Multi-boron-nitrogen derivative as well as preparation method and application thereof

Abstract

The invention provides a multi-boron nitrogen derivative and a preparation method and application thereof, the multi-boron nitrogen derivative has a structure of formula (I), in the formula (I), R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently represented as C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylamino, C1-C24 aryl, C1-C24 aryloxy or C1-C24 arylamino, and in the formula (I), R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently represented as C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylamino, C1-C24 aryl, C1-C24 aryloxy or C1-C24 arylamino. A, b, c, d, e, f, g, h and i are respectively and independently represented as positive integers of 0-5 and do not exceed the highest integers which can be substituted by a substituted benzene ring, and Z1, Z2 and Z3 are respectively and independently represented as alkylene, arylene, alkyleneamine, arylene amine, thionyl, sulfoxide, sulfonyl, carbonyl, selenium bond, sulfur bond, ether bond, single bond and double bond or do not exist. The multi-boron-nitrogen derivative adopted by the invention has good yellow light-emitting characteristic and keeps high photoluminescence efficiency. The synthesis method provided by the invention has the characteristic of directional reaction.

Description

Technical Field

[0001] This patent relates to the field of organic electroluminescence technology, and in particular to a polyboron nitrogen derivative and its preparation method and application. Background Art

[0002] Organic Light Emitting Diodes (OLED) have attracted the attention of researchers due to their advantages such as high color contrast, wide viewing angle, fast response speed, and flexibility and foldability.

[0003] In OLED display and lighting applications, yellow light emitting materials play a key role. As one of the key OLED emitting materials, yellow light materials are of great significance to improving the comprehensive performance of OLED screens. For example, in the RGB three-primary color system, the introduction of yellow light materials can effectively expand the color gamut, allowing display devices to present more vivid and realistic images. For example, in lighting applications, combining blue light and yellow light can produce white light lighting effects.

[0004] Although yellow light materials play an important role in OLED technology, there are still some problems with the existing yellow light materials. Yellow fluorescent materials are generally considered to have low photoluminescence efficiency due to the mechanism of the fluorescent materials themselves, and the efficiency of yellow light devices is also low. Yellow phosphorescent materials are mainly iridium complexes, such as yellow organic light-emitting materials including (2-(9,9-diethyl-fluorene-2-yl)-1-phenyl-1H-benzo[d]imidazole) acetylacetonate iridium, bis(2-phenylbenzothiazole)(acetylacetonate) iridium, tris[3-(2,6-dimethylphenol)-6-phenylpyridazine] iridium and bis(2-phenylpyridine)(3-(pyridin-2-yl)-2H-benzopyran-2-one) iridium. Iridium complexes contain iridium metal and are expensive, which limits their application in OLEDs. Yellow thermal delay materials do not contain metals, and the theoretical photoluminescence efficiency is high, but the efficiency of disclosed yellow light devices still needs to be further improved. Summary of the invention

[0005] In view of the deficiencies in the prior art, the present invention aims to provide a polyborane derivative and a preparation method and application thereof.

[0006] In order to achieve the above object, on the one hand, the present invention provides a polyborane derivative having a structure as shown in formula (I):

[0007] Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6, R 7 , R 8 , R 9 Each independently represents a C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylamino, C1-C24 aryl, C1-C24 aryloxy or C1-C24 arylamino; a, b, c, d, e, f, g, h, i are each independently represented by a positive integer of 0-5 and do not exceed the highest integer that can be substituted by the substituted benzene ring; Z 1 , Z 2 , Z 3 Each independently represents an alkylene group, an arylene group, an alkyleneamino group, an aryleneamino group, a sulfene group, a sulfoxide group, a sulfone group, a carbonyl group, a selenium bond, a sulfide bond, an ether bond, a single bond, a double bond, or does not exist.

[0008] As a preferred embodiment of the polyborane derivatives described in the present invention, the alkyl group is methyl, ethyl, propyl, butyl, pentyl or hexyl, the alkoxy group is methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyl, the alkylamino group is methylamino, ethylamino, propylamino, butylamino, pentylamino or hexylamino, the aryl group is phenyl, naphthyl, biphenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentyloxyphenyl, hexyloxyphenyl, methylaminophenyl, ethylaminophenyl or propylaminophenyl, the aryloxy group is phenoxy, tolyloxy, ethylphenoxy, propylphenoxy or butylphenoxy, and the arylamino group is aniline, toluidine, ethylaniline, propylaniline or butylaniline.

[0009] As a preferred embodiment of the polyborane derivatives described in the present invention, c is not zero.

[0010] As a preferred embodiment of the polyborane derivatives described in the present invention, the i is not zero.

[0011] As a preferred embodiment of the polyborane nitrogen derivative of the present invention, the polyborane nitrogen derivative has a structure as shown in formula (II):

[0012] Among them, Z 2 With Z 1 Same, R 1 With R 6 Same, R 2 With R 5 The same, a is the same as f, b is the same as e.

[0013] As a preferred embodiment of the polyborane nitrogen derivative of the present invention, the polyborane nitrogen derivative has one of the following structures:

[0014] As a preferred embodiment of the polyborane nitrogen derivative of the present invention, the polyborane nitrogen derivative has one of the following structures:

[0016] On the other hand, the present invention also provides an intermediate having a structure shown in formula (III):

[0017] Among them, R 1 , R 2 , R 3 , R 4 , R 9 Each independently represents a C1-C24 alkyl, C1-C24 alkoxy, C1-C24 alkylamino, C1-C24 aryl, C1-C24 aryloxy or C1-C24 arylamino; a, b, c, d, i each independently represent a positive integer from 0 to 5 and do not exceed the highest integer that can be substituted by the substituted benzene ring; Z1 represents an alkylene, arylene, alkyleneamino, aryleneamino, sulfide, sulfoxide, sulfone, carbonyl, selenium bond, sulfur bond, ether bond, single bond, double bond or does not exist; X 2 , X 3 Each independently represents one of fluorine, chlorine, bromine and iodine.

[0018] On the other hand, the present invention also provides a synthetic method for preparing the intermediate of formula (III), the synthetic steps are as follows: S1, reacting the compound represented by formula MM1 with the compound represented by formula MM2 to obtain the compound represented by formula MM3; wherein X 1 , X 2Each independently represents one of fluorine, chlorine, bromine and iodine, and X 1 The reactivity with the compound represented by formula MM1 is not less than X 2 ;

[0019] S2, reacting the compound represented by formula MM3 with the compound represented by formula MM4 to obtain the compound represented by formula MM5;

[0020] S3, reacting the compound represented by formula MM5 with the compound represented by formula MM6 to obtain the compound represented by formula MM7; X3, X4, and X5 each independently represent one of fluorine, chlorine, bromine, and iodine, and the reactivity of X3 with the compound represented by formula MM5 is not less than that of X4 and X5;

[0021] S4, reacting the compound represented by formula MM7 with boron tribromide to obtain a compound represented by formula (III);

[0022] The S1, S2, S3, and S4 represent step one, step two, step three, and step four, respectively.

[0023] On the other hand, the present invention also provides a synthetic method for preparing the polyborane derivative of the present invention, and the synthetic steps are as follows: SS1, reacting the compound represented by formula (III) with the compound represented by formula MM9 to obtain the compound represented by formula MM10;

[0024] SS2, reacting the compound represented by formula MM10 with the compound represented by formula MM11 to obtain the compound represented by formula MM12:

[0025] SS3, reacting the compound represented by formula MM12 with boron tribromide to obtain the compound represented by formula (I);

[0026] Said SS1, SS2 and SS3 respectively represent step 1, step 2 and step 3 in preparing the polyborane-nitrogen derivative having the structure shown in formula (I).

[0027] The synthetic method for preparing the polyborane derivatives of the present invention has the characteristics of directional reaction. In comparison, the polyborane derivatives of the present invention can also be obtained theoretically by reacting the compound represented by formula (V) with excess boron tribromide (hypothesized preparation method), and as the compound represented by synthetic formula (V), its coupling reaction can adopt the synthetic method commonly used by those skilled in the art. Therefore, as a hypothesized preparation method, it is theoretically possible to have lower cost than the synthetic method of the present invention.

[0028]

[0029] However, the polyborane derivatives of the present invention cannot be prepared by the conjectural preparation method, but the compound represented by formula (VI) is prepared. This results in failure to prepare the compound represented by formula (I) by the directed reaction using the conjectural preparation method.

[0030]

[0031] By way of example but not limitation, a compound B-Me was prepared using a hypothetical preparation method. Compound B-Me emits blue light and cannot be used to prepare compound 2-25 of the present invention.

[0032] The present invention prepares the intermediate (III), so that the synthesis method for preparing the compound represented by formula (I) has the characteristics of directional reaction, and the boron atom is introduced at the required position to prepare the compound represented by formula (I), which has good directional selectivity, thereby improving the synthesis efficiency.

[0033] On the other hand, the present invention also provides a synthetic method for preparing the polyborane derivative of the present invention, wherein the compound represented by formula (IV) is reacted with an oxidant to obtain the compound represented by formula (I):

[0034] In the formula (IV), Z 11 , Z 22 , Z 33 Each independently represents an alkylene group, an arylene group, an alkyleneamino group, an aryleneamino group, a sulfide group, a sulfoxide group, a sulfone group, a carbonyl group, a selenium bond, a sulfide bond, an ether bond, a single bond, a double bond or does not exist, and the Z 11 , Z 22 , Z 33 At least one of them is a methylene group, a sulfide group, a sulfoxide group, a selenium bond or a sulfur bond.

[0035] In the method of preparing the compound represented by formula (I) by using the compound represented by formula (IV), the oxidant is not limited, as long as it can oxidize the Z11, Z22 or Z33 substituent group. For example and not limitation, the oxidant is DDQ (2,3-dichloro-5,6-dicyanobenzoquinone), DMP (Dess-Martin periodinane), H2O2 (hydrogen peroxide), etc.

[0036] On the other hand, the present invention also provides a yellow light organic electroluminescent device, comprising an anode, a cathode, a hole transport layer, an electron transport layer, and a light-emitting layer between the hole transport layer and the electron transport layer, wherein the light-emitting layer contains at least one polyborane derivative represented by formula (I).

[0037] On the other hand, the present invention further provides a light-emitting device, characterized in that the light-emitting device adopts the yellow organic electroluminescent device described in the present invention.

[0038] Compared with the prior art, the polyboron nitrogen derivatives of the present invention have good yellow luminescence characteristics and maintain high photoluminescence efficiency. The synthesis method provided by the present invention has the characteristics of directional reaction, so the preparation cost is low. The intermediates provided by the present invention enable the synthesis method to achieve directional reaction. The polyboron nitrogen derivatives of the present invention can be applied to yellow electroluminescent devices as luminescent materials, and the yellow electroluminescent devices can be further applied to light-emitting devices, and have the characteristics of high external quantum efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] In order to more clearly illustrate the technical solution of the present invention, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0040] Figure 1 Schematic diagram of the structure of an embodiment of the device of the present invention, wherein 1-substrate, 2-hole transport layer, 3-electron blocking layer, 4-exciton blocking layer, 5-light-emitting layer, 6-electron transport layer, 6-electron injection layer, 8-cathode layer. DETAILED DESCRIPTION

[0041] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose, the specific implementation methods, methods, steps, structures, characteristics and effects of the polyborane derivatives proposed in the present invention are described in detail below in combination with the accompanying drawings and embodiments.

[0042] The above and other technical contents, features and effects of the present invention will be clearly presented in the following detailed description of the preferred embodiments with reference to the drawings. Through the description of the specific implementation methods, the technical means and effects adopted by the present invention to achieve the predetermined purpose can be more deeply and specifically understood. However, the drawings are only for reference and explanation purposes and are not used to limit the present invention.

[0043] The field of organic electroluminescent technology is an interdisciplinary subject. In different sub-disciplines, it is a common phenomenon to use different terms to express the same concept or phenomenon. Generally, different expressions can be regarded as having the same meaning unless they are confused or the context specifically indicates otherwise. It is understandable that "molecule", "compound", "derivative", "structure", "material", "solid" and "dye" can all refer to the polyboron nitrogen derivatives of the present invention, unless the context clearly states the distinction or it is easy for a person skilled in the art to understand the distinction. It is understandable that the above terms can refer to the polyboron nitrogen derivatives of the present invention, but they do not necessarily refer to them. For example, for "solid", in the embodiments of the present invention, there are multiple expressions of "solid", some of which refer to intermediates, and some refer to the polyboron nitrogen derivatives of the present invention. Whether they refer to the polyboron nitrogen derivatives of the present invention depends on the specific position of the corresponding terms in the present invention.

[0044] The "polyboron nitrogen derivatives" of the present invention belong to the technical field of "boron nitrogen derivatives". The "polyboron nitrogen derivatives" described in the present invention refer to derivatives having multiple boron atoms and nitrogen atoms in their structure, where multiple refers to four or more. More specifically, the "polyboron nitrogen derivatives" of the present invention have at least four boron atoms and at least two nitrogen atoms. This technical field is "boron nitrogen derivatives", which not only includes "polyboron nitrogen derivatives", but also includes "boron nitrogen derivatives" with only one boron atom or one nitrogen atom. It is understandable that, at least in order to complete the preparation, it is necessary to understand "boron nitrogen derivatives", such as some of the intermediates in the following examples are "boron nitrogen derivatives" rather than "polyboron nitrogen derivatives".

[0045] Regarding the abbreviations and symbols in the present invention, abbreviations that are easily understood by those skilled in the art are used, and some abbreviations are listed as follows: 2 (dba) 3 Refers to tris(dibenzylideneacetone)dipalladium(0), Pd(amphos)Cl 2 refers to bis(4-dimethylaminophenyldi-tert-butylphosphine)palladium dichloride, Sphos refers to 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl, tBuONa refers to sodium tert-butoxide, Toluene refers to toluene solution, o -DCB and dichlorobenzene refer to o-dichlorobenzene, Tert-butylbenzene refers to tert-butylbenzene, BBr3 refers to boron tribromide, mg refers to milligram, mmol refers to millimole, mL refers to milliliter, Pa refers to Pascal, wt% refers to weight percentage, nm refers to nanometer, ppm refers to part per million, FWHM refers to half maximum width, ℃ refers to degree Celsius, h refers to hour, min refers to minute, rt refers to room temperature, and EQEmax refers to the maximum luminous efficiency of the electroluminescent device.

[0046] Synthesis Example Example 1: Synthesis of Compound 1-1

[0047] Intermediate M1: 1-Bromo-3-chloro-benzene (8.22 g, 40 mmol), diphenylamine (6.77 g, 40 mmol) and Pd(amphos)Cl 2 (568.08 mg, 0.8 mmol) and sodium tert-butoxide (7.68 g, 80 mmol) were loaded into a sealed flask. The sealed flask was deoxygenated and dry toluene (300 mL) was added. The mixture was stirred at 90 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a white solid M1 (10.1 g, 92%).

[0048]

[0049] Intermediate M2: M1 (5.51 g, 20 mmol), aniline (7.45 g, 80 mmol), Pd 2 (dba) 3 (366.3 mg, 0.4 mmol), S-Phos (328.4 mg, 0.8 mmol) and sodium tert-butoxide (3.84 g, 40 mmol) were loaded into a sealed flask. The sealed flask was deoxygenated and dry toluene (300 mL) was added. The mixture was stirred at 180 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a powdery white solid M2 (5.05 g, 75%).

[0050]

[0051] Intermediate M3: Compound M3 was synthesized using intermediate M2 (3.34 g, 10 mmol), 5-bromo-1,3-dichloro-benzene (2.26 g, 10 mmol) and sodium tert-butoxide (1.92 g, 20 mmol) according to the same procedure for synthesizing intermediate M1. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to obtain white solid M3 (4.32 g, 90%).

[0052]

[0053] Intermediate M4: A mixture of compound M3 (2.41 g, 5 mmol) and 1,2-dichlorobenzene (20 mL) was placed in a sealed flask. The flask was deoxygenated. Then, BBr 3 The mixture was stirred for 20 hours at 4 ℃ for 1 h. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain a bright yellow product M4 (1.27 g, 52%).

[0054] Structural characterization of bright yellow solid M4: 1 H NMR (500 MHz, Chloroform- d ) δ 7.45 – 7.37(m, 3H), 7.35 (t, J = 1.6 Hz, 1H), 7.33 – 7.23 (m, 6H), 7.16 (ddd, J = 7.5,1.6, 0.9 Hz, 2H), 7.12 (t, J = 1.5 Hz, 1H), 7.10 – 7.06 (m, 2H), 7.04 (td, J = 7.5, 1.5 Hz, 2H), 6.95 (dd, J = 7.5, 1.6 Hz, 1H), 6.86 (dd, J = 7.5, 1.6Hz, 1H). MALDI-TOF: Calculated: 489.2060, Found: 489.2057.

[0055] Intermediate M5: Compound M4 (1.46 g, 3 mmol), diphenylamine (2.03 g, 12 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) were used to synthesize compound M5 according to the same procedure as the above-mentioned synthesis of compound M2. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to obtain a bright yellow powder M5 (1.02 g, 45%).

[0056]

[0057] Compound 1-1: Compound M5 (754.74 mg, 1 mmol), BBr 3 (0.5 mL, 5 mmol) and 1,2-dichlorobenzene (10 mL), refer to the same steps of the above-mentioned synthesis of compound M4 to synthesize compound 1-1. After cooling to room temperature, the mixture was added into ice water. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 1-1 (106.7 mg, 14%) as an orange powder.

[0058] Structural characterization of compound 1-1: 1 H NMR (500 MHz, Chloroform- d ) δ 7.48 (d, J = 7.5Hz, 2H), 7.43 (dd, J = 7.4, 1.5 Hz, 2H), 7.38 (t, J = 7.5 Hz, 1H), 7.33 –7.23 (m, 10H), 7.19 (ddd, J = 7.4, 3.6, 1.5 Hz, 2H), 7.14 – 7.01 (m, 14H), 6.95 (dd, J = 7.5, 1.5 Hz, 1H), 6.92 – 6.83 (m, 2H), 6.76 (dd, J = 8.7, 1.6Hz, 2H). MALDI-TOF: Calculated: 762.5300, Found: 762.5297.

[0059] Example 2: Synthesis of Compound 1-3

[0060] Intermediate M6: 1-Bromo-3-chloro-benzene (8.22 g, 40 mmol), dihydroacridine (7.25 g, 40 mmol) and Pd(amphos)Cl 2 (568.08 mg, 0.8 mmol) and sodium tert-butoxide (7.68 g, 80 mmol) were loaded into a sealed flask. The sealed flask was deoxygenated and dry toluene (300 mL) was added. The mixture was stirred at 90 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a white solid M6 (9.92 g, 85%).

[0061]

[0062] Intermediate M7: M6 (5.55 g, 20 mmol), aniline (7.45 g, 80 mmol), Pd 2 (dba) 3 (366.3 mg, 0.4 mmol), S-Phos (328.4 mg, 0.8 mmol) and sodium tert-butoxide (3.84 g, 40 mmol) were loaded into a sealed flask. The sealed flask was deoxygenated and dry toluene (300 mL) was added. The mixture was stirred at 180 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a powdery white solid M7 (5.23 g, 75%).

[0063]

[0064] Intermediate M8: Using intermediate M7 (3.48 g, 10 mmol), 5-bromo-1,3-dichloro-benzene (2.26 g, 10 mmol) and sodium tert-butoxide (1.92 g, 20 mmol), compound M8 was synthesized according to the same steps of the above-mentioned synthesis of intermediate M6. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to obtain a white solid M8 (4.44 g, 90%).

[0065]

[0066] Intermediate M9: A mixture of compound M8 (2.47 g, 5 mmol) and 1,2-dichlorobenzene (20 mL) was placed in a sealed flask. The flask was deoxygenated. Then, BBr 3The mixture was heated to 200 ° C and stirred for 20 hours. After cooling to room temperature, the mixture was added into ice water. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain a bright yellow product M9 (1.1 g, 45%).

[0067]

[0068] Intermediate M10: Compound M10 was synthesized using compound M9 (1.46 g, 3 mmol), dihydroacridine (543.7 mg, 3 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) according to the same procedure as the above synthesis of compound M7. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to obtain a bright yellow powder (775.2 mg, 40%).

[0069]

[0070] Intermediate M11: Compound M11 was synthesized using compound M10 (1.94 g, 3 mmol), diphenylamine (501 mg, 3 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) according to the same procedure as the above-mentioned synthesis of compound M7. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to obtain a bright yellow powder M11 (1.31 g, 56%).

[0071]

[0072] Compound 1-3: Compound M11 (778.7 mg, 1 mmol), BBr 3 (0.5 mL, 5 mmol) and 1,2-dichlorobenzene (10 mL), compound 1-3 was synthesized according to the same steps of the above-mentioned synthesis of compound M4. After cooling to room temperature, the mixture was carefully added into ice water. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 1-3 (94.4 mg, 12%) as an orange powder.

[0073] Structural characterization of compounds 1-3: 1 H NMR (500 MHz, Chloroform- d ) δ 7.48 (d, J= 7.5Hz, 1H), 7.42 – 7.35 (m, 2H), 7.31 – 7.22 (m, 3H), 7.21 (dd, J = 7.5, 1.5 Hz,1H), 7.17 – 7.08 (m, 3H), 7.12 – 7.05 (m, 5H), 6.99 – 6.83 (m, 5H), 6.76 (q, J = 1.5 Hz, 1H), 4.32 (t, J = 1.0 Hz, 3H). MALDI-TOF: Calculated: 786.5520, Found: 786.5517. Example 3: Synthesis of Compound 1-15

[0074]

[0075] Compound 1-15: Compound 1-3 (786.5 mg, 1 mmol) was dissolved in a mixed solvent of DCM (20 mL), 1,4-dioxane (10 mL) and water (2 mL). After the mixture was cooled to 0°C, DDQ (0.71 g, 4 mmol) was slowly added. The resulting mixture was then warmed to room temperature and stirred overnight. Saturated sodium bicarbonate solution (50 mL) was added to the mixture, the organic layer was extracted with dichloromethane, and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain compound 1-15 (94.4 mg, 12%) as a red powder. .

[0076] Structural characterization of compounds 1-15: 1 H NMR (500 MHz, Chloroform- d ) δ 8.05 – 7.99 (m,4H), 7.67 (dd, J = 7.5, 1.5 Hz, 2H), 7.48 (d, J = 7.5 Hz, 2H), 7.45 – 7.33(m, 5H), 7.30 – 7.22 (m, 4H), 7.18 (t, J = 7.5 Hz, 2H), 7.13 – 7.06 (m, 6H), 7.01 – 6.93 (m, 4H), 6.89 – 6.83 (m, 1H), 6.78 – 6.72 (m, 2H). MALDI-TOF:Calculated: 814.5180, Found: 814.5177. Example 4: Synthesis of Compound 2-25

[0077]

[0078] Intermediate M12: 1-Bromo-3-chloro-5-methylbenzene (8.22 g, 40 mmol), di-p-toluidine (7.89 g, 40 mmol) and Pd(amphos)Cl 2 (568.08 mg, 0.8 mmol) and sodium tert-butoxide (7.68 g, 80 mmol) were loaded into a sealed round-bottom flask. The sealed flask was deoxygenated and purged with nitrogen, and dry toluene (300 mL) was added. The mixture was stirred at 90 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a white solid (11.8 g, 92%).

[0079]

[0080] Intermediate M13: M12 (6.43 g, 20 mmol), p-toluidine (8.57 g, 80 mmol), Pd 2 (dba) 3 (366.3 mg, 0.4 mmol), S-Phos (328.4 mg, 0.8 mmol) and sodium tert-butoxide (3.84 g, 40 mmol) were loaded into a sealed round-bottom flask. The sealed flask was deoxygenated and purged with nitrogen, and dry toluene (300 mL) was added. The mixture was stirred at 180 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to give a powdery white solid (5.88 g, 75%).

[0081]

[0082] Intermediate M14: Compound M14 was synthesized using compound M13 (3.92 g, 10 mmol), 5-bromo-1,3-dichloro-2-methylbenzene (2.40 g, 10 mmol) and sodium tert-butoxide (1.92 g, 20 mmol) according to the same procedure for the synthesis of M12 described above. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to give the product (4.96 g, 90%) as a white solid.

[0083]

[0084] Intermediate M15: A mixture of compound M14 (2.76 g, 5 mmol) and 1,2-dichlorobenzene (20 mL) was placed in a sealed round-bottom flask. The flask was deoxygenated and purged with nitrogen. Then, BBr 3 The mixture was stirred for 20 hours at 4 ℃ for 1 h. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain the product (1.45 g, 52%) as a bright yellow solid.

[0085] Structural characterization of bright yellow solid M15: 1 H NMR (400 MHz, DMSO- d 6 ) δ 8.63 (s, 1H), 7.62(s, 1H), 7.58 (d, J = 8.0 Hz, 1H), 7.41–7.28 (m, 2H), 7.25 (d, J = 8.1 Hz,1H), 7.17 (d, J = 8.2 Hz, 1H), 7.08 (d, J = 8.3 Hz, 1H), 6.99 (d, J = 8.2 Hz,1H), 6.89 (d, J = 8.4 Hz, 1H), 6.81 (s, 1H), 6.58 (d, J = 8.7 Hz, 1H), 6.41–6.32 (m, 1H), 5.89 (d, J = 10.1 Hz, 1H), 5.76 (s, 5H), 2.61 (s, 1H), 2.49 (s,1H), 2.48 (s, 1H), 2.29 (d, J = 4.3 Hz, 2H), 2.24 (s, 1H). MALDI-TOF: Calculated: 559.3410, Found: 559.3410.

[0086] Intermediate M16: Compound M16 was synthesized using compound M15 (1.68 g, 3 mmol), di-p-tolylamine (2.36 g, 12 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) according to the same procedure for the synthesis of M13 described above. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to give the product (1.19 g, 45%) as a yellow solid.

[0087]

[0088] Compound 2-25: Compound M16 (880.98 mg, 1 mmol), BBr 3 (0.5 mL, 5 mmol) and 1,2-dichlorobenzene (10 mL), according to the same steps of the above synthesis of compound M4, compound 1-50 was synthesized. After cooling to room temperature, the mixture was carefully added into ice water. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain an orange powder (123 mg, 14%).

[0089] Structural characterization of orange solid 2-25: 1 H NMR (400 MHz, Methylene Chloride- d 2 ) δ 8.69(d, J = 2.2 Hz, 1H), 8.56 (dd, J = 11.0, 2.2 Hz, 2H), 8.40 (d, J = 2.2 Hz,1H), 7.74 (d, J = 8.8 Hz, 1H), 7.53 (s, 3H), 7.42 (dd, J = 8.8, 2.3 Hz, 1H),7.33 (dd, J = 8.8, 2.2 Hz, 1H), 7.18 (s, 4H), 7.13 (s, 1H), 6.98 (s, 2H), 6.75 (d, J = 8.8 Hz, 2H), 6.09 (s, 1H), 2.74 (s, 3H), 2.58 (s, 3H), 2.56 (s,6H), 2.36 (s, 3H), 2.26 (s, 6H), 1.96 (s, 3H), 1.55 (s, 3H), 1.31 (s, 2H),0.90 (t,J = 9.4 Hz, 1H), 0.14 (s, 2H), 0.12 (s, 1H), 0.10 (s, 1H). MALDI-TOF: Calculated: 888.7730, Found: 888.7729. Example 5: Synthesis of Compound 2-2

[0090]

[0091] Intermediate M17: 1-Bromo-3-chloro-5-methylbenzene (8.22 g, 40 mmol), 4-(tert-butyl)-N-(p-tolyl)aniline (9.574 g, 40 mmol) and Pd(amphos)Cl 2 (568.08 mg, 0.8 mmol) and sodium tert-butoxide (7.68 g, 80 mmol) were loaded into a sealed round-bottom flask. The sealed flask was deoxygenated and purged with nitrogen, and dry toluene (300 mL) was added. The mixture was stirred at 90 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a white solid (11.8 g, 92%).

[0092] Structural characterization of white solid M17: 1 H NMR (500 MHz, Chloroform- d ) δ 7.57 (t, J =1.6 Hz, 1H), 7.27 – 7.21 (m, 2H), 7.11 – 7.03 (m, 5H), 7.03 – 6.98 (m, 2H),2.40 (s, 3H), 2.35 (s, 3H), 1.35 (s, 9H). MALDI-TOF: Calculated: 363.9290, Found: 363.9290.

[0093] Intermediate M18: M17 (6.5 g, 20 mmol), p-toluidine (8.57 g, 80 mmol), Pd 2 (dba) 3(366.3 mg, 0.4 mmol), S-Phos (328.4 mg, 0.8 mmol) and sodium tert-butoxide (3.84 g, 40 mmol) were loaded into a sealed round-bottom flask. The sealed flask was deoxygenated and purged with nitrogen, and dry toluene (300 mL) was added. The mixture was stirred at 180 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a powdery white solid (6.5 g, 75%).

[0094]

[0095] Intermediate M19: Compound M19 was synthesized using compound M18 (4.3 g, 10 mmol), 5-bromo-1,3-dichloro-2-methylbenzene (2.40 g, 10 mmol) and sodium tert-butoxide (1.92 g, 20 mmol) according to the same procedure for the synthesis of M17 described above. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to give the product (5.2 g, 90%) as a white solid.

[0096]

[0097] Intermediate M20: A mixture of compound M19 (2.81 g, 5 mmol) and 1,2-dichlorobenzene (20 mL) was placed in a sealed round-bottom flask. The flask was deoxygenated and purged with nitrogen. Then, BBr 3 The mixture was stirred for 20 hours at 4 ℃ for 1 h. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain the product (1.53 g, 52%) as a bright yellow solid.

[0098] Structural characterization of bright yellow solid M20: 1 H NMR (500 MHz, Chloroform- d ) δ 7.43 (d, J =1.5 Hz, 1H), 7.33 (dd, J = 9.6, 1.5 Hz, 3H), 7.27 – 7.21 (m, 2H), 7.17 – 7.02(m, 7H), 6.77 – 6.72 (m, 2H), 2.44 (d, J = 0.8 Hz, 3H), 2.33 (d, J= 0.7 Hz,3H), 2.20 (s, 3H), 1.29 (s, 9H). MALDI-TOF: Calculated: 587.3950, Found:587.3949.

[0099] Intermediate M21: Compound M21 was synthesized using compound M20 (1.76 g, 3 mmol), 4-(tert-butyl)-N-(p-tolyl)aniline (616 mg, 3 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) according to the same procedure for the synthesis of M18 described above. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to give the product (1.06 g, 45%) as a yellow solid.

[0100]

[0101] Intermediate M22: Compound M21 (2.37 g, 3 mmol), p-xylidine (592 mg, 3 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) were used to synthesize compound M22 according to the same procedure as the above-mentioned synthesis of compound M18. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to obtain a bright yellow powder (1.60 g, 56%).

[0102] Structural characterization of bright yellow solid M22: 1 H NMR (500 MHz, Chloroform- d ) δ 7.28 – 7.21(m, 1H), 7.08 (q, J = 0.9 Hz, 1H), 7.07 – 6.99 (m, 6H), 6.80 – 6.75 (m, 1H), 6.52 (dd, J = 14.7, 1.4 Hz, 1H), 2.44 (d, J = 0.7 Hz, 1H), 2.37 – 2.32 (m,4H), 2.19 (s, 1H), 1.36 (s, 3H), 1.32 (s, 3H). MALDI-TOF: Calculated:951.1220, Found: 951.1219.

[0103] Compound 2-2: Compound M22 (951.1 mg, 1 mmol), BBr 3 (0.5 mL, 5 mmol) and 1,2-dichlorobenzene (10 mL) were added to synthesize compound 1-27 according to the same steps of the above-mentioned synthesis of compound M20. After cooling to room temperature, the mixture was carefully added into ice water. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain an orange powder (115 mg, 14%).

[0104] Structural characterization of orange solid 2-2: 1 H NMR (500 MHz, Chloroform- d ) δ 7.43 (d, J =1.5 Hz, 1H), 7.29 – 7.21 (m, 2H), 7.13 – 7.02 (m, 9H), 6.82 – 6.72 (m, 2H), 2.46 (s, 2H), 2.37 – 2.32 (m, 6H), 2.19 (s, 2H), 1.32 (d, J = 1.0 Hz, 9H).MALDI-TOF: Calculated: 958.9080, Found: 958.9079. Example 6: Synthesis of Compound 2-19

[0105]

[0106] Intermediate M23: 1-Bromo-3-chloro-5-methylbenzene (8.22 g, 40 mmol), 2,4,6-trimethyl-N-(p-tolyl)aniline (9.01 g, 40 mmol) and Pd(amphos)Cl 2 (568.08 mg, 0.8 mmol) and sodium tert-butoxide (7.68 g, 80 mmol) were loaded into a sealed round-bottom flask. The sealed flask was deoxygenated and purged with nitrogen, and dry toluene (300 mL) was added. The mixture was stirred at 90 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a white solid (12.8 g, 92%).

[0107] Structural characterization of white solid M23: 1 H NMR (500 MHz, Chloroform- d ) δ 7.67 (t, J=1.5 Hz, 1H), 7.07 – 7.01 (m, 2H), 6.98 – 6.90 (m, 5H), 2.40 (s, 3H), 2.35 (d, J = 0.9 Hz, 3H), 2.27 (s, 3H), 2.22 (s, 6H). MALDI-TOF: Calculated: 349.9020, Found: 349.9020.

[0108] Intermediate M24: M23 (7.0 g, 20 mmol), p-toluidine (8.57 g, 80 mmol), Pd 2 (dba) 3 (366.3 mg, 0.4 mmol), S-Phos (328.4 mg, 0.8 mmol) and sodium tert-butoxide (3.84 g, 40 mmol) were loaded into a sealed round-bottom flask. The sealed flask was deoxygenated and purged with nitrogen, and dry toluene (300 mL) was added. The mixture was stirred at 180 ° C for 12 hours. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated under vacuum. The residue was purified by silica gel column chromatography to obtain a powdery white solid (6.3 g, 75%).

[0109] Structural characterization of pink-white solid M24: 1 H NMR (500 MHz, Chloroform- d ) δ 7.15 (dd, J = 7.1, 1.0 Hz, 1H), 7.12 – 7.01 (m, 2H), 6.99 – 6.91 (m, 3H), 2.37 – 2.29 (m,4H), 2.26 (d, J = 11.6 Hz, 4H). MALDI-TOF: Calculated: 420.6000, Found: 420.5999.

[0110] Intermediate M25: Compound M25 was synthesized using compound M24 (4.2 g, 10 mmol), 5-bromo-1,3-dichloro-2-methylbenzene (2.40 g, 10 mmol) and sodium tert-butoxide (1.92 g, 20 mmol) according to the same procedure for the synthesis of M23 described above. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to give the product (5.1 g, 90%) as a white solid.

[0111] Structural characterization of white solid M25: 1 H NMR (500 MHz, Chloroform- d ) δ 7.54 (d, J =1.5 Hz, 2H), 7.25 (t, J = 1.5 Hz, 1H), 7.14 (t, J = 1.5 Hz, 1H), 7.08 – 7.01(m, 6H), 6.97 – 6.92 (m, 2H), 6.90 (s, 2H), 6.78 – 6.73 (m, 2H), 2.35 (d, J =0.7 Hz, 6H), 2.29 (d, J = 5.1 Hz, 6H), 2.20 (s, 6H). MALDI-TOF: Calculated:565.5820, Found: 565.2820.

[0112] Intermediate M26: A mixture of compound M25 (2.83 g, 5 mmol) and 1,2-dichlorobenzene (20 mL) was placed in a sealed round-bottom flask. The flask was deoxygenated and purged with nitrogen. Then, BBr 3 The mixture was stirred for 20 hours at 4 ℃ for 1 h. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain the product (1.53 g, 52%) as a bright yellow solid.

[0113] Structural characterization of bright yellow solid M26: 1 H NMR (500 MHz, Chloroform- d ) δ 7.32 (dd, J= 14.4, 1.4 Hz, 3H), 7.27 – 7.23 (m, 2H), 7.14 (dt, J = 7.7, 1.3 Hz, 2H),7.06 (t, J = 7.4 Hz, 2H), 6.86 (s, 2H), 6.80 – 6.76 (m, 1H), 6.76 – 6.72 (m,1H), 2.43 (d, J = 1.0 Hz, 6H), 2.28 (s, 3H), 2.20 (d, J = 3.0 Hz, 9H). MALDI-TOF: Calculated: 565.5820, Found: 565.5819.

[0114] Intermediate M27: Compound M27 was synthesized using compound M26 (1.76 g, 3 mmol), 2,4,6-trimethyl-N-(p-tolyl)aniline (676 mg, 3 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) according to the same procedure for the synthesis of M24 described above. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to give the product (1.03 g, 45%) as a yellow solid.

[0115]

[0116] Intermediate M28: Compound M27 (2.28 g, 3 mmol), p-xylidine (592 mg, 3 mmol) and sodium tert-butoxide (576.6 mg, 6 mmol) were used to synthesize compound M28 according to the same procedure as the above-mentioned synthesis of compound M24. After cooling to room temperature, the resulting solution was extracted with dichloromethane / water, and the organic layer was concentrated in vacuo. The residue was purified by silica gel column chromatography to obtain a bright yellow powder (1.55 g, 56%).

[0117]

[0118] Compound 2-19: Compound M28 (923.1 mg, 1 mmol), BBr 3(0.5 mL, 5 mmol) and 1,2-dichlorobenzene (10 mL), compound 2-19 was synthesized according to the same steps of the above-mentioned synthesis of compound M26. After cooling to room temperature, the mixture was carefully added into ice water. The organic layer was extracted with dichloromethane and then concentrated under reduced pressure. The crude product was purified by silica gel column chromatography to obtain an orange powder (130 mg, 14%).

[0119] Structural characterization of orange solid 2-19: 1 H NMR (500 MHz, Chloroform-d) δ 7.29 – 7.22(m, 2H), 7.14 (dt, J = 7.5, 1.1 Hz, 1H), 7.11 – 7.02 (m, 5H), 6.88 – 6.84 (m,2H), 6.82 – 6.77 (m, 1H), 6.75 (dd, J = 17.8, 1.5 Hz, 1H), 2.48 – 2.41 (m,4H), 2.35 (s, 3H), 2.27 (s, 3H), 2.22 – 2.17 (m, 7H). MALDI-TOF: Calculated:930.8540, Found: 930.8539.

[0120] Device Examples General Preparation Methods of Device Examples

[0121] A 110 nm thick indium tin oxide (ITO) glass was used as the substrate 1. After washing the glass substrate with detergent, deionized water, and isopropyl alcohol, the surface was activated by ultraviolet ozone. Vacuum evaporation was performed on the washed substrate to produce a cross-sectional view as shown in the figure. Figure 1 The luminous area shown is 0.09 cm 2 of organic electroluminescent devices.

[0122] First, the glass substrate was introduced into a vacuum deposition tank and the pressure was reduced to 1×10 -4 Pa. Then Figure 1On the glass substrate 1 shown in the figure, various functional layers are deposited in sequence, namely a hole transport layer 2, an electron blocking layer 3, an exciton blocking layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode layer 8. Specifically, 30 nm thick 1,1-bis[4-[N,N-di(p-tolyl)amino]phenyl]-cyclohexane) (TAPC) was vacuum-deposited in sequence as a hole transport layer (HTL) 2; 10 nm thick 4,4',4''-tri(carbazole-9-yl)triphenylamine (TCTA) was used as a hole blocking layer (HBL) 3; 10 nm thick N,N'-dicarbazole-3,5-benzene (mCP) was used as an exciton blocking layer (EBL) 4; 15 nm thick vacuum-deposited 1wt% doping ratio of 2-(9,9'-spirofluorene-3-yl)-4,6-diphenyl-1,3,5-triazine (SF3-TRZ) and the compound of the present invention composed of light-emitting layer 5 (wt% represents the doping ratio of the compound of the present invention); nm thick 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]bipyridine (TmPyPb) is used as the electron transport layer 6; 1 nm thick lithium fluoride (LiF) is used as the electron injection layer 7. Each organic material is vacuum deposited by resistance heating, and the film formation rate is 1 Å / s. Finally, a metal mask is arranged in a manner orthogonal to the ITO stripes to form a film cathode layer 8 with a film thickness of 100 nm. The thickness of each film is measured with a stylus film thickness meter (DEKTAK). Furthermore, the device is sealed in a nitrogen atmosphere glove box with a water and oxygen concentration of less than 1 ppm. The sealing uses a glass sealing cover and the aforementioned film-forming substrate epoxy ultraviolet curing resin (manufactured by Nagase ChemteX Corporation).

[0123] A direct current was applied to the prepared organic electroluminescent device, and the luminous efficiency was measured using a Hamamatsu C9920-02 integrating sphere, and the current-voltage characteristics were measured using a computer-controlled Keithley 2400 digital source meter.

[0124] Device Experimental Example-1 A device example was prepared using a general preparation method, wherein the luminescent material selected compound 1-1 to obtain corresponding device performance. The maximum luminescence peak of the luminescent device was 543 nm, and the maximum luminescence efficiency was 39.2%.

[0125] Device Experimental Example-2 A device example was prepared using a general preparation method, wherein the luminescent material selected was compound 1-3, and the corresponding evaporation type device performance was obtained. The maximum luminescence peak of the luminescent device was 554 nm, and the maximum luminescence efficiency was 37.4%.

[0126] Device Experimental Example-3 A device example was prepared using a general preparation method, wherein the luminescent material selected was compound 1-15, and the corresponding evaporation method device performance was obtained. The maximum luminescence peak of the luminescent device was 578nm, and the maximum luminescence efficiency was 36.7%.

[0127] Device Experiment Example-4 A device example was prepared using a general preparation method, wherein the luminescent material selected was compound 2-2, and the corresponding evaporation method device performance was obtained. The maximum luminescence peak of the luminescent device was 546 nm, and the maximum luminescence efficiency was 40.1%.

[0128] Device Experiment Example-5 A device example was prepared using a general preparation method, wherein the luminescent material selected was compound 2-19, and the corresponding evaporation method device performance was obtained. The maximum luminescence peak of the luminescent device was 544 nm, and the maximum luminescence efficiency was 40.3%.

[0129] Device Experiment Example-6 The device example was prepared by a general preparation method, wherein the luminescent material selected compound 2-25, and the corresponding evaporation method device performance was obtained. The maximum luminescence peak of the luminescent device was 544nm, and the maximum luminescence efficiency was 40.9%.

[0130] Device Experiment Example-7 A device example was prepared using a general preparation method, wherein the luminescent material selected compound 2-25, the doping ratio was changed from 1wt% to 1.3wt%, and the corresponding evaporation method device performance was obtained. The maximum luminescence peak of the luminescent device was 544nm, and the maximum luminous efficiency was 37.5%.

[0131] Device Experiment Example-8 A device example was prepared using a general preparation method, wherein the luminescent material selected compound 2-25, the doping ratio was changed from 1wt% to 1.5wt%, and the corresponding evaporation method device performance was obtained. The maximum luminescence peak of the luminescent device was 548nm, and the maximum luminous efficiency was 37.1%.

[0132] The yellow light electroluminescent device of the present invention refers to an emission spectrum in which the maximum emission peak of the device is located at 530-600nm, preferably an emission spectrum in which the emission peak is located at 535-595nm, and more preferably an emission spectrum in which the emission peak is located at 540-590nm. It can be understood by those skilled in the art that the maximum emission peak does not have a strict correspondence with the specific emission color. Due to the difference in chemical structure, when the polyborane nitrogen derivatives of the present invention are prepared into devices, the emission spectrum of the device may be yellowish green, or yellowish orange. As long as the maximum emission peak is located at 530-600nm, it belongs to the yellow light considered by the present invention, and the corresponding electroluminescent devices belong to the protection scope of the present invention. It can be understood by those skilled in the art that the maximum emission peak of the luminescence spectrum of the polyborane nitrogen compound described in the present invention in the solution is different from the maximum emission peak in the device, and the maximum emission peak of the emission spectrum in the solution is blue-shifted compared to the maximum emission peak of the device emission spectrum.

[0133] The polyboron nitrogen compound of the present invention maintains a high photoluminescence quantum efficiency. For example, but not limited to, the photoluminescence efficiency of compound 1-1 is 95%, and the photoluminescence efficiency of compound 2-25 is 95%.

[0134] There are two publicly reported light-emitting devices of yellow light materials. The maximum luminous efficiency of the device of compound B-1 is 32.9%, the maximum emission peak of the emission spectrum is 556 nm, and the CIE is (0.43, 0.56). The maximum luminous efficiency of the device of compound B-2 is 37.4%, the maximum emission peak of the emission spectrum is 551 nm, and the CIE is (0.32, 0.67). The device efficiency of the polyboron nitrogen compound of the present invention is significantly better than the device efficiency of the compound B-1, and the device efficiency of most of the embodiments is better than the device efficiency of the compound B-2. The synthesis routes of compounds B-1 and B-2 are relatively complicated, and no characteristics of directional reaction are found, and their costs are high.

[0135]

[0136] By using the polyborane derivatives of the present invention, the cost of the synthesis route is low, and the device performance of the present invention has a high device efficiency, and the EQEmax of the device embodiments is greater than 35%.

[0137] In the exemplary device design of the present invention, the number of layers of the evaporation method and the solution method are different. It can be understood by those skilled in the art that the number of layers of the evaporation method and the solution method can be the same or different. The lack of a hole injection layer in the device design does not mean that the device design does not consider the hole injection function, but means that the hole transport layer provides both hole injection and hole transport functions. It can be understood that the light-emitting layer also has a hole transport function, otherwise the light-emitting layer cannot emit light. As a description of different functional layers, whether it is a light-emitting layer, a transport layer or other layers, the main function is described but not all functions. Similarly, as a device of the present invention, the functional layer can be one layer or multiple layers.

[0138] The above description of the disclosed embodiments enables those skilled in the art to implement the present invention. The present invention will not be limited to these embodiments, but only needs to conform to the features disclosed herein.

Claims

1. A polyborane derivative, characterized in that: It has a structure as shown in formula (I): Wherein, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each independently represented by a C1-C24 alkyl group, a C1-C24 alkoxy group, a C1-C24 alkylamino group, a C1-C24 aryl group, a C1-C24 aryloxy group, or a C1-C24 arylamino group; a, b, c, d, e, f, g, h, and i are each independently represented by a positive integer from 0 to 5 and not exceeding the highest integer that can be substituted by the substituted benzene ring; and Z1, Z2, and Z3 are each independently represented by an alkylene group, an arylene group, an alkyleneamino group, an aryleneamino group, a sulfide group, a sulfoxide group, a sulfone group, a carbonyl group, a selenium bond, a sulfide bond, an ether bond, a single bond, a double bond, or do not exist.

2. The polyborane derivative according to claim 1, characterized in that: The alkyl group is methyl, ethyl, propyl, butyl, pentyl or hexyl, the alkoxy group is methoxy, ethoxy, propoxy, butoxy, pentyloxy or hexyl, the alkylamino group is methylamino, ethylamino, propylamino, butylamino, pentylamino or hexylamino, the aryl group is phenyl, naphthyl, biphenyl, tolyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentyloxyphenyl, hexyloxyphenyl, methylaminophenyl, ethylaminophenyl or propylaminophenyl, the aryloxy group is phenoxy, tolyloxy, ethylphenoxy, propylphenoxy or butylphenoxy, and the arylamino group is aniline, toluidine, ethylaniline, propylaniline or butylaniline.

3. The polyborane derivative according to claim 1, characterized in that: c is not zero.

4. The polyborane derivative according to claim 1, characterized in that: i is not zero.

5. The polyborane derivative according to claim 1, characterized in that: It has a structure as shown in formula (II): Among them, Z2 is the same as Z1, R1 is the same as R6, R2 is the same as R5, a is the same as f, and b is the same as e.

6. The polyborane derivative according to claim 1, characterized in that: Has one of the following structures: 。 7. The polyborane derivative according to claim 1, characterized in that: Has one of the following structures: 。 8. An intermediate, characterized in that Having a structure as shown in formula (III), Wherein, R1, R2, R3, R4, and R9 are each independently represented by a C1-C24 alkyl group, a C1-C24 alkoxy group, a C1-C24 alkylamino group, a C1-C24 aryl group, a C1-C24 aryloxy group, or a C1-C24 arylamino group; a, b, c, d, and i are each independently represented by a positive integer from 0 to 5 and do not exceed the highest integer that can be substituted by the substituted benzene ring; Z1 is represented by an alkylene group, an arylene group, an alkyleneamino group, an aryleneamino group, a sulfide group, a sulfoxide group, a sulfone group, a carbonyl group, a selenium bond, a sulfur bond, an ether bond, a single bond, a double bond, or does not exist; and X2 and X3 are each independently represented by one of fluorine, chlorine, bromine, and iodine.

9. A synthetic method for preparing the intermediate described in right 8, characterized in that: The synthesis steps are as follows: S1, reacting a compound represented by formula (MM1) with a compound represented by formula (MM2) to obtain a compound represented by formula (MM3); wherein X1 and X2 each independently represent one of fluorine, chlorine, bromine and iodine, and the reactivity of X1 with the compound represented by formula (MM1) is not less than that of X2; S2, reacting the compound represented by formula (MM3) with the compound represented by formula (MM4) to obtain the compound represented by formula (MM5); S3, reacting the compound represented by formula (MM5) with the compound represented by formula (MM6) to obtain the compound represented by formula (MM7); X3, X4, and X5 each independently represent one of fluorine, chlorine, bromine, and iodine, and the reactivity of X3 with the compound represented by formula (MM5) is not less than that of X4 and X5; S4, reacting the compound represented by formula (MM7) with boron tribromide to obtain the compound represented by formula (III).

10. A method for preparing any one of the polyborane derivatives of 1 to 7, characterized in that: The synthesis steps are as follows: SS1, reacting the compound represented by formula (III) with the compound represented by formula (MM9) to obtain the compound represented by formula (MM10); SS2, reacting the compound represented by formula (MM10) with the compound represented by formula (MM11) to obtain the compound represented by formula (MM12); S3, reacting the compound represented by formula (MM12) with boron tribromide to obtain the compound represented by formula (I).

11. A method for preparing any one of the polyborane derivatives of 1 to 7, characterized in that: The compound represented by formula (IV) is reacted with an oxidant to obtain the compound represented by formula (I): In the formula (IV), Z 11 , Z 22 , Z 33 Each independently represents an alkylene group, an arylene group, an alkyleneamino group, an aryleneamino group, a sulfide group, a sulfoxide group, a sulfone group, a carbonyl group, a selenium bond, a sulfide bond, an ether bond, a single bond, a double bond or does not exist, and the Z 11 , Z 22 , Z 33 At least one of them is a methylene group, a sulfide group, a sulfoxide group, a selenium bond or a sulfur bond.

12. A yellow organic electroluminescent device, comprising an anode, a cathode, a hole transport layer, an electron transport layer, and a light-emitting layer between the hole transport layer and the electron transport layer, characterized in that: The light-emitting layer contains at least one polyborane derivative represented by formula (I).

13. A light emitting device, characterized in that: The light-emitting device adopts the light-emitting device described in claim 12.

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