A carbazole compound and an organic electroluminescent device thereof

Abstract

The present invention provides a carbazole compound and an organic electroluminescent device, relating to the technical field of organic electroluminescent materials. This compound shown in Chemical Formula I is used as a host material for the light-emitting layer. Compared with conventional organic electroluminescent compounds, the triplet energy level of this compound is higher than that of the doping material; it has appropriate HOMO and LUMO energy levels, so that when applied to an organic light-emitting device, electrons and holes are more easily injected into the active layer, effectively reducing the driving voltage of the device; in addition, this compound also has good balanced carrier transport ability and thermal stability, enabling electrons and holes to effectively recombine in the light-emitting layer and extending the service life of the device. The preparation method of the carbazole compound described in the present invention is simple and can meet the industrialization requirements. When applied to an organic light-emitting device, it has remarkable optoelectronic properties, good application effects and industrialization prospects.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials technology, specifically to a carbazole compound and its organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are display devices that emit light through carrier injection and recombination in organic materials under the influence of an electric field. Compared to traditional light-emitting materials, OLEDs, as an emerging flat-panel display device, offer numerous advantages, including self-illumination, wide viewing angles, low power consumption, fast response, low temperature operation, wide operating range, and excellent shock resistance. Furthermore, OLEDs' greatest advantage lies in their ability to achieve flexible displays, allowing them to be folded, bent, and even fit in a pocket; therefore, OLEDs are considered a "dreamlike" display technology.

[0003] OLED devices consist of an anode, a cathode, and an organic functional layer sandwiched between the anode and cathode, forming a "sandwich" structure. The organic functional layer mainly includes a hole transport layer (HTL), an emissive layer (EML), and an electron transport layer (ETL). When driven by a certain voltage, charge carriers (electrons and holes) are injected from the cathode and anode into the organic layer, respectively. Under the influence of the built-in electric field, the charge carriers migrate to the emissive layer. Holes and electrons recombine in the emissive layer to form excitons. The excitons return from the excited state to the ground state through the light radiation process, thus producing light.

[0004] Organic light-emitting materials play a crucial role in OLED devices. The emissive layer, located between the hole transport region and the electron transport region, typically employs a host and guest doping system to minimize energy loss and improve luminous efficiency. Research indicates that the triplet energy level of the host material should be higher than that of the guest material to confine triplet excitons within the emissive layer and prevent energy from being transferred from the guest to the host. Host materials with HOMO and LUMO energy levels that match those of adjacent functional layers help reduce resistance to electron and hole injection, thereby lowering the device's driving voltage.

[0005] With the development of science and technology, OLEDs are now playing an important role in electronics, industry, medicine, and the military. However, developing host materials with high triplet energy levels and balanced charge transport capabilities is quite difficult. Therefore, it is crucial to develop host materials with good thermal stability and long service life. Summary of the Invention

[0006] To address the problems existing in the prior art, the carbazole compound and its organic electroluminescent device provided by the present invention can effectively improve the luminous efficiency of OLED devices and extend the service life of OLED devices.

[0007] Specifically, the present invention provides a carbazole compound, which is represented by the following formula I:

[0008]

[0009] Wherein, ring A represents a group represented by formula II that is fused with an adjacent ring at any position, and formula II is connected to formula I through a * site;

[0010] R1 and R2 are each independently selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic ring, and fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C2-C60 heteroaryl ring.

[0011] The n1 is selected from 0, 1, 2, 3 or 4; when n1 is greater than 1, two or more R1s are the same or different from each other, or two adjacent R1s are connected to each other to form a substituted or unsubstituted ring;

[0012] The n2 is selected from 0, 1 or 2; when n2 is greater than 1, two or more R2s are the same or different from each other, or two adjacent R2s are connected to each other to form a substituted or unsubstituted ring;

[0013] Each X is independently selected from CH and N; X fused with A represents C;

[0014] The Ar1 and Ar2 may be the same or different from each other, and at least one of Ar1 or Ar2 is selected from a fused cycloalcoholic group of a C3-C30 alicyclic group and a C6-C60 aromatic group, and the others are each independently selected from one or a combination of substituted or unsubstituted silyl groups, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted C3-C30 cycloalkyl groups, and substituted or unsubstituted C6-C60 aryl groups.

[0015] The substituted groups in Ar1 and Ar2, whether substituted or unsubstituted, are each independently selected from one or a combination of hydrogen, deuterium, tritium, cyano, -F, nitro, substituted or unsubstituted silyl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, and fused cycloalkanes of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic rings.

[0016] L1 and L2 are each independently selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene group, substituted or unsubstituted C3-C30 alicyclic group, and C6-C30 aromatic group.

[0017] In addition, the present invention also provides an organic electroluminescent device, comprising an anode, a cathode and an organic layer, wherein the organic layer comprises at least one of the carbazole compounds described in the present invention.

[0018] Beneficial effects

[0019] When the carbazole compound of Formula I provided by this invention is used as the main material in the light-emitting layer of an OLED device, it possesses excellent properties such as appropriate triplet energy levels, a narrow bandgap, and good stability. These properties effectively improve the luminous efficiency of the device, reduce the driving voltage of the organic light-emitting device, and extend the device's lifespan. In summary, the carbazole-containing compound provided by this invention, when applied to OLED devices, represents a class of highly efficient, stable, long-life OLED materials suitable for commercial production and with wide applications. Detailed Implementation

[0020] The technical solutions described below, in conjunction with embodiments of the present invention, will further clarify and fully illustrate the invention. Obviously, the described embodiments are merely some, not all, of the embodiments of the present invention. After reading this invention, any modifications of the present invention by those skilled in the art will fall within the scope defined by the present invention.

[0021] In this instruction manual, This refers to the portion that is connected to another substituent. It can be attached to any optional position of the attached group / fragment.

[0022] In this specification, when a substituent or linking site lies within a bond that extends through two or more rings, it indicates that the substituent or linking site can be linked to any one of the two or more rings, specifically to any one of the corresponding optional sites within the rings. For example, Can represent Can represent And so on.

[0023] In this specification, when the position of a substituent or linker site on the ring is not fixed, it means that it can be linked to any of the optional sites on the ring. For example, Can represent Can represent Can represent And so on.

[0024] In this invention, "integers selected from 0 to M" means that the value is selected from any one of the integers from 0 to M, including 0, 1, 2...M-2, M-1, M. For example, "n1 is selected from 0 to 4" means that n1 is selected from 0, 1, 2, 3, or 4. And so on.

[0025] Examples of halogens described in this invention may include fluorine, chlorine, bromine, and iodine.

[0026] The alkyl group referred to in this invention refers to the general term for monovalent groups remaining after removing one hydrogen atom from an alkane molecule. It can be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 15 carbon atoms, more preferably having 1 to 12 carbon atoms, and particularly preferably having 1 to 6 carbon atoms. Specific examples may include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, isopropyl, sec-butyl, isobutyl, tert-butyl, etc., but are not limited thereto.

[0027] The cycloalkyl group described in this invention refers to the general term for monovalent groups obtained by removing one hydrogen atom from a cyclic alkane molecule, preferably having 3 to 25 carbon atoms, more preferably 3 to 12 carbon atoms, particularly preferably 5 to 10 carbon atoms, and most preferably 5 to 7 carbon atoms. Specific examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, etc., but are not limited thereto.

[0028] The "substituted or unsubstituted silyl group" mentioned in this invention refers to -Si(R n )3 groups, wherein each R n Each R is independently selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkenyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic rings, and fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C2-C60 heteroaryl rings. Preferably, each R nEach group is independently selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, and substituted or unsubstituted C3-C30 cycloalkyl. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and particularly preferably 3 to 7 carbon atoms. Preferably, each R... n Each group is independently selected from the following groups: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted cycloheptyl, substituted or unsubstituted adamantyl, substituted or unsubstituted norbornel, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, but not limited thereto.

[0029] The aryl group described in this invention refers to the general term for the monovalent group obtained by removing a hydrogen atom from the aromatic carbon atom of an aromatic compound molecule. It can be a monocyclic aryl, polycyclic aryl, or fused-ring aryl, preferably having 6 to 30 carbon atoms, more preferably 6 to 22 carbon atoms, even more preferably 6 to 18 carbon atoms, further preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl refers to an aryl group with only one aromatic ring in the molecule, such as phenyl, but not limited to this. The polycyclic aryl refers to an aryl group containing two or more independent aromatic rings in the molecule; specific examples include biphenyl, terphenyl, etc., but not limited to this. The fused-ring aryl refers to an aryl group containing two or more aromatic rings fused together by sharing two adjacent carbon atoms; specific examples include naphthyl, anthracene, phenanthryl, pyrene, perylene, triphenylene, fluoranthyl, etc., but not limited to this.

[0030] The arylene group referred to in this invention refers to the collective term for the divalent group remaining after removing two hydrogen atoms from the aromatic carbon atom of an aromatic hydrocarbon molecule. It can be a monocyclic arylene, a polycyclic arylene, or a fused-ring arylene, preferably having 6 to 30 carbon atoms, more preferably 6 to 25 carbon atoms, even more preferably 6 to 18 carbon atoms, further preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene includes, but is not limited to, phenylene; the polycyclic arylene includes, but is not limited to, biphenylene, terphenylene; specific examples may include naphthylene, anthracene, phenanthrene, pyrene, terphenylene, fluoranthracene, etc., but are not limited to.

[0031] The alicyclic group mentioned in this invention refers to the general term for monovalent groups obtained by removing one hydrogen atom from an alicyclic hydrocarbon molecule. These groups can be cycloalkyl, cycloalkenyl, etc., preferably having 3 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, particularly preferably 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and most preferably 5 to 7 carbon atoms. Specific examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc., but are not limited thereto.

[0032] The fused alicyclic and aromatic cyclic groups described in this invention refer to the general term for monovalent groups obtained by removing one hydrogen atom after the alicyclic and aromatic rings are fused together. Preferably, they have 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 13 carbon atoms. Specific examples may include benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocycloheptyl, benzocyclopentenyl, benzocyclohexenyl, dihydroindenyl, indenyl, naphthocyclopropyl, naphthocyclobutyl, naphthocyclopentyl, naphthocyclohexyl, tetrahydronaphthyl, dihydronaphthyl, etc., but are not limited to these.

[0033] The alicyclic and aromatic ring fused cyclic groups described in this invention refer to the general term for divalent groups obtained by removing two hydrogen atoms after the alicyclic and aromatic rings are fused together. Preferably, they have 7 to 30 carbon atoms, more preferably 7 to 18 carbon atoms, and most preferably 7 to 13 carbon atoms. Specific examples may include benzocyclopropyl, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, benzocycloheptyl, benzocyclopentenyl, benzocyclohexenyl, dihydroindenyl, indenyl, naphthocyclopropyl, naphthocyclobutyl, naphthocyclopentyl, naphthocyclohexyl, tetrahydronaphthyl, dihydronaphthyl, etc., but are not limited thereto.

[0034] The substituents described in the "substituted or unsubstituted" of this invention may be independently selected from deuterium, cyano, nitro, halogen atom, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C30 aryl, but are not limited thereto, or adjacent substituents may be linked to form a ring. Preferred substituents include deuterium, cyano, nitro, halogen atoms, C1-C15 alkyl groups, C3-C25 cycloalkyl groups, and C6-C30 aryl groups. Specific examples may include deuterium, fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclopropyl, cyclohexyl, adamantyl, norbornel, phenyl, tolyl, mesitylene, pentadeuterated phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, perylene, pyrene, fluoranyl, etc., but are not limited thereto. Alternatively, when there are multiple substituents, the multiple substituents may be the same or different from each other; or adjacent substituents may be linked to form a ring.

[0035] The "ring formation" described in this invention refers to two groups being linked together by chemical bonds and optionally aromatized. An example is shown below:

[0036]

[0037] In this invention, the ring formed by the connection can be an aromatic ring system, an aliphatic ring system, or a ring system formed by the fusion of the two. It can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, or a fused ring. Examples may include benzene, naphthalene, indene, cyclopentene, cyclopentane, cyclopentanophenene, cyclohexene, cyclohexane, cyclohexanophenylene, or pyrene, but are not limited thereto.

[0038] This invention provides a carbazole compound, said carbazole compound being represented by the following formula I:

[0039]

[0040] Wherein, ring A represents a group represented by formula II that is fused with an adjacent ring at any position, and formula II is connected to formula I through a * site;

[0041] R1 and R2 are each independently selected from one or a combination of hydrogen, deuterium, tritium, cyano, halogen, nitro, C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic ring, and fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C2-C60 heteroaryl ring.

[0042] The n1 is selected from 0, 1, 2, 3 or 4; when n1 is greater than 1, two or more R1s are the same or different from each other, or two adjacent R1s are connected to each other to form a substituted or unsubstituted ring;

[0043] The n2 is selected from 0, 1 or 2; when n2 is greater than 1, two or more R2s are the same or different from each other, or two adjacent R2s are connected to each other to form a substituted or unsubstituted ring;

[0044] Each X is independently selected from CH and N; X fused with A represents C;

[0045] The Ar1 and Ar2 may be the same or different from each other, and at least one of Ar1 or Ar2 is selected from a fused cycloalcoholic group of a C3-C30 alicyclic group and a C6-C60 aromatic group, and the others are each independently selected from one or a combination of substituted or unsubstituted silyl groups, substituted or unsubstituted C1-C30 alkyl groups, substituted or unsubstituted C3-C30 cycloalkyl groups, and substituted or unsubstituted C6-C60 aryl groups.

[0046] The substituted groups in Ar1 and Ar2, whether substituted or unsubstituted, are each independently selected from one or a combination of hydrogen, deuterium, tritium, cyano, -F, nitro, substituted or unsubstituted silyl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, and fused cycloalkanes of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic rings.

[0047] L1 and L2 are each independently selected from one of the following: single bond, substituted or unsubstituted C6-C30 arylene group, substituted or unsubstituted C3-C30 alicyclic group, and C6-C30 aromatic group.

[0048] Preferably, the carbazole compound is selected from at least one of formula Ia.

[0049]

[0050] More preferably, the carbazole compound is selected from at least one of formulas I-1 to I-6.

[0051]

[0052] Preferably, in Formula I, Formula I-1 to Formula I-6, at most three X are selected from N, or at most two X are selected from N, or at most one X is selected from N.

[0053] Preferably, at least one of the Ar1 or Ar2 groups is selected from those represented by formulas III, IV, V or VI.

[0054]

[0055] The ring B is selected from an aromatic ring of C6 to C60; the rings C1 and C2 are each independently selected from an alicyclic ring of C3 to C30 that is fused with an adjacent ring at any position.

[0056] Wherein, R3 and R4 are each independently selected from one of hydrogen, deuterium, tritium, -F, cyano, nitro, substituted or unsubstituted silyl, substituted or unsubstituted C1 to C15 alkyl, substituted or unsubstituted C3 to C15 cycloalkyl, and substituted or unsubstituted C6 to C25 aryl.

[0057] The n3 is selected from 0, 1, 2 or 3;

[0058] The n4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; when n4 is greater than 1, two or more R4s are the same or different from each other, or two adjacent R4s are connected to each other to form a substituted or unsubstituted ring.

[0059] More preferably, at least one of Ar1 and Ar2 is selected from any of the following structures:

[0060]

[0061]

[0062] R3 and R4 are each independently selected from one of hydrogen, deuterium, tritium, -F, cyano, nitro, substituted or unsubstituted silyl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl, or two adjacent R4 are connected to each other to form a substituted or unsubstituted ring;

[0063] The n5 is selected from 0 or 1; the n6 is selected from 0, 1, 2, 3, 4, 5 or 6; the n7 is selected from 0, 1, 2, 3, 4 or 5; the n8 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; and the n9 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

[0064] More preferably, at least one of the Ar1 or Ar2 is selected from one of the following groups:

[0065]

[0066] Preferably, when Ar1 and Ar2 are not selected from any one of the fused cyclic groups of C3-C30 alicyclic and C6-C60 aromatic rings (e.g., chemical formula III, chemical formula IV, chemical formula V or chemical formula VI), they are each independently selected from one of the following groups.

[0067]

[0068]

[0069] Each of the R5s is independently selected from one of the following: hydrogen, deuterium, tritium, cyano, -F, nitro, substituted or unsubstituted silyl, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C25 cycloalkyl, substituted or unsubstituted C6-C25 aryl, fused cycloalcoholic group of substituted or unsubstituted C3-C30 alicyclic and C6-C60 aromatic ring, or two adjacent R5s are connected to each other to form a substituted or unsubstituted ring;

[0070] k1 is selected from 0, 1, 2, 3, 4 or 5; k2 is selected from 0, 1, 2, 3 or 4; k3 is selected from 0, 1, 2, 3, 4, 5 or 6; k4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; k5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; k6 is selected from 0, 1 or 2; k7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11; k8 is selected from 0, 1, 2 or 3; when there are two or more R5s, the two or more R5s are the same as or different from each other.

[0071] More preferably, when Ar1 and Ar2 are not selected from any one of the fused cyclic groups of C3-C30 alicyclic and C6-C60 aromatic rings (e.g., chemical formula III, chemical formula IV, chemical formula V or chemical formula VI), they are each independently selected from one of the following groups.

[0072]

[0073]

[0074] Preferably, L1 and L2 are each independently selected from a single bond or one of the following groups:

[0075]

[0076] Each of the R6 groups is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted silyl group, substituted or unsubstituted C1-C15 alkyl group, substituted or unsubstituted C3-C20 alicyclic group, and substituted or unsubstituted C6-C25 aryl group.

[0077] The m1 is selected from 0, 1, 2, 3 or 4; the m2 is selected from 0, 1, 2, 3, 4, 5 or 6; the m3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the m4 is selected from 0, 1 or 2; the m5 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m6 is selected from 0, 1, 2, 3, 4 or 5; the m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the m8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; when there are two or more R6, the two or more R6 are the same as or different from each other.

[0078] Most preferably, the carbazole compound is selected from any one of the following structures:

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] The above lists some specific structural forms of carbazole compounds represented by chemical formula I according to the present invention. However, the present invention is not limited to these listed chemical structures. Any structure based on the structure shown in chemical formula I, with substituents as defined above, should be included.

[0096] In addition, the present invention also provides an organic electroluminescent device comprising at least one of the carbazole compounds described in the present invention.

[0097] Preferably, the organic electroluminescent device includes an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the organic layer contains at least one of the carbazole compounds described in this invention.

[0098] More preferably, the organic electroluminescent device includes an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the organic layer includes a light-emitting layer, wherein the light-emitting layer contains at least one of the carbazole compounds described in this invention.

[0099] More preferably, the organic electroluminescent device includes an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the light-emitting layer includes a host material and a guest material, wherein the host material contains one or more of the carbazole-containing compounds described in this invention; further preferably, the host material contains one or more of the carbazole-containing compounds described in this invention and at least one other type of compound; even more preferably, the host material contains one or more of the carbazole-containing compounds described in this invention.

[0100] The anode material described in this invention is preferably a material with a high work function. The anode can be a transmission electrode, a reflection electrode, or a semi-transmission electrode. When the anode is a transmission electrode, the material used to form the anode can be selected from indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or any combination thereof; when the anode is a semi-transmission electrode or a reflection electrode, the material used to form the anode can be selected from magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof. The anode can have a single-layer structure or a multilayer structure including two or more layers. For example, the anode can have a single-layer structure of Al or a three-layer structure of ITO / Ag / ITO, but the structure of the anode is not limited to these.

[0101] The hole injection layer described in this invention can be a monolayer structure composed of a single substance, or a monolayer or multilayer structure composed of different substances. Triaromatic amine compounds, porphyrin compounds, styrene compounds, polythiophene and its derivatives, phthalocyanine derivatives, axialene compounds, and other substances with high hole injection properties can be used. Examples include 4,4',4”-tris[2-naphthylphenylamino]triphenylamine (2-TNATA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzenephenanthrene (HATCN), copper phthalocyanine (CuPC), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ), poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) (PEDOT / PSS), and the carbazole-containing aromatic amine compounds described in this invention, but are not limited thereto.

[0102] The hole transport layer material described in this invention is preferably a material with high hole mobility. In addition to the carbazole compound provided in this invention, the hole transport layer material may also include: phthalocyanine compounds, anthraquinone compounds, biphenyl diamine derivatives, triarylamine derivatives, carbazole derivatives, fluorene derivatives, stilbene derivatives, quinacridone compounds, hexanitrile hexaazabenzophenanthrene compounds, polythiophene, polyaniline, polyvinylcarbazole, etc., but is not limited to these.

[0103] The luminescent layer of this invention comprises a host material and a dopant material. Red, green, or blue luminescent materials can be used. The luminescent layer material may comprise multiple host materials and multiple dopant materials. The guest material can be a simple fluorescent material or a phosphorescent material, or a combination of fluorescent and phosphorescent materials. The doping ratio of the host material and the dopant material varies depending on the material used. Typically, the doping ratio of the dopant material is 0.01% to 20%, preferably 0.1% to 15%, and more preferably 1% to 10%. In addition to the carbazole compound provided in this invention, the host material of the luminescent layer may also include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentane derivatives, phenanthrene derivatives, fluoranthene derivatives, and heterocyclic compounds including carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, pyrimidine derivatives, stilbeneylaryl derivatives, mestilbene derivatives, etc., but is not limited to these. The guest material may include, but is not limited to, metal complexes (such as iridium complexes, platinum complexes, osmium complexes, rhodium complexes, terbium complexes, europium complexes, etc.), anthracene derivatives, pyrene derivatives, perylene derivatives, pyrrole derivatives, indole derivatives, carbazole derivatives, etc.

[0104] The electron transport layer described in this invention can be a single-layer structure composed of a single substance, or a single-layer or multi-layer structure composed of different substances. It can use aluminum complexes, beryllium complexes, zinc complexes, imidazole derivatives, benzimidazole derivatives, carbazole derivatives, phenanthroline derivatives, polymers, etc. with high electron transport properties. Examples include Alq3, bis(10-hydroxybenzo[h]quinoline)beryllium (BeBq2), BAlq, 2-(4-biphenyl)-5-phenyloxadiazole (PBD), etc., but are not limited to these.

[0105] The electron injection layer described in this invention is preferably made of a material with a low work function. It can be a monolayer structure composed of a single substance, or a monolayer or multilayer structure composed of different substances. It can be selected from one or more of the following structures: alkali metals, alkaline earth metals, alkali metal halides, alkaline earth metal halides, alkali metal oxides, alkaline earth metal oxides, alkali metal salts, alkaline earth metal salts, and other substances with high electron injection properties. Examples include Li, Ca, Sr, LiF, CsF, CaF2, BaO, Li2CO3, CaCO3, Li2C2O4, Cs2C2O4, CsAlF4, LiOx, Yb, Tb, etc., but are not limited to these.

[0106] As the cathode described in this invention, a material with a low work function is preferred. The cathode can be a transmission electrode, a semi-reflective electrode, or a reflective electrode. When the cathode is a transmission electrode, the material used to form the cathode can be selected from transparent metal oxides (e.g., ITO, IZO, etc.); when the cathode is a semi-reflective electrode or a reflective electrode, the material used to form the cathode can be selected from Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF / Ca, LiF / Al, Mo, Ti, compounds including them, or mixtures thereof (e.g., mixtures of Ag and Mg), but is not limited thereto.

[0107] The aforementioned organic layers, cathode, and anode can be prepared using any of the following methods: vacuum evaporation, inkjet printing, sputtering, plasma deposition, ion plating, spin coating, dip coating, or screen printing. There are no particular limitations on the thickness of each layer, as long as good device performance is achieved. The aforementioned organic layers are preferably prepared using vacuum evaporation, inkjet printing, or spin coating, but are not limited to these methods.

[0108] The organic electroluminescent device described in this invention is mainly used in the field of information display technology. It is widely used in various information displays, such as tablet computers, flat-screen TVs, mobile phones, smartwatches, digital cameras, VR, in-vehicle systems, wearable devices, etc.

[0109] Synthesis Examples

[0110] Preparation and characterization of compounds

[0111] Description of raw materials, reagents, and characterization equipment:

[0112] Raw materials and reagents: The present invention does not impose any particular restrictions on the source of raw materials and reagents used in the following examples and comparative examples. They can be commercially available products or prepared by methods known to those skilled in the art. All raw materials and reagents are reagent pure.

[0113] Instrumentation: Mass spectrometry was performed using a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer (UK), with chloroform as the solvent; elemental analysis was performed using a Vario EL cube organic elemental analyzer from Elementar GmbH (Germany), with sample mass ranging from 5 to 10 mg.

[0114] The following is one method for preparing the compound represented by Chemical Formula I of this invention, but the preparation method of this invention is not limited thereto. The core structure of the compound of Chemical Formula I can be prepared by the reaction route shown below, using conventional methods well known to those skilled in the art. For example, carbon-carbon coupling reaction, carbon-nitrogen coupling reaction, etc., and the type and position or number of substituents can be changed according to techniques known in the art.

[0115] Method 1:

[0116]

[0117] Method 2:

[0118]

[0119] Xa, Xb, and Xc are each independently selected from any one of I, Br, and Cl; the limitations of X, Ar1~Ar2, L1~L2, R1~R2, and n1~n2 are the same as those described above.

[0120] Synthesis Example 1: Preparation of Intermediate M-15

[0121]

[0122] Under nitrogen protection, m-15 (12.15 g, 75.00 mmol), n-15 (14.36 g, 75.00 mmol), K2CO3 (18.66 g, 135.00 mmol), and 750 mL of toluene solvent were added to a reaction flask and stirred. Pd(PPh3)4 (0.87 g, 0.75 mmol) catalyst and 132 mL of distilled water were added, the temperature was raised to reflux, and the reaction was stirred for 6 hours. After the reaction was complete, 188 mL of distilled water was added to terminate the reaction. The crude intermediate M-15 was obtained by filtration under reduced pressure, washed three times with distilled water, and then recrystallized from toluene / ethanol (10:1) to obtain intermediate M-15 (14.58 g, 85%). HPLC analysis showed a solid purity ≥99.84%. Mass spectrometry m / z: 228.0717 (theoretical value: 228.0706).

[0123] According to the above preparation method, the following intermediates were also synthesized in this invention:

[0124]

[0125]

[0126] Synthesis Example 2: Synthesis of Compound 15

[0127]

[0128] Under argon protection, D-15 (13.16 g, 30.00 mmol), M-15 (8.01 g, 35.00 mmol), copper powder (2.22 g, 35.00 mmol), 18-crown ether-6 (0.79 g, 3.00 mmol), K₂CO₃ (10.37 g, 75.00 mmol), and 1,2-dichlorobenzene (225 ml) were added to a reaction flask, and the mixture was stirred under reflux for 20 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene and dried to obtain compound 15 (13.82 g, yield 73%). HPLC analysis showed that the solid purity was ≥99.97%. Mass spectrometry m / z: 630.3048 (theoretical value: 630.3035). Theoretical elemental content (%) C 47 H 38 N2: C, 89.49; H, 6.07; N, 4.44. Measured elemental content (%): C, 89.54; H, 6.11; N, 4.41.

[0129] Synthesis Example 3: Synthesis of Compound 38

[0130]

[0131] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-38, and M-15 was replaced with an equimolar amount of M-38, yielding compound 38 (14.06 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 624.2554 (theoretical value: 624.2565). Theoretical elemental content (%) C 47 H 32 N2: C, 90.35; H, 5.16; N, 4.48. Measured elemental content (%): C, 90.40; H, 5.20; N, 4.52.

[0132] Synthesis Example 4: Synthesis of Compound 65

[0133]

[0134] Under argon protection, E-65 (7.99 g, 30.00 mmol), M-65 (20.49 g, 75.00 mmol), copper powder (4.77 g, 75.00 mmol), 18-crown ether-6 (0.79 g, 3.00 mmol), potassium carbonate (20.73 g, 150.00 mmol), and 1,2-dichlorobenzene (375 ml) were added to a reaction flask, and the mixture was stirred under reflux for 20 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene and dried to obtain compound 65 (14.45 g, yield 74%). HPLC analysis showed that the solid purity was ≥99.98%. Mass spectrometry m / z: 650.3520 (theoretical value: 650.3506). Theoretical elemental content (%) C 48 H 26 D 10 N2: C, 88.58; H, 7.12; N, 4.30. Measured elemental content (%): C, 88.63; H, 7.08; N, 4.33.

[0135] Synthesis Example 5: Synthesis of Compound 91

[0136]

[0137] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-91, and M-15 was replaced with an equimolar amount of d-91, yielding compound 91 (12.72 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 498.2083 (theoretical value: 498.2096). Theoretical elemental content (%) C 37 H 26N2: C, 89.13; H, 5.26; N, 5.62. Measured elemental content (%): C, 89.18; H, 5.23; N, 5.66.

[0138] Synthesis Example 6: Synthesis of Compound 94

[0139]

[0140] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-94, and M-15 was replaced with an equimolar amount of d-94, yielding compound 94 (12.86 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 498.2085 (theoretical value: 498.2096). Theoretical elemental content (%) C 37 H 26 N2: C, 89.13; H, 5.26; N, 5.62. Measured elemental content (%): C, 89.16; H, 5.21; N, 5.59.

[0141] Synthesis Example 7: Synthesis of Compound 98

[0142]

[0143] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-98, and M-15 was replaced with an equimolar amount of d-91, yielding compound 98 (13.03 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 529.2553 (theoretical value: 529.2566). Theoretical elemental content (%) C 39 H 23 D5N2: C, 88.43; H, 6.28; N, 5.29. Measured elemental content (%): C, 88.38; H, 6.32; N, 5.26.

[0144] Synthesis Example 8: Synthesis of Compound 104

[0145]

[0146] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-104, and M-15 was replaced with an equimolar amount of M-104, yielding compound 104 (13.10 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 614.2736 (theoretical value: 614.2722). Theoretical elemental content (%) C 46 H 34N2: C, 89.87; H, 5.57; N, 4.56. Measured element content (%): C, 89.82; H, 5.61; N, 4.53.

[0147] Synthesis Example 9: Synthesis of Compound 117

[0148]

[0149] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-117 to obtain compound 117 (13.45 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 574.2421 (theoretical value: 574.2409). Theoretical elemental content (%) C 43 H 30 N2: C, 89.86; H, 5.26; N, 4.87. Measured elemental content (%): C, 89.81; H, 5.30; N, 4.84.

[0150] Synthesis Example 10: Synthesis of Compound 118

[0151]

[0152] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-118, and M-15 was replaced with an equimolar amount of M-118, yielding compound 118 (13.22 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 579.2710 (theoretical value: 579.2723). Theoretical elemental content (%) C 43 H 25 D5N2: C, 89.08; H, 6.08; N, 4.83. Measured elemental content (%): C, 89.03; H, 6.12; N, 4.80.

[0153] Synthesis Example 11: Synthesis of Compound 159

[0154]

[0155] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-159, and M-15 was replaced with an equimolar amount of d-94, yielding compound 159 (13.49 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 583.2987 (theoretical value: 583.2974). Theoretical elemental content (%) C 43 H 21D9N2: C, 88.47; H, 6.73; N, 4.80. Measured elemental content (%): C, 88.52; H, 6.69; N, 4.83.

[0156] Synthesis Example 12: Synthesis of Compound 180

[0157]

[0158] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-180 to obtain compound 180 (14.83 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 658.3360 (theoretical value: 658.3348). Theoretical elemental content (%) C 49 H 42 N2: C, 89.32; H, 6.43; N, 4.25. Measured elemental content (%): C, 89.27; H, 6.39; N, 4.28.

[0159] Synthesis Example 13: Synthesis of Compound 188

[0160]

[0161] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-188, and M-15 was replaced with an equimolar amount of M-188, yielding compound 188 (16.14 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 802.3360 (theoretical value: 802.3348). Theoretical elemental content (%) C 61 H 42 N2: C, 91.24; H, 5.27; N, 3.49. Measured elemental content (%): C, 91.19; H, 5.30; N, 3.45.

[0162] Synthesis Example 14: Synthesis of Compound 193

[0163]

[0164] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-193, and M-15 was replaced with an equimolar amount of M-193, yielding compound 193 (15.35 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 700.2864 (theoretical value: 700.2878). Theoretical elemental content (%) C 53 H 36N2: C, 90.83; H, 5.18; N, 4.00. Measured elemental content (%): C, 90.78; H, 5.21; N, 3.96.

[0165] Synthesis Example 15: Synthesis of Compound 208

[0166]

[0167] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-208, and M-15 was replaced with an equimolar amount of M-65 to obtain compound 208 (13.70 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 600.2579 (theoretical value: 600.2565). Theoretical elemental content (%) C 45 H 32 N2: C, 89.97; H, 5.37; N, 4.66. Measured element content (%): C, 90.02; H, 5.41; N, 4.70.

[0168] Synthesis Example 16: Synthesis of Compound 225

[0169]

[0170] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-225, and M-15 was replaced with an equimolar amount of M-65, yielding compound 225 (14.58 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 674.2735 (theoretical value: 674.2722). Theoretical elemental content (%) C 51 H 34 N2: C, 90.77; H, 5.08; N, 4.15. Measured elemental content (%): C, 90.82; H, 5.12; N, 4.11.

[0171] Synthesis Example 17: Synthesis of Compound 227

[0172]

[0173] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-227, and M-15 was replaced with an equimolar amount of M-227 to obtain compound 227 (14.85 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 642.2458 (theoretical value: 642.2471). Theoretical elemental content (%) C 47 H 31FN2: C, 87.82; H, 4.86; N, 4.36. Measured elemental content (%): C, 87.77; H, 4.90; N, 4.32.

[0174] Synthesis Example 18: Synthesis of Compound 231

[0175]

[0176] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-231, and M-38 was replaced with an equimolar amount of d-231, yielding compound 231 (12.91 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 524.3019 (theoretical value: 524.3006). Theoretical elemental content (%) C 38 H 16 D 12 N2: C, 86.98; H, 7.68; N, 5.34. Measured elemental content (%): C, 87.03; H, 7.72; N, 5.30.

[0177] Synthesis Example 19: Synthesis of Compound 237

[0178]

[0179] Synthesis of intermediate D-237:

[0180] Under argon protection, E-237 (24.95 g, 70.00 mmol), M-237 (18.21 g, 75.00 mmol), copper powder (4.77 g, 75.00 mmol), 18-crown ether-6 (1.85 g, 7.00 mmol), potassium carbonate (20.73 g, 150.00 mmol), and 1,2-dichlorobenzene (875 ml) were added to a reaction flask, and the mixture was stirred under reflux for 13 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene and dried to obtain intermediate D-237 (32.69 g, yield 83%). The purity of the solid was ≥99.86% as determined by HPLC. Mass spectrometry m / z: 562.2397 (theoretical value: 562.2409).

[0181] Synthesis of compound 237:

[0182] Under argon protection, D-237 (16.88 g, 30.00 mmol), d-237 (6.47 g, 35.00 mmol), copper powder (2.22 g, 35.00 mmol), 18-crown ether-6 (0.79 g, 3.00 mmol), potassium carbonate (9.67 g, 70.00 mmol), and 1,2-dichlorobenzene (225 ml) were added to a reaction flask, and the mixture was stirred under reflux for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene and dried to obtain compound 237 (15.48 g, yield 73%). HPLC analysis showed that the solid purity was ≥99.91%. Mass spectrometry m / z: 706.2607 (theoretical value: 706.2596). Theoretical elemental content (%) C 49 H 33 F3N2: C, 83.27; H, 4.71; N, 3.96. Measured elemental content (%): C, 83.32; H, 4.67; N, 4.00.

[0183] Synthesis Example 20: Synthesis of Compound 238

[0184]

[0185] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-238, and M-15 was replaced with an equimolar amount of M-237, yielding compound 238 (14.58 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 714.3022 (theoretical value: 714.3035). Theoretical elemental content (%) C 54 H 38 N2: C, 90.72; H, 5.36; N, 3.92. Measured elemental content (%): C, 90.67; H, 5.40; N, 3.89.

[0186] Synthesis Example 21: Synthesis of Compound 280

[0187]

[0188] Following the same preparation method as compound 65 in Example 4, E-65 was replaced with an equimolar amount of E-280, and M-65 was replaced with an equimolar amount of M-280, yielding compound 280 (14.99 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 648.3370 (theoretical value: 648.3381). Theoretical elemental content (%) C 48 H 28D8N2: C, 88.85; H, 6.83; N, 4.32. Measured elemental content (%): C, 88.80; H, 6.79; N, 4.35.

[0189] Synthesis Example 22: Synthesis of Compound 283

[0190]

[0191] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-283, and M-15 was replaced with an equimolar amount of d-283, yielding compound 283 (12.40 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 464.1990 (theoretical value: 464.2001). Theoretical elemental content (%) C 32 H 24 N4: C, 82.73; H, 5.21; N, 12.06. Measured elemental content (%): C, 82.68; H, 5.17; N, 12.10.

[0192] Synthesis Example 23: Synthesis of Compound 300

[0193]

[0194] Preparation of intermediate A-300:

[0195] Under argon protection, a-300 (24.20 g, 120.00 mmol), b-300 (32.12 g, 150.00 mmol), copper powder (9.53 g, 150.00 mmol), 18-crown ether-6 (3.17 g, 12.00 mmol), potassium carbonate (33.17 g, 240.00 mmol), and 1,2-dichlorobenzene (720 ml) were added to a reaction flask, and the mixture was stirred under reflux for 8 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene and dried to obtain intermediate A-300 (34.16 g, yield 85%). The purity of the solid was ≥99.72% as determined by HPLC. Mass spectrometry m / z: 334.1267 (theoretical value: 334.1254).

[0196] Preparation of intermediate B-300:

[0197] Under argon protection, A-300 (30.14 g, 90.00 mmol), pinacol diborate (24.12 g, 95.00 mmol), 1,1-bis(diphenylphosphine)ferrocene palladium dichloride (0.66 g, 0.90 mmol), potassium acetate (17.67 g, 180.00 mmol), and DMF (450 ml) were added to a reaction flask and stirred under reflux for 9 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene:methanol (5:1) and dried to obtain intermediate B-300 (31.08 g, 81%). The purity of the solid was ≥99.76% as determined by HPLC. Mass spectrometry m / z: 426.2507 (theoretical value: 426.2496).

[0198] Preparation of intermediate C-300:

[0199] Under argon protection, B-300 (29.85 g, 70.00 mmol), C-300 (17.64 g, 70.00 mmol), Pd(PPh3)4 (0.81 g, 0.70 mmol), potassium carbonate (19.35 g, 140.00 mmol), THF (350 ml), and water (175 ml) were added to the reaction flask, and the mixture was stirred under reflux for 10 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene:methanol = 10:1 and dried to obtain intermediate C-300 (25.75 g, 78%). The purity of the solid was ≥99.80% as determined by HPLC. Mass spectrometry m / z: 471.1951 (theoretical value: 471.1964).

[0200] Preparation of intermediate D-300:

[0201] Under argon protection, C-300 (23.58 g, 50.00 mmol), triphenylphosphine (32.79 g, 125.00 mmol), and o-dichlorobenzene (250 ml) were added to the reaction flask, and the mixture was stirred under reflux for 13 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene:ethanol = 10:1 and dried to obtain intermediate D-300 (16.26 g, 74%). The purity of the solid was ≥99.87% as determined by HPLC. Mass spectrometry m / z: 439.2079 (theoretical value: 439.2066).

[0202] Preparation of compound 300:

[0203] Under argon protection, D-300 (13.19 g, 30.00 mmol), M-65 (8.01 g, 35.00 mmol), copper powder (2.22 g, 35.00 mmol), 18-crown ether-6 (0.79 g, 3.00 mmol), potassium carbonate (9.67 g, 70.00 mmol), and 1,2-dichlorobenzene (150 ml) were added to a reaction flask, and the mixture was stirred under reflux for 19 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from toluene and dried to obtain compound 300 (14.41 g, yield 76%). HPLC analysis showed that the solid purity was ≥99.95%. Mass spectrometry m / z: 631.3019 (theoretical value: 631.3005). Theoretical elemental content (%) C 47 H 25 D7N2: C, 89.35; H, 6.22; N, 4.43. Measured elemental content (%): C, 89.40; H, 6.18; N, 4.39.

[0204] Synthesis Example 24: Synthesis of Compound 303

[0205]

[0206] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-303, and M-15 was replaced with an equimolar amount of M-303, yielding compound 303 (13.25 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 538.2419 (theoretical value: 538.2409). Theoretical elemental content (%) C 40 H 30 N2: C, 89.19; H, 5.61; N, 5.20. Measured elemental content (%): C, 89.24; H, 5.57; N, 5.16.

[0207] Synthesis Example 25: Synthesis of Compound 329

[0208]

[0209] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-329, and M-15 was replaced with an equimolar amount of M-65, yielding compound 329 (13.19 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 529.2580 (theoretical value: 529.2566). Theoretical elemental content (%) C 39 H 23D5N2: C, 88.43; H, 6.28; N, 5.29. Measured elemental content (%): C, 88.38; H, 6.32; N, 5.26.

[0210] Synthesis Example 26: Synthesis of Compound 346

[0211]

[0212] Following the same preparation method as compound 300 in Synthesis Example 23, a-300 was replaced with an equimolar amount of a-346, b-300 with an equimolar amount of b-346, c-300 with an equimolar amount of c-346, and M-65 with an equimolar amount of d-346, yielding compound 346 (13.17 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 548.2239 (theoretical value: 548.2252). Theoretical elemental content (%) C 41 H 28 N2: C, 89.75; H, 5.14; N, 5.11. Measured elemental content (%): C, 89.80; H, 5.09; N, 5.07.

[0213] Synthesis Example 27: Synthesis of Compound 402

[0214]

[0215] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-402, and M-15 was replaced with an equimolar amount of M-402, yielding compound 402 (13.22 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 524.2269 (theoretical value: 524.2252). Theoretical elemental content (%) C 39 H 28 N2: C, 89.28; H, 5.38; N, 5.34. Measured element content (%): C, 89.33; H, 5.41; N, 5.30.

[0216] Synthesis Example 28: Synthesis of Compound 439

[0217]

[0218] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-439, and M-15 was replaced with an equimolar amount of M-439, yielding compound 439 (13.19 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 563.2349 (theoretical value: 563.2361). Theoretical elemental content (%) C 41 H29 N3: C, 87.36; H, 5.19; N, 7.45. Measured elemental content (%): C, 87.41; H, 5.23; N, 7.41.

[0219] Synthesis Example 29: Synthesis of Compound 443

[0220]

[0221] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-443, and M-15 was replaced with an equimolar amount of M-65, yielding compound 443 (14.83 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 726.3050 (theoretical value: 726.3035). Theoretical elemental content (%) C 55 H 38 N2: C, 90.88; H, 5.27; N, 3.85. Measured element content (%): C, 90.93; H, 5.31; N, 3.82.

[0222] Synthesis Example 30: Synthesis of Compound 458

[0223]

[0224] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-458, and M-15 was replaced with an equimolar amount of d-94, yielding compound 458 (13.11 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 598.2421 (theoretical value: 598.2409). Theoretical elemental content (%) C 45 H 30 N2: C, 90.27; H, 5.05; N, 4.68. Measured elemental content (%): C, 90.32; H, 5.01; N, 4.71.

[0225] Synthesis Example 31: Synthesis of Compound 471

[0226]

[0227] Following the same preparation method as compound 237 in Synthesis Example 19, E-237 was replaced with an equimolar amount of E-471, M-237 with an equimolar amount of M-471, and d-237 with an equimolar amount of M-303, yielding compound 471 (15.23 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 704.3179 (theoretical value: 704.3191). Theoretical elemental content (%) C 53 H 40N2: C, 90.31; H, 5.72; N, 3.97. Measured elemental content (%): C, 90.26; H, 5.68; N, 4.01.

[0228] Synthesis Example 32: Synthesis of Compound 512

[0229]

[0230] Following the same preparation method as compound 237 in Synthesis Example 19, E-237 was replaced with an equimolar amount of E-512, M-237 with an equimolar amount of d-94, and d-237 with an equimolar amount of d-512, yielding compound 512 (13.28 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 520.2348 (theoretical value: 520.2335). Theoretical elemental content (%) C 36 H 32 N₂Si: C, 83.03; H, 6.19; N, 5.38. Measured elemental content (%): C, 82.98; H, 6.22; N, 5.42.

[0231] Synthesis Example 33: Synthesis of Compound 545

[0232]

[0233] Following the same preparation method as compound 15 in Synthesis Example 2, D-15 was replaced with an equimolar amount of D-545, and M-15 was replaced with an equimolar amount of M-471, yielding compound 545 (12.91 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 524.2264 (theoretical value: 524.2252). Theoretical elemental content (%) C 39 H 28 N2: C, 89.28; H, 5.38; N, 5.34. Measured element content (%): C, 89.33; H, 5.41; N, 5.30.

[0234] [Device Example 1]

[0235] First, the ITO glass substrate was washed twice with distilled water, and then ultrasonically cleaned for 30 minutes. The substrate was then ultrasonically cleaned sequentially with solvents such as isopropanol, acetone, and methanol, dried on a hot plate heated to 120°C, and transferred to a plasma cleaner for 5 minutes before being transferred to a vacuum evaporator. Using a vacuum deposition apparatus, the prepared ITO transparent electrode served as the anode. On the glass substrate, using ITO as the anode, a 10 nm thick HI-1 film was vacuum-deposited to form a hole injection layer. HT-1 was then vacuum-deposited on the hole injection layer as a hole transport layer with a thickness of 50 nm. Under the same vacuum deposition conditions, a 30 nm thick host material and dopant (8 wt%) were deposited on the hole transport layer as a light-emitting layer. Compound 15 and H2-1 (mass ratio 1:1) prepared in the above examples were used as the host material, and Ir(ppy)3 as the dopant. Subsequently, HB-1 was deposited on the light-emitting layer to form a 5 nm thick hole blocking layer. On the hole blocking layer, ET-1 and LiF are sequentially deposited by vacuum evaporation as the electron transport layer (50 nm) and the electron injection layer (1 nm), respectively; on the electron injection layer, Al is vacuum evaporated as the cathode (120 nm) to prepare an organic electroluminescent device.

[0236]

[0237] [Device Examples 2-32]

[0238] Compounds 38, 65, 91, 94, 98, 104, 117, 118, 159, 180, 188, 193, 208, 225, 227, 231, 237, 238, 280, 283, 300, 303, 329, 346, 402, 439, 443, 458, 471, 512, and 545 of the present invention were used to replace compound 15 in device example 1 as the main material of the light-emitting layer. Otherwise, an organic electroluminescent device was prepared using the same preparation method as device example 1.

[0239] [Comparative Device Examples 1-3]

[0240] Comparative Examples 1-3: Fabrication of Comparative Organic Electroluminescent Devices 1-3

[0241] By replacing compound 15 in the light-emitting layer of Example 1 with comparative compounds 1-3, and keeping the other steps the same, comparative organic electroluminescent devices 1-3 were obtained.

[0242] A combined IVL testing system was used to test the luminous efficiency of organic electroluminescent devices (OLEDs), comprising testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter. Lifetime testing was performed using the McScience M6000 OLED lifetime testing system.

[0243] The test environment was atmospheric, and the temperature was room temperature. The luminescence characteristics test results of devices 1-32 in the device embodiments of the present invention, and those obtained in comparative embodiments 1-3 are shown in Table 1 below.

[0244] Table 1:

[0245]

[0246]

[0247] As shown in Table 1, when the carbazole compound described in this invention is used as the main material of the light-emitting layer of an organic electroluminescent device, the driving voltage, luminous efficiency, and lifespan of the device are significantly improved, indicating that the carbazole compound described in this invention is a high-performance OLED light-emitting layer main material.

[0248] [Device Example 33]

[0249] First, the ITO glass substrate was cleaned twice with distilled water, followed by ultrasonic cleaning for 30 minutes. The substrate was then ultrasonically cleaned sequentially with solvents such as isopropanol, acetone, and methanol, dried on a hot plate heated to 120°C, and transferred to a plasma cleaner for 5 minutes before being transferred to a vacuum evaporator. Using a vacuum deposition apparatus, an ITO transparent electrode was prepared as the anode. Using ITO as the anode on the glass substrate, a 50 nm thick HI-2 film was vacuum-deposited onto the anode to form a hole injection layer. HT-2 was then vacuum-deposited onto the hole injection layer as a hole transport layer with a thickness of 70 nm. Under the same vacuum deposition conditions, a 30 nm thick host material and a dopant (10 wt%) were deposited onto the hole transport layer as a light-emitting layer. Compound 15 and H2-2 (mass ratio 1:1) prepared in the above example were used as the host material, and (btp)2Ir(acac) was used as the dopant. Subsequently, HB-2 was deposited onto the light-emitting layer to form a 2 nm thick hole blocking layer. On the hole blocking layer, ET-2 and LiF were sequentially deposited by vacuum evaporation as the electron transport layer (40 nm) and the electron injection layer (1.5 nm), respectively; on the electron injection layer, Al was vacuum evaporated as the cathode (130 nm) to prepare an organic electroluminescent device.

[0250]

[0251] [Device Examples 33-64]

[0252] Compounds 38, 65, 91, 94, 98, 104, 117, 118, 159, 180, 188, 193, 208, 225, 227, 231, 237, 238, 280, 283, 300, 303, 329, 346, 402, 439, 443, 458, 471, 512, and 545 of the present invention were used to replace compound 15 in device example 1 as the main material of the light-emitting layer. Otherwise, an organic electroluminescent device was prepared by the same preparation method as device example 33.

[0253] [Comparative Device Examples 4-6]

[0254] Comparative Examples 4-6: Fabrication of Comparative Organic Electroluminescent Devices 4-6

[0255] By replacing compound 15 in the light-emitting layer of Example 33 with comparative compounds 4-6, and keeping the other steps the same, comparative organic electroluminescent devices 4-6 were obtained.

[0256] A combined IVL testing system was used to test the luminous efficiency of organic electroluminescent devices (OLEDs), comprising testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter. Lifetime testing was performed using the McScience M6000 OLED lifetime testing system.

[0257] The test environment was atmospheric, and the temperature was room temperature. The luminescence characteristics test results of devices 33-64 in the device embodiments of this invention, and those obtained in comparative embodiments 4-6 are shown in Table 2 below.

[0258] Table 2:

[0259]

[0260]

[0261] As shown in Table 2, when the carbazole compound described in this invention is used as the main material of the light-emitting layer of an organic electroluminescent device, the driving voltage, luminous efficiency, and lifespan of the device are significantly improved, indicating that the carbazole compound described in this invention is a high-performance OLED light-emitting layer main material.

[0262] It should be noted that the present invention has been specifically described with reference to individual embodiments, but those skilled in the art can make various forms or details of improvements to the present invention without departing from the principles of the present invention, and these improvements also fall within the protection scope of the present invention.

Claims

1. A carbazole compound, characterized by, The carbazole compound is selected from at least one of formulas I-1 to I-6. R1 and R2 are each independently selected from one of hydrogen, deuterium, tritium, cyano, halogen, C1-C6 alkyl, substituted or unsubstituted phenyl; The n1 is selected from 0, 1, 2, 3 or 4; when n1 is greater than 1, two or more R1s are the same or different from each other, or two adjacent R1s are connected to each other to form substituted or unsubstituted benzene rings; The n2 is selected from 0, 1 or 2; when n2 is greater than 1, two or more R2s are the same or different from each other, or two adjacent R2s are connected to each other to form substituted or unsubstituted benzene rings; Each X is independently selected from CH and N, and at most two X are selected from N; At least one of the Ar1 or Ar2 groups is selected from the following groups. Each of the R3s is independently selected from one of hydrogen, deuterium, tritium, -F, cyano, substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted phenyl; Each of the R4s is independently selected from one of hydrogen, deuterium, tritium, substituted or unsubstituted C1 to C6 alkyl groups; The n3 is selected from 0, 1, 2 or 3; the n4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the n6 is selected from 0, 1, 2, 3, 4, 5 or 6; the n8 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8. The remaining Ar1 and Ar2 are selected from one of the following groups. R 5a each independently is selected from one of hydrogen, deuterium, tritium, cyano, -F, -Si(R n )3, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl; each R n each independently is selected from one of deuterium-substituted or unsubstituted methyl, deuterium-substituted or unsubstituted ethyl, deuterium-substituted or unsubstituted propyl, deuterium-substituted or unsubstituted butyl; Each of the R5s is independently selected from one of hydrogen, deuterium, tritium, cyano, -F, substituted or unsubstituted C1 to C6 alkyl groups; said k1 is selected from 0, 1, 2, 3, 4, or 5; said k2 is selected from 0, 1, 2, 3, or 4; said k4 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; said k5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; when two or more R 5a are present, two or more of R 5a are the same or different from each other; when two or more R5are present, two or more of R5are the same or different from each other; L1 and L2 are each independently selected from a single bond or one of the groups shown below. and when Ar1, Ar2are L1, L2attached thereto can also be selected from one of the following groups: Each of the R6s is independently selected from any one of hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1 to C6 alkyl groups; The m1 is selected from 0, 1, 2, 3 or 4; the m2 is selected from 0, 1, 2, 3, 4, 5 or 6; the m3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; when there are two or more R6, the two or more R6 are the same as or different from each other; The substituents in "substituted or unsubstituted" are independently selected from deuterium, fluorine, chlorine, bromine, iodine, methyl, ethyl, n-propyl, isopropyl, n-butyl, and tert-butyl.

2. The carbazole compound according to claim 1, characterized by At least one of the Ar1 or Ar2 groups is selected from the following groups. Each of the R3s is independently selected from one of hydrogen, deuterium, tritium, substituted or unsubstituted C1-C6 alkyl groups, or substituted or unsubstituted phenyl groups; Each of the R4 atoms is independently selected from hydrogen, deuterium, and tritium.

3. The carbazole compound according to claim 1, characterized in that, At least one of the Ar1 or Ar2 groups is selected from the following groups. 。 4. The carbazole compound according to claim 1, characterized in that, The remaining Ar1 and Ar2 are selected from one of the following groups. 。 5. The carbazole compound according to claim 1, characterized in that, L1 and L2 are each independently selected from a single bond or one of the groups shown below. Each of the R6 molecules is independently selected from hydrogen, deuterium, and tritium.

6. A carbazole compound, characterized in that, The carbazole compound is selected from at least one of the structures shown below.

7. An organic electroluminescent device, characterized in that, The organic electroluminescent device contains the carbazole compound according to any one of claims 1 to 6.

8. The organic electroluminescent device according to claim 7, characterized in that, The organic light-emitting device includes an anode, a cathode, and an organic layer, wherein the organic layer is located between the anode and the cathode or outside one or more electrodes of the anode and the cathode, and the organic layer contains the carbazole compound as described in any one of claims 1 to 6.

Images