A triphenylethylene derivative containing a boron heterocycle and an organic electroluminescent device containing the same

Abstract

The invention discloses a triphenylethylene derivative containing a boron heterocycle and an organic electroluminescent device containing the same. The triphenylethylene derivative containing a boron heterocycle has a structure as shown in formula (1). The triphenylethylene derivative containing a boron heterocycle provided by the invention is used as a luminescent material of an organic electroluminescent device, and the prepared organic electroluminescent device has high luminous efficiency and high color purity.

Description

Technical Field

[0001] The invention belongs to the technical field of luminescent materials and luminescent devices, and in particular relates to a triphenylethylene derivative containing a boron heterocycle and an organic electroluminescent device containing the same. Background Art

[0002] An organic electroluminescent device includes an anode, a cathode, and a light-emitting layer between the anode and the cathode. In addition, there are organic electroluminescent devices with a stacked layer structure, including organic layers such as a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

[0003] When voltage is applied to an organic electroluminescent device, holes are injected from the anode and electrons are injected from the cathode. In the light-emitting layer, the injected holes and electrons combine to form excitons. In the process of the excitons returning from the excited state to the ground state, energy is released in the form of light.

[0004] By using different luminescent materials in the luminescent layer, multiple colors of light can be emitted. Therefore, organic electroluminescent devices are widely used in display. Among them, the research on the materials of the three primary colors of red, green and blue is the most active. Through the improvement of organic luminescent materials, the performance of organic electroluminescent devices is gradually improving.

[0005] For example, Patent Document 1 (JP 161218 / 2019) discloses a technology in which anthracene-based compound and a pyrene-based compound are used as light-emitting materials for an organic electroluminescent element, which can achieve a good carrier balance, thereby improving device efficiency and device life.

[0006] In addition, in order to improve the brightness efficiency and lifespan, Patent Document 2 (EP 3150579B1) discloses a compound for a light-emitting device, the compound having a fluoranthene skeleton and an aromatic heterocyclic ring containing an electron acceptor N atom.

[0007] In patent document 3 (US 2019 / 0013478A1), a bipolar p-conjugated boron compound is disclosed. As a fluorescent compound in an organic electroluminescent device, this compound can conform to various energy levels and can be used to prepare an organic electroluminescent device with high luminous efficiency and stable storage at high temperatures.

[0008] Although the luminescence performance of devices is constantly improving, high-performance devices have increasingly higher requirements for materials, and the field of organic electroluminescence still needs to develop new materials that can further improve device performance. Summary of the invention

[0009] The object of the present invention is to provide a triphenylethylene derivative containing a boron heterocycle, and a blue light emitting organic electroluminescent device with high luminous efficiency and high color purity using the same.

[0010] The purpose of the present invention is achieved through the following technical solutions:

[0011] A triphenylethylene derivative containing a boron heterocycle, the general structural formula of which is shown below:

[0012]

[0013] In formula (1),

[0014] One of X1 and X2 is B-Ar1, and the other is O, S or N-Ar2; Ar1 ​​and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms;

[0015] When one of X1 and X2 is N-Ar2, X3 and X4 are CR'; when one of X1 and X2 is O or S, X3 and X4 are each independently selected from N and CR'; wherein R' is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group, an acyl group, a carbonyl group, a carboxyl group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphonyl group having 0 to 20 carbon atoms, and combinations thereof;

[0016] R 11 ~R 14 each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms;

[0017] R 21 ~R 28Each of the following is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 2 ...aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group A substituted or unsubstituted alkenyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group, acyl group, carbonyl group, carboxyl group, ester group, nitrile group, isonitrile group, thiol group, sulfinyl group, sulfonyl group, phosphonyl group having 0 to 20 carbon atoms, and combinations thereof.

[0018] Preferably, X1 is O or S, X2 is B-Ar1, Ar1 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 carbon atoms, and X3 and X4 are selected from N or CR'.

[0019] Preferably, X1 is N-Ar2, X2 is B-Ar1, Ar1 and Ar2 are each independently selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 carbon atoms, and X3 and X4 are CR'.

[0020] Preferably, X1 is B-Ar1, X2 is O or S, Ar1 is selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 carbon atoms, and X3 and X4 are selected from N or CR'.

[0021] Preferably, X1 is B-Ar1, X2 is N-Ar2, Ar1 and Ar2 are each independently selected from substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, or substituted or unsubstituted heteroaryl having 5 to 30 carbon atoms, and X3 and X4 are CR'.

[0022] Preferably, R 11 ~R 14 A hydrogen atom or a deuterium atom.

[0023] Preferably, R 21 ~R 28 A hydrogen atom or a deuterium atom.

[0024] Preferably, Ar1 and Ar2 are each independently selected from substituted or unsubstituted phenyl.

[0025] Preferably, R' is methyl.

[0026] An organic electroluminescent device comprises the above-mentioned triphenylethylene derivative containing a boron heterocycle.

[0027] Preferably, the organic electroluminescent device comprises an anode, a cathode, and an organic layer between the anode and the cathode, wherein at least one organic layer is a light-emitting layer, and the light-emitting layer is a triphenylethylene derivative containing a boron heterocycle or a mixture containing a triphenylethylene derivative containing a boron heterocycle.

[0028] Preferably, the organic electroluminescent device is any one of a fluorescent or phosphorescent monochromatic light-emitting device, a fluorescent-phosphorescent mixed white light-emitting device, a simple light-emitting device with a single light-emitting unit, and a tandem light-emitting device with two or more light-emitting units.

[0029] Preferably, the organic electroluminescent device is applied to flat display devices, special-shaped display devices, curved display devices, flexible display devices and lighting devices, such as display devices of computers and televisions, visual display devices in printers, kitchen appliances and advertising panels, display devices in mobile phones, tablet computers, notebook computers and digital cameras, vehicle and destination displays on buses and trains, wearable devices such as smart watches, glasses or clothes, and light sources, display panels or navigation lights of instruments.

[0030] The compound of formula (1) of the present invention can be used as a luminescent material for an organic electroluminescent device, and can be used alone or as a component of a mixture in the luminescent layer of the device. According to the present invention, a blue light emitting organic electroluminescent device with high luminous efficiency and high color purity, and a material used in the organic thin layer of the organic light emitting device can be provided.

[0031] The present invention has the following beneficial effects:

[0032] The triphenylethylene derivative containing a boron heterocycle of the present invention is used as a light-emitting layer of an organic electroluminescent device and has high light-emitting efficiency and high color purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 A schematic structural diagram of an organic electroluminescent device provided by the present invention. DETAILED DESCRIPTION

[0034] The boron heterocyclic triphenylethylene derivative of the present invention is represented by the following formula (1):

[0035]

[0036] In formula (1), one of X1 and X2 is B-Ar1, and the other is O, S or N-Ar2.

[0037] When one of X1 and X2 is N—Ar2, X3 and X4 are CR′; when one of X1 and X2 is O or S, X3 and X4 are each independently selected from N and CR′.

[0038] X1 to X4 preferably satisfy any one of the following (1) to (7), more preferably any one of (4) to (7), and particularly preferably (7):

[0039] 1) X1 is B-Ar1, X2 is O, S or N-Ar2, and X3 and X4 are CR';

[0040] 2) X1 is B-Ar1, X2 is N-Ar2, and X3 and X4 are CR';

[0041] 3) X1 is B-Ar1, X2 is O or S, and X3 and X4 are N;

[0042] 4) X1 is O, S or N-Ar2, X2 is B-Ar1, X3 and X4 are CR';

[0043] 5) X1 is N-Ar2, X2 is B-Ar1, X3 and X4 are CR';

[0044] 6) X1 is O or S, X2 is B-Ar1, and X3 and X4 are N;

[0045] 7) X1 is O, X2 is B-Ar1, and X3 and X4 are N.

[0046] Wherein, Ar1 and Ar2 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 carbon atoms, preferably a substituted or unsubstituted phenyl group.

[0047] Preferably, Ar1 and Ar2 are each independently selected from phenyl, biphenyl, terphenyl, triphenylene, fluorenyl, naphthyl, dibenzothiophenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, indolecarbazolyl, imidazolyl, pyridyl, triazine, benzimidazolyl, 1,2-azaboryl, 1,3-azaboryl, 1,4-azaboryl and borazine.

[0048] More preferably, Ar1 and Ar2 each independently represent a phenyl group, a biphenyl group, a naphthyl group, an imidazolyl group, a pyridyl group, a triazine group and a benzimidazolyl group.

[0049] Most preferably, Ar1 and Ar2 each independently represent a phenyl group.

[0050] In addition, R' is independently selected from the groups included in the following group (A), preferably from the groups included in the following group (B), more preferably from the groups included in the following group (C), and most preferably from the groups included in the following group (D).

[0051] Group (A) includes hydrogen atoms, deuterium atoms, halogen atoms, cyano groups, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkyl groups having 2 to 20 carbon atoms, The invention also includes a substituted or unsubstituted alkenyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group, an acyl group, a carbonyl group, a carboxyl group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphonyl group having 0 to 20 carbon atoms, and combinations thereof.

[0052] Group (B) includes substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted cycloalkyl groups having 2 to 20 carbon atoms, The invention also includes an alkenyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group, an acyl group, a carbonyl group, a carboxyl group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphonyl group having 0 to 20 carbon atoms, and combinations thereof.

[0053] Group (C) includes substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof.

[0054] Group (D) includes substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, and combinations thereof.

[0055] R 11 To R 14 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.

[0056] Preferably, R 11 To R 14 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 5 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms.

[0057] More preferably, R 11 To R 14 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and a substituted or unsubstituted silyl group having 3 to 5 carbon atoms.

[0058] More preferably, R 11 To R 14 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a methyl group, an isopropyl group, a tert-butyl group or a trimethylsilyl group. 11 To R 14 Represents a hydrogen atom or a deuterium atom.

[0059] R 21 To R 28Each of the following is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 2 ...aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted arylalkyl group A substituted or unsubstituted alkenyl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted silyl group having 3 to 20 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 20 carbon atoms, a substituted or unsubstituted amine group, acyl group, carbonyl group, carboxyl group, ester group, nitrile group, isonitrile group, thiol group, sulfinyl group, sulfonyl group, phosphonyl group having 0 to 20 carbon atoms, and combinations thereof.

[0060] Preferably, R 21 To R 28 The alkyl radicals are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, a substituted or unsubstituted alkyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms, a substituted or unsubstituted alkyl group having 2 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 2 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryloxy group having 1 ...alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl The invention also includes a substituted or unsubstituted alkenyl group having 6 to 18 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 18 carbon atoms, a substituted or unsubstituted silyl group having 3 to 10 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 18 carbon atoms, a substituted or unsubstituted amine group, an acyl group, a carbonyl group, a carboxyl group, an ester group, a nitrile group, an isonitrile group, a thiol group, a sulfinyl group, a sulfonyl group, a phosphonyl group having 0 to 10 carbon atoms, and combinations thereof.

[0061] More preferably, R 21 To R 28 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted silyl group having 3 to 5 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 18 carbon atoms, and combinations thereof.

[0062] More preferably, R 21 To R28 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a methyl group, an isobutyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted triphenyl group, a substituted or unsubstituted benzophenanthryl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothienyl group.

[0063] Most preferably, R 21 To R 28 Represents a hydrogen atom or a deuterium atom.

[0064] In the present specification, "XX to YY carbon atoms" in "substituted or unsubstituted Z group having XX to YY carbon atoms" is the number of carbon atoms of the unsubstituted Z group, excluding any carbon atoms in the substituent that replaces the Z group. "YY" is greater than "XX", and "XX" and "YY" each represent an integer of 1 or more.

[0065] The "XX to YY carbon atoms" in the "substituted or unsubstituted ZZ group having XX to YY atoms" is the number of atoms of the unsubstituted ZZ group, excluding any atoms in the substituent that replaces the ZZ group. "YY" is greater than "XX", and "XX" and "YY" each represent an integer of 1 or more.

[0066] The “unsubstituted ZZ group” in the “substituted or unsubstituted ZZ group” refers to a ZZ group in which no hydrogen atom is substituted.

[0067] The definition of "hydrogen atom" as used herein includes isotopes having different numbers of neutrons, namely light hydrogen (protium), heavy hydrogen (deuterium), and tritium.

[0068] The definition of "halogen atom" used herein includes fluorine, chlorine and bromine.

[0069] The number of "ring carbon atoms" referred to herein refers to the number of carbon atoms contained in the members constituting the ring itself in a series of compounds (e.g., monocyclic compounds, condensed ring compounds, cross-linked compounds, carbocyclic compounds, and heterocyclic compounds) in which atoms are combined to form a ring. If the ring has a substituent, the carbon atoms in the substituent are not included in the ring carbon atoms. For example, a benzene ring has 6 ring carbon atoms, a naphthalene ring has 10 ring carbon atoms, a pyridyl group has 5 ring carbon atoms, and a furanyl group has 4 ring carbon atoms. If a benzene ring or a naphthalene ring has (for example) an alkyl substituent, the carbon atoms in the alkyl substituent are not counted as ring carbon atoms of the benzene ring or the naphthalene ring. If a fluorene ring has a fluorene substituent (including a spirofluorene ring), the carbon atoms in the fluorene substituent are not counted as ring carbon atoms of the fluorene ring.

[0070] The number of "ring atoms" referred to herein refers to the number of atoms that are members of the ring itself (e.g., monocyclic, fused rings, and ring assemblies), in which a series of atoms are combined to form a ring (e.g., monocyclic compounds, fused ring compounds, cross-linked compounds, carbocyclic compounds, and heterocyclic compounds). Atoms that do not form a ring (e.g., hydrogen atoms that saturate the valence of the ring atoms) and atoms in substituents (if the ring is substituted) are not counted as ring atoms. For example, a pyridine ring has 6 ring atoms, a quinazoline ring has 10 ring atoms, and a furan ring has 5 ring atoms. Hydrogen atoms on the ring carbon atoms of a pyridine ring or quinazoline ring and atoms in substituents are not counted as ring atoms. If there is a fluorene substituent (including a spirofluorene ring) on ​​a fluorene ring, the atoms in the fluorene substituent are not counted as ring atoms of the fluorene ring.

[0071] Alkyl as described herein includes straight chain and branched chain alkyl.Examples of alkyl include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl.In addition, alkyl can be selectively substituted.The carbon in the alkyl chain can be substituted by other heteroatoms.Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, S-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferred.

[0072] Cycloalkyl as described herein refers to cyclic alkyl. Cycloalkyl preferably has a group of 4 to 10 ring carbon atoms, including cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4,4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, etc. In addition, cycloalkyl can be selectively substituted. The carbon atoms in the ring can be substituted by other heteroatoms.

[0073] Alkenyl as described herein includes straight chain and branched alkenyl.Alkenyl preferably has a group of 2 to 15 carbon atoms.The example of alkenyl includes vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, styryl, 2,2-diphenylvinyl, 1,2-diphenylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1-phenylalkenyl, 2-phenylalkenyl, 3-phenylalkenyl, 3,3-diphenylallyl, 1,2-dimethylallyl, 1-phenyl 1-butenyl and 3-phenyl-1-butenyl.In addition, alkenyl can be selectively substituted.

[0074] The alkynyl groups described herein include straight chain and branched chain alkynyl groups. The alkynyl groups preferably have groups of 2 to 15 carbon atoms. In addition, the alkynyl groups can be selectively substituted.

[0075] Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylenyl, naphthyl, anthracenyl, phenanthrenyl, phenanthrenyl, fluorenyl, pyrenyl, chrysene, peryl and azulenyl, preferably phenyl, biphenyl, terphenyl, fluorenyl and naphthyl. In addition, the aryl group may be optionally substituted.

[0076] Examples of heteroaryl groups include dibenzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, indolecarbazolyl, imidazolyl, pyridyl, triazine, benzimidazolyl, 1,2-azaboryl, 1,3-azaboryl, 1,4-azaboryl, borazine and aza analogs thereof. In addition, the heteroaryl group may be optionally substituted.

[0077] Alkoxy is represented by -O-alkyl. Examples of alkoxy include alkoxy groups having 1 to 20, preferably 1 to 18, more preferably 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. Alkoxy groups having 3 or more carbon atoms may be linear, cyclic or branched.

[0078] The aryloxy group is represented by -O-aryl or -O-heteroaryl. Examples of the aryloxy group include aryl or heteroaryl groups having 6 to 30, preferably 6 to 25, more preferably 6 to 18 ring carbon atoms, and the substituents thereof are selected from the aryl or heteroaryl groups described above.

[0079] Aralkyl as used herein refers to an alkyl group having an aryl substituent. In addition, the aralkyl group may be selectively substituted. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2-α-naphthylethyl, 1-α-naphthylisopropyl, 2-α-naphthylisopropyl, 2-α-naphthylisopropyl, β-naphthylmethyl, 1-β-naphthylethyl, 2-β-naphthylethyl, 1-β-naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, The preferred alkyl radicals are benzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxy-2-phenylisopropyl and 1-chloro-2-phenylisopropyl. Among the above, benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl are preferred.

[0080] Examples of mono- or di-substituted amino groups include those substituted by an alkyl group having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms or an aryl group having 6 to 30, preferably 6 to 25, more preferably 6 to 18 ring carbon atoms, wherein the alkyl group and the aryl group are selected from the alkyl groups and aryl groups described above.

[0081] Examples of mono-, di- or tri-substituted silyl groups include those whose substituents are alkyl groups having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms or aryl groups having 6 to 30, preferably 6 to 25, more preferably 6 to 18 ring carbon atoms, wherein the alkyl and aryl groups are selected from the alkyl and aryl groups described above.

[0082] Examples of the halogenated alkyl group having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms include halogenated alkyl groups obtained by substituting one or more hydrogen atoms of the aforementioned alkyl group with a halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom.

[0083] Examples of substituted sulfonyl groups include those sulfonyl groups whose substituents are alkyl groups having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms or aryl groups having 6 to 30, preferably 6 to 25, more preferably 6 to 18 ring carbon atoms, wherein the alkyl groups and the aryl groups are selected from the alkyl groups and the aryl groups described above.

[0084] Examples of disubstituted phosphate groups include those in which the substituents are alkyl groups having 1 to 30, preferably 1 to 18, more preferably 1 to 8 carbon atoms or aryl groups having 6 to 30, preferably 6 to 25, more preferably 6 to 18 ring carbon atoms, wherein the alkyl and aryl groups are selected from the alkyl and aryl groups described above.

[0085] Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, aryl and heteroaryl groups may be unsubstituted or substituted with one or more of the following substituents:

[0086] deuterium, halogen, alkyl, cycloalkyl, aralkyl, alkoxy, aryloxy, amino, cycloamino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxyl, ether, ester, nitrile, isonitrile, sulfonyl, sulfinyl, phosphonyl, and combinations thereof.

[0087] It should be understood that when a molecular fragment is described as a substituent or otherwise attached to another molecule, its name can be written as if it is a fragment (such as phenyl, naphthyl, dibenzofuranyl) or the entire molecule (such as benzene, naphthalene, dibenzofuran). When used herein, these different ways of specifying substituents or attaching fragments are considered equivalent.

[0088] Specific examples of the nitrogen-containing heterocyclic triphenylethylene derivatives of the present invention are as follows, but are not limited thereto:

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103] The above-mentioned triphenylethylene derivative containing a boron heterocycle can be used as a luminescent material or a doping material for an organic electroluminescent device. When the triphenylethylene derivative containing a boron heterocycle is used as a dopant, the content is not particularly limited and can be 1wt% or more, preferably 1.0 to 80.0wt%, and more preferably 5.0 to 20.0wt%.

[0104] The organic electroluminescent device of the present invention comprises an anode, a cathode and an organic layer between the anode and the cathode, wherein at least one organic layer is a light-emitting layer and at least one organic layer contains the above-mentioned triphenylethylene derivative containing a boron heterocycle or as a component of a mixture.

[0105] The materials for organic electroluminescent devices mentioned in the present invention can be used as the main material or doping material of the light-emitting layer in the fluorescent light-emitting unit. They can also be used as functional layer materials used in fluorescent light-emitting units and phosphorescent light-emitting units, for example, materials used as the anode-side organic thin film layer formed between the anode and the light-emitting layer or the cathode-side organic thin film layer formed between the cathode and the light-emitting layer, that is, materials used for the hole transport layer, hole injection layer, electron transport layer, electron injection layer, hole blocking layer and electron blocking layer.

[0106] The organic electroluminescent device of the present invention can be any one of a fluorescent or phosphorescent monochromatic light-emitting device, a fluorescent-phosphorescent mixed white light-emitting device, a simple light-emitting device with a single light-emitting unit, and a tandem light-emitting device with two or more light-emitting units.

[0107] As a representative structure of a simple organic electroluminescent device, the device structure is given as follows:

[0108] (1) Anode / light-emitting unit / cathode

[0109] The above-mentioned light-emitting unit may be a stacked structure including multiple fluorescent light-emitting layers and phosphorescent light-emitting layers. In this case, in order to prevent the excitons generated in the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer, a spacer layer may be provided between the light-emitting layers.

[0110] A representative stacked structure of a light-emitting unit is given below.

[0111] (a) Hole transport layer / light-emitting layer ( / electron transport layer)

[0112] (b) Hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer ( / electron transport layer)

[0113] (c) Hole transport layer / phosphorescent emitting layer / spacer layer / fluorescent emitting layer ( / electron transport layer)

[0114] (d) hole transport layer / first phosphorescent light emitting layer / second phosphorescent light emitting layer / spacer layer / fluorescent light emitting layer ( / electron transport layer)

[0115] (e) hole transport layer / first phosphorescent emitting layer / spacer layer / second phosphorescent emitting layer / spacer layer / fluorescent emitting layer ( / electron transport layer)

[0116] (f) hole transport layer / phosphorescent emitting layer / spacer layer / first fluorescent emitting layer / second fluorescent emitting layer ( / electron transport layer)

[0117] (g) Hole transport layer / electron blocking layer / light-emitting layer ( / electron transport layer)

[0118] (h) Hole transport layer / light-emitting layer / hole blocking layer ( / electron transport layer)

[0119] (i) Hole transport layer / fluorescent emitting layer / triplet blocking layer ( / electron transport layer)

[0120] The phosphorescent or fluorescent light-emitting layer mentioned above can emit light of different colors. Specifically, in the stacked structure (d), the following examples can be cited: hole transport layer / first phosphorescent light-emitting layer (red light) / second phosphorescent light-emitting layer (green light) / spacer layer / fluorescent light-emitting layer (blue light) / electron transport layer.

[0121] An electron blocking layer may be appropriately provided between each light-emitting layer and the hole transport layer or the spacer layer. A hole blocking layer may be appropriately provided between each light-emitting layer and the electron transport layer. Since the electron blocking layer or the hole blocking layer is provided, electrons and holes may be confined in the light-emitting layer, thereby increasing the possibility of carrier recombination in the light-emitting layer, thereby extending the lifespan.

[0122] As a representative structure of a tandem organic electroluminescent device, the device structure is given as follows:

[0123] (2) Anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode

[0124] The layered structure of the first light emitting unit and the second light emitting unit may be selected from the representative layered structures of the emission units mentioned above.

[0125] Generally, the intermediate layer is also called an intermediate electrode, an intermediate conductive layer, a carrier-forming layer, or an electronic layer, and can provide electrons to the first light-emitting layer and holes to the second light-emitting layer through material configuration.

[0126] A schematic diagram of the structure of an example of an organic electroluminescent device of the present invention is shown in FIG. Figure 1 As shown, the organic electroluminescent device includes a substrate 1, an anode 2, a cathode 8, and an organic thin film layer 10 (light-emitting unit 10) disposed between the anode 2 and the cathode 8. The light-emitting unit 10 includes a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, and an electron injection layer 7. An electron blocking layer can be disposed on the anode 2 side of the light-emitting layer 5, and a hole blocking layer can be disposed on the cathode 8 side of the light-emitting layer 5. Through these blocking layers, electrons and holes are confined in the light-emitting layer 5 to increase the recombination degree of excitons in the light-emitting layer 5.

[0127] In the present invention, the host combined with the fluorescent dopant material is called the fluorescent host material, and the host combined with the phosphorescent dopant material is called the phosphorescent host material. Therefore, the fluorescent host material and the phosphorescent host material cannot be distinguished only by the difference in their molecular structures. In the present invention, the term "phosphorescent host" refers to a material used to constitute a phosphorescent light-emitting layer containing a phosphorescent dopant material, and does not refer to a material that cannot be used as a fluorescent light-emitting layer material. The same applies to the "fluorescent host".

[0128] substrate

[0129] The organic electroluminescent device of the present invention is formed on a transparent substrate. As a carrier of the organic electroluminescent device, a glass substrate with a visible light transmittance of 80% in the 400-700nm band is preferred. The glass plate can be made of soda-lime glass, barium-strontium glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz.

[0130] anode

[0131] As the anode material in the organic electroluminescent device of the present invention, it is suitable to inject holes into the hole transport layer or the light-emitting layer and have a work function of 4.5 eV or more, and can be indium tin oxide alloy (ITO), tin oxide (NESA), indium zinc oxide alloy, gold, silver, platinum and copper, etc., but not limited to these. The anode is formed by making the anode material into a thin film by a specific method, such as vapor deposition or sputtering. When the device emits light from the light-emitting layer through the anode, the transmittance of the anode to visible light is preferably 10% or higher. The sheet resistance of the anode is preferably several hundred Ω / ° or less. The film thickness of the anode depends on the type of material, generally 10nm-1μm, preferably 100-200nm.

[0132] cathode

[0133] The cathode injects electrons into the electron injection layer, the electron transport layer or the light emitting layer, and is preferably formed of a material having a small work function. Examples of materials for the cathode include, but are not limited to, indium, aluminum, magnesium, magnesium-indium alloys, magnesium-aluminum alloys, aluminum-lithium alloys, aluminum-scandium-lithium alloys, and magnesium-silver alloys. Like the anode, the cathode is formed by making a material into a thin film by methods such as vapor deposition and sputtering.

[0134] Luminescent layer

[0135] The light-emitting layer is an organic layer with a light-emitting function. When a doping system is adopted, it contains a host material and a dopant material. The main function of the host material is to promote the recombination of electrons and holes and confine the excitons in the light-emitting layer. The function of the dopant material is to make the excitons generated by the recombination emit light efficiently.

[0136] In order to control the carrier balance in the light-emitting layer, the light-emitting layer can be made into a dual-host (host / co-host) layer, for example, by using a combination of an electron-transporting host and a hole-transporting host.

[0137] The light-emitting layer can be made into a double-doped layer, where two or more doping materials with high quantum yields are used in combination, and each dopant material emits light in its own color. For example, by using a light-emitting layer formed by co-depositing a host material, a red light-emitting dopant material, and a green light-emitting dopant material, yellow light can be obtained.

[0138] In a stacked structure including two or more light-emitting layers, electrons and holes accumulate at the interface between the light-emitting layers, and thus a recombination zone is located at the interface between the light-emitting layers to improve quantum efficiency.

[0139] The ease of injecting holes into the light-emitting layer and the ease of injecting electrons into the light-emitting layer may be different. Likewise, the hole transporting ability and the electron transporting ability are represented by the mobility of holes and electrons in the light-emitting layer, respectively, and may be different from each other.

[0140] The light-emitting layer is formed by a known method, such as vapor deposition, spin coating, and LB method, but is not limited thereto. The light-emitting layer is preferably a molecular deposition film. The molecular deposition film is a thin film formed by depositing a vaporized material or by solidifying a material in a solution or liquid state. The molecular deposition film and the thin film formed by the LB method (molecular stacking film) can be distinguished by differences in assembly structure, high-order structure, and functional differences caused by structural differences.

[0141] The thickness of the light-emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and most preferably 10 to 50 nm. If it is less than 5 nm, it may be difficult to form the light-emitting layer and the color may be difficult to control. If it exceeds 50 nm, the driving voltage may increase.

[0142] (1) Fluorescent light-emitting layer

[0143] The fluorescent light-emitting layer generally includes at least one light-emitting material and at least one host material.

[0144] The host material used for the fluorescent light-emitting layer is usually selected from general host materials, which preferably have a wider band gap than the light-emitting material, and realize efficient light emission through the energy transfer mechanism from the host material to the light-emitting material. Specific examples of preferred fluorescent host materials are substituted or unsubstituted heterocyclic compounds or substituted or unsubstituted aromatic hydrocarbon compounds, for example, oligophenylene derivatives, naphthalene derivatives, fluorene derivatives, fluoranthene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, triphenylene derivatives, benzanthracene derivatives, chrysene derivatives, tetracene derivatives, benzochrysene derivatives, etc.

[0145] The luminescent material used for the fluorescent light-emitting layer is usually selected from general luminescent materials or fluorescent dyes, and it is preferably a material with high absorption coefficient and high quantum efficiency in order to obtain high light efficiency. Specific examples of preferred fluorescent light-emitting materials are the above-mentioned triphenylethylene derivatives, aromatic hydrocarbon derivatives, such as oligophenylene derivatives, naphthalene derivatives, fluorene derivatives, fluoranthene derivatives, fused fluorene derivatives, anthracene derivatives, phenanthrene derivatives, pyrene derivatives, triphenylene derivatives, chrysene derivatives, tetracene derivatives, benzochrysene derivatives, etc.

[0146] (2) Phosphorescent layer

[0147] The phosphorescent light-emitting layer generally includes at least one light-emitting material and at least one host material. The phosphorescent host material is a compound that effectively confines the triplet energy of the phosphorescent dopant material in the light-emitting layer so that the phosphorescent dopant material emits light efficiently.

[0148] The host material for the phosphorescent light-emitting layer is usually selected from known phosphorescent host materials. Specific examples of preferred phosphorescent host materials include nitrogen-containing heteroaromatic hydrocarbons, such as indole derivatives, carbazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, nitrided dibenzothiophene derivatives, nitrided dibenzofuran derivatives, imidazole derivatives, benzimidazole derivatives, imidazole pyridine derivatives, benzimidazole phenanthridine derivatives, benzimidazole-benzimidazole derivatives; oxygen- or sulfur-containing heteroaromatic hydrocarbons, such as thiophene derivatives, furan derivatives, benzothiophene derivatives, benzofuran derivatives, dibenzothiophene derivatives, dibenzofuran derivatives; aryl or heteroaryl substituted amine derivatives; metal complexes; aromatic hydrocarbon derivatives, such as benzene derivatives, naphthalene derivatives, phenanthrene derivatives, triphenyl derivatives, fluorene derivatives, and the like.

[0149] The doping material (phosphorescent luminescent material) used for the phosphorescent light-emitting layer is a compound that can emit light from a triplet excited state. The phosphorescent doping material is not limited as long as it can emit light from a triplet excited state. The phosphorescent doping material is preferably an organic metal complex containing at least one metal selected from Ir, Pt, Os, Au, Cu, Re and Ru and a ligand. The preferred ligand has an ortho-metallated bond. In order to obtain a device with high phosphorescent quantum yield and external quantum efficiency, the phosphorescent doping material is preferably a compound having a metal atom selected from Ir, Os and Pt. Further preferred are metal complexes, such as iridium complexes, osmium complexes and platinum complexes, and ortho-metallated complexes are more preferred. Among them, iridium complexes and platinum complexes are more preferred, and ortho-metallated iridium complexes are particularly preferred.

[0150] Electron transport layer

[0151] The electron transport layer is an organic layer disposed between the light-emitting layer and the cathode, and transfers electrons from the cathode to the light-emitting layer. If two or more electron transport layers are provided, the organic layer closer to the cathode may be referred to as an electron injection layer in some cases. The electron injection layer can effectively inject electrons from the cathode into the organic layer unit.

[0152] An aromatic heterocyclic compound having one or more heteroatoms in its molecule is preferably used as an electron transport material used in the electron transport layer, and a nitrogen-containing heterocyclic derivative is particularly preferred. In addition, the nitrogen-containing heterocyclic derivative is preferably an aromatic ring compound containing a 6- or 5-membered nitrogen heterocycle, or a condensed aromatic ring compound containing a 6- or 5-membered nitrogen heterocycle.

[0153] The thickness of the electron transport layer is preferably, but not particularly limited to, 1 to 100 nm.

[0154] Preferred examples of optional electron injection layer materials include inorganic compounds such as insulating materials and semiconductors in addition to nitrogen-containing heterocyclic derivatives. The electron injection layer containing insulating materials or semiconductors can effectively prevent current leakage to improve the performance of electron injection.

[0155] The insulating material is preferably at least one metal compound selected from alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. The alkali metal chalcogenides mentioned above are preferred because the electron injection performance of the electron injection layer is further enhanced. Examples of preferred alkali metal chalcogenides include Li2O, K2O, Na2S, Na2Se and Na2O, while examples of preferred alkaline earth metal chalcogenides include CaO, BaO, SrO, BeO, BaS and CaSe. Examples of preferred alkali metal halides include LiF, NaF, KF, LiCl, KCl and NaCl. Examples of alkaline earth metal halides include fluorides such as CaF2, BaF2, SrF2, MgF2 and BeF2, as well as halides other than fluorides.

[0156] Examples of semiconductors include oxides, nitrides or oxynitrides of at least one element in the group consisting of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb and Zn. The semiconductor can be used alone or in combination of two or more. The inorganic compound contained in the electron injection layer preferably forms a microcrystalline or amorphous insulating film. If the electron injection layer is formed by such an insulating film, pixel defects (such as black spots) can be reduced because a more uniform film is formed. Examples of such inorganic compounds include alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides.

[0157] When an insulating material or a semiconductor is used, the thickness of the layer is preferably about 0.1 to 15 nm.

[0158] Hole transport layer

[0159] The hole injection / transport layer is an organic layer formed between the light-emitting layer and the anode, and has the function of transporting holes from the anode to the light-emitting layer. When the hole transport layer is formed of two or more layers, in some cases, the layer closer to the anode can be defined as the hole injection layer. The hole injection layer has the function of efficiently injecting holes from the anode into the organic layer unit.

[0160] The hole transport layer may be made into a two-layer structure of a first hole transport layer (anode side) and a second hole transport layer (cathode side).

[0161] The thickness of the hole transport layer is preferably 10 to 200 nm, but is not particularly limited.

[0162] n / p doping

[0163] The carrier injection characteristics of the hole transport layer and the electron transport layer can be controlled by doping with electron donor materials (n) or with electron acceptor materials (p).

[0164] Typical examples of n-doping are electron transport materials doped with metals, such as Li and Cs, and typical examples of p-doping are hole transport materials doped with acceptor materials, such as F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane).

[0165] Spacer

[0166] In an organic electroluminescent device having a laminated structure of multiple fluorescent light-emitting layers and phosphorescent light-emitting layers, a spacer layer is provided between the fluorescent light-emitting layer and the phosphorescent light-emitting layer to prevent the excitons generated in the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer or to control the carrier balance. The spacer layer can also be provided between two or more phosphorescent light-emitting layers.

[0167] Since the spacer layer is disposed between the light-emitting layers, it is preferred to use a material having both electron transport capability and hole transport capability. In order to prevent the diffusion of triplet energy in the adjacent phosphorescent light-emitting layer, the triplet energy of the material used for the spacer layer is preferably 2.6 eV or higher. The materials described for the hole transport layer can be used as the material of the spacer layer.

[0168] Barrier layer

[0169] Blocking layers, such as electron blocking layers, hole blocking layers, and triplet blocking layers, are provided near the light-emitting layer. The electron blocking layer is a layer that prevents electrons from diffusing from the light-emitting layer to the hole transport layer. The hole blocking layer is a layer that prevents holes from diffusing from the light-emitting layer to the electron transport layer.

[0170] The triplet blocking layer prevents triplet excitons generated in the light-emitting layer from diffusing to adjacent layers and has the function of confining triplet excitons in the light-emitting layer, thereby preventing energy from being deactivated on molecules other than the light-emitting doping material of the triplet excitons, for example, on molecules in the electron transport layer.

[0171] The material of the triplet blocking layer preferably has an electron mobility of 10 at an electric field strength of 0.04 to 0.5 MV / cm. -6 cm 2 / Vs or higher. There are several methods to measure the electron mobility of organic materials, for example, time of flight. Here, electron mobility refers to the electron mobility determined by impedance spectroscopy.

[0172] The material of the electron injection layer is preferably such that the electron mobility is 10 at an electric field strength of 0.04 to 0.5 MV / cm. -6 cm 2Within the above range, the injection of electrons from the cathode to the electron transport layer can be promoted, and the injection of electrons to the adjacent blocking layer and the light-emitting layer can also be promoted, so that the device can be driven at a lower voltage.

[0173] The present invention also relates to an electronic device comprising the organic electroluminescent device of the present invention.

[0174] The organic electroluminescent device using the compound of formula (I) of the present invention can be used in a panel module used in various displays.

[0175] The organic electroluminescent device using the compound of formula (I) of the present invention can be used as a display element of a television, a mobile phone and a personal computer; or as an electronic device such as a lighting device or the like.

[0176] OLEDs (organic electroluminescent devices) using compounds of formula (I) of the present invention can be used in all devices using electroluminescence. Suitable devices are preferably selected from fixed and mobile visual display units and lighting units. Fixed visual display units, such as visual display units of computers, televisions, visual display units in printers, kitchen appliances and advertising panels, lighting and information panels. Mobile visual display units, such as visual display units in mobile phones, tablet computers, laptops, digital cameras, MP3 players, vehicles and destination displays on buses and trains. Other devices that can use the OLED of the present invention are keyboards, clothing, furniture, wallpaper, etc.

[0177] Example

[0178] The technical solution of the present invention is described in more detail below in conjunction with embodiments, but the scope of the present invention is not limited to the following examples.

[0179] Synthesis Example

[0180] Example 1: Synthesis of Compound 1

[0181] (1) Synthesis of intermediate 1

[0182]

[0183] Under argon atmosphere, CuO (160 mg, 2 mmol), tetrabutylammonium bromide (TBAB) (645 mg, 2 mmol), Cs2CO3 (3.26 g, 10 mmol) and 2-bromo-1H-indole (3.92 g, 20 mmol) were added to a DMF (150 mL) solution of 1H-indole-2-ol (2.93 g, 22 mmol) while stirring. The reaction mixture was stirred at 145°C for 24 hours. The reaction was quenched with water and extracted with EtOAc. The organic phase was dried with MgSO4 and then the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography to obtain intermediate 1 (yield: 80%).

[0184] (2) Synthesis of Intermediate 2

[0185]

[0186] In the CH3CN solution (50mL) of intermediate 1 (2.48g, 10mmol) and NH4OAc (154mg, 2mmol), NBS (4.45g, 25mmol) was slowly added while stirring, and the dropping time was 10-15 minutes. The reaction mixture was kept under magnetic stirring overnight (16 hours) at room temperature. After the reaction was completed, the reaction mixture was dissolved in ethyl acetate and washed with distilled water (3 times), then dried with anhydrous MgSO4, and the solvent was removed under reduced pressure. The crude product was purified by rapid silica gel column chromatography (10% ethyl acetate and hexane) to obtain intermediate 2 in a yield of 68%.

[0187] (3) Synthesis of Intermediate 3

[0188]

[0189] Intermediate 2 (1.02 g, 2.5 mmol) was dissolved in 50 mL of diethyl ether, and the solution was cooled to -78 ° C. Butyl lithium (10.9 ml, 1.7 M pentane solution, 18.6 mmol) was slowly added dropwise, and the reaction mixture was warmed to 0 ° C. After stirring at 0 ° C for 30 minutes, the reaction mixture was recooled to -78 ° C. Dimethyl phenylborate (480 mg, 3.2 mmol) was dissolved in 10 mL of diethyl ether and added dropwise to the reaction mixture. After warming to room temperature, reflux reaction for 12 h, cooled, filtered and rinsed with dichloromethane. The crude product was purified by silica gel column chromatography (7: 3 hexane / dichloromethane) and recrystallized from hexane / dichloromethane to obtain 0.66 g of intermediate 3 (yield 79%).

[0190] (4) Synthesis of Compound 1

[0191]

[0192] Under nitrogen atmosphere, a mixture of intermediate 3 (501 mg, 1.5 mmol), 2-(4-bromophenyl)-(1,1-diphenyl)ethylene (1.21 g, 3.6 mmol), CuI (113 mg, 0.6 mmol), K3PO4 (1.33 g, 6.3 mmol), trans-1,2-diaminocyclohexane (136 mg, 1.2 mmol) and 25 ml of o-xylene was heated at 110°C for 24 hours. After cooling to room temperature, the reaction mixture was washed 3 times with 10 ml of water and extracted with dichloromethane. The organic solution was dried over Mg2SO4 and then evaporated to remove the solvent. The residue was purified by column chromatography eluting with petroleum ether to obtain 0.88 g of compound 1 with a yield of 70%.

[0193] Example 2: Synthesis of Compound 2

[0194] (1) Synthesis of intermediate 4

[0195]

[0196] Under argon atmosphere, CuO (160 mg, 2 mmol), tetrabutylammonium bromide (TBAB) (645 mg, 2 mmol), Cs2CO3 (3.26 g, 10 mmol) and 2-bromo-1H-indole (3.92 g, 20 mmol) were added to a DMF (150 mL) solution of 1H-indole-2-thiol (3.28 g, 22 mmol) with stirring. The reaction mixture was stirred at 145°C for 24 hours. The reaction was quenched with water and extracted with EtOAc. The organic phase was dried over MgSO4 and then the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography to give intermediate 4 (yield: 77%).

[0197] (2) Synthesis of Intermediate 5

[0198]

[0199] In the CH3CN solution (50mL) of intermediate 4 (2.64g, 10mmol) and NH4OAc (154mg, 2mmol), NBS (4.45g, 25mmol) was slowly added while stirring, and the dropping time was 10-15 minutes. The reaction mixture was kept under magnetic stirring overnight (16 hours) at room temperature. After the reaction was completed, the reaction mixture was dissolved in ethyl acetate and washed with distilled water (3 times), then dried with anhydrous MgSO4, and the solvent was removed under reduced pressure. The crude product was purified by rapid silica gel column chromatography (10% ethyl acetate and hexane) to obtain intermediate 5 in a yield of 67%.

[0200] (3) Synthesis of intermediate 6

[0201]

[0202] Intermediate 5 (1.06 g, 2.5 mmol) was dissolved in 50 mL of diethyl ether, and the solution was cooled to -78 ° C. Butyl lithium (10.9 ml, 1.7 M pentane solution, 18.6 mmol) was slowly added dropwise, and the reaction mixture was warmed to 0 ° C. After stirring at 0 ° C for 30 minutes, the reaction mixture was recooled to -78 ° C. Dimethyl phenylborate (480 mg, 3.2 mmol) was dissolved in 10 mL of diethyl ether and added dropwise to the reaction mixture. After warming to room temperature, reflux reaction for 12 h, cooled, filtered and rinsed with dichloromethane. The crude product was purified by silica gel column chromatography (7: 3 hexane / dichloromethane) and recrystallized from hexane / dichloromethane to obtain 0.63 g of intermediate 6 (yield 71%).

[0203] (4) Synthesis of Compound 2

[0204]

[0205] Under nitrogen atmosphere, a mixture of intermediate 6 (525 mg, 1.5 mmol), 2-(4-bromophenyl)-(1,1-diphenyl)ethylene (1.21 g, 3.6 mmol), CuI (113 mg, 0.6 mmol), K3PO4 (1.33 g, 6.3 mmol), trans-1,2-diaminocyclohexane (136 mg, 1.2 mmol) and 25 ml of o-xylene was heated at 110°C for 24 hours. After cooling to room temperature, the reaction mixture was washed 3 times with 10 ml of water and extracted with dichloromethane. The organic solution was dried over Mg2SO4 and then evaporated to remove the solvent. The residue was purified by column chromatography eluting with petroleum ether to obtain 0.93 g of compound 1 with a yield of 72%.

[0206] Example 3: Synthesis of Compound 3

[0207] (1) Synthesis of intermediate 7

[0208]

[0209] Under argon atmosphere, CuO (160 mg, 2 mmol), tetrabutylammonium bromide (TBAB) (645 mg, 2 mmol), Cs2CO3 (3.26 g, 10 mmol) and 3-bromo-1H-indole (3.92 g, 20 mmol) were added to a DMF (150 mL) solution of 1H-indole-3-ol (2.93 g, 22 mmol) while stirring. The reaction mixture was stirred at 145°C for 24 hours. The reaction was quenched with water and extracted with EtOAc. The organic phase was dried with MgSO4 and then the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography to obtain intermediate 7 (yield: 75%).

[0210] (2) Synthesis of Intermediate 8

[0211]

[0212] In the CH3CN solution (50mL) of intermediate 7 (2.48g, 10mmol) and NH4OAc (154mg, 2mmol), NBS (4.45g, 25mmol) was slowly added while stirring, and the dropping time was 10-15 minutes. The reaction mixture was kept under magnetic stirring overnight (16 hours) at room temperature. After the reaction was completed, the reaction mixture was dissolved in ethyl acetate and washed with distilled water (3 times), then dried with anhydrous MgSO4, and the solvent was removed under reduced pressure. Rapid silica gel column chromatography (10% ethyl acetate and hexane) was used to purify the crude product to obtain intermediate 8, and the yield was 64%.

[0213] (3) Synthesis of Intermediate 9

[0214]

[0215] Intermediate 8 (1.02 g, 2.5 mmol) was dissolved in 50 mL of diethyl ether, and the solution was cooled to -78 ° C. Butyl lithium (10.9 ml, 1.7 M pentane solution, 18.6 mmol) was slowly added dropwise, and the reaction mixture was warmed to 0 ° C. After stirring at 0 ° C for 30 minutes, the reaction mixture was recooled to -78 ° C. Dimethyl phenylborate (480 mg, 3.2 mmol) was dissolved in 10 mL of diethyl ether and added dropwise to the reaction mixture. After warming to room temperature, reflux reaction for 12 h, cooled, filtered and rinsed with dichloromethane. The crude product was purified by silica gel column chromatography (7: 3 hexane / dichloromethane) and recrystallized from hexane / dichloromethane to obtain 0.59 g of intermediate 9 (yield 71%).

[0216] (4) Synthesis of Compound 3

[0217]

[0218] Under nitrogen atmosphere, a mixture of intermediate 9 (501 mg, 1.5 mmol), 2-(4-bromophenyl)-(1,1-diphenyl)ethylene (1.21 g, 3.6 mmol), CuI (113 mg, 0.6 mmol), K3PO4 (1.33 g, 6.3 mmol), trans-1,2-diaminocyclohexane (136 mg, 1.2 mmol) and 25 ml of o-xylene was heated at 110°C for 24 hours. After cooling to room temperature, the reaction mixture was washed 3 times with 10 ml of water and extracted with dichloromethane. The organic solution was dried over Mg2SO4 and then evaporated to remove the solvent. The residue was purified by column chromatography eluting with petroleum ether to obtain 0.85 g of compound 3 with a yield of 67%.

[0219] Example 4: Synthesis of Compound 4

[0220] (1) Synthesis of Intermediate 10

[0221]

[0222] Under argon atmosphere, CuO (160 mg, 2 mmol), tetrabutylammonium bromide (TBAB) (645 mg, 2 mmol), Cs2CO3 (3.26 g, 10 mmol) and 3-bromo-1H-indole (3.92 g, 20 mmol) were added to a DMF (150 mL) solution of 1H-indole-3-thiol (3.28 g, 22 mmol) with stirring. The reaction mixture was stirred at 145°C for 24 hours. The reaction was quenched with water and extracted with EtOAc. The organic phase was dried over MgSO4 and then the solvent was removed by distillation under reduced pressure. The residue was purified by silica gel column chromatography to give intermediate 10 (yield: 73%).

[0223] (2) Synthesis of intermediate 11

[0224]

[0225] In the CH3CN solution (50mL) of intermediate 10 (2.64g, 10mmol) and NH4OAc (154mg, 2mmol), NBS (4.45g, 25mmol) was slowly added while stirring, and the dropping time was 10-15 minutes. The reaction mixture was kept under magnetic stirring overnight (16 hours) at room temperature. After the reaction was completed, the reaction mixture was dissolved in ethyl acetate and washed with distilled water (3 times), then dried with anhydrous MgSO4, and the solvent was removed under reduced pressure. The crude product was purified by rapid silica gel column chromatography (10% ethyl acetate and hexane) to obtain intermediate 11, and the yield was 61%.

[0226] (3) Synthesis of intermediate 12

[0227]

[0228] Intermediate 11 (1.06 g, 2.5 mmol) was dissolved in 50 mL of diethyl ether, and the solution was cooled to -78 ° C. Butyl lithium (10.9 ml, 1.7 M pentane solution, 18.6 mmol) was slowly added dropwise, and the reaction mixture was warmed to 0 ° C. After stirring at 0 ° C for 30 minutes, the reaction mixture was recooled to -78 ° C. Dimethyl phenylborate (480 mg, 3.2 mmol) was dissolved in 10 mL of diethyl ether and added dropwise to the reaction mixture. After warming to room temperature, reflux reaction for 12 h, cooled, filtered and rinsed with dichloromethane. The crude product was purified by silica gel column chromatography (7: 3 hexane / dichloromethane) and recrystallized from hexane / dichloromethane to obtain 0.60 g of intermediate 12 (yield 69%).

[0229] (4) Synthesis of Compound 4

[0230]

[0231] Under nitrogen atmosphere, a mixture of intermediate 12 (525 mg, 1.5 mmol), 2-(4-bromophenyl)-(1,1-diphenyl)ethylene (1.21 g, 3.6 mmol), CuI (113 mg, 0.6 mmol), K3PO4 (1.33 g, 6.3 mmol), trans-1,2-diaminocyclohexane (136 mg, 1.2 mmol) and 25 ml of o-xylene was heated at 110°C for 24 hours. After cooling to room temperature, the reaction mixture was washed three times with 10 ml of water and extracted with dichloromethane. The organic solution was dried over Mg2SO4 and then evaporated to remove the solvent. The residue was purified by column chromatography eluting with petroleum ether to obtain 0.90 g of compound 4 with a yield of 70%.

[0232] Example 5: Synthesis of Compound 5

[0233] (1) Synthesis of intermediate 13

[0234]

[0235] Under argon, KO was added to a toluene solution (100 mL) of 3-bromo-1H-indene (2.93 g, 15 mmol). tBu (3.38 g, 30 mmol) was added and stirred at room temperature for 1.5 hours. CH3I (0.95 ml, 15 mmol) was added to form a white KI precipitate. After the reaction mixture was stirred for 2 hours, Pd(dba)2 (864 mg, 1.5 mmol), PPh3 (786 mg, 3.0 mmol) and 1-(chloromethyl)-4-iodobenzene (3.79 g, 15 mmol) were added and stirred at 100°C for 12 hours. After the reaction was completed, the reaction was quenched with water and extracted with ether (3×50 mL). The organic layers were then combined, dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain intermediate 13 in a yield of 55%.

[0236] (2) Synthesis of intermediate 14

[0237]

[0238] Intermediate 13 (5.0 g, 15 mmol) was dissolved in 100 mL of diethyl ether, and the solution was cooled to -78 °C. Butyl lithium (65.4 ml, 1.7 M pentane solution, 111.6 mmol) was slowly added dropwise, and the reaction mixture was warmed to 0 °C. After stirring at 0 °C for 30 minutes, the reaction mixture was recooled to -78 °C. Dimethyl phenylborate (2.88 g, 19.2 mmol) was dissolved in 30 mL of diethyl ether and added dropwise to the reaction mixture. After warming to room temperature, refluxed for 12 h, cooled, filtered and rinsed with dichloromethane. The crude product was purified by silica gel column chromatography (7:3 hexane / dichloromethane) and recrystallized from hexane / dichloromethane to obtain intermediate 14 (yield 63%).

[0239] (3) Synthesis of intermediate 15

[0240]

[0241] In the CH3CN solution (80mL) of intermediate 14 (5.95g, 10mmol) and NH4OAc (154mg, 2mmol), NBS (4.45g, 25mmol) was slowly added with stirring, and the dropping time was 10-15 minutes. The reaction mixture was kept under magnetic stirring at room temperature overnight (16 hours). After the reaction was completed, the reaction mixture was dissolved in ethyl acetate and washed with distilled water (3 times), then dried with anhydrous MgSO4, and the solvent was removed under reduced pressure. The crude product was purified by rapid silica gel column chromatography (10% ethyl acetate and hexane) to obtain intermediate 15 in a yield of 59%.

[0242] (4) Synthesis of intermediate 16

[0243]

[0244] Intermediate 15 (4.52 g, 6.0 mmol) was dissolved in triethyl phosphite (1.25 g, 7.5 mmol), and the resulting mixture was stirred at room temperature for 2 hours, then heated to 170°C and stirred for another 5 hours. After cooling to room temperature, benzophenone (2.0 g, 11.0 mmol), THF (30 mL) and KO were added in sequence. t Bu (2.89 g, 26.0 mmol). The reaction mixture was stirred at room temperature for 20 hours. Then, the mixture was washed twice with water and extracted with dichloromethane. The organic layer was collected, and after evaporation of the solvent, the crude product was purified by silica gel column chromatography using n-hexane as eluent to obtain intermediate 16 in a yield of 60%.

[0245] (5) Synthesis of Compound 5

[0246]

[0247] 2.53 g (2.5 mmol) of intermediate 16, 233 mg (2.5 mmol) of aniline, 145 mg (0.25 mmol) of Pd2(dba)3, 0.25 ml of tri-tert-butylphosphine (ttbp) (50% toluene solution, 5.04 mmol) and 484 mg (5.0 mmol) of sodium tert-butoxide were added to 30 ml of xylene and mixed. The mixed solution was heated to 120° C. and stirred. After the reaction was completed, the resulting reaction solution was cooled to room temperature and filtered through silica gel under reduced pressure. The filtrate was concentrated under reduced pressure. The resulting residue was then separated by silica gel column chromatography to obtain 0.83 g of compound 5 with a yield of 35%.

[0248] Example 6: Synthesis of Compound 6

[0249] (1) Synthesis of intermediate 17

[0250]

[0251] Under nitrogen, intermediate 16 (2.53 g, 2.5 mmol), CuI (95 mg, 0.5 mmol), 1,10-phenanthroline (180 mg, 1.0 mmol) and KOH (1.12 g, 20.0 mmol) were added to DMSO / H2O (5:1, 30 mL). The mixture was stirred at room temperature for 10 minutes and then heated at 100°C for 24 hours. The reaction mixture was then cooled to room temperature, acidified with dilute hydrochloric acid, diluted with 4-5 ml of ethyl acetate, filtered through a silica gel plug, and washed with 10-20 ml of ethyl acetate. The organic phases were combined and concentrated, and the resulting residue was purified by silica gel column chromatography to give intermediate 17 in a yield of 57%.

[0252] (2) Synthesis of Compound 6

[0253]

[0254] 887 mg (1.0 mmol) of intermediate 17 and 205 mg (1.0 mmol) of p-toluenesulfonic acid were dissolved in 20 ml of toluene, and the mixed solution was stirred at 100° C. for 12 hours. After the reaction solution was cooled to room temperature, K2CO3 solution was added thereto. The organic layer was extracted three times with 10 ml of ethyl acetate and then dried over MgSO4. The solvent was distilled off, and the residue was separated / purified by silica gel chromatography to obtain 0.53 g of compound 6 with a yield of 61%.

[0255] Example 7: Synthesis of Compound 7

[0256]

[0257] Intermediate 16 (1.01 g, 1.0 mmol), Pd(dba)2 (57.5 mg, 0.1 mmol), 1,1'-bis(diphenylphosphino)ferrocene (77.6 mg, 0.14 mmol), potassium thioacetate (115 mg, 1.0 mmol) and K3PO4 (255 mg, 1.2 mmol) were placed in a round-bottom flask, and toluene (30 mL) and acetone (15 mL) were added. The reaction mixture was stirred at 110 °C for 6 hours under nitrogen. After cooling to room temperature, the reaction mixture was poured into 10 mL of saturated aqueous ammonium chloride solution and extracted with Et2O (3x15 mL). The organic phases were combined, washed with brine (40 ml), dried over MgSO4 and filtered. The solvent was removed under vacuum and the crude product was purified by silica gel column chromatography. The product was eluted with ethyl acetate in hexane to give compound 7 in a yield of 61%.

[0258] Example 8: Synthesis of Compound 8

[0259] (1) Synthesis of intermediate 18

[0260]

[0261] Under argon, KO was added to a toluene solution (100 mL) of 2-bromo-1H-indene (2.93 g, 15 mmol). tBu (3.38 g, 30 mmol) was added and stirred at room temperature for 1.5 hours. CH3I (0.95 ml, 15 mmol) was added to form a white KI precipitate. After the reaction mixture was stirred for 2 hours, Pd(dba)2 (864 mg, 1.5 mmol), PPh3 (786 mg, 3.0 mmol) and 1-(chloromethyl)-4-iodobenzene (3.79 g, 15 mmol) were added and stirred at 100°C for 12 hours. After the reaction was completed, the reaction was quenched with water and extracted with ether (3×50 mL). The organic layers were then combined, dried over Na2SO4 and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain intermediate 18 in a yield of 51%.

[0262] (2) Synthesis of intermediate 19

[0263]

[0264] Intermediate 18 (5.0 g, 15 mmol) was dissolved in 100 mL of diethyl ether, and the solution was cooled to -78 °C. Butyl lithium (65.4 ml, 1.7 M pentane solution, 111.6 mmol) was slowly added dropwise, and the reaction mixture was warmed to 0 °C. After stirring at 0 °C for 30 minutes, the reaction mixture was recooled to -78 °C. Dimethyl phenylborate (2.88 g, 19.2 mmol) was dissolved in 30 mL of diethyl ether and added dropwise to the reaction mixture. After warming to room temperature, refluxed for 12 h, cooled, filtered and rinsed with dichloromethane. The crude product was purified by silica gel column chromatography (7:3 hexane / dichloromethane) and recrystallized from hexane / dichloromethane to obtain intermediate 19 (yield 59%).

[0265] (3) Synthesis of Intermediate 20

[0266]

[0267] In the CH3CN solution (80mL) of intermediate 19 (5.95g, 10mmol) and NH4OAc (154mg, 2mmol), NBS (4.45g, 25mmol) was slowly added while stirring, and the dropping time was 10-15 minutes. The reaction mixture was kept under magnetic stirring overnight (16 hours) at room temperature. After the reaction was completed, the reaction mixture was dissolved in ethyl acetate and washed with distilled water (3 times), then dried with anhydrous MgSO4, and the solvent was removed under reduced pressure. The crude product was purified by rapid silica gel column chromatography (10% ethyl acetate and hexane) to obtain intermediate 20 in a yield of 56%.

[0268] (4) Synthesis of Intermediate 21

[0269]

[0270] Intermediate 20 (4.52 g, 6.0 mmol) was dissolved in triethyl phosphite (1.25 g, 7.5 mmol), and the resulting mixture was stirred at room temperature for 2 hours, then heated to 170°C and stirred for another 5 hours. After cooling to room temperature, benzophenone (2.0 g, 11.0 mmol), THF (30 mL) and KO were added in sequence. t Bu (2.89 g, 26.0 mmol). The reaction mixture was stirred at room temperature for 20 hours. Then, the mixture was washed twice with water and extracted with dichloromethane. The organic layer was collected, and after evaporation of the solvent, the crude product was purified by silica gel column chromatography using n-hexane as eluent to obtain intermediate 21 in a yield of 62%.

[0271] (5) Synthesis of Compound 8

[0272]

[0273] 2.53 g (2.5 mmol) of intermediate 21, 233 mg (2.5 mmol) of aniline, 145 mg (0.25 mmol) of Pd2(dba)3, 0.25 ml of tri-tert-butylphosphine (ttbp) (50% toluene solution, 5.04 mmol) and 484 mg (5.0 mmol) of sodium tert-butoxide were added to 30 ml of xylene and mixed. The mixed solution was heated to 120° C. and stirred. After the reaction was completed, the resulting reaction solution was cooled to room temperature and filtered through silica gel under reduced pressure. The filtrate was concentrated under reduced pressure. The resulting residue was then separated by silica gel column chromatography to obtain 0.71 g of compound 8 with a yield of 30%.

[0274] Example 9: Synthesis of Compound 9

[0275] (1) Synthesis of intermediate 22

[0276]

[0277] Under nitrogen, intermediate 21 (2.53 g, 2.5 mmol), CuI (95 mg, 0.5 mmol), 1,10-phenanthroline (180 mg, 1.0 mmol) and KOH (1.12 g, 20.0 mmol) were added to DMSO / H2O (5:1, 30 mL). The mixture was stirred at room temperature for 10 minutes and then heated at 100°C for 24 hours. The reaction mixture was then cooled to room temperature, acidified with dilute hydrochloric acid, diluted with 4-5 ml of ethyl acetate, filtered through a silica gel plug, and washed with 10-20 ml of ethyl acetate. The organic phases were combined and concentrated, and the resulting residue was purified by silica gel column chromatography to give intermediate 22 in a yield of 53%.

[0278] (2) Synthesis of Compound 9

[0279]

[0280] 887 mg (1.0 mmol) of intermediate 22 and 205 mg (1.0 mmol) of p-toluenesulfonic acid were dissolved in 20 ml of toluene, and the mixed solution was stirred at 100° C. for 12 hours. After the reaction solution was cooled to room temperature, K2CO3 solution was added thereto. The organic layer was extracted three times with 10 ml of ethyl acetate and then dried over MgSO4. The solvent was distilled off, and the residue was separated / purified by silica gel chromatography to obtain 0.50 g of compound 9 with a yield of 58%.

[0281] Example 10: Synthesis of Compound 10

[0282] (1) Synthesis of Compound 10

[0283]

[0284] Intermediate 21 (1.01 g, 1.0 mmol), Pd(dba)2 (57.5 mg, 0.1 mmol), 1,1'-bis(diphenylphosphino)ferrocene (77.6 mg, 0.14 mmol), potassium thioacetate (115 mg, 1.0 mmol) and K3PO4 (255 mg, 1.2 mmol) were placed in a round-bottom flask, and toluene (30 mL) and acetone (15 mL) were added. The reaction mixture was stirred at 110 °C for 6 hours under nitrogen. After cooling to room temperature, the reaction mixture was poured into 10 mL of saturated aqueous ammonium chloride solution and extracted with Et2O (3x15 mL). The organic phases were combined, washed with brine (40 ml), dried over MgSO4 and filtered. The solvent was removed under vacuum and the crude product was purified by silica gel column chromatography. The product was eluted with ethyl acetate in hexane to give compound 10 with a yield of 60%.

[0285] Application Examples

[0286] Application Example 1

[0287] On a glass substrate with a size of 25×75×1.1mm, a 50nm thick transparent electrode formed of indium tin oxide is provided. This transparent electrode is used as an anode. After ultraviolet ozone cleaning, the glass substrate is placed in a vacuum evaporation device.

[0288] First, a 40nm thick film formed of NPD is deposited as a hole injection layer. Then, a 15nm thick film formed of TCTA and a 15nm mCP layer are deposited thereon. BH-1 is then co-deposited as the main material and Compound 1 as the doping material at a mass ratio of 99:1 to form a 20nm light-emitting layer. Then, a 30nm thick film formed of TSPO1 is deposited on the light-emitting layer as an electron transport layer. In the last step, a 1nm thick LiF film is deposited as an electron injection layer, and a 100nm thick aluminum film is deposited as a cathode. Thus, an organic electroluminescent device is obtained.

[0289] Device structure: ITO (50nm) / NPD (40nm) / TCTA (15nm) / mCP (15nm) / BH-1: Compound 1 (99:1, 20nm) / TSPO1 (30nm) / LiF (1nm) / Al (100nm).

[0290] The compounds used in the embodiments of the present invention are as follows:

[0291]

[0292] For the organic electroluminescent device thus obtained, the current density of 10 mA / cm was measured by the following method: 2 The device performance (luminous efficiency) and CIE1931 (x, y) chromaticity coordinates are shown in Table 1.

[0293] Brightness: measured by a spectrophotometer (CS-2000, Konica Minolta Holdings, Inc.).

[0294] CIE1931 (x, y) chromaticity coordinates: measured by a spectrophotometer (CS-2000, Konica Minolta Holdings, Inc.).

[0295] Luminous efficiency (L / J): L / J is the ratio of brightness to current density. Current and voltage are measured by SOURCEMEASURE UNIT236 (Keithley Instruments Inc.), and brightness is measured by a spectrophotometer. The current density is calculated based on the current value and the luminous area, and then L / J is obtained. Luminous efficiency (lm / W) is obtained by the following formula: Luminous efficiency (lm / W) = L / J / voltage × π.

[0296] Application Examples 2-10

[0297] The manufacturing and measuring methods of the organic electroluminescent device are the same as those in Example 1, except for the doping materials, and the specific changes are shown in Table 1. The results are shown in Table 1.

[0298] Comparative Example 1

[0299] The manufacturing and measurement methods of the organic electroluminescent device are the same as those in Example 1, except that the doping material is BD-1, reference Nat. Photonics 13, 678–682 (2019), and the device test results are summarized in Table 1.

[0300] Table 1

[0301]

[0302] It can be seen from Table 1 that the device of the embodiment has high luminous efficiency and high color purity. Therefore, the triphenylethylene derivative containing a boron heterocycle of the present invention can realize a display device with low power consumption and high color purity.

[0303] Industrial Applications

[0304] The organic electroluminescent device of the present invention can be used as a planar light emitter, such as a flat panel display of a wall-mounted television, a backlight of a copier / printer, or a light source of a measuring instrument, a display panel, a logo lamp, etc.

[0305] Only several embodiments and / or examples of the present invention have been described in detail above, but those skilled in the art can easily modify and alter these exemplary embodiments and / or examples without substantially departing from the novel teachings and effects of the present invention. All these modifications are also included in the scope of the present invention.

Claims

1. A triphenylethylene derivative containing a boron heterocycle, characterized in that: The general structural formula is shown below: In formula (1), One of X1 and X2 is B-Ar1, and the other is O, S or N-Ar2; Ar1 ​​and Ar2 are each independently selected from phenyl, biphenyl, terphenyl, triphenylene, fluorenyl, naphthyl, dibenzothienyl, dibenzofuranyl, carbazolyl, imidazolyl, pyridyl, triazine, benzimidazolyl; When one of X1 and X2 is N-Ar2, X3 and X4 are CR'; when one of X1 and X2 is O or S, X3 and X4 are each independently selected from N and CR'; wherein R' is independently selected from a hydrogen atom, a deuterium atom, a methyl group, an ethyl group, a propyl group, an isopropyl group; R 11 ~R 14 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, and an alkyl group having 1 to 8 carbon atoms; R 21 ~R 28 Each is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a methyl group, an isobutyl group, and a phenyl group.

2. The boron heterocyclic triphenylethylene derivative according to claim 1, characterized in that: X1 is O or S, X2 is B-Ar1, and X3 and X4 are selected from N or CR'.

3. The triphenylethylene derivative containing a boron heterocycle according to claim 1, characterized in that: X1 is N-Ar2, X2 is B-Ar1, and X3 and X4 are CR'.

4. The triphenylethylene derivative containing a boron heterocycle according to claim 1, characterized in that: X1 is B-Ar1, X2 is O or S, X3 and X4 are selected from N or CR'; Or, X1 is B-Ar1, X2 is N-Ar2, and X3 and X4 are CR'.

5. The triphenylethylene derivative containing a boron heterocycle according to any one of claims 1 to 4, characterized in that: R 11 ~R 14 A hydrogen atom.

6. The triphenylethylene derivative containing a boron heterocycle according to any one of claims 1 to 4, characterized in that: R 21 ~R 28 A hydrogen atom.

7. An organic electroluminescent device, characterized in that: A triphenylethylene derivative comprising the boron heterocycle according to any one of claims 1 to 6.

8. An organic electroluminescent device according to claim 7, characterized in that: The organic electroluminescent device comprises an anode, a cathode, and an organic layer between the anode and the cathode, wherein at least one organic layer is a light-emitting layer, and the light-emitting layer is a triphenylethylene derivative containing a boron heterocycle or a mixture containing a triphenylethylene derivative containing a boron heterocycle.

9. The organic electroluminescent device according to any one of claims 7 to 8, characterized in that: The organic electroluminescent device is any one of a fluorescent or phosphorescent single-color light-emitting device, a fluorescent-phosphorescent mixed white light-emitting device, a simple light-emitting device having a single light-emitting unit, and a tandem light-emitting device having two or more light-emitting units.

10. The organic electroluminescent device according to any one of claims 7 to 8, characterized in that: The organic electroluminescent device is applied to a flat display device, a special-shaped display device, a curved display device, a flexible display device and a lighting device.

Images