CN117209524A

CN117209524A - Heterocyclic compound and organic electroluminescent device thereof

Info

Publication number: CN117209524A
Application number: CN202311092478.7A
Authority: CN
Inventors: 孙敬; 杜明珠; 刘喜庆; 李梦茹
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2023-08-28
Filing date: 2023-08-28
Publication date: 2023-12-12

Abstract

The invention 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 invention has higher triplet state energy level and proper HOMO and LUMO energy levels, can balance the distribution of electrons and holes in a luminescent layer, and improves the recombination probability of excitons, thereby realizing the maximum recombination of carriers and avoiding the problem of efficiency roll-off; in addition, the heterocyclic compound provided by the invention also has higher glass transition temperature, is not easy to crystallize during vapor deposition film formation, and has good film forming property and thermal stability. When the organic light-emitting diode is applied to an organic light-emitting diode as a main material of a light-emitting layer, the driving voltage of the device can be effectively reduced, the light-emitting efficiency of the device can be improved, and the service life of the device can be prolonged.

Description

Heterocyclic compound and organic electroluminescent device thereof

Technical Field

The invention relates to the technical field of organic electroluminescent materials, in particular to a heterocyclic compound and an organic electroluminescent device thereof.

Background

With the development of science and technology, people gradually enter an information society, and a display is used as a bridge for people and information, so that the display market is continuously updated and iterated, a traditional CRT display is gradually replaced by a plasma display PDP (Plasma Display Panel) liquid crystal display LCD (Liquid Crystal Display), along with the continuous development of the display market, the requirements of people on the display are higher and higher, the liquid crystal display can not meet the requirements of people any more, an Organic Light-Emitting Diode (OLED) is grown with the advantages of high efficiency, high brightness, low driving voltage, good flexibility, wide viewing angle, high response speed, high resolution, wide material selection range and the like, and the OLED is a novel flat panel display technology with the forefront in recent years and is a development trend of the flat panel display industry in the future.

The organic electroluminescent device is a carrier dual injection type device that converts electric energy into light energy. The light-emitting principle is that under the action of an externally applied electric field, holes generated by an anode material and electrons generated by a cathode material are respectively injected into an OLED device to be combined to form excitons; the excitons transfer energy to organic light-emitting molecules in the light-emitting layer, which molecules transition from a ground state to an excited state as a result of obtaining energy; the molecules in the excited state are unstable and return to the ground state in the form of radiative transitions, in which energy is released in the form of light energy, resulting in an electroluminescent phenomenon. The organic electroluminescent device includes an anode, a cathode, and an organic layer, which generally includes a hole transport region, an electron transport region, a light emitting layer, and the like. Wherein the hole transport region can be divided into a hole injection layer, a hole transport layer, and an electron blocking layer; the electron transport region may be divided into an electron injection layer, an electron transport layer, and a hole blocking layer; the light-emitting layer is divided into a host material and a guest material by adopting a host-guest doping mode.

To date, OLED display technology has been developed with a series of breakthroughs and successes, but there is still a need to overcome the difficulties in the development process. The luminous layer is used as a core part of the OLED, has an important influence on the overall performance of the device, and the luminous efficiency of the device is determined by the used materials; the problems of mismatching of the energy level of the main material and the adjacent functional layer, mismatching of the triplet energy level of the main guest material and the like can lead to unbalanced migration of electrons and holes in the light-emitting layer, so that the efficiency of forming excitons by combining the electrons and the holes is low, and the light-emitting efficiency of the organic electroluminescent device is further affected.

Therefore, aiming at the problems of the prior luminescent layer materials, the luminescent layer main body material with excellent performance needs to be researched, the driving voltage of the device is reduced, the luminescent efficiency of the device is improved, the service life of the device is prolonged, and the performance of the OLED device is improved.

Disclosure of Invention

In view of the above problems in the prior art, the present invention provides a heterocyclic compound and an organic electroluminescent device thereof. Specifically, the technical scheme of the invention is as follows:

the invention provides a heterocyclic compound, which has the following structure:

the x is selected from N or CH identically or differently; x at the bond is selected from C;

the R is ₁ The halogen is selected from any one of hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring condensed ring group and group shown in formula III; or two adjacent R ₁ May be linked to each other to form a substituted or unsubstituted ring;

said a is selected from 1, 2, 3 or 4; when two or more R's are present ₁ When two or more R' s ₁ Are the same as or different from each other;

the ring A is selected from substituted or unsubstituted C6-C20 aryl or substituted or unsubstituted C4-C20 heteroaryl;

". Times." are attachment sites, formula II is fused to ring A by ". Times."; the formula II may be fused to ring A in any position;

the Ar is as follows ₁ 、Ar ₂ Independently selected from any one of the following groups:

said y ₁ Identically or differently selected from N or CH; and said y ₁ At most two of which are selected from N; y at bond ₁ Selected from C;

said y is identically or differently selected from N or CH; y at the bond is selected from C;

the ring B is selected from substituted or unsubstituted C3-C15 alicyclic groups;

the R is ₂ The halogen is selected from any one of hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted C6-C30 aryl, fused ring group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring and group shown in a formula III; or two adjacent R ₂ Can be connected with each other to form a substituted or unsubstituted ring;

said b ₁ Selected from 1, 2, 3, 4 or 5; said b ₂ Selected from 1, 2, 3, 4, 5, 6 or 7; said b ₃ Selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; said b ₄ Selected from 1, 2, 3 or 4; said b ₅ Selected from 1 or 2; said b ₆ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; said b ₇ Selected from 1, 2 or 3; when two or more R's are present ₂ When two or more R' s ₂ Are the same as or different from each other;

the L is ₁ 、L ₂ Independently selected from a single bond or any one of the following groups;

said z ₁ Identically or differently selected from N or CH; and said z ₁ At most two of which are selected from N; z at bond ₁ Selected from C;

the z is identically or differently selected from N or CH; z at the bond is selected from C;

the ring C is selected from substituted or unsubstituted C3-C15 alicyclic groups;

the R is ₆ The halogen is selected from any one of hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted C6-C30 aryl, fused ring group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring and group shown in a formula III; or two adjacent R ₆ Can be connected with each other to form a substituted or unsubstituted ring;

the c ₁ Selected from 1, 2, 3 or 4; the c ₂ Selected from 1, 2 or 3; the c ₃ Selected from 1 or 2; when two or more R's are present ₆ When two or more R' s ₆ Are the same as or different from each other;

Provided that the structure comprises at least one group of formula III:

the R is ₃ 、R ₄ 、R ₅ Independently selected from hydrogen, deuterium, tritium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C1-C15 alkenyl;

and the heterocyclic compound is not of the structure:

the invention also provides an organic electroluminescent device which comprises at least one heterocyclic compound.

The beneficial effects are that:

the heterocyclic compound provided by the invention has higher triplet state energy level and proper HOMO and LUMO energy levels, can balance the distribution of electrons and holes in a luminescent layer, and improves the recombination probability of excitons, thereby realizing the maximum recombination of carriers and avoiding the roll-off of efficiency; in addition, the heterocyclic compound provided by the invention also has higher glass transition temperature, is not easy to crystallize during vapor deposition film formation, and has good film forming property and thermal stability. When the organic light-emitting diode is applied to an organic light-emitting diode as a main material of a light-emitting layer, the driving voltage of the device can be effectively reduced, the light-emitting efficiency of the device can be improved, and the service life of the device can be prolonged.

Detailed Description

The following description of the embodiments of the present invention will be made more complete and obvious by the following description of the embodiments of the present invention, wherein the embodiments are described in some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.

In the compounds of the present invention, any atom not designated as a particular isotope is included as any stable isotope of that atom, and includes atoms in both its natural isotopic abundance and non-natural abundance.

Examples of halogens described herein may include fluorine, chlorine, bromine and iodine.

The alkyl group according to the present invention is a generic term for monovalent groups obtained by removing one hydrogen atom from an alkane molecule, and may 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 alkyl group may 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, dodecyl and the like; the branched alkyl group includes, but is not limited to, isopropyl, isobutyl, sec-butyl, tert-butyl, an isomeric group of n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, and the like.

The alicyclic group according to the present invention means a monovalent group obtained by removing one hydrogen atom from an alicyclic hydrocarbon molecule, and may be a cycloalkyl group, a cycloalkenyl group, etc., preferably having 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, most preferably 3 to 7 carbon atoms, and examples may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, etc., but are not limited thereto.

Aryl in the context of the present invention is understood to mean the generic term for monovalent radicals obtained by removing one hydrogen atom from the aromatic nucleus of an aromatic compound molecule, which may be a monocyclic aryl, polycyclic aryl or fused ring aryl, preferably having from 6 to 30 carbon atoms, particularly preferably from 6 to 20 carbon atoms, most preferably from 6 to 12 carbon atoms. Aryl groups may be substituted or unsubstituted. The monocyclic aryl refers to aryl having only one aromatic ring in the molecule, such as phenyl, etc., but is not limited thereto; the polycyclic aryl group refers to an aryl group having two or more independent aromatic rings in the molecule, for example, biphenyl, terphenyl, etc., but is not limited thereto; the condensed ring aryl group refers to an aryl group having two or more aromatic rings in the molecule and condensed by sharing two adjacent carbon atoms with each other, for example, but not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylenyl, fluoranthryl, 9' -spirobifluorenyl, and the like.

Heteroaryl according to the present invention refers to the generic term for monovalent radicals obtained by substitution of one or more aromatic nucleus carbon atoms in an aryl group with heteroatoms, including but not limited to oxygen, sulfur, nitrogen, silicon or phosphorus atoms, preferably having 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, still preferably 2 to 12 carbon atoms, most preferably 2 to 7 carbon atoms. The heteroaryl group may be substituted or unsubstituted. The attachment site of the heteroaryl group may be located on a ring-forming carbon atom or on a ring-forming heteroatom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, a fused ring heteroaryl group, or the like. The monocyclic heteroaryl group includes, but is not limited to, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, and the like; the polycyclic heteroaryl group includes bipyridyl, bipyrimidinyl, phenylpyridyl, phenylpyrimidinyl, etc., but is not limited thereto; the condensed ring heteroaryl group includes, but is not limited to, quinolinyl, isoquinolinyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiazinyl, spirofluorene oxaanthracyl, spirofluorene thiaanthracyl, and the like.

The group formed by fusing an aromatic ring and an aliphatic ring refers to a monovalent group formed by fusing an aromatic ring and an aliphatic ring (cycloalkyl, cycloalkenyl, cycloalkynyl) together and removing one hydrogen atom. The aromatic ring is preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, most preferably 6 to 12 carbon atoms, the aliphatic ring is preferably 3 to 15 carbon atoms, still preferably 3 to 12 carbon atoms, most preferably 3 to 7 carbon atoms, and examples include benzocyclopropane group, benzocyclobutane group, benzocyclopentane group, benzocyclohexen group, benzocycloheptane group, benzocyclobutenyl group, benzocyclopentene group, benzocyclohexen group, benzocycloheptene group, naphthocyclopropane group, naphthocyclobutane group, naphthocyclopentane group, naphthocyclohexen group, naphthocyclopentene group, naphthocyclohexen group, and the like, but are not limited thereto.

"substituted" as used herein means that a hydrogen atom in a compound group is replaced with another atom or group, and the position of substitution is not limited.

"substituted or unsubstituted" as used herein means unsubstituted or mono-or polysubstituted with: protium, deuterium, tritium, cyano, nitro, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C3-C30 alicyclic, substituted or unsubstituted C2-C12 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C1-C12 alkylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylamino, and the like, but are not limited thereto, or when the substituents are plural, adjacent substituents may bond to a ring; when the substituent is plural, plural substituents are the same or different from each other. Deuterium, tritium, halogen, cyano, C1-C12 alkyl, C3-C12 alicyclic group, C6-C20 aryl, C3-C20 heteroaryl, specific examples may include deuterium, tritium, fluorine, chlorine, bromine, iodine, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropane group, cyclobutyl group, cyclopentanyl, cyclohexenyl, cyclopropenyl, cyclobutenyl, cyclopentadienyl, cyclohexanedienyl, adamantyl, norbornyl, benzocyclopropane group, benzocyclobutanyl, benzocyclopentenyl, benzocyclohexenyl, benzocycloheptanyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, perylenyl, pyrenyl, benzyl, pyridyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, acridinyl, phenanthroline, etc., but are not limited thereto.

In the specification, "-" means a moiety attached to another substituent. "-" may be attached at any optional position of the attached group/fragment. For example, the number of the cells to be processed,can indicate->Can representCan represent And so on.

In this specification, when a substituent or linkage site is located across two or more rings, it is meant that it may be attached to either of the two or two rings, in particular to either of the respective selectable sites of the rings. For example, the number of the cells to be processed,can indicate-> Can indicate->And so on.

As used herein, "adjacent groups are linked to each other to form a ring" means that adjacent groups are bonded to each other and optionally aromatized to form a substituted or unsubstituted aromatic, heteroaromatic or aliphatic ring. The ring formed by the connection may be a three-membered ring, four-membered ring, five-membered ring, six-membered ring or condensed ring, and further, the ring formed by the connection may be as follows: such as benzene, naphthalene, anthracene, phenanthrene, pyrene, indene, cyclopentene, cyclopentane, cyclopentaacene, cyclohexene, cyclohexane acene, pyridine, pyrimidine, quinoline, isoquinoline, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, but are not limited thereto.

As exemplified below:

the R is ₂ The halogen is selected from any one of hydrogen, deuterium, tritium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 alicyclic group, substituted or unsubstituted C6-C30 aryl, fused ring group of substituted or unsubstituted C3-C15 alicyclic and C6-C30 aromatic ring and group shown in a formula III; or phase ofTwo adjacent R ₂ Can be connected with each other to form a substituted or unsubstituted ring;

provided that the structure comprises at least one group of formula III:

the R is ₃ 、R ₄ 、R ₅ Independently selected from hydrogen, deuterium, tritium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C2-C15 alkenyl;

and the heterocyclic compound is not of the structure:

preferably, the heterocyclic compound is selected from any one of the following structures:

preferably, said R ₁ 、Ar ₁ 、Ar ₂ 、L ₁ 、L ₂ At least one of A comprises one or more groups of formula III.

Still more preferably, the R ₁ 、Ar ₁ 、Ar ₂ 、L ₁ 、L ₂ Comprising one or more groups of formula III.

More preferably, the Ar ₁ 、Ar ₂ Comprising one or more groups of formula III.

The R is ₁ 、Ar ₁ 、Ar ₂ 、L ₁ 、L ₂ At least one of A and A containing one or more compounds of formula III means that R ₁ 、Ar ₁ 、Ar ₂ 、L ₁ 、L ₂ At least one hydrogen atom in A is replaced by formula III; specifically, the Ar is ₁ Comprising at least one or more groups of formula III means Ar ₁ At least one hydrogen atom of said Ar is substituted with a group of formula III ₂ Comprising at least one or more groups of formula III means Ar ₂ At least one hydrogen atom of which is replaced by a group of the formula III, and so on.

Preferably, said R ₁ The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, a group shown in a formula III or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, cyclopropene, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, perylene, pyrenyl, A group, a benzocyclobutanyl group, a benzocyclopentanyl group, a benzocyclohexenyl group, a benzocyclobutenyl group, a benzocyclohexenyl group, an indenyl group, a fluorenyl group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group, an indolyl group, a carbazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinazolinyl group, a quinoxalinyl group, an acridinyl group, a phenanthroline group, a phenothiazinyl group, a phenoxazinyl group; or two adjacent R ₁ May be linked to each other to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, or a substituted or unsubstituted C3-C8 alicyclic ring.

Still more preferably, the R ₁ The groups are selected from the groups shown in the formula III identically or differently. In particular, R ₁ One, two or three or more of which are identically or differently selected from the groups of formula III.

The R is ₁ The substituent of the "substituted or unsubstituted" in (a) is selected from deuterium, tritium, halogen, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropane, cyclobutane, cyclopentane radicalOne or more of a cyclohexenyl group, an adamantyl group, a norbornyl group, a phenyl group, a biphenyl group, and a naphthyl group, and when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, the ring a is selected from any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, and a substituted or unsubstituted cinnolinyl group.

More preferably, the ring a is selected from any one of the following groups:

preferably, said R _a The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, a group shown in a formula III or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropenyl, cyclobutyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cycloheptenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, indenyl, fluorenyl, furanyl, benzofuranyl, dibenzofuranyl, thiophenyl, benzothienyl, dibenzothiophenyl, benzoxazolyl, benzothiophenyl Oxazolyl, benzimidazolyl, indolyl, carbazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl;

said d ₁ Selected from 1 or 2; said d ₂ Selected from 1, 2, 3 or 4; said d ₃ Selected from 1, 2, 3, 4, 5 or 6; said d ₄ Selected from 1; said d ₅ Selected from 1, 2 or 3; when two or more R's are present _a When two or more R' s _a Are the same as or different from each other.

The R is _a The substituent of the "substituted or unsubstituted" in (a) is selected from one or more of deuterium, tritium, halogen, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, naphthyl, and when two or more substituents are present, the two or more substituents may be the same or different from each other.

Preferably, the Ar ₁ 、Ar ₂ Independently selected from any one of the following groups:

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the R is ₂ The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, a group shown in a formula III or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocyclobutenyl, benzocyclo-alkyl, and mixtures thereof Pentenyl, benzocyclohexenyl, indenyl; or two adjacent R ₂ Can be connected with each other to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring or a substituted or unsubstituted C3-C8 alicyclic ring;

the R is _b The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocyclobutenyl, benzocyclohexenyl, indenyl;

said b ₁ Selected from 1, 2, 3, 4 or 5; said b ₂ Selected from 1, 2, 3, 4, 5, 6 or 7; said b ₃ Selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9; said b ₄ Selected from 1, 2, 3 or 4; said b ₅ Selected from 1 or 2; said b ₆ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; said b ₇ Selected from 1, 2 or 3; said b ₈ Selected from 1, 2, 3, 4, 5 or 6; said b ₉ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; when two or more R's are present ₂ 、R _b When two or more R' s ₂ 、R _b Are the same as or different from each other.

Still more preferably, the R ₂ The groups are selected from the groups shown in the formula III identically or differently. In particular, R ₂ One, two or three or more of which are identically or differently selected from the groups of formula III.

The R is ₂ 、R _b The substituents of the "substituted or unsubstituted" in (a) are selected from deuterium, tritium, halogen, cyano, trifluoromethyl, methyl,One or more of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, adamantyl, norbornyl, phenyl, biphenyl, and naphthyl, and when two or more substituents are present, the two or more substituents may be the same as or different from each other.

Preferably, said R ₃ 、R ₄ 、R ₅ Independently selected from hydrogen, deuterium, tritium, or any of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, ethylene, propylene, butene, pentene, heptene;

The R is ₃ ～R ₅ The substituent of the "substituted or unsubstituted" in (a) is selected from one or more of deuterium, tritium, halogen, cyano, trifluoromethyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, and when two or more substituents are present, the two or more substituents are the same or different from each other.

More preferably, the formula III is selected from any one of the following groups:

preferably, the L ₁ 、L ₂ Independently selected from a single bond or any one of the following groups:

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the R is ₆ The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, a group shown in a formula III or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butylIsobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexenyl, cycloheptyl, cyclooctyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, perylenyl, pyrenyl, and,A group, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, indenyl; or two adjacent R ₆ Can be connected with each other to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring or a substituted or unsubstituted C3-C8 alicyclic ring;

the R is _c The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, triphenylene, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, indenyl;

the c ₁ Selected from 1, 2, 3 or 4; the c ₂ Selected from 1, 2 or 3; the c ₃ Selected from 1 or 2; the c ₄ Selected from 1, 2, 3, 4, 5 or 6; the c ₅ Selected from 1, 2, 3, 4, 5, 6, 7 or 8; the c ₆ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; the c ₇ Selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; when two or more R's are present ₆ 、R _c When two or more R' s ₆ 、R _c Are the same as or different from each other.

Preferably, said R ₆ Are identically or differently selected from the group of formula IIIThe method comprises the steps of carrying out a first treatment on the surface of the In particular, R ₆ One, two or three or more of which are identically or differently selected from the groups of formula III.

The R is ₆ 、R _c The substituent of the "substituted or unsubstituted" in (a) is 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 and norbornane, and when two or more substituents are present, the two or more substituents may be the same or different from each other.

In one embodiment of the invention, the heterocyclic compound comprises at least two, or at least three, or at least four groups of formula III.

In one embodiment of the invention, the heterocyclic compound comprises no more than six, or no more than five, or no more than four, or no more than three, or no more than two groups of formula III.

Preferably, the heterocyclic compound comprises one, two, three, four or more groups of formula III.

Preferably, R ₁ 、R ₂ 、R ₆ One, two, three, four or more of which are identically or differently selected from the groups of formula III.

Preferably, R ₁ One, two or three of which are identically or differently selected from the groups of the formula III.

More preferably, R of formula I ₁ One of the radicals R of the formula II ₁ Is selected from the group of formula III, identically or differently.

Preferably, R ₂ One, two, three or four of which are identically or differently selected from the groups of the formula III.

More preferably, ar ₁ R of (2) ₂ One or two of which are identically or differently selected from the groups of the formula III. Alternatively, ar ₂ R of (2) ₂ One or two of them are identically or differently selected fromA group of formula III. Alternatively, ar ₁ R of (2) ₂ One or both of Ar ₂ R of (2) ₂ One or two of which are identical or different and are selected from the groups of the formula III.

Preferably, R ₆ One, two or three of which are identically or differently selected from the groups of the formula III.

In a preferred embodiment, R ₁ One or both of them and R ₂ One or two of which are identically or differently selected from the groups of the formula III. Alternatively, R ₁ One or both of them and R ₆ One or two of which are identically or differently selected from the groups of the formula III.

In a preferred embodiment, R ₂ One or both of them and R ₆ One or two of which are identically or differently selected from the groups of the formula III.

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

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the heterocyclic compounds of the present invention are exemplified above in terms of some specific structures, but the present invention is not limited to these chemical structures, and substituents are included as defined above, even if they are based on the structures shown.

Preferably, the organic electroluminescent device comprises an anode, a cathode and one or more organic layers, the organic layers being located between the anode and the cathode, the organic layers comprising at least one of the heterocyclic compounds according to the present invention.

Preferably, the organic layer comprises a light-emitting layer comprising at least one of the heterocyclic compounds described in the present invention.

Preferably, the light-emitting layer comprises a host material and a doping material, and the host material comprises at least one heterocyclic compound of the present invention.

The organic layer of the present 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, a capping layer, and the like.

The organic layer of the invention can be of a single-layer structure, a double-layer structure or a multi-layer structure, and meanwhile, each organic layer can also comprise a single-layer structure or a multi-layer structure, and the single-layer structure can be formed by a single substance or two or more substances. However, the structure of the organic electroluminescent device is not limited thereto, and may include fewer or more organic layers, for example, the hole transport layer includes a first hole transport layer and a second hole transport layer; the electron transport layer includes a first electron transport layer and a second electron transport layer.

The organic electroluminescent device of the present invention is generally formed on a substrate. The substrate may be a substrate made of glass, plastic, polymer film, silicon, or the like, as long as it is not changed when an electrode is formed or an organic layer is formed.

In the organic electroluminescent device according to the present invention, the anode material preferably uses a high work function material capable of promoting injection of holes into the organic layer. Specific examples of the anode material that can be used in the present invention may include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc 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), and the like, but are not limited thereto.

In the organic electroluminescent device of the present invention, the hole injection material is preferably a material having a good hole accepting ability. Specific examples of the hole injecting material that can be used in the present invention may include: silver oxide, vanadium oxide, tungsten oxide, copper oxide, titanium oxide, other metal oxides, phthalocyanine compounds, biphenylamine compounds, phenazine compounds, other materials, such as copper phthalocyanine (CuPc), titanyl phthalocyanine, N ' -diphenyl-N, N ' -di- [4- (N, N-diphenylamine) phenyl ] benzidine (NPNPB), N ' -tetra (4-methoxyphenyl) benzidine (MeO-TPD), and bisquinoxalino [2,3-a:2',3' -c ] phenazine (HATNA), 4',4 "-tris [ 2-naphthylphenylamino ] triphenylamine (2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazabenzophenanthrene (HAT-CN), 4',4" -tris (N, N-diphenylamino) triphenylamine (TDATA), and the like, but are not limited thereto.

In the organic electroluminescent device according to the present invention, the hole transport layer material is preferably a material having high hole mobility, and specific examples of the hole transport material that can be used in the present invention may include materials such as diphenylamine-based compounds, triphenylamine-based compounds, fluorene-based compounds, carbazole-based compounds, and the like, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (α -NPD), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 4- [1- [4- [ bis (4-methylphenyl) amino ] phenyl ] cyclohexyl ] -N- (3-methylphenyl) -N- (4-methylphenyl) aniline (TAPC), and the like, but is not limited thereto.

In the organic electroluminescent device, the luminescent layer material comprises a luminescent layer main body material and a luminescent layer doping material.

The host material of the light emitting layer may be selected from 4,4 '-bis (9-Carbazolyl) Biphenyl (CBP), 4' -bis (9-carbazolyl) -2,2 '-dimethylbiphenyl (CDBP), 9- (4-tert-butylphenyl) -3, 6-bis (triphenylsilyl) -9H-Carbazole (CZSi), 9' - (2, 6-pyridyldiyl-3, 1-phenylene) bis-9H-carbazole (26 DCZPPY), 9 '-diphenyl-9H, 9' H-3,3 '-dicarbazole (BCzPh), 9- (5- (3- (9H-carbazol-9-yl) phenyl) pyridin-3-yl) -9H-carbazole (CPPyC), 4' -bis (carbazol-9-yl) -2,2 '-dimethylbiphenyl (CDBP), 1, 3-bis (N-carbazolyl) benzene (MCP), 9-dimethyl-N, N-diphenyl-7- (4- (1-phenyl-1H-benzo [ d ] imidazol-2-yl) phenyl) -9H-fluoren-2-amine (EFIN), 10- (4' - (diphenylamino) biphenyl-4-yl) acridin-9 (10H) -one (ADBP), tris [4- (pyrenyl) -phenyl ] amine (TPyPA), 9, 10-bis (2-naphthyl) Anthracene (ADN), 2-tert-butyl-9, 10-bis (2-naphthyl) anthracene (TBADN), 1- (7- [9,9 '-dianthracen ] -10-yl-9, 9-dioctyl-9H-fluoren-2-yl) pyrene (BAnF 8 Pye), 9,9,9',9 '-tetrakis (4-methylphenyl) -2,2' -bi-9H-fluorene (BDAF), tris (6-fluoro-8-hydroxyquinoline) aluminum (6 FAlq 3), tris (8-hydroxyquinoline) aluminum (Alq 3), bis (10-hydroxybenzo [ H ] quinoline) beryllium (BeBq 2), bis (8-hydroxyquinoline) zinc (Znq 2), and the like, but are not limited thereto.

The light-emitting layer doping material can be selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA), 2,5,8, 11-tetra-tert-butylperylene (TBPe), 4' -di [4- (diphenylamino) styryl)]Biphenyl (BDAVBi), 4' -di [4- (di-p-tolylamino) styryl]Diphenyl (DPAVBi), bis (2-hydroxyphenylpyridine) beryllium (Bepp 2), bis (4, 6-difluorophenylpyridine-C2, N) iridium picolinate (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy) ₃ ) Bis (2-phenylpyridine) iridium acetylacetonate (Ir (ppy) ₂ (acac)), 9, 10-bis [ N- (p-tolyl) anilino group]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq) ₃ ) Ir (piq) iridium bis (1-phenylisoquinoline) (acetylacetonate) ₂ (acac)) and the like, but is not limited thereto.

In the organic electroluminescent device according to the present invention, the hole blocking layer material preferably has a low energy level, a wide band gap, and a material having a hole blocking ability, and specific examples of the hole blocking layer material that can be used in the present invention include: phenanthroline derivatives, rare earth derivatives, oxazole derivatives, triazole derivatives, triazine derivatives, and the like, but are not limited thereto.

In the organic electroluminescent device according to the present invention, the electron transport material is preferably a material having high electron mobility, and specific examples of the electron transport material that can be used in the present invention include: imidazoles, triazoles, phenanthroline derivatives, quinolines and the like, such as 2,9- (dimethyl) -4, 7-biphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris [ (3-pyridyl) -phenyl ] benzene (TmPyPB), 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- (naphthalen-2-yl) -4,7- (diphenyl) -1, 10-phenanthroline (hnephen), 8-hydroxyquinoline-lithium and the Like (LiQ), and the like, but are not limited thereto.

In the organic electroluminescent device according to the present invention, the electron injection material preferably has a small potential barrier difference from an adjacent organic transport material, host material, or the like, and at the same time has an effect of injecting electrons from the cathode. Examples of electron injection materials that can be used in the present invention include: alkali metal salts (e.g., liF, csF), alkaline earth metal salts (e.g., mgF) ₂ ) Metal oxides (such as Al ₂ O ₃ 、MoO ₃ ) But is not limited thereto.

In the organic electroluminescent device according to the present invention, the cathode material preferably has a low work function, and specific examples of the cathode material that can be used in the present invention may include: metals such as aluminum, magnesium, silver, indium, tin, titanium, and the like, and alloys thereof; multilayer metallic materials, e.g. LiF/Al, mg/Ag, li/Al, liO ₂ /Al、BaF ₂ Al, etc., but is not limited thereto.

In the organic electroluminescent device according to the present invention, the material for the cover layer is preferably a material for improving optical coupling. Specific examples of the cover layer material usable in the present invention include: arylamine derivatives, carbazole derivatives, benzimidazole derivatives, triazole derivatives, lithium fluoride, and the like, but are not limited thereto. The coating layer may be formed at the same time on the outer side of the anode and the outer side of the cathode, or may be disposed on the outer side of the anode or the outer side of the cathode, and preferably, the coating layer according to the present invention is disposed on the outer side of the cathode.

The thickness of each organic layer of the organic electroluminescent device is not particularly limited, and may be any thickness commonly used in the art.

The method for producing the thin films of each layer in the organic electroluminescent device of the present invention is not particularly limited, and vacuum deposition, sputtering, spin coating, spray coating, screen printing, laser transfer, etc. may be used, but are not limited thereto.

The organic electroluminescent device is mainly applied to the technical field of information display and the field of illumination, and is widely applied to various information displays in the aspect of information display, such as mobile phones, tablet computers, flat televisions, smart watches, VR, vehicle-mounted systems, digital cameras, wearable devices and the like.

Synthetic examples

The present invention is explained more fully by the following examples, but is not intended to be limited thereby. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue burden.

The method for producing the heterocyclic compound of the present invention is not particularly limited, and can be produced by methods known to those skilled in the art. The present invention provides a method for preparing the heterocyclic compound of the present invention, but the method for preparing the present invention is not limited thereto.

Method 1:

method 2:

the X is _a 、X _b 、X _c 、X _d 、X _e Independently selected from any one of I, br and Cl.

The present invention may bond the above substituents by methods known in the art, and the kind, position and number of substituents may be changed according to techniques known in the art.

Description of the starting materials, reagents and characterization equipment:

the raw materials and reagent sources used in the following examples are not particularly limited, and may be commercially available products or prepared by methods well known to those skilled in the art.

The mass spectrum uses a Waters G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer, chloroform as solvent.

The elemental analysis was performed using a Vario EL cube organic elemental analyzer from Elementar, germany.

Synthesis example 1: preparation of raw material b-63:

to the reaction flask were added g-63 (16.58 g,60.00 mmol), h-63 (17.03 g,60.00 mmol), tetrakis (triphenylphosphine) palladium (0.55 g,0.75 mmol), potassium carbonate (16.59 g,120 mmol) and 300mL (toluene: ethanol: water=2:1:1) of the mixed solvent under argon atmosphere, and stirred under reflux for 5 hours. After the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, and toluene was used: ethanol=10:1 recrystallisation, drying gives starting material b-63 (14.89 g, 81% yield), HPLC purity ≡99.81%. Mass spectrum m/z:305.0249 (theory: 305.0235).

The raw materials were replaced correspondingly, and the raw materials b were prepared according to the preparation method of the raw materials b-63 in synthetic example 1, and the raw materials are shown in the following table:

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synthesis example 2: preparation of Compound 2

A reaction flask was charged with a-2 (12.67 g,20.00 mmol), b-2 (7.53 g,25.00 mmol), copper powder (1.59 g,25.00 mmol), 18-crown-6 (0.53 g,2.00 mmol), K under argon ₂ CO ₃ (6.91 g,50.00 mmol), and 1, 2-dichlorobenzene (150 ml) were stirred under reflux for 20 hours. After the reaction was completed, cooled to room temperature, distilled water was added, extraction was performed with methylene chloride, the organic phase was dried over anhydrous magnesium sulfate, filtration was performed, the filtrate was concentrated by distillation under reduced pressure, recrystallization was performed with toluene, and drying was performed to obtain compound 2 (8.67 g, yield 75%); the purity of the solid detected by HPLC is not less than 99.97%. Mass spectrum m/z:577.2382 (theory: 577.2370). Theoretical element content (%) C ₃₇ H ₃₅ N ₃ Si ₂ : c,76.90; h,6.11; n,7.27. Measured element content (%): c,76.87; h,6.07; n,7.31.

Synthesis example 3: preparation of Compound 3

According to the preparation method of synthetic example 2, a-2 and b-2 were replaced with equimolar amounts of a-3 and b-3 to give compound 3 (8.07 g) with an HPLC purity of 99.98%. Mass spectrum m/z:530.2168 (theory: 530.2178). Theoretical element content (%) C ₃₇ H ₃₀ N ₂ Si: c,83.73; h,5.70; n,5.28. Measured element content (%): c,83.75; h,5.67; n,5.32.

Synthesis example 4: preparation of Compound 8

Under the protection of argonNext, a-8 (5.33 g,20.00 mmol), b-8 (11.46 g,50.00 mmol), copper powder (3.18 g,50.00 mmol), 18-crown-6 (0.53 g,2.00 mmol), potassium carbonate (13.82 g,100.00 mmol), and 1, 2-dichlorobenzene (250 ml) were charged into the reaction flask, and stirred under reflux for 20 hours. After the reaction was completed, cooled to room temperature, distilled water was added, extraction was performed with methylene chloride, the organic phase was dried over anhydrous magnesium sulfate, filtration was performed, the filtrate was concentrated by distillation under reduced pressure, recrystallization was performed with toluene, and drying was performed to obtain compound 8 (8.56 g, yield 76%); the purity of the solid detected by HPLC is not less than 99.98%. Mass spectrum m/z:562.3057 (theory: 562.3045). Theoretical element content (%) C ₃₅ H ₂₆ D ₁₀ N ₂ Si ₂ : c,76.81; h,8.23; n,4.98. Measured element content (%): c,76.78; h,8.25; n,5.01.

Synthesis example 5: preparation of Compound 10

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-10 and b-10 to give Compound 10 (7.95 g), with HPLC purity of ≡99.97%. Mass spectrum m/z:522.2479 (theory: 522.2491). Theoretical element content (%) C ₃₆ H ₃₄ N ₂ Si: c,82.71; h,6.56; n,5.36. Measured element content (%): c,82.73; h,6.57; n,5.38.

Synthesis example 6: preparation of Compound 18

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-18 and b-18, to obtain compound 18 (9.10 g), with HPLC purity of ≡99.97%. Mass spectrum m/z:606.2482 (theory: 606.2491). Theoretical element content (%) C ₄₃ H ₃₄ N ₂ Si: c,85.11; h,5.65; n,4.62. Measured element content (%): c,85.09; h,5.62; n,4.63.

Synthesis example 7: preparation of Compound 32

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-32 and b-32 to obtain compound 32 (8.61 g), with HPLC purity of ≡99.96%. Mass spectrum m/z:566.1974 (theory: 566.1990). Theoretical element content (%) C ₃₇ H ₂₈ F ₂ N ₂ Si: c,78.42; h,4.98; n,4.94. Measured element content (%): c,78.47; h,5.02; n,4.90.

Synthesis example 8: preparation of Compound 37

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-37 and b-37, to obtain Compound 37 (9.35 g), with an HPLC purity of ≡99.95%. Mass spectrum m/z:631.2459 (theory: 631.2444). Theoretical element content (%) C ₄₄ H ₃₃ N ₃ Si: c,83.64; h,5.26; n,6.65. Measured element content (%): c,83.67; h,5.28; n,6.64.

Synthesis example 9: preparation of Compound 63

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According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-63 and b-63 to obtain compound 63 (9.13 g), with an HPLC purity of ≡99.96%. Mass spectrum m/z:608.2381 (theory: 608.2396). Theoretical element content (%) C ₄₁ H ₃₂ N ₄ Si: c,80.89; h,5.30; n,9.20. Measured element content (%): c,80.92; h,5.29; n,9.75.

Synthesis example 10: preparation of Compound 89

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-89, b-89 to give compound 89 (9.10 g) with an HPLC purity of > 99.97%. Mass spectrum m/z:606.2502 (theory: 606.2491). Theoretical element content (%) C ₄₃ H ₃₄ N ₂ Si: c,85.11; h,5.65; n,4.62. Measured element content (%): c,85.15; h,5.63; n,4.64.

Synthesis example 11: preparation of Compound 103

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-103 and b-103, to obtain compound 103 (9.87 g), with HPLC purity of ≡99.95%. Mass spectrum m/z:666.2320 (theory: 666.2303). Theoretical element content (%) C ₄₅ H ₃₂ F ₂ N ₂ Si: c,81.05; h,4.84; n,4.20. Measured element content (%): c,81.01; h,4.86; n,4.19.

Synthesis example 12: preparation of Compound 145

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-145, b-145 to give compound 145 (9.83 g) with an HPLC purity of > 99.94%. Mass spectrum m/z:672.2973 (theory: 672.2961). Theoretical element content (%) C ₄₈ H ₄₀ N ₂ Si: c,85.67; h,5.99; n,4.16. Measured element content (%): c,85.69; h,6.02; n,4.14.

Synthesis example 13: preparation of Compound 165

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Preparation of A-165:

to the flask were added c-165 (25.17 g,100.00 mmol), d-165 (38.16 g,125.00 mmol), copper powder (7.94 g,125.00 mmol), 18-crown-6 (2.64 g,10.00 mmol), potassium carbonate (27.64 g,200.00 mmol) and 1, 2-dichlorobenzene (600 ml) under reflux and stirred for 10 hours under argon. After the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated by distillation under reduced pressure, recrystallized from toluene, and dried to give A-165 (40.94 g, yield 86%); the purity of the solid detected by HPLC is not less than 99.75%. Mass spectrum m/z:475.1535 (theory: 475.1523).

Preparation of B-165:

a-165 (38.09 g,80.00 mmol), pinacol biborate (20.32 g,80.00 mmol), 1-bis (diphenylphosphine) ferrocene palladium dichloride (0.66 g,0.90 mmol), potassium acetate (15.70 g,160.00 mmol), DMF (400 ml) were added to the flask under argon and stirred under reflux for 6 hours. After the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, and toluene was used: methanol=5: 1 recrystallisation and drying to give B-165 (37.69 g, 83%); HPLC detection of solid purity ∈ 99.68%. Mass spectrum m/z:567.2751 (theory: 567.2765).

Preparation of C-165:

b-165 (34.06 g,60.00 mmol), e-165 (12.12 g,60.00 mmol), pd (PPh) were added to the flask under argon ₃ ) ₄ (0.69 g,0.60 mmol), potassium carbonate (16.59 g,120.00 mmol), THF (300 ml) and water (150 ml) were stirred under reflux for 8 hours. After the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, and toluene was used: methanol=10: 1 recrystallisation and drying to give C-165 (27.35 g, 81%); the purity of the solid detected by HPLC is not less than 99.79%. Mass spectrum m/z:562.2092 (theory: 562.2077).

Preparation of D-165:

to the flask, C-165 (22.51 g,40.00 mmol), triphenylphosphine (26.23 g,100.00 mmol) and o-dichlorobenzene (200 ml) were added under argon and stirred under reflux for 14 hours. After the reaction was completed, cooled to room temperature, distilled water was added, extracted with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by distillation under reduced pressure, and toluene was used: ethanol=10: 1 recrystallisation and drying to give D-165 (16.13 g, 76%); the purity of the solid detected by HPLC is not less than 99.89%. Mass spectrum m/z:530.2199 (theory: 530.2178).

Preparation of compound 165:

to the reaction flask were added D-165 (10.61 g,20.00 mmol), D-165 (3.82 g,25.00 mmol), copper powder (1.59 g,25.00 mmol), 18-crown-6 (0.53 g,2.00 mmol), potassium carbonate (6.91 g,50.00 mmol), and 1, 2-dichlorobenzene (100 ml) under reflux and stirred for 20 hours under reflux. After the completion of the reaction, cooled to room temperature, distilled water was added, extraction was performed with methylene chloride, and the organic phase was dried over anhydrous magnesium sulfate, filtration, concentration of the filtrate by distillation under reduced pressure, recrystallization from toluene and drying were performed to obtain compound 165 (9.57 g, yield 74%); the purity of the solid detected by HPLC is not less than 99.96%. Mass spectrum m/z:646.2819 (theory: 646.2804). Theoretical element content (%) C ₄₆ H ₃₈ N ₂ Si: c,85.41; h,5.92; n,4.33. Measured element content (%): c,85.38; h,5.93; n,4.37.

Synthesis example 14: preparation of Compound 169

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-169 and b-3, whereby Compound 169 (7.50 g) was obtained with an HPLC purity of ≡99.98%. Mass spectrum m/z:480.2036 (theory: 480.2022). Theoretical element content (%) C ₃₃ H ₂₈ N ₂ Si: c,82.46; h,5.87; n,5.83. Measured element content (%): c,82.42; h,5.91; n,5.85.

Synthesis example 15: preparation of Compound 172

According to the preparation method of synthetic example 2, a-2 and b-2 are replaced by equimolar a-172. b-3, to give compound 172 (9.22 g) with an HPLC purity of > 99.98%. Mass spectrum m/z:614.3129 (theory: 614.3117). Theoretical element content (%) C ₄₃ H ₄₂ N ₂ Si: c,83.99; h,6.88; n,4.56. Measured element content (%): c,84.03; h,6.91; n,4.54.

Synthesis example 16: preparation of Compound 179

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-179, b-179 to give compound 179 (9.16 g) with an HPLC purity of > 99.98%. Mass spectrum m/z:610.3089 (theory: 610.3076). Theoretical element content (%) C ₄₀ H ₃₀ D ₈ N ₂ Si ₂ : c,78.63; h,7.59; n,4.59. Measured element content (%): c,78.66; h,7.61; n,4.57.

Synthesis example 17: preparation of Compound 185

The preparation of Synthesis example 4 was followed by substituting a-8, b-8 with equimolar a-185, b-3 to give compound 185 (10.18 g) with an HPLC purity of ≡99.96%. Mass spectrum m/z:696.3216 (theory: 696.3208). Theoretical element content (%) C ₄₂ H ₅₂ N ₂ Si ₄ : c,72.35; h,7.52; n,4.02. Measured element content (%): c,72.39; h,7.49; n,4.05.

Synthesis example 18: preparation of Compound 198

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-198 and b-198 to obtain compound 198 (8.74 g), with HPLC purity of 99.97%. Mass spectrum m/z:574.2255 (theory: 574.2241). Theoretical element content (%) C ₃₉ H ₃₁ FN ₂ Si: c,81.50; h,5.44; n,4.87. Measured element content (%): c,81.45; h,5.46; n,4.86.

Synthesis example 19: preparation of Compound 199

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-199, b-199 to give compound 199 (10.15 g) with an HPLC purity of > 99.94%. Mass spectrum m/z:704.3054 (theory: 704.3043). Theoretical element content (%) C ₄₈ H ₄₄ N ₂ Si ₂ : c,81.77; h,6.29; n,3.97. Measured element content (%): c,81.80; h,6.31; n,3.95.

Synthesis example 20: preparation of Compound 219

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-219, b-3 to give compound 219 (9.22 g) with an HPLC purity of > 99.98%. Mass spectrum m/z:606.2479 (theory: 606.2491). Theoretical element content (%) C ₄₃ H ₃₄ N ₂ Si: c,85.11; h,5.65; n,4.62. Measured element content (%): c,85.16; h,5.61; n,4.65.

Synthesis example 21: preparation of Compound 228

The preparation of Synthesis example 4 was followed by substituting a-8, b-8 with equimolar a-228, b-228 to give 228 (11.27 g) as a compound with an HPLC purity of 99.92%. Mass spectrum m/z:804.3372 (theory: 804.3356). Theoretical element content (%) C ₅₆ H ₄₈ N ₂ Si ₂ : c,83.54; h,6.01; n,3.48. Measured element content (%): c,83.57; h,5.98; n,3.45.

Synthesis example 22: preparation of Compound 258

According to the preparation method of Synthesis example 13, c-165, d-165 and f-165 are replaced with equimolar amounts of c-251, d-258 and f-258, to obtain compound 258 (10.55 g), with HPLC purity of ≡ 99.93%. Mass spectrum m/z:742.3478 (theory: 742.3492). Theoretical element content (%) C ₅₁ H ₄₆ N ₄ Si: c,82.44; h,6.24; n,7.54. Measured element content (%): c,82.45; h,6.27; n,7.52.

Synthesis example 23: preparation of Compound 259

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-259 and b-3 to obtain compound 259 (8.17 g) having an HPLC purity of 99.98%. Mass spectrum m/z:530.2193 (theory: 530.2178). Theoretical element content (%) C ₃₇ H ₃₀ N ₂ Si: c,83.73; h,5.70; n,5.28. Measured element content (%): c,83.79; h,5.68; n,5.26.

Synthesis example 24: preparation of Compound 263

According to the preparation method of Synthesis example 13, c-165, d-165 and f-165 were replaced with equimolar amounts of c-263, b-3 and f-263 to give compound 263 (9.97 g) with an HPLC purity of ≡ 99.95%. Mass spectrum m/z:682.2821 (theory: 682.2804). Theoretical element content (%) C ₄₉ H ₃₈ N ₂ Si: c,86.18; h,5.61; n,4.10. Measured element content (%): c,86.20; h,5.58; n,4.08.

Synthesis example 25: preparation of Compound 279

Following the procedure for the preparation of Synthesis example 4, substituting a-8, b-8 with equimolar amounts of a-279, b-279, compound 279 (11.24 g) was obtained with an HPLC purity of ≡99.91%. Mass spectrum m/z:802.3191 (theory: 802.3200). Theoretical element content (%) C ₅₆ H ₄₆ N ₂ Si ₂ : c,83.75; h,5.77; n,3.49. Measured element content (%): c,83.78; h,5.81; n,3.47.

Synthesis example 26: preparation of Compound 289

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar amounts of a-289, b-289 to give compound 289 (9.35 g) with an HPLC purity of ≡99.96%. Mass spectrum m/z:631.2457 (theory: 631.2444). Theoretical element content (%) C ₄₄ H ₃₃ N ₃ Si: c,83.64; h,5.26; n,6.65. Measured element content (%): c,83.69; h,5.24; n,6.66.

Synthesis example 27: preparation of Compound 291

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-291 and b-291, to obtain Compound 291 (8.23 g), with an HPLC purity of ≡99.97%. Mass spectrum m/z:541.2069 (theory: 541.2054). Theoretical element content (%) C ₃₈ H ₂₃ D ₃ N ₂ Si: c,84.25; h,5.39; n,5.17. Measured element content (%): c,84.24; h,5.41; n,5.20.

Synthesis example 28: preparation of Compound 308

According to synthetic example 2The preparation method replaces a-2 and b-2 with equimolar a-308 and b-3 to obtain a compound 308 (8.28 g), wherein the HPLC purity is not less than 99.98%. Mass spectrum m/z:530.2196 (theory: 530.2178). Theoretical element content (%) C ₃₇ H ₃₀ N ₂ Si: c,83.73; h,5.70; n,5.28. Measured element content (%): c,83.75; h,5.67; n,5.33.

Synthesis example 29: preparation of Compound 332

Following the procedure for the preparation of Synthesis example 4 substituting a-8 with equimolar a-332, compound 332 (9.66 g) was obtained with an HPLC purity of ≡ 99.96%. Mass spectrum m/z:652.2715 (theory: 652.2730). Theoretical element content (%) C ₄₄ H ₄₀ N ₂ Si ₂ : c,80.93; h,6.17; n,4.29. Measured element content (%): c,80.96; h,6.19; n,4.26.

Synthesis example 30: preparation of Compound 335

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-335 and b-335, to obtain compound 335 (9.45 g), with an HPLC purity of ≡99.97%. Mass spectrum m/z:629.3231 (theory: 629.3213). Theoretical element content (%) C ₄₄ H ₂₇ D ₉ N ₂ Si: c,83.90; h,7.20; n,4.45. Measured element content (%): c,83.85; h,7.17; n,4.51.

Synthesis example 31: preparation of Compound 337

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According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-337 and b-3 to obtain compound 337 (9.10 g), with HPLC purity of 99.98%. Mass spectrum m/z:606.2501 (theory: 606.2491). Theoretical elementElement content (%) C ₄₃ H ₃₄ N ₂ Si: c,85.11; h,5.65; n,4.62. Measured element content (%): c,85.09; h,5.66; n,4.65.

Synthesis example 32: preparation of Compound 365

The preparation method of Synthesis example 4 was followed by substituting a-8 and b-8 with equimolar amounts of a-365 and b-365 to give compound 365 (10.72 g) with an HPLC purity of 99.96%. Mass spectrum m/z:754.3219 (theory: 754.3200). Theoretical element content (%) C ₅₂ H ₄₆ N ₂ Si ₂ : c,82.71; h,6.14; n,3.71. Measured element content (%): c,82.75; h,6.16; n,3.68.

Synthesis example 33: preparation of Compound 402

The preparation of synthetic example 4 was followed by substituting a-8, b-8 with equimolar a-365, b-402 to give compound 402 (11.80 g) with an HPLC purity of > 99.94%. Mass spectrum m/z:854.3525 (theory: 854.3513). Theoretical element content (%) C ₆₀ H ₅₀ N ₂ Si ₂ : c,84.26; h,5.89; n,3.28. Measured element content (%): c,84.29; h,5.91; n,3.25.

Synthesis example 34: preparation of Compound 415

According to the preparation method of Synthesis example 13, c-165, d-165 and f-165 were replaced with equimolar amounts of c-415, d-415 and f-415, to obtain compound 415 (10.51 g), with HPLC purity ≡ 99.92%. Mass spectrum m/z:739.3221 (theory: 739.3211). Theoretical element content (%) C ₅₁ H ₃₇ D ₃ N ₄ Si: c,82.78; h,5.86; n,7.57. Measured element content (%):C,82.81；H,5.87；N,7.55。

synthesis example 35: preparation of Compound 428

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-428, b-428 to give compound 428 (9.47 g) with an HPLC purity of > 99.95%. Mass spectrum m/z:639.3069 (theory: 639.3056). Theoretical element content (%) C ₄₅ H ₂₅ D ₉ N ₂ Si: c,84.46; h,6.77; n,4.38. Measured element content (%): c,84.42; h,6.80; n,4.41.

Synthesis example 36: preparation of Compound 433

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-433 and b-433, to obtain compound 433 (9.69 g) with HPLC purity of 99.96%. Mass spectrum m/z:654.2505 (theory: 654.2491). Theoretical element content (%) C ₄₇ H ₃₄ N ₂ Si: c,86.20; h,5.23; n,4.28. Measured element content (%): c,86.15; h,5.26; n,4.32.

Synthesis example 37: preparation of Compound 455

According to the preparation method of Synthesis example 13, c-165, d-165 and f-165 were replaced with equimolar amounts of c-415, b-3 and f-455, to obtain compound 455 (10.44 g) with an HPLC purity of ≡ 99.93%. Mass spectrum m/z:734.2879 (theory: 734.2866). Theoretical element content (%) C ₅₁ H ₃₈ N ₄ Si: c,83.34; h,5.21; n,7.62. Measured element content (%): c,83.38; h,5.25; n,7.57.

Synthesis example 38: preparation of Compound 465

According to the preparation method of Synthesis example 4, a-8 and b-8 were replaced with equimolar amounts of a-465 and b-465, to give compound 465 (8.56 g), with HPLC purity ≡ 99.97%. Mass spectrum m/z:562.3060 (theory: 562.3045). Theoretical element content (%) C ₃₆ H ₂₆ D ₁₀ N ₂ Si ₂ : c,76.81; h,8.23; n,4.98. Measured element content (%): c,76.79; h,8.25; n,5.03.

Synthesis example 39: preparation of Compound 491

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-491 and b-491 to give compound 491 (9.97 g), with HPLC purity ≡99.94%. Mass spectrum m/z:682.2812 (theory: 682.2804). Theoretical element content (%) C ₄₉ H ₃₈ N ₂ Si: c,86.18; h,5.61; n,4.10. Measured element content (%): c,86.22; h,5.58; n,4.06.

Synthesis example 40: preparation of Compound 508

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-508, b-508 to give compound 508 (9.80 g) with an HPLC purity of > 99.95%. Mass spectrum m/z:661.2926 (theory: 661.2913). Theoretical element content (%) C ₄₆ H ₃₉ N ₃ Si: c,83.47; h,5.94; n,6.35. Measured element content (%): c,83.50; h,5.99; n,6.31.

Synthesis example 41: preparation of Compound 514

According to the preparation method of Synthesis example 13, c-165, d-165 and f-165 were replaced with equimolar amounts of c-514, d-514 and f-514, to obtain compound 514 (9.86 g), with HPLC purity of ≡ 99.96%. Mass spectrum m/z:674.2985 (theory: 674.2969). Theoretical element content (%) C ₄₃ H ₄₆ N ₂ Si ₃ : c,76.50; h,6.87; n,4.15. Measured element content (%): c,76.52; h,6.91; n,4.13.

Synthesis example 42: preparation of Compound 559

The preparation method of Synthesis example 2 was followed by substituting a-2 and b-2 with equimolar amounts of a-559 and b-89 to give compound 559 (9.97 g) having an HPLC purity of ≡99.97%. Mass spectrum m/z:682.2819 (theory: 682.2804). Theoretical element content (%) C ₄₉ H ₃₈ N ₂ Si: c,86.18; h,5.61; n,4.10. Measured element content (%): c,86.23; h,5.59; n,4.05.

Synthesis example 43: preparation of Compound 594

The preparation of synthetic example 2 was followed by substituting a-2, b-2 with equimolar a-594, b-594 to give compound 594 (9.83 g) with an HPLC purity of ∈ 99.95%. Mass spectrum m/z:663.3054 (theory: 663.3070). Theoretical element content (%) C ₄₆ H ₄₁ N ₃ Si: c,83.22; h,6.22; n,6.33. Measured element content (%): c,83.26; h,6.24; n,6.29.

Synthesis example 44: preparation of Compound 613

Following the preparation method of Synthesis example 2, a-2, b-2 were replaced with equimolar amounts of a-613, b-613 to give compound 613 (8.51 g),HPLC purity. Mass spectrum m/z:559.2192 (theory: 559.2192). Theoretical element content (%) C ₃₆ H ₂₉ N ₅ Si: c,77.25; h,5.22; n,12.51. Measured element content (%): c,77.29; h,5.19; n,12.47.

Synthesis example 45: preparation of Compound 619

According to the preparation method of Synthesis example 13, c-165, d-165 and f-165 were replaced with equimolar amounts of c-619, d-619 and f-619, to give compound 619 (8.65 g) having an HPLC purity of ≡ 99.96%. Mass spectrum m/z:568.2323 (theory: 568.2335). Theoretical element content (%) C ₄₀ H ₃₂ N ₂ Si: c,84.47; h,5.67; n,4.93. Measured element content (%): c,84.45; h,5.71; n,4.95.

Synthesis example 46: preparation of Compound 621

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-621 and b-621 to obtain compound 621 (8.25 g), with HPLC purity ≡ 99.98%. Mass spectrum m/z:542.2195 (theory: 542.2178). Theoretical element content (%) C ₃₈ H ₃₀ N ₂ Si: c,84.09; h,5.57; n,5.16. Measured element content (%): c,84.13; h,5.55; n,5.17.

Synthesis example 47: preparation of Compound 638

According to the preparation method of Synthesis example 2, a-2 and b-2 were replaced with equimolar amounts of a-638 and b-638, to obtain compound 638 (9.78 g), with HPLC purity of 99.96%. Mass spectrum m/z:660.2881 (theory: 660.2899). Theoretical element content (%) C ₄₇ H ₃₂ D ₄ N ₂ Si：C,85.41; h,6.10; n,4.24. Measured element content (%): c,85.37; h,6.08; n,4.27.

Device example 1

Firstly, placing a glass substrate on which ITO/Ag/ITO is evaporated in distilled water for cleaning for 2 times, washing for 30 minutes by ultrasonic waves, repeatedly cleaning for 2 times by using distilled water, washing by ultrasonic waves for 10 minutes, after the distilled water is cleaned, sequentially washing by using isopropanol, acetone and methanol solvents by ultrasonic waves, drying on a hot plate heated to 120 ℃, transferring to a plasma cleaning machine after drying, and transferring the substrate to a vapor deposition machine after washing for 5 minutes.

Then, HI-1 was evaporated on the cleaned ITO/Ag/ITO substrate as a hole injection layer with an evaporation thickness of 10nm, HT-1 was evaporated on the hole injection layer as a hole transport layer with an evaporation thickness of 60nm, then a mixture of the compound 2, H2-1 and GD-1 according to the present invention (with a mass ratio of 47:47:6) was vacuum evaporated on the hole transport layer to form a light-emitting layer with an evaporation thickness of 35nm, ET-1 and Liq (with a mass ratio of 1:1) were evaporated on the light-emitting layer as an electron transport layer with an evaporation thickness of 40nm, liF was evaporated on the electron transport layer as an electron injection layer with an evaporation thickness of 1nm, mg: ag (with a mass ratio of 1:9) was evaporated on the electron injection layer with an evaporation thickness of 20nm, and then vacuum CP-1 was evaporated on the cathode as a cover layer with an evaporation thickness of 60nm, thereby preparing an organic electroluminescent device 1 (the material structure of each functional layer in the organic electroluminescent device preparation process is as follows).

Device examples 2 to 35

The organic electroluminescent devices 2 to 35 were produced by replacing the compound 2 in the light-emitting layer of example 1 with the compound 8, the compound 18, the compound 32, the compound 63, the compound 89, the compound 103, the compound 165, the compound 169, the compound 172, the compound 179, the compound 185, the compound 199, the compound 219, the compound 228, the compound 259, the compound 263, the compound 279, the compound 289, the compound 308, the compound 332, the compound 335, the compound 337, the compound 365, the compound 402, the compound 415, the compound 428, the compound 455, the compound 465, the compound 508, the compound 514, the compound 594, the compound 613, the compound 621, the compound 638, and the other steps.

Comparative device examples 1 to 3

The comparative devices 1 to 3 were prepared by substituting the compound 2 in the light-emitting layer of example 1 with R-1, R-2, R-3, respectively, in the same manner.

Test software, a computer, a K2400 digital source list manufactured by Keithley company in U.S. and a PR788 spectrum scanning luminance meter manufactured by Photo Research company in U.S. are combined into a combined IVL test system to test the driving voltage and luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature.

Examples 1 to 35 of the inventive devices, and comparative examples 1 to 3 of the comparative devices, the results of the light emitting characteristics of the organic electroluminescent devices obtained are shown in table 1 below.

Table 1 light emission characteristic test data of organic electroluminescent device

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As can be seen from the results in table 1, the heterocyclic compound of the present invention has lower driving voltage, higher luminous efficiency and longer service life when being used as a host material of a light emitting layer of an organic electroluminescent device, compared to a comparative device.

Device example 36

The organic electroluminescent device 37 was prepared by evaporating HI-1 as a hole injection layer, evaporating LiF as an electron injection layer to a thickness of 15nm, evaporating HT-1 as a hole transport layer on the hole injection layer to a thickness of 50nm, vacuum evaporating a mixture (mass ratio of 45:45:10) of the compound 2, H2-1 and RD-1 of the present invention on the hole transport layer to form a light-emitting layer, evaporating ET-1 and Liq (mass ratio of 1:1) as electron transport layers on the light-emitting layer to a thickness of 40nm, evaporating LiF as an electron injection layer on the electron transport layer to a thickness of 1nm, evaporating Mg to Ag (mass ratio of 1:9) as a cathode on the electron injection layer to a thickness of 10nm, and vacuum evaporating CP-1 as a cover layer on the cathode to a thickness of 70 nm.

Device examples 37 to 70

The organic electroluminescent devices 37 to 70 were fabricated by replacing compound 2 in the light-emitting layer of example 1 with compound 3, compound 8, compound 10, compound 18, compound 37, compound 89, compound 145, compound 172, compound 179, compound 185, compound 198, compound 199, compound 219, compound 228, compound 258, compound 259, compound 263, compound 279, compound 291, compound 308, compound 332, compound 335, compound 337, compound 365, compound 402, compound 428, compound 433, compound 465, compound 491, compound 514, compound 559, compound 613, compound 621, compound 638, and the like, respectively.

Comparative device examples 4 to 6

The comparative devices 4 to 6 were prepared by substituting the compound 2 in the light-emitting layer of example 36 with R-1, R-2, R-3, respectively, and the other steps were the same.

The results of the light emitting characteristics test of the organic electroluminescent devices obtained in device examples 36 to 70 according to the present invention, and comparative device examples 4 to 6 are shown in table 2 below.

Table 2 light emission characteristic test data of organic electroluminescent device

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As can be seen from the results of table 2, the device has lower driving voltage, higher luminous efficiency and longer service life when the heterocyclic compound of the present invention is used as a host material of a light-emitting layer of an organic electroluminescent device, compared to a comparative device.

It should be noted that while the present invention has been specifically described with reference to individual embodiments, it will be apparent to those skilled in the art that numerous modifications and variations can be made without departing from the principles of the present invention, and such modifications and variations fall within the scope of the present invention.

Claims

1. A heterocyclic compound, wherein the heterocyclic compound has the structure:

said a is selected from 1, 2, 3 or 4; when presentTwo or more R ₁ When two or more R' s ₁ Are the same as or different from each other;

the L is ₁ 、L ₂ Independently selected from single bond or lowerAny one of the column groups;

provided that the structure comprises at least one group of formula III:

and the heterocyclic compound is not of the structure:

2. the heterocyclic compound according to claim 1, wherein R ₁ The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, a group shown in a formula III or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, cyclopropene, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylene, perylene, pyrenyl,a group, a benzocyclobutanyl group, a benzocyclopentanyl group, a benzocyclohexenyl group, a benzocyclobutenyl group, a benzocyclohexenyl group, an indenyl group, a fluorenyl group, a furanyl group, a benzofuranyl group, a dibenzofuranyl group, a thienyl group, a benzothienyl group, a dibenzothienyl group, a benzoxazolyl group, a benzothiazolyl group, a benzimidazolyl group, an indolyl group, a carbazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a quinazolinyl group, a quinoxalinyl group, an acridinyl group, a phenanthroline group, a phenothiazinyl group, a phenoxazinyl group; or two adjacent R ₁ May be linked to each other to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, or a substituted or unsubstituted C3-C8 alicyclic ring.

3. The heterocyclic compound according to claim 1, wherein the ring a is preferably selected from any one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted cinnolinyl group.

4. The heterocyclic compound according to claim 1, wherein Ar ₁ 、Ar ₂ Independently selected from any one of the following groups:

The R is ₂ The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, a group shown in a formula III or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentenyl, cyclohexenyl, adamantyl, norbornyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthrenyl, triphenylenyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, benzocyclobutenyl, benzocyclohexenyl, indenyl; or two adjacent R ₂ Can be connected with each other to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, or a substitutedOr an unsubstituted phenanthrene ring, a substituted or unsubstituted pyridine ring, a substituted or unsubstituted pyrimidine ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, or a substituted or unsubstituted C3-C8 alicyclic ring;

5. The heterocyclic compound according to claim 1, wherein the formula III is selected from any one of the following groups:

6. the heterocyclic compound according to claim 1, wherein L ₁ 、L ₂ Independently selected from a single bond or any one of the following groups:

the R is ₆ The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, a group shown in a formula III or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, cyclopropane, cyclobutyl, cyclopentane, cyclohexane, cycloheptane, cyclooctane, adamantane, norbornane, cyclopropene, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, triphenylene, perylene, pyrenyl, A group, benzocyclobutanyl, benzocyclopentanyl, benzocyclohexenyl, benzocyclobutenyl, benzocyclopentenyl, benzocyclohexenyl, indenyl; or two adjacent R ₆ Can be connected with each other to form a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring or a substituted or unsubstituted C3-C8 alicyclic ring;

the R is _c The same or different groups are selected from hydrogen, deuterium, tritium, cyano, halogen, trifluoromethyl, or any one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropanyl, cyclobutylalkyl, cyclopentanyl, and cycloA hexanyl group, adamantyl group, norbornyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, phenyl group, biphenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, triphenylene group, benzocyclobutanyl group, benzocyclopentanyl group, benzocyclohexenyl group, benzocyclobutenyl group, benzocyclopentenyl group, benzocyclohexenyl group, indenyl group;

7. The heterocyclic compound according to claim 1, wherein the heterocyclic compound is selected from any one of the following compounds:

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8. an organic electroluminescent device, characterized in that it comprises at least one of the heterocyclic compounds according to any one of claims 1 to 7.

9. The organic electroluminescent device according to claim 8, comprising an anode, a cathode and one or more organic layers between the anode and the cathode, wherein the organic layers comprise at least one of the heterocyclic compounds according to any one of claims 1 to 7.

10. The organic electroluminescent device according to claim 8, wherein the organic layer comprises a light-emitting layer comprising at least one of the heterocyclic compounds according to any one of claims 1 to 7.