A resonance-type organic compound containing a BN heterocyclic structure and its application

Abstract

The present invention relates to a resonance-type organic compound containing a B-N heterocyclic structure and an application thereof, belonging to the field of semiconductor technology. The structure of the organic compound of the present invention is shown in the general formula (1): #imgabs0# The compound of the present invention has a narrow half-width, a high fluorescence quantum yield, strong rigidity, a high glass transition temperature and molecular thermal stability, and suitable HOMO and LUMO energy levels, and can maintain the emission characteristics of the B-N resonance-type material. When used as a dopant material in the light-emitting layer material of an OLED light-emitting device, the current efficiency of the device is significantly improved, and the luminescent color purity and the device life are also greatly improved. The organic compound of the present invention, as a dopant material for the light-emitting layer, enables the device to have good photoelectric properties.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular to a resonance-type organic compound containing a BN heterocyclic structure and applications thereof. Background Art

[0002] Traditional fluorescent doped materials, limited by early technology, can only utilize the 25% of singlet excitons formed by electrical excitation to emit light. This results in low internal quantum efficiency (up to 25%) and external quantum efficiency generally below 5%, significantly lagging behind the efficiency of phosphorescent devices. However, phosphorescent materials, due to the strong spin-orbit coupling at the heavy atom center that enhances intersystem crossing, can effectively utilize singlet and triplet excitons formed by electrical excitation to emit light, resulting in a device internal quantum efficiency of 100%.

[0003] With the advent of the 5G era, higher requirements are being placed on color rendering standards. In addition to being efficient and stable, luminescent materials also need to have a narrower half-width to improve the color purity of the device's luminescent color. Fluorescent doping materials can achieve high fluorescence quantum and narrow half-width through molecular engineering. Blue fluorescent doping materials have achieved a phased breakthrough, and the half-width of boron-based materials can be reduced to below 30nm. However, research in the green light region, to which the human eye is more sensitive, has mainly focused on phosphorescent doping materials. However, their luminescent peak shape is difficult to narrow through simple methods. Therefore, to meet higher color rendering standards, it is of great significance to study efficient green fluorescent doping materials with narrow half-width.

[0004] In addition, TADF-sensitized fluorescence technology (TSF) combines TADF materials with fluorescent doping materials, using TADF materials as exciton-sensitizing media to convert triplet excitons formed by electrical excitation into singlet excitons, and transfers energy to fluorescent doping materials through long-range energy transfer of singlet excitons, which can also achieve 100% device quantum efficiency. This technology can make up for the shortcomings of insufficient exciton utilization of fluorescent doping materials, and effectively give play to the characteristics of high fluorescence quantum yield, high device stability, high color purity and low price of fluorescent doping materials, and has broad prospects in OLEDs applications.

[0005] Boron compounds with resonant structures are more likely to achieve narrow half-width luminescence. Such materials are used in TADF-sensitized fluorescence technology to achieve the preparation of devices with high efficiency and narrow half-width emission. For example, CN 107507921 A and CN110492006 A disclose a TADF material with a difference between the lowest singlet state and the lowest triplet state energy level of less than or equal to 0.2eV as the main body, and a boron-containing material as the doping luminescent layer combination technology; CN 110492005 A and CN 110492009 A disclose a luminescent layer combination scheme with an exciplex as the main body and a boron-containing material as the doping; both can achieve efficiency comparable to phosphorescence and a relatively narrow half-width. Therefore, the development of TADF-sensitized fluorescence technology based on narrow half-width boron-containing luminescent materials has unique advantages and strong potential in terms of BT.2020 display indicators. Summary of the Invention

[0006] In response to the above-mentioned problems existing in the prior art, the present invention provides a resonant organic compound containing a BN heterocyclic structure and its application. After the structural fragment represented by the general formula (2) is introduced into the skeleton of the specific compound of the present invention, it has the effect of significantly adjusting the light color, improving the quantum yield, and increasing the device life. The compound of the present invention can maintain the emission characteristics of the BN resonant material. When used as a dopant material in the light-emitting layer material of an OLED light-emitting device, the current efficiency of the device is significantly improved, and the luminous color purity and device life are also greatly improved. The organic compound of the present invention, as a dopant material for the light-emitting layer, enables the device to have good photoelectric properties.

[0007] The technical solution of the present invention is as follows: a resonance-type organic compound containing a BN heterocyclic structure, the structure of the organic compound is shown in the general formula (1):

[0008]

[0009] X1 and X2 are independently a single bond, -O-, -S-, -Se-, -Si(R1)2-, -C(R1)2-, or -N(R1-, and X1 and X2 are the same or different; m is 0 or 1;

[0010] A1-A3 are independently substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 A heteroaryl group or one of the structures represented by the general formula (2), and at least one of A1-A3 is represented by the structure represented by the general formula (2); the B atom in the general formula (1) is connected to A1 and A2 through a CB bond;

[0011] Each occurrence of Z, whether the same or different, is represented by C-R2;

[0012] Each occurrence of R1 is the same or different and represents H, deuterium atom, tritium, C 1-10 Alkyl or silyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 One of the heteroaryl groups;

[0013] R2, which is the same or different each time, represents H, deuterium atom, tritium, halogen atom, cyano group, C 1-10 Alkyl or silyl, C 6-30 Aryl or C 3-30 Heteroaryl-substituted amino, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 One of the heteroaryl groups;

[0014] The substituents for the substituent group are optionally selected from halogen atoms, deuterium atoms, cyano groups, C 1-10 Alkyl, C 1-10 Alkoxy, C 3-20 Cycloalkyl, C6- 30 Aryl, C 3-30 one or more of heteroaryl groups;

[0015] R1 in X1 can also form C through C-C bond with A1 6-30 Aryl or C 3-30 Heteroaryl structures.

[0016] In a preferred embodiment, R1 and R2 are the same or different and each occurrence represents hydrogen, deuterium, tritium, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated substituted biphenyl, tritiated biphenyl, deuterated terphenyl, tritiated terphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, quinolyl, furyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, tritiated methyl-substituted phenyl, tritiated ethyl-substituted biphenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted biphenyl, tritiated ethyl-substituted biphenyl, tritiated isopropyl-substituted biphenyl or tritiated tert-butyl-substituted biphenyl.

[0017] More preferably, A1-A3 are each independently represented by a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a diphenyl ether group, a methyl-substituted diphenyl ether group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a phenyl-substituted amino group, a tert-butyl-substituted dibenzofuranyl group, a methyl-substituted phenyl group, an ethyl-substituted phenyl group, an isopropyl-substituted phenyl group, a tert-butyl-substituted phenyl group, a methyl-substituted biphenyl group, an ethyl-substituted biphenyl group, an isopropyl-substituted biphenyl group, a tert-butyl-substituted biphenyl group, or a xanthone group;

[0018] It is further preferred that the substituents for the substituent group are selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, -CF3, an adamantyl group, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a methoxy group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a quinolyl group, an isoquinolyl group, a furyl group, a thienyl group, an indolyl group, a pyrrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a carbazolinyl group, and an azaphenanthrenyl group.

[0019] More preferably, X1 is -N(R1)-, and each occurrence of R1 is the same or different and represents hydrogen, deuterium, tritium, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, phenyl, deuterated phenyl, tritiated phenyl , diphenyl, deuterated diphenyl, tritiated diphenyl, deuterated terphenyl, tritiated terphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, quinolyl, furyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted The present invention further comprises a deuterated phenyl, an isopropyl-substituted phenyl, a tert-butyl-substituted phenyl, a methyl-substituted biphenyl, an ethyl-substituted biphenyl, an isopropyl-substituted biphenyl, a tert-butyl-substituted biphenyl, a deuterated methyl-substituted phenyl, a deuterated ethyl-substituted phenyl, a deuterated isopropyl-substituted phenyl, a deuterated tert-butyl-substituted phenyl, a deuterated methyl-substituted biphenyl, a deuterated ethyl-substituted biphenyl, a deuterated isopropyl-substituted biphenyl, a deuterated tert-butyl-substituted biphenyl, a tritiated methyl-substituted phenyl, a tritiated ethyl-substituted biphenyl, a tritiated isopropyl-substituted biphenyl, a tritiated tert-butyl-substituted phenyl, a tritiated methyl-substituted biphenyl, a tritiated ethyl-substituted biphenyl, a tritiated isopropyl-substituted biphenyl or a tritiated tert-butyl-substituted biphenyl.

[0020] More preferably, R1 in -N(R1)- is connected to A1 via a CC bond;

[0021] In a preferred embodiment, the structure of the organic compound is as shown in any one of the general formulas (3) to (5):

[0022]

[0023] Z, X1-X2, and m are as defined above;

[0024] A1-A3 are independently represented by C 6-30 Aryl, C 3-30 Heteroaryl, one of the structures represented by general formula (2);

[0025] Y1 and Y2 are each independently represented by B or N, and Y1 and Y2 are different.

[0026] More preferably, A1-A3 are each independently represented by a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a diphenyl ether group, a methyl-substituted diphenyl ether group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a phenyl-substituted amino group, a tert-butyl-substituted dibenzofuranyl group, a methyl-substituted phenyl group, an ethyl-substituted phenyl group, an isopropyl-substituted phenyl group, a tert-butyl-substituted phenyl group, a methyl-substituted biphenyl group, an ethyl-substituted biphenyl group, an isopropyl-substituted biphenyl group, a tert-butyl-substituted biphenyl group, or a xanthone group;

[0027] The substituents for the substituent group are optionally selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, -CF3, an adamantyl group, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a methoxy group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a quinolyl group, an isoquinolyl group, a furyl group, a thienyl group, an indolyl group, a pyrrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a carbazolinyl group, and an azaphenanthrenyl group.

[0028] More preferably, X1 is -N(R1)-, wherein R1 in -N(R1)- is connected to A1 via a CC bond.

[0029] In a preferred embodiment, the structure of the organic compound is as shown in any one of the general formulas (3-1) to (5-1):

[0030]

[0031] The definitions of Z, X2, m, R1, and R2 are as defined above;

[0032] A1-A3 are independently substituted or unsubstituted C 6-30 Aryl, C 3-30 A heteroaryl group or one of the structures represented by general formula (2); the B atom is connected to A1 and A2 through a CB bond;

[0033] Y1 and Y2 are each independently represented by B or N, and Y1 and Y2 are different.

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

[0035]

[0036] In general formula (6-1) to general formula (6-6), X0 represents one of a single bond, -O-, -S-, -C(R1)2-, and -N(R1)-;

[0037] Each occurrence of R1 is the same or different and represents H, deuterium atom, tritium, C 1-10 Alkyl or silyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 One of the heteroaryl groups;

[0038] R3 represents H, deuterium atom, tritium, C 1-10 Alkyl or silyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 One of the heteroaryl groups;

[0039] Z, X2, and m are as defined above;

[0040] Y1 and Y2 are each independently represented by B or N, and Y1 and Y2 are different.

[0041] In a preferred embodiment, R3 is hydrogen, deuterium, tritium, methyl, deuterated methyl, tritiated methyl, ethyl, deuterated ethyl, tritiated ethyl, isopropyl, deuterated isopropyl, tritiated isopropyl, tert-butyl, deuterated tert-butyl, tritiated tert-butyl, deuterated cyclopentyl, tritiated cyclopentyl, cyclopentyl, phenyl, deuterated phenyl, tritiated phenyl, biphenyl, deuterated biphenyl, tritiated biphenyl Phenyl, deuterated terphenyl, tritiated terphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, quinolyl, furanyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted phenyl, isopropyl substituted Phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl, tritiated methyl-substituted phenyl, tritiated ethyl-substituted biphenyl, tritiated isopropyl-substituted phenyl, tritiated tert-butyl-substituted phenyl, tritiated methyl-substituted biphenyl, tritiated ethyl-substituted biphenyl, tritiated isopropyl-substituted biphenyl or tritiated tert-butyl-substituted biphenyl.

[0042] In a preferred embodiment, A1, A2, and A3 are independently represented by any one of the following ring structures:

[0043]

[0044] Preferably, the R1 is represented by any one of the following structures:

[0045]

[0046] More preferably, A1-A3 are each independently represented by a phenyl group, a deuterated phenyl group, a biphenyl group, a deuterated biphenyl group, a terphenyl group, a diphenyl ether group, a methyl-substituted diphenyl ether group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a phenyl-substituted pyridyl group, a quinolyl group, a furyl group, a thienyl group, a benzofuranyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group, an N-phenylcarbazolyl group, a 9,9-dimethylfluorenyl group, a phenyl-substituted amino group, a tert-butyl-substituted dibenzofuranyl group, a methyl-substituted phenyl group, an ethyl-substituted phenyl group, an isopropyl-substituted phenyl group, a tert-butyl-substituted phenyl group, a methyl-substituted biphenyl group, an ethyl-substituted biphenyl group, an isopropyl-substituted biphenyl group, a tert-butyl-substituted biphenyl group, or a xanthone group;

[0047] The substituents for the substituent group are optionally selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, -CF3, an adamantyl group, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, a butyl group, a methoxy group, a phenyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a quinolyl group, an isoquinolyl group, a furyl group, a thienyl group, an indolyl group, a pyrrolyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, a spirofluorenyl group, a carbazolyl group, an N-phenylcarbazolyl group, a carbazolinyl group, and an azaphenanthrenyl group.

[0048] In a preferred embodiment, the specific structural formula of the resonance-type organic compound containing a BN heterocyclic structure is any one of the following structures:

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] An organic light-emitting device comprises a cathode, an anode and a functional layer, wherein the functional layer is located between the cathode and the anode and comprises the resonance-type organic compound containing the BN heterocyclic structure.

[0061] Preferably, the functional layer comprises a light-emitting layer, and the doping material of the light-emitting layer is the resonance-type organic compound containing the BN heterocyclic structure;

[0062] Preferably, the light-emitting layer comprises a first host material, a second host material and a doping material, at least one of the first host material and the second host material is a TADF material, and the doping material is the resonance-type organic compound containing the BN heterocyclic structure.

[0063] Preferably, the light-emitting layer comprises a first main material, a second main material, a first doping material and a second doping material, characterized in that the first main material is a P-type organic compound, the second main material is an N-type organic compound, the first doping material is an organic phosphorescent complex containing Ir, Pt, Au, Ag, or Cu as a metal center, and the second doping material is the resonance-type organic compound containing a BN heterocyclic structure.

[0064] Compared with the prior art, the present invention has the following beneficial technical effects:

[0065] (1) The compounds of the present invention are applied to OLED devices and can be used as doping materials for light-emitting layer materials. They can emit fluorescence under the action of an electric field and can be applied to OLED lighting or OLED display fields.

[0066] (2) The compound of the present invention has a high fluorescence quantum efficiency as a doping material, and the fluorescence quantum efficiency of the material is close to 100%;

[0067] (3) The compound of the present invention is used as a doping material and introduced into a TADF sensitizer, which can effectively improve the device efficiency;

[0068] (4) The compound of the present invention is used as a doping material and introduced into a phosphorescent sensitizer, which can effectively improve the device efficiency and extend the device life;

[0069] (5) The spectral FWHM of the compound of the present invention is relatively narrow, which can effectively improve the color gamut of the device and enhance the luminous efficiency of the device;

[0070] (6) The vapor deposition decomposition temperature of the compound of the present invention is relatively high, which can inhibit the vapor deposition decomposition of the material and effectively improve the life of the device.

[0071] (7) After replacing the benzene ring in the BN organic compound, the fragment represented by general formula (2) can significantly adjust the light color, expand the resonance delocalization degree of the conjugated framework, and improve the quantum yield;

[0072] (8) The introduction of the fragment represented by general formula (2) into the compound of the present invention can enhance the rigidity of the molecule itself, further reduce the adverse factors of widening the emission half-peak width caused by vibration and rotation of the fragment in the molecule, and will not affect the excited state characteristics of this type of resonance-type compound. BRIEF DESCRIPTION OF THE DRAWINGS

[0073] Figure 1 This is a schematic diagram of the structure of an OLED device in which the materials listed in the present invention are applied;

[0074] Among them, 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 DESCRIPTION

[0075] The present invention will be described in detail below with reference to the accompanying drawings and embodiments.

[0076] In the present invention, unless otherwise specified, HOMO means the highest occupied molecular orbital of a molecule, and LUMO means the lowest unoccupied molecular orbital of a molecule. In addition, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and comparison between energy levels also refers to comparison of their absolute values. Those skilled in the art will appreciate that the larger the absolute value of an energy level, the lower the energy of that energy level.

[0077] Any numerical range listed herein is intended to include all subranges with the same numerical precision within the listed range. For example, "1.0 to 10.0" means all subranges (including 1.0 and 10.0) included between the listed minimum value 1.0 and the listed maximum value 10.0, that is, all subranges with a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0. Any maximum numerical limit listed herein is intended to include all smaller numerical limits included herein, and any minimum numerical limit listed herein is intended to include all larger numerical limits included herein. Therefore, the applicant reserves the right to amend this specification, including the claims, to clearly describe any subranges falling within the scope clearly described herein.

[0078] In the drawings, the dimensions of layers and regions may be exaggerated for clarity. It will also be understood that when a layer or element is referred to as being "on" another layer or substrate, the layer or element may be directly on the other layer or substrate, or intervening layers may be present. Furthermore, it will be understood that when a layer is referred to as being "between" two layers, the layer may be the only layer between the two layers, or one or more intervening layers may be present. Like reference numerals refer to like elements throughout.

[0079] In the present invention, when describing electrodes, organic electroluminescent devices, and other structures, terms such as "upper," "lower," "top," and "bottom" that indicate orientation refer only to a particular state and do not imply that the structure can exist only in the described orientation. Conversely, if the structure can be repositioned, such as inverted, the orientation of the structure will change accordingly. Specifically, in the present invention, the "bottom" or "lower" side of an electrode refers to the side of the electrode closest to the substrate during fabrication, while the opposite side, farther from the substrate, is the "top" or "upper" side.

[0080] In the present invention, substituted or unsubstituted C6-C 30 Aryl and / or substituted or unsubstituted C3-C 30 Heteroaryl refers to substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted substituted or unsubstituted triphenylene, substituted or unsubstituted perylene, substituted or unsubstituted indenyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, 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 pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted unsubstituted benzimidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenanthrazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, combinations thereof, or fused rings of combinations thereof, but are not limited thereto.

[0081] The C of the present invention 1-10 Alkyl (including straight-chain alkyl and branched-chain alkyl) refers 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 is not limited thereto.

[0082] The halogen atom mentioned in the present invention refers to a chlorine atom, a fluorine atom or a bromine atom, but is not limited thereto.

[0083] The C1-C of the present invention 10 The alkoxy group refers to, but is not limited to, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, isopropoxy, and the like.

[0084] The C3-C 20 A cycloalkyl group refers to a monovalent monocyclic saturated hydrocarbon group containing 3 to 20 carbon atoms as ring atoms. In this article, a C4-C9 cycloalkyl group is preferably used, a C5-C8 cycloalkyl group is more preferably used, and a C5-C7 cycloalkyl group is particularly preferably used. Non-limiting examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, adamantyl, and cycloheptyl.

[0085] As the substrate for the organic electroluminescent device of the present invention, any substrate commonly used for 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 varying mechanical strength, thermal stability, transparency, surface smoothness, and water resistance. Depending on the properties of the substrate, its use varies. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.

[0086] A first electrode is formed on a substrate, and the first electrode and the second electrode may be opposite to 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 metal mixture. The thickness of the first electrode layer depends on the material used, and is typically 50-500 nm, preferably 70-300 nm, and more preferably 100-200 nm.

[0087] The organic functional material layer disposed between the first electrode and the second electrode includes, from bottom to top, a hole transport region, a light emitting layer and an electron transport region.

[0088] Herein, the hole transport region constituting the organic electroluminescent device can be exemplified by a hole injection layer, a hole transport layer, an electron blocking layer, and the like.

[0089] As materials for the hole injection layer, the hole transport layer, and the electron blocking layer, any material can be selected from known materials used in OLED devices.

[0090] Examples of the above materials include phthalocyanine derivatives, triazole derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, oxadiazole derivatives, hydrazone derivatives, stilbene derivatives, pyridinoline derivatives, polysilane derivatives, imidazole derivatives, phenylenediamine derivatives, amino-substituted quilone derivatives, styrylanthracene derivatives, styrylamine derivatives and other styrene compounds, fluorene derivatives, spirofluorene derivatives, silazane derivatives, aniline copolymers, porphyrin compounds, carbazole derivatives, polyarylalkane derivatives, polyphenylene vinyl and its derivatives, polythiophene and its derivatives, poly-N-vinylcarbazole derivatives, thiophene oligomers and other conductive polymer oligomers, aromatic tertiary amine compounds, styrene amination compounds, compounds, triamines, tetraamines, benzidines, propargyl diamine derivatives, p-phenylenediamine derivatives, m-phenylenediamine derivatives, 1,1'-bis(4-diarylaminophenyl)cyclohexane, 4,4'-bis(diarylamino)biphenyls, bis[4-(diarylamino)phenyl]methanes, 4,4'-bis(diarylamino)terphenyls, 4,4'-bis(diarylamino)quaterphenyls, 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.

[0091] 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 article, the thickness of the various hole carrier conductive film layers with different functions described above is not particularly limited.

[0092] The hole injection layer contains a host organic material that can conduct holes, and also contains a P-type dopant material with a deep HOMO energy level (the corresponding LUMO energy level will also be very deep). Based on empirical summary, in order to achieve smooth hole injection from the anode to the organic film layer, the HOMO energy level of the host organic material used in the anode interface buffer layer must have certain characteristics with the P-doped material. Only then can the charge transfer state between the host material and the dopant material be achieved, and ohmic contact between the buffer layer and the anode can be achieved, achieving efficient injection and conduction of holes from the electrode.

[0093] In view of the above empirical summary, for hole-type host materials with different HOMO energy levels, different P-doped materials need to be selected to match them in order to achieve ohmic contact at the interface and improve the hole injection effect.

[0094] Therefore, in one embodiment of the present invention, in order to better inject holes, the hole injection layer further includes a P-type dopant material with charge conductivity selected from the following: quinone derivatives, such as tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinodimethane (F4-TCNQ); or hexaazatriphenylene derivatives, such as 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN); or cyclopropane derivatives, such as 4,4',4"-((1E,1'E,1"E)-cyclopropane-1,2,3-trimethylenetris(cyanoformylidene))tris(2,3,5,6-tetrafluorobenzyl); or metal oxides, such as tungsten oxide and molybdenum oxide, but not limited thereto.

[0095] In the hole injection layer of the present invention, the ratio of the hole transport material to the P-type doping material is 99:1-95:5, preferably 99:1-97:3, based on mass.

[0096] The thickness of the hole injection layer of the present invention may be 5-100 nm, preferably 5-50 nm, and more preferably 5-20 nm, but the thickness is not limited to this range.

[0097] The thickness of the hole transport layer of the present invention may be 5 to 200 nm, preferably 10 to 150 nm, and more preferably 20 to 100 nm, but the thickness is not limited to this range.

[0098] The thickness of the electron blocking layer of the present invention may be 1-20 nm, preferably 5-10 nm, but the thickness is not limited to this range.

[0099] After forming the hole injection layer, the hole transport layer and the electron blocking layer, a corresponding light emitting layer is formed on the electron blocking layer.

[0100] The light-emitting layer may include a host material and a dopant material. The host material may be a common green light host material in the art, and the dopant material may be a boron-containing organic compound represented by the general formula (1) of the present invention.

[0101] In the light-emitting layer of the present invention, the ratio of the host material to the dopant material used is 99:1-70:30, preferably 99:1-85:15 and more preferably 97:3-87:13, based on mass.

[0102] The thickness of the light-emitting layer can be adjusted to optimize the luminous efficiency and driving voltage. The preferred thickness range is 5 nm to 50 nm, more preferably 10-50 nm, and more preferably 15-30 nm, but the thickness is not limited to this range.

[0103] In the present 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.

[0104] The hole blocking layer is a layer that blocks the holes injected from the anode from passing through the light-emitting layer and entering the cathode, thereby extending the life of the device and improving the performance of the device. The hole blocking layer of the present invention can be arranged on the light-emitting layer. As the hole blocking layer material of the organic electroluminescent device of the present invention, compounds with hole blocking effects known in the prior art can be used, for example, phenanthroline derivatives such as bathocuproine (called BCP), metal complexes of hydroxyquinoline derivatives such as aluminum (III) bis (2-methyl-8-quinolinol) -4-phenylphenolate (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 ) and other pyrimidine derivatives, etc. The thickness of the hole blocking layer of the present invention may be 2-200 nm, preferably 5-150 nm and more preferably 10-100 nm, but the thickness is not limited to this range.

[0105] The electron transport layer can be disposed on the light-emitting layer or (if present) the hole blocking layer. The electron transport layer material is a material that readily accepts electrons from the cathode and transfers the received electrons to the light-emitting layer. Preferably, the material has a high electron mobility. As the electron transport layer of the organic electroluminescent device of the present invention, electron transport layer materials for organic electroluminescent devices known in the prior art can be used, for example, metal complexes of hydroxyquinoline derivatives represented by Alq3, BAlq and Liq, various rare earth metal complexes, triazole derivatives, 2,4-bis(9,9-dimethyl-9H-fluoren-2-yl)-6-(naphthalene-2-yl)-1,3,5-triazine (CAS No.: 1459162-51-6) and other triazine derivatives, 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole (CAS No.: 561064-11-7, commonly known as LG201) and other imidazole derivatives, 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 may be 10-80 nm, preferably 20-60 nm, and more preferably 25-45 nm, but the thickness is not limited to this range.

[0106] The electron injection layer may be provided above the electron transport layer. The electron injection layer material is generally preferably a material having a low work function so that electrons are easily injected into the organic functional material layer. As the electron injection layer material of the organic electroluminescent device of the present invention, the electron injection layer materials for organic electroluminescent devices known in the prior art can be used, for example, lithium; lithium salts such as 8-hydroxyquinoline lithium, 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.

[0107] The second electrode may be disposed above the electron transport region. The second electrode may be a cathode. The second electrode may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode. When the second electrode is a transmissive electrode, the second electrode may include, for example, Li, Yb, Ca, LiF / Ca, LiF / Al, Al, Mg, BaF, Ba, Ag, or a compound or mixture thereof; when the second electrode is a semi-transmissive electrode or a reflective electrode, the second electrode may include, but is not limited to, Ag, Mg, Yb, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, or a compound or mixture thereof. The thickness of the cathode depends on the material used and is typically 10-50 nm, preferably 15-20 nm.

[0108] The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign 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.

[0109] The method for preparing an organic electroluminescent device of the present invention comprises 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 cover layer, on a substrate. In this regard, vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, or LITI methods 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.

[0110] The raw materials involved in the synthesis examples of the present invention can be purchased from the market or prepared by conventional preparation methods in the art;

[0111] Example 1 Synthesis of Compound 2:

[0112]

[0113]

[0114] Preparation of intermediate I1:

[0115] To a three-necked flask, add raw material A1 (50.0 mmol) and 500 mL of anhydrous tetrahydrofuran. Use nitrogen protection and cool to -78°C in a low-temperature tank. Slowly add 32 mL of a 1.6 M solution of tert-butyl lithium in n-hexane. Stir at -78°C for 2 hours. Continue to add raw material A2 (52 mmol). Keep stirring at -78°C for 6 hours. Slowly return to room temperature and stir for 10 hours. After the reaction is completed, 10 mL of ethanol is added to quench the reaction. The reaction solution is concentrated and purified by silica gel column using petroleum ether: ethyl acetate = 1:1 as a developing solvent to obtain intermediate I1 with a yield of 80.2%. LC-MS: Measured value: 256.01 ([M+H] + ), theoretical value: 255.16.

[0116] Preparation of intermediate I2:

[0117] To a three-necked flask, raw material A4 (10 mmol) was added sequentially, followed by 50 mL of anhydrous DMF. Under nitrogen protection, 65% NaH (net content 12 mmol) coated in mineral oil was added portionwise in an ice-water bath. The mixture was stirred for 0.5 hours, and a solution of raw material A3 dissolved in 10 mL of anhydrous DMF was slowly added dropwise. After the reaction was completed, 100 mL of water was added to quench the reaction, and the large amount of white precipitate was filtered. The precipitate was collected and dissolved in dichloromethane solution, dried over anhydrous sodium sulfate, and filtered. The reaction solution was concentrated and purified on a silica gel column using a developing solvent of petroleum ether:ethyl acetate = 100:1 to obtain intermediate I2 in a yield of 75.5%. LC-MS: Measured value: 468.18 ([M+H] + ), theoretical value: 467.10.

[0118] Preparation of intermediate I3:

[0119] To a two-necked flask were added intermediate I2 (10.0 mmol), intermediate I1 (10.0 mmol), 0.1 mmol of Pd(PPh3)4 catalyst, a 10:1 mixture of tetrahydrofuran and water, and potassium carbonate (20 mmol), followed by stirring at 80°C for 6 hours under nitrogen. After cooling, the organic phase was separated and collected, dried over anhydrous sodium sulfate, filtered, concentrated, and separated by silica gel column development using petroleum ether and ethyl acetate in a 10:1 ratio to afford intermediate I3 in a yield of 92.5%. LC-MS: Measured value: 517.56 ([M+H] + ), theoretical value: 516.25.

[0120] Preparation of compound 2:

[0121] Intermediate I3 (5.0 mmol) and tert-butylbenzene (50 mL) were added sequentially to a cryogenic eggplant-shaped flask. The temperature was lowered to -78°C, and a solution of tert-butyllithium (5.5 mmol) in n-hexane was slowly added. The mixture was stirred and warmed to room temperature. The n-hexane was then removed under negative pressure at 60°C. A nitrogen atmosphere was then applied. After reacting for 2 hours, BBr3 (6.0 mmol) was added at -42°C. The temperature was maintained with stirring for 2 hours, and the mixture was slowly returned to room temperature. After stirring at room temperature for 10 hours, DIPEA (N,N-diisopropylethylamine) (10 mmol) was added in an ice-water bath, and the mixture was heated to 120°C and refluxed for 36 hours. The reaction mixture was cooled to room temperature, filtered through celite, and the organic phase was collected and the high-boiling solvent was removed by distillation under reduced pressure. The mixture was dissolved in dichloromethane, dried over anhydrous sodium sulfate, filtered, and the organic phase was concentrated and purified by silica gel column chromatography using toluene as the developing solvent to obtain compound 2 in a yield of 52.2%. LC-MS: Measured value: 491.27 ([M+H] + ), theoretical value: 490.26.

[0122] Example 2 Synthesis of Compound 12:

[0123]

[0124] Preparation of intermediate I4:

[0125] To a two-necked flask were added starting material A4 (10.0 mmol), starting material A5 (10.0 mmol), 0.1 mmol of Pd2(dba)3 catalyst, 20 mmol of potassium tert-butoxide, 0.3 mmol of tri-tert-butylphosphine, and 50 mL of toluene. The mixture was then stirred under reflux at 110°C for 6 hours under nitrogen protection. After cooling, the organic phase was filtered and concentrated. The compound was separated by silica gel column development using petroleum ether:ethyl acetate = 50:1 to obtain intermediate I3 in a yield of 75.2%. LC-MS: Measured value: 454.09 ([M+H] + ), theoretical value: 453.05.

[0126] The preparation of intermediate I5 was based on intermediate I3. LC-MS: Measured value: 503.18 ([M+H] + ), theoretical value: 502.20.

[0127] Preparation of compound 12: Reference compound 2; LC-MS: Measured value: 477.32 ([M+H] + ), theoretical value: 476.22.

[0128] Example 3 Synthesis of Compound 18:

[0129]

[0130]

[0131] The preparation method of intermediate I6 refers to intermediate I2; LC-MS: measured value: 430.26 ([M+H] + ), theoretical value: 429.28.

[0132] The preparation method of intermediate I7 refers to intermediate I3; LC-MS: measured value: 221.08 ([M+H] + ), theoretical value: 220.12.

[0133] Preparation of intermediate I8:

[0134] To a two-necked flask were added intermediate I7 (10.0 mmol), starting material A8 (12.0 mmol), 0.5 mmol of Pd(OAc)2 catalyst, and 50 mL of anhydrous DMF. The mixture was stirred under nitrogen for 24 hours at room temperature. The organic phase was concentrated and the compound was separated by silica gel column development using petroleum ether:ethyl acetate = 100:1 to obtain intermediate I8 in a yield of 40.2%. LC-MS: Measured value: 221.10 ([M+H] + ), theoretical value: 220.12.

[0135] The preparation method of intermediate I9 refers to intermediate I6; LC-MS: measured value: 628.40 ([M+H] + ), theoretical value: 627.38.

[0136] Preparation of compound 18:

[0137] To a single-necked flask, intermediate I9 (1 mmol) and tert-butylbenzene (30 mL) were added sequentially. Under nitrogen protection, a tert-butylbenzene solution of BI3 (2.0 mmol) was added, and the mixture was refluxed at 180°C for 48 hours. The mixture was cooled and directly spin-dried. A buffer solution was then added, and the mixture was extracted with ethyl acetate (300 mL). The mixture was washed with saturated brine and dried over anhydrous sodium sulfate. The organic phase was concentrated and purified by silica gel column chromatography using toluene as the developing solvent. The yield was 32.1%. LC-MS: Measured value: 636.44 ([M+H] + ), theoretical value: 635.36.

[0138] Example 4 Synthesis of Compound 41:

[0139]

[0140]

[0141] Preparation of intermediate I10:

[0142] NBS (10.0 mmol), AlCl3 (10.0 mmol), and 50 mL of dichloromethane were added to a single-necked flask in sequence and stirred at room temperature for 3 hours under nitrogen protection. The reaction solution was then cooled to -42°C and raw material A1 (15 mmol) was added for 4 hours. After returning to room temperature, stirring was continued for 24 hours. The organic phase was concentrated and the compound was separated by silica gel column development using petroleum ether:ethyl acetate = 100:1 to obtain intermediate I10 in a yield of 61.5%. LC-MS: Measured value: 207.89 ([M+H] + ), theoretical value: 206.99.

[0143] Preparation of intermediate I11:

[0144] To a single-necked flask, intermediate I10 (10.0 mmol), palladium acetate (0.5 mmol), sodium tert-butoxide (20 mmol), 50 mL of 1,4-dioxane, and starting material A9 (15 mmol) were added sequentially. The mixture was heated under reflux for 10 hours under nitrogen protection. The reaction mixture was then filtered, the organic phase was concentrated, and the compound was separated by silica gel column development using petroleum ether:ethyl acetate = 1:1 to obtain intermediate I11 in a yield of 85.5%. LC-MS: Measured value: 256.19 ([M+H] + ), theoretical value: 255.16.

[0145] The preparation of intermediate I12 was based on intermediate I5. LC-MS: Measured value: 503.18 ([M+H] + ), theoretical value: 502.20.

[0146] Preparation of intermediate I13 was based on compound 12. LC-MS: Measured value: 477.21 ([M+H] + ), theoretical value: 476.22.

[0147] Preparation of intermediate I14:

[0148] To a single-necked flask, intermediate I13 (10.0 mmol), starting material A9 (15 mmol), [Ir(COD)(OCH3)]2 (0.06 mmol), and 50 mL of tetrahydrofuran were added sequentially. The reaction was allowed to react at room temperature for 10 hours under nitrogen. The reaction was then filtered, the organic phase concentrated, and the compound was separated by silica gel column development using petroleum ether:ethyl acetate in a ratio of 1:1 to afford intermediate I14 in a 92.1% yield. This reaction exhibited good selectivity (reference DOI: 10.31635 / ccschem.021.202101033). LC-MS: Measured: 603.20 ([M+H] + ), theoretical value: 602.31.

[0149] Preparation of compound 41:

[0150] To a two-necked flask were added intermediate I14 (10.0 mmol), starting material A10 (10.0 mmol), 0.1 mmol of Pd(PPh3)4 catalyst, 50 mL of a 10:1 tetrahydrofuran:water mixture, and 20 mmol of potassium carbonate. The mixture was stirred at 80°C for 6 hours under nitrogen atmosphere. After cooling, the organic phase was separated and collected, dried over anhydrous sodium sulfate, filtered, and concentrated. The compound was separated by silica gel column chromatography using petroleum ether:ethyl acetate (10:1) as the developing solvent to obtain compound 41 in a yield of 95.2%. LC-MS: Measured value: 708.41 ([M+H] + ), theoretical value: 707.30.

[0151] Example 5 Synthesis of Compound 43:

[0152]

[0153]

[0154] Preparation of intermediate 115.

[0155] To a two-necked flask were added the raw material A11 (10.0 mmol), the intermediate I10 (10.0 mmol), 0.1 mmol of Pd2(dba)3 catalyst, 20 mmol of potassium tert-butoxide, 0.3 mmol of tri-tert-butylphosphine, and 100 mL of toluene. The mixture was then stirred under nitrogen at reflux at 120°C for 6 hours. After cooling, the organic phase was filtered and concentrated. The compound was separated by silica gel column chromatography using petroleum ether as the developing solvent to obtain the intermediate I15 in a yield of 82.1%. LC-MS: Measured value: 221.15 ([M+H] + ), theoretical value: 220.12.

[0156] The preparation of intermediate I16 was based on intermediate I4. LC-MS: Measured value: 608.25 ([M+H] + ), theoretical value: 607.29.

[0157] Preparation of intermediate I17 was based on compound 12. LC-MS: Measured value: 582.33 ([M+H] + ), theoretical value: 581.32.

[0158] Preparation of intermediate I18 was based on compound I14. LC-MS: Measured value: 708.35 ([M+H] + ), theoretical value: 707.40.

[0159] The preparation of compound 43 was based on compound 41. LC-MS: Measured value: 813.46 ([M+H]+ ), theoretical value: 812.40.

[0160] Example 6 Synthesis of Compound 49:

[0161]

[0162] The preparation of intermediate I19 was based on intermediate I16. LC-MS: Measured value: 606.25 ([M+H] + ), theoretical value: 605.28.

[0163] Preparation of intermediate I20 Compound 12. LC-MS: Found: 580.33 ([M+H] + ), theoretical value: 579.30.

[0164] The preparation of intermediate I21 was based on intermediate I14. LC-MS: Measured value: 706.38 ([M+H] + ), theoretical value: 705.39.

[0165] The preparation of compound 49 was based on compound 41. LC-MS: Measured value: 811.39 ([M+H] + ), theoretical value: 810.38.

[0166] Example 7 Synthesis of Compound 64:

[0167]

[0168] The preparation of compound 64 was based on the synthesis of compound 49. LC-MS: Measured value: 784.35 ([M+H] + ), theoretical value: 783.33.

[0169] Example 8 Synthesis of Compound 65:

[0170]

[0171] The preparation of compound 65 was based on the synthesis of compound 49. LC-MS: Measured value: 889.48 ([M+H] + ), theoretical value: 888.43.

[0172] Example 9 Synthesis of Compound 115:

[0173]

[0174] Preparation of intermediate I22:

[0175] To a single-necked flask, raw material A6 (10.0 mmol), raw material A13 (10.0 mmol), cesium carbonate (12.0 mmol), and 100 mL of NMP were added sequentially. Under nitrogen protection, the mixture was sealed and stirred at 160°C for 14 hours. After cooling, the organic phase was filtered and concentrated. The compound was separated by silica gel column using petroleum ether as the developing solvent to obtain intermediate I22 in a yield of 66.8%. LC-MS: Measured value: 301.25 ([M+H] + ), theoretical value: 300.19.

[0176] The preparation of intermediate I23 was based on intermediate I9. LC-MS: Found: 499.25 ([M+H] + ), theoretical value: 498.28.

[0177] Compound 115 was prepared by referring to compound 18. The crude product was separated by column chromatography using pure petroleum ether and purified by sublimation. The yield was 10%. LC-MS: Measured value: 507.35 ([M+H] + ), theoretical value: 506.27.

[0178] Example 10 Synthesis of Compound 116:

[0179] Compound 116 was prepared by referring to compound 115 and separated by petroleum ether column chromatography. Compound 116 had a higher yield than compound 115. The two had a certain difference in polarity. The crude product was further separated by gradient sublimation, and the final yield of compound 116 was 18%. LC-MS: Measured value: 507.12 ([M+H] + ), theoretical value 506.26.

[0180] The structural characteristics of the compounds obtained in each example are shown in Table 1

[0181] Table 1

[0182] Compound Structural characterization 2 <![CDATA[Elemental analysis structure (C 34 H 32 B2N2) Theoretical values: C, 83.30; H, 6.58; N, 5.71. Test values: C, 83.27; H, 6.52; N, 5.70.]]> 12 <![CDATA[Elemental analysis structure (C 32 H 26 B2N2O) Theoretical values: C, 80.71; H, 5.50; N, 5.88; Measured values: C, 80.73; H, 5.48; N, 5.91.]]> 18 <![CDATA[Elemental analysis structure (C 44 H 43 B2N3) Theoretical values: C, 83.16; H, 6.82; N, 6.61; Measured values: C, 83.11; H, 6.86; N, 6.65.]]> 41 <![CDATA[Elemental analysis structure (C 47 H 35 B2N5O) Theoretical values: C, 79.80; H, 4.99; N, 9.90; Measured values: C, 79.82; H, 4.97; N, 9.95.]]> 43 <![CDATA[Elemental analysis structure (C 55 H 46 B2N6) Theoretical values: C, 81.29; H, 5.71; N, 10.34; Measured values: C, 81.26; H, 5.72; N, 10.36.]]> 49 <![CDATA[Elemental analysis structure (C 55 H 44 B2N6) Theoretical values: C, 81.49; H, 5.47; N, 10.37; Test values: C, 81.50; H, 5.49; N, 10.34.]]> 64 <![CDATA[Elemental analysis structure (C 53 H 39 B2N5O) Theoretical values: C, 81.24; H, 5.02; N, 8.94; Measured values: C, 81.21; H, 5.01; N, 8.92.]]> 65 <![CDATA[Elemental analysis structure (C 61 H 50 B2N6) Theoretical values: C, 82.44; H, 5.67; N, 9.46; Measured values: C, 82.42; H, 5.69; N, 9.43.]]> 115 <![CDATA[Elemental analysis structure (C 34 H 32 B2N2O) Theoretical values: C, 80.66; H, 6.37; N, 5.53; Test values: C, 80.64; H, 6.34; N, 5.55.]]> 116 <![CDATA[Elemental analysis structure (C 34 H 32 B2N2O) Theoretical values: C, 80.66; H, 6.37; N, 5.53; Measured values: C, 80.65; H, 6.39; N, 5.51.]]>

[0183] The compounds of the present invention can be used in light-emitting devices as doping materials for the light-emitting layer. The physical and chemical properties of the compounds prepared in the above embodiments of the present invention were tested, and the test results are shown in Table 2:

[0184] Table 2

[0185]

[0186] Note: Glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter from NETZSCH, Germany) at a heating rate of 10°C / min. The thermal gravimetric temperature (Td) is the temperature at which the weight loss reaches 1% in a nitrogen atmosphere, measured on a TGA-50H thermogravimetric analyzer from Shimadzu Corporation, Japan, with a nitrogen flow rate of 20 mL / min. The highest occupied molecular orbital (HOMO) energy level was determined using an ionization energy measurement system (IPS-3) in a nitrogen environment. Eg was determined using a dual-beam UV-visible spectrophotometer (Model: TU-1901), where LUMO = HOMO + Eg. PLQY (fluorescence quantum yield) and FWHM (full width at half maximum) were measured in thin films using a Horiba Fluorolog-3 series fluorescence spectrometer.

[0187] As can be seen from the data in the table above, the compounds of the present invention have high glass transition temperatures and decomposition temperatures. When used as dopants in the light-emitting layer, they can inhibit the crystallization and film phase separation of the material; they can also inhibit the decomposition of the material at high brightness, thereby improving the device's operating life. Furthermore, the compounds of the present application have shallow HOMO energy levels. When added as dopants to the host material, they can help suppress the generation of carrier traps, improve the host-guest energy transfer efficiency, and thus enhance the device's luminous efficiency.

[0188] The compounds of the present invention have a high fluorescence quantum efficiency as doping materials, and the fluorescence quantum efficiency of the materials is greater than 85%; at the same time, the spectral FWHM of the materials is narrow, which can effectively improve the color gamut of the device and improve the luminous efficiency of the device; finally, the evaporation decomposition temperature of the materials is high, which can inhibit the evaporation decomposition of the materials and effectively improve the life of the device.

[0189] The following describes in detail the application effects of the OLED materials synthesized by the present invention in devices using device Examples 1-10 and Comparative Example 1. The device fabrication processes for Device Examples 2-10 and Comparative Example 1 are identical to those of Device Example 1, utilizing the same substrate and electrode materials, with the same electrode thickness. The only difference is the material used in the light-emitting layer. The layer structures and test results for each device example are shown in Table 3.

[0190] Device Example 1

[0191] like Figure 1As shown, the transparent substrate layer 1 is a transparent PI film. The ITO anode layer 2 (film thickness 150nm) is washed, i.e., washed with a detergent (Semiclean M-L20), washed with pure water, dried, and then subjected to UV-ozone cleaning to remove organic residues on the transparent ITO surface. On the washed ITO anode layer 2, a 10nm thick layer of HT-1 and HI-1 is deposited using a vacuum evaporation apparatus as a hole injection layer 3. The mass ratio of HT-1 to HI-1 is 97:3. HT-1 is then evaporated to a thickness of 60nm as a hole transport layer 4. EB-1 is then evaporated to a thickness of 30nm as an electron blocking layer 5. After the electron blocking material deposition is completed, the light-emitting layer 6 of the OLED light-emitting device is fabricated. CBP is used as the first host material, DMAC-BP is used as the second host material, and Compound 2 is used as the dopant material. The mass ratio of CBP, the second host material, and Compound 2 is 67:30:3, and the light-emitting layer thickness is 30nm. After the light-emitting layer 6, HB-1 was vacuum-deposited to a thickness of 5 nm. This layer served as the hole-blocking layer 7. After the hole-blocking layer 7, ET-1 and Liq were vacuum-deposited in a 1:1 weight ratio to form a 30 nm thick film. This served as the electron-transporting layer 8. On the electron-transporting layer 8, a 1 nm thick LiF layer was vacuum-deposited. This served as the electron-injection layer 9. On the electron-injection layer 9, an 80 nm thick Mg:Ag electrode layer was vacuum-deposited in a 1:9 weight ratio. This served as the cathode layer 10.

[0192] The molecular structure formula of the relevant materials is shown below:

[0193]

[0194] After completing the OLED light-emitting device as described above, the anode and cathode were connected using a known drive circuit, and the device's current efficiency and lifetime were measured. Examples and comparative examples of devices prepared using the same method are shown in Table 3; the test results for the current efficiency and LT95 lifetime of the resulting devices are shown in Table 4.

[0195] Table 3

[0196]

[0197] Table 4

[0198]

[0199] Note: Voltage, current efficiency, and luminescence peak were measured using an IVL (current-voltage-luminance) test system (Suzhou Fushida Scientific Instrument Co., Ltd.); the lifespan test system was an EAS-62C OLED device lifespan tester from Japan System Giken Co., Ltd.; LT95 refers to the time it takes for the device's luminance to decay to 95%; all data are measured at 10 mA / cm 2 Next test.

[0200] It can be seen from the device data results in Table 4 that, compared with the device comparative example 1, the current efficiency and device life of the organic light-emitting devices of Examples 1-10 of the present invention are greatly improved compared with the OLED devices of known materials.

[0201] In summary, the above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A resonance-type organic compound containing a BN heterocyclic structure, characterized in that: The structure of the organic compound is shown in any one of the general formulas (6-2) to (6-6): In general formula (6-2) to general formula (6-6), X0 is one of -O- and -S-; X1 represents one of -O- and -S-; X2 represents one of a single bond, -O- and -S-; m represents 0 or 1; R3 represents a substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 One of the heteroaryl groups; Y1 and Y2 are independently represented by B or N, and Y1 and Y2 are different; Each occurrence of Z, whether the same or different, is represented by C-R2; R2 appears the same or different each time and represents H, deuterium atom, halogen atom, cyano group, C 1-10 Alkyl or silyl, substituted or unsubstituted C 6-30 Aryl, substituted or unsubstituted C 3-30 One of the heteroaryl groups; The substituents for the substituent group are optionally selected from halogen atoms, deuterium atoms, cyano groups, C 1-10 One or more of alkyl groups.

2. The resonance type organic compound according to claim 1, characterized in that The substituted or unsubstituted C6-C 30 Aryl refers to substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted tetraphenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted p-terphenyl, substituted or unsubstituted m-terphenyl, substituted or unsubstituted substituted or unsubstituted triphenylene, substituted or unsubstituted perylenyl, substituted or unsubstituted indenyl; The substituted or unsubstituted C3-C 30 Heteroaryl refers to substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted pyrrolyl, 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 triazinyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted benzo imidazolyl, substituted or unsubstituted indolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted naphthyridinyl, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted acridinyl, substituted or unsubstituted phenanthazinyl, substituted or unsubstituted phenathiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl; The C 1-10 Alkyl refers 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; The halogen atom refers to a chlorine atom, a fluorine atom or a bromine atom.

3. The resonance type organic compound according to claim 1, characterized in that The R2 each time appears the same or different represents hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, phenyl, deuterated phenyl, biphenyl, deuterated biphenyl, deuterated terphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, pyridyl, quinolyl, furyl, thienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, N-phenylcarbazolyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirofluorenyl, methyl substituted phenyl, ethyl substituted deuterated phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, methyl-substituted biphenyl, ethyl-substituted biphenyl, isopropyl-substituted biphenyl, tert-butyl-substituted biphenyl, deuterated methyl-substituted phenyl, deuterated ethyl-substituted phenyl, deuterated isopropyl-substituted phenyl, deuterated tert-butyl-substituted phenyl, deuterated methyl-substituted biphenyl, deuterated ethyl-substituted biphenyl, deuterated isopropyl-substituted biphenyl, deuterated tert-butyl-substituted biphenyl; The substituent for the substituent group may be selected from one or more of a deuterium atom, a chlorine atom, a fluorine atom, a cyano group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-amyl group, a tert-butyl group, and a butyl group.

4. A resonance type organic compound, characterized in that The specific structural formula of the organic compound is any one of the following structures:

5. An organic light-emitting device comprising a cathode, an anode, and a functional layer, wherein the functional layer is located between the cathode and the anode, characterized in that: The functional layer comprises the resonance-type organic compound containing a BN heterocyclic structure according to any one of claims 1 to 4.

6. The organic light-emitting device according to claim 5, wherein the functional layer comprises a light-emitting layer, The doping material of the light-emitting layer is the resonance-type organic compound containing a BN heterocyclic structure according to any one of claims 1 to 4.

7. The organic light-emitting device according to claim 6, characterized in that: The light-emitting layer comprises a first host material, a second host material and a doping material, at least one of the first host material and the second host material is a TADF material, and the doping material is the resonance-type organic compound containing a BN heterocyclic structure according to any one of claims 1 to 4.

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