An organic electroluminescent device comprising a boron-containing organic compound and a preparation method thereof

Abstract

The application discloses a boron-containing organic compound and an organic electroluminescent device prepared from the same, and belongs to the technical field of semiconductors. The structure of the organic compound is shown in general formula (1). The compound has a narrow half-peak width and can be used as a green light doping material of an emitting layer of an organic electroluminescent device, so that the light-emitting color purity and efficiency of the device are improved.

Description

Technical Field

[0001] This invention relates to the field of semiconductor technology, and in particular to a boron-containing organic compound and an organic electroluminescent device prepared therefrom. Background Technology

[0002] Traditional fluorescent doped materials, limited by early technologies, can only emit light using 25% of singlet excitons generated by electrical excitation. This results in low internal quantum efficiency (maximum 25%) and external quantum efficiency generally below 5%, significantly lower than that of phosphorescent devices. Phosphorescent materials, due to the strong spin-orbit coupling at their heavy atom centers, enhance intersystem crossing and can effectively utilize both singlet and triplet excitons generated by electrical excitation, achieving an internal quantum efficiency of 100%. However, most phosphorescent materials are expensive, have poor material stability, low color purity, and suffer from severe efficiency roll-off, limiting their application in OLEDs.

[0003] With the advent of the 5G era, higher requirements have been placed on color rendering standards. In addition to high efficiency and stability, luminescent materials also need narrower half-widths (HWHMs) to improve the purity of the emitted color in devices. Fluorescent dopants can achieve high fluorescence quantum density and narrow HWHM through molecular engineering. Significant breakthroughs have been achieved in blue fluorescent dopants, with the HWHM of boron-based materials reduced to below 30 nm. However, research on the green light region, which is more sensitive to the human eye, has mainly focused on phosphorescent dopants. However, the peak shape of these dopants is difficult to narrow using simple methods. Therefore, researching efficient green fluorescent dopants with narrow HWHMs is of great significance in meeting higher color rendering standards.

[0004] In addition, sensitization technology combines triplet exciton sensitizing materials with fluorescent doping materials. By using triplet exciton sensitizing materials as exciton sensitization media, it makes full use of triplet excitons and transfers energy to fluorescent doping materials through energy transfer, achieving 100% in-device quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization in fluorescent doping materials and effectively leverage the high fluorescence quantum yield, high device stability, high color purity, and low cost of fluorescent doping materials, showing broad prospects in OLED applications.

[0005] Boron compounds with resonant structures are more likely to achieve narrow half-width emission (HWHM). When applied to sensitization techniques, these materials can enable the fabrication of devices with high efficiency and narrow HWHM emission. For example, CN 107507921 A and CN 110492006 A disclose a light-emitting layer combination technique using TADF materials with a minimum singlet and triplet energy level difference of less than or equal to 0.2 eV as the main body and boron-containing materials as dopants; CN 110492005 A and CN 110492009 A disclose a light-emitting layer combination scheme using excitocomplexes as the main body and boron-containing materials as dopants; both achieve efficiencies comparable to phosphorescence and relatively narrow HWHM. Therefore, developing sensitization techniques based on narrow HWHM boron-based light-emitting materials has unique advantages and strong potential for improving BT.2020 display performance. Summary of the Invention

[0006] To address the aforementioned problems in the existing technology, this application provides a boron-containing organic compound and an organic electroluminescent device prepared therefrom. The compound of this invention has a narrow half-width at half-maximum and can be used as a green light doping material for the emitting layer of an organic electroluminescent device, thereby improving the purity of the emitted color and the lifetime of the device.

[0007] The technical solution of the present invention is as follows:

[0008] A boron-containing organic compound, the structure of which is shown in general formula (1):

[0009]

[0010] In general formula (1), each occurrence of Z, whether the same or different, is represented by C-R3 or N; each occurrence of R3, whether the same or different, is represented by hydrogen atom, deuterium atom, tritium atom, halogen atom, substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; adjacent R3 groups can also connect to form a ring;

[0011] Each occurrence of R1 and R2, whether identical or different, represents a hydrogen atom, deuterium atom, tritium atom, or substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0012] Further preferred, R1 and R2 appearing in the same or different ways each time represent hydrogen atoms, deuterium atoms, tritium atoms, substituted or unsubstituted C1 to C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy;

[0013] The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amino groups.

[0014] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formulas (2-1) to (2-3):

[0015]

[0016] In general formulas (2-2) to (2-4), the meanings of Z, R1, and R2 are the same as those defined above. Z1 and Z2 are independently represented as C-R4; each occurrence of R4, whether the same or different, represents a hydrogen atom, deuterium atom, tritium atom, halogen atom, or substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0017] The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amino groups.

[0018] In a preferred embodiment, the structure of the boron-containing organic compound is any one of general formulas (3-1) to (3-3):

[0019]

[0020] In general formulas (3-1) to (3-3), the meanings of Z, R1, R2, Z1, and Z2 are the same as those defined above;

[0021] R a R b Represented independently as hydrogen atoms, deuterium atoms, tritium atoms, halogen atoms, and substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0022] The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amino groups.

[0023] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formula (4-1):

[0024]

[0025] In general formula (4-1), the recurrence of R1 and R2, whether identical or different, represents hydrogen atom, deuterium atom, tritium atom, substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0026] R a R b R c R d Each occurrence, whether identical or different, is represented by hydrogen atom, deuterium atom, tritium atom, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; R a R b R c R d The connection method is either single bond substitution or the formation of a loop;

[0027] The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amino groups.

[0028] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formula (5-1):

[0029]

[0030] In general formula (5-1), each occurrence of Z, whether the same or different, is represented by C-R3 or N; each occurrence of R3, whether the same or different, is represented by hydrogen atom, deuterium atom, tritium atom, halogen atom, substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; adjacent R3 groups can also connect to form a ring;

[0031] Each occurrence of R1 and R2, whether identical or different, represents a hydrogen atom, deuterium atom, tritium atom, or substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0032] R a R b R c R dEach occurrence, whether identical or different, is represented by hydrogen atom, deuterium atom, tritium atom, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0033] The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amino groups.

[0034] In a preferred embodiment, the structure of the boron-containing organic compound is any one of general formulas (6-1) to (6-4):

[0035]

[0036]

[0037] In general formulas (6-1) to (6-4), each occurrence of Z, whether the same or different, is represented by C-R3 or N; each occurrence of R3, whether the same or different, is represented by hydrogen atom, deuterium atom, tritium atom, halogen atom, substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10 Aryloxy group, substituted or unsubstituted aromatic amino group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups; adjacent R3 groups can also connect to form a ring;

[0038] R a R b R c R d Each occurrence, whether identical or different, is represented by hydrogen atom, deuterium atom, tritium atom, substituted or unsubstituted C1-C. 10 Alkyl, substituted or unsubstituted C3-C 10 Cycloalkyl, substituted or unsubstituted C1-C 10 Alkoxy, substituted or unsubstituted C6-C 10aryloxy group, substituted or unsubstituted C6-C 30 Aryl, substituted or unsubstituted C2-C 30 One of the heteroaryl groups;

[0039] The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 cycloalkyl, C6-C 30 Aryl, C2-C 30 One or more of heteroaryl and amino groups.

[0040] Further preferably, the R3, whether appearing the same or different each time, is represented as hydrogen atom, deuterium atom, tritium atom, halogen atom, adamantyl, methyl, deuterated methyl, tritated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritated ethyl, isopropyl, deuterated isopropyl, tritated isopropyl, tert-butyl, deuterated tert-butyl, tritated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritated cyclopentyl, methyl-substituted cyclopentyl Cyclohexyl, phenyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthrene, pyrene, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole, N -One of the following: phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted diphenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boronyl, methoxy, tert-butoxy;

[0041] The recurrence of R1 and R2, whether identical or different, represents hydrogen atom, deuterium atom, tritium atom, adamantyl, methyl, deuterated methyl, tritated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritated ethyl, isopropyl, deuterated isopropyl, tritated isopropyl, tert-butyl, deuterated tert-butyl, tritated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritated cyclopentyl, methyl-substituted cyclopentyl Cyclohexyl, phenyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthrene, pyrene, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene The following are included: carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazine, phenyl-substituted boronyl, methoxy, and tert-butoxy.

[0042] Further preferred, the R a R bThe following are represented independently as adamantyl, methyl, deuterated methyl, tritriated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritriated ethyl, isopropyl, deuterated isopropyl, tritriated isopropyl, tert-butyl, deuterated tert-butyl, tritriated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritriated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, tritriated phenyl, diphenyl, deuterated diphenyl, tritriated diphenyl, terphenyl, deuterated terphenyl, tritriated terphenyl, diphenyl etheryl, methyl-substituted diphenyl etheryl, naphthyl, anthranilyl, phenanthryl, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazoleyl, N-phenylcarbazoleyl, 9, 9-Dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthoneyl, phenyl-substituted triazineyl, phenyl-substituted boronyl, methoxy, tert-butoxy.

[0043] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formula (4-1), wherein in general formula (4-1), R1, R2, R3, and R... a R b R c R dEach instance of the same or different atoms is represented by: hydrogen atom, deuterium atom, tritium atom, adamantyl group, methyl group, deuterated methyl group, tritated methyl group, trifluoromethyl group, ethyl group, deuterated ethyl group, tritated ethyl group, isopropyl group, deuterated isopropyl group, tritated isopropyl group, tert-butyl group, deuterated tert-butyl group, tritated tert-butyl group, cyclopentyl group, deuterated cyclopentyl group, tritated cyclopentyl group, methyl-substituted cyclopentyl group, cyclohexyl group, phenyl group. Deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthrene, pyrene, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, benzothiophene, dibenzothiophene The following is a list of compounds: carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazine, phenyl-substituted boronyl, methoxy, and tert-butoxy.

[0044] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formula (5-1), wherein in general formula (5-1), R1, R2, R3, and R... a R b R c R dEach instance of the same or different atoms is represented by: hydrogen atom, deuterium atom, tritium atom, adamantyl, methyl, deuterated methyl, tritated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritated ethyl, isopropyl, deuterated isopropyl, tritated isopropyl, tert-butyl, deuterated tert-butyl, tritated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, benzene. alkyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthryl, pyrene, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole The following is a list of: N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazine, phenyl-substituted boronyl, methoxy, and tert-butoxy.

[0045] In a preferred embodiment, the structure of the boron-containing organic compound is shown in general formulas (6-1) to (6-4), wherein in general formulas (6-1) to (6-4), R3, R... a R b R c R dEach instance of the same or different atoms is represented by: hydrogen atom, deuterium atom, tritium atom, adamantyl, methyl, deuterated methyl, tritated methyl, trifluoromethyl, ethyl, deuterated ethyl, tritated ethyl, isopropyl, deuterated isopropyl, tritated isopropyl, tert-butyl, deuterated tert-butyl, tritated tert-butyl, cyclopentyl, deuterated cyclopentyl, tritated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, benzene. alkyl, deuterated phenyl, tritated phenyl, diphenyl, deuterated diphenyl, tritated diphenyl, terphenyl, deuterated terphenyl, tritated terphenyl, diphenyl ether, methyl-substituted diphenyl ether, naphthyl, anthracene, phenanthryl, pyrene, pyridyl, phenyl-substituted pyridyl, quinolinyl, furanyl, thiophene, benzofuranyl, dibenzofuranyl, dibenzothiophene, carbazole The following is a list of: N-phenylcarbazolyl, 9,9-dimethylfluorenyl, spirofluorenyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, tert-butyl-substituted dibenzofuranyl, phenyl-substituted tert-butyl, xanthone, phenyl-substituted triazine, phenyl-substituted boronyl, methoxy, and tert-butoxy.

[0046] In a preferred embodiment, the boron-containing organic compound has a specific structural formula of any one of the following:

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057] An organic electroluminescent device includes a cathode and an anode, and an organic light-emitting functional layer therebetween, the organic light-emitting functional layer including a light-emitting layer containing the boron-containing organic compound.

[0058] Further preferably, the light-emitting layer comprises a host material and a dopant material, wherein the dopant material contains the aforementioned boron-containing organic compound.

[0059] Further preferably, the light-emitting layer comprises a first host material, a second host material, and a dopant material, wherein at least one of the first host material and the second host material is a TADF material, and the dopant material is the boron-containing organic compound.

[0060] Further preferably, the light-emitting layer comprises a host material, an exciton-sensitizing material, and a dopant material, wherein the exciton-sensitizing material is a complex containing a metal element, and the dopant material is the boron-containing organic compound.

[0061] The beneficial technical effects of this invention are as follows:

[0062] (1) The compound of the present invention can be used as a dopant material for the light-emitting layer of OLED devices. It can emit green fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields; (2) The compound of the present invention, as a dopant material, introduces phosphorescent material as an exciton sensitizer, which can effectively improve the device lifespan.

[0063] (3) The compounds of the present invention have a narrower FWHM spectrum, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device. Attached Figure Description

[0064] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in this invention are applied;

[0065] Wherein, 1 is a transparent substrate layer, 2 is an anode layer, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an electron blocking layer, 6 is a light-emitting layer, 7 is a hole blocking layer, 8 is an electron transport layer, 9 is an electron injection layer, and 10 is a cathode layer. Detailed Implementation

[0066] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings. In the absence of conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.

[0067] In this invention, the terms "upper," "lower," "top," and "bottom," used to describe electrodes, organic electroluminescent devices, and other structures, indicate orientation only in a specific state and do not imply that the structure can only exist in that orientation. Conversely, if the structure can be repositioned, such as by inverting it, the orientation of the structure changes accordingly. Specifically, in this invention, the "bottom" or "lower" side of the electrode refers to the side of the electrode closer to the substrate during fabrication, while the opposite side farther from the substrate is the "top" or "upper" side.

[0068] In this invention, C6-C is substituted or unsubstituted. 30 aryl and / or substituted or unsubstituted C2-C 30 Heteroaryl refers to substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraquinone, substituted or unsubstituted phenanthrene, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrene, substituted or unsubstituted biphenyl, substituted or unsubstituted para-triphenyl, substituted or unsubstituted meta-triphenyl, and substituted or unsubstituted phenyl groups. Substituted or unsubstituted triphenyl, substituted or unsubstituted perylene, substituted or unsubstituted indole, substituted or unsubstituted furanyl, substituted or unsubstituted thiophene, substituted or unsubstituted pyrrole, substituted or unsubstituted pyrazolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted triazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted oxadiazolyl, substituted or unsubstituted thiadiazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazine, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophene, substituted or Unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted naphridyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridineyl, substituted or unsubstituted phenazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fumonyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazoleyl, combinations thereof, or fused rings of the foregoing groups, but not limited thereto.

[0069] The C1-C of this invention 10 Alkyl groups (including straight-chain alkyl and branched-chain alkyl) refer to methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, sec-butyl, neopentyl, n-pentyl, isopentyl, octyl, heptyl, n-decyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1-butylpentyl, etc., but are not limited to these.

[0070] The halogen atom mentioned in this invention refers to chlorine atom, fluorine atom or bromine atom, etc., but is not limited to these.

[0071] The C3-C of this invention 10 Cycloalkyl refers to a monovalent monocyclic saturated hydrocarbon group comprising 3 to 10 carbon atoms as cyclic atoms. In this document, C4-C9 cycloalkyl groups are preferred, C5-C8 cycloalkyl groups are more preferred, and C5-C7 cycloalkyl groups are particularly preferred. Non-limiting examples may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl, and cycloheptyl.

[0072] As the substrate for the organic electroluminescent device of this invention, any substrate commonly used in organic electroluminescent devices can be used. Examples include transparent substrates, such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; and flexible PI film substrates. Different substrates have different mechanical strengths, thermal stability, transparency, surface smoothness, and water resistance. Their application varies depending on their properties. In this invention, a transparent substrate is preferred. There are no particular limitations on the thickness of the substrate.

[0073] A first electrode is formed on a substrate, and the first electrode and a second electrode may be opposite each other. The first electrode may be an anode. The first electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the first electrode is a transmissive electrode, it may be formed using a transparent metal oxide, such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), or indium tin zinc oxide (ITZO). When the first electrode is a semi-transmissive electrode or a reflective electrode, it may include Ag, Mg, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, or a mixture of metals. The thickness of the first electrode layer depends on the material used, typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0074] The organic functional material layer disposed between the first and second electrodes comprises, from bottom to top, a hole transport region, a light-emitting layer, and an electron transport region. In this paper, the hole transport region constituting an organic electroluminescent device can be exemplified as a hole injection layer, a hole transport layer, an electron blocking layer, etc. As materials for the hole injection layer, hole transport layer, and electron blocking layer, any known materials used in OLED devices can be selected.

[0075] Examples of the aforementioned materials include phthalocyanine derivatives, triazole derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, oxadiazole derivatives, hydrazone derivatives, stilbene derivatives, pyridinium derivatives, polysilane derivatives, imidazole derivatives, phenylenediamine derivatives, amino-substituted quinone derivatives, styrene-based anthracene derivatives, styrene-based amine derivatives, styrene compounds, fluorene derivatives, spirofluorene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, carbazole derivatives, polyaryl alkane derivatives, polyphenylene oxide and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and other conductive polymers, aromatic tertiary amine compounds, and styrene aminations. Compounds, triamines, tetraamines, benzidines, propyne diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamine)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4'-bis(diarylamino)terphenyls, 4,4'-bis(diarylamino)tetraphenyls, 4,4'-bis(diarylamino)diphenyl ethers, 4,4'-bis(diarylamino)diphenylsulfanes, bis[4-(diarylamino)phenyl]dimethylmethanes, bis[4-(diarylamino)phenyl]-bis(trifluoromethyl)methanes, or 2,2-diphenylethylene compounds, etc.

[0076] Furthermore, depending on the device configuration requirements, the hole transport film layer between the hole transport auxiliary layer and the hole injection layer of the organic electroluminescent device can be a single film layer or a stacked structure of multiple hole transport materials. In this paper, the film thickness of the various hole carrier conduction films with different functions is not particularly limited.

[0077] The hole injection layer comprises a host organic material capable of conducting holes, and a p-type doped material with a deep HOMO level (correspondingly, a deep LUMO level). Based on empirical observations, to achieve smooth hole injection from the anode to the organic film, the HOMO level of the host organic material used in the anode interface buffer layer must possess certain characteristics with the p-doped material. This is necessary to enable charge transfer states between the host and doped materials, achieve ohmic contact between the buffer layer and the anode, and realize efficient hole injection conduction from the electrode to the hole injection layer.

[0078] Based on the above empirical summary, different P-doped materials need to be selected to match the hole-based host materials of different HOMO energy levels in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0079] Therefore, in one embodiment of the present invention, in order to improve hole injection, the hole injection layer further comprises a p-type dopant material selected from the following charge-conducting materials: quinone derivatives, such as tetracyanoquinone dimethyl (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinone dimethyl (F4-TCNQ); or hexaazatriphenyl derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenyl (HAT-CN); or cyclopropane derivatives, such as 4,4',4”-((1E,1'E,1”E)-cyclopropane-1,2,3-trimethylenetris(cyanoformyl))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited thereto.

[0080] In the hole injection layer of the present invention, the ratio of hole transport material to P-type doped material is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0081] The thickness of the hole injection layer of the present invention can be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range. The thickness of the hole transport layer of the present invention can be 5-200 nm, preferably 10-150 nm, and more preferably 20-100 nm, but the thickness is not limited to this range.

[0082] The thickness of the electron blocking layer of the present invention can be 10-50 nm, preferably 20-30 nm, but the thickness is not limited to this range.

[0083] After forming the hole injection layer, hole transport layer, and electron blocking layer, a corresponding light-emitting layer is formed on top of the electron blocking layer. The light-emitting layer may comprise a host material and a dopant material. The host material may be a green light host material commonly used in the art, and the dopant material may be a boron-containing organic compound represented by the general formula (1) of this invention. In the light-emitting layer of this invention, the ratio of the host material to the dopant material is 99:1-70:30, preferably 99:1-85:15, and more preferably 97:3-87:13, based on mass.

[0084] The thickness of the light-emitting layer can be adjusted to optimize luminous efficiency and driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, and even more preferably 15-30 nm, but the thickness is not limited to this range.

[0085] In this invention, the electron transport region may include, from bottom to top, a hole blocking layer, an electron transport layer, and an electron injection layer disposed on the light-emitting layer, but is not limited thereto.

[0086] A hole-blocking layer is a layer that prevents holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the device's lifetime and improving its efficiency. The hole-blocking layer of this invention can be disposed on the light-emitting layer. As the hole-blocking layer material for the organic electroluminescent device of this invention, compounds with hole-blocking properties known in the prior art can be used, such as phenanthroline derivatives like copper hydroxide (BCP), metal complexes of hydroxyquinoline derivatives like aluminum(III)bis(2-methyl-8-quinoline)-4-phenylphenol (BAlq), various rare earth complexes, oxazole derivatives, triazole derivatives, triazine derivatives, 9,9'-(5-(6-([1,1'-biphenyl]-4-yl)-2-phenylpyrimidin-4-yl)-1,3-phenylene)bis(9H-carbazole) (CAS No.: 1345338-69-3 Pyrimidine derivatives, etc. The thickness of the hole blocking layer of the present invention can be 2-200 nm, preferably 5-150 nm and more preferably 10-100 nm, but the thickness is not limited to this range.

[0087] An electron transport layer may be disposed above the light-emitting layer or (if present) a hole-blocking layer. The electron transport layer material is one that readily receives electrons from the cathode and transfers the received electrons to the light-emitting layer. Materials with high electron mobility are preferred. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials known in the prior art for organic electroluminescent devices can be used, such as metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and Liq, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6-(naphthyl-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6), imidazole derivatives such as 2-(4-(9,10-bis(naphthyl-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201), oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silicon-based compound derivatives, etc. The thickness of the electron transport layer of the present invention can be 10-80 nm, preferably 20-60 nm and more preferably 25-45 nm, but the thickness is not limited to this range.

[0088] An electron injection layer may be disposed above the electron transport layer. The electron injection layer material is typically preferably a material with a low work function, allowing electrons to be easily injected into the organic functional material layer. As the electron injection layer material for the organic electroluminescent device of the present invention, electron injection layer materials known in the art for organic electroluminescent devices can be used, such as lithium; lithium salts, such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate, or lithium azide; or cesium salts, such as cesium fluoride, cesium carbonate, or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1-5 nm, preferably 0.5-3 nm, and more preferably 0.8-1.5 nm, but the thickness is not limited to this range.

[0089] The second electrode can be disposed above the electron transport region. The second electrode can be a cathode. The second electrode can be a transmission electrode, a semi-transmission electrode, or a reflection electrode. When the second electrode is a transmission electrode, it can include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or compounds or mixtures thereof; when the second electrode is a semi-transmission electrode or a reflection electrode, it can include Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or compounds or mixtures thereof, but is not limited thereto. The thickness of the cathode depends on the material used, typically 50-90 nm, preferably 70-80 nm.

[0090] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure preventing external substances such as moisture and oxygen from entering the organic layer of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass or metal can; or a thin film covering the entire surface of the organic layer.

[0091] The method for preparing the organic electroluminescent device of the present invention includes sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer, and a cathode, and optionally a capping layer, onto a substrate. In this regard, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI can be used, but are not limited thereto. In the present invention, vacuum evaporation is preferably used to form the various layers. Those skilled in the art can conventionally select the various process conditions in the vacuum evaporation method according to actual needs.

[0092] All raw materials involved in the synthesis embodiments of the present invention can be purchased from the market or obtained by conventional preparation methods in the art;

[0093] Example 1: Synthesis of Compound 28:

[0094]

[0095] Under air atmosphere, 11.5 mmol of starting material A-1, 27.0 mmol of NaH, and 50 mL of DMF were added to a dry round-bottom flask equipped with a magnetic stir bar. After stirring at room temperature for 0.5 h, 5 mmol of starting material B-1 was added to the reaction mixture, and the mixture was stirred at 140 °C for 12 h. After cooling to room temperature, the mixture was filtered, and the solid was washed with DMF. The residue was dissolved in tetrahydrofuran, and the insoluble matter was filtered off. The solution was then evaporated under reduced pressure to give intermediate a-1. LC-MS: Measured value: 499.29 ([M+H)) + Theoretical value: 498.17.

[0096] In a three-necked flask under nitrogen protection, 1.05 mL of 2.5 mol / L n-butylhexane solution was slowly added dropwise to 100 mL of a toluene solution of intermediate a-1 (2.5 mmol). The mixture was stirred at -60 °C for 1 h, then heated to -40 °C, and 3.75 mmol BBr3 was added. The mixture was stirred at room temperature for 1 h, and then 10.0 mmol N,N-diisopropylethylamine was added at 0 °C. The mixture was heated to 120 °C. After stirring for 8 h, the mixture was cooled to room temperature. The solution was filtered through a diatomaceous earth filter and washed with dichloromethane. The filtrate was evaporated under reduced pressure, and the product was purified by silica gel column chromatography (petroleum ether:dichloromethane = 20:1, v / v) and recrystallized from dichloromethane and methanol to give intermediate b-1. LC-MS: Measured value: 429.11 ([M+H) + Theoretical value: 428.24.

[0097] At room temperature, 6.5 mmol of intermediate b-1, 6.6 mmol of starting material C-1, and 60 mL of THF were added to a three-necked flask. Then, 0.065 mmol of [Ir(COD)(OCH3)]2 and 0.13 mmol of dtbpy were added. The mixture was then bubbled under nitrogen for 5 min and refluxed with stirring for 24 h. After cooling to room temperature, the reactants were concentrated under reduced pressure. The product was purified by silica gel column chromatography (petroleum ether:dichloromethane = 20:1, v / v) to obtain intermediate c-1. LC-MS: Measured value: 555.38 ([M+H) + Theoretical value: 554.33.

[0098] In a three-necked flask, 0.6 mmol of starting material D-1, 0.5 mmol of intermediate c-1, 1 mmol of K2CO3 and 16 ml of THF were added. The mixture was bubbled with nitrogen for 5 min, and 0.025 mmol of Pd(PPh3)4 was added under high flow rate nitrogen. The mixture was then stirred and heated under reflux. The organic layers were condensed and combined under vacuum. The product was purified by silica gel column chromatography (petroleum ether: dichloromethane = 20:1, v / v) to obtain the target compound 28. 1¹H NMR (400MHz, Chloroform-d) δ 8.22–8.14 (m, 6H), 8.01–7.93 (m, 2H), 7.62–7.60 (d, 2H), 7.51–7.43 (m, 4H), 7.13–7.10 (d, 2H), 6.72–6.69 (m, 2H), 1.38–1.25 (d, 36H). FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 27 nm.

[0099] Example 2: Synthesis of Compound 51:

[0100]

[0101] The preparation method of intermediate a-2 is the same as that of intermediate a-1, except that raw material A-1 is replaced by raw material A-2 to obtain intermediate a-2. LC-MS: Measured value: 555.10 ([M+H]). + Theoretical value: 554.23.

[0102] Intermediate b-2 was prepared in the same way as intermediate b-1, except that intermediate a-1 was replaced with intermediate a-2 to obtain intermediate b-2. LC-MS: Measured value: 485.41 ([M+H]). + Theoretical value: 484.30.

[0103] Intermediate c-2 was prepared in the same way as intermediate c-1, except that intermediate b-1 was replaced with intermediate b-2 to obtain intermediate c-2. LC-MS: Measured value: 611.30 ([M+H]). + Theoretical value: 610.39.

[0104] Compound 51 was prepared in the same manner as compound 28, except that intermediate c-1 was replaced by intermediate c-2 and starting material D-1 was replaced by starting material D-2, thus obtaining compound 51. FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 26 nm.

[0105] Example 3: Synthesis of Compound 79:

[0106]

[0107] The preparation method of compound 79 is the same as that of compound 51, except that the raw material D-2 is replaced by raw material D-3 to obtain compound 79. 1¹H NMR (400 MHz, Chloroform-d) δ 8.17 (s, 2H), 7.72–7.64 (m, 4H), 7.62–7.54 (m, 8H), 7.48–7.31 (m, 6H), 7.20 (d, 2H), 7.13 (d, 2H), 2.42–2.35 (d, 12H), 1.31–1.27 (s, 18H). FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 28 nm.

[0108] Example 4: Synthesis of Compound 94:

[0109]

[0110] Under nitrogen protection, 11 mmol of starter E-4, 10 mmol of starter F-4, 100 mL of ethanol, and 10.7 mL of 0.1 mol / L sulfuric acid were added to a three-necked flask, and the mixture was refluxed at 90 °C overnight. After the reaction was complete, the mixture was cooled to room temperature, and then precipitated in ice water. The precipitate was filtered, and the residue was dried in a vacuum oven to obtain starter A-4. LC-MS: 230.25 ([M+H)) + Theoretical value: 229.18.

[0111] The preparation method of intermediate a-4 is the same as that of intermediate a-1, except that raw material A-1 is replaced by raw material A-4 to obtain intermediate a-4. LC-MS: Measured value: 611.21 ([M+H]). + Theoretical value: 610.29.

[0112] Intermediate b-4 was prepared in the same way as intermediate b-1, except that intermediate a-1 was replaced with intermediate a-4 to obtain intermediate b-4. LC-MS: Measured value: 541.41 ([M+H]). + Theoretical value: 540.37.

[0113] Intermediate c-4 was prepared in the same way as intermediate c-1, except that intermediate b-1 was replaced with intermediate b-4 to obtain intermediate c-4. LC-MS: Measured value: 667.30 ([M+H]). + Theoretical value: 666.45.

[0114] Compound 94 was prepared in the same manner as compound 28, except that intermediate c-1 was replaced by intermediate c-4 and starting material D-1 was replaced by starting material D-2, thus obtaining compound 94. FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 25 nm.

[0115] Example 5: Synthesis of Compound 98:

[0116]

[0117] The preparation method of raw material A-5 is the same as that of raw material A-4, except that raw material F5 is used instead of raw material F-4 to obtain raw material A-5. LC-MS: Measured value: 286.09 ([M+H]). + Theoretical value: 285.25.

[0118] The preparation method of intermediate a-5 is the same as that of intermediate a-1, except that raw material A-5 is used to replace raw material A-1 to obtain intermediate a-5. LC-MS: Measured value: 723.50 ([M+H]). + Theoretical value: 722.42.

[0119] Intermediate b-5 was prepared in the same way as intermediate b-1, except that intermediate a-1 was replaced with intermediate a-5 to obtain intermediate b-5. LC-MS: Measured value: 653.37 ([M+H]). + Theoretical value: 652.49.

[0120] Intermediate c-5 was prepared in the same way as intermediate c-1, except that intermediate b-1 was replaced with intermediate b-5 to obtain intermediate c-5. LC-MS: Measured value: 779.66 ([M+H]). + Theoretical value: 778.58.

[0121] Compound 98 was prepared in the same manner as compound 28, except that intermediate c-1 was replaced by intermediate c-5 and starting material D-1 was replaced by starting material D-2, thus obtaining compound 98. FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 27 nm.

[0122] Example 6: Synthesis of Compound 134:

[0123]

[0124] The preparation method of raw material A-6 is the same as that of raw material A-4, except that raw material F-4 is replaced by raw material F-6 to obtain raw material A-6. LC-MS: Measured value: 306.33 ([M+H]). + Theoretical value: 305.21.

[0125] The preparation method of intermediate a-6 is the same as that of intermediate a-1, except that raw material A-1 is replaced by raw material A-6 to obtain intermediate a-6. LC-MS: Measured value: 763.50 ([M+H]). + Theoretical value: 762.35.

[0126] Intermediate b-6 was prepared in the same way as intermediate b-1, except that intermediate a-1 was replaced with intermediate a-6 to obtain intermediate b-6. LC-MS: Measured value: 693.37 ([M+H]). + Theoretical value: 692.43.

[0127] Intermediate c-6 was prepared in the same way as intermediate c-1, except that intermediate b-1 was replaced with intermediate b-6 to obtain intermediate c-6. LC-MS: Measured value: 819.66 ([M+H]). + Theoretical value: 818.52.

[0128] Compound 134 was prepared in the same way as compound 28, except that intermediate c-1 was replaced by intermediate c-6 to obtain compound 134. 1 ¹H NMR (400 MHz, Chloroform-d) δ 8.53 (d, 2H), 8.18–8.14 (dd, 6H), 7.63–7.54 (m, 4H), 7.53–7.29 (m, 12H), 1.45–1.40 (s, 18H), 1.37–1.31 (d, 36H). FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 28 nm.

[0129] Example 7: Synthesis of Compound 141:

[0130]

[0131] The preparation method of intermediate a-7 is the same as that of intermediate a-1, except that raw material A-1 is replaced by raw material A-7 to obtain intermediate a-7. LC-MS: Measured value: 691.33 ([M+H]). + Theoretical value: 690.17.

[0132] Intermediate b-7 was prepared in the same way as intermediate b-1, except that intermediate a-1 was replaced with intermediate a-7 to obtain intermediate b-7. LC-MS: Measured value: 621.37 ([M+H]). + Theoretical value: 620.24.

[0133] Intermediate c-7 was prepared in the same way as intermediate c-1, except that intermediate b-1 was replaced with intermediate b-7 to obtain intermediate c-7. LC-MS: Measured value: 747.66 ([M+H]). + Theoretical value: 746.33.

[0134] Compound 141 was prepared in the same manner as compound 28, except that intermediate c-1 was replaced by intermediate c-7 and starting material D-1 was replaced by starting material D-2, thus obtaining compound 141. FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 26 nm.

[0135] Example 8: Synthesis of Compound 158:

[0136]

[0137] The preparation method of compound 158 is the same as that of compound 141, except that the raw material D-2 is replaced by raw material D-8 to obtain compound 158. 1 ¹H NMR (400MHz, Chloroform-d) δ 8.69 (t, 2H), 8.60–8.56 (m, 2H), 8.17 (s, 2H), 7.74–7.09 (m, 40H). FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 27 nm.

[0138] Example 9: Synthesis of Compound 176:

[0139]

[0140] The preparation method of intermediate a-9 is the same as that of intermediate a-1, except that raw material A-9 is used to replace raw material A-1 to obtain intermediate a-9. LC-MS: Measured value: 915.68 ([M+H]). + Theoretical value: 914.42.

[0141] The preparation method of intermediate b-9 is the same as that of intermediate b-9, except that intermediate a-1 is replaced by intermediate a-9 to obtain intermediate b-9. LC-MS: Measured value: 845.32 ([M+H]). + Theoretical value: 844.49.

[0142] The preparation method of intermediate c-9 is the same as that of intermediate c-1, except that intermediate b-1 is replaced by intermediate b-9 to obtain intermediate c-9. LC-MS: Measured value: 971.64 ([M+H]). + Theoretical value: 970.58.

[0143] Compound 176 was prepared in the same manner as compound 28, except that intermediate c-1 was replaced by intermediate c-9 and starting material D-1 was replaced by starting material D-2, thus obtaining compound 176. FWHM (obtained in thin film state by a Horiba Fluorolog-3 series fluorescence spectrometer): 29 nm.

[0144] The structural characterization of the compounds obtained in each embodiment is shown in Table 1.

[0145] Table 1

[0146]

[0147] The following details the application effects of the OLED materials synthesized in this invention in devices through Device Examples 1-9 and Comparative Examples 1-4. Device Examples 2-9 and Comparative Examples 1-4 of this invention have the same fabrication process as Device Example 1, and use the same substrate and electrode materials, with consistent electrode film thickness. The only difference is the replacement of the light-emitting layer material. The layer structures and test results of each device example are shown in Tables 2 and 3, respectively.

[0148] Device Example 1

[0149] like Figure 1 As shown, the transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed sequentially with a cleaning agent (Semiclean M-L20), followed by washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues from the transparent ITO surface. After the above washing, HT-1 and HI-1 with a thickness of 10nm are deposited on the ITO anode layer 2 using a vacuum evaporation apparatus as a hole injection layer 3, with a mass ratio of HT-1 to HI-1 of 97:3. Next, a 60nm thick layer of HT-1 is deposited as a hole transport layer 4. Subsequently, a 30nm thick layer of EB-1 is deposited as an electron blocking layer 5. After the electron blocking materials are deposited, the light-emitting layer 6 of the OLED light-emitting device is fabricated, using GH-1 and GH-2 as the host materials and compound 28 as the dopant material, with a mass ratio of GH-1, GH-2, and compound 28 of 69:30:1, and a film thickness of 30nm. Following the aforementioned light-emitting layer 6, HB-1 is vacuum-deposited to a thickness of 5 nm; this layer serves as the hole-blocking layer 7. Following the hole-blocking layer 7, ET-1 and Liq are vacuum-deposited at a mass ratio of 1:1, resulting in a film thickness of 30 nm; this layer serves as the electron transport layer 8. On the electron transport layer 8, a LiF layer with a thickness of 1 nm is fabricated using a vacuum evaporation apparatus; this layer serves as the electron injection layer 9. On the electron injection layer 9, an 80 nm thick Mg:Ag electrode layer is fabricated using a vacuum evaporation apparatus, with a Mg:Ag mass ratio of 1:9; this layer serves as the cathode layer 10.

[0150] The application effects of the OLED material synthesized in this invention in devices are described in detail below through device examples 10-18 and device comparative examples 5-7. The fabrication processes of device examples 11-18 and device comparative examples 5-7 are exactly the same as those of device example 10, and the same substrate and electrode materials are used. The film thickness of the electrode materials is also kept consistent. The only difference is that the light-emitting layer material in the device is replaced. The layer structure and test results of each device example are shown in Tables 2 and 3, respectively.

[0151] Device Example 10

[0152] The transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed sequentially with a cleaning agent (Semiclean M-L20), followed by washing with pure water, drying, and then ultraviolet-ozone washing to remove organic residues from the transparent ITO surface. After the above washing, a 10nm thick layer of HT-1 and HI-1 is deposited on the ITO anode layer 2 using a vacuum evaporation apparatus as a hole injection layer 3, with a mass ratio of HT-1 to HI-1 of 97:3. Next, a 60nm thick layer of HT-1 is deposited as a hole transport layer 4. Finally, a 30nm thick layer of EB-1 is deposited as an electron blocking layer 5. After the electron blocking material is deposited, the emitting layer 6 of the OLED light-emitting device is fabricated. GH-1 and GH-2 are used as the host materials, GD-1 is used as the first dopant, and compound 28 is used as the second dopant. The mass ratio of GH-1, GH-2, GD-1, and compound 28 is 66:30:3:1, and the thickness of the emitting layer is 30 nm. After the emitting layer 6, HB-1 is vacuum-deposited to a thickness of 5 nm; this layer is the hole blocking layer 7. After the hole blocking layer 7, ET-1 and Liq are vacuum-deposited to a mass ratio of 1:1; the thickness of this layer is 30 nm; this layer is the electron transport layer 8. On the electron transport layer 8, a LiF layer with a thickness of 1 nm is fabricated using a vacuum evaporation apparatus; this layer is the electron injection layer 9. On the electron injection layer 9, a Mg:Ag electrode layer with a thickness of 80 nm is fabricated using a vacuum evaporation apparatus; the mass ratio of Mg to Ag is 1:9; this layer is used as the cathode layer 10.

[0153] The molecular structural formulas of the relevant materials are shown below:

[0154]

[0155] After completing the OLED light-emitting device as described above, the anode and cathode are connected using a known driving circuit, and the device's voltage, current efficiency, and lifetime are measured. Examples and comparative examples of devices prepared using the same method are shown in Table 2; the test results for the voltage, current efficiency, and lifetime of the obtained devices are shown in Table 3.

[0156] Table 2

[0157]

[0158]

[0159] Table 3

[0160]

[0161] Note: Voltage, current efficiency, and emission peak were measured using an IVL (current-voltage-brightness) testing system (Suzhou Fushida Scientific Instruments Co., Ltd.); the lifetime testing system was the EAS-62C OLED device lifetime tester from System Technology Inc., Japan; LT95 refers to the time it takes for the device brightness to decay to 95%; all data are within 10 mA / cm². 2 Next test.

[0162] As can be seen from the device data results in Table 3, compared with devices Comparative Examples 1-4, the compound of the present invention has a higher device lifetime in the single-doped system. In the single-doped system, the device efficiency also shows a better effect. This is because the boron-nitrogen fused ring core can adjust the light color, enhance the resonance intensity, and improve the device efficiency. Compared with devices Comparative Examples 5-7, the compound of the present invention, in the dual-doped system using exciton-sensitized material as the first dopant, shows a significant improvement in both current efficiency and device lifetime compared with OLED devices made of known materials. Moreover, in the dual-doped device, the device efficiency is also significantly improved compared with the single-doped device.

[0163] In summary, the above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A boron-containing organic compound, characterized in that, The structure of the boron-containing organic compound is shown in general formula (1): In general formula (1), each occurrence of Z, whether the same or different, is represented as C-R3; each occurrence of R3, whether the same or different, is represented as hydrogen atom, deuterium atom, halogen atom, substituted or unsubstituted C1 to C2. 10 Alkyl, substituted or unsubstituted C3-C 10 One of the following: cycloalkyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl; Each occurrence of R1 and R2, whether identical or different, represents a hydrogen atom, a deuterium atom, or substituted or unsubstituted C1-C1 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 One of cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted biphenyl; The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 One or more of the cycloalkyl groups.

2. The boron-containing organic compound according to claim 1, characterized in that, The structures of the organic compounds are shown in general formulas (2-1) to (2-3): In general formulas (2-1) to (2-3), the meanings of Z, R1, and R2 are the same as those defined in claim 1; Z1 and Z2 are independently represented as C-R4; each occurrence of R4, whether the same or different, represents a hydrogen atom, a deuterium atom, a halogen atom, or C1 to C2. 10 Alkyl, C3-C 10 One of the cycloalkyl groups.

3. The boron-containing organic compound according to claim 2, characterized in that, The organic compound has the structure of any one of general formulas (3-1) to (3-3): In general formulas (3-1) to (3-3), the meanings of Z, R1, R2, Z1, and Z2 are the same as those defined in claim 2; R a R b Represented independently as halogen atoms, substituted or unsubstituted C1 to C2 atoms. 10 Alkyl, substituted or unsubstituted C3-C 10 One of the following: cycloalkyl, phenyl-substituted amino, tert-butylbenzene-substituted amino, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl; The substituents used for the substituent groups are optionally selected from deuterium atoms, halogen atoms, cyano groups, C1-C... 10 Alkyl, C3-C 10 One or more of the cycloalkyl groups.

4. The boron-containing organic compound according to claim 1, characterized in that, The R3 appearing the same or different each time represents a hydrogen atom, deuterium atom, halogen atom, adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, diphenyl, deuterated diphenyl, terphenyl, deuterated terphenyl, naphthyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl One of the following: substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, deuterated tert-butyl-substituted diphenyl, phenyl-substituted amino, and tert-butylbenzene-substituted amino. The terms R1 and R2, which appear the same or different each time, represent hydrogen atom, deuterium atom, adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, diphenyl, deuterated diphenyl, terphenyl, deuterated terphenyl, naphthyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl One of the following: substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, and deuterated tert-butyl-substituted diphenyl.

5. The boron-containing organic compound according to claim 3, characterized in that, The R a R b The following are represented independently: adamantyl, methyl, deuterated methyl, trifluoromethyl, ethyl, deuterated ethyl, isopropyl, deuterated isopropyl, tert-butyl, deuterated tert-butyl, cyclopentyl, deuterated cyclopentyl, methyl-substituted cyclopentyl, cyclohexyl, phenyl, deuterated phenyl, diphenyl, deuterated diphenyl, terphenyl, deuterated terphenyl, naphthyl, methyl-substituted phenyl, ethyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted. One of the following: phenyl, methyl-substituted diphenyl, ethyl-substituted diphenyl, isopropyl-substituted diphenyl, tert-butyl-substituted diphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted diphenyl, deuterated ethyl-substituted diphenyl, deuterated isopropyl-substituted diphenyl, and deuterated tert-butyl-substituted diphenyl.

6. The boron-containing organic compound according to claim 1, characterized in that, The organic compound has a specific structural formula of any of the following:

7. An organic electroluminescent device, comprising a cathode and an anode, and an organic light-emitting functional layer therebetween, said organic light-emitting functional layer comprising a light-emitting layer, characterized in that, The light-emitting layer contains a boron-containing organic compound as described in any one of claims 1-6.

8. The organic electroluminescent device according to claim 7, characterized in that, The light-emitting layer comprises a host material and a dopant material, wherein the dopant material contains a boron-containing organic compound as described in any one of claims 1-6.

9. The organic electroluminescent device according to claim 7, wherein the light-emitting layer comprises a first host material, a second host material, and a dopant material, characterized in that, At least one of the first and second main materials is a TADF material, and the doping material is a boron-containing organic compound as described in any one of claims 1-6.

10. The organic light-emitting device according to claim 7, wherein the light-emitting layer comprises a host material, an exciton-sensitizing material, and a dopant material, characterized in that, The exciton sensitizing material is a complex containing a metal element, and the doping material is a boron-containing organic compound as described in any one of claims 1-6.

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