Fluorene-containing arylamine derivative and organic electroluminescent device thereof

Abstract

This invention provides a fluorene-containing aromatic amine derivative and its organic electroluminescent device, relating to the field of organic electroluminescent materials technology. The fluorene-containing aromatic amine derivative of this invention has a structure as shown in Formula 1, wherein a fluorene group, such as diphenylfluorene or spirofluorene, is bonded to the nitrogen side of the aromatic amine, and the other side contains substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, or substituted silyl groups. The fluorene-containing aromatic amine derivative of this invention exhibits high hole transport capability, improving the recombination efficiency of holes and electrons in the light-emitting layer to form excitons. Furthermore, the material has good stability. Therefore, when used as a hole transport material in organic electroluminescent devices, the organic electroluminescent devices exhibit high luminous efficiency and long lifespan, significantly improving device performance and demonstrating good industrialization prospects. It can be widely applied in panel displays, lighting sources, electronic paper, organic photosensitive materials, signs, signal lights, and other fields.

Description

Technical Field

[0001] This invention relates to the field of organic electroluminescent materials technology, specifically to a fluorene-containing aromatic amine derivative and its organic electroluminescent device. Background Technology

[0002] Organic light-emitting diodes (OLEDs), also known as organic electroluminescent displays, organic light-emitting diodes, or organic light-emitting semiconductors, refer to the phenomenon where organic semiconductor materials and light-emitting materials emit light through carrier injection and recombination under the influence of an electric field. Compared to traditional liquid crystal displays (LCDs), OLEDs offer advantages such as thinner and lighter designs, higher brightness, lower power consumption, faster response times, higher resolution, greater flexibility, and higher luminous efficiency, meeting consumers' evolving demands for display technology and thus attracting extensive research.

[0003] OLEDs are electroluminescent devices that utilize multiple organic layers. They are easy to fabricate and require only low driving voltages, making them highly suitable for flat panel display applications. An OLED consists of an anode, a cathode, and organic layers. These organic layers may include a hole injection layer (HIL), an electron injection layer (EIL), a hole transport layer (HTL), an electron transport layer (ETL), an electron block layer (EBL), a hole block layer (HBL), and an emission layer (EML). The principle involves using an ITO transparent electrode and a metal electrode as the anode and cathode, respectively. Under a certain voltage, electrons and holes are injected from the cathode and anode into the electron and hole transport layers, respectively. The electrons and holes then migrate through the electron and hole transport layers to the emission layer, where they meet, forming excitons and exciting the light-emitting molecules. These molecules then emit visible light through radiative relaxation. Multilayer structures can fully utilize the function of each layer, better regulate the balance of charge carriers, and more effectively improve the performance of OLED devices.

[0004] Hole transport materials are a crucial component for hole transport and play an indispensable role in organic light-emitting devices (OLEDs). Their function is to improve hole injection and transport efficiency, lower the hole injection barrier, and effectively block electrons within the emissive layer. While significant research has been conducted on hole transport layer materials in recent years, numerous problems have been discovered when applied to devices, such as short device lifetime, low luminous efficiency, and high driving voltage. Therefore, research on OLED hole transport materials still has considerable room for development, and finding hole transport materials that are compatible with current and future OLED technologies is an urgent problem that needs to be solved by those skilled in the art. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a fluorene-containing aromatic amine derivative and its organic electroluminescent device.

[0006] This invention provides a fluorene-containing aromatic amine derivative having the structure shown in Formula 1.

[0007]

[0008] L1 and L2 are independently selected from single bonds.

[0009] p1 is selected from 0 or 1, and p2 is selected from 0 or 1;

[0010] A is selected from the structure shown in Equation 2:

[0011]

[0012] Wherein, Ar1 is selected from substituted or unsubstituted C6-C60 aryl groups, R5, R6, and R7 are independently selected from one or more of substituted or unsubstituted C1-C15 alkyl groups, substituted or unsubstituted C1-C15 alkenyl groups, and substituted or unsubstituted C1-C10 alkynyl groups, and n is selected from 1, 2, 3, 4, or 5.

[0013] R1, R2, R3, and R4 are independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent groups bonded together to form a ring;

[0014] The n1 and n2 are independently selected from 0, 1, 2, 3, 4 or 5;

[0015] The n3 is selected from 0, 1, 2, 3 or 4;

[0016] The n4 is selected from 0, 1, 2 or 3;

[0017] The R a R b R c R d It is independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent groups bonded together to form a ring;

[0018] The m1 and m2 are independently selected from 0, 1, 2, 3, 4 or 5;

[0019] The m3 is selected from 0, 1, 2, 3 or 4;

[0020] The m4 is selected from 0, 1, 2 or 3;

[0021] The L3, L4, and L5 are independently selected from single-bonded or substituted or unsubstituted C6 to C30 aryl groups.

[0022] The present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, and a cathode, 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 fluorene-containing aromatic amine derivative of the present invention described above.

[0023] Beneficial effects:

[0024] In the fluorene-containing aromatic amine derivatives of this invention, fluorene groups such as diphenylfluorene and spirofluorene are bonded to the nitrogen side of the aromatic amine, exhibiting significant steric hindrance and robust rigidity, thus providing excellent thermal stability. Furthermore, the fluorene-containing aromatic amine derivatives of this invention also contain substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, or substituted silyl groups, making it difficult for planar triarylamines to stack, reducing molecular crystallinity, and improving the film-forming properties of the material. Therefore, when the fluorene-containing aromatic amine derivatives of this invention are used as hole transport materials in organic electroluminescent devices, the organic electroluminescent devices exhibit higher luminous efficiency and longer lifespan, resulting in a significant improvement in device performance. Detailed Implementation

[0025] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. After reading the present invention, any modifications of the present invention in various equivalent forms by those skilled in the art will fall within the scope of protection claimed in this application.

[0026] In the compounds of the present invention, any atom not specified as a particular isotope is included as any stable isotope of that atom, and includes atoms at both their natural and non-natural isotopic abundances.

[0027] In this invention, "C6-C60" in "substituted or unsubstituted C6-C60 aryl groups" refers to the number of carbon atoms in the unsubstituted aryl group, excluding the number of carbon atoms in the substituents. Similarly, "C1-C15" in "substituted or unsubstituted C1-C15 alkyl groups" refers to the number of carbon atoms in the unsubstituted alkyl group, excluding the number of carbon atoms in the substituents. And so on.

[0028] The aryl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from the aromatic carbon atom of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl, polycyclic aryl, and fused-ring aryl groups. The number of carbon atoms in the aryl group is C6 to C60, preferably C6 to C30, more preferably C6 to C15, and even more preferably C6 to C12. Examples of the aryl group include, but are not limited to, the following groups: phenyl, biphenyl, terphenyl, tetraphenyl, pentaphenyl, naphthyl, indene, dihydroindene, dihydronaphthyl, tetrahydronaphthyl, phenanthrene, triphenylene, anthracene, pyrene, fluorenyl, spirodifluorenyl, spiroanthracenefluorenyl, benzo[a]fluorenyl, benzo[a]spirodifluorenyl, etc.

[0029] The alkyl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from an alkane molecule, including straight-chain and branched alkyl groups. The alkyl group has 1 to 15 carbon atoms, preferably 1 to 10, and even more preferably 1 to 5. Examples of alkyl groups include, but are not limited to, the following groups: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecanyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl, etc. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, and neopentyl are preferred.

[0030] The chain alkyl groups with more than three carbon atoms described in this invention include their isomers. For example, propyl includes n-propyl and isopropyl, and butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl. And so on.

[0031] The alkenyl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from an olefin molecule, including straight-chain and branched olefin groups. The alkenyl group has 2 to 15 carbon atoms, preferably 2 to 10. Examples of alkenyl groups include, but are not limited to, the following groups: vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, 1-methylvinyl, 1-methylallyl, 1,1-dimethylallyl, 2-methylallyl, 1,2-dimethylallyl, etc.

[0032] The alkynyl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from an alkyne molecule, including straight-chain and branched alkyne groups. The alkynyl group has 2 to 10 carbon atoms, preferably 2 to 6.

[0033] The cycloalkyl group described in this invention refers to a monovalent group formed by removing one hydrogen atom from a cycloalkane molecule. The cycloalkyl group has 3 to 20 carbon atoms, preferably 3 to 15, and even more preferably 3 to 10. Examples of cycloalkyl groups include, but are not limited to, the following groups: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, camphenyl, norbornyl, ferruginyl, isocamphenyl, etc.

[0034] The "substituted or unsubstituted silyl group" mentioned in this invention refers to —Si(R k )3 groups, wherein each R k The same or different groups are selected from the following: 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 k The same or different groups are selected from the following: hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, even more preferably 1 to 10, and most preferably 1 to 8. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, even more preferably 3 to 10, and most preferably 3 to 7. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 13, even more preferably 6 to 12, and most preferably 6 to 10. Preferably, each R... kThe same or different groups are selected from the following: 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. The term "alkylsilyl" refers to at least one substituent R of a silyl (-SiH3) group. k It is an alkyl group, and the preferred alkylsilyl groups specifically include trimethylsilyl, triethylsilyl, triisopropylsilyl, tert-butyldimethylsilyl, vinyldimethylsilyl, and propyldimethylsilyl, but are not limited thereto; the "arylsilyl" refers to at least one substituent R of the alkyl (-SiH3) group. k It is an aryl group, and preferred arylsilyl groups include triphenylsilyl, diphenylmethylsilyl, phenyldimethylsilyl, etc., but are not limited to these.

[0035] In this invention, "substituted or unsubstituted" means either unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium, halogen atom, amino, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C3-C30 heterocyclic, substituted or unsubstituted C3-C30 alkoxy, substituted or unsubstituted C6-C60 aryl. The substituted or unsubstituted C6-C60 aryloxy group, substituted or unsubstituted C2-C60 heteroaryl group, substituted or unsubstituted alkylsilyl group, substituted or unsubstituted arylsilyl group, preferably deuterium, halogen atom, cyano group, C1-C12 alkyl group, C3-C12 cycloalkyl group, C6-C30 aryl group, alkylsilyl group, arylsilyl group, when substituted by multiple substituents, the multiple substituents may be the same or different from each other, or the multiple substituents may be linked together to form a ring.

[0036] Preferably, it means not being substituted or being substituted by one or more substituents selected from the group consisting of: deuterium, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano, nitro, methyl, deuterated methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclopropane, deuterated cyclopropane, methyl-substituted cyclopropane, ethyl-substituted cyclopropane, cyclobutane, deuterated cyclobutane, methyl-substituted cyclobutane, ethyl-substituted cyclobutane, cyclopentane, deuterated cyclopentane, Methyl-substituted cyclopentyl, ethyl-substituted cyclopentyl, cyclohexyl, deuterium-substituted cyclohexyl, methyl-substituted cyclohexyl, ethyl-substituted cyclohexyl, n-propyl-substituted cyclohexyl, n-butyl-substituted cyclohexyl, cyclohexane-substituted cyclohexyl, cycloheptyl, cyclopentenyl, deuterium-substituted cyclopentenyl, methyl-substituted cyclopentenyl, ethyl-substituted cyclopentenyl, cyclohexenyl, cycloheptenyl, adamantyl, deuterium-substituted adamantyl, methyl-substituted adamantyl, ethyl-substituted adamantyl, norbornyl, deuterium-substituted norbornyl Borneolyl, methyl-substituted norbornolyl, ethyl-substituted norbornolyl, tetrahydropyrrolyl, piperidinyl, morpholinyl, thiomorpholinyl, methyl-substituted piperazine, ethyl-substituted piperazine, phenyl-substituted piperazine, naphthyl-substituted piperazine, methoxy, ethoxy, phenyl, deuterium-substituted phenyl, methyl-substituted phenyl, ethyl-substituted phenyl, propyl-substituted phenyl, isopropyl-substituted phenyl, tert-butyl-substituted phenyl, biphenyl, deuterium-substituted biphenyl, terphenyl, naphthyl, anthraceneyl, phenanthrene, triphenylene, pyrene, 9,9- Dimethylfluorenyl, 9,9-diphenylfluorenyl, spirodifluorenyl, spiro-cyclopentyl-fluorenyl, spiro-cyclohexyl-fluorenyl, spiro-adamantyl-fluorenyl, spiro-cyclopentenyl-fluorenyl, spiro-cyclohexenyl-fluorenyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, N-phenylcarbazoyl, dibenzofuranyl, dibenzothiophenyl, trimethylsilyl, triphenylsilyl, when substituted with multiple substituents, the multiple substituents may be the same or different from each other, or the multiple substituents may be linked together to form a ring.

[0037] The arylene group described 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 compound molecule. It can be a monocyclic arylene, a polycyclic arylene, or a fused-ring arylene. The arylene has 6 to 30 carbon atoms, preferably 3 to 15, and even more preferably 3 to 10. The monocyclic arylene includes, but is not limited to, phenylene; the polycyclic arylene includes, but is not limited to, biphenylene, terphenylene; the fused-ring arylene includes, but is not limited to, naphthylene, anthracene, phenanthrene, fluorene, pyrene, tricrene, fluorene, phenylfluorene, etc., but is not limited to. The aforementioned arylene groups are preferably phenylene, biphenylene, terphenylene, naphthyl, fluorene, or phenylfluorene.

[0038] In this specification, when the position of the substituent on the ring is not fixed, it means that it can be attached to any of the corresponding optional sites on the ring.

[0039] For example, Can represent Can represent Can represent And so on.

[0040] In this invention, "the formation of a ring by bonding two adjacent groups" refers to the formation of a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle by bonding adjacent groups together and optionally aromatizing them. The hydrocarbon ring can be an aliphatic or aromatic hydrocarbon ring. The heterocycle can be an aliphatic or aromatic heterocycle. The aliphatic hydrocarbon ring can be a saturated or unsaturated aliphatic hydrocarbon ring, and the aliphatic heterocycle can be a saturated or unsaturated aliphatic heterocycle. The hydrocarbon ring and heterocycle can be monocyclic or polycyclic groups. Furthermore, the ring formed by the bonding of adjacent groups can be connected to another ring to form a spirostructure. An example is shown below:

[0041]

[0042] In this invention, the ring formed by the connection can be a five-membered ring, a six-membered ring, or a fused ring, such as benzene, naphthalene, phenanthrene, triphenylene, cyclopentane, cyclohexane, cyclopentene, cyclohexene, fluorene, pyridine, pyrimidine, dibenzofuran, dibenzothiophene, but not limited thereto.

[0043] This invention provides a fluorene-containing aromatic amine derivative having the structure shown in Formula 1.

[0044]

[0045] L1 and L2 are independently selected from single bonds.

[0046] p1 is selected from 0 or 1, and p2 is selected from 0 or 1;

[0047] A is selected from the structure shown in Equation 2:

[0048]

[0049] Wherein, Ar1 is selected from substituted or unsubstituted C6-C60 aryl groups, R5, R6, and R7 are independently selected from one or more of substituted or unsubstituted C1-C15 alkyl groups, substituted or unsubstituted C2-C15 alkenyl groups, and substituted or unsubstituted C2-C10 alkynyl groups, and n is selected from 1, 2, 3, 4, or 5.

[0050] R1, R2, R3, and R4 are independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent groups bonded together to form a ring;

[0051] The n1 and n2 are independently selected from 0, 1, 2, 3, 4 or 5;

[0052] The n3 is selected from 0, 1, 2, 3 or 4;

[0053] The n4 is selected from 0, 1, 2 or 3;

[0054] The R a R b R c R d It is independently selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent groups bonded together to form a ring;

[0055] The m1 and m2 are independently selected from 0, 1, 2, 3, 4 or 5;

[0056] The m3 is selected from 0, 1, 2, 3 or 4;

[0057] The m4 is selected from 0, 1, 2 or 3;

[0058] The L3, L4, and L5 are independently selected from single-bonded or substituted or unsubstituted C6 to C30 aryl groups.

[0059] Preferably, the Selected from one of the following groups:

[0060]

[0061] Further selection, Selected from one of the following groups:

[0062]

[0063] Preferably, the Ar1 is selected from one of the following groups:

[0064]

[0065] Wherein, the R fSelected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted alkylsilyl, substituted or unsubstituted arylsilyl, substituted or unsubstituted C3-C20 cycloalkyl, or substituted or unsubstituted C6-C30 aryl;

[0066] f1 is selected from 1, 2, 3, 4 or 5;

[0067] f2 is selected from 1, 2, 3, or 4;

[0068] The f3 is selected from 1, 2, or 3;

[0069] The f4 is selected from 1, 2, 3, 4, 5, 6 or 7;

[0070] The f5 is selected from 1, 2, 3, 4, 5 or 6;

[0071] f6 is selected from 1 or 2;

[0072] And at least one of the above groups is R. f Selected from

[0073] The asterisk (*) indicates a binding site with an adjacent atom.

[0074] More preferably, the Ar1 is selected from one of the following groups:

[0075]

[0076] Wherein, the R f Selected from hydrogen, deuterium, cyano, halogen, 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;

[0077] f1 is selected from 1, 2, 3, 4 or 5;

[0078] f2 is selected from 1, 2, 3, or 4;

[0079] The f3 is selected from 1, 2, or 3;

[0080] The f4 is selected from 1, 2, 3, 4, 5, 6 or 7;

[0081] The f5 is selected from 1, 2, 3, 4, 5 or 6;

[0082] f6 is selected from 1 or 2;

[0083] And at least one of the above groups is R. f Selected from

[0084] Preferably, Formula 2 is selected from one of the following groups:

[0085]

[0086]

[0087] R5, R6, and R7 are independently selected from 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 vinyl, substituted or unsubstituted propenyl, and substituted or unsubstituted ethynyl.

[0088] More preferably, Formula 2 is selected from one of the following groups:

[0089]

[0090]

[0091] Preferably, the Selected from one of the following groups:

[0092]

[0093] The n1 is selected from 0, 1, 2, 3, 4 or 5; the n2 is selected from 0, 1, 2, 3, 4 or 5; the n3 is selected from 0, 1, 2, 3 or 4; the n4 is selected from 0, 1, 2 or 3.

[0094] The R1, R2, R3, and R4 are the same or different and are selected from hydrogen, deuterium, cyano, halogen, 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 trimethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, 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 terphenyl, substituted or unsubstituted naphthyl; or adjacent R1, adjacent R2, adjacent R3, and adjacent R4 form a saturated or unsaturated ring with 5 to 13 substituted or unsubstituted carbon atoms;

[0095] When there are two or more R1s, they are the same or different from each other; when there are two or more R2s, they are the same or different from each other; when there are two or more R3s, they are the same or different from each other; when there are two or more R4s, they are the same or different from each other.

[0096] Further preferably, the Selected from one of the following groups:

[0097]

[0098] The n1 is selected from 0, 1, 2, 3, 4 or 5; the n2 is selected from 0, 1, 2, 3, 4 or 5; the n3 is selected from 0, 1, 2, 3 or 4; the n4 is selected from 0, 1, 2 or 3; the n5 is selected from 0, 1, 2, 3, 4, 5 or 6; the n6 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

[0099] The R1, R2, R3, and R4 are the same or different and are selected from one of hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, methyl, trifluoromethyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, trimethylsilyl, triphenylsilyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, and naphthyl; or adjacent R1, adjacent R2, adjacent R3, and adjacent R4 form a substituted or unsubstituted benzene ring;

[0100] When there are two or more R1s, they are the same or different from each other; when there are two or more R2s, they are the same or different from each other; when there are two or more R3s, they are the same or different from each other; when there are two or more R4s, they are the same or different from each other.

[0101] Preferably, the Selected from one of the following groups:

[0102]

[0103] The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3, 4 or 5; the m3 is selected from 0, 1, 2, 3 or 4; the m4 is selected from 0, 1, 2 or 3.

[0104] The R a R b R c R d The same or different from one selected from hydrogen, deuterium, cyano, halogen, 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 trimethylsilyl, substituted or unsubstituted triphenylsilyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, 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 terphenyl, substituted or unsubstituted naphthyl; or adjacent R a Adjacent R b Adjacent R c Adjacent R d It forms saturated or unsaturated rings with 5 to 13 substituted or unsubstituted carbon atoms;

[0105] When there are two or more R a At that time, two or more R a They may be the same as or different from each other; when there are two or more R... b At that time, two or more R b They may be the same as or different from each other; when there are two or more R... c At that time, two or more R c They may be the same as or different from each other; when there are two or more R... d At that time, two or more R d They may be the same as or different from each other.

[0106] Further preferably, the Selected from one of the following groups:

[0107]

[0108] The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3, 4 or 5; the m3 is selected from 0, 1, 2, 3 or 4; the m4 is selected from 0, 1, 2 or 3; the m5 is selected from 0, 1, 2, 3, 4, 5 or 6; the m6 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.

[0109] The R a R b R c R d The same or different R is selected from one of hydrogen, deuterium, fluorine, chlorine, bromine, iodine, cyano, methyl, trifluoromethyl, deuterated methyl, ethyl, propyl, butyl, pentyl, hexyl, trimethylsilyl, triphenylsilyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, phenyl, methylphenyl, ethylphenyl, isopropylphenyl, tert-butylphenyl, deuterated phenyl, biphenyl, deuterated biphenyl, terphenyl, naphthyl; or adjacent R a Adjacent R b Adjacent R c Adjacent R d Formation of substituted or unsubstituted benzene rings;

[0110] When there are two or more R a At that time, two or more R a They may be the same as or different from each other; when there are two or more R... b At that time, two or more R b They may be the same as or different from each other; when there are two or more R... c At that time, two or more R c They may be the same as or different from each other; when there are two or more R... d At that time, two or more R d They may be the same as or different from each other.

[0111] Preferably, L3, L4, and L5 are selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthraceneylene, substituted or unsubstituted phenanthylene, substituted or unsubstituted fluoreneylene, substituted or unsubstituted triphenylene, or substituted or unsubstituted pyreneylene.

[0112] More preferably, L3, L4, and L5 are independently selected from single bonds or one of the following groups:

[0113]

[0114] Most preferably, the fluorene-containing aromatic amine derivative represented by structural formula 1 is selected from one of the following structures.

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131] The above lists some specific chemical structures of the fluorene-containing aromatic amine derivatives of structural formula 1 of the present invention. However, the present invention is not limited to these listed chemical structures. All fluorene-containing aromatic amine derivatives based on structural formula 1 with substituents as defined above should be included.

[0132] Furthermore, the present invention also provides an organic electroluminescent device, comprising an anode, an organic layer, and a cathode, 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 fluorene-containing aromatic amine derivative of the present invention described above.

[0133] Preferably, the organic layer includes a hole transport region containing the fluorene-containing aromatic amine derivative of the present invention.

[0134] Preferably, the hole transport region includes at least one of a hole injection layer and a hole transport layer, the hole transport layer being located between the hole injection layer and the cathode, and at least one of the hole injection layer and the hole transport layer containing the fluorene-containing aromatic amine derivative of the present invention described above.

[0135] Preferably, the hole transport region includes a hole transport layer containing the fluorene-containing aromatic amine derivative of the present invention.

[0136] Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer being located between the first hole transport layer and the cathode, and at least one of the first hole transport layer and the second hole transport layer containing the fluorene-containing aromatic amine derivative of the present invention described above.

[0137] Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer being located between the first hole transport layer and the cathode, and the second hole transport layer containing the fluorene-containing aromatic amine derivative of the present invention described above.

[0138] Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer being located between the first hole transport layer and the cathode, and the first hole transport layer containing the fluorene-containing aromatic amine derivative of the present invention described above.

[0139] Preferably, the hole transport layer comprises a first hole transport layer and a second hole transport layer, the second hole transport layer being located between the first hole transport layer and the cathode, and the first hole transport layer and the second hole transport layer containing the fluorene-containing aromatic amine derivative of the present invention described above.

[0140] The light-emitting device of the present invention is typically formed on a substrate. The substrate need not change during the formation of electrodes and organic layers; for example, substrates made of glass, plastic, polymer films, silicon, etc. When the substrate is opaque, the electrodes opposite it are preferably transparent or translucent.

[0141] This invention does not impose any particular limitation on the materials of the thin films in the organic electroluminescent device; substances known in the art can be used. The organic functional layers of the aforementioned organic electroluminescent device and the electrodes on both sides of the device are described below:

[0142] The anode material needs to have a high work function. Materials include metals or their alloys, metal oxides, multilayer materials, conductive polymers, etc. Specific examples may include chromium (Cr), nickel (Ni), gold (Au), zinc (Zn), platinum (Pt), indium tin oxide (ITO), aluminum zinc oxide (AZO), zinc gallium oxide (GZO), indium zinc oxide (IZO), indium tin oxide / silver / indium tin oxide (ITO / Ag / ITO), silver / germanium / silver (Ag / Ge / Ag), polyaniline, etc., but are not limited to these.

[0143] The cathode material needs to have a low work function. Materials include metals or their alloys, laminated materials, etc. Specific examples may include aluminum (Al), gold (Au), silver (Ag), indium (In), magnesium (Mg), magnesium:silver (Mg:Ag), lithium-calcium-magnesium (Li:Ca:Al), lithium fluoride / aluminum (LiF / Al), barium / silver (Ba / Ag), ytterbium / silver (Yb / Ag), etc., but are not limited to these.

[0144] Hole injection materials are preferably materials that can reduce the interfacial barrier between the anode and the hole transport layer. These materials include, as described below, polycyano-conjugated organic compounds, axial alkene compounds, phthalocyanine metal complexes, aromatic amine derivatives, polymers, etc. Specific examples may include, but are not limited to, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzphenanthrene (HAT-CN), 2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanodimethyl-p-benzoquinone (F4-TCNQ), 2,2',2''-(cyclopropane-1,2,3-tripyridyl)-tris(2-perfluorophenylacetonitrile), copper phthalocyanine (CuPC), N4,N4'-(biphenyl-4,4'-diacyl)bis(N4,N4',N4'-triphenylbiphenyl-4,4'-diamine) (TPT1), N,N-phenyl-N,N-(9-phenyl-3-carbazolyl)-1,1'-biphenyl-4,4'-diamine, poly(3,4-ethylenedioxythiophene) (PEDOT) / poly(styrenesulfonic acid) (PSS), etc.

[0145] Hole transport materials, preferably those with good hole transport capability and good stability. Materials as described below include aromatic amine derivatives, carbazole derivatives, polymers, etc. Specific examples may include N-([1,1'-biphenyl]-4-yl)-N-(4-(dibenzo[b,d]furan-4-yl)phenyl)dibenzo[b,d]furan-4-amine, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), N4,N4-di([ [1,1'-biphenyl]-4-yl)-N4'-([1,1':4',1”-terphenyl]-4-yl)-N4'-phenyl-[1,1'-biphenyl]-4,4'-diamine, N,N,N',N'-tetraphenylbiphenyldiamine, 9,9'-diphenyl-6-(9-phenyl-9H-carbazole-3-yl)-9H,4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), p-phenylenevinylene (PPV), etc., but not limited thereto. Preferably, the fluorene-containing aromatic amine derivatives of Formula 1 of the present invention are preferred.

[0146] The main material of the light-emitting layer, as described below, includes fused aromatic ring derivatives, heterocyclic compounds, metal complexes, silicon-containing compounds, etc. Specific examples may include 9,10-bis(1-naphthyl)anthracene (ADNF), 2-methyl-9,10-bis(naphthyl-2-yl)anthracene (MADN), 4,4'-bis[10-(naphthyl-1-yl)anthracene-9-yl]biphenyl, tris[4-(pyrene)-phenyl]amine (TPyPA), 9-phenyl-9'-(4-phenylquinazolin-2-yl)-3,3'-bicarbazole, and 1,3-bis(carbazole-9-yl)benzene. (MCP), 4,4'-bis(carbazole-9-yl)biphenyl (CBP), 2-[9,9-di(4-methylphenyl)fluoren-2-yl]-9,9-di(4-methylphenyl)fluorenyl (BDAF), 2,8-di(9H-carbazole-9-yl)dibenzo[b,d]thiophene (DCzDBT), tris(6-fluoro-8-hydroxyquinoline)aluminum (6FAlq3), bis(2-methylphenyl)diphenylsilane (UGH-1), triphenyl(4-(9-phenyl-9H-fluorenyl)phenyl)silane (TPSiF), etc., but not limited to these.

[0147] The doped material of the light-emitting layer includes, as described below, fused aromatic compounds, metal complexes, styrene-amine compounds, aromatic amine derivatives, heterocyclic compounds, etc. Specific examples may include N1,N1,N6,N6 tetrakis([1,1'-biphenyl]-3-yl)pyrene-1,6-diamine, N1,N6 bis(6-(tert-butyl)dibenzo[b,d]furan-4-yl)-N1,N6-di-m-methylphenyl-pyrene-1,6-diamine, 2,5,8,11-tetra-tert-butylperylene (TBPe), 10,10'-bis(3,5-bis(trifluoromethyl)phenyl)-9,9'-bianthracene (Ban-(3,5)-CF3), bis(3,5-difluoro-2-(2-pyridyl)phenyl-(2-carboxypyridyl)iridium(III) (FIrPic), tris[2-(p-tolyl)pyridine]iridium(III) (Ir(mppy)3), bis[2-(3,5-dimethylphenyl)-4-methylquinoline](acetyl) Examples of fluorene compounds include, but are not limited to, iridium(III)(Ir(mphmq)2acac), 4,4'-bis[4-(di-p-tolylamino)styryl]biphenyl (DPAVBi), 2,7-bis[4-(diphenylamine)styryl]-9,9-spirodifluorene (Spiro-BDAVBi), 4,4'-BIS(9-ethyl-3-carbazole)-1,1'-biphenyl (BCzVBi), 2,7-bis{2-[phenyl(m-tolyl)amino]-9,9-dimethyl-fluorene-7-yl}-9,9-dimethylfluorene (MDP3FL), and 2,3,6,7-tetrahydro-1,1,7,7,-tetramethyl-1H,5H,11H-10-(2-benzothiazolyl)quinoline[9,9a,1gh]coumarin (C545T).

[0148] Hole-blocking materials are materials that possess good hole-blocking capabilities to contain holes within the light-emitting layer. Examples include imidazole derivatives, phenanthroline derivatives, metal complexes, and triazine derivatives. Specific examples may include, but are not limited to, 1,3,5-tris(N-phenyl-2-benzimidazole)benzene (TPBi), 2-(naphth-2-yl)-4,7-diphenyl-1,10-phenanthroline (HNBphen), 4,7-diphenyl-1,10-phenanthroline (Bphen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), di(2-methyl-8-hydroxyquinoline-N1,O8)-(1,1'-biphenyl-4-hydroxy)aluminum (BAlq), 2-(9,9-dimethyl-9H-fluorene-2-yl)4-(9,9-diphenyl-9H-fluorene-4-yl)-6-phenyl-1,3,5-triazine, etc.

[0149] Electron transport materials, particularly electron transport layer materials, are preferably materials with good electron transport capabilities and stability. Materials such as imidazole derivatives, phenanthroline derivatives, pyridine derivatives, triazine derivatives, quinoline derivatives, oxadiazole derivatives, triazole derivatives, and metal complexes are included. Specific examples include 2-(4-(9,10-bis(naphthyl-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazolium, 2-(naphthyl-2-yl)-4,7-diphenyl-1,10-phenanthroline (HNBphen), 2,9-(dimethyl)-4,7-biphenyl-1,10-o-phenanthroline (BCP), 3,3'-[5'-[3-(3-pyridyl)phenyl](TmPyPB), 1,4-bis(4-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)naphthalene, 2-(3-(phenanthroline-9-)... 1,3,5-triazine (-yl)-5-(pyridin-3-yl)phenyl)-4,6-diphenyl-1,3,5-triazine, 1,3,5-tris(4-(pyridin-4-yl)quinoline-2-yl)benzene (TPyQB), 2,5-di-(4-naphthyl)-1,3,4-oxadiazole (BND), 3-(biphenyl-4-yl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (TAZ), di(2-methyl-8-hydroxyquinoline)(4-phenylphenol)aluminum(III) (BAlq), lithium 8-hydroxyquinoline (LiQ), etc., but not limited to these.

[0150] The electron injection material, preferably the electron injection layer material, is a material capable of reducing the interfacial barrier between the cathode and the electron transport layer. Materials described below include, but are not limited to, metals, metal compounds, and metal oxides. Specific examples may include, but are not limited to, magnesium (Mg), rubidium (Rb), lithium fluoride (LiF), lithium 8-hydroxyquinoline (LiQ), rubidium fluoride (RbF), cesium carbonate (Cs₂CO₃), lithium boron oxide (LiBO₂), molybdenum oxide (MoO₃), aluminum oxide (Al₂O₃), vanadium oxide (V₂O₅), etc.

[0151] The capping layer material is preferably a material that can improve the luminous efficiency of the device. Materials include, but are not limited to, metal compounds, aromatic amine derivatives, carbazole derivatives, etc. Specific examples may include, but are not limited to, aluminum(III)tris(8-hydroxyquinoline) (Alq3), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), 4,4'-di(9-carbazole)biphenyl (CBP), etc.

[0152] There are no particular limitations on the preparation method of each thin film in the organic electroluminescent device of the present invention. Vacuum evaporation, sputtering, spin coating, spraying, screen printing, laser transfer, etc. can be used, but are not limited to these methods.

[0153] The organic electroluminescent device of 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.

[0154] Synthesis Examples

[0155] Raw materials and reagents: This invention does not impose any particular limitations on the raw materials or reagents used in the following synthesis examples. They can be commercially available products or prepared using methods well-known to those skilled in the art. All raw materials and reagents used in this invention are of reagent purity.

[0156] Instruments: G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer (Waters Corporation, UK); Vario ELcube organic elemental analyzer (Elementar Corporation, Germany).

[0157] There are no particular limitations on the preparation method of the fluorene-containing aromatic amine derivative of structural formula 1 of the present invention, and conventional methods well known to those skilled in the art can be used. For example, carbon-nitrogen coupling reaction, carbon-carbon coupling reaction, etc. For example, the fluorene-containing aromatic amine derivative of structural formula 1 of the present invention can be prepared by the following synthetic route.

[0158]

[0159] X1 and X2 are halogen atoms, for example, they may be the same or different halogen atoms selected from the following: I, Br, Cl.

[0160] Synthesis Example 1: Preparation of Intermediate B-58

[0161]

[0162] Preparation of intermediate B-58:

[0163] Under nitrogen protection, c-5 (19.87 g, 50.00 mmol), d-58 (10.32 g, 50 mmol), Pd(PPh3)4 (0.87 g, 0.75 mmol), K2CO3 (13.82 g, 100.00 mmol), and 210 mL of mixed solvent (toluene:ethanol:water = 2:1:1) were added to the reaction flask. The reaction was carried out under reflux for 4 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered to obtain a filter cake, and washed with ethanol. Finally, the filter cake was recrystallized from toluene:ethanol = 5:1 to obtain intermediate B-58 (18.68 g, 78%); HPLC purity ≥99.84%. Mass spectrometry m / z: 478.1498 (theoretical value: 478.1488).

[0164] By substituting the raw materials accordingly, intermediate B can be prepared according to the preparation method of intermediate B-58 in Synthesis Example 1. The raw materials are shown in the table below:

[0165]

[0166] Synthesis Example 2: Preparation of Intermediate C-257

[0167]

[0168] Under nitrogen protection, e-257 (17.60 g, 100.00 mmol), f-257 (11.80 g, 100.00 mmol), K2CO3 (22.11 g, 160.00 mmol), and 420 mL of mixed solvent (toluene:ethanol:water = 2:1:1) were added sequentially to the reaction flask. After purging the air three times with nitrogen, Pd(PPh3)4 (1.16 g, 1.00 mmol) was added. The reaction was stirred at reflux temperature for 3.5 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. The mixture was allowed to stand and separated, and the organic layer was collected, dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The obtained solid was recrystallized from toluene and dried to obtain intermediate C-257 (18.05 g, yield 73%) with an HPLC purity of ≥99.83%. Mass spectrometry m / z: 246.0277 (theoretical value: 246.0267).

[0169]

[0170] Synthesis Example 3: Preparation of Compound 5

[0171]

[0172] Synthetic intermediate I-5

[0173] Under nitrogen protection, toluene (300 mL), a-5 (19.76 g, 50.00 mmol), e-5 (8.27 g, 50.00 mmol), palladium acetate (0.17 g, 0.75 mmol), sodium tert-butoxide (9.61 g, 100.00 mmol), and tri-tert-butylphosphine (3 mL of 0.50 M toluene solution) were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 3 hours. After the reaction was complete, the reaction solution was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. Recrystallization was performed using toluene:ethanol (10:1) to obtain intermediate I-5 (19.91 g, 83%). The purity of the solid was ≥99.88% as determined by HPLC. Mass spectrometry m / z: 479.2055 (theoretical value: 479.2069).

[0174] Synthetic compound 5

[0175] Under nitrogen protection, toluene (200 ml), intermediate I-5 (11.99 g, 25.00 mmol), c-5 (9.93 g, 25.00 mmol), Pd2(dba)3 (0.23 g, 0.25 mmol), sodium tert-butoxide (4.81 g, 50.00 mmol), and BINAP (0.25 g, 0.40 mmol) were added sequentially to a reaction flask. The mixture was stirred and heated under reflux for 5 hours. After the reaction was complete, the reaction solution was cooled to room temperature, water was added, and the mixture was extracted with dichloromethane. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by vacuum distillation. The mixture was recrystallized from toluene to give compound 5 (15.13 g, 76%). The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrometry m / z: 795.3336 (theoretical value: 795.3321). Theoretical elemental content (%) C 59 H 45 NSi: C, 89.01; H, 5.70; N, 1.76. Measured elemental content (%): C, 89.03; H, 5.72; N, 1.71.

[0176] Synthesis Example 4: Preparation of Compound 58

[0177]

[0178] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, and c-5 was replaced with an equimolar amount of B-58, yielding compound 58 (16.83 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 921.3778 (theoretical value: 921.3791). Theoretical elemental content (%) C 69 H 51 NSi: C, 89.86; H, 5.57; N, 1.52. Measured elemental content (%): C, 89.84; H, 5.55; N, 1.55.

[0179] Synthesis Example 5: Preparation of Compound 87

[0180]

[0181] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, and e-5 was replaced with an equimolar amount of e-87, yielding compound 87 (16.35 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 871.3644 (theoretical value: 871.3634). Theoretical elemental content (%) C 65 H 49NSi: C, 89.51; H, 5.66; N, 1.61. Measured elemental content (%): C, 89.52; H, 5.62; N, 1.64.

[0182] Synthesis Example 6: Preparation of Compound 99

[0183]

[0184] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, e-5 with an equimolar amount of e-87, and c-5 with an equimolar amount of c-99, yielding compound 99 (18.21 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 983.4875 (theoretical value: 983.4886). Theoretical elemental content (%) C 73 H 65 NSi: C, 89.07; H, 6.66; N, 1.42. Measured elemental content (%): C, 89.05; H, 6.64; N, 1.38.

[0185] Synthesis Example 7: Preparation of Compound 105

[0186]

[0187] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-105, e-5 with an equimolar amount of e-105, and c-5 with an equimolar amount of c-105, yielding compound 105 (16.36 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 947.3959 (theoretical value: 947.3947). Theoretical elemental content (%) C 71 H 53 NSi: C, 89.93; H, 5.63; N, 1.48. Measured elemental content (%): C, 89.95; H, 5.67; N, 1.45.

[0188] Synthesis Example 8: Preparation of Compound 112

[0189]

[0190] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, e-5 with an equimolar amount of e-87, and c-5 with an equimolar amount of B-112, yielding compound 112 (17.62 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 951.4182 (theoretical value: 951.4198). Theoretical elemental content (%) C 71 H 49D4NSi: C, 89.55; H, 6.03; N, 1.47. Measured elemental content (%): C, 89.58; H, 6.05; N, 1.43.

[0191] Synthesis Example 9: Preparation of Compound 115

[0192]

[0193] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, and e-5 was replaced with an equimolar amount of C-115, yielding compound 115 (17.06 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 921.3780 (theoretical value: 921.3791). Theoretical elemental content (%) C 69 H 51 NSi: C, 89.86; H, 5.57; N, 1.52. Measured elemental content (%): C, 89.88; H, 5.52; N, 1.56.

[0194] Synthesis Example 10: Preparation of Compound 129

[0195]

[0196] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5 to obtain compound 129 (15.36 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 797.3488 (theoretical value: 797.3478). Theoretical elemental content (%) C 59 H 47 NSi: C, 88.79; H, 5.94; N, 1.76. Measured elemental content (%): C, 88.75; H, 5.96; N, 1.78.

[0197] Synthesis Example 11: Preparation of Compound 168

[0198]

[0199] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-168, e-5 with an equimolar amount of e-168, and c-5 with an equimolar amount of a-168, yielding compound 168 (14.66 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 825.3773 (theoretical value: 825.3791). Theoretical elemental content (%) C 61 H 51 NSi: C, 88.68; H, 6.22; N, 1.70. Measured elemental content (%): C, 88.64; H, 6.24; N, 1.71.

[0200] Synthesis Example 12: Preparation of Compound 181

[0201]

[0202] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-168, and c-5 was replaced with an equimolar amount of c-181, yielding compound 181 (16.64 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 923.4897 (theoretical value: 923.4886). Theoretical elemental content (%) C 68 H 65 NSi: C, 88.36; H, 7.09; N, 1.52. Measured elemental content (%): C, 88.35; H, 7.06; N, 1.55.

[0203] Synthetic Example 13: Preparation of Compound 190

[0204]

[0205] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, and c-5 was replaced with an equimolar amount of c-190, yielding compound 190 (15.83 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 878.4117 (theoretical value: 878.4105). Theoretical elemental content (%) C 65 H 46 D5NSi: C, 88.79; H, 6.42; N, 1.59. Measured elemental content (%): C, 88.76; H, 6.46; N, 1.61.

[0206] Synthetic Example 14: Preparation of Compound 194

[0207]

[0208] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-194, e-5 with an equimolar amount of e-194, and c-5 with an equimolar amount of c-194, yielding compound 194 (15.28 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 872.3570 (theoretical value: 872.3587). Theoretical elemental content (%) C 64 H 48 N₂Si: C, 88.03; H, 5.54; N, 3.21. Measured elemental content (%): C, 88.01; H, 5.52; N, 3.24.

[0209] Synthesis Example 15: Preparation of Compound 201

[0210]

[0211] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-201, and c-5 was replaced with an equimolar amount of c-201, yielding compound 201 (16.08 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 931.4584 (theoretical value: 931.4573). Theoretical elemental content (%) C 69 H 61 NSi: C, 88.89; H, 6.60; N, 1.50. Measured elemental content (%): C, 88.85; H, 6.62; N, 1.53.

[0212] Synthesis Example 16: Preparation of Compound 236

[0213]

[0214] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, e-5 with an equimolar amount of e-236, and c-5 with an equimolar amount of B-236, yielding compound 236 (16.67 g). HPLC analysis showed a solid purity ≥99.91%. Mass spectrometry m / z: 965.4403 (theoretical value: 965.4417). Theoretical elemental content (%) C 72 H 59 NSi: C, 89.49; H, 6.15; N, 1.45. Measured elemental content (%): C, 89.46; H, 6.14; N, 1.47.

[0215] Synthesis Example 17: Preparation of Compound 243

[0216]

[0217] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-243, and c-5 was replaced with an equimolar amount of B-243, yielding compound 243 (17.37 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 991.4557 (theoretical value: 991.4573). Theoretical elemental content (%) C 74 H 61 NSi: C, 89.56; H, 6.20; N, 1.41. Measured elemental content (%): C, 89.52; H, 6.22; N, 1.39.

[0218] Synthesis Example 18: Preparation of Compound 248

[0219]

[0220] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-248, e-5 with an equimolar amount of e-248, and c-5 with an equimolar amount of c-248, yielding compound 248 (18.08 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 1017.4561 (theoretical value: 1017.4581). Theoretical elemental content (%) C 71 H 67 NSi3: C, 83.72; H, 6.63; N, 1.38. Measured elemental content (%): C, 83.75; H, 6.61; N, 1.36.

[0221] Synthetic Example 19: Preparation of Compound 257

[0222]

[0223] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, e-5 with an equimolar amount of C-257, and c-5 with an equimolar amount of c-248, yielding compound 257 (16.25 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 877.4033 (theoretical value: 877.4042). Theoretical elemental content (%) C 65 H 47 D4NSi: C, 88.90; H, 6.31; N, 1.59. Measured elemental content (%): C, 88.92; H, 6.29; N, 1.61.

[0224] Synthesis Example 20: Preparation of Compound 275

[0225]

[0226] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, e-5 with an equimolar amount of e-275, and c-5 with an equimolar amount of a-201, yielding compound 275 (15.79 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 901.4117 (theoretical value: 901.4104). Theoretical elemental content (%) C 67 H 55 NSi: C, 89.19; H, 6.14; N, 1.55. Measured elemental content (%): C, 89.15; H, 6.15; N, 1.57.

[0227] Synthesis Example 21: Preparation of Compound 276

[0228]

[0229] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, and e-5 was replaced with an equimolar amount of e-87, yielding compound 276 (16.61 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 873.3775 (theoretical value: 873.3791). Theoretical elemental content (%) C 65 H 51 NSi: C, 89.30; H, 5.88; N, 1.60. Measured elemental content (%): C, 89.33; H, 5.85; N, 1.61.

[0230] Synthesis Example 22: Preparation of Compound 293

[0231]

[0232] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, e-5 with an equimolar amount of e-87, and c-5 with an equimolar amount of c-181, yielding compound 293 (17.51 ​​g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 985.5060 (theoretical value: 985.5043). Theoretical elemental content (%) C 73 H 67 NSi: C, 88.89; H, 6.85; N, 1.42. Measured elemental content (%): C, 88.87; H, 6.82; N, 1.46.

[0233] Synthesis Example 23: Preparation of Compound 294

[0234]

[0235] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-294, e-5 with an equimolar amount of e-87, and c-5 with an equimolar amount of a-294, yielding compound 294 (17.26 g). HPLC analysis showed a solid purity ≥99.97%. Mass spectrometry m / z: 985.5028 (theoretical value: 985.5043). Theoretical elemental content (%) C 73 H 67 NSi: C, 88.89; H, 6.85; N, 1.42. Measured elemental content (%): C, 88.84; H, 6.87; N, 1.44.

[0236] Synthesis Example 24: Preparation of Compound 308

[0237]

[0238] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-294, e-5 with an equimolar amount of e-87, and c-5 with an equimolar amount of c-308, yielding compound 308 (17.98 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 1041.5680 (theoretical value: 1041.5669). Theoretical elemental content (%) C 77 H 75 NSi: C, 88.71; H, 7.25; N, 1.34. Measured elemental content (%): C, 88.72; H, 7.21; N, 1.36.

[0239] Synthesis Example 25: Preparation of Compound 323

[0240]

[0241] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, e-5 was replaced with an equimolar amount of e-323, and c-5 was replaced with an equimolar amount of c-323, yielding compound 323 (16.76 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 943.4563 (theoretical value: 943.4573). Theoretical elemental content (%) C 70 H 61 NSi: C, 89.03; H, 6.51; N, 1.48. Measured elemental content (%): C, 89.05; H, 6.52; N, 1.44.

[0242] Synthesis Example 26: Preparation of Compound 325

[0243]

[0244] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-325, e-5 with an equimolar amount of e-325, and c-5 with an equimolar amount of c-325, yielding compound 325 (16.33 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 959.4722 (theoretical value: 959.4731). Theoretical elemental content (%) C 71 H 45 D 10 NSi: C, 88.80; H, 6.82; N, 1.46. Measured elemental content (%): C, 88.85; H, 6.81; N, 1.43.

[0245] Synthesis Example 27: Preparation of Compound 339

[0246]

[0247] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, and e-5 was replaced with an equimolar amount of C-339, yielding compound 339 (17.11 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 949.4119 (theoretical value: 949.4104). Theoretical elemental content (%) C 71 H 55 NSi: C, 89.74; H, 5.83; N, 1.47. Measured elemental content (%): C, 89.71; H, 5.85; N, 1.45.

[0248] Synthesis Example 28: Preparation of Compound 346

[0249]

[0250] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, e-5 was replaced with an equimolar amount of e-346, and c-5 was replaced with an equimolar amount of c-346, yielding compound 346 (15.48 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 847.3644 (theoretical value: 847.3634). Theoretical elemental content (%) C 63 H 49 NSi: C, 89.21; H, 5.82; N, 1.65. Measured elemental content (%): C, 89.23; H, 5.85; N, 1.62.

[0251] Synthesis Example 29: Preparation of Compound 354

[0252]

[0253] Following the method of Example 3, a-5 was replaced with an equimolar amount of c-5, and e-5 was replaced with an equimolar amount of C-354, yielding compound 354 (16.69 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 913.4115 (theoretical value: 913.4104). Theoretical elemental content (%) C 68 H 55 NSi: C, 89.33; H, 6.06; N, 1.53. Measured elemental content (%): C, 89.34; H, 6.02; N, 1.54.

[0254] Synthesis Example 30: Preparation of Compound 366

[0255]

[0256] Following the method in Example 3, a-5 was replaced with an equimolar amount of c-5, and e-5 was replaced with an equimolar amount of C-366, yielding compound 366 (15.94 g). HPLC analysis showed a solid purity ≥99.98%. Mass spectrometry m / z: 897.3777 (theoretical value: 897.3791). Theoretical elemental content (%) C 67 H 51 NSi: C, 89.59; H, 5.72; N, 1.56. Measured elemental content (%): C, 89.54; H, 5.73; N, 1.58.

[0257] Synthesis Example 31: Preparation of Compound 412

[0258]

[0259] Following the method of Example 3, e-5 was replaced with an equimolar amount of e-412, and c-5 was replaced with an equimolar amount of c-412, yielding compound 412 (16.57 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 959.4898 (theoretical value: 959.4886). Theoretical elemental content (%) C 71 H 65 NSi: C, 88.80; H, 6.82; N, 1.46. Measured elemental content (%): C, 88.82; H, 6.81; N, 1.49.

[0260] Synthesis Example 32: Preparation of Compound 429

[0261]

[0262] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, and c-5 was replaced with an equimolar amount of B-429, yielding compound 429 (16.65 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 911.3936 (theoretical value: 911.3947). Theoretical elemental content (%) C 68 H 53 NSi: C, 89.53; H, 5.86; N, 1.54. Measured elemental content (%): C, 89.55; H, 5.84; N, 1.52.

[0263] Synthesis Example 33: Preparation of Compound 433

[0264]

[0265] Following the method of Example 3, c-5 was replaced with an equimolar amount of B-433 to obtain compound 433 (17.03 g). HPLC analysis showed a solid purity ≥99.94%. Mass spectrometry m / z: 945.3778 (theoretical value: 945.3791). Theoretical elemental content (%) C 71 H 51 NSi: C, 90.12; H, 5.43; N, 1.48. Measured elemental content (%): C, 90.14; H, 5.41; N, 1.45.

[0266] Synthesis Example 34: Preparation of Compound 450

[0267]

[0268] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, and c-5 was replaced with an equimolar amount of c-450, yielding compound 450 (14.64 g). HPLC analysis showed a solid purity ≥99.95%. Mass spectrometry m / z: 801.3679 (theoretical value: 801.3667). Theoretical elemental content (%) C 59 H 35 D8NSi: C, 88.35; H, 6.41; N, 1.75. Measured elemental content (%): C, 88.32; H, 6.42; N, 1.73.

[0269] Synthesis Example 35: Preparation of Compound 485

[0270]

[0271] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, e-5 with an equimolar amount of e-485, and c-5 with an equimolar amount of c-485, yielding compound 485 (16.44 g). HPLC analysis showed a solid purity ≥99.93%. Mass spectrometry m / z: 925.4116 (theoretical value: 925.4104). Theoretical elemental content (%) C 69 H 55 NSi: C, 89.47; H, 5.99; N, 1.51. Measured elemental content (%): C, 89.46; H, 5.95; N, 1.55.

[0272] Synthesis Example 36: Preparation of Compound 511

[0273]

[0274] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, e-5 was replaced with an equimolar amount of C-511, and c-5 was replaced with an equimolar amount of a-58, yielding compound 511 (16.74 g). HPLC analysis showed a solid purity ≥99.92%. Mass spectrometry m / z: 969.3781 (theoretical value: 969.3791). Theoretical elemental content (%) C 73 H 51 NSi: C, 90.36; H, 5.30; N, 1.44. Measured elemental content (%): C, 90.31; H, 5.32; N, 1.45.

[0275] Synthesis Example 37: Preparation of Compound 516

[0276]

[0277] Following the method of Example 3, a-5 was replaced with an equimolar amount of a-58, e-5 with an equimolar amount of e-516, and c-5 with an equimolar amount of a-58, yielding compound 516 (14.88 g). HPLC analysis showed a solid purity ≥99.96%. Mass spectrometry m / z: 849.3778 (theoretical value: 849.3791). Theoretical elemental content (%) C 63 H 51 NSi: C, 89.00; H, 6.05; N, 1.65. Measured elemental content (%): C, 89.04; H, 6.02; N, 1.61.

[0278] Device Examples

[0279] In this invention, the ITO glass substrate is ultrasonically cleaned twice with a 5% glass cleaning solution for 20 minutes each time, followed by ultrasonic cleaning twice with deionized water for 10 minutes each time. It is then ultrasonically cleaned sequentially with acetone and isoacetone for 20 minutes each time, and dried at 120°C. All organic materials are sublimated and have a purity of over 99.99%.

[0280] A combined IVL testing system was constructed, consisting of testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectrophotometer, to test the driving voltage, luminous efficiency, and CIE color coordinates of organic electroluminescent devices. Lifetime testing was performed using a McScience M6000 OLED lifetime testing system. The testing environment was ambient air at room temperature.

[0281] The device was fabricated using a vacuum evaporation system, with continuous evaporation under uninterrupted vacuum conditions. The materials used were housed in separate quartz crucibles containing different evaporation sources, the temperatures of which could be individually controlled. The thermal evaporation rate of organic materials was typically set at 0.1 nm / s, while the evaporation rate of electrode metals ranged from 0.4 to 0.6 nm / s. The prepared glass substrate was then placed in an OLED vacuum coating machine. During the thin film fabrication process, the system vacuum level should be maintained at 5 × 10⁻⁶. -5 Below Pa, organic layers and metal electrodes were deposited by changing the mask. The deposition rate was measured using an Inficon SQM160 quartz crystal film thickness gauge, and the film thickness was measured using a quartz crystal oscillator.

[0282] Red organic electroluminescent device

[0283] Example 1: Fabrication of Organic Electroluminescent Device 1

[0284] ITO is used as the anode on a glass substrate; 60 nm of PPDN is vacuum-deposited on the anode to form a hole injection layer; 30 nm of compound 5 of the present invention is vacuum-deposited on the hole injection layer to form a first hole transport layer; 30 nm of m-CBP:Ir(piq)2(acac) (mixed at a mass ratio of 95%:5%) is vacuum-deposited on the first hole transport layer to form a light-emitting layer; 30 nm of Alq3 is vacuum-deposited on the light-emitting layer to form an electron transport layer; 1.0 nm of Liq is vacuum-deposited on the electron transport layer to form an electron injection layer; and 120 nm of Al is vacuum-deposited on the electron injection layer to form a cathode.

[0285] Examples 2-35: Fabrication of Organic Electroluminescent Devices 2-35

[0286] In Example 1, compound 5 in the first hole transport layer was replaced with compounds 58, 87, 99, 105, 112, 115, 129, 168, 181, 190, 194, 201, 243, 236, 248, 257, 275, 276, 293, 294, 308, 323, 325, 339, 346, 354, 366, 412, 429, 433, 450, 485, 511, and 516, respectively. All other steps remained the same, resulting in organic electroluminescent devices 2-35.

[0287] Comparative Examples 1-3: Fabrication of Comparative Organic Electroluminescent Devices 1-3

[0288] By replacing compound 5 in the first hole transport layer of Example 1 with R-1, R-2, and R-3 respectively, and keeping the other steps the same, comparative organic electroluminescent devices 1 to 3 were obtained.

[0289]

[0290]

[0291] The luminescence characteristics test results of the organic electroluminescent devices prepared in Examples 1 to 35 and Comparative Examples 1 to 3 of the present invention are shown in Table 1.

[0292] Table 1. Test data on the luminescence characteristics of organic electroluminescent devices.

[0293]

[0294]

[0295] Note: T95 refers to a current density of 10 mA / cm². 2 Under certain conditions, the time it takes for the device's brightness to decay to 95%;

[0296] As can be seen from Table 1, compared with Comparative Examples 1-3, the luminous efficiency and lifespan of the organic electroluminescent device of the present invention are further improved. This is because the fluorene-containing aromatic amine derivative of the present invention has better stability and better film-forming properties. When used in organic electroluminescent devices, the devices exhibit better photoelectric performance, especially with a significant improvement in lifespan.

[0297] Green organic light-emitting devices

[0298] Example 36: Fabrication of Organic Electroluminescent Device 36

[0299] ITO is used as the anode on a glass substrate; a 60 nm thick HATCN layer is vacuum-deposited on the anode to form a hole injection layer; a 30 nm thick NPB layer is vacuum-deposited on the hole injection layer to form a first hole transport layer; compound 5 of the present invention is vacuum-deposited on the first hole transport layer as a second hole transport layer with a thickness of 15 nm; a 35 nm thick Alq3:MQD layer (mixed at a mass ratio of 96%:4%) is vacuum-deposited on the second hole transport layer to form a light-emitting layer; a 30 nm thick ETM layer is vacuum-deposited on the light-emitting layer to form an electron transport layer; a 1.0 nm thick Liq layer is vacuum-deposited on the electron transport layer to form an electron injection layer; and a 120 nm thick Al layer is vacuum-deposited on the electron injection layer to form a cathode.

[0300] Examples 37-70: Fabrication of Organic Electroluminescent Devices 37-70

[0301] In Example 36, compound 5 in the second hole transport layer was replaced with compounds 58, 87, 99, 105, 112, 115, 129, 168, 181, 190, 194, 201, 243, 236, 248, 257, 275, 276, 293, 294, 308, 323, 325, 339, 346, 354, 366, 412, 429, 433, 450, 485, 511, and 516, respectively. All other steps remained the same, resulting in organic electroluminescent devices 37–70.

[0302] Example 71: Fabrication of Organic Electroluminescent Device 71

[0303] By replacing compound NPB in the first hole transport layer of Example 36 with compound 5, and following the same other steps, an organic electroluminescent device 71 is obtained.

[0304] Example 72: Fabrication of Organic Electroluminescent Device 72

[0305] By replacing compound NPB in the first hole transport layer of Example 36 with compound 87, and replacing compound 5 in the second hole transport layer with compound 87, and keeping the other steps the same, an organic electroluminescent device 72 is obtained.

[0306] Example 73: Fabrication of Organic Electroluminescent Device 73

[0307] By replacing compound NPB in the first hole transport layer of Example 36 with compound 308, and compound 5 in the second hole transport layer with compound 58, and keeping the other steps the same, an organic electroluminescent device 73 is obtained.

[0308] Example 74: Fabrication of Organic Electroluminescent Device 74

[0309] By replacing compound NPB in the first hole transport layer of Example 36 with compound 293, and compound 5 in the second hole transport layer with compound 129, and keeping the other steps the same, an organic electroluminescent device 74 is obtained.

[0310] Example 75: Fabrication of Organic Electroluminescent Device 75

[0311] By replacing compound NPB in the first hole transport layer of Example 36 with compound 276, and compound 5 in the second hole transport layer with compound 294, and keeping the other steps the same, an organic electroluminescent device 75 is obtained.

[0312] Comparative Examples 4-5: Fabrication of Comparative Organic Electroluminescent Devices 4-5

[0313] By replacing compound 5 in the second hole transport layer of Example 36 with R-4 and R-5 respectively, and keeping the other steps the same, comparative organic electroluminescent devices 4-5 were obtained.

[0314]

[0315] The luminescence characteristics test results of the organic electroluminescent devices prepared in Examples 36-75 and Comparative Examples 4-5 of this invention are shown in Table 2.

[0316] Table 2. Test data on the luminescence characteristics of organic electroluminescent devices.

[0317]

[0318]

[0319]

[0320] Note: T95 refers to a current density of 10 mA / cm². 2 Under certain conditions, the time it takes for the device's brightness to decay to 95%;

[0321] As shown in Table 2, the fluorene-containing aromatic amine derivatives of the present invention, when used as the second hole transport layer material in organic electroluminescent devices, exhibit significantly improved device performance compared to Comparative Examples 4-5, demonstrating advantages such as high luminous efficiency and long lifespan. When the fluorene-containing aromatic amine derivatives of the present invention are used as the first and second hole transport layer materials in organic electroluminescent devices, both luminous efficiency and lifespan are improved compared to Comparative Examples 4-5. This is because, compared to Comparative Examples 4-5, in the compounds of the present invention, fluorene groups such as diphenylfluorene and spirofluorene, which have significant steric hindrance and robust rigidity, are bound to the nitrogen side of the aromatic amine, thus giving it excellent thermal stability. Furthermore, the compounds contain substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, and substituted silyl groups, making it less prone to planar stacking, reducing molecular crystallinity, and improving the film-forming properties of the material. Therefore, when the fluorene-containing aromatic amine derivatives of the present invention are used as hole transport materials in organic electroluminescent devices, the organic electroluminescent devices exhibit high luminous efficiency and long lifespan.

[0322] 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 fluorene-containing aromatic amine derivative, characterized in that, It has the structure shown in Equation 1. L1 and L2 are independently selected from single bonds. p1 is selected from 0 or 1, and p2 is selected from 0 or 1; A is selected from the structure shown in Equation 2: Formula 2 is selected from one of the following groups: R5, R6, and R7 are independently selected from substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, and substituted or unsubstituted butyl. The Selected from one of the following groups: The n1 is selected from 0, 1, 2, 3, 4 or 5; the n2 is selected from 0, 1, 2, 3, 4 or 5; the n3 is selected from 0, 1, 2, 3 or 4; the n4 is selected from 0, 1, 2 or 3. The R1, R2, R 1a R 2a The same or different from one selected from hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted phenyl; or adjacent R 1a Adjacent R 2a Formation of substituted or unsubstituted benzene rings; The R3s, whether identical or different, are selected from hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, and substituted or unsubstituted phenyl; or adjacent R3s form a substituted or unsubstituted benzene ring. The R4 that is the same or different is selected from hydrogen and deuterium; When there are two or more R1s, they are the same or different from each other; when there are two or more R2s, they are the same or different from each other; when there are two or more R3s, they are the same or different from each other; when there are two or more R4s, they are the same or different from each other. The Selected from one of the following groups: The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3, 4 or 5; the m3 is selected from 0, 1, 2, 3 or 4; the m4 is selected from 0, 1, 2 or 3. The R a R b R a1 R b1 The same or different from one selected from hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted phenyl; or adjacent R a1 Adjacent R b1 Formation of substituted or unsubstituted benzene rings; The R c The same or different from one selected from hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted trimethylsilyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted phenyl; or adjacent R c Formation of substituted or unsubstituted benzene rings; The R d The same or different ones are selected from one of hydrogen and deuterium; When there are two or more R a At that time, two or more R a They may be the same as or different from each other; when there are two or more R... b At that time, two or more R b They may be the same as or different from each other; when there are two or more R... c At that time, two or more R c They may be the same as or different from each other; when there are two or more R... d At that time, two or more R d They are the same as or different from each other; The aforementioned "substituted or unsubstituted" means either not substituted or substituted by one or more substituents selected from the group consisting of: deuterium, methyl, deuterated methyl; L3 and L4 are selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene; L5 is selected from single bonds, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthracene; the term "substituted or unsubstituted" in "substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthylene" means unsubstituted or substituted by one or more substituents selected from the group consisting of: deuterium, methyl, deuterated methyl.

2. The fluorene-containing aromatic amine derivative according to claim 1, characterized in that, The Selected from one of the following groups:

3. The fluorene-containing aromatic amine derivative according to claim 1, characterized in that, Formula 2 is selected from one of the following groups:

4. The fluorene-containing aromatic amine derivative according to claim 1, characterized in that, The R1, R2, R 1a R 2a R3, whether the same or different, is selected from one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, or substituted or unsubstituted butyl.

5. The fluorene-containing aromatic amine derivative according to claim 1, characterized in that, The R a R b R a1 R b1 R c The same or different is selected from one of hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl.

6. The fluorene-containing aromatic amine derivative according to claim 1, characterized in that, L3, L4, and L5 are selected from single-bonded, substituted, or unsubstituted phenylene compounds.

7. A fluorene-containing aromatic amine derivative, characterized in that, The fluorene-containing aromatic amine derivative of Formula 1 is selected from one of the following structures:

8. An organic electroluminescent device, comprising 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, characterized in that, The organic layer contains any one of the fluorene-containing aromatic amine derivatives as described in any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, wherein the organic layer comprises a hole transport region, a light-emitting layer, an electron transport region, or a capping layer, characterized in that, At least one layer in the hole transport region contains any one of the fluorene-containing aromatic amine derivatives as described in any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 9, characterized in that, The hole transport region includes a hole transport layer, which contains any one of the fluorene-containing aromatic amine derivatives according to any one of claims 1 to 7.

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