g, yield: 38%).

[0208] Elemental analysis of structure (C 58 H 54 B 2 F 8 N 6 O 4 ): Theoretical values: C, 64.94; H, 5.07; B, 2.02; F, 14.17; N, 7.83; O, 5.97; Measured values: C, 64.99; H, 5.09; B, 2.06; F, 14.14; N, 7.86; O, 5.92.

[0209] MALDI-TOF-MS: Theoretical value: 1072.4265; Experimental value: 1072.5712.

[0210] Example 23

[0211]

[0212] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous ether was slowly added dropwise, and the mixture was stirred until the lithium was completely dissolved. A mixed solution of 11-1 (89.93 g, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 d. To a 500 mL single-necked flask was added 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene, and it was slowly added to the reaction system, and the mixture was refluxed under condensation at 65 °C for 3 d. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, and the aqueous phase was extracted with ether. The combined organic phases were dried over anhydrous sodium sulfate and filtered. To the filtrate was added an aqueous solution of HBF 4 (24 mL, 200 mmol), and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous ether. The crude product was separated by silica gel column chromatography to obtain product 11-2 (68.3 g, yield: 60%).

[0213] Elemental analysis structure (C 72 H 68 B 2 F 8 N 4 O 12 ): Theoretical values: C, 63.08; H, 5.06; B, 1.60; F, 11.22; N, 4.14; O, 14.17; Test values: C, 63.04; H, 5.03; B, 1.65; F, 11.27; N, 4.10; O, 14.11.

[0214] MALDI-TOF-MS: Theoretical value: 1354.4892; Experimental value: 1354.6929.

[0215] Under an argon atmosphere, 11-2 (866.8 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and reacted for 3 h. The reaction mixture was cooled, extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography and then recrystallized from ethyl acetate (50 mL) to obtain product M85 (230.4 mg, yield: 41%).

[0216] Elemental analysis structure (C 44 H 24 B 2 F 8 N 4 O 6 ): Theoretical values: C, 60.17; H, 2.75; B, 2.46; F, 17.30; N, 6.38; O, 10.93; Test values: C, 60.12; H, 2.71; B, 2.49; F, 17.34; N, 6.35; O, 10.97.

[0217] MALDI-TOF-MS: Theoretical value: 878.1754; Experimental value: 878.3507.

[0218] Example 24

[0219]

[0220] Under an argon atmosphere, 11-2 (8.7 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and the mixture was heated under reflux for 20 h. During the reaction, isopropylamine (1.0 mL × 2) was added twice. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M86 (2.3 g, yield: 33%).

[0221] Elemental analysis of structure (C 62 H 66 B 2 F 8 N 10 ): Theoretical values: C, 66.20; H, 5.91; B, 1.92; F, 13.51; N, 12.45; Measured values: C, 66.25; H, 5.94; B, 1.94; F, 13.56; N, 12.48.

[0222] MALDI-TOF-MS: Theoretical value: 1124.5530; Experimental value: 1124.8782.

[0223] Example 25

[0224]

[0225] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous ether were added to a 1 L two-necked flask. Under an ice bath condition, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous ether was slowly added dropwise, and the mixture was stirred until the lithium was completely dissolved. A mixed solution of 12-1 (62.7 g, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 d. To a 500 mL single-necked flask, 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added, and it was slowly added to the reaction system, and the reaction was condensed and refluxed at 65 °C for 3 d. After the reaction was completed, it was cooled to room temperature, 2M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HBF 4 (24 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous ether. The crude product was separated by silica gel column chromatography to obtain product 12-2 (61.6 g, yield: 69%).

[0226] Elemental analysis of structure (C 48 H 56B 2 F 8 O 16 ):Theoretical values: C, 54.26; H, 5.31; B, 2.03; F, 14.30; O, 24.09; Measured values: C, 54.29; H, 5.36; B, 2.07; F, 14.35; O, 24.06.

[0227] MALDI-TOF-MS: Theoretical value: 1062.3627; Experimental value: 1062.6291.

[0228] Under an argon atmosphere, 12-2 (679.9 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone, and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, and extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography, and then recrystallized from ethyl acetate (50 mL) to obtain product M97 (216.3 mg, yield: 43%).

[0229] Elemental analysis of structure (C 36 H 20 B 2 F 8 O 10 ):Theoretical values: C, 55.00; H, 2.56; B, 2.75; F, 19.33; O, 20.35; Measured values: C, 55.05; H, 2.59; B, 2.73; F, 19.34; O, 20.31.

[0230] MALDI-TOF-MS: Theoretical value: 786.1115; Experimental value: 786.3718.

[0231] Example 26

[0232]

[0233] Under an argon atmosphere, 12-2 (6.8 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol), and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask. The mixture was heated under reflux for 20 h, and isopropylamine (1.0 mL × 2) was added twice during the reaction. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water, and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M98 (2.64 g, yield: 40%).

[0234] Elemental analysis structure (C 54 H 62 B 2 F 8 N 6 O 4 ): Theoretical values: C, 62.80; H, 6.05; B, 2.09; F, 14.72; N, 8.14; O, 6.20; Test values: C, 62.85; H, 6.01; B, 2.06; F, 14.74; N, 8.16; O, 6.25.

[0235] MALDI-TOF-MS: Theoretical value: 1032.4891; Experimental value: 1032.6384.

[0236] Example 27

[0237]

[0238] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous diethyl ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous diethyl ether was slowly added dropwise. After stirring until the lithium was completely dissolved, a mixed solution of 13-1 (76.9 g, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 d. 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, and slowly added to the reaction system, and the reaction was refluxed under condensation at 65 °C for 3 d. After the reaction was completed, it was cooled to room temperature, 2 M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with diethyl ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HBF 4 (24 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous diethyl ether. The crude product was separated by silica gel column chromatography to obtain product 13-2 (73.4 g, yield: 72%).

[0239] Elemental analysis structure (C 48 H 44 B 2 F 20 O 12 ): Theoretical values: C, 47.47; H, 3.65; B, 1.78; F, 31.29; O, 15.81; Test values: C, 47.49; H, 3.61; B, 1.74; F, 31.25; O, 15.86.

[0240] MALDI-TOF-MS: Theoretical value: 1214.2700; Experimental value: 1214.6145.

[0241] Under an argon atmosphere, 13-2 (777.1 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone, and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, and extracted three times with dichloromethane (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by column chromatography using methanol / dichloromethane. After recrystallization from ethyl acetate (50 mL), the product M107 (228.1 mg, yield: 38%) was obtained.

[0242] Elemental analysis of structure (C 36 H 8 B 2 F 20 O 6 ): Theoretical values: C, 46.10; H, 0.86; B, 2.30; F, 40.51; O, 10.23; Measured values: C, 46.14; H, 0.88; B, 2.33; F, 40.54; O, 10.26.

[0243] MALDI-TOF-MS: Theoretical value: 938.0188; Experimental value: 938.2114.

[0244] 1 1H-NMR (400 MHz, CD 2 3 5 OD): δ ppm 7.35 (s, 4H), 7.10 (s, 4H).

[0245] Example 28

[0246]

[0247] Under an argon atmosphere, 13-2 (7.8 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol), and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask. The mixture was heated under reflux for 20 h, and isopropylamine (1.0 mL × 2) was added twice during the reaction. After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water, and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, recrystallization from acetonitrile gave the solid M108 (2.80 g, yield: 37%).

[0248] Elemental analysis of structure (C 54 H 50 B 2 F20 N 6 ):Theoretical values: C, 54.75; H, 4.25; B, 1.83; F, 32.07; N, 7.09; Measured values: C, 54.71; H, 4.27; B, 1.86; F, 32.10; N, 7.05.

[0249] MALDI-TOF-MS: Theoretical value: 1184.3964; Experimental value: 1184.6412.

[0250] 1 H-NMR(400MHz, C 2 D 5 OD): δ ppm 7.29(s, 4H), 7.05(s, 4H), 2.8(m, 6H), 1.15(d, J = 2.5, 36H).

[0251] Example 29

[0252]

[0253] Under an argon atmosphere, lithium strips (6.1 g, 860 mmol) and 100 mL of anhydrous diethyl ether were added to a 1 L two-necked flask. Under ice bath conditions, a solution of bromobenzene (45.5 mL, 429 mmol) dissolved in 70 mL of anhydrous diethyl ether was slowly added dropwise. After stirring until the lithium was completely dissolved, a mixed solution of 14-1 (95.5 g, 373 mmol) and 150 mL of anhydrous benzene was added, and the reaction was refluxed at 35 °C for 3 days. 1-2 (28.9 g, 84 mmol) dissolved in 75 mL of anhydrous benzene was added to a 500 mL single-necked flask, and it was slowly added to the reaction system, and the reaction was refluxed under condensation at 65 °C for 3 days. After the reaction was completed, it was cooled to room temperature, 2M NaOH (150 mL, 300 mmol) solution was added, the aqueous phase was extracted with diethyl ether, the combined organic phases were dried over anhydrous sodium sulfate and filtered, and HBF 4 (24 mL, 200 mmol) aqueous solution was added, and a precipitate was immediately formed. The precipitate was filtered out and washed thoroughly with anhydrous diethyl ether. The crude product was separated by silica gel column chromatography to obtain product 14-2 (83.2 g, yield: 70%).

[0254] Elemental analysis structure (C 80 H 88 B 2 F 8 O 12 ):Theoretical values: C, 67.90; H, 6.27; B, 1.53 F, 10.74; O, 13.57; Measured values: C, 67.94; H, 6.29; B, 1.56 F, 10.77; O, 13.59.

[0255] MALDI-TOF-MS: Theoretical value: 1414.6334; Experimental value: 1414.1975.

[0256] Under an argon atmosphere, 14-2 (905.4 mg, 0.64 mmol), LiI (1.7 g, 12.8 mmol), 50 mL of N-methylpyrrolidone and three drops of 2,4,6-trimethylpyridine were added to a 500 mL two-necked flask. The temperature was raised to 140 °C and the reaction was carried out for 3 h. The reaction mixture was cooled, and extracted with dichloromethane three times (150 mL × 3). The organic phase was dried over anhydrous sodium sulfate, filtered, concentrated, and the crude product was separated by methanol / dichloromethane column chromatography, and then recrystallized from ethyl acetate (50 mL) to obtain the product M109 (253.3 mg, yield: 35%).

[0257] Elemental analysis of structure (C 68 H 52 B 2 F 8 O 6 ): Theoretical value: C, 71.72; H, 4.60; B, 1.90; F, 13.35; O, 8.43; Test value: C, 71.76; H, 4.65; B, 1.93; F, 13.38; O, 8.41.

[0258] MALDI-TOF-MS: Theoretical value: 1138.3822; Experimental value: 1138.6725.

[0259] Example 30

[0260]

[0261] Under an argon atmosphere, 14-2 (90.5 g, 6.4 mmol), isopropylamine (10.21 g, 172.8 mmol), benzoic acid (10.92 g, 134.4 mmol) and 90 mL of N-methylpyrrolidone were added to a 500 mL two-necked flask, and heated under reflux for 20 h. During the reaction, isopropylamine was added twice (1.0 mL × 2). After cooling to room temperature, the reaction mixture was poured into water, and the formed precipitate was collected by filtration, washed with water and dried under vacuum. The crude product was dissolved in 25 mL of dichloromethane and precipitated in 500 mL of ether for further purification. After filtration, it was recrystallized from acetonitrile to obtain solid M110 (2.9 g, yield: 33%).

[0262] Elemental analysis of structure (C 86 H 94 B 2 F 8 N 6Theory value: C, 74.56; H, 6.84; B, 1.56; F, 10.97; N, 6.07; Test value: C, 74.59; H, 6.81; B, 1.52; F, 10.95; N, 6.09.

[0263] MALDI-TOF-MS: Theory value: 1384.7598; Experimental value: 1384.4327.

[0264] Example 31

[0265]

[0266] Under an argon atmosphere, 1-3 (4.9 g, 6.4 mmol), 20 mL of 3,5-dimethylaniline, and sodium hydride (60% w / w, 2.05 g, 51.2 mmol) were added to a 500 mL two-necked flask, and the mixture was heated to reflux for 0.5 h. After the reaction was completed, the reaction mixture was cooled to room temperature, the reaction was quenched by slowly adding deionized water, and the mixture was extracted twice with dichloromethane. The organic phase was dried over anhydrous sodium sulfate and filtered, then the dichloromethane was removed by rotary evaporation, and the residue was further purified by precipitation in 500 mL of ether. The precipitated solid was separated by ethanol / dichloromethane column chromatography and recrystallized by slowly evaporating dichloromethane in dichloromethane / toluene to obtain M111 (2.47 g, yield: 30%).

[0267] Elemental analysis structure (C 80 H 66 B 2 F 8 N 6 ) : Theory value: C, 74.77; H, 5.18; B, 1.68; F, 11.83; N, 6.54; Test value: C, 74.72; H, 5.16; B, 1.64; F, 11.80; N, 6.52.

[0268] MALDI-TOF-MS: Theory value: 1284.5396; Experimental value: 1284.4548.

[0269] See Table 1. Table 1 shows the photophysical properties of the dicationic compounds prepared in the examples of the present invention.

[0270] Table 1 Photophysical properties of the dicationic compounds prepared in the examples of the present invention

[0271]

[0272]

[0273] Note: The delayed fluorescence lifetime in the table was obtained by doping the compound in polystyrene at a concentration of 1 wt% to prepare the sample to be measured, and measured using a time-resolved fluorescence spectrometer. The test instrument is Edinburgh fluorescence spectrometer (FLS-1000, UK).

[0274] As can be seen from Table 1, the dicationic compounds in the examples provided by the present invention exhibit delayed fluorescence effect, and their delayed fluorescence lifetimes are in the range of 42 - 82 μs.

[0275] Device Examples

[0276] The present invention uses three device fabrication processes to illustrate the device fabrication process, where

[0277] The fabrication process of Device Structure A is as follows:

[0278] The process of fabricating the device with the organic light-emitting layer by vacuum evaporation is as follows: On indium tin oxide (ITO) loaded on a glass substrate, TAPC, TCTA, EML (the invented light-emitting compound co-evaporated with SIMCP2 and DPAc-DtCzBN in a mass ratio of 1:2:7), TmPyPB and LiF / Al cathode are sequentially deposited under a vacuum of 4×10 -4 Pa to obtain an organic light-emitting device, where TAPC and TmPyPB serve as the hole transport layer and the electron transport layer respectively, and TCTA is the exciton blocking layer. Its structural formula is shown as follows:

[0279]

[0280] The specific device structure of Device Structure A is:

[0281] ITO / TAPC(50nm) / TCTA(5nm) / EML(30nm) / TmPyPB(30nm) / LiF(0.8nm) / Al(100nm).

[0282] The fabrication process of Device Structure B is as follows:

[0283] The process of fabricating the device with the organic light-emitting layer by solution processing is as follows: On indium tin oxide (ITO) loaded on a glass substrate, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) is spin-coated, annealed at 120 °C for 30 min, and then a toluene solution of the invented light-emitting compound mixed with SIMCP2 and DPAc-DtCzBN in a mass ratio of 1:2:7 is spin-coated at a speed of 1500 rpm for 1 minute and annealed at 80 °C for 30 min. Then under a vacuum of 4×10 -4Under a vacuum of Pa, TSPO1, TmPyPB, and LiF / Al cathode were successively deposited to obtain an organic light-emitting device, where TSPO1 and TmPyPB served as a hole-blocking layer, an electron-transporting layer, and a host material, respectively. Their structural formulas are shown as follows:

[0284]

[0285] The specific device structure of device structure B is as follows:

[0286] ITO / PEDOT:PSS(40nm) / EML(30nm) / TSPO1(8nm) / TmPyPB(42nm) / LiF(1nm) / Al(100nm).

[0287] The preparation process of device structure C is as follows:

[0288] In the process of preparing a device with the organic light-emitting layer by solution processing, poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT:PSS) was spin-coated on indium tin oxide loaded on a glass substrate and annealed at 150 °C for 15 min. Then, in a glove box filled with nitrogen, an acetonitrile solution obtained by mixing the host material TmPyPB, the invented light-emitting compound, and the auxiliary ionic compound I9 in a mass ratio of 100:10:1 was spin-coated on top of the PEDOT:PSS layer at a speed of 1500 rpm. The active layer was heated on a hot plate to remove the residual solvent. Then, the substrate coated with the film was transferred to a vacuum chamber integrated with the glove box (<5×10 -4 Pa). The Al cathode was thermally evaporated onto the active layer.

[0289] The specific device structure of device structure C is as follows:

[0290] ITO / PEDOT:PSS(30nm) / TmPyPB:10wt%EML:1wt%I9(30nm) / Al(100nm)

[0291] Example 32

[0292] Taking the dicationic compound M6 in Example 1 as the implementation object, the dicationic compound M6, SIMCP2, and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic light-emitting device was prepared by adopting the structure described in "device structure B", and the obtained device was tested.

[0293] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M6 provided by the present invention.

[0294] Example 33

[0295] Taking the dicationic compound M9 in Example 2 as the implementation object, the dicationic compound M9, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure A", and the obtained device is tested.

[0296] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M9 provided by the present invention.

[0297] Example 34

[0298] Taking the dicationic compound M22 in Example 3 as the implementation object, the dicationic compound M22, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure A", and the obtained device is tested.

[0299] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M22 provided by the present invention.

[0300] Example 35

[0301] Taking the dicationic compound M23 in Example 4 as the implementation object, TmPyPB, the dicationic compound M23 and I9 are mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure C", and the obtained device is tested.

[0302] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M23 provided by the present invention.

[0303] Example 36

[0304] Taking the dicationic compound M25 in Example 5 as the implementation object, the dicationic compound M25, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0305] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M25 provided by the present invention.

[0306] Example 37

[0307] Taking the dicationic compound M43 in Example 6 as the implementation object, TmPyPB, the dicationic compound M43, and I9 were mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure C", and the obtained device was tested.

[0308] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M43 provided by the present invention.

[0309] Example 38

[0310] Taking the dicationic compound M44 in Example 7 as the implementation object, the dicationic compound M44, SIMCP2, and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure A", and the obtained device was tested.

[0311] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M44 provided by the present invention.

[0312] Example 39

[0313] Taking the dicationic compound M45 in Example 8 as the implementation object, the dicationic compound M45, SIMCP2, and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure B", and the obtained device was tested.

[0314] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M45 provided by the present invention.

[0315] Example 40

[0316] Taking the dicationic compound M53 in Example 9 as the implementation object, TmPyPB, the dicationic compound M53, and I9 were mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure C", and the obtained device was tested.

[0317] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M53 provided by the present invention.

[0318] Example 41

[0319] Taking the dicationic compound M54 in Example 10 as the object of implementation, TmPyPB, the dicationic compound M54 and I9 were mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure C", and the obtained device was tested.

[0320] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M54 provided by the present invention.

[0321] Example 42

[0322] Taking the dicationic compound M55 in Example 11 as the object of implementation, the dicationic compound M55, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure A", and the obtained device was tested.

[0323] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M55 provided by the present invention.

[0324] Example 43

[0325] Taking the dicationic compound M56 in Example 12 as the object of implementation, the dicationic compound M56, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure B", and the obtained device was tested.

[0326] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M56 provided by the present invention.

[0327] Example 44

[0328] Taking the dicationic compound M57 in Example 13 as the object of implementation, the dicationic compound M57, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure A", and the obtained device was tested.

[0329] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M57 provided by the present invention.

[0330] Example 45

[0331] Taking the dicationic compound M58 in Example 14 as the object of implementation, TmPyPB, the dicationic compound M58 and I9 were mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure C", and the obtained device was tested.

[0332] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M58 provided by the present invention.

[0333] Example 46

[0334] Taking the dicationic compound M59 in Example 15 as the object of implementation, the dicationic compound M59, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure A", and the obtained device was tested.

[0335] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M59 provided by the present invention.

[0336] Example 47

[0337] Taking the dicationic compound M60 in Example 16 as the object of implementation, the dicationic compound M60, SIMCP2 and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure A", and the obtained device was tested.

[0338] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M60 provided by the present invention.

[0339] Example 48

[0340] Taking the dicationic compound M61 in Example 17 as the object of implementation, TmPyPB, the dicationic compound M61 and I9 were mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure C", and the obtained device was tested.

[0341] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M61 provided by the present invention.

[0342] Example 49

[0343] Taking the dicationic compound M62 in Example 18 as the object of implementation, the dicationic compound M62, SIMCP2, and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure A", and the obtained device was tested.

[0344] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M62 provided by the present invention.

[0345] Example 50

[0346] Taking the dicationic compound M65 in Example 19 as the object of implementation, TmPyPB, the dicationic compound M65, and I9 were mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure C", and the obtained device was tested.

[0347] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M65 provided by the present invention.

[0348] Example 51

[0349] Taking the dicationic compound M66 in Example 20 as the object of implementation, the dicationic compound M66, SIMCP2, and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure B", and the obtained device was tested.

[0350] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M66 provided by the present invention.

[0351] Example 52

[0352] Taking the dicationic compound M73 in Example 21 as the object of implementation, the dicationic compound M73, SIMCP2, and DPAc-DtCzBN were mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device was prepared by adopting the structure described in "Device Structure A", and the obtained device was tested.

[0353] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M73 provided by the present invention.

[0354] Example 53

[0355] Taking the dicationic compound M74 in Example 22 as the object of implementation, the dicationic compound M74, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0356] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M74 provided by the present invention.

[0357] Example 54

[0358] Taking the dicationic compound M85 in Example 23 as the object of implementation, the dicationic compound M85, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0359] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M85 provided by the present invention.

[0360] Example 55

[0361] Taking the dicationic compound M86 in Example 24 as the object of implementation, TmPyPB, the dicationic compound M86 and I9 are mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure C", and the obtained device is tested.

[0362] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M86 provided by the present invention.

[0363] Example 56

[0364] Taking the dicationic compound M97 in Example 25 as the object of implementation, the dicationic compound M97, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0365] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M97 provided by the present invention.

[0366] Example 57

[0367] Taking the dicationic compound M98 in Example 26 as the object of implementation, the dicationic compound M98, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0368] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M98 provided by the present invention.

[0369] Example 58

[0370] Taking the dicationic compound M107 in Example 27 as the object of implementation, the dicationic compound M107, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0371] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M107 provided by the present invention.

[0372] Example 59

[0373] Taking the dicationic compound M108 in Example 28 as the object of implementation, the dicationic compound M108, SIMCP2, and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0374] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M108 provided by the present invention.

[0375] Example 60

[0376] Taking the dicationic compound M109 in Example 29 as the object of implementation, TmPyPB, the dicationic compound M109, and I9 are mixed in a mass ratio of 100:10:1 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure C", and the obtained device is tested.

[0377] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M109 provided by the present invention.

[0378] Example 61

[0379] Taking the dicationic compound M110 in Example 30 as the implementation object, the dicationic compound M110, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure A", and the obtained device is tested.

[0380] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M110 provided by the present invention.

[0381] Example 62

[0382] Taking the dicationic compound M111 in Example 31 as the implementation object, the dicationic compound M111, SIMCP2 and DPAc-DtCzBN are mixed in a mass ratio of 1:2:7 as the organic light-emitting layer. An organic electroluminescent device is prepared by adopting the structure described in "Device Structure B", and the obtained device is tested.

[0383] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with the dicationic compound M111 provided by the present invention.

[0384] Table 2 Performance parameters of electroluminescent devices prepared with the dicationic compounds provided by the present invention

[0385]

[0386] Note: The maximum external quantum efficiency in the table is obtained according to the calculation method described in the literature (Jpn. J. Appl. Phys. 2001, 40, L783) based on the current-voltage curve and electroluminescent spectrum of the device; the full width at half maximum is the peak width at half of the peak height of the electroluminescent spectrum at room temperature, that is, a straight line parallel to the peak bottom is 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.

[0387] As can be seen from Table 2, the devices prepared with the dicationic compounds provided by the present invention have a very narrow electroluminescent spectrum, with a full width at half maximum of less than 40 nm, overcoming the problem of the relatively wide electroluminescent spectrum (70 - 100 nm) of traditional D-A structure TADF compounds. At the same time, the devices prepared with the dicationic compounds provided by the present invention all have relatively high device efficiency, and their maximum external quantum efficiency reaches 21.7%.

Claims

1. A dicarbocationic compound, characterized in that: Its structural formula is shown in formula (I): Wherein, X1 and X2 are independently selected from O, S, Se, Te, N (R 1 )、B(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ); Y1 to Y4 are independently selected from N(R 1 ), O, S, Se or Te; Ar1-Ar4 are independently selected from substituted or unsubstituted C6-C60 aryl rings, or substituted or unsubstituted C3-C60 heteroaryl rings; wherein the heteroatoms of the heteroaryl rings are independently selected from Si, Ge, N, P, O, S or Se; R1-R4 are each independently selected from H, D, F, Cl, Br, I, -CN, -NO2, -CF3, -OH, -SH, -NH2, C1-C30 straight-chain alkyl, C3-C30 branched-chain alkyl, C3-C30 cycloalkyl, C1-C30 alkoxy, C1-C30 alkylthio, C1-C30 alkylamino, C6-C60 aryl, C6-C60 aromatic ether, C3-C60 heteroaryl or C3-C60 heteroaromatic ether; wherein the heteroatoms of the heteroaromatic group are independently selected from Si, Ge, N, P, O, S or Se; The R 1 and R 2 Each is independently selected from H, D, a C1-C30 straight-chain alkyl group, a C3-C30 branched-chain alkyl group, a C3-C30 cycloalkyl group, a C6-C60 aryl group or a C5-C60 heteroaryl group; wherein the heteroatoms of the heteroaryl group are independently selected from Si, Ge, N, P, O, S or Se; Wherein, a, b, c and d are each independently an integer from 0 to 3; A1 - and A2 - is a monovalent anion, each independently selected from but not limited to F - , Cl - Br - ,I - 、ClO4 - 、BF4 - 、FeCl4 - 、GaCl4 - PF6 - 、SbCl6 - Or one of the following monovalent anions:

2. The dicarbocation compound according to claim 1, characterized in that The X1 and X2 are independently selected from O, S or N (R 1 ).

3. The dicarbocation compound according to claim 1, characterized in that The Y1-Y4 are independently selected from O, S or N (R 1 ).

4. The dicarbocation compound according to claim 1, characterized in that The Ar1 to Ar4 are each independently selected from one of the groups represented by A1 to A19: Wherein, L1, L2, and L3 are each independently selected from H, D, a substituted or unsubstituted C1-C30 straight-chain alkyl group, a substituted or unsubstituted C1-C30 branched alkyl group, a substituted or unsubstituted C1-C30 halogenated alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C5-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se.

5. The dicarbocation compound according to claim 1, characterized in that: It is selected from any one of the following structures:

6. A method for preparing the dicarbocationic compound according to any one of claims 1 to 5, characterized in that: The following steps are involved: When X1-X2, Y1-Y4 are all O or all S, or X1-X2 are S, Se, Te, N (R 1 )、B(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ), when Y1-Y4 are all O, the preparation method comprises the following steps: Under an argon atmosphere, intermediate A-1, A-2 or A-3, LiI and N-methylpyrrolidone are placed in a reaction bottle, and then 2,4,6-trimethylpyridine is added. After the reaction is completed, the reaction mixture is cooled and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and filtered. After concentration, the crude product is separated by silica gel column chromatography and recrystallized to obtain a dicarbon cation compound shown in B-1, B-2 or B-4; When X1~X2, Y1~Y4 are all N(R 1 ), and R 1 When X1-X2 is S, Se, Te, N(R 1 )、B(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ), Y1~Y4 are all N(R 1 ), and R 1 When it is an alkyl group, the preparation method comprises the following steps: Under an argon atmosphere, add intermediate A-1 or A-3, alkylamine, benzoic acid and N-methylpyrrolidone to a two-necked flask, heat and stir, add alkylamine twice during the reaction, cool to room temperature after the reaction, pour the reaction mixture into deionized water, collect the formed precipitate by filtration, wash with water and vacuum dry, dissolve the crude product in dichloromethane and precipitate in ether for purification, filter and recrystallize from acetonitrile to obtain the dicarbon cation compound shown in B-3-1 or B-5-1; When X1~X2, Y1~Y4 are all N(R 1 ), and R 1 When X1-X2 is S, Se, Te, N(R 1 )、B(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ), Y1~Y4 are all N(R 1 ), and R 1 When it is an aryl group, the preparation method comprises the following steps: Under an argon atmosphere, add intermediate A-1 or A-3 and aromatic amine to a two-necked flask, then add sodium hydride and heat the temperature from room temperature to reflux temperature. After the reaction is completed, the reaction mixture is cooled to room temperature, the reaction is quenched by adding deionized water, and extracted with dichloromethane. The organic phase is dried over anhydrous sodium sulfate and filtered, and then dichloromethane is removed by rotary evaporation. Diethyl ether is added to precipitate a solid and filter it. The precipitated solid is separated by ethanol and dichloromethane columns, and then recrystallized in dichloromethane and toluene by evaporating dichloromethane to obtain a dicarbon cation compound shown in B-3-2 or B-5-2; In the above structural formula, when X1 to X2 are all O and Y1 to Y4 are all O, the structural formula is marked as A-1; When X1 to X2 are all S and Y1 to Y4 are all S, the structural formula is marked as A-2; In the above structural formula A-3, X1 to X2 are S, Se, Te, N (R 1 )、B(R 1 )、C(R 1 R 2 )、Si(R 1 R 2 )、Y1~Y4 are all O; In the above structural formula, when X1 to X2 are all O and Y1 to Y4 are all O, the structural formula is marked as B-1; When X1 to X2 are all S and Y1 to Y4 are all S, the structural formula is marked as B-2; When X1~X2 are all N(R 1 ), Y1~Y4 are all N(R 1 ), and R 1 When it is an alkyl group, the structural formula is marked as B-3-1; When X1~X2 are all N(R 1 ), Y1~Y4 are all N(R 1 ), and R 1 When it is an aromatic group, the structural formula is marked as B-3-2; When X1-X2 is S, Se, Te, N (R 1 )、B(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ), when Y1 to Y4 are all O, the structural formula is marked as B-4; When X1-X2 is S, Se, Te, N (R 1 )、B(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ), Y1~Y4 are all N(R 1 ), and R 1 When it is an alkyl group, the structural formula is marked as B-5-1; When X1-X2 is S, Se, Te, N (R 1 )、B(R 1 )、C(R 1 R 2 ) or Si(R 1 R 2 ), Y1~Y4 are all N(R 1 ), and R 1 When it is an aromatic group, the structural formula is marked as B-5-2; In the three structural formulas shown above, Ar1 to Ar4, (R1) a ~(R4) d , R 1 ~R 2 All are as defined in claims 1-5.

7. The method for preparing a dicarbocationic compound according to claim 6, characterized in that: When X1-X2, Y1-Y4 are all O or all S, or X1-X2 are S, Se, Te, N (R 1 )、B(R 1 )、C(R 1 R 2 )、Si(R 1 R 2 ), when Y1-Y4 are all O, the reaction system is heated to 140°C for 3h; When X1~X2, Y1~Y4 are all N(R 1 ), and R 1 When X1-X2 is S, Se, Te, N(R 1 )、B(R 1 )、C(R 1 R 2 )、Si(R 1 R 2 ), Y1~Y4 are all N(R 1 ), and R 1 When it is an alkyl group, the heating reflux time is 20h; When X1~X2, Y1~Y4 are all N(R 1 ), and R 1 When X1-X2 is S, Se, Te, N(R 1 )、B(R 1 )、C(R 1 R 2 )、Si(R 1 R 2 ), Y1~Y4 are all N(R 1 ), and R 1 When the compound is an aromatic group, the reaction mixture is heated from room temperature to reflux temperature within 20 min.

8. An organic electroluminescent device, comprising an anode, a cathode and an organic thin film layer located between the anode and the cathode; characterized in that: The organic thin film layer comprises the dicarbocation compound according to any one of claims 1 to 5.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic thin film layer comprises a light-emitting layer; the light-emitting layer comprises the dicarbocationic ion compound according to any one of claims 1 to 5.

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