A polyboron-nitrogen derivative and a deep blue light-emitting device and a light-emitting apparatus

Abstract

The present application provides a polyboron-nitrogen derivative, a deep blue light-emitting device and a light-emitting apparatus, the polyboron-nitrogen derivative having a structure of formula (I), wherein R 1 , R 2 each independently represent a C1-C36 alkyl or aryl substituent; R 3 , R 4 , R 5 , R 6 , R 7 , R 8 each independently represent hydrogen or a C1-C36 substituent; the C1-C36 substituent is substituted in a single bond or in a ring; A1, A2 each independently represent oxygen, sulfur, selenium, a sulfoxide group, a sulfone group, a carbon substituent of a C1-C36 alkyl or aryl substituent, a nitrogen substituent of a C1-C36 alkyl or aryl substituent, or are not present. The polyboron-nitrogen derivative used in the present application has the characteristics of high light-emitting efficiency, high color purity, and suitability for solution process devices.

Description

Technical Field

[0001] This patent relates to the field of organic electroluminescence technology, and in particular to a polyboron nitrogen derivative and its deep blue light device and light-emitting equipment. Background Technology

[0002] Organic light-emitting diodes (OLEDs) have attracted the attention of governments and researchers around the world due to their advantages such as high color contrast, wide viewing angle, fast response speed, and flexibility.

[0003] The development of high-performance luminescent materials has always been the core of OLED technology development. Currently, based on differences in their light-emitting principles, OLED luminescent materials can be mainly divided into traditional fluorescent, phosphorescent, and thermally activated delayed fluorescence (TADF) materials. Traditional fluorescent materials often exhibit extremely poor device efficiency because they can only utilize 25% of the singlet excitons generated by electroluminescence. Phosphorescent materials greatly accelerate the flipping of triplet energy levels through the heavy atom effect of metal complexes, allowing both singlet and triplet excitons to be effectively utilized. However, related blue phosphorescent materials still suffer from poor color purity and low device lifetime. In recent years, TADF materials based on the Multiple Resonance Effect (MR) constructed from organic boron have been designed with smaller band gaps (Δ) for the lowest excited singlet state (S1) and lowest excited triplet state (T1). E ST The molecules of ) enable 75% of the triplet excitons generated in electroluminescence to be converted into singlet excitons through the reverse intersystem crossing process T1→S1 and emit light. Therefore, theoretically, 100% exciton utilization can be achieved.

[0004] Nevertheless, MR-TADF materials have low actual exciton utilization, wide emission half-width, insufficient color purity, and lack of suitability for solution-based devices.

[0005] A compound (denoted as) has been reported in the literature. f -DOABNA), the light-emitting device is a vapor-deposited device, the luminous efficiency of the device is generally low, and the emission half-width is relatively wide, and the purity of the emission color is still insufficient.

[0006] (recorded as) f -DOABNA)

[0007] Therefore, it is necessary to develop deep blue light-emitting multiple resonance thermally activated delayed fluorescence molecules that possess both high luminous efficiency and high color purity and are suitable for solution-based devices. Summary of the Invention

[0008] To address one of the aforementioned technical problems in the existing technology, this invention designs a novel type of deep blue light-emitting multi-boron nitrogen derivative, which features high luminous efficiency, high color purity, and suitability for solution-based devices.

[0009] On one hand, the present invention provides a polyboron nitrogen derivative having the following structure:

[0010]

[0011] Among them, R 1 R 2 Each independently represents an alkyl or aryl substituent from C1 to C36;

[0012] R 3 R 4 R 5 R 6 R 7 R 8 Each substituent represents hydrogen or C1-C36; the C1-C36 substituents are substituted by single bonds or cyclic substitution;

[0013] A1 and A2 independently represent oxygen, sulfur, selenium, sulfoxide, sulfone, C1-C36 alkyl or aryl substituted carbon substituents, C1-C36 alkyl or aryl substituted nitrogen substituents, or none at all.

[0014] As an alkyl substituent, it can be an alkyl group composed of carbon and hydrogen atoms, or an alkyl group containing atoms other than carbon and hydrogen atoms. The alkyl group can be a chain alkyl group or a cyclic alkyl group. When the number of carbon atoms in the alkyl substituent exceeds two carbon atoms, isomers of the alkyl group are all within the scope of protection of this invention. The alkyl substituent can be further replaced by an aryl group. When the alkyl substituent is replaced by an aryl group, the number of substituents can be one or more.

[0015] Alkyl substituents include isomers. For example, but not limited to, propyl includes n-propyl and isopropyl; butyl includes n-butyl, isobutyl, tert-butyl, and cyclobutyl; pentyl includes n-pentyl, isopentyl, and cyclopentyl; and hexyl includes n-hexyl and cyclohexyl. For example, but not limited to, the alkyl group consisting of C1-C6 hydrocarbons is selected from one of the following structures:

[0016] The asterisk indicates the substitution position of the alkyl substituent. It is understood that any hydrogen substituent of the alkyl substituents mentioned above can be further substituted by other groups.

[0017] As an aryl substituent, it can be an aryl group whose aromatic ring consists only of carbon atoms, or an aryl group whose aromatic ring consists of atoms other than carbon atoms. The aryl substituent can be further substituted by other groups, which can be alkoxy or alkylamine groups, aryloxy or arylamine groups, or aryl or alkyl groups substituted by other linking atoms or other linking groups that are non-oxygen or non-nitrogen atoms. Examples of other linking atoms include sulfur atoms, and examples of other linking groups include sulfoxide or sulfone groups, as long as the aryl or alkyl group is linked to the aryl substituent by a chemical bond. The aryl substituent can be substituted by one or more other groups.

[0018] As an aryl substituent, there are multiple sites that can be substituted into the structure of the present invention. For example, but not limited to, the aryl substituent can be selected from one of the following structures:

[0019] The asterisk indicates the substitution position of the aryl substituent. It is understood that any hydrogen substituent of the aryl substituent can be further substituted by other groups.

[0020] As a preferred embodiment of the polyboron nitrogen derivative of the present invention, the alkyl or aryl substituent is a C1-C36 alkyl or a C1-C36 aryl.

[0021] The C1-C36 alkyl group is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, aryl-substituted methyl, aryl-substituted ethyl, aryl-substituted propyl, aryl-substituted butyl, aryl-substituted pentyl, or aryl-substituted hexyl; the aryl group is phenyl, tolyl, ethylphenyl, propphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl, heptoxyphenyl, methylaminophenyl, ethylaminophenyl, propylaminophenyl, butylaminophenyl, pentaminophenyl, hexylaminophenyl, heptylaminophenyl, biphenyl, or carbazole.

[0022] The aryl group of C1-C36 is selected from aryl groups that are hydrogen-substituted, alkyl-substituted, alkoxy-substituted, or alkylamine-substituted; the alkyl group in the alkyl-substituted, alkoxy-substituted, or alkylamine-substituted group is methyl, ethyl, propyl, butyl, pentyl, hexyl, or heptyl; the aryl group is selected from one of the following groups: phenyl, biphenyl, terphenyl, tetraphenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, indolyl, phenothiazinyl, furanyl, thiopheneyl, pyrroleyl, thiazolyl, isothiazinyl, pyrazolyl, imidazoleyl, oxazolyl, isoxazolyl, naphthyl, anthraceneyl, phenanthryl, pyrene, peryl, fluorenyl, carbazolyl, coumarinyl, quinoloneyl, benzocarbazolyl, benzofluorenyl, or benzothiopheneyl.

[0023] As a preferred embodiment of the polyboron nitrogen derivative described in this invention, the substituents of C1-C36 are selected from one of the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, phenyl-substituted methyl, phenyl-substituted ethyl, phenyl-substituted propyl, phenyl-substituted butyl, phenyl-substituted pentyl, phenyl-substituted hexyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, phenoxy, dimethylamino, diethylamino, dipropylamino, dibutylamino, dipentylamino, dihexylamino, diphenylamino, dinaphthylamino, phenylnaphthylamino, aryl group whose aromatic ring cyclic atom contains only a carbon atom or aryl group whose aromatic ring cyclic atom contains atoms other than a carbon atom; wherein the aromatic ring cyclic atom contains only a carbon atom The aryl group of the atom is phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, propyl-substituted phenyl, butyl-substituted phenyl, pentyl-substituted phenyl, hexyl-substituted phenyl, methoxyphenyl, ethoxyphenyl, propoxyphenyl, butoxyphenyl, pentoxyphenyl, hexoxyphenyl, dimethylaminophenyl, diethylaminophenyl, dipropylaminophenyl, dibutylaminophenyl, biphenyl, terphenyl, tetraphenyl, or naphthyl; the aryl group containing atoms other than carbon atoms in the aromatic ring is pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, indolyl, phenothiazinyl, furanyl, thiopheneyl, pyrroleyl, thiazolyl, isothiazolyl, pyrazolyl, imidazoleyl, oxazolyl, isoxazolyl, carbazoleyl, or benzothiopheneyl.

[0024] In a preferred embodiment of the polyboron nitrogen derivatives described in this invention, A1 and A2 are each identical, representing oxygen, sulfur, or selenium.

[0025] In a preferred embodiment of the polyboron nitrogen derivative described in this invention, A1 and A2 are oxygen.

[0026] In a preferred embodiment of the polyboron nitrogen derivative described in this invention, A1 and A2 are sulfur.

[0027] In a preferred embodiment of the polyboron nitrogen derivative described in this invention, A1 and A2 are selenium.

[0028] As a preferred embodiment of the polyboron nitrogen derivative described in this invention, the R 1 R 2 Indicates the same substituent.

[0029] As a preferred embodiment of the polyboron nitrogen derivative described in this invention, the R 3 R 5 Indicates the same substituent.

[0030] As a preferred embodiment of the polyboron nitrogen derivative described in this invention, the R 4 R 6 Indicates the same substituent.

[0031] As a preferred embodiment of the polyboron nitrogen derivative described in this invention, the R 7 R 8 Indicates the same substituent.

[0032] As a preferred embodiment of the polyboron nitrogen derivative described in this invention, the R 3 R 4 R 5 R 6 Indicates the same substituent.

[0033] As a preferred embodiment of the polyboron nitrogen derivative described in this invention, the R 3 R 4 R 5 R 6 R 7 R 8 Indicates the same substituent.

[0034] As a preferred embodiment of the polyboron nitrogen derivative of the present invention, the polyboron nitrogen derivative has one of the following structures: .

[0035] As a preferred embodiment of the polyboron nitrogen derivatives described in this invention, the polyboron nitrogen derivatives have a structure similar to that shown in compounds 1-1 to 1-120, except that the oxygen atoms are replaced with sulfur atoms, and the compound names are respectively changed to compounds 2-1 to 2-120.

[0036] As a preferred embodiment of the polyboron nitrogen derivative of the present invention, the polyboron nitrogen derivative has one of the following structures: .

[0037] On the one hand, the present invention also provides a deep blue light-emitting device, wherein the deep blue light-emitting device contains the polyboron nitrogen derivative described in the above technical solution.

[0038] As a preferred embodiment of the deep blue light device of the present invention, the deep blue light device contains at least one light-emitting layer, and the at least one light-emitting layer contains at least one polyboron nitrogen derivative of the present invention. More preferably, the at least one light-emitting layer may contain only one type of polyboron nitrogen derivative of the present invention, or it may contain organic light-emitting materials with other structures.

[0039] On the one hand, the present invention also provides a light-emitting device, wherein the light-emitting device employs a deep blue light device containing the polyboron nitrogen derivative described in the above technical solution.

[0040] On the one hand, the light-emitting device of the present invention can be applied in the display field as well as in the lighting field. Preferably, the light-emitting device of the present invention can be a smartphone, or a laptop, display screen, television, tablet, digital camera, head-mounted display device, micro-display device, wristband, in-vehicle display device, videophone device, instrument panel of a water device, instrument panel of an underwater device, instrument panel of an aerial device, and other devices that need to realize the light-emitting function.

[0041] Compared with the prior art, the technical solution of the present invention has at least one or more of the following beneficial effects:

[0042] The polyboron nitrogen derivatives described in this invention exhibit excellent deep blue light emission characteristics, enabling the simultaneous fabrication of solution-based and vapor-deposited organic electroluminescent optoelectronic devices. These devices possess high external quantum efficiency and high color purity. The luminescent materials can be fabricated into high-performance light-emitting devices, which can then be further applied in light-emitting equipment. Attached Figure Description

[0043] To more clearly illustrate the technical solution of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0044] Figure 1 The schematic diagrams of Experimental Example-1 and Experimental Example-3 of the present invention are shown, wherein 1-substrate, 2-hole transport layer, 3-light-emitting layer, 4-electron transport layer, 5-electron blocking layer, 6-electron injection layer, and 7-cathode layer.

[0045] Figure 2 The schematic diagrams of Experimental Example-2 and Experimental Example-4 of the present invention are shown, wherein 1-substrate, 2-hole injection layer, 3-hole transport layer, 4-light emission layer, 5-electron blocking layer, 6-electron transport layer, 7-electron injection layer, and 8-cathode layer. Detailed Implementation

[0046] To further illustrate the technical means and effects of the present invention in order to achieve the intended purpose, the following detailed description, in conjunction with the accompanying drawings and embodiments, provides a detailed explanation of the specific implementation methods, steps, structures, features, and effects of the polyboron nitrogen derivatives proposed in accordance with the present invention.

[0047] The foregoing and other technical contents, features, and effects of the present invention will be clearly presented in the following detailed description of preferred embodiments with reference to the accompanying drawings. Through the description of the specific embodiments, a more in-depth and specific understanding can be gained of the technical means and effects adopted by the present invention to achieve the intended purpose. However, the accompanying drawings are only provided for reference and illustration and are not intended to limit the present invention.

[0048] Organic electroluminescence technology is an interdisciplinary field. It is common for different sub-disciplines to use different terms to describe the same concept or phenomenon. Unless there is confusion or the context specifically indicates otherwise, different expressions can generally be considered to have the same meaning. It is understood that "molecule," "compound," "derivative," "structure," "material," "solid," and "dye" can all refer to the polyboron nitrogen derivatives of this invention, unless the context explicitly distinguishes them or it is easily understood by those skilled in the art to be different. It is understood that the above terms can refer to the polyboron nitrogen derivatives of this invention, but are not necessarily required to do so. For example, regarding "solid," in the embodiments of this invention, there are multiple expressions for "solid." Some "solid" refer to intermediates, while others refer to the polyboron nitrogen derivatives of this invention. Whether it refers to the polyboron nitrogen derivatives of this invention depends on the specific position of the corresponding term in this invention.

[0049] The "polyboron-nitrogen derivative" of this invention belongs to the technical field of "boron-nitrogen derivatives". The "polyboron-nitrogen derivative" described in this invention refers to a derivative structure containing multiple boron and nitrogen atoms, specifically four or more. More specifically, the "polyboron-nitrogen derivative" of this invention has at least four boron atoms and at least two nitrogen atoms. This technical field of "boron-nitrogen derivatives" includes not only "polyboron-nitrogen derivatives" but also "boron-nitrogen derivatives" with only one boron atom or one nitrogen atom. It is understood that, at least for the purpose of preparation, it is necessary to understand "boron-nitrogen derivatives," as the intermediate in the following examples is a "boron-nitrogen derivative" rather than a "polyboron-nitrogen derivative".

[0050] Regarding the abbreviations and symbols used in this invention, abbreviations that are easily understood by those skilled in the art are used. Some abbreviations are illustrated below: Pd2(dba)3 refers to cesium carbonate, Sphos refers to dimethylacetamide, tBuONa refers to sodium tert-butoxide, and Toluene refers to toluene solution. o -DCB refers to o-dichlorobenzene, BBr3 refers to boron tribromide, mg refers to milligrams, mmol refers to millimoles, mL refers to milliliters, Pa refers to Pascals, wt% refers to weight percentage, nm refers to nanometers, ppm refers to parts per million, FWHM refers to half the peak width at half maximum, ℃ refers to degrees Celsius, h refers to hours, min refers to minutes, rt refers to room temperature, EQE max Efficiency refers to the efficiency of electroluminescent devices. Example

[0051] Example 1: Synthetic route of compounds 1-28

[0052]

[0053] Intermediate M1: 3,5-Dibromo-N,N-diphenylaniline (4.03 g, 10.0 mmol), 2,4,6-trimethylaniline (3.40 g, 25.0 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (492 mg, 1.20 mmol), and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give a white solid M1 (4.72 g, 92%).

[0054] Structural characterization of white solid M1: 1 H NMR (400 MHz, CD2Cl2): δ 7.28 – 7.22 (m, 4H), 7.16 – 7.11 (m, 4H), 7.03 – 6.97 (m, 2H), 6.91 (s, 4H), 5.71 (d, J = 2.0 Hz, 2H), 5.47 (t, J = 2.0 Hz, 1H), 4.91 (s, 2H), 2.32 (s, 6H), 2.22 (s, 12H).MALDI-TOF: Calculated: 511.299, Found: 511.306.

[0055]

[0056] Intermediate M2: M1 (1.94 g, 3.80 mmol), 7-bromo-2,12-dimethyl-5,9-dioxa-13b-borona[3,2,1-de]anthracene (3.62 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M2 (3.44 g, 82%).

[0057] Structural characterization of M2: 1 H NMR (400 MHz, CD2Cl2): 8.70 (d, J = 2.5 Hz, 4H), 7.73(dd,J = 8.8, 2.5 Hz, 4H), 7.38 (d, J = 8.8 Hz, 4H), 7.30 (dd, J = 8.4, 7.3Hz, 4H), 7.20 – 7.15 (m, 4H), 6.98 – 6.91 (m, 6H), 6.65 (t, J = 1.3 Hz, 2H), 6.58 (s, 4H), 6.33 (t, J = 2.0 Hz, 1H), 2.27 (s, 6H), 2.01 (s, 12H), 1.53 (s,12H). MALDI-TOF: Calculated: 1103.501, Found: 1103.503.

[0058]

[0059] Synthesis of compound 1-28: M2 (563 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 1-28 (86 mg, 15%).

[0060] Characterization of compounds 1-28: 1 H NMR (400 MHz, CD2Cl2) δ: 8.97 (dd, J = 7.8, 1.7Hz, 2H), 8.85 (dd, J = 21.8, 2.5 Hz, 4H), 8.43 (d, J = 8.4 Hz, 2H), 7.90 (dd, J = 8.8, 2.5 Hz, 2H), 7.75 (dd, J = 8.7, 2.5 Hz, 2H), 7.69 (d, J = 8.7 Hz, 2H), 7.66 (ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.45 (ddd, J = 7.9, 7.0, 1.1 Hz,2H), 7.40 (d, J= 8.7 Hz, 2H), 7.08 (s, 2H), 7.00 (d, J = 1.7 Hz, 2H), 6.57(s, 2H), 5.48 (s, 1H), 2.53 (s, 6H), 1.81 (s, 6H), 1.72 (s, 6H), 1.58-1.54(m, 12H). MALDI-TOF: Calculated: 1119.472, Found: 1119.475.

[0061] Example 2: Synthetic routes of compounds 1-52

[0062]

[0063] Intermediate M3: M1 (1.94 g, 3.80 mmol), 7-bromo-3,11-dimethyl-5,9-dioxa-13b-borona[3,2,1-de]anthracene (3.62 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M3 (3.52 g, 84%).

[0064] Structural characterization of M3: 1 H NMR (400 MHz, CD2Cl2): 8.73 (d, J = 2.5 Hz, 4H), 7.76(dd, J = 8.8, 2.5 Hz, 4H), 7.40 (d, J = 8.8 Hz, 4H), 7.33 (dd, J = 8.4, 7.3Hz, 4H), 7.22 – 7.16 (m, 4H), 7.01 – 6.94 (m, 6H), 6.68 (t, J = 1.3 Hz, 2H), 6.61 (s, 4H), 6.35 (t, J= 2.0 Hz, 1H), 2.31 (s, 6H), 2.04 (s, 12H), 1.55 (s,12H). MALDI-TOF: Calculated: 1103.501, Found: 1103.503.

[0065]

[0066] Synthesis of compound 1-52: M3 (563 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 1-52 (93 mg, 16%).

[0067] Characterization of compounds 1-52: 1 H NMR (400 MHz, CD2Cl2) δ: 8.97 (dd, J = 7.8, 1.7Hz, 2H), 8.85 (dd, J = 21.8, 2.5 Hz, 4H), 8.43 (d, J = 8.4 Hz, 2H), 7.90 (dd, J = 8.8, 2.5 Hz, 2H), 7.75 (dd, J = 8.7, 2.5 Hz, 2H), 7.69 (d, J = 8.7 Hz, 2H), 7.66 (ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.45 (ddd, J = 7.9, 7.0, 1.1 Hz,2H), 7.40 (d, J = 8.7 Hz, 2H), 7.08 (s, 2H), 7.00 (d, J = 1.7 Hz, 2H), 6.57(s, 2H), 5.48 (s, 1H), 2.53 (s, 6H), 1.81 (s, 6H), 1.72 (s, 6H), 1.56-1.52(m, 12H). MALDI-TOF: Calculated: 1119.472, Found: 1119.475.

[0068] Example 3: Synthetic route of compounds 1-76

[0069]

[0070] Intermediate M4: M1 (1.94 g, 3.80 mmol), 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13b-boronaphthalene[3,2,1-de]anthracene (4.46 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain a yellow solid M2 (4.16 g, 86%).

[0071] Structural characterization of yellow solid M2: 1 H NMR (400 MHz, CD2Cl2): 8.72 (d, J = 2.5 Hz, 4H), 7.75 (dd, J = 8.8, 2.5 Hz, 4H), 7.40 (d, J = 8.8 Hz, 4H), 7.31 (dd, J =8.4, 7.3 Hz, 4H), 7.22 – 7.18 (m, 4H), 7.00 – 6.94 (m, 6H), 6.69 (t, J = 1.3Hz, 2H), 6.63 (s, 4H), 6.37 (t, J = 2.0 Hz, 1H), 2.29 (s, 6H), 2.04 (s, 12H), 1.51 (s, 36H). MALDI-TOF: Calculated: 1271.689, Found: 1271.693.

[0072]

[0073] Synthesis of compound 1-76: M4 (650 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 1-76 (112 mg, 17%).

[0074] Characterization of compounds 1-76: 1 H NMR (400 MHz, CD2Cl2) δ: 8.99 (dd, J = 7.8, 1.7Hz, 2H), 8.88 (dd, J = 21.8, 2.5 Hz, 4H), 8.47 (d, J = 8.4 Hz, 2H), 7.93 (dd, J = 8.8, 2.5 Hz, 2H), 7.79 (dd, J = 8.7, 2.5 Hz, 2H), 7.72 (d, J = 8.7 Hz, 2H), 7.68 (ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.48 (ddd, J = 7.9, 7.0, 1.1 Hz,2H), 7.40 (d, J = 8.7 Hz, 2H), 7.12 (s, 2H), 7.02 (d, J = 1.7 Hz, 2H), 6.60(s, 2H), 5.51 (s, 1H), 2.54 (s, 6H), 1.84 (s, 6H), 1.74 (s, 6H), 1.59-1.58(m, 12H). (d, J = 6.1 Hz, 36H). MALDI-TOF: Calculated: 1287.660, Found: 1287.613.

[0075] Example 4: Synthetic route of compound 1-100

[0076]

[0077] Intermediate M5: M5 (1.94 g, 3.80 mmol), 7-bromo-3,11-di-tert-butyl-5,9-dioxa-13b-boronaphthalene[3,2,1-de]anthracene (4.46 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M5 (4.25 g, 88%).

[0078] Structural characterization of M5: 1 H NMR (400 MHz, CD2Cl2): 8.75 (d, J = 2.5 Hz, 4H), 7.77(dd, J = 8.8, 2.5 Hz, 4H), 7.45 (d, J = 8.8 Hz, 4H), 7.34 (dd, J = 8.4, 7.3Hz, 4H), 7.25 – 7.20 (m, 4H), 7.03 – 6.96 (m, 6H), 6.72 (t, J = 1.3 Hz, 2H), 6.63 (s, 4H), 6.41 (t, J = 2.0 Hz, 1H), 2.33 (s, 6H), 2.07 (s, 12H), 1.54 (s,36H). MALDI-TOF: Calculated: 1271.689, Found: 1271.693.

[0079]

[0080] Synthesis of compound 1-100: M5 (650 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 1-100 (125 mg, 19%).

[0081] Characterization of compounds 1-100: 1H NMR (400 MHz, CD2Cl2) δ: 9.02 (dd, J = 7.8, 1.7Hz, 2H), 8.90 (dd, J = 21.8, 2.5 Hz, 4H), 8.52 (d, J = 8.4 Hz, 2H), 7.97 (dd, J = 8.8, 2.5 Hz, 2H), 7.82 (dd, J = 8.7, 2.5 Hz, 2H), 7.75 (d, J = 8.7 Hz, 2H), 7.70 (ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.52 (ddd, J = 7.9, 7.0, 1.1 Hz,2H), 7.43 (d, J = 8.7 Hz, 2H), 7.16 (s, 2H), 7.05 (d, J = 1.7 Hz, 2H), 6.64(s, 2H), 5.54 (s, 1H), 2.53 (s, 6H), 1.87 (s, 6H), 1.76 (s, 6H), 1.62-1.56(m, 36H). MALDI-TOF: Calculated: 1287.660, Found: 1287.613.

[0082] Example 5: Synthetic route of compound 2-28

[0083]

[0084] Intermediate M6: M1 (1.94 g, 3.80 mmol), 7-bromo-2,12-dimethyl-5,9-dithia-13b-borona[3,2,1-de]anthracene (3.93 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M6 (3.46 g, 78%).

[0085] Structural characterization of M6: 1H NMR (400 MHz, CD2Cl2): 8.77 (d, J = 2.5 Hz, 4H), 7.81(dd, J = 8.8, 2.5 Hz, 4H), 7.45 (d, J = 8.8 Hz, 4H), 7.38 (dd, J = 8.4, 7.3Hz, 4H), 7.26 – 7.20 (m, 4H), 7.05 – 6.98 (m, 6H), 6.73 (t, J = 1.3 Hz, 2H), 6.64 (s, 4H), 6.43 (t, J = 2.0 Hz, 1H), 2.32 (s, 6H), 2.09 (s, 12H), 1.62 (s,12H). MALDI-TOF: Calculated: 1167.409, Found: 1167.413.

[0086]

[0087] Synthesis of compound 2-28: M6 (596 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 2-28 (86 mg, 15%).

[0088] Characterization of compound 2-28: 1 H NMR (400 MHz, CD2Cl2) δ: 9.07 (dd, J = 7.8, 1.7Hz, 2H), 8.96 (dd, J = 21.8, 2.5 Hz, 4H), 8.54 (d, J = 8.4 Hz, 2H), 8.11 (dd, J = 8.8, 2.5 Hz, 2H), 7.86 (dd, J = 8.7, 2.5 Hz, 2H), 7.81 (d, J = 8.7 Hz, 2H), 7.76 (ddd, J= 8.6, 7.0, 1.7 Hz, 2H), 7.57 (ddd, J = 7.9, 7.0, 1.1 Hz,2H), 7.52 (d, J = 8.7 Hz, 2H), 7.18 (s, 2H), 7.11 (d, J = 1.7 Hz, 2H), 6.68(s, 2H), 5.59 (s, 1H), 2.65 (s, 6H), 1.92 (s, 6H), 1.82 (s, 6H), 1.54-1.50(m, 12H). MALDI-TOF: Calculated: 1183.381, Found: 1183.385.

[0089] Example 6: Synthetic route of compound 3-35

[0090]

[0091] Intermediate M7: 3,5-Dibromo-N,N-diphenylaniline (4.03 g, 10.0 mmol), 4-aminopyridine (2.35 g, 25.0 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (492 mg, 1.20 mmol), and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain a white solid, M7 (2.78 g, 65%).

[0092] Structural characterization of white solid M7: 1 H NMR (400 MHz, CD2Cl2): δ 8.48 (d, J = 2.0 Hz, 4H), 7.24 (t, J = 2.0 Hz, 4H), 7.16 – 7.11 (m, 4H), 7.03 – 6.97 (m, 2H), 6.91(s, 4H), 5.71 (d, J = 2.0 Hz, 2H), 5.47 (t, J = 2.0 Hz, 1H), 4.91 (s, 2H).MALDI-TOF: Calculated: 429.195, Found: 429.197.

[0093]

[0094] Intermediate M8: M7 (1.63 g, 3.80 mmol), 7-bromo-2,12-dimethyl-5,9-dithia-13b-borona[3,2,1-de]anthracene (3.93 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M8 (2.58 g, 57%).

[0095] Structural characterization of M8: 1 H NMR (400 MHz, CD2Cl2): 8.82 (d, J = 2.5 Hz, 4H), 8.52(d, J = 2.0 Hz, 4H), 7.80 (dd, J = 8.8, 2.5 Hz, 4H), 7.47 (d, J = 8.8 Hz, 4H), 7.35 (dd, J = 8.4, 7.3 Hz, 4H), 7.28 – 7.24 (m, 4H), 7.07 – 7.01 (m,6H), 6.76 (t, J = 1.3 Hz, 2H), 6.69 (d, J = 2.0 Hz, 4H), 6.47 (t, J = 2.0 Hz,1H), 1.62 (s, 36H). MALDI-TOF: Calculated: 1189.585, Found: 1189.583.

[0096]

[0097] Synthesis of compound 3-35: M8 (607 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 3-35 (157 mg, 13%).

[0098] Characterization of compound 3-35: 1 H NMR (400 MHz, CD2Cl2) δ: 9.07 (t, J = 7.8, 1.7 Hz, 2H), 8.96 (t, J = 21.8, 2.5 Hz, 4H), 8.67 (d, J = 2.0 Hz, 2H), 8.58 (d, J =8.4 Hz, 2H), 8.15 (dd, J = 8.8, 2.5 Hz, 2H), 7.86 (dd, J = 8.7, 2.5 Hz, 2H), 7.81 (d, J = 8.7 Hz, 2H), 7.78 (ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.60 (ddd, J = 7.9, 7.0, 1.1 Hz, 2H), 7.57 (d, J = 8.7 Hz, 2H), 7.23 (s, 2H), 7.15 (d, J =1.7 Hz, 2H), 6.65 (s, 2H), 5.55 (s, 1H), 1.52-1.48 (m, 36H). MALDI-TOF: Calculated: 1205.557, Found: 1205.561.

[0099] Example 7: Synthetic route of compound 3-50

[0100]

[0101] Intermediate M9: 3,5-Dibromo-N,N-diphenylaniline (4.03 g, 10.0 mmol), 2-aminopyrimidine (2.38 g, 25.0 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (492 mg, 1.20 mmol), and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain a white solid, M9 (2.68 g, 62%).

[0102] Structural characterization of white solid M9: 1 H NMR (400 MHz, CD2Cl2): δ 8.42 (t, J = 2.0 Hz, 4H), 7.24 (t, J = 2.0 Hz, 2H), 7.16 – 7.11 (m, 4H), 7.03 – 6.97 (m, 2H), 6.91(s, 4H), 5.71 (d, J = 2.0 Hz, 2H), 5.47 (t, J = 2.0 Hz, 1H), 4.91 (s, 2H).MALDI-TOF: Calculated: 431.186, Found: 431.182.

[0103]

[0104] Intermediate M10: M9 (1.64 g, 3.80 mmol), 7-bromo-2,12-dimethyl-5,9-dithia-13b-borona[3,2,1-de]anthracene (3.93 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M10 (2.40 g, 53%).

[0105] Structural characterization of M10: 1 H NMR (400 MHz, CD2Cl2): 8.82 (t, J= 2.0 Hz, 4H), 8.52(t, J = 2.0 Hz, 2H), 7.80 (dd, J = 8.8, 2.5 Hz, 4H), 7.47 (d, J = 8.8 Hz, 4H), 7.35 (dd, J = 8.4, 7.3 Hz, 4H), 7.28 – 7.24 (m, 4H), 7.07 – 7.01 (m,6H), 6.76 (t, J = 1.3 Hz, 2H), 6.69 (d, J = 2.0 Hz, 4H), 6.47 (t, J = 2.0 Hz,1H), 1.62 (s, 36H). MALDI-TOF: Calculated: 1191.575, Found: 1191.578.

[0106]

[0107] Synthesis of compound 3-50: M10 (608 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 3-50 (80 mg, 13%).

[0108] Characterization of compound 3-50: 1 H NMR (400 MHz, CD2Cl2) δ: 9.07 (t, J = 2.0 Hz, 2H), 8.96 (t, J = 21.8, 2.0 Hz, 4H), 8.56 (d, J = 8.4 Hz, 2H), 8.16 (dd, J = 8.8, 2.5 Hz, 2H), 7.83 (dd, J = 8.7, 2.5 Hz, 2H), 7.78 (d, J = 8.7 Hz, 2H), 7.73(ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.61 (ddd, J= 7.9, 7.0, 1.1 Hz, 2H), 7.56(d, J = 8.7 Hz, 2H), 7.21 (s, 2H), 7.11 (d, J = 1.7 Hz, 2H), 6.71 (s, 2H), 5.62 (s, 1H), 1.57-1.45 (m, 36H) MALDI-TOF: Calculated: 1207.547, Found: 1207.551.

[0109] Example 8: Synthetic route of compound 3-65

[0110]

[0111] Intermediate M11: 3,5-Dibromo-N,N-diphenylaniline (4.03 g, 10.0 mmol), 5-aminopyrimidine (2.38 g, 25.0 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (492 mg, 1.20 mmol), and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give a white solid M9 (2.90 g, 67%).

[0112] Structural characterization of white solid M9: 1 H NMR (400 MHz, CD2Cl2): δ 8.45 (d, J = 2.0 Hz, 4H), 7.27 (s, J = 2.0 Hz, 2H), 7.18 – 7.13 (m, 4H), 7.05 – 7.01 (m, 2H), 6.93(s, 4H), 5.75 (d, J = 2.0 Hz, 2H), 5.47 (t, J = 2.0 Hz, 1H), 4.94 (s, 2H).MALDI-TOF: Calculated: 431.186, Found: 431.182.

[0113]

[0114] Intermediate M12: M11 (1.64 g, 3.80 mmol), 7-bromo-2,12-dimethyl-5,9-dithia-13b-borona[3,2,1-de]anthracene (3.93 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M12 (2.76 g, 53%).

[0115] Structural characterization of M12: 1 H NMR (400 MHz, CD2Cl2): 8.85 (t, J = 2.0 Hz, 4H), 8.56(t, J = 2.0 Hz, 2H), 7.78 (dd, J = 8.8, 2.5 Hz, 4H), 7.45 (d, J = 8.8 Hz, 4H), 7.28 (dd, J = 2.0 Hz, 2H), 7.26 – 7.21 (m, 4H), 7.09 – 7.03 (m, 6H), 6.71 (t, J = 1.3 Hz, 2H), 6.65 (d, J = 2.0 Hz, 4H), 6.45 (t, J = 2.0 Hz, 1H),1.65 (s, 36H). MALDI-TOF: Calculated: 1191.575, Found: 1191.578.

[0116]

[0117] Synthesis of compound 3-65: M10 (608 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 3-65 (92 mg, 15%).

[0118] Characterization of compound 3-65:1 H NMR (400 MHz, CD2Cl2) δ: 9.05 (t, J = 2.0 Hz, 2H), 8.95 (t, J = 21.8, 2.0 Hz, 4H), 8.53 (d, J = 8.4 Hz, 2H), 8.13 (dd, J = 8.8, 2.5 Hz, 2H), 7.80 (dd, J = 8.7, 2.5 Hz, 2H), 7.76 (d, J = 8.7 Hz, 2H), 7.70(ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.58 (ddd, J = 7.9, 7.0, 1.1 Hz, 2H), 7.53(d, J = 8.7 Hz, 2H), 7.28 (s, 2H), 7.16 (d, J = 1.7 Hz, 2H), 6.75 (s, 2H), 5.65 (s, 1H), 1.55-1.42 (m, 36H) MALDI-TOF: Calculated: 1207.547, Found: 1207.551.

[0119] Example 9: Synthetic route of compound 3-95

[0120]

[0121] Intermediate M13: 3,5-Dibromo-N,N-diphenylaniline (4.03 g, 10.0 mmol), 1-naphthylamine (3.58 g, 25.0 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (492 mg, 1.20 mmol), and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain a white solid, M13 (3.80 g, 72%).

[0122] Structural characterization of white solid M13: 1 H NMR (400 MHz, CD2Cl2): δ 8.41 (d, J= 2.0 Hz, 4H), 7.23 (s, J = 2.0 Hz, 2H), 7.13 – 7.09 (m, 12H), 7.02 – 6.97 (m, 2H), 6.87 (s, 4H), 5.73 (d, J = 2.0 Hz, 2H), 5.45 (t, J = 2.0 Hz, 1H), 4.96 (s,2H). MALDI-TOF: Calculated: 527.236, Found: 527.239.

[0123]

[0124] Intermediate M14: M13 (2.01 g, 3.80 mmol), 7-bromo-2,12-dimethyl-5,9-dithia-13b-borona[3,2,1-de]anthracene (3.93 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M14 (4.01 g, 82%).

[0125] Structural characterization of M14: 1 H NMR (400 MHz, CD2Cl2): 8.81 (d, J = 2.5 Hz, 4H), 7.86(dd, J = 8.8, 2.5 Hz, 4H), 7.48 (d, J = 8.8 Hz, 4H), 7.41 (dd, J = 8.4, 7.3Hz, 4H), 7.28 – 7.22 (m, 12H), 7.08 – 7.03 (m, 6H), 6.78 (t, J = 1.3 Hz, 2H), 6.68 (s, 4H), 6.47 (t, J = 2.0 Hz, 1H), 1.66 (s, 36H). MALDI-TOF: Calculated:1287.626, Found: 1287.629.

[0126]

[0127] Synthesis of compound 3-95: M14 (642 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 3-95 (113 mg, 17%).

[0128] Characterization of compound 3-95: 1 H NMR (400 MHz, CD2Cl2) δ: 9.03 (dd, J = 7.8, 1.7Hz, 2H), 8.92 (dd, J = 21.8, 2.5 Hz, 4H), 8.50 (d, J = 8.4 Hz, 2H), 8.07 (dd, J = 8.8, 2.5 Hz, 2H), 7.83 (dd, J = 8.7, 2.5 Hz, 2H), 7.76 (d, J = 8.7 Hz, 2H), 7.71 (ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.52 (ddd, J = 7.9, 7.0, 1.1 Hz,2H), 7.45 (d, J = 8.7 Hz, 2H), 7.12 - 6.62 (m, 18H), 5.57 (s, 1H), 1.63-1.60(m, 36H). MALDI-TOF: Calculated: 1303.597, Found: 1303.595.

[0129] Example 10: Synthetic route of compound 3-110

[0130]

[0131] Intermediate M15: 3,5-Dibromo-N,N-diphenylaniline (4.03 g, 10.0 mmol), 2-naphthylamine (3.58 g, 25.0 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (492 mg, 1.20 mmol), and sodium tert-butoxide (2.88 g, 30.0 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain a white solid, M15 (4.01 g, 76%).

[0132] Structural characterization of white solid M15: 1 H NMR (400 MHz, CD2Cl2): δ 8.45 (d, J = 2.0 Hz, 4H), 7.25 (s, J = 2.0 Hz, 2H), 7.15 – 7.11 (m, 12H), 7.05 – 6.91 (m, 2H), 6.77 (s, 4H), 5.76 (d, J = 2.0 Hz, 2H), 5.47 (t, J = 2.0 Hz, 1H), 4.99 (s,2H). MALDI-TOF: Calculated: 527.236, Found: 527.237.

[0133]

[0134] Intermediate M16: M15 (2.01 g, 3.80 mmol), 7-bromo-2,12-dimethyl-5,9-dithia-13b-borona[3,2,1-de]anthracene (3.93 g, 9.60 mmol), Pd2(dba)3 (550 mg, 0.60 mmol), SPhos (985 mg, 2.40 mmol), and sodium tert-butoxide (1.50 g, 15.2 mmol) were added to a reaction flask. The mixture was stirred at 110 °C under nitrogen protection for 12 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to obtain M16 (4.21 g, 86%).

[0135] Structural characterization of M16: 1 H NMR (400 MHz, CD2Cl2): 8.78 (d, J= 2.5 Hz, 4H), 7.84(dd, J = 8.8, 2.5 Hz, 4H), 7.58 (d, J = 8.8 Hz, 4H), 7.43 (dd, J = 8.4, 7.3Hz, 4H), 7.33 – 7.28 (m, 12H), 7.18 – 7.13 (m, 6H), 6.73 (t, J = 1.3 Hz, 2H), 6.65 (s, 4H), 6.43 (t, J = 2.0 Hz, 1H), 1.65 (s, 36H). MALDI-TOF: Calculated:1287.626, Found: 1287.627.

[0136]

[0137] Synthesis of compound 3-110: M16 (642 mg, 0.51 mmol), boron tribromide (1.0 mL, 10.2 mmol), and o-dichlorobenzene (10 mL) were added to a reaction flask. The mixture was stirred at 200 °C under nitrogen protection for 36 hours. After cooling to room temperature, the reaction mixture was poured into water, and the crude product was collected by vacuum filtration. The crude product was then purified by column chromatography to give compound 3-110 (120 mg, 18%).

[0138] Characterization of compound 3-110: 1 H NMR (400 MHz, CD2Cl2) δ: 9.06 (dd, J = 7.8, 1.7Hz, 2H), 8.95 (dd, J = 21.8, 2.5 Hz, 4H), 8.55 (d, J = 8.4 Hz, 2H), 8.10 (dd, J = 8.8, 2.5 Hz, 2H), 7.85 (dd, J = 8.7, 2.5 Hz, 2H), 7.81 (d, J = 8.7 Hz, 2H), 7.75 (ddd, J = 8.6, 7.0, 1.7 Hz, 2H), 7.56 (ddd, J = 7.9, 7.0, 1.1 Hz,2H), 7.48 (d, J= 8.7 Hz, 2H), 7.16 - 6.68 (m, 18H), 5.62 (s, 1H), 1.65-1.62(m, 36H). MALDI-TOF: Calculated: 1303.597, Found: 1303.561.

[0139] A 110 nm thick indium tin oxide (ITO) glass substrate was used as substrate 1. The glass substrate was washed with detergent, deionized water, and isopropanol, followed by surface activation treatment with ultraviolet ozone. Vacuum evaporation was then performed on the washed substrate to deposit each layer, and a cross-sectional view is shown below. Figure 2 The luminescent area shown is 0.09 cm². 2 Organic electroluminescent devices.

[0140] First, the aforementioned glass substrate is introduced into a vacuum evaporation bath, and the pressure is reduced to 1×10⁻⁶. -4 Pa. Then Figure 2On the glass substrate 1 shown, the functional layers are sequentially deposited as follows: hole injection layer 2, hole transport layer 3, light emission layer 4, electron blocking layer 5, electron transport layer 6, electron injection layer 7, and cathode layer 8. Specifically, a 5 nm thick layer of 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (TAPC) is vacuum-deposited as a hole injection layer 2; a 35 nm thick layer of 1,1-bis[4-[N,N-di(p-tolyl)amino]phenyl]cyclohexane (TAPC) is deposited as a hole injection layer (HIL) 2; a 10 nm thick layer of 4,4',4''-tris(carbazole-9-yl)triphenylamine (TCTA) is deposited as a hole transport layer (HTL) 3; a 20 nm thick layer of 1,3-dicarbazole-9-ylbenzene (mCP) with a vacuum evaporation ratio of XX:YY (wt%) is deposited as a light-emitting layer 4 composed of the compound of the present invention (XX and YY are numbers, added together to 100, YY wt% represents the doping ratio of the compound of the present invention); and a 6 nm thick layer is deposited as a light-emitting layer. A thick 2,8-bis(diphenyloxyphosphine)dibenzothiophene (PPT) layer was used as the electron blocking layer 5, a 30 nm thick 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]dipyridine (TmPyPb) layer as the electron transport layer 6, and a 1 nm thick lithium fluoride (LiF) layer as the electron injection layer 7. Each organic material was deposited by vacuum deposition using resistance heating at a deposition rate of 1 Å / s. Finally, a metal mask was arranged orthogonally to the ITO stripes to form a 100 nm thick film cathode layer 8. The thickness of each film was measured using a stylus-type film thickness gauge (DEKTAK). The device was then sealed in a nitrogen atmosphere glove box with a water and oxygen concentration of less than 1 ppm. The sealing was achieved using a glass sealing cap and the aforementioned epoxy UV-curable resin for the film substrate (manufactured by Nagase ChemteX Corporation).

[0141] A direct current was applied to the prepared organic electroluminescent device, and the luminous efficiency was determined using a Hamamatsu C9920-02 integrating sphere. The current-voltage characteristics were measured using a computer-controlled Keithley 2400 digital source meter.

[0142] Experimental Example-1

[0143] The vapor deposition method was used, with XX:YY ratio of 99.0:1.0 and compound 1-76, to obtain the corresponding vapor deposition device performance.

[0144] The vapor deposition method was used to obtain the performance of the vapor-deposited device with an XX:YY ratio of 98.6:1.4 and a compound of 1-76.

[0145] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.2:1.8 and compound 1-76, to obtain the corresponding performance of the vapor deposition device.

[0146] The vapor deposition method was used for the experiment, with XX:YY ratio of 99.0:1.0 and compound 1-28, to obtain the corresponding vapor deposition device performance.

[0147] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.6:1.4 and compound 1-28, to obtain the corresponding performance of the vapor deposition device.

[0148] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.2:1.8 and compound 1-28, to obtain the corresponding performance of the vapor deposition device.

[0149] The vapor deposition method was used, with XX:YY ratio of 99.0:1.0 and compound 1-52, to obtain the corresponding performance of the vapor deposition device.

[0150] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.6:1.4 and compound 1-52, to obtain the corresponding performance of the vapor deposition device.

[0151] The vapor deposition method was used, with XX:YY ratio of 98.2:1.8 and compound 1-52, to obtain the corresponding performance of the vapor deposition device.

[0152] The vapor deposition method was used for the experiment, with XX:YY ratio of 99.0:1.0 and compound ratio of 1-100, to obtain the corresponding vapor deposition device performance.

[0153] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.6:1.4 and compound 1-100, to obtain the corresponding performance of the vapor deposition device.

[0154] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.2:1.8 and compound 1-100, to obtain the corresponding vapor deposition device performance.

[0155] The vapor deposition method was used, with XX:YY ratio of 99.0:1.0 and compound 2-28, to obtain the corresponding vapor deposition device performance.

[0156] The vapor deposition method was used, with an XX:YY ratio of 98.6:1.4 and a compound of 2-28, to obtain the corresponding performance of the vapor deposition device.

[0157] The vapor deposition method was used, with XX:YY ratio of 98.2:1.8 and compound 2-28, to obtain the corresponding performance of the vapor deposition device.

[0158] The vapor deposition method was used, with XX:YY ratio of 99.0:1.0 and compound 3-35, to obtain the corresponding vapor deposition device performance.

[0159] Test Example-17

[0160] The vapor deposition method was used, with an XX:YY ratio of 98.6:1.4 and a compound of 3-35, to obtain the corresponding performance of the vapor deposition device.

[0161] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.2:1.8 and compound 3-35, to obtain the corresponding performance of the vapor deposition device.

[0162] The vapor deposition method was used, with XX:YY ratio of 99.0:1.0 and compound 3-50, to obtain the corresponding vapor deposition device performance.

[0163] The vapor deposition method was used for the experiment, with an XX:YY ratio of 98.6:1.4 and a compound of 3-50, to obtain the corresponding performance of the vapor deposition device.

[0164] The vapor deposition method was used, with an XX:YY ratio of 98.2:1.8 and a compound of 3-50, to obtain the corresponding performance of the vapor deposition device.

[0165] The vapor deposition method was used, with XX:YY ratio of 99.0:1.0 and compound 3-65, to obtain the corresponding vapor deposition device performance.

[0166] The vapor deposition method was used, with an XX:YY ratio of 98.6:1.4 and a compound of 3-65, to obtain the corresponding vapor deposition device performance.

[0167] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.2:1.8 and compound 3-65, to obtain the corresponding performance of the vapor deposition device.

[0168] The vapor deposition method was used, with XX:YY ratio of 99.0:1.0 and compound 3-95, to obtain the corresponding vapor deposition device performance.

[0169] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.6:1.4 and compound 3-95, to obtain the corresponding vapor deposition device performance.

[0170] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.2:1.8 and compound 3-95, to obtain the corresponding performance of the vapor deposition device.

[0171] The vapor deposition method was used for the experiment, with XX:YY ratio of 99.0:1.0 and compound 3-110, to obtain the corresponding performance of the vapor deposition device.

[0172] The vapor deposition method was used, with an XX:YY ratio of 98.6:1.4 and a compound of 3-110, to obtain the corresponding performance of the vapor deposition device.

[0173] The vapor deposition method was used for the experiment, with XX:YY ratio of 98.2:1.8 and compound 3-110, to obtain the corresponding performance of the vapor deposition device.

[0174] Fabrication and performance evaluation of organic electroluminescent devices fabricated using the compounds of this invention as fluorescent doped dyes via solution processing (hereinafter referred to as the solution method).

[0175] A 110 nm thick indium tin oxide (ITO) glass substrate was used as substrate 1. The glass substrate was washed with detergent, deionized water, and isopropanol, followed by surface activation treatment with ultraviolet ozone. Vacuum evaporation was then performed on the washed substrate to deposit each layer, and a cross-sectional view is shown below. Figure 1 The luminescent area shown is 0.09 cm². 2 Organic electroluminescent devices.

[0176] First, the aforementioned glass substrate is introduced into a vacuum evaporation bath, and the pressure is reduced to 1×10⁻⁶. -4 Pa. Then Figure 1 On the glass substrate 1 shown, each functional layer is sequentially deposited, namely hole transport layer 3, light-emitting layer 4, electron transport layer 5, electron injection layer 6, and cathode layer 7. Specifically, a 40 nm thick layer of poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT / PSS) is spin-coated as a hole transport layer 3; a 20 nm thick layer of a light-emitting layer 4 composed of 1,3-dicarbazole-9-ylbenzene (mCP) and the compound of the present invention in a 99:1 (wt%) ratio is vacuum-deposited; a 6 nm thick layer of 2,8-bis(diphenyloxyphosphine)dibenzothiophene (PPT) is vacuum-deposited as an electron blocking layer 5; a 30 nm thick layer of 3,3'-[5'-[3-(3-pyridyl)phenyl][1,1':3',1''-terphenyl]-3,3''-diyl]dipyridine (TmPyPb) is deposited as an electron transport layer 6; and a 1 nm thick layer of lithium fluoride (LiF) is deposited as an electron injection layer 7. Each organic material is deposited by vacuum deposition using resistance heating at a deposition rate of 1 Å / s. Finally, a metal mask was configured orthogonally to the ITO stripes to form the film cathode layer 8, with a deposited film thickness of 100 nm. The thickness of each film was measured using a stylus-type film thickness gauge (DEKTAK). The device was then sealed in a nitrogen atmosphere glove box with a water and oxygen concentration of less than 1 ppm. The sealing was achieved using a glass sealing cap and the aforementioned epoxy UV-curable resin for the film-forming substrate (manufactured by Nagase ChemteX Corporation).

[0177] A direct current was applied to the prepared organic electroluminescent device, and the luminous efficiency was determined using a Hamamatsu C9920-02 integrating sphere. The current-voltage characteristics were measured using a computer-controlled Keithley 2400 digital source meter.

[0178] Test Example-31

[0179] The solution method was used to obtain the corresponding device performance using compound 1-76.

[0180] The solution method was used to obtain the corresponding device performance using compound 1-28.

[0181] The solution method was used for the experiment, with compound 1-52, to obtain the corresponding performance of the solution-based device.

[0182] The solution method was used for experiments, with compound 1-100, to obtain the corresponding solution-based device performance.

[0183] The solution method was used to obtain the corresponding device performance using compound 2-28.

[0184] The solution method was used for the experiment, with compound 3-35, to obtain the corresponding solution-based device performance.

[0185] The solution method was used for experiments, with compound 3-50, to obtain the corresponding solution-based device performance.

[0186] Test Case-38

[0187] The solution method was used for the experiment, with compound 3-65, to obtain the corresponding solution-based device performance.

[0188] The solution method was used for the experiment, with compound 3-95, to obtain the corresponding solution-based device performance.

[0189] The solution method was used to obtain the corresponding device performance using compound 3-110.

[0190] The key point of this invention is the design of a compound with meta-tetraboron multiple resonance, which can effectively obtain a solution and a deep blue thermally activated delayed fluorescence material with high solubility, narrow half-width (FWHM≤20 nm), and high fluorescence quantum yield.

[0191] The above-prepared polyboron nitrogen derivative organic electroluminescent devices have the following properties:

[0192]

[0193]

[0194]

[0195] In the prior art, the evaporation method of existing compound devices generally has low efficiency, wide half-width, and insufficient color purity. The performance of existing compound devices in solution-based methods is unknown.

[0196] The devices utilizing the polyboron nitrogen derivatives of this invention exhibit high device efficiency and excellent color purity. The performance of solution-based devices is comparable to that of vapor-deposited devices. Through rational device design, the material properties can be fully utilized.

[0197] The exemplary embodiments of the present invention all achieve ultra-high color purity of CIEy≤0.050.

[0198] In the exemplary device designs of this invention, the number of layers differs between the vapor deposition method and the solution method. Those skilled in the art will understand that the number of layers in the vapor deposition method and the solution method can be the same or different. The absence of a hole injection layer in the device design does not mean that the device design does not consider hole injection functionality, but rather that the hole transport layer provides both hole injection and hole transport functions. It is understood that the light-emitting layer also has hole transport functionality; otherwise, the light-emitting layer could not emit light. As a description of different functional layers, whether it is a light-emitting layer, a transport layer, or other layers, it describes the main functions but not all functions. Similarly, in the device of this invention, the functional layers can be one or multiple.

[0199] The above description of the disclosed embodiments enables those skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art. The present invention is not to be limited to the embodiments shown herein, but only requires conformity with the principles and features disclosed herein.

Claims

1. A polyboron nitrogen derivative, characterized in that, Polyboron nitrogen derivatives have the following structures: Among them, R 1 R 2 Each independently represents an aryl substituent of C1-C36; the R 1 R 2 The same substituent is indicated; the C1-C36 aryl group is selected from hydrogen-substituted or alkyl-substituted aryl groups; the alkyl group in the alkyl substitution is methyl, ethyl, propyl or butyl; the aryl group is selected from one of the following groups: phenyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl or naphthyl; R 3 R 4 R 5 R 6 R 7 R 8 Each substituent represents hydrogen or C1-C36; the C1-C36 substituents are substituted by single bonds; the C1-C36 substituents are selected from one of the following groups: methyl, ethyl, propyl or butyl; A1 and A2 each independently represent oxygen, sulfur, or selenium.

2. The polyboron nitrogen derivative according to claim 1, characterized in that, Polyboron nitrogen derivatives have one of the following structures:

3. The polyboron nitrogen derivative according to claim 1, characterized in that, Polyboron nitrogen derivatives have one of the following structures:

4. The polyboron nitrogen derivative according to claim 1, characterized in that, Polyboron nitrogen derivatives have one of the following structures:

5. A deep blue light device, wherein the deep blue light device contains the polyboron nitrogen derivative according to any one of claims 1-4.

6. A light-emitting device, wherein the light-emitting device employs the deep blue light-emitting device described in claim 5.

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