Boron-nitrogen compound and organic electroluminescent device and application thereof

Abstract

The invention relates to the technical field of preparation of organic photoelectric materials, in particular to a boron-nitrogen compound and an organic electroluminescent device and application thereof. The boron-containing nitrogen compound provided by the invention has good carrier transmission capability, good energy transmission performance between a subject and an object, good exciton utilization efficiency and good thermal stability; a large-steric-hindrance triphenyl silicon group is introduced around a luminescent group, so that the interaction force between luminescent molecules can be weakened, and the concentration quenching effect can be reduced; when the compound is applied to the organic electroluminescent device as a functional layer, especially as a luminescent layer, higher current efficiency and longer service life of the device are realized.

Description

Technical Field

[0001] The present invention relates to the technical field of the preparation of organic optoelectronic materials, and particularly relates to a boron nitride compound, an organic electroluminescent device and an application thereof. Background Art

[0002] With the development of multimedia technology and the improvement of information requirements, the requirements for the performance of panel displays are getting higher and higher. Among them, OLED has a series of advantages such as self-luminescence, low-voltage DC drive, all-solid-state, wide viewing angle, and rich colors, and has attracted wide attention due to its potential applications in new-generation displays and lighting technologies, and has a very broad application prospect. An organic electroluminescent device is a self-luminous device. The mechanism of OLED luminescence is that under the action of an external electric field, electrons and holes are respectively injected from the positive and negative electrodes, migrate, recombine and decay in the organic material to generate luminescence. The typical structure of OLED includes one or several functional layers among a cathode layer, an anode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a hole transport layer, a hole injection layer and a light-emitting layer. Although the research on organic electroluminescence has advanced very rapidly, new luminescent materials are still urgently needed to be developed, especially the development and design of high-efficiency and long-life luminescent materials. Summary of the Invention

[0003] The object of the present invention is to provide a boron nitride compound, an organic electroluminescent device and an application in view of the deficiencies of the prior art. The boron nitride compound provided by the present invention has good thermal stability, improves its carrier transport ability by introducing an N-containing electron-donating group, and at the same time introduces multiple bulky triphenylsilyl groups around the light-emitting group to reduce the interaction between luminescent molecules, and can effectively improve the energy transfer performance between the host and the guest after preparing the device.

[0004] In order to achieve the object of the present invention, the technical solution of the present invention is as follows:

[0005] According to one or more embodiments, the present invention provides a boron nitride compound having a structure represented by the following formula (I):

[0006]

[0007] In formula (I), ring A and ring B are each independently selected from a five-membered carbon ring, a five-membered heterocyclic ring, a six-membered carbon ring or a six-membered heterocyclic ring; the substituents R2 and R3 on ring A and ring B are mono-substituted or multi-substituted, and R2 and R3 are each independently selected from hydrogen, deuterium, C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl; when containing substituents, the substituents are selected from any one or more of deuterium, C1-C24 alkyl; and adjacent groups among R2 and R3 are optionally joined or fused into a polycyclic ring, preferably a five-membered carbon ring, a five-membered heterocyclic ring, a six-membered carbon ring or a six-membered heterocyclic ring; R1 and R4 are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl; when R1 and R4 contain substituents, the substituents are mono-substituted or multi-substituted, and the substituents are selected from any one or more of deuterium, C1-C24 alkyl, C3-C24 cycloalkyl.

[0008] Preferably, adjacent groups among R2 and R3 are optionally joined or fused into a polycyclic ring, preferably a five-membered carbon ring, a five-membered heterocyclic ring, a six-membered carbon ring or a six-membered heterocyclic ring.

[0009] More preferably, R1 and R4 are each independently selected from one or more of substituted or unsubstituted C6-C12 aryl, substituted fluorenyl, dibenzofuranyl, dibenzothiophenyl, methyl-substituted tetrahydronaphthyl; the substitution is selected from deuterium, methyl, ethyl, propyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl.

[0010] More preferably, R2 and R3 are each independently selected from one or more of deuterium, methyl, ethyl, propyl, tert-butyl, adamantyl, phenyl substituted or unsubstituted with C1-C6 alkyl, dimethylfluorenyl, methyl-substituted tetrahydronaphthyl.

[0011] Preferably, ring A is independently selected from the following structures, and the dotted line indicates the connection position:

[0012] Among them, X and Z are each independently selected from O, S, and R5-R7 are mono-substituted or multi-substituted, and R5-R7 are each independently selected from one or more of hydrogen, deuterium, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C12 aryl.

[0013] More preferably, ring A is independently selected from the following structures, and the dotted line indicates the connection position:

[0014]

[0015] Preferably, ring B is independently selected from the following structures, and the dotted line indicates the connection position:

[0016]

[0017] Among them, R8 - R 20 may be unsubstituted, monosubstituted or polysubstituted; in the case of being substituted by multiple substituents, the multiple substituents are the same or different from each other, and adjacent substituents can be connected to form a ring; R8 - R 20 are each independently the same or different and are selected from one or more of hydrogen, deuterium, C1 - C24 alkyl, substituted or unsubstituted C3 - C24 cycloalkyl, and substituted or unsubstituted C6 - C30 aryl; when containing substituents, the substituents are selected from deuterium, C1 - C24 alkyl.

[0018] More preferably, the ring B is independently selected from the following structures, where the dotted line indicates the connection position:

[0019]

[0020] Preferably, at least one hydrogen in the compound of formula (I) of the present invention can be substituted by deuterium, tritium, cyano or halogen.

[0021] According to one or more embodiments, the boron - nitrogen compound provided by the present invention is selected from the following chemical structures, where "D" represents deuterium:

[0022]

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033] According to one or more embodiments, the present invention also provides the use of the boron - nitrogen compound having the general formula structure shown in formula (I) above in the preparation of electronic devices.

[0034] Preferred embodiment, the electronic device includes an organic light-emitting device (OLED), an organic integrated circuit (O-IC), an organic field-effect transistor (O-FET), an organic thin-film transistor (O-TFT), an organic light-emitting transistor (O-LET), an organic solar cell (O-SC), an organic optoelectronic device, an organic optical detector, an organic photoreceptor, an organic field quenching device (O-FQD), a light-emitting electrochemical cell (LEC), and an organic laser diode (O-laser).

[0035] According to one or more embodiments, the present invention further provides an organic light-emitting device, which includes a cathode, an anode, and an organic functional layer therebetween; the organic functional layer contains a light-emitting layer, and the light-emitting layer contains a boron nitride compound having a general formula structure as shown in formula (I) above. Preferably, the mass percentage of the boron nitride compound is 0.1%-50%.

[0036] According to one or more embodiments, the present invention further provides an organic optoelectronic device, including a substrate layer; a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode, wherein the light-emitting material layer contains a boron nitride compound having a general formula structure as shown in formula (I) above. For example, the boron nitride compound can be included as a guest material in the light-emitting material layer.

[0037] The present invention further provides a composition, which contains a boron nitride compound having a general formula structure as shown in formula (I) above.

[0038] The present invention further provides a preparation, which contains a boron nitride compound having a general formula structure as shown in formula (I) above or the composition as described above and at least one solvent. The solvent is not particularly limited, and solvents well-known to those skilled in the art can be used, such as unsaturated hydrocarbon solvents, halogenated saturated hydrocarbon solvents, halogenated unsaturated hydrocarbon solvents, ether solvents, or ester solvents; among them, the unsaturated hydrocarbon solvent is toluene, xylene, mesitylene, tetrahydronaphthalene, n-butylbenzene, sec-butylbenzene, or tert-butylbenzene; the halogenated saturated hydrocarbon solvent is carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, or bromocyclohexane; the halogenated unsaturated hydrocarbon solvent is chlorobenzene, dichlorobenzene, or trichlorobenzene; the ether solvent is tetrahydrofuran or tetrahydropyran; the ester solvent is an alkyl benzoate.

[0039] The present invention further provides a display or lighting device, which contains one or more of the organic light-emitting devices or organic optoelectronic devices as described above.

[0040] Compared with the prior art, the beneficial effects of the present invention are:

[0041] All the boron nitride compounds involved in the present invention have good thermal stability and narrow full width at half maximum; in particular, electron-donating groups such as arylamine groups, thiophene groups, furan groups or carbazole groups are simultaneously introduced around the luminescent groups in the compounds, so that the compounds exhibit good carrier transport ability. In addition, the compounds of the present invention can also effectively improve the energy transfer performance and exciton utilization efficiency between the host and the guest, and the bulky groups containing triphenylsilicon can effectively reduce the interaction force between the luminescent molecules. Specifically, when the boron nitride compound of the present invention is used as a functional layer, especially as a light-emitting layer to fabricate an organic electroluminescent device, the current efficiency is improved, and at the same time, the lifetime of the device is also greatly improved, indicating that after most electrons and holes are recombined, the energy is effectively transferred to the boron nitride compound of the present invention for luminescence rather than heat generation. Detailed Description of the Invention

[0042] The content of the present invention will be described in detail below. The description of the constituent elements recorded below is sometimes based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples. The present disclosure can be more easily understood by referring to the following detailed description and the examples included therein. Before disclosing and describing the compounds, devices and / or methods of the present invention, it should be understood that unless otherwise specified, they are not limited to specific synthesis methods or specific reagents, because these can vary. It should also be understood that the terms used in the present invention are only for describing specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used for this practice or test, exemplary methods and materials are now described.

[0043] For the purposes of the present invention, the present invention does not intend to be limited in any way by the substituents permitted for organic compounds. Similarly, the term "substituted" or "substituent" includes the implicit condition that such substitution conforms to the allowed valence bonds of the substituted atoms and the substituent, and the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that in some aspects, unless explicitly stated to the contrary, a single substituent can further optionally be substituted (i.e., further substituted or unsubstituted).

[0044] As used herein, "substituted...", such as substituted C3-C24 cycloalkyl, substituted C6-C30 aryl, substituted C6-C30 heteroaryl, etc., means mono- or poly-substituted by a group independently selected from deuterium, C1-C14 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, etc., but not limited thereto. Preferably, it is mono- or poly-substituted by a group selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, tolyl, fluorenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, diphenylamino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuranyl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl, adamantyl. Additionally, the above substituents may also be substituted by one or more deuterium, halogen atoms, cyano groups, alkyl groups, cycloalkyl groups, silyl groups, or substituents as described for aryl groups. The substitution may be by single-bond substitution or fused substitution.

[0045] For example, "substituted fluorenyl" may have the following structures (including but not limited to) by single-bond substitution:

[0046]

[0047] Or it may have the following structures (including but not limited to) by fused substitution:

[0048]

[0049] As used herein, "alkyl" refers to a monovalent alkyl group having 1-24 carbon atoms, preferably 1-10 carbon atoms, more preferably 1-6 carbon atoms. Examples of this term include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, etc.

[0050] As used herein, "cycloalkyl" refers to a cyclic alkyl group having 3-24 carbon atoms and having a single ring or multiple fused rings, which may be optionally substituted by 1-3 alkyl groups. Such cycloalkyl groups include, for example, those with a single-ring structure such as cyclopropyl, cyclobutyl, cyclopentyl, cyclooctyl, 1-methylcyclopropyl, and 2-methylcyclopentyl, 2-methylcyclooctyl, etc., or those with a poly-ring structure such as adamantyl, etc.

[0051] As used herein, "aryl" refers to an unsaturated aromatic carbocyclic ring having 6 to 30 carbon atoms and having a monocyclic ring (such as phenyl) or a polycyclic fused ring (such as naphthyl or anthryl). Preferably, it has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Preferred aryl groups include phenyl, naphthyl, etc. Unless otherwise defined for individual substituents, such aryl groups may optionally be substituted with 1 to 3 of the following substituents: hydroxyl, acyl, acyloxy, alkyl, alkoxy, alkenyl, alkynyl, amino, aminoacyl, aryl, aryloxy, carboxyl, carboxylate, aminocarboxylate, cyano, halogen, nitro, heteroaryl, heterocycle, thioalkoxy, trihalomethyl, etc. Preferred substituents include alkyl, alkoxy, halogen, cyano, nitro, trihalomethyl, and thioalkoxy. However, it is not limited thereto.

[0052] As used herein, "heteroaryl" refers to a general term for groups obtained by replacing one or more aromatic ring carbons in aryl with heteroatoms, and the heteroatoms include, but are not limited to, oxygen, sulfur, or nitrogen atoms. The heteroaryl may be a monocyclic heteroaryl or a fused-ring heteroaryl. Examples may include pyridyl, pyrrolyl, pyridyl, thienyl, furyl, indolyl, quinolinyl, isoquinolinyl, benzothienyl, benzofuryl, dibenzofuryl, dibenzothienyl, carbazolyl, etc. However, it is not limited thereto. The singular forms "a", "an", and "the" as used in the specification and the appended claims include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes a mixture of two or more components.

[0053] Unless otherwise specified, all commercial reagents involved in the following experiments were used directly after purchase.

[0054] In a preferred embodiment of the present invention, the OLED device of the present invention contains a hole transport layer, and the hole transport material may preferably be selected from known or unknown materials, particularly preferably selected from the following structures, but this does not mean that the present invention is limited to the following structures (Ph is phenyl):

[0055]

[0056] In a preferred embodiment of the present invention, the OLED device of the present invention contains a hole injection layer. The preferred hole injection layer material of the present invention has the following structures, but this does not mean that the present invention is limited to the following structures:

[0057]

[0058] In a preferred embodiment of the present invention, the electron transport layer may be selected from at least one of the following compounds, but this does not mean that the present invention is limited to the following structures:

[0059]

[0060] In a preferred embodiment of the present invention, the OLED device of the present invention contains a host material, and the host material can be selected from known or unknown materials, and is particularly preferably selected from the following structures, but it does not mean that the present invention is limited to the following structures:

[0061] The preparation method of the boron nitrogen compound of the present invention and the luminescent properties of the device are explained in detail in conjunction with the following examples.

[0062] Example 1: Synthesis of Compound 1

[0063]

[0064]

[0065] (1) Synthesis of compound 1-3: Compound 1-1 (316 mg, 1 mmoL) and compound 1-2 (149 mg, 1 mmoL) were dissolved in 50 mL of toluene solution. Under nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmoL), palladium acetate (12 mg, 0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added. The reaction system was heated under reflux for 48 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:2, to obtain product 1-3 (197 mg, yield 58%). Mass spectrum m / z, theoretical value 337.28; measured value M+H: 338.30.

[0066] (2) Synthesis of compound 1-6: Compound 1-4 (301 mg, 1 mmoL) and compound 1-5 (632 mg, 2 mmoL) were dissolved in 50 mL of toluene solution. Under nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmoL), palladium acetate (12 mg, 0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added. The reaction system was heated under reflux for 24 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:5, to obtain product 1-6 (362 mg, yield 74%). Mass spectrum m / z, theoretical value 489.20; measured value M+H: 490.23.

[0067] (3) Synthesis of compound 1-7: Compound 1-6 (489 mg, 1 mmoL) and compound 1-2 (149 mg, 1 mmoL) were dissolved in 50 mL toluene solution. Under nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmoL), palladium acetate (12 mg, 0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added. The reaction system was heated under reflux for 48 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:4, to obtain product 1-7 (308 mg, yield 55%). Mass spectrum m / z, theoretical value 558.40; measured value M+H: 559.42.

[0068] (4) Synthesis of compound 1-9: BuLi (0.5 mL, 1 mmoL, 2 M in hexane) was slowly added to a solution of compound 1-8 (396 mg, 1 mmoL) in anhydrous ether (50 mL) at -78 °C. After reacting for 3 hours, triphenylsilyl chloride (294 mg, 1 mmoL) was slowly added. After slowly warming to room temperature, the reaction was allowed to proceed overnight, and then the temperature was raised to 80 °C for 6 hours. After cooling to room temperature, 1 mL of ice water was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:8, to obtain product 1-9 (232 mg, yield 44%). Mass spectrum m / z, theoretical value 525.92; measured value M+H: 526.95.

[0069] (5) Synthesis of compound 1-10: Compound 1-9 (525 mg, 1 mmoL) and compound 1-3 (337 mg, 1 mmoL) were dissolved in 50 mL of toluene solution. Under nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmoL), palladium acetate (12 mg, 0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added. The reaction system was heated under reflux for 48 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by vacuum distillation, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:6, to obtain product 1-10 (316 mg, yield 40%). Mass spectrum m / z, theoretical value 783.27; measured value M+H: 784.29.

[0070] (6) Synthesis of compound 1-11: Compound 1-10 (783 mg, 1 mmoL) and compound 1-7 (558 mg, 1 mmoL) were dissolved in 50 mL of toluene solution. Under nitrogen atmosphere, sodium tert-butoxide (192 mg, 2 mmoL), palladium acetate (12 mg, 0.05 mmoL), and tri-tert-butylphosphine tetrafluoroborate (145 mg, 0.5 mmoL) were added. The reaction system was heated under reflux for 48 hours and then cooled to room temperature. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3×100 mL). The organic phase was washed with water and dried with sodium sulfate. The solvent was removed by distillation under reduced pressure, and the resulting crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:4, to obtain product 1-11 (456 mg, yield 36%). Mass spectrum m / z, theoretical value 1261.74; measured value M+H: 1262.77.

[0071] (7) Synthesis of compound 1: Under nitrogen atmosphere and zero temperature, tert-butyl lithium (1.88 mL, 1.6 M pentane solution, 3 mmol) was slowly added dropwise to a solution of compound 1-11 (1261 mg, 1 mmol) in tert-butylbenzene (100 mL). The system was reacted at 60 °C for 4 hours, then cooled to -50 °C, and then BBr3 (494 mg, 2 mmol) was added. After reacting at room temperature for 1 hour, N,N-diisopropylethylamine (259 mg, 2 mmol) was added. The temperature was then raised to 120 °C and reacted for 12 hours. After cooling to room temperature, 5 mL of sodium acetate aqueous solution (1 M) was added. The solvent was removed by rotary evaporation, and the residue was extracted with dichloromethane (3 × 100 mL). The organic phase was washed with water and dried over sodium sulfate. The solvent was removed by distillation under reduced pressure, and the crude product was separated and purified by silica gel chromatography, with the eluent being dichloromethane: petroleum ether = 1:5, to obtain product 1 (255 mg, yield 21%). Mass spectrum m / z, theoretical value 1235.76; measured value M+H: 1236.78.

[0072] Example 2: Synthesis of Compound 3

[0073] Compound 3 was synthesized by referring to the synthetic route of compound 1. The yield of the final product was 26%. Mass spectrum m / z, theoretical value: 1199.67; measured value: M+H: 1200.68.

[0074] Example 3: Synthesis of Compound 5

[0075] Compound 5 was synthesized by referring to the synthetic route of compound 1. The yield of the final product was 22%. Mass spectrum m / z, theoretical value 1255.73; measured value M+H: 1256.76.

[0076] Example 4: Synthesis of Compound 10

[0077] Referring to the synthetic route of Compound 1, Compound 10 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1289.81; measured value M+H: 1290.83.

[0078] Example 5: Synthesis of Compound 12

[0079] Referring to the synthetic route of Compound 1, Compound 12 was synthesized. The yield of the final product was 24%. Mass spectrometry m / z, theoretical value 1313.81; measured value M+H: 1314.82.

[0080] Example 6: Synthesis of Compound 14

[0081] Referring to the synthetic route of Compound 1, Compound 14 was synthesized. The yield of the final product was 22%. Mass spectrometry m / z, theoretical value 1209.65; measured value M+H: 1210.67.

[0082] Example 7: Synthesis of Compound 15

[0083] Referring to the synthetic route of Compound 1, Compound 15 was synthesized. The yield of the final product was 26%. Mass spectrometry m / z, theoretical value 1275.70; measured value M+H: 1276.72.

[0084] Example 8: Synthesis of Compound 19

[0085] Referring to the synthetic route of Compound 1, Compound 19 was synthesized. The yield of the final product was 28%. Mass spectrometry m / z, theoretical value 1259.67; measured value M+H: 1260.68.

[0086] Example 9: Synthesis of Compound 21

[0087] Referring to the synthetic route of Compound 1, Compound 21 was synthesized. The yield of the final product was 27%. Mass spectrometry m / z, theoretical value 1255.73; measured value M+H: 1256.74.

[0088] Example 10: Synthesis of Compound 24

[0089] Referring to the synthetic route of Compound 1, Compound 24 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1213.65; measured value M+H: 1214.67.

[0090] Example 11: Synthesis of Compound 27

[0091] Referring to the synthetic route of Compound 1, Compound 27 was synthesized. The yield of the final product was 25%. Mass spectrometry m / z, theoretical value 1229.63; measured value M+H: 1230.64.

[0092] Example 12: Synthesis of Compound 30

[0093] Referring to the synthetic route of reference compound 1, compound 30 was synthesized. The yield of the final product was 25%. Mass spectrometry m / z, theoretical value 1265.68; measured value M+H: 1266.70.

[0094] Example 13: Synthesis of Compound 31

[0095] Referring to the synthetic route of reference compound 1, compound 31 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1281.66; measured value M+H: 1282.68.

[0096] Example 14: Synthesis of Compound 32

[0097] Referring to the synthetic route of reference compound 1, compound 32 was synthesized. The yield of the final product was 26%. Mass spectrometry m / z, theoretical value 1265.68; measured value M+H: 1266.69.

[0098] Example 15: Synthesis of Compound 33

[0099] Referring to the synthetic route of reference compound 1, compound 33 was synthesized. The yield of the final product was 24%. Mass spectrometry m / z, theoretical value 1281.66; measured value M+H: 1282.67.

[0100] Example 16: Synthesis of Compound 37

[0101] Referring to the synthetic route of reference compound 1, compound 37 was synthesized. The yield of the final product was 21%. Mass spectrometry m / z, theoretical value 1341.84; measured value M+H: 1342.86.

[0102] Example 17: Synthesis of Compound 38

[0103] Referring to the synthetic route of reference compound 1, compound 38 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1377.80; measured value M+H: 1378.82.

[0104] Example 18: Synthesis of Compound 39

[0105] Referring to the synthetic route of reference compound 1, compound 39 was synthesized. The yield of the final product was 26%. Mass spectrometry m / z, theoretical value 1343.73; measured value M+H: 1344.74.

[0106] Example 19: Synthesis of Compound 41

[0107] Referring to the synthetic route of reference compound 1, compound 41 was synthesized. The yield of the final product was 22%. Mass spectrometry m / z, theoretical value 1235.67; measured value M+H: 1236.68.

[0108] Example 20: Synthesis of Compound 42

[0109] Referring to the synthetic route of Reference Compound 1, Compound 42 was synthesized. The yield of the final product was 27%. Mass spectrometry m / z, theoretical value 1219.69; measured value M+H: 1220.71.

[0110] Example 21: Synthesis of Compound 44

[0111] Referring to the synthetic route of Reference Compound 1, Compound 44 was synthesized. The yield of the final product was 26%. Mass spectrometry m / z, theoretical value 1279.70; measured value M+H: 1280.71.

[0112] Example 22: Synthesis of Compound 47

[0113] Referring to the synthetic route of Reference Compound 1, Compound 47 was synthesized. The yield of the final product was 22%. Mass spectrometry m / z, theoretical value 1253.64; measured value M+H: 1254.66.

[0114] Example 23: Synthesis of Compound 49

[0115] Referring to the synthetic route of Reference Compound 1, Compound 49 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1321.74; measured value M+H: 1322.76.

[0116] Example 23: Synthesis of Compound 50

[0117] Referring to the synthetic route of Reference Compound 1, Compound 50 was synthesized. The yield of the final product was 24%. Mass spectrometry m / z, theoretical value 1337.72; measured value M+H: 1338.75.

[0118] Example 24: Synthesis of Compound 57

[0119] Referring to the synthetic route of Reference Compound 1, Compound 57 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1339.79; measured value M+H: 1340.81.

[0120] Example 25: Synthesis of Compound 65

[0121] Referring to the synthetic route of Reference Compound 1, Compound 65 was synthesized. The yield of the final product was 25%. Mass spectrometry m / z, theoretical value 1219.70; measured value M+H: 1220.72.

[0122] Example 26: Synthesis of Compound 67

[0123] Referring to the synthetic route of Compound 1, Compound 67 was synthesized. The yield of the final product was 26%. Mass spectrometry m / z, theoretical value 1325.68; measured value M+H: 1326.71.

[0124] Example 27: Synthesis of Compound 78

[0125] Referring to the synthetic route of Compound 1, Compound 78 was synthesized. The yield of the final product was 24%. Mass spectrometry m / z, theoretical value 1285.65; measured value M+H: 1286.68.

[0126] Example 28: Synthesis of Compound 86

[0127] Referring to the synthetic route of Compound 1, Compound 86 was synthesized. The yield of the final product was 27%. Mass spectrometry m / z, theoretical value 1299.70; measured value M+H: 1300.71.

[0128] Example 29: Synthesis of Compound 89

[0129] Referring to the synthetic route of Compound 1, Compound 89 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1235.67; measured value M+H: 1236.69.

[0130] Example 30: Synthesis of Compound 91

[0131] Referring to the synthetic route of Compound 1, Compound 91 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1285.65; measured value M+H: 1286.67.

[0132] Example 31: Synthesis of Compound 102

[0133] Referring to the synthetic route of Compound 1, Compound 102 was synthesized. The yield of the final product was 27%. Mass spectrometry m / z, theoretical value 1283.73; measured value M+H: 1284.74.

[0134] Example 32: Synthesis of Compound 103

[0135] Referring to the synthetic route of Compound 1, Compound 103 was synthesized. The yield of the final product was 25%. Mass spectrometry m / z, theoretical value 1245.75; measured value M+H: 1246.77.

[0136] Example 33: Synthesis of Compound 106

[0137] Referring to the synthetic route of Compound 1, Compound 106 was synthesized. The yield of the final product was 26%. Mass spectrometry m / z, theoretical value 1281.75; measured value M+H: 1282.77.

[0138] Example 34: Synthesis of Compound 112

[0139] Referring to the synthetic route of Compound 1, Compound 112 was synthesized. The yield of the final product was 28%. Mass spectrometry m / z, theoretical value 1337.72; measured value M+H: 1338.75.

[0140] Example 35: Synthesis of Compound 113

[0141] Referring to the synthetic route of Compound 1, Compound 113 was synthesized. The yield of the final product was 24%. Mass spectrometry m / z, theoretical value 1321.74; measured value M+H: 1322.76.

[0142] Example 36: Synthesis of Compound 115

[0143] Referring to the synthetic route of Compound 1, Compound 115 was synthesized. The yield of the final product was 26%. Mass spectrometry m / z, theoretical value 1311.66; measured value M+H: 1312.68.

[0144] Example 37: Synthesis of Compound 117

[0145] Referring to the synthetic route of Compound 1, Compound 117 was synthesized. The yield of the final product was 24%. Mass spectrometry m / z, theoretical value 1209.62; measured value M+H: 1210.65.

[0146] Example 38: Synthesis of Compound 118

[0147] Referring to the synthetic route of Compound 1, Compound 118 was synthesized. The yield of the final product was 24%. Mass spectrometry m / z, theoretical value 1331.73; measured value M+H: 1332.75.

[0148] Example 39: Synthesis of Compound 120

[0149] Referring to the synthetic route of Compound 1, Compound 120 was synthesized. The yield of the final product was 23%. Mass spectrometry m / z, theoretical value 1301.72; measured value M+H: 1302.74.

[0150] Example 40: Synthesis of Compound 123

[0151] Referring to the synthetic route of Compound 1, Compound 123 was synthesized. The yield of the final product was 25%. Mass spectrometry m / z, theoretical value 1249.65; measured value M+H: 1250.66.

[0152] Example 41: Synthesis of Compound 126

[0153] Refer to the synthetic route of Compound 1 to synthesize Compound 126. The yield of the final product is 24%. Mass spectrometry m / z, theoretical value 1265.68; measured value M+H: 1266.71.

[0154] Example 42: Synthesis of Compound 137

[0155] Refer to the synthetic route of Compound 1 to synthesize Compound 137. The yield of the final product is 25%. Mass spectrometry m / z, theoretical value 1150.64; measured value M+H: 1151.66.

[0156] Example 43: Synthesis of Compound 141

[0157] Refer to the synthetic route of Compound 1 to synthesize Compound 141. The yield of the final product is 26%. Mass spectrometry m / z, theoretical value 1282.68; measured value M+H: 1283.70.

[0158] Manufacture of OLED device:

[0159] As a reference preparation method for a device embodiment, in the present invention, a p-doped material is evaporated on the surface or anode of ITO glass with a light-emitting area of 2 mm × 2 mm, or this p-doped material is co-evaporated with a hole-transporting material at a concentration of 1% to 50% to form a 5-100 nm hole injection layer (HIL). A 5-200 nm hole-transporting layer (HTL) is formed on the hole injection layer. Then, a 10-100 nm light-emitting layer (EML) is co-evaporated on the hole-transporting layer with a host material and the boron nitride compound prepared by the present invention at a weight ratio of 96:4. A 35 nm electron-transporting layer (ETL) is co-evaporated, and a cathode Al of 70 nm is evaporated to manufacture an organic light-emitting diode.

[0160] In a preferred specific embodiment, the structure of the bottom-emitting OLED device provided by the present invention is as follows: The glass containing ITO is the anode, the evaporated HIL is HT-4:P-3 (weight ratio 94:6), with a thickness of 10 nm; the HTL is HT-15, with a thickness of 90 nm; the EBL is HT-4, with a thickness of 10 nm, the EML is the host material (H-3): Compound 1 (weight ratio 96:4), with a thickness of 35 nm, the ETL is ET-4:LiQ (weight ratio 50:50), with a thickness of 35 nm, and then a cathode Al of 70 nm is evaporated to prepare an organic light-emitting diode, denoted as Application Example 1.

[0161] Referring to the method provided in Application Example 1, the boron nitride compounds in Table 1 are respectively selected as the implementation objects to replace Compound 1 in Application Example 1 to prepare organic light-emitting diodes, denoted as Application Examples 2 - 35, and Comparative Examples 1 - 2.

[0162] The chemical structures of Ref-1 and Ref-2 in the comparative examples are as follows:

[0163]

[0164] The current efficiency, voltage, lifetime and other characteristics of the above-prepared device examples and comparative examples were tested by standard methods, and the device luminescence characteristic data are shown in Table 1.

[0165] Table 1. Data table of device luminescence characteristics

[0166]

[0167]

[0168] As can be seen from Table 1, compared with Comparative Examples 1-2, the compounds provided by the present invention show more prominent advantages in terms of current efficiency and lifetime after being fabricated into devices, reflecting their good device performance. The improvement in the performance of each device of the present invention in the application examples is based on the boron nitride compound with a specific substitution structure. In particular, the introduction of an electron-donating group around the luminescent group enables the compound to have better charge carrier transport ability, and at the same time, the introduction of multiple sterically hindered groups can reduce the interaction force between luminescent molecules. Using the compound of the present invention as the host material of the luminescent layer to fabricate an electronic device makes the device have higher current efficiency and lifetime. This indicates that the boron nitride compound provided by the present invention has certain commercial application value.

[0169] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and should be covered by the protection scope of the present invention.

Claims

1. A boron nitride compound, characterized in that, The boron nitride compound has a structure represented by formula (I), In formula (I), ring A and ring B are each independently selected from a five-membered carbon ring, a five-membered heterocyclic ring, a six-membered carbon ring or a six-membered heterocyclic ring; the substituents R2 and R3 on ring A and ring B are mono-substituted or multi-substituted, and R2 and R3 are each independently selected from hydrogen, deuterium, C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl; when R2 and R3 contain substituents, the substituents are selected from any one or more of deuterium, C1-C24 alkyl; R1 and R4 are each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl; when R1 and R4 contain substituents, the substituents are mono-substituted or multi-substituted, and the substituents are selected from any one or more of deuterium, C1-C24 alkyl, C3-C24 cycloalkyl.

2. The boron nitride compound according to claim 1, characterized in that, R1 and R4 are each independently selected from one or more of substituted or unsubstituted C6-C12 aryl, substituted fluorenyl, dibenzofuranyl, dibenzothiophenyl, methyl-substituted tetrahydronaphthyl; the substitution is selected from deuterium, methyl, ethyl, propyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl.

3. The boron nitride compound according to claim 1, wherein R2 and R3 are each independently selected from one or more of deuterium, methyl, ethyl, propyl, tert-butyl, adamantyl, phenyl substituted or unsubstituted with C1-C6 alkyl, dimethylfluorenyl, methyl-substituted tetrahydronaphthyl.

4. The boron nitride compound according to claim 1, characterized in that, Ring A is independently selected from the following structures: wherein X and Z are each independently selected from O and S, R5-R7 are mono-substituted or multi-substituted, and R5-R7 are each independently selected from one or more of hydrogen, deuterium, C1-C12 alkyl, C3-C12 cycloalkyl, and C6-C12 aryl.

5. The boron nitride compound according to claim 3, characterized in that, Ring A is independently selected from the following structures:

6. The boron nitride compound according to claim 1, wherein Ring B is independently selected from the following structures, and the dotted line indicates the connection position: Among them, R8-R 20 may be unsubstituted, monosubstituted or polysubstituted; in the case of being substituted by multiple substituents, the multiple substituents are the same as or different from each other, and adjacent substituents may be connected to form a ring; R8-R 20 are each independently the same as or different from each other and are selected from one or more of hydrogen, deuterium, C1-C24 alkyl, substituted or unsubstituted C3-C24 cycloalkyl, and substituted or unsubstituted C6-C30 aryl; when containing a substituent, the substituent is selected from deuterium and C1-C24 alkyl.

7. The boron nitride compound according to claim 1, wherein At least one hydrogen in formula (I) can be substituted by deuterium, tritium, cyano or halogen.

8. The boron nitride compound according to claim 1, wherein The boron nitride compound is selected from any one of the following chemical structures, where "D" represents deuterium:

9. Use of the boron nitride compound according to any one of claims 1-8 in the preparation of an electronic device.

10. The application according to claim 9, characterized in that, The electronic device is an organic electroluminescent device, an organic integrated circuit, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic solar cell, an organic optoelectronic device, an organic optical detector, an organic photoreceptor, an organic field quenching device, a light-emitting electrochemical cell and an organic laser diode.

11. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a cathode, an anode and at least one organic functional layer therebetween; the organic functional layer contains the boron nitride compound according to any one of claims 1-8.

12. An organic optoelectronic device, characterized in that, The organic optoelectronic device includes: a substrate layer; a first electrode; a second electrode facing the first electrode; and a light-emitting material layer disposed between the first electrode and the second electrode; the light-emitting material layer contains the boron nitride compound according to any one of claims 1-8.

13. A composition, characterized in that, The composition contains the boron nitride compound according to any one of claims 1-8.

14. A preparation, characterized in that, The preparation contains the boron nitride compound according to any one of claims 1-8 and at least one solvent.

15. A display or lighting device, characterized in that, The device contains one or more of the organic electroluminescent device according to claim 11 or the organic optoelectronic device according to claim 12.

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