Heterocyclic compound and organic electroluminescent device thereof

Abstract

The application provides a heterocyclic compound and an organic electroluminescent device thereof, and particularly relates to the technical field of organic electroluminescent materials.The heterocyclic compound provided by the application has suitable HOMO and LUMO energy levels, can be well matched with adjacent functional layers, can make the hole and electron distribution in the organic electroluminescent device balanced, can improve the recombination probability of excitons, and thus can realize the maximum recombination of carriers; in addition, the heterocyclic compound provided by the application also has a high triplet energy level, good film-forming property and thermal stability.When the heterocyclic compound provided by the application is applied to an organic electroluminescent device as the host material of a light-emitting layer, the luminous efficiency of the device can be effectively improved, the service life of the device can be prolonged, and the overall performance of the device can be significantly improved.

Description

Technical Field

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

[0002] Organic light-emitting diodes (OLEDs) are a new type of flat panel display technology with the greatest development potential in recent years. They have many advantages, such as low driving voltage, high efficiency, high brightness, good flexibility, wide viewing angle, fast response speed, high resolution, light weight, low cost, and wide range of material selection. They have broad application prospects in the display and lighting fields and have received much attention from the scientific and industrial communities in recent years.

[0003] Organic light-emitting diodes (OLEDs) are dual-injection carrier devices that convert electrical energy into light energy. OLEDs typically have a sandwich structure, where an organic functional layer is sandwiched between the anode and cathode on either side of the device. The organic layer usually includes a hole transport region, an electron transport region, and an emissive layer. The hole transport region can be further divided into a hole injection layer, a hole transport layer, and an electron blocking layer; the electron transport region can be divided into an electron injection layer, an electron transport layer, and a hole blocking layer; the emissive layer often employs host-guest doping, consisting of a host material and a guest material. The light-emitting principle is as follows: Under the influence of an applied electric field, holes generated by the anode material and electrons generated by the cathode material are injected into the OLED device. These two materials recombine in the emissive layer to generate excitons. The excited molecules are unstable and return to the ground state via radiative transitions. During this transition, energy is released in the form of light energy, producing electroluminescence.

[0004] As the core component of organic electroluminescent devices, the material used in the emissive layer plays a decisive role in the device's luminous efficiency. Currently, emissive layer materials suffer from problems such as energy level mismatch between the host material and adjacent functional layers, as well as triplet energy level mismatch between the host and guest materials. These issues lead to an imbalance in electron and hole migration within the emissive layer, reducing the exciton recombination probability and consequently affecting the device's luminous efficiency. Furthermore, the material technology and expertise required for emissive layer materials are highly specialized, and the market has historically been largely monopolized by foreign companies.

[0005] Therefore, in order to continuously improve the performance of organic electroluminescent devices, it is urgent to develop high-performance light-emitting layer materials to reduce the driving voltage, improve the luminous efficiency, and extend the lifespan of the devices, in order to address the existing problems of current light-emitting layer materials. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a heterocyclic compound and its organic electroluminescent device. Specifically, the technical solution of this invention is as follows:

[0007] This invention provides a heterocyclic compound, which is represented by the structure shown in Formula I-1 or Formula I-2:

[0008]

[0009] At least one of Ar1 and Ar2 is selected from the group shown in Formula II-1 or Formula II-2, and the remainder is selected from one or a combination of deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring, and fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl:

[0010]

[0011] Y1 and Y2 are independently selected from O or S;

[0012] The ring B and ring C are independently selected from none or any one of the following groups:

[0013]

[0014] The x are selected from C(R2) or N, either the same or different; and at most one of the x is selected from N;

[0015] The R2 is selected from one or a combination thereof, either identically or differently, from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring, or fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl; or two adjacent R2s may be interconnected to form substituted or unsubstituted rings;

[0016] The z is selected from C(R1) or N, whether the same or different; the R1 is selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl ring; or adjacent R1 are connected to form a substituted or unsubstituted ring;

[0017] The ring A is selected from substituted or unsubstituted C6-C20 aryl groups or substituted or unsubstituted C4-C20 heteroaryl groups;

[0018] L1 and L2 are independently selected from one or a combination of single bonds, substituted or unsubstituted C6-C30 arylene groups, substituted or unsubstituted C2-C30 heteroarylene groups, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic groups, substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaromatic groups.

[0019] The present invention also provides an organic electroluminescent device comprising at least one of the heterocyclic compounds described in the present invention.

[0020] Beneficial effects

[0021] This invention provides a heterocyclic compound and its organic electroluminescent device. The heterocyclic compound provided by this invention possesses suitable HOMO and LUMO energy levels, which can be well matched with adjacent functional layers, achieving a balanced distribution of holes and electrons within the device, increasing the exciton recombination probability, and thus achieving maximum carrier recombination. Furthermore, the heterocyclic compound provided by this invention also exhibits a high triplet energy level, good film-forming properties, and thermal stability. When applied as the main material of the light-emitting layer in an organic electroluminescent device, it can improve the luminous efficiency and extend the device's lifespan. In summary, the heterocyclic compound provided by this invention is a high-performance organic electroluminescent material, and its application in organic electroluminescent devices can significantly improve the overall performance of the device. Detailed Implementation

[0022] The technical solutions of this invention will be clearly and completely described below with reference to specific embodiments. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of this invention.

[0023] 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.

[0024] 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.

[0025] In this specification, "*" refers to a connection site or fusion site.

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

[0028] The alkyl group referred to in this invention is the collective term for the monovalent group remaining after removing one hydrogen atom from an alkane molecule. It can be a straight-chain alkyl group or a branched-chain alkyl group. The alkyl group can be substituted or unsubstituted. The straight-chain alkyl group includes, but is not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, and dodecyl groups; the branched-chain alkyl group includes, but is not limited to, isomers of isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl groups. The alkyl group has 1 to 15 carbon atoms, more preferably 1 to 15, and particularly preferably 1 to 6.

[0029] The alicyclic group referred to in this invention is the general term for the monovalent group remaining after removing one hydrogen atom from an alicyclic hydrocarbon molecule. It can be cycloalkyl, cycloalkenyl, etc., and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornel, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc., but are not limited thereto. The alicyclic group has 3 to 15 carbon atoms, more preferably 3 to 12, and particularly preferably 3 to 8.

[0030] The "substituted or unsubstituted silyl group" mentioned in this invention refers to -Si(R z )3 groups, wherein each R z 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 z The same or different groups are selected from the following: 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, 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. Preferably, each R... z The 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, etc., but not limited to these. Examples may include, but are not limited to, trimethylsilyl, triethylsilyl, triisopropylsilyl, tritert-butylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, dimethyltert-butylsilyl, tricyclopentylsilyl, tricyclohexylsilyl, triphenylsilyl, triphenylsilyl, tripyridylsilyl, tripyridylsilyl, etc.

[0031] The aryl group described in this invention refers to the collective term for the monovalent group remaining after 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. The aryl group can be substituted or unsubstituted. A monocyclic aryl refers to an aryl group with only one aromatic ring in the molecule, such as phenyl, but not limited to this; a polycyclic aryl refers to an aryl group containing two or more independent aromatic rings in the molecule, such as biphenyl, terphenyl, etc., but not limited to this; a fused-ring aryl refers to an aryl group containing two or more aromatic rings fused together by sharing two adjacent carbon atoms, such as naphthyl, anthracene, phenanthryl, pyrene, peryl, fluorenyl, benzo[a]fluorenyl, triphenylene, fluoranyl, 9,9'-spirodifluorenyl, etc., but not limited to this. The number of carbon atoms in the aryl group is C6 to C30, preferably C6 to C20, more preferably C6 to C14, and particularly preferably C6 to C12.

[0032] The heteroaryl group described in this invention refers to the collective term for the monovalent group remaining after one or more aromatic carbon atoms in an aryl group are replaced by heteroatoms. The heteroatoms include, but are not limited to, oxygen, sulfur, nitrogen, silicon, or phosphorus atoms. The heteroaryl group can be substituted or unsubstituted. The linking site of the heteroaryl group can be located on a cyclic carbon atom or on a cyclic heteroatom, and the heteroaryl group can be a monocyclic heteroaryl, polycyclic heteroaryl, or fused-ring heteroaryl, etc. The monocyclic heteroaryl groups include pyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furanyl, thiopheneyl, pyrroloyl, oxazolyl, thiazolyl, imidazolyl, etc., but are not limited thereto; the polycyclic heteroaryl groups include bipyridinyl, bipyrimidinyl, phenylpyridinyl, phenylpyrimidinyl, etc., but are not limited thereto; the fused-ring heteroaryl groups include quinolinyl, isoquinolinyl, indolyl, benzothiopheneyl, benzofuranyl, benzooxazolyl, benzoimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothiopheneyl, benzodibenzothiopheneyl, carbazoleyl, benzocarbazoleyl, acridineyl, 9,10-dihydroacridinyl, phenoxazinyl, phenthiazinyl, phenoxthiazyl, spirofluorenexanthraceneyl, spirofluorenethionthanthraceneyl, etc., but are not limited thereto. The heteroaryl group has 2 to 30 carbon atoms, preferably 2 to 20, more preferably 2 to 14, and particularly preferably 2 to 12.

[0033] The fused alicyclic and aromatic ring groups described in this invention refer to the general term for monovalent groups remaining after removing one hydrogen atom from the fused alicyclic and aromatic rings. Examples of fused alicyclic and aromatic ring groups include, but are not limited to, the following groups: benzocyclopropane, benzocyclobutane, benzocyclobutenyl, dihydroindenyl, indenyl, tetrahydronaphthyl, dihydronaphthyl, benzocycloheptane, benzocycloheptenyl, etc., but are not limited thereto. The alicyclic ring has 3 to 15 carbon atoms, more preferably 3 to 12, and particularly preferably 3 to 8. The aromatic ring has 6 to 30 carbon atoms, preferably 6 to 20, more preferably 6 to 14, and particularly preferably 6 to 12.

[0034] The fused cyclic group of alicyclic and heteroaromatic rings described in this invention refers to the general term for a monovalent group remaining after removing one hydrogen atom from the fused alicyclic and heteroaromatic rings. Examples of fused cyclic groups of alicyclic and aromatic rings include, but are not limited to, the following groups: pyridocyclobutane, pyridocyclopentane, pyridocyclohexane, pyridocyclopentenyl, pyridocyclohexenyl, pyrimidinocyclopentane, pyrimidinocyclohexane, etc., but are not limited thereto. The alicyclic ring has 3 to 15 carbon atoms, more preferably 3 to 12, and particularly preferably 3 to 8. The heteroaromatic ring has 2 to 30 carbon atoms, preferably 2 to 20, more preferably 2 to 14, and particularly preferably 2 to 12.

[0035] The arylene group referred to in this invention is a general term for the divalent group remaining after removing two hydrogen atoms from the aromatic carbon atom. Apart from being divalent groups, they can be described in the same way as the aryl group described above.

[0036] The term "hybrid aryl" as used in this invention refers to the collective term for divalent groups remaining after removing two hydrogen atoms from the nucleus carbon of an aromatic heterocycle composed of carbon and heteroatoms. Apart from being divalent groups, they are subject to the same description of heteroaryl groups as described above.

[0037] The alicyclic and aromatic ring fused groups described in this invention refer to the general term for the divalent groups remaining after removing two hydrogen atoms from the fused alicyclic and aromatic rings. Apart from being divalent groups, they are similar to the fused alicyclic and aromatic ring fused groups described above.

[0038] The fused alicyclic and heteroaromatic ring groups described in this invention refer to the general term for the divalent groups remaining after removing two hydrogen atoms from the fused alicyclic and heteroaromatic rings. Apart from being divalent groups themselves, they are applicable to the above description of fused alicyclic and heteroaromatic ring groups.

[0039] In this invention, "forming a ring by connecting two adjacent groups" refers to the formation of a substituted or unsubstituted aromatic ring, aromatic heterocycle, aliphatic ring, or aliphatic heterocycle by combining adjacent groups with each other and optionally aromatizing them. The aliphatic ring or aliphatic heterocycle can be a saturated ring or an unsaturated ring. Specifically, the ring formed by the connection can be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a seven-membered ring, a spirocyclic ring, or a fused ring. Further, the ring formed by the connection can be, for example, benzene, naphthalene, phenanthrene, triphenylene, pyrene, indene, fluorene, cyclopentene, cyclopentane, cyclopentanophenene, cyclohexene, cyclohexane, cyclohexanophenene, pyridine, pyrimidine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, or dibenzothiophene, etc., but is not limited to these.

[0040]

[0041] In this invention, "unsubstituted" in "substituted or unsubstituted" means that the hydrogen atom on the group is not replaced by any substituent. "Substituted" in this invention means that at least one hydrogen atom on the group is replaced by a substituent, and the position of substitution is not limited, as long as the position is where a hydrogen atom is substituted. When multiple hydrogen atoms are replaced by multiple substituents, the multiple substituents can be the same or different.

[0042] The substituents represented by "substituted or unsubstituted" in this invention include the following groups: deuterium, tritium, cyano, nitro, hydroxyl, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C2-C15 alkenyl, substituted or unsubstituted C3-C15 alicyclic, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30... Heteroaryl groups, fused cycloalcohols of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic rings, fused cycloalcohols of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaromatic rings, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C6-C30 aryloxy groups, substituted or unsubstituted C6-C30 aromatic amino groups, etc., but not limited to these. The substituents are preferably the following groups: deuterium, tritium, cyano, fluorine, chlorine, bromine, iodine, nitro, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclobutenyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornel, trifluoromethyl, benzocyclopropane, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocycloheptane, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthrene, triphenylene, anthracene, pyrene. The substituents include 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, 9,9'-spirodifluorenyl, pyridyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phenantholinyl, benzoxazolyl, benzothiazolyl, benzoimidazolyl, benzofuranyl, dibenzofuranyl, benzothiopheneyl, dibenzothiopheneyl, indolyl, carbazoleyl, 9-phenylcarbazoleyl, trimethylsilyl, triethylsilyl, tri-tert-butylsilyl, triphenylsilyl, etc. Furthermore, each of the above substituents can be substituted or unsubstituted, and two adjacent substituents can be linked to form a ring.

[0043] This invention provides a heterocyclic compound, which is represented by the structure shown in Formula I-1 or Formula I-2:

[0044]

[0045] At least one of Ar1 and Ar2 is selected from the group shown in Formula II-1 or Formula II-2, and the remainder is selected from one or a combination of deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring, and fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl:

[0046]

[0047] Y1 and Y2 are independently selected from O or S;

[0048] The ring B and ring C are independently selected from none or any one of the following groups:

[0049]

[0050] The x are selected from C(R2) or N, either the same or different; and at most one of the x is selected from N;

[0051] The R2 is selected from one or a combination thereof, either identically or differently, from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring, or fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl; or two adjacent R2s may be interconnected to form substituted or unsubstituted rings;

[0052] The z is selected from C(R1) or N, whether the same or different; the R1 is selected from hydrogen, deuterium, tritium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl ring; or adjacent R1 are connected to form a substituted or unsubstituted ring;

[0053] The ring A is selected from substituted or unsubstituted C6-C20 aryl groups or substituted or unsubstituted C4-C20 heteroaryl groups;

[0054] L1 and L2 are independently selected from one or a combination of single bonds, substituted or unsubstituted C6-C30 arylene groups, substituted or unsubstituted C2-C30 heteroarylene groups, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic groups, substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaromatic groups.

[0055] Preferably, at least one of Ar1 and Ar2 is selected from any one of the following groups derived from formula II-1 or formula II-2:

[0056]

[0057]

[0058]

[0059] More preferably, at least one of Ar1 and Ar2 is selected from any one of the following groups derived from formula II-1 or formula II-2:

[0060]

[0061] a1 is selected from 0, 1, 2, or 3; a2 is selected from 0, 1, 2, 3, 4, or 5; a3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; a4 is independently selected from 0, 1, 2, 3, or 4; a5 is selected from 0, 1, 2, 3, 4, 5, or 6; a6 is selected from 0, 1, or 2; when there are two or more R2s, the two or more R2s are the same as or different from each other;

[0062] R2 is selected, either identically or differently, from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or substituted or unsubstituted of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, phenylenetriene, benzocyclobutane, benzocyclopentane, benzocyclohexane, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, indenyl, fluorenyl, furanyl, benzofuran One or a combination thereof of the following: alkyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, indolyl, carbazoyl, benzoxazolyl, benzothiazoyl, benzimidazolyl, pyridyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, acridineyl, o-phenanthrolinel, trimethylsilyl, triethylsilyl, tripropylsilyl, triphenylsilyl; or two adjacent R2s connected to form a substituted or unsubstituted benzene ring, naphthyl ring, pyridine ring, pyrimidine ring, or aliphatic ring.

[0063] Preferably, the substituents in R2 that are “substituted or unsubstituted” are selected from one or more of deuterium, tritium, halogen, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornyl, phenyl, and biphenyl. When two or more substituents are present, the two or more substituents are the same as or different from each other.

[0064] Preferably, when Ar1 or Ar2 is not of formula II-1 or II-2, it is selected from any one of the following groups:

[0065]

[0066] The y is selected from N or C(R3), either the same or different.

[0067] The R3s are selected, either identically or differently, from one or a combination thereof, of hydrogen, deuterium, tritium, cyano, fluorine, substituted or unsubstituted C1-C15 alkyl groups, substituted or unsubstituted C3-C15 alicyclic groups, substituted or unsubstituted silyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic groups, or fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl groups; or adjacent R3s may be interconnected to form substituted or unsubstituted rings;

[0068] The ring D is selected from substituted or unsubstituted C3-C10 alicyclic groups;

[0069] The Y3 is selected from O, S, N(R) c ) or C(R d R e );

[0070] The Y4 is selected from O, S, N(R) f ) or C(R g R h Y5 is selected from N or C(R) n );

[0071] The R c R f Independently selected from one or a combination of substituted or unsubstituted C1-C15 alkyl groups, substituted or unsubstituted C3-C15 alicyclic groups, substituted or unsubstituted silyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic groups, and fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl groups; or the R c R f It can be directly bonded to L1 or L2;

[0072] The R d R e R g R h R n Independently selected from one or a combination thereof: hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring, fused cycloalcoholic group of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl; or Rd R e They can connect to each other to form substituted or unsubstituted spirofluorene rings or aliphatic rings; or R d R e Any one of them can be directly bonded to L1 or L2.

[0073] More preferably, when Ar1 or Ar2 is not of formula II-1 or II-2, it is selected from any one of the following groups:

[0074]

[0075]

[0076]

[0077] The b1 is selected from 0, 1, 2, 3, 4, or 5; the b2 is selected from 0, 1, 2, 3, or 4; the b3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; the b4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, or 9; the b5 is selected from 0, 1, 2, or 3; the b6 is selected from 0, 1, or 2; the b7 is selected from 0, 1, 2, 3, 4, 5, or 6; the b8 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; the b9 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; the b 10 Selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, or 14; when there are two or more R3s, the two or more R3s are the same or different from each other.

[0078] The R3 is selected, either identically or differently, from hydrogen, deuterium, tritium, cyano, fluorine, trifluoromethyl, or substituted or unsubstituted of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornene, benzocyclobutane, benzocyclopentane, benzocyclohexane, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, phenylenetriene, indene, fluorenyl, furanyl, benzo[] One or a combination of furanyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, benzooxazolyl, benzothiazolyl, benzimidazolyl, indolyl, carbazoleyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, and triphenylsilyl; or two adjacent R3s may be linked together to form substituted or unsubstituted rings.

[0079] The R c R fThe group is independently selected from the following groups, whether substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, benzocyclopentyl, benzocyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, indole, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophene, dibenzothiophene, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, carbazole, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triphenylsilyl, or a combination thereof.

[0080] The R d R e R g R h R n The group is independently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or substituted or unsubstituted of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, benzocyclopentyl, benzocyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, indole, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophene, dibenzothiophene, benzoxazolyl, benzothiazolyl, benzimidazolyl, indolyl, carbazole, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triphenylsilyl, or a combination thereof.

[0081] The R i The following groups, selected from hydrogen, deuterium, tritium, cyano, fluorine, trifluoromethyl, or substituted or unsubstituted, may be the same or different: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornel, benzocyclobutane, benzocyclopentane, benzocyclohexane, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, phenylenetriethylene, indole, fluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophene, benzothiophene, dibenzothiophene, indolyl, carbazoyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, or a combination thereof; or two adjacent R groups. i They can connect to each other to form substituted or unsubstituted rings.

[0082] Preferably, R3, R c R d R e Rf R g R h R i R n The substituents in "substituted or unsubstituted" are selected from one or more of deuterium, tritium, fluorine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornyl, phenyl, and biphenyl. When two or more substituents are present, the two or more substituents are the same as or different from each other.

[0083] Preferably, L1 and L2 are selected from single bonds or any one of the following groups:

[0084]

[0085] The term e is selected from N or C(R4), either identically or differently.

[0086] The R4s are selected, either identically or differently, from one or a combination thereof, of hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic, substituted or unsubstituted silyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic, or fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl; or adjacent R4s may be interconnected to form substituted or unsubstituted rings;

[0087] The ring M is selected from substituted or unsubstituted C3-C10 alicyclic groups;

[0088] The R j R k Independently selected from one or a combination of substituted or unsubstituted C1-C15 alkyl groups, substituted or unsubstituted C3-C15 alicyclic groups, substituted or unsubstituted silyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic groups, and fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl groups; or R j R k They can connect with each other to form substituted or unsubstituted spirofluorene rings or aliphatic rings;

[0089] The R lIt is selected from one or a combination of substituted or unsubstituted C1-C15 alkyl groups, substituted or unsubstituted C3-C15 alicyclic groups, substituted or unsubstituted silyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups, fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic groups, and fused cycloalcoholic groups of substituted or unsubstituted C3-C15 alicyclic and C2-C30 heteroaryl groups.

[0090] More preferably, L1 and L2 are selected from single bonds or any one of the following groups:

[0091]

[0092]

[0093] c1 is selected from 0, 1, 2, 3, or 4; c2 is selected from 0, 1, 2, or 3; c3 is selected from 0, 1, or 2; c4 is selected from 0, 1, 2, 3, 4, 5, or 6; c5 is selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; c6 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10; c7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 13, or 14; c8 is selected from 0 or 1; when there are two or more R4s, the two or more R4s are the same as or different from each other.

[0094] The R4 groups are selected from hydrogen, deuterium, tritium, cyano, fluorine, trifluoromethyl, or substituted or unsubstituted groups of the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, benzocyclobutyl, benzocyclopentyl, benzocyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, indyl, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophene, dibenzothiophene, indolyl, carbazoyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triphenylsilyl; or adjacent R4 groups may be linked together to form substituted or unsubstituted rings.

[0095] The R j R kThe group is independently selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or substituted or unsubstituted of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, benzocyclopentyl, benzocyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, indole, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophene, dibenzothiophene, indolyl, carbazoyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triphenylsilyl, or a combination thereof.

[0096] The R l The group is selected from the following groups, whether substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, benzocyclopentyl, benzocyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, indole, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophene, dibenzothiophene, indolyl, carbazoyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triphenylsilyl, or a combination thereof.

[0097] The R m The same or different from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or substituted or unsubstituted of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, indole, fluorene, benzofuranyl, benzothiophene, dibenzofuranyl, dibenzothiophene, indolyl, carbazoyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl

[0098] Preferably, R4, R j R k R l R m The substituents in "substituted or unsubstituted" are selected from one or more of deuterium, tritium, fluorine, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornyl, phenyl, and biphenyl. When two or more substituents are present, the two or more substituents are the same as or different from each other.

[0099] Preferably, ring A is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthraquinyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, and substituted or unsubstituted quinoxalinyl.

[0100] More preferably, ring A is selected from any one of the following groups:

[0101]

[0102]

[0103] The n1 is selected from 1 or 2; the n2 is selected from 1, 2, 3 or 4; the n3 is selected from 1, 2, 3, 4, 5 or 6; the n4 is selected from 1; the n5 is selected from 1, 2 or 3; when there are two or more R o At that time, two or more R o They may be the same as or different from each other.

[0104] The R o The group is selected, either identically or differently, from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or substituted or unsubstituted of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, adamantyl, norbornel, benzocyclopentyl, benzocyclohexyl, phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthrene, triphenylene, indole, fluorenyl, benzofuranyl, dibenzofuranyl, benzothiophene, dibenzothiophene, indolyl, carbazoyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, trimethylsilyl, triethylsilyl, tripropylsilyl, triphenylsilyl, or a combination thereof.

[0105] Preferably, the R o The substituents in "substituted or unsubstituted" are selected from one or more of deuterium, tritium, halogen, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornene, phenyl, biphenyl, and naphthyl. When two or more substituents are present, the two or more substituents are the same as or different from each other.

[0106] Most preferably, the heterocyclic compound is selected from any one of the following compounds:

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126] The above lists some specific structural forms of the heterocyclic compounds described in this invention. However, this invention is not limited to these listed chemical structures. Any structure based on the structure shown in Formula I-1 or Formula I-2, with substituents defined above, should be included.

[0127] The present invention also provides an organic electroluminescent device comprising at least one of the heterocyclic compounds described in the present invention.

[0128] Preferably, the organic electroluminescent device comprises an anode, a cathode, and one or more organic layers located between the anode and the cathode, the organic layers comprising at least one of the heterocyclic compounds described in this invention.

[0129] Preferably, the organic layer includes a light-emitting layer, which contains at least one of the heterocyclic compounds described in this invention.

[0130] Preferably, the light-emitting layer comprises a host material, which comprises at least one of the heterocyclic compounds described in this invention.

[0131] The organic layer of this invention may include a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, and a capping layer, etc. The organic layer of this invention may be formed from a single-layer structure or from a multi-layer structure, and each organic layer may also contain one or more materials.

[0132] The organic electroluminescent device of the present invention is typically formed on a substrate. The substrate can be any material that remains unchanged when forming electrodes or organic layers, such as glass, plastic, polymer films, silicon, etc.

[0133] The anode material described in this invention is preferably a high work function material that can promote hole injection into the organic layer. Specific examples may include: metals, such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); combinations of metals and oxides, such as ITO-Ag-ITO; conductive polymers, such as poly(3-methylthiophene), polypyrrole, polyaniline, poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), etc., but are not limited thereto.

[0134] The hole injection material described in this invention is preferably a material that can improve the efficiency of hole injection from the anode into the hole transport layer and the light-emitting layer, and has excellent hole acceptance capability. Specific examples may include: metal oxides such as silver oxide, vanadium oxide, tungsten oxide, copper oxide, and titanium oxide; phthalocyanine compounds; benzidine compounds; phenazine compounds; and other materials, such as copper phthalocyanine (CuPc), titanium phthalocyanine, N,N'-diphenyl-N,N'-di-[4-(N,N-diphenylamine)phenyl]benzidine (NPNPB), N,N,N',N'-tetra(4-methoxyphenyl)benzidine (MeO-TPD), diquinoxolino[2,3-a:2',3'-c]phenazine (HATNA), 4,4',4”-tris[2-naphthylphenylamino]triphenylamine (2T-NATA), 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazabenzophenanthrene (HAT-CN), and 4,4',4”-tris(N,N-diphenylamino)triphenylamine (TDATA), but are not limited to these.

[0135] The hole transport layer material described in this invention is preferably a material with high hole mobility that can transport holes to the light-emitting layer. Specific examples may include materials such as diphenylamine compounds, triphenylamine compounds, fluorene compounds, and carbazole compounds, such as N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB), N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine, 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline] (TAPC), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), 2,2,7,7-tetra(diphenylamino)-9,9-spirodifluorene (Spiro-TAD), and 4,4',4”-tris(carbazole-9-yl)triphenylamine (TCTA), but are not limited to these.

[0136] In the organic electroluminescent device of the present invention, the light-emitting layer material includes a host material and a dopant material. Specific examples of the host material may include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentane derivatives, phenanthrene derivatives, fluoranthene derivatives, carbazole derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, pyrimidine derivatives, etc., such as 4,4'-bis(9-carbazole)biphenyl (CBP), 4,4'-bis(9-carbazolyl)-2,2'-dimethylbiphenyl (CDBP), 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CZSi), 9 9'-(2,6-pyridinidyldi-3,1-phenylene)bis-9H-carbazole (26DCZPPY), 9,9'-diphenyl-9H,9'H-3,3'-bicarbazole (BCzPh), 9-(5-(3-(9H-carbazole-9-yl)phenyl)pyridin-3-yl)-9H-carbazole (CPPyC), 4,4'-bis(carbazole-9-yl)-2,2'-dimethylbiphenyl (CDBP), 1,3-bis(N-carbazole)benzene (MCP), 9,9 -Dimethyl-N,N-diphenyl-7-(4-(1-phenyl-1Hbenzimidazol-2-yl)phenyl)-9H-fluorene-2-amine (EFIN), 10-(4'-(diphenylamino)biphenyl-4-yl)acridin-9(10H)-one (ADBP), tris[4-(pyrene)-phenyl]amine (TPyPA), 9,10-di(2-naphthyl)anthracene (ADN), 2-tert-butyl-9,10-di(2-naphthyl)anthracene (TBADN), 1-(7-[ Examples of materials used include, but are not limited to, [9,9'-bianthra]-10-yl-9,9-dioctyl-9H-fluorene-2-yl]pyrene (BAnF8Pye), 9,9,9',9'-tetra(4-methylphenyl)-2,2'-bi-9H-fluorene (BDAF), tris(6-fluoro-8-hydroxyquinoline)aluminum (6FAlq3), tris(8-hydroxyquinoline)aluminum (Alq3), bis(10-hydroxybenzo[H]quinoline)beryllium (BeBq2), and bis(8-hydroxyquinoline)zinc (Znq2). Preferably, the host material of the luminescent layer is selected from the heterocyclic compounds described in this invention.

[0137] Specific examples of the doped material for the light-emitting layer may include fused polycyclic aromatic derivatives, styrene amine derivatives, fused cyclic amine derivatives, boron-containing compounds, pyrrole derivatives, indole derivatives, carbazole derivatives, heavy metal complexes, phosphorescent rare earth metal complexes, etc., such as (6-(4-(diphenylamino(phenyl)-N,N-diphenylpyrene-1-amine)(DPAP-DPPA), 2,5,8,11-tetra-tert-butylperylene (TBPe), 4,4'-bis[4-(diphenylamino)styrene]biphenyl (BDAVBi), 4,4'-bis[4-(di-p-tolylamino)styrene]biphenyl (DPAVBi), bis(2-hydroxyphenylpyridine)beryllium (Be Examples of iridium bis(4,6-difluorophenylpyridine-C2,N)pyridinecarboxylate (FIrpic), iridium tri(2-phenylpyridine) (Ir(ppy)3), iridium bis(2-phenylpyridine)acetylacetonate (Ir(ppy)2(acac)), 9,10-bis[N-(p-tolyl)anilino]anthracene (TPA), 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM), tri[1-phenylisoquinoline-C2,N]iridium(III) (Ir(piq)3), iridium bis(1-phenylisoquinoline)(acetylacetonate) (Ir(piq)2(acac)), etc., but not limited to these.

[0138] The electron transport material described in this invention is preferably a material capable of transporting electrons and balancing charge carriers, and has a high electron mobility. Specific examples may include: imidazoles, triazoles, phenanthroline derivatives, quinolines, and other materials, such as 2,9-(dimethyl)-4,7-biphenyl-1,10-o-phenanthroline (BCP), 1,3,5-tris[(3-pyridyl)-phenyl]benzene (TmPyPB), 4,4'-bis(4,6-diphenyl-1,3,5-triazinyl)biphenyl (BTB), 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi), 3-(biphenyl-4-yl)-5-(4-tert-butylphenyl)-4-phenyl-4H-1,2,4-triazole (TAZ), 2-(naphthyl-2-yl)-4,7-(diphenyl)-1,10-o-phenanthroline (HNBphen), 8-hydroxyquinoline-lithium, etc. (LiQ), but are not limited to these.

[0139] The electron injection material described in this invention is preferably a material that can improve the efficiency of electron injection from the cathode into the electron transport layer and the light-emitting layer, and has excellent electron injection effect. Specific examples may include: alkali metal salts (such as LiF, CsF), alkaline earth metal salts (such as MgF2), metal oxides (such as Al2O3, MoO3), but are not limited thereto.

[0140] The cathode material described in this invention is preferably a low power function material that can improve the efficiency of electron injection from the cathode into the electron transport layer and the light-emitting layer. Specific examples may include: metals such as aluminum, magnesium, silver, indium, tin, titanium, and their alloys; multilayer metal materials such as LiF / Al, Mg / Ag, Li / Al, LiO2 / Al, BaF2 / Al, etc., but are not limited thereto.

[0141] The capping material described in this invention is preferably a material that can improve the light extraction efficiency of the device. Specific examples may include, but are not limited to, arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, etc.

[0142] The present invention does not impose any special restrictions on the thickness of each organic layer of the organic electroluminescent device; thicknesses commonly used in the field can be adopted.

[0143] 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 it is not limited to these methods.

[0144] The organic light-emitting device described in this invention can be widely used in panel displays, lighting sources, flexible OLEDs, electronic paper, signs, signal lights, organic solar cells, organic photosensitive materials, or organic thin-film transistors.

[0145] There are no particular limitations on the preparation method of the heterocyclic compounds shown in this invention, and they can be prepared using methods well known to those skilled in the art. This invention provides a method for preparing the heterocyclic compounds described herein, but the preparation method of this invention is not limited thereto.

[0146] Method 1:

[0147]

[0148] Method 2:

[0149]

[0150] The X a X b X c X d X e It is independently selected from any one of I, Br, and Cl.

[0151] Description of raw materials, reagents, and characterization equipment:

[0152] The present invention does not impose any particular restrictions on the source of raw materials and reagents used in the following embodiments, which can be commercially available products or prepared using preparation methods well known to those skilled in the art.

[0153] Mass spectrometry was performed using a Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer from the UK.

[0154] Elemental analysis was performed using the Vario EL cube organic elemental analyzer from Elementar GmbH, Germany.

[0155] Synthesis Example 1: Preparation of raw material b-61:

[0156]

[0157] Preparation of intermediate g-61:

[0158] f-61 (19.41 g, 80.00 mmol), B2Pin2 (22.85 g, 90.00 mmol), K2CO3 (24.88 g, 180.00 mmol), Pd(PPh3)4 (1.04 g, 0.90 mmol), and DMF (400 mL) were added to a reaction flask. The reaction system was purged with nitrogen and stirred under reflux for 4.5 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 mixture was allowed to stand and separated. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The obtained solid was recrystallized from ethyl acetate and dried to give intermediate g-61 (22.46 g, yield 84%); HPLC purity ≥ 99.81%.

[0159] Preparation of raw material b-61:

[0160] G-61 (16.71 g, 50.00 mmol), h-61 (10.82 g, 50.00 mmol), K2CO3 (13.82 g, 100.00 mmol), Pd(PPh3)4 (0.69 g, 0.60 mmol), and 250 mL of a toluene / ethanol / water (2:1:1) mixed solvent were added to a reaction flask. The reaction system was purged with nitrogen and stirred under reflux for 6 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 layers were allowed to stand and separated. The organic layer was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The filtrate was recrystallized from ethyl acetate and dried to obtain the starting material b-61 (14.09 g, yield 82%); HPLC purity ≥ 98.86%.

[0161] By substituting the raw materials accordingly, and following the preparation method of raw material b-61 in Synthesis Example 1, raw material b can be prepared. The raw materials are shown in the table below:

[0162]

[0163]

[0164] Synthesis Example 2: Preparation of Compound 32

[0165]

[0166] a-32 (11.67 g, 25.00 mmol), f-61 (8.49 g, 35.00 mmol), copper powder (2.22 g, 35.00 mmol), 18-crown ether-6 (0.66 g, 2.50 mmol), K2CO3 (4.84 g, 35.00 mmol), and DMF (120 ml) were added to a reaction flask. The reaction system was purged with nitrogen and 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 32 (11.77 g, 70% yield). HPLC analysis showed that the solid purity was ≥99.98%. Mass spectrometry m / z: 672.2790 (theoretical value: 672.2777). Theoretical elemental content (%) C 48 H 36 N2O2: C, 85.69; H, 5.39; N, 4.16. Measured elemental content (%): C, 85.72; H, 5.41; N, 4.15.

[0167] Synthesis Example 3: Preparation of Compound 37

[0168]

[0169] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-37 and f-213 to obtain compound 37 (13.24 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 778.2611 (theoretical value: 778.2620). Theoretical elemental content (%) C 57 H 34 N2O2: C, 87.90; H, 4.40; N, 3.60. Measured elemental content (%): C, 87.86; H, 4.42; N, 3.57.

[0170] Synthesis Example 4: Preparation of Compound 45

[0171]

[0172] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-45 and f-213 to obtain compound 45 (12.78 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 740.2475 (theoretical value: 740.2464). Theoretical elemental content (%) C 54 H32 N2O2: C, 87.55; H, 4.35; N, 3.78. Measured elemental content (%): C, 87.56; H, 4.33; N, 3.81.

[0173] Synthesis Example 5: Preparation of Compound 61

[0174]

[0175] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-61 and b-61 to obtain compound 61 (11.37 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 640.1911 (theoretical value: 640.1899). Theoretical elemental content (%) C 44 H 24 N4O2: C, 82.49; H, 3.78; N, 8.74. Measured elemental content (%): C, 82.51; H, 3.81; N, 8.72.

[0176] Synthesis Example 6: Preparation of Compound 75

[0177]

[0178] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-75 and b-75 to obtain compound 75 (11.06 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 614.1978 (theoretical value: 614.1994). Theoretical elemental content (%) C 44 H 26 N2O2: C, 85.97; H, 4.26; N, 4.56. Measured elemental content (%): C, 86.01; H, 4.29; N, 4.51.

[0179] Synthesis Example 7: Preparation of Compound 78

[0180]

[0181] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-78 and b-78 to obtain compound 78 (13.90 g), with an HPLC purity ≥ 99.93%. Mass spectrometry m / z: 829.2715 (theoretical value: 829.2729). Theoretical elemental content (%) C 60 H 35 N3O2: C, 86.83; H, 4.25; N, 5.06. Measured elemental content (%): C, 86.85; H, 4.22; N, 5.10.

[0182] Synthesis Example 8: Preparation of Compound 81

[0183]

[0184] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-103 and f-308 to obtain compound 103 (12.05 g), with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 688.2166 (theoretical value: 688.2151). Theoretical elemental content (%) C 50 H 28 N2O2: C, 87.19; H, 4.10; N, 4.07. Measured elemental content (%): C, 87.22; H, 4.13; N, 4.03.

[0185] Synthesis Example 9: Preparation of Compound 120

[0186]

[0187] Preparation of A-120:

[0188] C-120 (33.98 g, 135.00 mmol), F-120 (50.24 g, 175.00 mmol), copper powder (11.12 g, 175.00 mmol), 18-crown ether-6 (3.57 g, 13.50 mmol), K₂CO₃ (24.19 g, 175.00 mmol), and DMF (600 mL) were added to a reaction flask. The reaction system was purged with nitrogen and stirred under reflux for 12 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 A-120 (49.45 g, 80% yield). The purity of the solid was determined by HPLC to be ≥99.81%.

[0189] Preparation of B-120:

[0190] A-120 (45.79 g, 100.00 mmol), B2Pin2 (27.93 g, 110.00 mmol), Pd(dppf)Cl2 (0.80 g, 1.10 mmol), KOAc (29.44 g, 300.00 mmol), and DMF (400 ml) were added to a reaction flask. The reaction system was purged with nitrogen and stirred under reflux for 7 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with ethyl acetate. 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 (10:3) and dried to obtain B-120 (45.05 g, 82% yield). The purity of the solid was determined by HPLC to be ≥99.83%.

[0191] Preparation of C-120:

[0192] B-120 (41.21 g, 75.00 mmol), d-120 (18.18 g, 90.00 mmol), Pd(PPh3)4 (0.92 g, 0.80 mmol), K2CO3 (20.73 g, 150.00 mmol), THF (400 ml), and water (200 ml) were added to a reaction flask. The reaction system was purged with nitrogen and 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 ethyl acetate. 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 C-120 (31.04 g, 76% yield). The purity of the solid was determined by HPLC to be ≥99.86%.

[0193] Preparation of D-120:

[0194] C-120 (27.23 g, 50.00 mmol), triphenylphosphine (32.79 g, 125.00 mmol), and o-dichlorobenzene (200 mL) were added to a reaction flask. The reaction system was purged with nitrogen and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with ethyl acetate. 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 (20:1) and dried to obtain D-120 (18.97 g, 74% yield). The purity of the solid was determined by HPLC to be ≥99.87%.

[0195] Preparation of compound 120:

[0196] D-120 (12.81 g, 25.00 mmol), e-120 (8.01 g, 35.00 mmol), copper powder (2.22 g, 35.00 mmol), 18-crown ether-6 (0.66 g, 2.50 mmol), K₂CO₃ (4.84 g, 35.00 mmol), and DMF (120 ml) were added to a reaction flask. The reaction system was purged with nitrogen and 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 120 (12.16 g, yield 69%). HPLC analysis showed that the solid purity was ≥99.98%. Mass spectrometry m / z: 704.2451 (theoretical value: 704.2464). Theoretical elemental content (%) C 51 H 32N2O2: C, 86.91; H, 4.58; N, 3.97. Measured elemental content (%): C, 86.95; H, 4.61; N, 3.94.

[0197] Synthesis Example 10: Preparation of Compound 129

[0198]

[0199] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-129 and b-129 to obtain compound 129 (11.70 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 668.2419 (theoretical value: 668.2402). Theoretical elemental content (%) C 48 H 24 D4N2O2: C, 86.20; H, 4.82; N, 4.19. Measured elemental content (%): C, 86.15; H, 4.86; N, 4.22.

[0200] Synthetic Example 11: Preparation of Compound 145

[0201]

[0202] Following the preparation method of Synthesis Example 2, a-32 was replaced with an equimolar amount of a-145 to obtain compound 145 (10.69 g), with an HPLC purity ≥ 99.99%. Mass spectrometry m / z: 593.2166 (theoretical value: 593.2152). Theoretical elemental content (%) C 42 H 19 D5N2O2: C, 84.97; H, 4.92; N, 4.72. Measured elemental content (%): C, 84.96; H, 4.89; N, 4.73.

[0203] Synthesis Example 12: Preparation of Compound 150

[0204]

[0205] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-150 and f-213 to obtain compound 150 (11.96 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 673.2725 (theoretical value: 673.2716). Theoretical elemental content (%) C 48 H 19 D9N2O2: C, 85.56; H, 5.53; N, 4.16. Measured elemental content (%): C, 85.58; H, 5.56; N, 4.14.

[0206] Synthetic Example 13: Preparation of Compound 152

[0207]

[0208] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-152 and f-213 to obtain compound 152 (11.80 g), with an HPLC purity ≥ 99.98%. Mass spectrometry m / z: 664.2168 (theoretical value: 664.2151). Theoretical elemental content (%) C 48 H 28 N2O2: C, 86.73; H, 4.25; N, 4.21. Measured elemental content (%): C, 86.74; H, 4.27; N, 4.23.

[0209] Synthesis Example 14: Preparation of Compound 169

[0210]

[0211] Following the preparation method of Synthesis Example 2, a-32 was replaced with an equimolar amount of a-169 to obtain compound 169 (12.33 g), with an HPLC purity ≥ 99.98%. Mass spectrometry m / z: 714.2291 (theoretical value: 714.2307). Theoretical elemental content (%) C 52 H 30 N2O2: C, 87.37; H, 4.23; N, 3.92. Measured elemental content (%): C, 87.40; H, 4.25; N, 3.89.

[0212] Synthesis Example 15: Preparation of Compound 189

[0213]

[0214] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-189 and f-213 to obtain compound 189 (13.17 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 774.2267 (theoretical value: 774.2279). Theoretical elemental content (%) C 54 H 26 D4N2O2S: C, 83.70; H, 4.42; N, 3.62. Measured elemental content (%): C, 83.67; H, 4.46; N, 3.64.

[0215] Synthetic Example 16: Preparation of Compound 190

[0216]

[0217] Following the preparation method of Synthesis Example 9, a-32 and f-61 were replaced with equimolar amounts of a-190 and b-78 to obtain compound 190 (11.80 g), with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 664.2166 (theoretical value: 664.2151). Theoretical elemental content (%) C 48 H 28 N2O2: C, 86.73; H, 4.25; N, 4.21. Measured elemental content (%): C, 86.75; H, 4.26; N, 4.22.

[0218] Synthetic Example 17: Preparation of Compound 197

[0219]

[0220] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-197 and b-197 to obtain compound 197 (11.63 g), with an HPLC purity ≥ 99.8%. Mass spectrometry m / z: 664.2164 (theoretical value: 664.2151). Theoretical elemental content (%) C 48 H 28 N2O2: C, 86.73; H, 4.25; N, 4.21. Measured elemental content (%): C, 86.74; H, 4.27; N, 4.23.

[0221] Synthesis Example 18: Preparation of Compound 213

[0222]

[0223] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-213 and b-213 to obtain compound 213 (13.35 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 796.3082 (theoretical value: 796.3090). Theoretical elemental content (%) C 58 H 40 N2O2: C, 87.41; H, 5.06; N, 3.52. Measured elemental content (%): C, 87.36; H, 5.10; N, 3.55.

[0224] Synthesis Example 19: Preparation of Compound 219

[0225]

[0226] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-197 and b-219 to obtain compound 219 (12.78 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 740.2452 (theoretical value: 740.2464). Theoretical elemental content (%) C 54 H 32 N2O2: C, 87.55; H, 4.35; N, 3.78. Measured elemental content (%): C, 87.58; H, 4.33; N, 3.81.

[0227] Synthesis Example 20: Preparation of Compound 269

[0228]

[0229] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-269 and f-75 to obtain compound 269 (11.83 g), with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 685.2393 (theoretical value: 685.2383). Theoretical elemental content (%) C 48 H 19 D7N2O3: C, 84.07; H, 4.85; N, 4.08. Measured elemental content (%): C, 84.11; H, 4.82; N, 4.12.

[0230] Synthesis Example 21: Preparation of Compound 279

[0231]

[0232] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-197 and b-279 to obtain compound 279 (11.80 g), with an HPLC purity ≥ 99.99%. Mass spectrometry m / z: 664.2137 (theoretical value: 664.2151). Theoretical elemental content (%) C 48 H 28 N2O2: C, 86.73; H, 4.25; N, 4.21. Measured elemental content (%): C, 86.75; H, 4.27; N, 4.20.

[0233] Synthesis Example 22: Preparation of Compound 285

[0234]

[0235] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-285 and b-285 to obtain compound 285 (13.28 g), with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 780.2762 (theoretical value: 780.2777). Theoretical elemental content (%) C 57 H 36 N2O2: C, 87.67; H, 4.65; N, 3.59. Measured elemental content (%): C, 87.66; H, 4.67; N, 3.62.

[0236] Synthesis Example 23: Preparation of Compound 286

[0237]

[0238] a-286 (7.96 g, 25.00 mmol), f-213 (16.99 g, 70.00 mmol), copper powder (4.45 g, 70.00 mmol), 18-crown ether-6 (0.66 g, 2.50 mmol), K2CO3 (9.67 g, 70.00 mmol), and DMF (240 ml) were added to a reaction flask. The reaction system was purged with nitrogen and stirred under reflux for 24 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 286 (12.61 g, yield 69%). HPLC analysis showed that the solid purity was ≥99.97%. Mass spectrometry m / z: 730.2657 (theoretical value: 730.2646). Theoretical elemental content (%) C 50 H 14 D 12 N₂O₄: C, 82.17; H, 5.24; N, 3.83. Measured elemental content (%): C, 82.20; H, 5.22; N, 3.86.

[0239] Synthesis Example 24: Preparation of Compound 291

[0240]

[0241] Following the preparation method of Synthesis Example 2, a-32 was replaced with an equimolar amount of a-291 to obtain compound 291 (10.60 g), with an HPLC purity ≥ 99.98%. Mass spectrometry m / z: 588.1828 (theoretical value: 588.1838). Theoretical elemental content (%) C 42 H 24 N2O2: C, 85.70; H, 4.11; N, 4.76. Measured elemental content (%): C, 85.74; H, 4.14; N, 4.74.

[0242] Synthesis Example 25: Preparation of Compound 308

[0243]

[0244] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-308 and b-308 to obtain compound 308 (12.44 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 720.2789 (theoretical value: 720.2777). Theoretical elemental content (%) C 52 H 36 N2O2: C, 86.64; H, 5.03; N, 3.89. Measured elemental content (%): C, 86.66; H, 5.04; N, 3.91.

[0245] Synthesis Example 26: Preparation of Compound 315

[0246]

[0247] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-315 and f-75 to obtain compound 315 (11.88 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 678.1925 (theoretical value: 678.1943). Theoretical elemental content (%) C 48 H 26 N2O3: C, 84.94; H, 3.86; N, 4.13. Measured elemental content (%): C, 84.91; H, 3.90; N, 4.16.

[0248] Synthesis Example 27: Preparation of Compound 332

[0249]

[0250] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-332 and b-332 to obtain compound 332 (12.23 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 698.1844 (theoretical value: 698.1828). Theoretical elemental content (%) C 48 H 27 N₂OS: C, 82.50; H, 3.89; N, 4.01. Measured elemental content (%): C, 82.55; H, 3.91; N, 3.98.

[0251] Synthesis Example 28: Preparation of Compound 339

[0252]

[0253] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-339 and b-339 to obtain compound 339 (11.21 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 631.1730 (theoretical value: 631.1718). Theoretical elemental content (%) C 43 H 25 N3OS: C, 81.75; H, 3.99; N, 6.65. Measured elemental content (%): C, 81.79; H, 4.02; N, 6.63.

[0254] Synthesis Example 29: Preparation of Compound 345

[0255]

[0256] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-345 and b-332 to obtain compound 345 (12.19 g), with an HPLC purity ≥ 99.98%. Mass spectrometry m / z: 706.2065 (theoretical value: 706.2079). Theoretical elemental content (%) C 50 H 30 N₂OS: C, 84.96; H, 4.28; N, 3.96. Measured elemental content (%): C, 84.97; H, 4.30; N, 3.95.

[0257] Synthesis Example 30: Preparation of Compound 348

[0258]

[0259] Following the preparation method of Synthesis Example 23, a-286 and f-213 were replaced with equimolar amounts of a-348 and f-348 to obtain compound 348 (14.16 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 844.2085 (theoretical value: 844.2070). Theoretical elemental content (%) C 52 H 40 N2O2S2Si2: C, 73.90; H, 4.77; N, 3.31. Measured elemental content (%): C, 73.88; H, 4.76; N, 3.30.

[0260] Synthesis Example 31: Preparation of Compound 349

[0261]

[0262] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-349 and f-349 to obtain compound 349 (11.45 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 644.1939 (theoretical value: 644.1922). Theoretical elemental content (%) C 45 H 28 N₂OS: C, 83.82; H, 4.38; N, 4.34. Measured elemental content (%): C, 83.85; H, 4.40; N, 4.32.

[0263] Synthesis Example 32: Preparation of Compound 351

[0264]

[0265] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-351 and b-332 to obtain compound 351 (11.23 g), with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 632.1658 (theoretical value: 632.1671). Theoretical elemental content (%) C 42 H 24 N4OS: C, 79.73; H, 3.82; N, 8.85. Measured elemental content (%): C, 79.77; H, 3.85; N, 8.81.

[0266] Synthesis Example 33: Preparation of Compound 375

[0267]

[0268] Following the preparation method of Synthesis Example 9, c-123, f-123, and e-123 were replaced with equimolar amounts of c-375, f-348, and e-375 to obtain compound 375 (12.25 g), with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 720.1854 (theoretical value: 720.1871). Theoretical elemental content (%) C 50 H 28 N2O2S: C, 83.31; H, 3.92; N, 3.89. Measured elemental content (%): C, 83.29; H, 3.95; N, 3.86.

[0269] Synthesis Example 34: Preparation of Compound 385

[0270]

[0271] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-385 and f-385 to obtain compound 385 (12.16 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 704.1934 (theoretical value: 704.1922). Theoretical elemental content (%) C 50 H 28 N₂OS: C, 85.20; H, 4.00; N, 3.97. Measured elemental content (%): C, 85.17; H, 4.02; N, 4.01.

[0272] Synthesis Example 35: Preparation of Compound 465

[0273]

[0274] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-465 and b-339 to obtain compound 465 (13.34 g), with an HPLC purity ≥ 99.98%. Mass spectrometry m / z: 796.2534 (theoretical value: 796.2548). Theoretical elemental content (%) C 57 H 36 N₂OS: C, 85.90; H, 4.55; N, 3.51. Measured elemental content (%): C, 85.93; H, 4.51; N, 3.56.

[0275] Synthesis Example 36: Preparation of Compound 482

[0276]

[0277] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-482 and f-482 to obtain compound 482 (10.90 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 605.1571 (theoretical value: 605.1562). Theoretical elemental content (%) C 41 H 23 N3OS: C, 81.30; H, 3.83; N, 6.94. Measured elemental content (%): C, 81.34; H, 3.85; N, 6.93.

[0278] Synthesis Example 37: Preparation of Compound 520

[0279]

[0280] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-520 and b-520 to obtain compound 520 (12.20 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 696.1681 (theoretical value: 696.1694). Theoretical elemental content (%) C 48 H 28 N2S2: C, 82.73; H, 4.05; N, 4.02. Measured elemental content (%): C, 82.75; H, 4.07; N, 4.03.

[0281] Synthesis Example 38: Preparation of Compound 589

[0282]

[0283] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-589 and b-589 to obtain compound 589 (12.44 g), with an HPLC purity ≥ 99.96%. Mass spectrometry m / z: 720.1709 (theoretical value: 720.1694). Theoretical elemental content (%) C 50 H 28 N2S2: C, 83.30; H, 3.92; N, 3.89. Measured elemental content (%): C, 83.31; H, 3.96; N, 3.87.

[0284] Synthesis Example 39: Preparation of Compound 612

[0285]

[0286] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-197 and b-612 to obtain compound 612 (13.38 g), with an HPLC purity ≥ 99.94%. Mass spectrometry m / z: 786.1818 (theoretical value: 786.1800). Theoretical elemental content (%) C 54 H 30 N₂OS₂: C, 82.42; H, 3.84; N, 3.56. Measured elemental content (%): C, 82.46; H, 3.87; N, 3.54.

[0287] Synthesis Example 40: Preparation of Compound 615

[0288]

[0289] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-197 and b-615 to obtain compound 615 (11.59 g), with an HPLC purity ≥ 99.92%. Mass spectrometry m / z: 671.1476 (theoretical value: 671.1490). Theoretical elemental content (%) C 45 H 25 N3S2: C, 80.45; H, 3.75; N, 6.25. Measured elemental content (%): C, 80.47; H, 3.79; N, 6.22.

[0290] Synthesis Example 41: Preparation of Compound 635

[0291]

[0292] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-635 and b-635 to obtain compound 635 (12.20 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 696.1681 (theoretical value: 696.1694). Theoretical elemental content (%) C 48 H 28 N2S2: C, 82.73; H, 4.05; N, 4.02. Measured elemental content (%): C, 82.76; H, 4.09; N, 3.99.

[0293] Synthesis Example 42: Preparation of Compound 639

[0294]

[0295] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-639 and b-639 to obtain compound 639 (12.47 g), with an HPLC purity ≥ 99.95%. Mass spectrometry m / z: 722.1862 (theoretical value: 722.1850). Theoretical elemental content (%) C 50 H 30 N2S2: C, 83.07; H, 4.18; N, 3.88. Measured elemental content (%): C, 83.02; H, 4.22; N, 3.91.

[0296] Synthesis Example 43: Preparation of Compound 644

[0297]

[0298] Following the preparation method of Synthesis Example 2, a-32 and f-61 were replaced with equimolar amounts of a-644 and f-644 to obtain compound 644 (10.73 g), with an HPLC purity ≥ 99.97%. Mass spectrometry m / z: 604.1622 (theoretical value: 604.1609). Theoretical elemental content (%) C 42 H 24 N₂OS: C, 83.42; H, 4.00; N, 4.63. Measured elemental content (%): C, 83.43; H, 4.05; N, 4.59.

[0299] [Device Example 1]

[0300] First, the glass substrate coated with ITO / Ag / ITO was washed three times in distilled water and ultrasonically cleaned for 15 minutes. After the distilled water cleaning, it was ultrasonically cleaned in sequence with isopropanol, acetone and methanol solvents. Then it was dried on a hot plate heated to 120°C. After drying, it was transferred to a plasma cleaner and cleaned for 5 minutes before being transferred to a vapor deposition machine.

[0301] Then, HI-1 is deposited as a hole injection layer with a thickness of 12 nm on the cleaned ITO / Ag / ITO substrate. HT-1 is then deposited as a hole transport layer with a thickness of 55 nm on the hole injection layer. A mixture of compounds 32, H2-1, and GD-1 (mass ratio 49:49:2) of the present invention is then vacuum-deposited on the hole transport layer to form a light-emitting layer with a thickness of 40 nm. ET-1 and Liq (mass ratio 1:1) are then deposited on the light-emitting layer as an electron transport layer with a thickness of 36 nm. LiF is then deposited on the electron transport layer as an electron injection layer with a thickness of 1 nm. Mg:Ag (mass ratio 1:9) is then deposited on the electron injection layer as a cathode with a thickness of 15 nm. Finally, CP-1 is vacuum-deposited on the cathode as a capping layer with a thickness of 60 nm, thereby preparing an organic electroluminescent device 1 (the structural formulas of the functional layer materials in the organic electroluminescent device preparation process are as follows).

[0302]

[0303] [Device Examples 2-30]

[0304] In Example 1, the compound 32 of the present invention in the light-emitting layer was replaced with compounds 45, 61, 75, 103, 123, 129, 145, 150, 152, 169, 189, 197, 213, 219, 269, 279, 285, 286, 291, 308, 332, 345, 349, 385, 465, 520, 589, 612, and 635 of the present invention, respectively, while the other steps were the same, to prepare organic electroluminescent devices 2-30.

[0305] [Comparative Examples 1-2]

[0306] Replace compound 32 of the present invention in the light-emitting layer of Example 1 with R-1 and R-2 respectively, and follow the same steps to prepare comparative devices 1 and 2.

[0307] A combined IVL testing system was constructed using testing software, a computer, a Keithley K2400 digital source meter, and a PhotoResearch PR788 spectral scanning luminance meter to test the driving voltage and luminous efficiency of the organic electroluminescent devices. Lifetime testing was performed using a McScience M6000 OLED lifetime testing system. The testing environment was atmospheric, and the temperature was room temperature. The luminous characteristics test results of the organic electroluminescent devices obtained in Examples 1-30 of this invention and Comparative Examples 1-2 are shown in Table 1 below.

[0308] [Table 1] Test data on the luminescence characteristics of organic electroluminescent devices

[0309]

[0310]

[0311] Note: T97 refers to a current density of 10 mA / cm². 2 Under these conditions, the time it takes for the device's brightness to decay to 97%;

[0312] As can be seen from the results in Table 1, compared with Comparative Example 1 and Comparative Example 2, when the heterocyclic compound described in this invention is used as the host material of the light-emitting layer of the organic electroluminescent device, the device has higher luminous efficiency and longer lifespan.

[0313] [Device Example 31]

[0314] First, the glass substrate coated with ITO / Ag / ITO was washed three times in distilled water and ultrasonically cleaned for 15 minutes. After the distilled water cleaning, it was ultrasonically cleaned in sequence with isopropanol, acetone and methanol solvents. Then it was dried on a hot plate heated to 120°C. After drying, it was transferred to a plasma cleaner and cleaned for 5 minutes before being transferred to a vapor deposition machine.

[0315] HI-1 is deposited as a hole injection layer with a thickness of 15 nm on a cleaned ITO / Ag / ITO substrate. HT-1 is then deposited as a hole transport layer with a thickness of 60 nm on the hole injection layer. A mixture of compounds 32, H2-1, and RD-1 (mass ratio 48:48:4) of the present invention is then vacuum-deposited on the hole transport layer to form a light-emitting layer with a thickness of 35 nm. ET-1 and Liq (mass ratio 1:1) are then deposited on the light-emitting layer as an electron transport layer with a thickness of 35 nm. LiF is then deposited on the electron transport layer as an electron injection layer with a thickness of 1 nm. Mg:Ag (mass ratio 1:9) is then deposited on the electron injection layer as a cathode with a thickness of 13 nm. Finally, CP-1 is vacuum-deposited on the cathode as a capping layer with a thickness of 65 nm, thereby fabricating an organic electroluminescent device 33.

[0316] [Device Examples 32-60]

[0317] In Example 31, the compound 32 of the present invention in the light-emitting layer was replaced with compounds 37, 75, 78, 123, 129, 145, 150, 152, 169, 190, 197, 213, 219, 279, 285, 291, 308, 315, 339, 345, 348, 349, 351, 375, 465, 520, 589, 615, and 644 of the present invention, respectively, while the other steps were the same, to prepare organic electroluminescent devices 32-60.

[0318] [Comparative Examples 3-4]

[0319] Replace compound 32 of the present invention in the light-emitting layer of Example 31 with R-1 and R-2 respectively, and follow the same steps to prepare comparative devices 3-4.

[0320] The luminescence characteristics test results of the organic electroluminescent devices obtained in Device Examples 32-60 of the present invention and Comparative Device Examples 3-4 are shown in Table 2 below.

[0321] [Table 2] Test data on the luminescence characteristics of organic electroluminescent devices

[0322]

[0323]

[0324] As can be seen from the results in Table 2, compared with Comparative Examples 3 and 4, when the heterocyclic compound described in this invention is used as the host material of the light-emitting layer of the organic electroluminescent device, the device has higher luminous efficiency and longer lifespan.

[0325] It should be noted that the present invention has been specifically described with reference to specific embodiments. For those skilled in the art, various improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the present invention.

Claims

1. A heterocyclic compound, characterized in that, The heterocyclic compound is represented by the structure shown in Formula I-1 or Formula I-2: At least one of Ar1 and Ar2 is selected from any one of the following groups derived from formula II-1 or formula II-2: a1 is selected from 0, 1, 2, or 3; a2 is selected from 0, 1, 2, 3, 4, or 5; a3 is selected from 0, 1, 2, 3, 4, 5, 6, or 7; a4 is independently selected from 0, 1, 2, 3, or 4; a5 is selected from 0, 1, 2, 3, 4, 5, or 6; when there are two or more R2s, the two or more R2s are the same as or different from each other; The R2 is selected from hydrogen, deuterium, tritium, cyano, halogen, or substituted or unsubstituted groups of the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, or a combination thereof; When Ar1 or Ar2 is not of formula II-1 or II-2, it is selected from any one of the following groups: b1 is selected from 0, 1, 2, 3, 4 or 5; b2 is selected from 0, 1, 2, 3 or 4; b3 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; b4 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9; when there are two or more R3s, the two or more R3s are the same as or different from each other; The R3 is selected from hydrogen, deuterium, tritium, cyano, fluorine, or substituted or unsubstituted groups of the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, adamantane, norbornene, phenyl, or a combination thereof. The R d R e The group is independently selected from one or a combination of the following groups, whether substituted or unsubstituted: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, biphenyl, terphenyl, and naphthyl. The z is selected from C(R1) or N, and at most one of them is selected from N; the R1 is selected from hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C6 alkyl, trimethylsilyl, triethylsilyl, triisopropylsilyl, tritert-butylsilyl, dimethylethylsilyl, dimethylisopropylsilyl, dimethyltert-butylsilyl, substituted or unsubstituted phenyl, or a combination thereof; or two adjacent R1 are connected to form a substituted or unsubstituted benzene ring; The ring A is selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, or substituted or unsubstituted pyridyl. L1 and L2 are selected from single bonds or any one of the following groups: c1 is selected from 0, 1, 2, 3 or 4; c2 is selected from 0, 1, 2 or 3; when there are two or more R4s, the two or more R4s are the same as or different from each other; The R4 is selected from one or a combination thereof, either identically or differently, from hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1 to C6 alkyl groups; The R j R k Alkyl groups selected independently from substituted or unsubstituted C1-C6 groups; When Ar1 or Ar2 is not a group derived from formula II-1 or II-2, the L1 or L2 attached to it is not... ; The substituents represented by "substituted or unsubstituted" include the following groups: deuterium, tritium, cyano, fluorine, chlorine, bromine, iodine, methyl, ethyl, propyl, and butyl.

2. The heterocyclic compound according to claim 1, characterized in that, At least one of Ar1 and Ar2 is selected from any one of the following groups derived from formula II-1 or formula II-2: The R2 is selected from hydrogen, deuterium, and tritium, either the same or different.

3. The heterocyclic compound according to claim 1, characterized in that, When Ar1 or Ar2 is not of formula II-1 or II-2, it is selected from any one of the following groups: The R3 is selected, either identically or differently, from hydrogen, deuterium, tritium, or substituted or unsubstituted of the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, or a combination thereof.

4. The heterocyclic compound according to claim 1, characterized in that, L1 and L2 are selected from single bonds or any one of the following groups: The R4 is selected from one or a combination of hydrogen, deuterium, tritium, or different types of hydrogen.

5. The heterocyclic compound according to claim 1, characterized in that, The ring A is selected from any one of substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl groups.

6. A heterocyclic compound, characterized in that, The heterocyclic compound is selected from any one of the following compounds: 。 7. An organic electroluminescent device, characterized in that, The organic layer includes a light-emitting layer, which contains at least one of the heterocyclic compounds according to any one of claims 1 to 6.

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