Heterocyclic derivative and organic light emitting device thereof

Abstract

The application provides a heterocyclic derivative and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The application mainly solves the problems of low light-emitting efficiency and short service life of most organic light-emitting devices. The compound of the application contains a benzofuran / benzothiophene group. The introduction of the group into the double-carbazole main structure of the application is beneficial to the film formation of the molecule and improves the glass transition temperature of the compound. The compound of the application is applied to the cover layer material in the organic light-emitting device, can reduce the total reflection loss and waveguide loss in the OLED device, and effectively improves the light-emitting efficiency and service life of the device. The application can be widely applied to the fields of panel display, lighting source, organic solar cell, organic photoreceptor or organic thin film transistor.

Description

Technical Field

[0001] The present invention relates to the technical field of organic photoelectric materials, and in particular to a heterocyclic derivative and an organic light-emitting device thereof. Background Art

[0002] Organic Light-Emitting Diodes (OLEDs) are light-emitting devices that use organic solid-state semiconductors as their luminescent materials. They have broad application prospects due to their simple manufacturing process, low cost, low power consumption, high brightness, and wide operating temperature range. With the continuous development of display products, users are demanding higher and higher resolution, and the performance requirements of OLED devices are becoming increasingly higher.

[0003] At present, organic light-emitting devices are developing rapidly, and the organic optoelectronic materials therein have also become a research hotspot in this field. Organic light-emitting devices convert electrical energy into light by applying electricity to organic electroluminescent materials, and generally include an anode, a cathode, and an organic layer formed between the two electrodes or outside the two electrodes. The organic layer may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescence auxiliary layer, an electron blocking layer, a light-emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, a covering layer, and the like. In an organic light-emitting device, holes from the anode and electrons from the cathode are injected into the light-emitting layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. The organic light-emitting compound emits light by the energy transferred to the excited state and when the excited state returns to the ground state.

[0004] The optimization and performance improvement of OLED devices can be achieved by improving any layer in the device and the combination of different layers of materials. Among them, the covering layer in the OLED device is specifically a layer of organic or inorganic transparent material with a high refractive index. The covering layer material can effectively improve the light coupling efficiency of the device, improve the light output mode, and enable the light originally confined inside the device to be emitted from the device, showing a higher light extraction efficiency. However, the current covering layer materials still have limited improvement in the light extraction efficiency of OLED devices, and the luminous performance of OLED devices cannot meet user needs. In addition, the covering layer material absorbs less ultraviolet light from the external environment, resulting in a shorter lifespan of the OLED device, affecting the user experience. Therefore, it is an urgent problem to develop a new covering layer material to improve the film forming properties of the material and the thermal stability of the film, and to improve the luminous efficiency and service life of the device. Summary of the Invention

[0005] The purpose of the present invention is to provide a heterocyclic derivative and an organic light-emitting device thereof based on the existing technology and with the goal of industrialization. The organic light-emitting device prepared by using the heterocyclic derivative is applied to the cover layer to develop an organic light-emitting device with high efficiency and long life. The general molecular structure is shown in Formula I:

[0006]

[0007] wherein the u are the same or different and are selected from CR or N;

[0008] The R groups are the same or different, and at least one R group is selected from the group of formula a below, and the remaining R groups are each independently selected from one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl; or two adjacent R groups may be bonded to form a ring;

[0009]

[0010] Said X is selected from O or S;

[0011] The L a One selected from a single bond, a substituted or unsubstituted C6-C25 arylene group, and a substituted or unsubstituted C2-C20 heteroarylene group;

[0012] The R a are the same or different and are independently selected from one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl; or two adjacent R a Groups can bond together to form rings;

[0013] Said a is selected from 0, 1, 2, 3, 4 or 5;

[0014] The z are the same or different and are selected from CR b or N;

[0015] The R b are the same or different, and are each independently selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl;

[0016] The L is selected from any one of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted quinolylene, substituted or unsubstituted isoquinolylene, substituted or unsubstituted quinazolinylene, substituted or unsubstituted quinoxalinylene, substituted or unsubstituted phthalazinylene, substituted or unsubstituted naphthyridinylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, or combinations thereof, and the total number of carbon atoms in the L is C6 to C40.

[0017] The present invention also provides an organic light-emitting 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, and the organic layer contains any one or a combination of at least two of the heterocyclic derivatives described in the present invention.

[0018] Beneficial effects of the present invention:

[0019] The present invention provides a heterocyclic derivative and an organic light-emitting device thereof. The compound of the present invention contains a benzofuran / benzothiophene group. The introduction of such a group on the basis of the main structure of the biscarbazole of the present invention is conducive to molecular film formation and improves the glass transition temperature of the compound. The compound of the present invention is applied to the covering layer material in the organic light-emitting device, which can reduce the total reflection loss and waveguide loss in the OLED device, and effectively improve the luminous efficiency and service life of the device. DETAILED DESCRIPTION

[0020] The following is a clear and complete description of the technical solutions of the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without making any creative efforts shall fall within the scope of protection of the present invention.

[0021] In the compounds of the present invention, any atom not designated as a specific isotope is included as any stable isotope of that atom, and includes the atom at both its natural isotopic abundance and unnatural abundance.

[0022] As used herein, the terms "H" and "hydrogen" refer to hydrogen atoms in a chemical structure containing no more than the natural abundance of deuterium or tritium atoms, e.g., no more than 0.0156 atomic % of deuterium. "D" and "deuterium" refer to deuterium with an abundance above the natural abundance, e.g., any value exceeding 0.1 atomic %, exceeding 1 atomic %, or exceeding 10 atomic %, e.g., approximately 95 atomic % of the deuterium content. As used herein, "H" or "hydrogen" is used to represent hydrogen atoms not shown.

[0023] In this specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example, Can represent And so on.

[0024] The halogen mentioned in the present invention refers to fluorine, chlorine, bromine and iodine.

[0025] The alkyl group described in the present invention refers to a hydrocarbon group formed by missing one hydrogen atom from an alkane molecule. It can be a straight-chain alkyl group or a branched-chain alkyl group, preferably having 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight-chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, etc., but is not limited thereto; the branched-chain alkyl group includes isopropyl, isobutyl, sec-butyl, tert-butyl, isomeric groups of n-pentyl, isomeric groups of n-hexyl, isomeric groups of n-heptyl, isomeric groups of n-octyl, isomeric groups of n-nonyl, isomeric groups of n-decyl, etc., but is not limited thereto. The above-mentioned alkyl group is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.

[0026] The chain alkyl group having more than three carbon atoms described in the present invention includes its isomers. For example, propyl includes n-propyl and isopropyl, butyl includes n-butyl, sec-butyl, isobutyl, and tert-butyl, and so on.

[0027] The cycloalkyl group herein refers to a hydrocarbon group formed by removing one hydrogen atom from a cycloalkane molecule, preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, bornyl, and norbornyl. Preferred cycloalkyl groups include cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, and norbornyl.

[0028] The aryl group described in the present invention refers to a monovalent group remaining after removing a hydrogen atom from the aromatic carbon nucleus of an aromatic compound molecule. It can be a monocyclic aryl group, a polycyclic aryl group, or a condensed aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic aryl group refers to an aryl group with only one aromatic ring in the molecule, such as, but not limited to, phenyl; the polycyclic aryl group refers to an aryl group containing two or more independent aromatic rings in the molecule, such as, but not limited to, biphenyl and terphenyl; the condensed aryl group refers to an aryl group containing two or more aromatic rings in the molecule that are fused together by sharing two adjacent carbon atoms, such as, but not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, etc. The aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthracenyl group (preferably a 2-anthryl group), a phenanthrenyl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylene group, or a spirobifluorenyl group.

[0029] The heteroaryl group described in the present invention refers to a general term for a group in which one or more aromatic carbon atoms in an aromatic group are replaced by a heteroatom, wherein the heteroatom includes but is not limited to oxygen, sulfur, nitrogen or phosphorus atoms, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms. The attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a condensed-ring heteroaryl group. The monocyclic heteroaryl groups include, but are not limited to, pyridyl, pyrimidinyl, triazine, furyl, thienyl, pyrrolyl, imidazolyl, etc.; the polycyclic heteroaryl groups include, but are not limited to, bipyridyl, bipyrimidinyl, phenylpyridyl, etc.; the fused-ring heteroaryl groups include, but are not limited to, quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothienyl, benzodibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9,10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl, etc., but are not limited to. The above-mentioned heteroaryl group is preferably pyridyl, pyrimidinyl, thienyl, furyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, benzodibenzothienyl, benzodibenzofuranyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, or phenoxathiyl.

[0030] The arylene group described in the present invention refers to the general term for a divalent group remaining after removing two hydrogen atoms from the aromatic carbon nucleus of an aromatic compound molecule. It can be a monocyclic arylene group, a polycyclic arylene group, or a condensed-ring arylene group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 carbon atoms. The monocyclic arylene group includes, but is not limited to, phenylene groups; the polycyclic arylene group includes, but is not limited to, biphenylene groups and terphenylene groups; the condensed-ring arylene group includes, but is not limited to, naphthylene groups, anthrylene groups, phenanthrenyl groups, fluorenyl groups, pyrenyl groups, triphenylene groups, fluoranthenyl groups, and phenylenefluorenyl groups. The above-mentioned arylene groups are preferably phenylene groups, biphenylene groups, terphenylene groups, naphthylene groups, fluorenyl groups, and phenylenefluorenyl groups.

[0031] The heteroarylene group of the present invention is a general term for a group in which one or more aromatic carbon atoms in an arylene group are replaced by a heteroatom, including but not limited to oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably, the group has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms. The attachment point of the heteroarylene group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom. The heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a condensed-ring heteroarylene group. The monocyclic heteroarylene group includes, but is not limited to, pyridylene, pyrimidylene, triazinylene, furylene, thienylene, etc.; the polycyclic heteroarylene group includes, but is not limited to, bipyridylene, bipyrimidylene, phenylpyridylene, etc.; the condensed-ring heteroarylene group includes, but is not limited to, quinolylene, isoquinolylene, indolylene, benzothiophenylene, benzofuranylene, benzoxazolylene, benzimidazolylene, benzothiazolylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothiophenylene, benzodibenzothiophenylene, carbazolylene, benzocarbazolylene, acridinylene, 9,10-dihydroacridinylene, phenoxazinylene, phenothiazinylene, phenoxathiylene, etc., but is not limited to. The above-mentioned heteroaryl group is preferably a pyridylene group, a pyrimidylene group, a thienylene group, a furylene group, a benzothienylene group, a benzofurylene group, a benzoxazolylene group, a benzimidazolylene group, a benzothiazolylene group, a dibenzofurylene group, a dibenzothienylene group, a benzodibenzothienylene group, a benzodibenzofurylene group, a carbazolylene group, an acridinylene group, a phenoxazinylene group, a phenothiazinylene group, or a phenoxathiylene group.

[0032] The “unsubstituted…” mentioned in the present invention, such as unsubstituted alkyl, unsubstituted cycloalkyl, unsubstituted aryl, unsubstituted heteroaryl, unsubstituted arylene, unsubstituted heteroarylene, etc., means that the “hydrogen” (H) in the group is not replaced by other groups including deuterium.

[0033] The "substituted..." in the present invention, such as substituted alkyl, substituted cycloalkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, etc., refers to being monosubstituted or polysubstituted by groups independently selected from, but not limited to, deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amino, etc., preferably selected from, deuterium, halogen, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, The cyclohexyl group, adamantyl group, norbornyl group, bornyl group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, triphenylenyl group, peryl group, pyrenyl group, benzyl group, tolyl group, fluorenyl group, 9,9-dimethylfluorenyl group, 9,9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, diphenylamino group, dimethylamino group, carbazolyl group, 9-phenylcarbazolyl group, acridinyl group, furanyl group, thienyl group, benzofuranyl group, benzothienyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, dibenzofuranyl group, dibenzothienyl group, phenothiazinyl group, phenoxazinyl group, and indolyl group may be mono- or poly-substituted. Furthermore, the above substituents may be substituted by one or more substituents described for deuterium, halogen atoms, cyano groups, alkyl groups, cycloalkyl groups, and aryl groups.

[0034] The term "bonded to form a ring structure" as used herein refers to two groups being connected to each other by a chemical bond and optionally aromatized. For example:

[0035]

[0036] In the present invention, the ring formed by connection can be a five-membered ring, a six-membered ring or a condensed ring, such as benzene, naphthalene, fluorene, cyclopentene, cyclohexene, cyclopentane, cyclohexane, cyclohexanedone, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.

[0037] Preferably, two adjacent R a The groups may be bonded together to form a ring.

[0038] More preferably, two adjacent R a The groups may be bonded together to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, a substituted or unsubstituted triazine ring, a substituted or unsubstituted pyrazine ring, or a substituted or unsubstituted pyridazine ring;

[0039] More preferably, two adjacent R a The groups may be bonded to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring.

[0040] Most preferably, two adjacent R aThe groups may be bonded together to form a substituted or unsubstituted benzene ring.

[0041] The present invention provides a heterocyclic derivative, the general molecular structure of which is shown in Formula I:

[0042]

[0043] wherein the u are the same or different and are selected from CR or N;

[0044] The R groups are the same or different, and at least one R group is selected from the group of formula a below, and the remaining R groups are each independently selected from one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl; or two adjacent R groups may be bonded to form a ring;

[0045]

[0046] Said X is selected from O or S;

[0047] The L a One selected from a single bond, a substituted or unsubstituted C6-C25 arylene group, and a substituted or unsubstituted C2-C20 heteroarylene group;

[0048] The R a are the same or different and are independently selected from one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl; or two adjacent R a Groups can bond together to form rings;

[0049] Said a is selected from 0, 1, 2, 3, 4 or 5;

[0050] The z are the same or different and are selected from CR b or N;

[0051] The R b are the same or different, and are each independently selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, and substituted or unsubstituted C2-C20 heteroaryl;

[0052] The L is selected from any one of substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthrylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridylene, substituted or unsubstituted pyrimidylene, substituted or unsubstituted pyridazinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted quinolylene, substituted or unsubstituted isoquinolylene, substituted or unsubstituted quinazolinylene, substituted or unsubstituted quinoxalinylene, substituted or unsubstituted phthalazinylene, substituted or unsubstituted naphthyridinylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, or combinations thereof, and the total number of carbon atoms in the L is C6 to C40.

[0053] Preferably, the group of formula a is selected from one of the following groups:

[0054]

[0055] Said X is selected from O or S;

[0056] The L a Selected from a single bond or one of the following groups:

[0057]

[0058] The R p Any one selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0059] The V's are the same or different, each independently selected from CR0 or N, and at least one V is selected from N;

[0060] R0 is selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, or two adjacent R0 are connected to form a substituted or unsubstituted benzene ring;

[0061] Said p1 is selected from 0, 1, 2, 3 or 4;

[0062] The R athe same or different selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl, terphenyl, naphthyl, phenyl-naphthyl, naphthyl-phenyl, pyridyl, pyrimidinyl, triazinyl one or more; wherein the substituent in said "substituted or unsubstituted" is selected from deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl one or more, in the case of being substituted by multiple substituents, the multiple substituents are the same or different; or optionally two adjacent R a The groups may be bonded together to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, or a substituted or unsubstituted pyrazine ring;

[0063] The a is selected from 0, 1, 2, 3, 4 or 5.

[0064] More preferably, the L a Selected from a single bond or one of the following groups:

[0065]

[0066] Preferably, the group of formula a One selected from the following groups:

[0067]

[0068]

[0069]

[0070]

[0071] The X is selected from O or S.

[0072] Preferably, at least one R is selected from a group of formula a, and the remaining R are the same or different and are independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and one of the following groups, or a combination of the above groups,

[0073]

[0074] The R mThe same or different R is selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, or two adjacent R m The groups may be bonded together to form a substituted or unsubstituted benzene ring or a substituted or unsubstituted naphthalene ring;

[0075] The T is the same or different and is selected from CR t or N, and at least one T is selected from N;

[0076] The R t any one selected from the group consisting of hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, and substituted or unsubstituted pyridazinyl, which are the same or different; said m1 is selected from 0, 1, 2, 3, 4 or 5; said m2 is selected from 0, 1, 2, 3 or 4.

[0077] Preferably, at least one R is selected from a group of formula a, and the remaining R are the same or different and are independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and one of the following groups, or a combination of the above groups,

[0078]

[0079]

[0080] The R m the same as or different from each other, and are selected from hydrogen or one of the following substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, phenyl, biphenyl, terphenyl, naphthyl;

[0081] m1 is selected from 0, 1, 2, 3, 4 or 5; m2 is selected from 0, 1, 2, 3 or 4; m3 is selected from 0, 1, 2 or 3; m4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; m5 is selected from 0, 1 or 2; m6 is selected from 0, 1, 2, 3, 4, 5 or 6; m7 is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9;

[0082] Wherein, the “at least one R selected from the group of formula a” includes one R, two Rs, three Rs, four Rs, five Rs, six Rs, seven Rs, eight Rs or more R selected from the group of formula a.

[0083] Preferably, among the four six-membered rings containing u in formula I, one, two, three or four six-membered rings are independently selected from the group of formula a.

[0084] Preferably, among the four six-membered rings containing u in formula I, one of the four u in one six-membered ring is selected from the group of formula a.

[0085] Preferably, among the four six-membered rings containing u in formula I, one of the four u in two six-membered rings is selected from the group of formula a.

[0086] Preferably, among the four six-membered rings containing u in formula I, one of the four u in three six-membered rings is selected from the group of formula a.

[0087] Preferably, in the four six-membered rings containing u in formula I, one of the four u in the four six-membered rings is selected from the group of formula a.

[0088] The substituent in the "substituted or unsubstituted" is selected from one or more of deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, phenyl, biphenyl, and naphthyl. When substituted by multiple substituents, the multiple substituents are the same or different from each other.

[0089] More preferably, at least one R is selected from a group of formula a, and the remaining R are the same or different and are independently selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, one of the following groups, or a combination of the above groups,

[0090]

[0091]

[0092] Preferably, in each six-membered ring containing u in formula I, when the ring does not contain a group of formula a, R therein can be selected from any one of the R groups defined herein above.

[0093] Preferably, in each six-membered ring containing u of formula I, when the ring contains a group of formula a, the remaining R of the ring can be selected from any one of the R groups defined herein above; preferably, it can be selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

[0094] Preferably, L is selected from one of the following groups:

[0095]

[0096] The R q Any one selected from hydrogen, deuterium, cyano, trifluoromethyl, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0097] The Y's are the same or different and are selected from CR' or N, and at least one Y is selected from N;

[0098] R' is selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, deuterated phenyl, deuterated biphenyl, and deuterated naphthyl;

[0099] The q0 is selected from 0, 1, 2 or 3; the q1 is selected from 0, 1, 2, 3 or 4; the q2 is selected from 0, 1, 2, 3, 4, 5 or 6; the q3 is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.

[0100] More preferably, the L is selected from one of the following groups:

[0101]

[0102] The above bridging group L may be further substituted by one or more of deuterium, cyano, fluoro, trifluoromethyl, methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, biphenyl, naphthyl, deuterated phenyl, deuterated biphenyl, deuterated naphthyl, pyridine, and pyrimidine.

[0103] R' is selected from any one of hydrogen, deuterium, cyano, trifluoromethyl, halogen, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, deuterated phenyl, deuterated biphenyl, and deuterated naphthyl.

[0104] Most preferably, L is selected from one of the following groups:

[0105]

[0106] Most preferably, the heterocyclic derivative is selected from any one of the following chemical structures:

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134] The preparation method of the heterocyclic derivatives of Formula I of the present invention can be prepared by conventional coupling reactions in the art, for example, by the following synthetic route, but the present invention is not limited thereto:

[0135]

[0136] Formula a is prepared by conventional reactions in the art to obtain a boronic acid compound, which is then subjected to a Suzuki reaction with a carbazole / azacarbazole raw material, and then reacted with a bridging compound to ultimately obtain a compound of formula I, wherein X1, X3, and X4 are independently selected from Cl, Br, or I.

[0137] The present invention has no particular limitation on the sources of the raw materials used in the above-mentioned reactions. Commercially available raw materials or preparation methods well known to those skilled in the art can be used.

[0138] The present invention also provides an organic light-emitting 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, and the organic layer contains any one or a combination of at least two of the heterocyclic derivatives described in the present invention.

[0139] Preferably, the organic layer is located between the anode and the cathode, and the organic layer comprises a hole transport region, a light-emitting layer, and an electron transport region, and the hole transport region and / or the light-emitting layer contain any one or a combination of at least two of the heterocyclic derivatives described in the present invention.

[0140] Preferably, the organic layer comprises a hole transport region, which is located between the anode and the light-emitting layer, and the hole transport region contains any one or a combination of at least two of the heterocyclic derivatives described in the present invention.

[0141] Preferably, the organic layer comprises a light-emitting layer, which is located between the hole transport region and the electron transport region, and the light-emitting layer contains any one or a combination of at least two of the heterocyclic derivatives described in the present invention.

[0142] Preferably, the light-emitting layer comprises a host material and / or a dopant material, and the host material contains any one or a combination of at least two of the heterocyclic derivatives described in the present invention.

[0143] More preferably, the organic layer is located outside any one of the anode and the cathode, and the organic layer comprises a covering layer, wherein the covering layer contains any one or a combination of at least two of the heterocyclic derivatives described in the present invention.

[0144] Based on the direction of light emission, the organic light-emitting diode provided by the present invention can be made into any one of a top emitter device, a bottom emitter device, and a double-sided emitter device; based on the substrate, the organic light-emitting diode provided by the present invention can be made into a device with a rigid glass substrate as a substrate, or a device with a flexible substrate as a substrate.

[0145] The organic light-emitting device of the present invention may be a light-emitting device with a top emission structure, for example, comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and a transparent or semi-transparent cathode in sequence on a substrate.

[0146] The organic light-emitting device of the present invention may also be a bottom-emitting structure light-emitting device, for example, comprising a transparent or semi-transparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode structure in sequence on a substrate.

[0147] The organic light-emitting device of the present invention may also be a light-emitting device with a double-sided light-emitting structure, for example, comprising a transparent or semi-transparent anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a transparent or semi-transparent cathode structure in sequence on a substrate.

[0148] The anode can be made of a high-power function electrode material, which can be a single-layer structure or a multi-layer composite structure. For example, the anode can be made of transparent materials such as indium tin oxide (ITO) and indium zinc oxide (IZO), or can be made of a metal material with good conductivity sandwiched between two layers of indium tin oxide (ITO). The metal material can be any one of aluminum (Al), silver (Ag), titanium (Ti), molybdenum (Mo), or any alloy of any of the above.

[0149] The cathode can be made of a metal material. For example, the cathode can be made of any one of lithium (Li), aluminum (Al), magnesium (Mg), silver (Ag), or an alloy of any of the above materials.

[0150] The hole transport zone can include at least one selected from a hole injection layer, a hole transport layer, a hole buffer layer, and an electron blocking layer. The hole transport zone can have a single layer structure (such as a hole injection layer and / or a hole transport layer) or a single layer formed using a hole injection material and a hole transport material. In some embodiments, the hole transport zone can have, without limitation, a single layer formed using a plurality of different materials, or a multi-layer laminate structure of a hole injection layer / hole transport layer, a hole injection layer / hole transport layer / hole buffer layer, a hole injection layer / hole buffer layer, a hole transport layer / hole buffer layer, or a hole injection layer / hole transport layer / electron blocking layer laminated from the anode (e.g., on or over the anode). The thickness of the hole transport zone can be about 100 nm to about 150 nm.

[0151] The hole injection layer is a layer that injects holes from the electrode, and as a hole injection substance, is preferably a compound that has the ability to transport holes, has a hole injection effect from the anode, has an excellent hole injection effect to the light emitting layer or light emitting material, prevents excitons generated in the light emitting layer from migrating to the electron injection layer or electron injection material, and has excellent film formation ability. The HOMO (highest occupied molecular orbital) of the hole injection substance is preferably between the work function of the anode substance and the HOMO of the surrounding organic layer. Specific examples of the hole injection substance include metalloporphyrin, oligothiophene, arylamine-based organic matter, hexacyno hexaazatriphenylene-based organic matter, quinacridone-based organic matter, perylene-based organic matter, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

[0152] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and is preferably a substance with a large hole mobility. As specific examples, the hole transport layer material can be selected from small molecule materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyl diamine derivatives, styrene compounds, butadiene compounds, and polymer materials such as poly-p-phenylene derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polyvinyl carbazole and its derivatives, polysilane and its derivatives, but is not limited thereto.

[0153] The electron blocking layer is a layer that prevents holes injected from the hole injection layer from passing through the light emitting layer to enter the electron injection layer, thereby improving the service life and efficiency of the device, and if necessary, a known material can be used to form a suitable portion between the light emitting layer and the electron injection layer.

[0154] The luminescent material of the light-emitting layer is a substance that can receive holes and electrons from the hole transport layer and electron transport layer, respectively, and combine them to emit light in the visible light range. It is preferably a substance with high quantum efficiency for fluorescence or phosphorescence. Specific examples include, but are not limited to, 8-hydroxyquinoline aluminum complexes (Alq3); carbazole compounds; diphenylvinyl compounds; BAlq; 10-hydroxybenzoquinoline metal compounds; benzoxazole, benzothiazole, and benzimidazole compounds; poly(p-phenylene vinylene) polymers; spiro compounds; polyfluorenes and rubrene.

[0155] The light-emitting layer may include a host material and a dopant material. The host material may include aromatic fused-ring derivatives or heterocyclic compounds. Specifically, examples of aromatic fused-ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of heterocyclic compounds include, but are not limited to, carbazole derivatives and dibenzofuran derivatives. The host material may be a single structure composed of a single substance, or a single-layer or multi-layer structure composed of different substances. The host material may comprise a single layer, or it may include a light-emitting layer composed of a first host material, a second host material, or more.

[0156] Doping materials include aromatic amine derivatives, styryl heterocyclic derivatives, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, aromatic amine derivatives include aromatic fused ring derivatives having substituted or unsubstituted arylamine groups, such as pyrene, anthracene, and diindenopyrene. Styryl heterocyclic derivatives include compounds having at least one aryl vinyl group substituted on a substituted or unsubstituted arylamine, and are substituted or unsubstituted with one or more substituents selected from aryl, silyl, alkyl, cycloalkyl, and arylamine groups. Specifically, styrylamine, styryldiamine, styryltriamine, and styryltetramine are examples, but are not limited thereto. In addition, metal complexes include iridium complexes and platinum complexes, but are not limited thereto. Doping materials can be single structures composed of a single substance, or single-layer structures or multi-layer structures formed of different substances.

[0157] The electron transport region may include at least one of an electron injection layer, an electron transport layer, a buffer layer, and a hole blocking layer. It may be a single structure composed of a single substance, or a single-layer structure or a multi-layer structure formed by different substances. The electron transport layer may include a single layer, or may include a first electron transport layer and a second electron transport layer or more layers. The type of the electron transport region may be a structure of electron injection layer / electron transport layer, a structure of electron injection layer / electron transport layer / buffer layer, a structure of electron injection layer / buffer layer, a structure of electron transport layer / buffer layer, or a structure of electron injection layer / electron transport layer / hole blocking layer, wherein the layers of each structure are stacked successively from the cathode in the order described, but the structure of the electron transport region is not limited thereto.

[0158] The electron transport layer is a layer that receives electrons from the electron injection layer and transfers the electrons to the light-emitting layer. The electron transport material is a material that can well receive electrons from the cathode and transfer them to the light-emitting layer, preferably a material with high electron mobility. As specific examples, there are Al complexes of 8-hydroxyquinoline, complexes containing Alq3, organic free radical compounds, hydroxyflavone-metal complexes, etc., but are not limited to these. In particular, examples of suitable cathode materials are common materials with low work functions and accompanied by an aluminum layer or a silver layer. Specifically, cesium, barium, calcium, ytterbium and samarium, in the case of each material, are accompanied by an aluminum layer or a silver layer.

[0159] The electron injection layer is a layer that injects electrons from the electrode. Compounds that have the ability to transport electrons, inject electrons from the cathode, and inject electrons into the light-emitting layer or light-emitting material are preferably selected. Compounds that prevent excitons generated in the light-emitting layer from migrating to the hole injection layer and have excellent thin-film forming properties are also preferred. Specific examples include, but are not limited to, fluorenone, anthraquinone dimethane, diphenoquinone, azole, diazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylene methane, anthrone, and their derivatives, metal complexes, and nitrogen-containing five-membered ring derivatives. Metal complexes include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato) zinc, bis(8-hydroxyquinolinato) copper, bis(8-hydroxyquinolinato) manganese, tris(8-hydroxyquinolinato) aluminum, tris(2-methyl-8-hydroxyquinolinato) aluminum, tris(8-hydroxyquinolinato) gallium, bis(10-hydroxybenzo[h]quinolinato) beryllium, bis(10-hydroxybenzo[h]quinolinato) zinc, bis(2-methyl-8-quinolinato) gallium chloride, bis(2-methyl-8-quinolinato)(o-cresol) gallium, bis(2-methyl-8-quinolinato)(1-naphthol) aluminum, and the like, but are not limited thereto.

[0160] The hole blocking layer is a layer that prevents holes from reaching the cathode and can generally be formed using the same conditions as the hole injection layer. Specific examples include, but are not limited to, diazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, and aluminum complexes.

[0161] The covering layer may be made of Alq3, TPBi, or other known materials suitable for the covering layer, or the heterocyclic derivatives described in the present invention.

[0162] There is no particular limitation on the method for preparing and forming each layer in the organic light-emitting device, and the layers may be formed by vacuum evaporation, spin coating, vapor deposition, doctor blade coating, inkjet printing, laser printing, or laser-induced thermal imaging (LITI).

[0163] The organic light-emitting device of the present invention can be widely used in the fields of panel display, lighting source, flexible OLED, electronic paper, organic solar cell, organic photoreceptor or organic thin film transistor, signboard, signal light, etc.

[0164] The present invention is explained in more detail by the following examples, but it is not intended that the present invention be limited thereby. Based on this description, those of ordinary skill in the art will be able to implement the present invention and prepare other compounds and devices according to the present invention within the disclosed entire range without inventive effort.

[0165] Description of raw materials, reagents and characterization equipment:

[0166] The present invention has no particular limitation on the sources of the raw materials used in the following examples. The raw materials may be commercially available products or prepared using methods well known to those skilled in the art.

[0167] Mass spectrometry was performed using a British Waters G2-Si quadrupole tandem time-of-flight high-resolution mass spectrometer, with chloroform as the solvent;

[0168] The elemental analysis was performed using a Vario EL cube organic element analyzer from Elementar, Germany, with a sample mass of 5 to 10 mg.

[0169] Synthesis Example 1: Synthesis of Compound 1

[0170]

[0171] Synthesis of intermediate a-1:

[0172] c-1 (47.29 g, 240 mmol) was cooled (-78°C) in 500 mL of dry tetrahydrofuran, followed by the dropwise addition of 80 mL of 2.5 M n-butyllithium solution. The mixture was stirred at -78°C for 3.5 hours. Trimethyl borate solution (62.34 g, 480 mmol) was slowly added, and the mixture was allowed to react for 1 hour before returning to room temperature and allowing to stand overnight. The resulting mixture was then acidified by the addition of 300 mL of 10% HCl solution and stirred at room temperature for 1.5 hours. The crude product was extracted with 3 × 400 mL of ether and washed several times with sodium carbonate solution and water. Finally, the ether was distilled off, and the crude product was recrystallized from a mixture of water and ethanol (95:5) and dried under vacuum at 60°C overnight to yield intermediate a-1 (33.43 g, 86%). The solid purity was 99.70% as determined by HPLC. Mass spectrum m / z: 162.0480 (theoretical value: 162.0488).

[0173] Synthesis of intermediate A-1:

[0174] Under nitrogen, compound a-1 (14.58 g, 90.00 mmol), compound b-1 (22.15 g, 90.00 mmol), K2CO3 (37.32 g, 270.00 mmol), and 600 mL of toluene solvent were added and stirred. Catalyst Pd(PPh3)4 (1.04 g, 0.90 mmol) and 150 mL of distilled water were added, the temperature was raised to reflux, and the reaction was stirred for 10 hours. After sufficient reaction, 225 mL of distilled water was added to terminate the reaction. The filter cake obtained was filtered under reduced pressure, and the crude intermediate A-1 was washed three times with distilled water. The product was then recrystallized from toluene and ethanol (10:1) to obtain intermediate A-1 (19.89 g, 78%). HPLC analysis revealed a solid purity of 99.78%. Mass spectrum: m / z: 283.0985 (theoretical value: 283.0997).

[0175] Synthesis of compound 1:

[0176] Under nitrogen protection, intermediate A-1 (17.00g, 60.00mmol), f-1 (9.36g, 30.00mmol), and sodium tert-butoxide (7.21g, 75.00mmol) were dissolved in 300ml of dehydrated toluene, and a toluene solution of palladium acetate (0.13g, 0.60mmol) and tri-tert-butylphosphine (0.49g, 2.40mmol) was added with stirring. The mixture was refluxed for 8 hours. After cooling, the mixture was filtered through a diatomaceous earth / silica gel funnel, and the filtrate was distilled under reduced pressure to remove the organic solvent. The concentrate was recrystallized from toluene and filtered to obtain compound 1 (14.83g, 69%). The solid purity was 99.92% as determined by HPLC. Mass spectrum m / z: 716.2475 (theoretical value: 716.2464). Theoretical element content (%) C 52 H 32 N2O2: C, 87.13; H, 4.50; N, 3.91. Measured element content (%): C, 87.11; H, 4.53; N, 3.95.

[0177] Synthesis Example 2: Synthesis of Compound 7

[0178]

[0179] Following the same preparation method as compound 1 in Example 1, equimolar amounts of b-1 were replaced with equimolar amounts of b-7 to obtain compound 7 (15.48 g). HPLC analysis revealed a solid purity of ≥99.94%. Mass spectrum m / z: 716.2471 (theoretical value: 716.2464). Theoretical element content (%): C 52 H 32 N2O2: C, 87.13; H, 4.50; N, 3.91. Measured element content (%): C, 87.16; H, 4.48; N, 3.95.

[0180] Synthesis Example 3: Synthesis of Compound 10

[0181]

[0182] Following the same preparation method as compound 1 in Synthesis Example 1, equal moles of c-1 were replaced with equal moles of c-10 to obtain compound 10 (14.62 g). The purity of the solid was ≥99.99% as determined by HPLC. Mass spectrum m / z: 716.2456 (theoretical value: 716.2464). Theoretical element content (%): C 52 H 32 N2O2: C, 87.13; H, 4.50; N, 3.91. Measured element content (%): C, 87.09; H, 4.52; N, 3.94.

[0183] Synthesis Example 4: Synthesis of Compound 22

[0184]

[0185] Following the same preparation method as compound 1 in Example 1, equimolar amounts of c-1 were replaced with equimolar amounts of c-22 to obtain compound 22 (14.53 g). HPLC analysis revealed a solid purity of ≥99.96%. Mass spectrum m / z: 744.2789 (theoretical value: 744.2777). Theoretical element content (%): C 54 H 36 N2O2: C, 87.07; H, 4.87; N, 3.76. Measured element content (%): C, 87.04; H, 4.85; N, 3.80.

[0186] Synthesis Example 5: Synthesis of Compound 47

[0187]

[0188] Synthesis of intermediate a-10:

[0189] Following the same preparation method as that of intermediate a-1 in Synthesis Example 1, an equal mole of c-1 was replaced with an equal mole of c-10 to obtain intermediate a-10 (33.04 g, 85%). The solid purity was determined by HPLC to be ≥99.72%. Mass spectrum: m / z: 162.0480 (theoretical value: 162.0488).

[0190] Synthesis of intermediate A-47:

[0191] Under nitrogen, a 1L reaction flask was charged with compound a-10 (29.15 g, 180.00 mmol), compound b-47 (29.25 g, 90.00 mmol), K2CO3 (74.63 g, 540.00 mmol), and 800 mL of toluene solvent, with stirring. Catalyst Pd(PPh3)4 (1.04 g, 1.80 mmol) and 300 mL of distilled water were added, the temperature was raised to reflux, and the reaction was stirred for 10 hours. After sufficient reaction, 300 mL of distilled water was added to terminate the reaction. The filter cake obtained was filtered under reduced pressure, resulting in the crude intermediate A-1. This was washed three times with distilled water and then recrystallized from toluene and ethanol (10:1) to obtain intermediate A-47 (26.97 g, 75%). HPLC analysis revealed a solid purity of 99.78%. Mass spectrum: m / z: 399.1250 (theoretical value: 399.1259).

[0192] Synthesis of intermediate B-47:

[0193] Under nitrogen, intermediate A-47 (23.97 g, 60.00 mmol), f-47 (21.54 g, 60.00 mmol), and sodium tert-butoxide (7.21 g, 75.00 mmol) were dissolved in 300 ml of dehydrated toluene. A toluene solution of palladium acetate (0.13 g, 0.60 mmol) and tri-tert-butylphosphine (0.49 g, 2.40 mmol) was added with stirring, and the mixture was refluxed for 8 hours. After cooling, the mixture was filtered through a celite / silica gel funnel, and the organic solvent was removed by vacuum distillation. The concentrate was recrystallized from toluene and filtered to obtain intermediate B-47 (27.23 g, 72%). HPLC analysis of the solid showed a purity of 99.72%. Mass spectrum m / z: 629.0981 (theoretical value: 629.0990).

[0194] Synthesis of compound 47:

[0195] Under nitrogen protection, intermediate B-47 (18.92g, 30.00mmol), g-47 (9.58g, 30.00mmol), and sodium tert-butoxide (3.60g, 37.50mmol) were dissolved in 200ml of dehydrated toluene, and a toluene solution of palladium acetate (0.07g, 0.30mmol) and tri-tert-butylphosphine (0.24g, 1.20mmol) was added with stirring. The mixture was refluxed for 4 hours. After cooling, the mixture was filtered through a diatomaceous earth / silica gel funnel, and the organic solvent was removed by vacuum distillation of the filtrate. The concentrate was recrystallized from toluene and filtered to obtain compound 47 (16.95g, 65%). The solid purity was 99.97% as determined by HPLC. Mass spectrum m / z: 868.3098 (theoretical value: 868.3090). Theoretical element content (%) C 64 H 40 N2O2: C, 88.45; H, 4.64; N, 3.22. Measured element content (%): C, 88.41; H, 4.62; N, 3.25.

[0196] Synthesis Example 6: Synthesis of Compound 56

[0197]

[0198] Synthesis of intermediate A-10:

[0199] Following the same preparation method as that of Intermediate A-1 in Synthesis Example 1, an equal mole of c-1 was replaced with an equal mole of c-10 to obtain Intermediate A-10 (19.63 g, 77%). The solid purity was ≥99.90% as determined by HPLC. Mass spectrum: m / z: 283.0990 (theoretical value: 283.0997).

[0200] Synthesis of compound 56:

[0201] Following the same preparation method as compound 47 in Example 5, equimolar amounts of A-47 and g-47 were replaced with equimolar amounts of A-10 and g-56, respectively, to obtain compound 56 (15.59 g, 69%). HPLC analysis of the solid showed a purity of ≥99.95%. Mass spectrum m / z: 752.2818 (theoretical value: 752.2828). Theoretical element content (%): C 56 H 36 N2O: C, 89.33; H, 4.82; N, 3.72. Measured element content (%): C, 89.30; H, 4.84; N, 3.76.

[0202] Synthesis Example 7: Synthesis of Compound 72

[0203]

[0204] Synthesis of intermediate A-47:

[0205] Intermediate A-47 (26.97 g, 75%) was synthesized by the same preparation method as that of Intermediate A-47 in Synthesis Example 5. The purity of the solid was 99.78% as determined by HPLC. Mass spectrum: m / z: 399.1250 (theoretical value: 399.1259).

[0206] Synthesis of compound 72:

[0207] Following the same preparation method as compound 1 in Synthesis Example 1, equimolar amounts of A-1 were replaced with equimolar amounts of A-47 to obtain compound 72 (20.50 g, 72%). HPLC analysis of the solid showed a purity of ≥99.98%. Mass spectrum m / z: 948.2982 (theoretical value: 948.2988). Theoretical element content (%): C 68 H 40 N2O4: C, 86.06; H, 4.25; N, 2.95. Measured element content (%): C, 86.08; H, 4.21; N, 2.98.

[0208] Synthesis Example 8: Synthesis of Compound 79

[0209]

[0210] Following the same preparation method as compound 1 in Example 1, equimolar amounts of c-1 were replaced with equimolar amounts of c-79 to obtain compound 79 (17.21 g). HPLC analysis revealed a solid purity of ≥99.90%. Mass spectrum m / z: 868.3097 (theoretical value: 868.3090). Theoretical element content (%): C 64 H 40N2O2: C, 88.45; H, 4.64; N, 3.22. Found (mass %): C, 88.41; H, 4.66; N, 3.25.

[0211] Synthesis Example 9: Synthesis of compound 81

[0212]

[0213] According to the same preparation method of compound 1 in synthesis example 1, equal moles of c-1 were replaced by equal moles of c-81, respectively, to obtain compound 81 (19.77 g), with a solid purity of ≥ 99.95% detected by HPLC. Mass spectrum m / z: 968.3412 (theoretical value: 968.3403). Theoretical elemental content (%) C 72 H 44 N2O2: C, 89.23; H, 4.58; N, 2.89. Found (mass %): C, 89.20; H, 4.54; N, 2.91.

[0214] Synthesis Example 10: Synthesis of compound 88

[0215]

[0216] According to the same preparation method of compound 1 in synthesis example 1, equal moles of c-1, f-1 were replaced by equal moles of c-88, f-88, respectively, to obtain compound 88 (19.15 g), with a solid purity of ≥ 99.92% detected by HPLC. Mass spectrum m / z: 996.3708 (theoretical value: 996.3716). Theoretical elemental content (%) C 74 H 48 N2O2: C, 89.13; H, 4.85; N, 2.81. Found (mass %): C, 89.10; H, 4.89; N, 2.83.

[0217] Synthesis Example 11: Synthesis of compound 97

[0218]

[0219] According to the same preparation method of compound 1 in synthesis example 1, equal moles of c-1, b-1 were replaced by equal moles of c-10, b-97, respectively, to obtain compound 97 (15.35 g), with a solid purity of ≥ 99.96% detected by HPLC. Mass spectrum m / z: 730.3330 (theoretical value: 730.3343). Theoretical elemental content (%) C 52 H 18 D 14N2O2: C, 85.45; H, 6.34; N, 3.83. Measured element content (%): C, 85.47; H, 6.37; N, 3.79.

[0220] Synthesis Example 12: Synthesis of Compound 98

[0221]

[0222] Following the same preparation method as compound 1 in Example 1, equimolar amounts of c-1 were replaced with equimolar amounts of c-98 to obtain compound 98 (15.96 g). HPLC analysis revealed a solid purity of ≥99.93%. Mass spectrum m / z: 718.2598 (theoretical value: 718.2589). Theoretical element content (%): C 52 H 30 D2N2O2: C, 86.88; H, 4.77; N, 3.90. Measured element content (%): C, 86.90; H, 4.74; N, 3.86.

[0223] Synthesis Example 13: Synthesis of Compound 161

[0224]

[0225] Following the same preparation method as that for compound 56 in Example 5, equimolar amounts of c-10, b-1, and g-56 were replaced with equimolar amounts of c-161, b-7, and g-161, respectively, to obtain compound 161 (14.41 g). The purity of the solid was ≥99.95% as determined by HPLC. Mass spectrum: m / z: 716.2279 (theoretical value: 716.2286). Theoretical element content (%): C 52 H 32 N2S: C, 87.12; H, 4.50; N, 3.91. Measured element content (%): C, 87.10; H, 4.46; N, 3.94.

[0226] Synthesis Example 14: Synthesis of Compound 178

[0227]

[0228] Following the same preparation method as compound 1 in Example 1, equimolar amounts of c-1 and f-1 were replaced with equimolar amounts of c-178 and f-178, respectively, to obtain compound 178 (22.12 g). HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 1052.3245 (theoretical value: 1052.3259). Theoretical element content (%): C 76 H 48N2S2: C, 86.66; H, 4.59; N, 2.66. Measured element content (%): C, 86.69; H, 4.55; N, 2.64.

[0229] Synthesis Example 15: Synthesis of Compound 183

[0230]

[0231] Following the same preparation method as compound 47 in Example 5, equimolar amounts of c-10 and g-47 were replaced with equimolar amounts of c-183 and g-183, respectively, to obtain compound 183 (17.32 g). HPLC analysis of the solid showed a purity of ≥99.91%. Mass spectrum m / z: 843.2327 (theoretical value: 848.2320). Theoretical element content (%): C 60 H 36 N2S2: C, 84.88; H, 4.27; N, 3.30. Measured element content (%): C, 84.90; H, 4.23; N, 3.33.

[0232] Synthesis Example 16: Synthesis of Compound 225

[0233]

[0234] Under nitrogen, c-10 (41.38 g, 210.00 mmol), e-225 (33.25 g, 210.00 mmol), K2CO3 (58.05 g, 420.00 mmol), Pd(PPh3)4 (2.43 g, 2.10 mmol), 420 ml of ethanol, and 420 ml of water were added to 1260 ml of toluene. The mixture was stirred and heated under reflux for 7 h. After the reaction, the mixture was cooled to room temperature, distilled water was added, and the mixture was extracted with dichloromethane. After standing, the organic layer was collected and dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by vacuum distillation. The temperature was lowered for crystallization, and the resulting solid was filtered with suction. The resulting solid was recrystallized from toluene / methanol (volume ratio 9:1) to obtain intermediate d-225 (41.17 g, yield 85%). The purity of the solid was ≥99.76% as determined by HPLC. Mass spectrum m / z: 230.0238 (theoretical value: 230.0247).

[0235] Compound 225 (16.31 g, 62%) was obtained by the same preparation method as in Example 1, except that equimolar amounts of c-1 and f-1 were replaced with equimolar amounts of d-225 and f-225, respectively. HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 876.3163 (theoretical value: 876.3151). Theoretical element content (%): C 60 H 32C, 82.17; H, 4.60; N, 9.58. Found (%): C, 82.14; H, 4.58; N, 9.60.

[0236] Synthesis Example 17: Synthesis of compound 229

[0237]

[0238] Compound 229 (19.12 g) was obtained in the same manner as in the preparation of compound 225 of Synthesis Example 16, by replacing e-225, b-1, f-225 with e-229, b-229, f-229, respectively, in equal molar amounts. HPLC detection of solid purity ≥ 99.92%. Mass spectrum m / z: 950.3629 (theoretical value: 950.3621). Theoretical elemental content (%) C 68 H 46 N4O2: C, 85.87; H, 4.87; N, 5.89. Found (%): C, 85.84; H, 4.85; N, 5.93.

[0239] Synthesis Example 18: Synthesis of compound 242

[0240]

[0241] Compound 242 (18.95 g) was obtained in the same manner as in the preparation of compound 225 of Synthesis Example 16, by replacing e-225, f-225 with e-242, f-1, respectively, in equal molar amounts. HPLC detection of solid purity ≥ 99.96%. Mass spectrum m / z: 876.3585 (theoretical value: 876.3592). Theoretical elemental content (%) C 64 H 32 D8N2O2: C, 87.64; H, 5.51; N, 3.19. Found (%): C, 87.62; H, 5.55; N, 3.23.

[0242] Synthesis Example 19: Synthesis of compound 261

[0243]

[0244] Compound 261 (19.52 g) was obtained in the same manner as in the preparation of compound 225 of Synthesis Example 16, by replacing c-10, e-225, b-1, f-225 with c-261, e-261, b-7, f-1, respectively, in equal molar amounts. HPLC detection of solid purity ≥ 99.93%. Mass spectrum m / z: 1000.2954 (theoretical value: 1000.2946). Theoretical elemental content (%) C 72H 44 N2S2: C, 86.37; H, 4.43; N, 2.80. Measured element content (%): C, 86.34; H, 4.39; N, 2.82.

[0245] Synthesis Example 20: Synthesis of Compound 287

[0246]

[0247] Following the same preparation method as in Example 1, Compound 1 was synthesized by replacing equal moles of C-1 and F-1 with equal moles of C-287 and F-287, respectively, to obtain Compound 287 (18.82 g). HPLC analysis revealed a solid purity of ≥99.97%. Mass spectrum: m / z: 908.3128 (theoretical value: 908.3135). Theoretical element content (%): C 64 H 32 D8N2S2: C, 84.55; H, 5.32; N, 3.08. Measured element content (%): C, 84.53; H, 5.35; N, 3.11.

[0248] Synthesis Example 21: Synthesis of Compound 303

[0249]

[0250] Following the same preparation method as compound 1 in Example 1, equimolar amounts of c-1 and f-1 were replaced with equimolar amounts of c-10 and f-303, respectively, to obtain compound 303 (17.37 g). The purity of the solid was ≥99.94% as determined by HPLC. Mass spectrum: m / z: 792.27786 (theoretical value: 792.2777). Theoretical element content (%): C 58 H 36 N2O2: C, 87.86; H, 4.58; N, 3.53. Measured element content (%): C, 87.89; H, 4.60; N, 3.51.

[0251] Synthesis Example 22: Synthesis of Compound 308

[0252]

[0253] Following the same preparation method as compound 1 in Synthesis Example 1, equimolar amounts of c-1 and f-1 were replaced with equimolar amounts of c-308 and f-308, respectively, to obtain compound 308 (20.90 g). HPLC analysis of the solid showed a purity of ≥99.90%. Mass spectrum m / z: 994.3552 (theoretical value: 994.3559). Theoretical element content (%): C 74 H 46N2O2: C, 89.31; H, 4.66; N, 2.81. Measured element content (%): C, 89.27; H, 4.62; N, 2.83.

[0254] Synthesis Example 23: Synthesis of Compound 315

[0255]

[0256] Following the same preparation method as compound 1 in Example 1, equimolar amounts of b-1 and f-1 were replaced with equimolar amounts of b-315 and f-315, respectively, to obtain compound 315 (14.68 g). HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 719.2329 (theoretical value: 719.2321). Theoretical element content (%): C 49 H 29 N5O2: C, 81.76; H, 4.06; N, 9.73. Measured element content (%): C, 81.79; H, 4.08; N, 9.71.

[0257] Synthesis Example 24: Synthesis of Compound 327

[0258]

[0259] Following the same preparation method as compound 1 in Synthesis Example 1, equimolar amounts of c-1 and f-1 were replaced with equimolar amounts of c-10 and f-327, respectively, to obtain compound 327 (14.25 g). HPLC analysis revealed a solid purity of ≥99.94%. Mass spectrum: m / z: 730.2266 (theoretical value: 730.2256). Theoretical element content (%): C 52 H 30 N2O3: C, 85.46; H, 4.14; N, 3.83. Measured element content (%): C, 85.42; H, 4.17; N, 3.81.

[0260] Synthesis Example 25: Synthesis of Compound 346

[0261]

[0262] Following the same preparation method as compound 1 in Synthesis Example 1, equimolar amounts of c-1 and f-1 were replaced with equimolar amounts of c-346 and f-346, respectively, to obtain compound 346 (15.33 g). The purity of the solid was ≥99.95% as determined by HPLC. Mass spectrum m / z: 830.3635 (theoretical value: 830.3621). Theoretical element content (%): C 58 H 46N4O2: C, 83.83; H, 5.58; N, 6.74. Measured element content (%): C, 83.86; H, 5.54; N, 6.72.

[0263] Synthesis Example 26: Synthesis of Compound 393

[0264]

[0265] Following the same preparation method as compound 1 in Example 1, equimolar amounts of c-1 were replaced with equimolar amounts of c-393 to obtain compound 393 (14.88 g). HPLC analysis revealed a solid purity of ≥99.93%. Mass spectrum: m / z: 718.2376 (theoretical value: 718.2369). Theoretical element content (%): C 50 H 30 N4O2: C, 83.55; H, 4.21; N, 7.79. Measured element content (%): C, 83.59; H, 4.23; N, 7.82.

[0266] Synthesis Example 27: Synthesis of Compound 424

[0267]

[0268] Following the same preparation method as that for compound 225 in Example 16, equimolar amounts of c-10, e-225, b-1, and f-225 were replaced with equimolar amounts of c-393, e-424, b-7, and f-424, respectively, to obtain compound 424 (16.72 g). The purity of the solid was ≥99.92% as determined by HPLC. Mass spectrum: m / z: 870.2981 (theoretical value: 870.2995). Theoretical element content (%): C 62 H 38 N4O2: C, 85.50; H, 4.40; N, 6.43. Measured element content (%): C, 85.54; H, 4.42; N, 6.39.

[0269] Synthesis Example 28: Synthesis of Compound 462

[0270]

[0271] Following the same preparation method as that for compound 225 in Example 16, equimolar amounts of c-10, e-225, b-1, and f-225 were replaced with equimolar amounts of c-462, e-462, b-462, and f-462, respectively, to obtain compound 462 (21.29 g). The purity of the solid was ≥99.96% as determined by HPLC. Mass spectrum: m / z: 1058.4568 (theoretical value: 1058.4560). Theoretical element content (%): C 76 H58 N4O2: C, 86.17; H, 5.52; N, 5.29. Measured element content (%): C, 86.19; H, 5.48; N, 5.26.

[0272] Synthesis Example 29: Synthesis of Compound 464

[0273]

[0274] Following the same preparation method as compound 1 in Example 1, equimolar amounts of c-1 and f-1 were replaced with equimolar amounts of c-464 and f-464, respectively, to obtain compound 464 (17.60 g). HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 862.1606 (theoretical value: 862.1615). Theoretical element content (%): C 50 H 22 F8N4O2: C, 69.61; H, 2.57; N, 6.49. Measured element content (%): C, 69.65; H, 2.53; N, 6.47.

[0275] Synthesis Example 30: Synthesis of Compound 470

[0276]

[0277] Following the same preparation method as compound 1 in Synthesis Example 1, equal moles of c-1 and b-1 were replaced with equal moles of c-464 and b-470, respectively, to obtain compound 470 (16.98 g). HPLC analysis of the solid showed a purity of ≥99.91%. Mass spectrum m / z: 870.2986 (theoretical value: 870.2995). Theoretical element content (%): C 62 H 38 N4O2: C, 85.50; H, 4.40; N, 6.43. Measured element content (%): C, 85.52; H, 4.43; N, 6.39.

[0278] Synthesis Example 31: Synthesis of Compound 484

[0279]

[0280] Following the same preparation method as in Example 1, Compound 1 was prepared by replacing equal moles of C-1 and B-1 with equal moles of C-484 and B-484, respectively, to obtain Compound 484 (15.52 g). The purity of the solid was ≥99.92% as determined by HPLC. Mass spectrum: m / z: 820.2573 (theoretical value: 820.2587). Theoretical element content (%): C 56 H 32N6O2: C, 81.94; H, 3.93; N, 10.24. Measured element content (%): C, 81.92; H, 3.90; N, 10.21.

[0281] Synthesis Example 32: Synthesis of Compound 504

[0282]

[0283] Following the same preparation method as that of intermediate A-47 in Synthesis Example 5, an equal mole of c-10 was replaced with an equal mole of a-504 to obtain intermediate g-504 (28.48 g, 73%). The solid purity was ≥99.80% as determined by HPLC. Mass spectrum: m / z: 433.0715 (theoretical value: 433.0707).

[0284] Following the same preparation method as compound 56 in Example 5, equimolar amounts of c-10 and g-56 were replaced with equimolar amounts of c-504 and g-504, respectively, to obtain compound 504 (17.51 ​​g). HPLC analysis of the solid showed a purity of ≥99.96%. Mass spectrum m / z: 883.1891 (theoretical value: 883.1898). Theoretical element content (%): C 57 H 33 N5S3: C, 77.44; H, 3.76; N, 7.92. Measured element content (%): C, 77.41; H, 3.79; N, 7.90.

[0285] Synthesis Example 33: Synthesis of Compound 570

[0286]

[0287] Following the same preparation method as that for compound 225 in Example 16, equimolar amounts of c-10, e-225, and f-225 were replaced with equimolar amounts of c-570, e-570, and f-570, respectively, to obtain compound 570 (18.30 g). The purity of the solid was ≥99.92% as determined by HPLC. Mass spectrum: m / z: 896.2911 (theoretical value: 896.2900). Theoretical element content (%): C 62 H 36 N6O2: C, 83.02; H, 4.05; N, 9.37. Measured element content (%): C, 83.05; H, 4.01; N, 9.33.

[0288] Synthesis Example 34: Synthesis of Compound 651

[0289]

[0290] Compound 651 (14.97 g) was obtained by the same preparation method as in Example 1, with equal moles of c-1 and f-1 replaced by equal moles of c-651 and f-651, respectively. HPLC analysis of the solid showed a purity of ≥99.91%. Mass spectrum m / z: 750.1923 (theoretical value: 750.1912). Theoretical element content (%): C 50 H 30 N4S2: C, 79.97; H, 4.03; N, 7.46. Measured element content (%): C, 79.99; H, 4.00; N, 7.43.

[0291] Synthesis Example 35: Synthesis of Compound 741

[0292]

[0293] Compound 741 (14.38 g) was obtained by the same preparation method as in Example 1, except that equal moles of c-1 and b-1 were replaced with equal moles of c-10 and b-741, respectively. The purity of the solid was ≥99.91% as determined by HPLC. Mass spectrum m / z: 720.2259 (theoretical value: 720.2274). Theoretical element content (%): C 48 H 28 N6O2: C, 79.99; H, 3.92; N, 11.66. Measured element content (%): C, 79.96; H, 3.95; N, 11.63.

[0294] Blue organic light-emitting device (covering layer)

[0295] [Comparative Example 1-2] Device Preparation Example:

[0296] Comparative Example 1: Preparation of an organic light-emitting device using vacuum thermal evaporation. The experimental steps were as follows: An ITO-Ag-ITO substrate was rinsed three times in distilled water, ultrasonically cleaned for 15 minutes, and then ultrasonically cleaned with isopropyl alcohol, acetone, and methanol, sequentially. The substrate was then dried at 120°C and placed in a vapor deposition machine.

[0297] On the prepared ITO-Ag-ITO transparent electrode, a hole injection layer HI / 55nm, a hole transport layer HT / 70nm, a light-emitting layer main body BH+Ir(Fppy)3 (mass ratio 92%:8% mixed) / 22nm, and then an electron transport layer TPBi:Liq (doping ratio is 1:1 by mass) / 28nm, an electron injection layer LiF / 1nm, a cathode Mg-Ag / 16nm, and a cover layer CP-1 / 64nm are evaporated on the cathode by vacuum evaporation layer by layer. The device is sealed in a glove box to prepare an organic light-emitting device. After completing the production of the organic light-emitting device according to the above steps, the photoelectric performance of the device is measured. The molecular structure formula of the relevant materials is as follows:

[0298]

[0299] Comparative Example 2: The cover layer material CP-1 in Comparative Example 1 was replaced with CP-2, and the organic light-emitting device of Comparative Example 2 was manufactured in the same manner as Comparative Example 1.

[0300] [Application Examples 1-35]

[0301] Application Examples 1-35: The cover layer material CP-1 of the organic light-emitting device was replaced with Compounds 1, 7, 10, 22, 47, 56, 72, 79, 81, 88, 97, 98, 161, 178, 183, 225, 229, 242, 261, 287, 303, 308, 315, 327, 346, 393, 424, 462, 464, 470, 484, 504, 570, 651, and 741 of the present invention, respectively. All other steps were the same as in Comparative Example 1. The test results of the luminescence characteristics of the resulting organic light-emitting devices are shown in Table 1. Table 1 shows the test results of the luminescence characteristics of the compounds prepared in the examples of the present invention and the light-emitting devices prepared using the comparative substances.

[0302] [Table 1] Luminous characteristics test of light-emitting devices

[0303]

[0304]

[0305] Note: T97 refers to the current density of 10mA / cm 2 Under the condition of , the time taken for the device brightness to decay to 97%;

[0306] As can be seen from the results in Table 1, the heterocyclic derivatives of the present invention can be used as covering layer materials in organic light-emitting devices. Compared with Comparative Examples 1-2, they can effectively improve the light extraction efficiency, thereby improving the luminous efficiency of the organic light-emitting device. In addition, they can also increase the lifespan of the organic light-emitting device, and are excellent covering layer materials for organic light-emitting devices.

[0307] It should be noted that the present invention is particularly described using individual embodiments. However, without departing from the principles of the present invention, a person skilled in the art may make various improvements in form or detail to the present invention, and these improvements also fall within the scope of protection of the present invention.

Claims

1. A heterocyclic compound, characterized in that The molecular structure is shown in Formula I: wherein the u are the same or different and are selected from CR or N; u is not all selected from N; The R groups are the same or different, and at least one R group is selected from the group of formula a below, and the remaining R groups are each independently selected from hydrogen, deuterium, deuterium-substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, and one of the following groups: The R m1 are the same as or different from each other and are selected from hydrogen, deuterium, and deuterium-substituted or unsubstituted C1-C6 alkyl groups; The R m The same or different groups are selected from the following groups which are substituted or unsubstituted by hydrogen or deuterium: methyl, ethyl, propyl, butyl, pentyl, and hexyl; The m1 is selected from 0, 1, 2, 3, 4 or 5; the m2 is selected from 0, 1, 2, 3 or 4; the m3 is selected from 0, 1, 2 or 3; the m4 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; the m6 is selected from 0, 1, 2, 3, 4, 5 or 6; Alternatively, two adjacent R groups may be bonded together to form a benzene ring; The at least one R is selected from the following formula a group, which means that in the four six-membered rings containing u in formula I, the R of one of the four u in one, two, three or four six-membered rings is selected from the formula a group: The group of formula a is selected from one of the following groups: Said X is selected from O or S; The L a Selected from a single bond or one of the following groups: The R p Any one selected from hydrogen, deuterium, and deuterium-substituted or unsubstituted C1-C6 alkyl; The V's are the same or different, each independently selected from CR0 or N, and at least one V is selected from N; R0 is selected from any one of hydrogen, deuterium, methyl, ethyl, isopropyl, and tert-butyl; Said p1 is selected from 0, 1, 2, 3 or 4; The R a The same or different R is selected from one or more of hydrogen, deuterium, substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, biphenyl, naphthyl; wherein the substituents in the "substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, pentyl, hexyl" are selected from deuterium, and the substituents in the "substituted or unsubstituted groups: phenyl, biphenyl, naphthyl" are selected from deuterium, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl; or optionally two adjacent R a The groups can bond together to form deuterium-substituted or unsubstituted benzene rings; Said a is selected from 0, 1, 2, 3, 4 or 5; The L is selected from one of the following groups: The above bridging group L may be further substituted by one or more of deuterium, fluoro, methyl, ethyl, isopropyl, and tert-butyl; R' is selected from any one of hydrogen, deuterium, fluoro, methyl, ethyl, isopropyl, and tert-butyl.

2. The heterocyclic compound according to claim 1, characterized in that The group of formula a is selected from one of the following groups: The L a Selected from a single bond or one of the following groups:

3. The heterocyclic compound according to claim 1, characterized in that The group of formula a One selected from the following groups:

4. The heterocyclic compound according to claim 1, characterized in that At least one R is selected from the group of formula a, and the remaining R are the same or different and are independently selected from hydrogen, deuterium, deuterium-substituted or unsubstituted groups: methyl, ethyl, propyl, butyl, and one of the following groups, 5. The heterocyclic compound according to claim 1, characterized in that The L is selected from one of the following groups: The above bridging group L may be further substituted by one or more of deuterium, fluoro group, and methyl group.

6. A heterocyclic compound, characterized in that The heterocyclic compound is selected from any one of the following chemical structures:

7. An organic light-emitting 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 of the anode and the cathode, wherein: The organic layer comprises a hole transport region, a light-emitting layer, an electron transport region and a covering layer, wherein at least one of the covering layers contains any one or a combination of at least two of the heterocyclic compounds according to any one of claims 1 to 6.

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