CN114075192B

CN114075192B - Heterocyclic compound, and electronic element and electronic device using same

Info

Publication number: CN114075192B
Application number: CN202011506875.0A
Authority: CN
Inventors: 薛震; 李晓攀; 王金平
Original assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Current assignee: Shaanxi Lighte Optoelectronics Material Co Ltd
Priority date: 2020-12-18
Filing date: 2020-12-18
Publication date: 2023-04-07
Anticipated expiration: 2040-12-18
Also published as: CN114075192A

Abstract

The present disclosure relates to a heterocyclic compound, and an electronic element and an electronic device using the same. The structure of the heterocyclic compound consists of formula I-1 and formula I-2, wherein formula I-1 and formula I-2 are fused, and represents the connection point of formula I-1 and formula I-2. The heterocyclic compound is applied to an organic electroluminescent device, so that the driving voltage of the device can be obviously reduced, and the service life of the device is prolonged; in addition, the compounds of the present application can also improve the efficiency of the device.

Description

Heterocyclic compound, and electronic element and electronic device using same

Technical Field

The disclosure belongs to the technical field of organic materials, and particularly provides a heterocyclic compound, and an electronic element and an electronic device using the heterocyclic compound.

Background

With the development of electronic technology and the progress of material science, the application range of electronic components for realizing electroluminescence or photoelectric conversion is more and more extensive. Such electronic components generally include a cathode and an anode that are oppositely disposed, and a functional layer disposed between the cathode and the anode. The functional layer is composed of multiple organic or inorganic film layers and generally includes an energy conversion layer, a hole transport layer between the energy conversion layer and the anode, and an electron transport layer between the energy conversion layer and the cathode.

Taking an organic electroluminescent device as an example, the organic electroluminescent device generally includes an anode, a hole transport layer, an electroluminescent layer as an energy conversion layer, an electron transport layer, and a cathode, which are sequentially stacked. When voltage is applied to the anode and the cathode, the two electrodes generate an electric field, electrons on the cathode side move to the electroluminescent layer under the action of the electric field, holes on the anode side also move to the luminescent layer, the electrons and the holes are combined in the electroluminescent layer to form excitons, and the excitons are in an excited state and release energy outwards, so that the electroluminescent layer emits light outwards.

At present, the problems of reduced luminous efficiency, shortened service life and the like exist in the using process of an organic electroluminescent device, so that the performance of the organic electroluminescent device is reduced.

Disclosure of Invention

In view of the above problems in the prior art, an object of the present application is to provide a heterocyclic compound that can be used in an organic electroluminescent device to improve the performance of the organic electroluminescent device, and an electronic element and an electronic device using the same.

In order to achieve the above objects, the present application provides, in a first aspect, a heterocyclic compound having a structure consisting of formula I-1 and formula I-2:

wherein, formula I-1 and formula I-2 are fused and connected, and represents the fused connection point in formula I-1 and formula I-2;

X ₁ 、X ₂ 、X ₃ 、X ₄ are identical or different from each other, are each independently selected from N or CH, and X ₁ 、X ₂ 、X ₃ 、X ₄ At least one of which is N;

Y ₁ and Y ₂ Each independently selected from the group consisting of a single bond, O, S, C (R) ₃ R ₄ ) Or N (R) ₅ ) And Y is ₁ And Y ₂ At most one of them is a single bond; r is ₃ ～R ₅ Selected from substituted or unsubstituted alkyl with 1-10 carbon atoms, substituted or unsubstituted aryl with 6-20 carbon atoms or substituted or unsubstituted heteroaryl with 4-18 carbon atoms;

Ar ₁ selected from substituted or unsubstituted aryl with 6-30 carbon atoms and substituted or unsubstituted heteroaryl with 4-25 carbon atoms;

l is selected from a single bond or substituted or unsubstituted arylene with 6-20 carbon atoms;

R ₁ 、R ₂ the same or different, and each is independently selected from substituted or unsubstituted aryl with 6-20 carbon atoms, carbon atomSubstituted or unsubstituted heteroaryl groups in the number from 3 to 18; a is ₁ 、a ₂ Each represents R ₁ 、R ₂ The number of (2); a is a ₁ Selected from 0, 1,2 or 3, when a ₁ When greater than 1, any two R ₁ The same or different; a is ₂ Selected from 0, 1 or 2, when a ₂ When 2, any two R ₂ The same or different;

L、Ar ₁ and R ₁ ～R ₅ Wherein the substituents are independently selected from deuterium, a halogen group, a cyano group, a heteroaryl group having 4 to 12 carbon atoms, an aryl group having 6 to 15 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, a triphenylsilyl group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, and an arylthio group having 6 to 12 carbon atoms; or optionally, any two adjacent substituents form a 5-13 membered ring.

In a second aspect, the present application provides an electronic component comprising the heterocyclic compound described in the first aspect of the present application.

A third aspect of the present application provides an electronic device comprising the electronic component according to the second aspect of the present application.

The heterocyclic compound comprises a nitrogen-containing heteroaryl part and a condensed heteroaryl part, wherein the nitrogen-containing heteroaryl part belongs to an electron-deficient group and has a better electron transmission rate, the condensed heteroaryl part belongs to an electron-rich group and has a better hole transmission rate, and the two parts are connected through a single bond or an electron-rich aryl conjugate, so that the whole molecule has higher carrier transmission efficiency.

The driving voltage of the device can be obviously reduced, and the service life of the device is prolonged; in addition, the compounds of the present application can also improve the efficiency of the device.

Additional features and advantages of the present application will be described in detail in the detailed description which follows.

Drawings

Fig. 1 is a schematic structural view of an organic electroluminescent device according to an embodiment of the present application.

Fig. 2 is a schematic structural diagram of a first electronic device according to an embodiment of the present application.

Fig. 3 is a schematic structural view of a photoelectric conversion device according to an embodiment of the present application.

Fig. 4 is a schematic structural diagram of a second electronic device according to an embodiment of the present application.

Description of the reference numerals

100. An anode; 200. a cathode; 300. a functional layer; 310. a hole injection layer; 320. a hole transport layer; 321. a first hole transport layer; 322. a second hole transport layer; 330. an organic light emitting layer; 340. an electron transport layer; 350. an electron injection layer; 360. a photoelectric conversion layer; 400. a first electronic device; 500. a second electronic device.

Detailed Description

The following detailed description of the embodiments of the disclosure refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

In a first aspect, the present application provides a heterocyclic compound having the structure consisting of formula I-1 and formula I-2:

Y ₁ and Y ₂ Each independently selected from the group consisting of a single bond, O, S, C (R) ₃ R ₄ ) Or N (R) ₅ ) And Y is ₁ And Y ₂ At most one of them is a singleA key; r ₃ ～R ₅ Selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted heteroaryl group having 4 to 18 carbon atoms;

R ₁ 、R ₂ the same or different, and each is independently selected from substituted or unsubstituted aryl with 6-20 carbon atoms, substituted or unsubstituted heteroaryl with 3-18 carbon atoms; a is ₁ 、a ₂ Each represents R ₁ 、R ₂ The number of (2); a is ₁ Selected from 0, 1,2 or 3, when a ₁ When greater than 1, any two R ₁ The same or different; a is a ₂ Selected from 0, 1 or 2, when a ₂ When it is 2, any two R ₂ The same or different;

In the application, the description mode of ' each 8230 ' \8230; ' and ' 8230 '; ' 823030 '; ' and ' 8230 '; ' are independently selected from ' interchangeable ' and should be broadly understood, which can mean that specific options expressed between the same symbols in different groups do not affect each other, or that specific options expressed between the same symbols in the same groups do not affect each other. For example, in the case of a liquid,

wherein each q is independently 0, 1,2 or 3, each R "is independently selected from hydrogen, deuterium, fluoro, chloro" and has the meaning: the formula Q-1 represents that Q substituent groups R ' are arranged on a benzene ring, each R ' can be the same or different, and the options of each R ' are not influenced mutually; the formula Q-2 represents that each benzene ring of biphenyl has Q substituent groups R ', the number Q of the substituent groups R' on the two benzene rings can be the same or different, each R 'can be the same or different, and the options of each R' are not influenced with each other.

In the present application, the term "substituted or unsubstituted" means that a functional group described later in the term may or may not have a substituent (hereinafter, for convenience of description, the substituent is collectively referred to as R _x ). For example, "substituted or unsubstituted aryl" means having a substituent R _x Or an unsubstituted aryl group. Wherein the above-mentioned substituents are R _x For example, deuterium, a halogen group, a cyano group, a heteroaryl group having 3 to 12 carbon atoms, an aryl group having 6 to 15 carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms, a triphenylsilyl group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an arylthio group having 6 to 12 carbon atoms; when two substituents R are attached to the same atom _x When two substituents R are present _x May be independently present or attached to each other to form a ring with said atoms; when two adjacent substituents R are present on the functional group _x When adjacent substituents R _x May be present independently or form a ring with the function to which it is attached.

L、Ar ₁ And R ₁ ～R ₅ In (3), the number of carbon atoms means all the number of carbon atoms. For example, if Ar ₁ And is selected from substituted or unsubstituted aryl groups having 12 carbon atoms, all of the carbon atoms of the aryl group and substituents thereon are 12. For example, 2, 4-diphenyl-1, 3, 5-triazinyl is a substituted heteroaryl group having 15 carbon atoms.

In this applicationIn this application, aryl refers to an optional functional group or substituent derived from an aromatic carbon ring. The aryl group may be a monocyclic aryl group (e.g., phenyl) or a polycyclic aryl group, in other words, the aryl group may be a monocyclic aryl group, a fused aryl group, two or more monocyclic aryl groups connected through a carbon-carbon bond conjugate, a monocyclic aryl group and a fused aryl group connected through a carbon-carbon bond conjugate, two or more fused aryl groups connected through a carbon-carbon bond conjugate. That is, unless otherwise specified, two or more aromatic groups conjugated through a carbon-carbon bond may also be considered as aryl groups herein. The fused ring aryl group may include, for example, a bicyclic fused aryl group (e.g., naphthyl group), a tricyclic fused aryl group (e.g., phenanthryl group, fluorenyl group, anthracyl group), and the like. In this specification, biphenyl, terphenyl, and fluorenyl groups are all considered aryl groups in the present application. Specific examples of aryl groups include, but are not limited to, phenyl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl, biphenyl, terphenyl, benzo [9,10 ]]Phenanthryl, perylene, pyrenyl, benzofluoranthenyl,

And the like. In this application, reference to arylene is to a divalent group formed by an aryl group further deprived of a hydrogen atom.

In the present application, the substituted aryl group may be an aryl group in which one or two or more hydrogen atoms are substituted with a group such as deuterium atom, halogen group, cyano group, aryl group, heteroaryl group, trialkylsilyl group, alkyl group, haloalkyl group, alkylsilyl group, arylsilyl group, cycloalkyl group, alkoxy group, alkylthio group, or the like. It is understood that the number of carbon atoms of a substituted aryl group, as used herein, refers to the total number of carbon atoms in the aryl group and the substituents on the aryl group, e.g., a substituted aryl group having a carbon number of 18, refers to a total carbon number of 18 in the aryl group and the substituents.

In the present invention, the number of carbon atoms of the substituted or unsubstituted aryl group may be selected from 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 25 or 30. In some embodiments, the aryl group is an aryl group having from 6 to 30 carbon atoms, in other embodiments from 6 to 20 carbon atoms, in other embodiments from 6 to 18 carbon atoms, and in other embodiments from 6 to 15 carbon atoms. Specific examples of the aryl group having 6 to 15 carbon atoms include, but are not limited to: phenyl, naphthyl, anthryl, phenanthryl, biphenyl, fluorenyl, dimethylfluorenyl.

In the present invention, the arylene group is a 2-valent group, and the above description of the aryl group can be applied thereto.

Examples of the aryl group as a substituent in the present application include, but are not limited to, phenyl, naphthyl, anthryl, phenanthryl, biphenyl, fluorenyl and dimethylfluorenyl.

In the present application, heteroaryl refers to a monovalent aromatic ring containing 1,2, 3,4, or 5 heteroatoms in the ring, which may be at least one of B, O, N, P, si, se, and S, or derivatives thereof. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group, in other words, the heteroaryl group may be a single aromatic ring system or a plurality of aromatic ring systems connected by carbon-carbon bonds in a conjugated manner, and any one of the aromatic ring systems is an aromatic monocyclic ring or an aromatic fused ring. Exemplary heteroaryl groups may include, but are not limited to, thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, oxadiazolyl, triazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, phenoxazinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzopyrimidiyl, benzopyridyl, benzothiazolyl, benzocarbazolyl, benzothienyl, benzothiophenyl, benzofuranyl, phenanthrolinyl, isoxazolyl, thiadiazolyl, benzothiazolyl, phenothiazinyl, dibenzofuranyl, and N-phenylcarbazolyl. In this application, a heteroarylene group refers to a divalent group formed by a heteroaryl group further lacking one hydrogen atom.

In the present application, substituted heteroaryl groups may be heteroaryl groups in which one or more hydrogen atoms are substituted with groups such as deuterium atoms, halogen groups, cyano groups, aryl groups, heteroaryl groups, trialkylsilyl groups, alkyl groups, haloalkyl groups, alkylsilyl groups, cycloalkyl groups, alkoxy groups, alkylthio groups, and the like. It is understood that the number of carbon atoms in the substituted heteroaryl group refers to the total number of carbon atoms in the heteroaryl group and the substituent on the heteroaryl group.

In the present invention, the number of carbon atoms of the substituted or unsubstituted heteroaryl group may be selected from 3,4, 5, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30. In some embodiments, heteroaryl is a heteroaryl having from 4 to 25 carbon atoms, in other embodiments, heteroaryl is a heteroaryl having from 4 to 18 carbon atoms, and in other embodiments, heteroaryl is a heteroaryl having from 4 to 12 carbon atoms. Specific examples of the heteroaryl group having 4 to 12 carbon atoms include, but are not limited to, pyridyl, bipyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, quinolyl, quinazolinyl, quinoxalinyl, isoquinolyl, indolyl, carbazolyl, dibenzothienyl, dibenzofuranyl.

Heteroaryl as a substituent in this application is exemplified by, but not limited to, pyridyl, pyrimidinyl, quinolinyl, dibenzothienyl, dibenzofuranyl, benzopyrimidinyl, isoquinolinyl, benzopyridyl.

In the present application, "any two adjacent substituents form a ring," any two adjacent "may include two substituents on the same atom, and may also include one substituent on each of two adjacent atoms; wherein, when two substituents are present on the same atom, these two substituents may form a saturated or unsaturated spiro ring with the atom to which they are both attached; when two adjacent atoms each have a substituent, the two substituents form a saturated or unsaturated fused ring with the group to which they are commonly attached.

In the present invention, the ring system formed by n atoms is an n-membered ring. For example, phenyl is 6-membered aryl. The 6-to 13-membered aromatic ring means a benzene ring, an indene ring, a naphthalene ring and the like.

The "ring" in the present application includes saturated rings, unsaturated rings; saturated rings, i.e., cycloalkyl, heterocycloalkyl, unsaturated rings, i.e., cycloalkenyl, heterocycloalkenyl, aryl, and heteroaryl. The 5-13 membered ring means a ring system formed by 5-13 ring atoms, and for example, the fluorene ring belongs to the 13 membered ring.

The non-positional connection key referred to in this application

Or>

Refers to a single bond extending from the ring system, which means that one end of the connecting bond can be attached to any position in the ring system through which the bond extends, and the other end is attached to the rest of the compound molecule.

For example, as shown in formula (f), naphthyl represented by formula (f) is connected to other positions of the molecule through two non-positioned bonds penetrating through the bicyclic ring, and the meaning of the naphthyl represented by the formula (f-1) to the formula (f-10) includes any possible connection mode shown in the formula (f-1) to the formula (f-10).

An delocalized substituent, as used herein, refers to a substituent attached by a single bond extending from the center of the ring system, meaning that the substituent may be attached at any possible position in the ring system. For example, as shown in the following formula (Y), the substituent R' represented by the formula (Y) is bonded to the quinoline ring through an delocalized bond, and the meaning thereof includes any possible bonding manner as shown in the formulae (Y-1) to (Y-7).

In the present application, the alkyl group having 1 to 10 carbon atoms may include a straight-chain alkyl group having 1 to 10 carbon atoms and a branched-chain alkyl group having 3 to 10 carbon atoms, and the number of carbon atoms may be, for example, 1,2, 3,4, 5, 6, 7, 8, 9, and 10. In some embodiments, the alkyl group contains 1 to 6 carbon atoms, and in other embodiments, the alkyl group contains 1 to 4 carbon atoms. Carbon atomExamples of alkyl groups having a number of 1 to 4 include, but are not limited to, methyl (Me, -CH) ₃ ) Ethyl (Et, -CH) ₂ CH ₃ ) N-propyl (n-Pr, -CH) ₂ CH ₂ CH ₃ ) Isopropyl (i-Pr, -CH (CH) ₃ ) ₂ ) N-butyl (n-Bu, -CH) ₂ CH ₂ CH ₂ CH ₃ ) 2-methylpropyl or isobutyl (i-Bu, -CH) ₂ CH(CH ₃ ) ₂ ) 1-methylpropyl or sec-butyl (s-Bu, -CH (CH) ₃ )CH ₂ CH ₃ ) Tert-butyl (t-Bu, -C (CH) ₃ ) ₃ ) And the like.

In the present application, the halogen group may include fluorine, iodine, bromine, chlorine, and the like.

In the present application, specific examples of the trialkylsilyl group having 3 to 12 carbon atoms include, but are not limited to, a trimethylsilyl group, a triethylsilyl group, and the like.

In the present application, specific examples of the cycloalkyl group having 5 to 10 carbon atoms include, but are not limited to, cyclopentyl, cyclohexyl, adamantyl, and the like.

In some embodiments of the present application, Y in formulas 1-2 ₁ And Y ₂ One of which is a single bond, or no single bond. Y is ₁ When it is a single bond, Y ₂ Is O, S, C (R) ₃ R ₄ ) Or N (R) ₅ )，Y ₂ When it is a single bond, Y ₁ Is O, S, C (R) ₃ R ₄ ) Or N (R) ₅ ) (ii) a Or Y ₁ And Y ₂ Are all selected from O, S and C (R) ₃ R ₄ ) Or N (R) ₅ )。

In the present application, optionally, the heterocyclic compound has a structure represented by any one of formulas 2-1 to 2-3:

in some embodiments of the present applicationSaid X is ₁ 、X ₂ 、X ₃ 、X ₄ One or both of which are N.

In some embodiments of the present application, L is a single bond.

In the present application, optionally, X ₁ 、X ₂ 、X ₃ 、X ₄ Is N.

In a more specific embodiment, X ₁ Is N, X ₂ Is C, X ₃ 、X ₄ Are each CH.

In a more specific embodiment, X ₃ Is N, X ₂ Is C, X ₁ 、X ₄ Are each CH.

In a more specific embodiment, X ₂ Is N, X ₁ Is C, X ₃ 、X ₄ Are each CH.

In a more specific embodiment, X ₂ Is N, X ₃ Is C, X ₁ 、X ₄ Are each CH.

In the present application, optionally, X ₁ 、X ₂ 、X ₃ 、X ₄ Two of which are N.

In a more specific embodiment, X ₁ 、X ₃ Is N, X ₂ Is C, X ₄ Is CH.

In a more specific embodiment, X ₁ 、X ₄ Is N, X ₂ Is C, X ₃ Is CH.

In a more specific embodiment, X ₁ 、X ₄ Is N, X ₃ Is C, X ₂ Is CH.

In a more specific embodiment, X ₂ 、X ₄ Is N, X ₁ Is C, X ₃ Is CH.

In a more specific embodiment, X ₂ 、X ₄ Is N, X ₃ Is C, X ₁ Is CH.

In some embodiments of the present invention, the formula 1-1 has a structure of the following formulae 3-1 to 3-4:

in some embodiments of the present application, the R is ₁ 、R ₂ Each independently selected from the group consisting of substituted or unsubstituted: phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthryl, dibenzothienyl, dibenzofuranyl, fluorenyl, pyridyl, said substitution being by a substituent selected from deuterium, fluorine, chlorine, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, phenyl, naphthyl, pyridyl.

In some embodiments of the present application, said a ₁ 、a ₂ Each independently selected from 0 or 1.

In some embodiments of the present application, the R is ₃ ～R ₅ Selected from the group consisting of a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and a substituted or unsubstituted heteroaryl group having 4 to 12 carbon atoms.

In some embodiments of the present application, the R is ₃ 、R ₄ And R ₅ Each independently selected from the group consisting of substituted or unsubstituted: methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, dibenzothienyl, dibenzofuranyl, fluorenyl, said substitution being by a substituent selected from deuterium, fluorine, chlorine, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, pyridyl.

In some embodiments of the present application, the R is ₃ 、R ₄ Each independently selected from methyl, ethyl, phenyl, biphenyl;

R ₅ selected from the group consisting of substituted or unsubstituted: methyl, ethyl, phenyl, biphenyl, terphenyl, anthracenyl, phenanthrenyl, dibenzothienyl, dibenzofuranyl, fluorenyl, wherein R is ₅ Wherein the substituents are each independently selected from deuterium, fluoro, cyano,Trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl and pyridyl.

In some embodiments of the present application, the R is ₃ ～R ₅ Wherein the substituents are each independently selected from the group consisting of deuterium, fluoro, chloro, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, phenyl, naphthyl, and pyridyl.

In some embodiments of the present application, L is selected from substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene.

In some embodiments of the present application, the substituents in L, which are the same or different from each other, are each independently selected from the group consisting of deuterium, fluoro, chloro, cyano, methyl, ethyl, isopropyl, n-propyl, tert-butyl, methoxy, ethoxy, phenyl, trifluoromethyl, trimethylsilyl, phenyl, pyridyl.

In some embodiments herein, the L is selected from a single bond or from a substituted or unsubstituted group W selected from the group consisting of:

the substituted group W is a group formed by substituting unsubstituted W with one or more substituents independently selected from deuterium, fluorine, chlorine, cyano, methyl, ethyl, isopropyl, n-propyl, tert-butyl, methoxy, ethoxy, phenyl, trifluoromethyl, trimethylsilyl, pyridyl.

In some embodiments of the present application, the L is selected from a single bond or the group consisting of:

in some embodiments of the present applicationIn the scheme, ar is ₁ Selected from substituted or unsubstituted aryl groups having 6 to 18 carbon atoms and substituted or unsubstituted heteroaryl groups having 4 to 12 carbon atoms.

In some embodiments of the present application, the Ar is ₁ Selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidine, substituted or unsubstituted quinolyl, substituted or unsubstituted benzopyrimidinyl, and substituted or unsubstituted pyrazinyl.

In some embodiments of the present application, the Ar is ₁ Wherein the substituents are each independently selected from the group consisting of deuterium, fluoro, chloro, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, phenyl, naphthyl, and pyridyl.

In some embodiments of the present application, the Ar is ₁ Selected from the group consisting of substituted or unsubstituted V, said unsubstituted V being selected from the group consisting of:

wherein the substituted group V is a group in which unsubstituted V is substituted with one or more substituents selected from deuterium, fluorine, chlorine, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, trifluoromethyl, phenyl, naphthyl, and pyridyl, and when the number of substituents on V is plural, any two substituents are the same or different.

Further optionally, the Ar ₁ Is selected from the group consisting ofThe group consisting of:

in some embodiments of the present application, the formula I-2

Selected from the group consisting of substituted or unsubstituted U, said unsubstituted U being selected from the group consisting of:

substituted U has one or more substituents thereon, each substituent on substituted U being independently selected from deuterium, fluoro, chloro, cyano, trifluoromethyl, trimethylsilyl, methyl, ethyl, isopropyl, tert-butyl, methoxy, ethoxy, isopropoxy, phenyl, naphthyl, pyridyl; when the number of the substituents is more than 1, the substituents are the same or different, and optionally, any two adjacent substituents form a ring.

In this application, optionally, the heterocyclic compound is selected from the group consisting of:

the synthesis method of the heterocyclic compound provided herein is not particularly limited, and those skilled in the art can determine an appropriate synthesis method according to the heterocyclic compound of the present invention in combination with the preparation method provided in the synthesis examples section. In other words, the synthetic examples of the present invention provide, as an example, methods for preparing heterocyclic compounds, and the starting materials used may be obtained commercially or by methods well known in the art. All heterocyclic compounds provided herein are available to those skilled in the art from these exemplary preparative methods, and all specific preparative methods for preparing the heterocyclic compounds will not be described in detail herein, and those skilled in the art should not be construed as limiting the present application.

A second aspect of the present application provides an electronic component including an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode; the functional layer comprises a heterocyclic compound according to the first aspect of the present application.

The heterocyclic compounds provided herein can be used to form at least one organic film layer in a functional layer to improve efficiency and lifetime characteristics of an electronic component.

In a specific embodiment, the functional layer includes an organic light-emitting layer including the heterocyclic compound. Generally, the organic light-emitting layer may comprise a host material and a guest material, wherein the host material comprises the heterocyclic compound of the present application.

In one embodiment according to the present application, the electronic component is an organic electroluminescent device, for example a red light device. As shown in fig. 1, the organic electroluminescent device may include an anode 100, a first hole transport layer 321, a second hole transport layer 322, an organic light emitting layer 330 as an energy conversion layer, an electron transport layer 340, and a cathode 200, which are sequentially stacked.

Optionally, the anode 100 comprises an anode material, preferably a material with a large work function that facilitates hole injection into the functional layer. Specific examples of the anode material include: metals such as nickel, platinum, vanadium, chromium, copper, zinc and gold or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combined metals and oxides, e.g. ZnO: al or SnO ₂ Sb; or a conductive polymer such as poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene](PEDT), polypyrrole, and polyaniline, but are not limited thereto. Preferably, a transparent electrode including Indium Tin Oxide (ITO) as an anode is included.

Alternatively, the first hole transport layer 321 and the second hole transport layer 322 each include one or more hole transport materials, which may be selected from carbazole multimers, carbazole-linked triarylamine-based compounds, or other types of compounds. According to a specific embodiment, NDDP acts as the first hole transport layer. TPD acts as the second hole transport layer.

Alternatively, the organic light emitting layer 330 may be composed of a single light emitting material, and may also include a host material and a guest material. The host material of the organic light emitting layer 330 may contain the heterocyclic compound of the present application. Further alternatively, the organic light emitting layer 330 may be composed of a host material and a guest material, and a hole injected into the organic light emitting layer 330 and an electron injected into the organic light emitting layer 330 may be combined in the organic light emitting layer 330 to form an exciton, and the exciton transfers energy to the host material, and the host material transfers energy to the guest material, so that the guest material can emit light.

The guest material of the organic light emitting layer 330 may be a compound having a condensed aryl ring or a derivative thereof, a compound having a heteroaryl ring or a derivative thereof, an aromatic amine derivative, or other materials, which is not particularly limited in the present application. According to a specific embodiment, the organic electroluminescent device is a red light device, wherein the organic light-emitting layer 330 may be composed of the heterocyclic compound provided herein; alternatively, the organic light emitting layer 330 may be composed of the heterocyclic compound provided herein together with other materials. Other materials such as, but not limited to, DCM2 or Ir (piq) ₂ (acac)。

The electron transport layer 340 may have a single-layer structure or a multi-layer structure, and may include one or more electron transport materials, which may be selected from, but not limited to, benzimidazole derivatives, oxadiazole derivatives, quinoxaline derivatives, or other electron transport materials. In an exemplary embodiment of the present application, the electron transport layer 340 may be composed of DBimiBphen and LiQ.

In the present application, the cathode 200 may include a cathode material, which is a material having a small work function that facilitates electron injection into the functional layer. Specific examples of the cathode material include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; or a multilayer material such as LiF/Al, liq/Al, liO ₂ Al, liF/Ca, liF/Al and BaF ₂ and/Ca. Preferably, a metal electrode comprising magnesium and silver is included as a cathode.

Optionally, as shown in fig. 1, a hole injection layer 310 may be further disposed between the anode 100 and the first hole transport layer 321 to enhance the ability to inject holes into the first hole transport layer 321. The hole injection layer 310 may be made of benzidine derivatives, starburst arylamine compounds, phthalocyanine derivatives, or other materials, which are not limited in this application. For example, the hole injection layer 310 may be composed of HAT-CN.

Optionally, as shown in fig. 1, an electron injection layer 350 may be further disposed between the cathode 200 and the electron transport layer 340 to enhance the ability to inject electrons into the electron transport layer 340. The electron injection layer 350 may include an inorganic material such as an alkali metal sulfide or an alkali metal halide, or may include a complex of an alkali metal and an organic material. For example, the electron injection layer 350 may include LiQ.

According to another embodiment, the electronic component may be a photoelectric conversion device. As shown in fig. 3, the photoelectric conversion device may include an anode 100 and a cathode 200 disposed opposite to each other, and a functional layer 300 disposed between the anode 100 and the cathode 200; the functional layer 300 comprises a heterocyclic compound as provided herein.

According to an exemplary embodiment, as shown in fig. 3, the functional layer 300 includes an organic light emitting layer 330, and the organic light emitting layer 330 may include the heterocyclic compound of the present application. Optionally, the organic light emitting layer 330 may further include an inorganic doping material to improve light emitting performance of the organic light emitting layer 330.

According to a specific embodiment, as shown in fig. 3, the photoelectric conversion device may include an anode 100, a hole transport layer 320, an organic light emitting layer 330, an electron transport layer 340, and a cathode 200, which are sequentially stacked.

Alternatively, the photoelectric conversion device may be a solar cell, and particularly may be an organic thin film solar cell. For example, in one embodiment of the present application, a solar cell may include an anode, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode, which are sequentially stacked, wherein the organic light emitting layer includes the heterocyclic compound of the present application.

According to one embodiment, as shown in fig. 2, the electronic device is a first electronic device 400, and the first electronic device 400 includes the organic electroluminescent device. The first electronic device 400 may be, for example, a display device, a lighting device, an optical communication device or other types of electronic devices, which may include, but are not limited to, a computer screen, a mobile phone screen, a television, electronic paper, an emergency light, an optical module, etc.

In another embodiment, as shown in fig. 4, the electronic device is a second electronic device 500, and the second electronic device 500 includes the above-mentioned photoelectric conversion device. The second electronic device 500 may be, for example, a solar power generation apparatus, a light detector, a fingerprint recognition apparatus, a light module, a CCD camera, or other types of electronic devices.

The following will specifically describe the synthesis method of the compound of the present application with reference to the synthesis examples.

In the synthetic examples described below, all temperatures are in degrees celsius unless otherwise noted. Some of the reagents were purchased from commercial suppliers such as Aldrich Chemical Company, arco Chemical Company and Alfa Chemical Company, and some of the intermediates that could not be purchased directly were prepared by simple reaction of commercially available starting materials and were used without further purification unless otherwise stated. The other conventional reagents are purchased from Nanjing Congralin chemical industry practice Co., ltd, tianjin Haoyouyu chemical Co., ltd, fuchen chemical reagent factory of Tianjin City, wuhanxin Huayuan scientific and technological development Co., ltd, qingdao Tenglong chemical reagent Co., ltd, qingdao maritime chemical plant, etc. The anhydrous solvent such as anhydrous tetrahydrofuran, dioxane, toluene, diethyl ether and the like is obtained by refluxing and drying the metal sodium. The reactions in the various synthesis examples were generally carried out under a positive pressure of nitrogen or argon, or by placing a drying tube over an anhydrous solvent (unless otherwise stated); in the reaction, the reaction flask was closed with a suitable rubber stopper, and the substrate was injected into the reaction flask via a syringe. The individual glassware used was dried.

In purification, the column was silica gel column, silica gel (80-120 mesh) was purchased from Qingdao oceanic plant.

In each synthesis example, the conditions for measuring low resolution Mass Spectrometry (MS) data were: agilent 6120 four-stage rod HPLC-M (column model: zorbax SB-C18, 2.1X 30mm,3.5 micron, 6min, flow rate 0.6mL/min. Mobile phase: ratio of 5% -95% (acetonitrile containing 0.1% formic acid) in (water containing 0.1% formic acid)) using electrospray ionization (ESI) at 210nm/254nm, with UV detection.

Hydrogen nuclear magnetic resonance spectroscopy: bruker 300MHz NMR spectrometer at room temperature in CDCl ₃ TMS (0 ppm) was used as a reference standard for the solvent (in ppm). When multiple peaks occur, the following abbreviations will be used: s (singleton), d (doublet), t (triplet), m (multiplet).

The target compounds were detected by UV at 210nm/254nm using Agilent 1260pre-HPLC or Calesep pump 250pre-HPLC (column model: NOVASEP 50/80mm DAC).

Example 1: synthesis of Compound 3

(1) After nitrogen replacement in a three-neck reaction flask equipped with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, the raw material 3a (200 mmol), the raw material 3b (240 mmol), potassium acetate (400 mmol) and 300.0mL of 1, 4-dioxane are sequentially added, stirring is started, the temperature is raised to 45-50 ℃, and X-Phos (1.2 mmol) and Pd are added ₂ (dba) ₃ (0.6 mmol), the temperature is continuously increased to 90-100 ℃, and the reaction is carried out for 2h. Cooling the reaction liquid to room temperature, adding 300.0mL of dichloromethane and 300.0mL of water, stirring, standing, separating, extracting the water phase for 1 time by using 150.0mL of dichloromethane, separating, combining the organic phases, washing for 2 times by using 300.0mL of water, separating, adding 15g of anhydrous sodium sulfate into the organic phase, drying, filtering, passing the organic phase through a silica gel chromatographic column, leaching by using 300.0mL of dichloromethane, stopping concentration when the organic phase is concentrated to (-0.09 to-0.08MPa, 40 to 50 ℃) and 60.0mL of the organic phase is remained, adding 120.0mL of petroleum ether, stirring for 1.0h at room temperature, filtering, leaching a filter cake by using the petroleum ether, obtaining an intermediate 3-1 (213.5 mmol), and obtaining the yield of 85%.

(2) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, sequentially adding an intermediate 3-1 (213.5 mmol), a raw material 3c (234.85 mmol), 300.0mL of tetrabutylammonium bromide (21.35 mmol), 150.mL of ethanol, 150.0mL of water and potassium carbonate (427 mmol), heating to 45-50 ℃, adding palladium tetratriphenylphosphine (1.07 mmol), continuously heating to reflux, and reacting for 8 hours under heat preservation. Adding 300.0mL of water, separating, extracting the water phase with 200.0mL of toluene, combining organic phases, adding 200.0mL of water, washing for 2 times, separating, adding 15g of anhydrous sodium sulfate into the organic phase, stirring, drying, filtering, concentrating the organic phase (-0.09 to-0.08MPa, 55-65 ℃) when 120.0mL of the residual organic phase is left, stopping heating, cooling to 15-20 ℃, separating out a large amount of solids, filtering, leaching a filter cake with ethanol to obtain an intermediate 3-2 (150.0 mmol), wherein the yield is 75%.

(3) Under the protection of nitrogen in a three-necked reaction flask equipped with a mechanical stirrer, a thermometer and a condenser, 3-2 (150.0 mmol) of the intermediate, 250.0ml of PhCl, m-CPBA (225.0 mmol) and BF were sequentially added ₃ ·OEt ₂ (45.0 mmol) and 4-iodotoluene (37.5 mmol) are started to stir, the temperature is raised to 110 ℃ for reaction for 2h, the reaction solution is poured into 200.0mL of water, 300.0mL of toluene is added to stir, the mixture is kept stand, liquid separation is carried out, the water phase is extracted by 200.0mL of toluene, the organic phase is combined, the organic phase is washed by 250.0mL of water for 2 times, dried by 15g of anhydrous sodium sulfate and filtered, the filtrate passes through a (80-120) mesh silica gel column, the column passing solution (50-70 ℃ and-0.09 to-0.08 MPa) is concentrated until the organic phase is not separated out, 100.00mL of n-heptane is added to stir, and filtration is carried out, thus obtaining the intermediate 3-3 (89.16 mmol) with the yield of 60%.

(4) Under the protection of nitrogen gas in a three-port reaction bottle with a mechanical stirrer, a thermometer and a condenser, the raw material 3d (200 mmol), the raw material 3e (181.82 mmol), sodium tert-butyl alcohol (400 mmol) and 500.0mL of toluene are sequentially added, the temperature is raised to reflux, water is separated for 1h, the temperature is reduced to 70-80 ℃, X-phos (1.2 mmol) and Pd2 (dba) 3 (0.6 mmol) are added, the temperature is raised to reflux, and the reaction is carried out for 1h. Cooling the reaction liquid to room temperature, adding 500.0mL of water, washing with water, separating, extracting the water phase with 200.0mL of toluene, separating, combining organic phases, washing the organic phase with 300.0mL of water for 2 times, drying with 10g of anhydrous sodium sulfate, filtering, passing the filtrate through a (80-120) mesh silica gel column, concentrating the solution passing through the column (50-70 ℃ and-0.09 to-0.08 MPa), and remaining 120.0mL of organic phase, stopping concentration, adding 240.0mL of anhydrous ethanol, cooling to 15-20 ℃, separating out a large amount of solids, and filtering to obtain an intermediate 3-4 (362 mmol) with the yield of 85%.

(5) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, adding 3-4 (362 mmol) of an intermediate, cesium carbonate (580 mmol), tricyclohexylphosphine tetrafluoroborate (26.2 mmol), cesium carbonate (115 mmol) Pd (OAc) 2 (7.24 mmol) and 1800.0mL of N, N-dimethylacetamide in sequence, starting stirring, heating to 130-140 ℃ for reaction for 10 hours, pouring the reaction solution into 1000.0mL of water, adding 1500.0mL of dichloroethane while stirring, standing, separating, extracting the water phase twice with 900.0mL of dichloroethane, combining the organic phases, washing the organic phases with 1000.0mL of water for 2 times, drying with 100g of anhydrous sodium sulfate, filtering, passing the filtrate through a (80-120) mesh silica gel column, passing the column passing solution (50-70 ℃, 0.09-0.08 MPa) through the column, adding 500.00mL of N-heptane while stirring, filtering, and using 1g of the obtained solid crude product: recrystallization from 3.2ml of ethyl acetate gave intermediate 3-5 (194.2 mmol) in 60% yield.

(6) Under the protection of nitrogen gas in a three-port reaction bottle with a mechanical stirrer, a thermometer and a condenser, the intermediate 3-5 (194.2 mmol), the raw material 3f (213.62 mmol), cesium carbonate (388.4 mmol), 4-dimethylaminopyridine (19.42 mmol) and 500.0ml of DMSO are sequentially added, the temperature is raised to 100-110 ℃, and the reaction is carried out for 2h. And (2) adding 600.0mL of toluene and 600.0mL of water into the reaction solution at room temperature, washing with water, separating liquid, extracting a water phase with 300.0mL of toluene, combining organic phases, washing the organic phase with 500.0mL of water for 2 times, drying with 20g of anhydrous sodium sulfate, filtering, passing the filtrate through a (80-120) mesh silica gel chromatographic column, concentrating the residual 150.0mL of organic phase by column passing liquid (50-70 ℃ and-0.09-0.08 MPa), stopping concentration, cooling to 15-20 ℃, separating out a large amount of solids, and filtering to obtain an intermediate 3-6 (181.66 mmol) with the yield of 75%.

(7) After nitrogen replacement in a three-neck reaction flask with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, 3-6 (181.66 mmol) of an intermediate, 3b (218 mmol) of a raw material, potassium acetate (363.32 mmol) and 560.0mL of 1, 4-dioxane are sequentially added, stirring is started, the temperature is raised to 45-50 ℃, and X-Phos (1.09 mmol) and Pd are added ₂ (dba) ₃ (0.55 mmol), the temperature is continuously increased to 90-100 ℃, and the reaction is carried out for 2h. Cooling the reaction liquid to room temperature, adding 300.0mL of dichloromethane and 300.0mL of water, stirring, standing, separating, extracting the water phase for 1 time by using 150.0mL of dichloromethane, separating, combining the organic phases, washing for 2 times by using 300.0mL of water, separating, adding 15g of anhydrous sodium sulfate into the organic phase, drying, filtering, passing the organic phase through a silica gel chromatographic column, leaching by using 300.0mL of dichloromethane, stopping concentration when the organic phase is concentrated to (-0.09 to-0.08MPa, 40 to 50 ℃) and 80.0mL of the organic phase is remained, adding 160.0mL of petroleum ether, stirring for 1.0h at room temperature, filtering, leaching a filter cake by using petroleum ether, obtaining an intermediate 3 to 7 (191.23 mmol), and obtaining the yield of 85%.

(8) Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, sequentially adding an intermediate 3-3 (89.16 mmol), an intermediate 3-7 (98.08 mmol), tetrabutylammonium bromide (8.92 mmol), 120.0mL of toluene, 60.0mL of ethanol, 60.0mL of water and potassium carbonate (178.32 mmol), heating to 45-50 ℃, adding tetratriphenylphosphine palladium (0.45 mmol), continuously heating to reflux, and carrying out heat preservation reaction for 8 hours. Adding 200.0mL of water, separating, extracting the water phase with 100.0mL of toluene, combining organic phases, adding 150.0mL of water, washing for 2 times, separating, adding 10g of anhydrous sodium sulfate into the organic phase, stirring, drying, filtering, concentrating the organic phase (-0.09 to-0.08MPa, 55-65 ℃) when 100.0mL of the residual organic phase is left, stopping heating, cooling to room temperature, separating out a large amount of solids, filtering, leaching a filter cake with ethanol, and obtaining a compound 3 (142.46 mmol) with the yield of 65%.

LC-MS(ESI,pos.ion)m/z：528.15[M+H] ⁺ ；

The nuclear magnetic data for compound 3 are as follows: ¹ H NMR(CDCl ₃ ，300MHz)：δ(ppm)＝7.29(d，1H)，δ(ppm)＝7.41-7.69(m，10H)，δ(ppm)＝7.93-8.05(d，2H)，δ(ppm)＝8.13(s，1H)，δ(ppm)＝8.20(d，1H),δ(ppm)＝8.45-8.48(m，2H)，δ(ppm)＝8.61-8.68(m，2H)，δ(ppm)＝8.71(d，1H)，δ(ppm)＝8.95(d，1H)。

example 2: synthesis of Compound 51

Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, sequentially adding an intermediate 3-1 (200.0 mmol), a raw material 51a (220.0 mmol), 280.0mL of tetrabutylammonium bromide (20.0 mmol), 140.0mL of ethanol, 140.0mL of water and potassium carbonate (400 mmol), heating to 45-50 ℃, adding tetratriphenylphosphine palladium (1.0 mmol), continuously heating to reflux, and carrying out heat preservation reaction for 8 hours. Adding 300.0mL of water, separating, extracting the water phase with 200.0mL of toluene, combining organic phases, adding 200.0mL of water, washing for 2 times, separating, adding 15g of anhydrous sodium sulfate into the organic phases, stirring, drying, filtering, concentrating the organic phases (-0.09 to-0.08MPa, 55-65 ℃) when 120.0mL of the residual organic phases are left, stopping heating, cooling to 15-20 ℃, separating out a large amount of solids, filtering, leaching filter cakes with ethanol to obtain an intermediate 51-1 (141.3 mmol), wherein the yield is 75%.

Under the protection of nitrogen gas in a three-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a condenser, 51-1 (141.3 mmol) of an intermediate, 180.0mL of PhCl, m-CPBA (211.95 mmol), BF. OEt2 (42.39 mmol) and 4-iodotoluene (35.34 mmol) are sequentially added, stirring is started, the temperature is increased to 110 ℃ for reaction for 2 hours, the reaction liquid is poured into 200.0mL of water, 300.0mL of toluene is added under stirring, standing is carried out, liquid separation is carried out, 200.0mL of toluene is used for extraction of an aqueous phase, organic phases are combined, the organic phase is washed by 250.0mL of water for 2 times, dried by 15g of anhydrous sodium sulfate and filtered, the filtrate passes through a (80-120) mesh silica gel column, the column passing liquid (50-70 ℃, minus 0.09-0.08 MPa) is concentrated to be not discharged, 100.00mL of n-heptane is added under stirring, and filtering is carried out, so that 51-2 (84.0 mmol) of the intermediate is obtained, and the yield is 60%.

Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirring device, a thermometer and a condenser, sequentially adding an intermediate 51-2 (89.16 mmol), an intermediate 3-7 (98.08 mmol), tetrabutylammonium bromide (8.92 mmol), 120.0mL of toluene, 60.0mL of ethanol, 60.0mL of water and potassium carbonate (178.32 mmol), heating to 45-50 ℃, adding tetratriphenylphosphine palladium (0.45 mmol), continuously heating to reflux, and carrying out heat preservation reaction for 8 hours. Adding 200.0mL of water, separating, extracting the water phase with 100.0mL of toluene, combining organic phases, adding 150.0mL of water, washing for 2 times, separating, adding 10g of anhydrous sodium sulfate into the organic phases, stirring, drying, filtering, concentrating the organic phases (-0.09 to-0.08MPa, 55-65 ℃) when 100.0mL of the residual organic phases are left, stopping heating, cooling to room temperature, separating out a large amount of solids, filtering, leaching filter cakes with ethanol, and obtaining a compound 51 (142.46 mmol) with the yield of 65%.

LC-MS(ESI,pos.ion)m/z：529.14[M+H] ⁺

Nuclear magnetic data for compound 51 are as follows: ¹ H NMR(CDCl ₃ ，300MHz)：δ(ppm)＝7.47-7.52(m，3H)，δ(ppm)＝7.56-7.63(m，3H)，δ(ppm)＝7.62-7.70(m，4H)，δ(ppm)＝7.74(s，1H)，δ(ppm)＝7.84-8.05(m，3H)，δ(ppm)＝8.22(d，1H)，δ(ppm)＝8.45-8.62(m，3H),δ(ppm)＝8.95(d，1H),δ(ppm)＝9.46(s，1H)。

example 3: synthesis of Compound 75

After nitrogen replacement is carried out in a three-mouth reaction bottle provided with a mechanical stirring device, a thermometer and a constant pressure dropping funnel, raw materials 75a (200 mmol) and 220.0mL of THF are sequentially added, the temperature is reduced to-40 to-50 ℃, a tetrahydrofuran solution of iodine (240.0 mL) is dropwise added, after the dropwise addition is finished, the temperature is kept at-40 to-50 ℃ for 1h, the reaction liquid is cooled to the room temperature, 300.0mL of dichloromethane and 300.0mL of water are added, the mixture is stirred, kept stand and separated, an aqueous phase is extracted for 1 time by 150.0mL of dichloromethane, separated, an organic phase is combined, washed for 2 times by 300.0mL of water, separated, 15g of anhydrous sodium sulfate is added to the organic phase for drying, filtration is carried out, when the organic phase is concentrated to-0.08MPa at (-0.09 to 40 to 50 ℃), and 60.0mL of the organic phase is remained, concentration is stopped, 120.0mL of petroleum ether is added, the mixture is stirred for 1.0h at the room temperature, filtration is carried out, and a filter cake is leached by petroleum ether, so that an intermediate 75-1 (218.93 mmol) is obtained and the yield is 65%.

After nitrogen gas replacement in a three-neck reaction flask equipped with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, the intermediate 75-1 (218.93 mmol), the raw material 75b (208.0 mmol), 400.0mL of toluene, 200.0mL of ethanol, 200.0mL of water, 21.9mmol of tetrabutylammonium bromide and 437.86mmol of potassium carbonate are sequentially added, the temperature is raised to 45-50 ℃, the palladium tetratriphenylphosphine (1.1 mmol) is added, the temperature is raised to 68-70 ℃ continuously, and the reaction is kept for 4 hours. Cooling the reaction liquid to room temperature, adding 300.0mL of water, stirring, standing, separating, extracting the water phase for 1 time by 200.0mL of toluene, separating, combining the organic phases, washing for 2 times by 300.0mL of water, separating, adding 15g of anhydrous sodium sulfate into the organic phase, drying, filtering, passing the organic phase through a silica gel chromatographic column, leaching by 300.0mL of toluene, concentrating the organic phase (-0.09 to-0.08MPa, 55 to 65 ℃) to obtain the residual 90.0mL of organic phase, stopping concentration, adding 160.0mL of ethanol, cooling to 15 to 20 ℃, separating out a large amount of solids, and filtering to obtain an intermediate 75-2 (110.26 mmol) with the yield of 60%.

After nitrogen gas replacement in a three-neck reaction flask equipped with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, the intermediate 75-2 (110.26 mmol), the raw material 75c (132.31 mmol), potassium acetate (220.52 mmol) and 150.0mL of 1, 4-dioxane were sequentially added, stirring was started, the temperature was raised to 45-50 ℃, X-Phos (0.66 mmol) and Pd2 (dba) 3 (0.33 mmol) were added, the temperature was raised to 90-100 ℃ and the reaction was continued for 2 hours. Cooling the reaction liquid to room temperature, adding 150.0mL of dichloromethane and 150.0mL of water, stirring, standing, separating, extracting the water phase for 1 time by using 75.0mL of dichloromethane, separating, combining the organic phases, washing for 2 times by using 150.0mL of water, separating, adding 15g of anhydrous sodium sulfate into the organic phase, drying, filtering, passing the organic phase through a silica gel chromatographic column, leaching by using 200.0mL of dichloromethane, stopping concentration when the organic phase is concentrated to (-0.09 to-0.08MPa, 40 to 50 ℃) and remaining 50.0mL of the organic phase, adding 80.0mL of petroleum ether, stirring for 1.0h at room temperature, filtering, leaching a filter cake by using the petroleum ether, obtaining an intermediate 75-3 (110.68 mmol), and obtaining the yield of 85%.

Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirring device, a thermometer and a condenser, the intermediate 75-3 (110.68 mmol), the raw material 75d (121.75 mmol), tetrabutylammonium bromide (11.07 mmol), 200.0mL of toluene, 100.0mL of ethanol, 100.0mL of water and potassium carbonate (221.36 mmol) are sequentially added, the temperature is raised to 45-50 ℃, tetratriphenylphosphine palladium (0.56 mmol) is added, the temperature is continuously raised to reflux, and the reaction is kept for 8 hours. Adding 200.0mL of water, separating, extracting the water phase with 100.0mL of toluene, combining organic phases, adding 200.0mL of water, washing for 2 times, separating, adding 15g of anhydrous sodium sulfate into the organic phase, stirring, drying, filtering, concentrating the organic phase (from-0.09 to-0.08MPa, 55-65 ℃) when 60.0mL of the residual organic phase is left, stopping heating, cooling to 15-20 ℃, separating out a large amount of solids, filtering, leaching a filter cake with ethanol to obtain an intermediate 75-4 (79.11 mmol), wherein the yield is 75%.

Under the protection of nitrogen in a three-port reaction flask equipped with a mechanical stirrer, a thermometer and a condenser, the intermediates 75-4 (79.11 mmol), 150.0ml of PhCl, m-CPBA (118.67 mmol) and BF were sequentially added ₃ ·OEt ₂ (23.74 mmol) and 4-iodotoluene (19.78 mmol) were stirred, the temperature was raised to 110 ℃ and the reaction was allowed to proceed for 2h, the reaction mixture was poured into 100.0mL of water, and 150.0mL of toluene was added with stirring. Standing, separating, extracting the water phase with 100.0mL of toluene, combining the organic phases, washing the organic phases with 150.0mL of water for 2 times, drying with 15g of anhydrous sodium sulfate, filtering, passing the filtrate through a (80-120) mesh silica gel column, concentrating the column-passing liquid (-0.09 to-0.08MPa, 50-70 ℃) until the organic phase cannot be separated, adding 60.00mL of n-heptane under stirring, and filtering to obtain an intermediate 75-5 (47.14 mmol) with the yield of 60%.

Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, sequentially adding 75-5 (47.14 mmol) of an intermediate, 3-7 (51.86 mmol) of an intermediate, 4.72mmol of tetrabutylammonium bromide, 60.0mL of toluene, 30.0mL of ethanol, 30.0mL of water and 94.28mmol of potassium carbonate, heating to 45-50 ℃, adding 0.24mmol of palladium tetratriphenylphosphine, continuously heating to reflux, and reacting for 8 hours under heat preservation. Adding 100.0mL of water, separating, extracting the water phase with 50.0mL of toluene, combining organic phases, adding 75.0mL of water, washing for 2 times, separating, adding 10g of anhydrous sodium sulfate into the organic phase, stirring, drying, filtering, concentrating the organic phase (-0.09 to-0.08MPa, 55-65 ℃) when 50.0mL of the residual organic phase is left, stopping heating, cooling to room temperature, separating out solids, filtering, leaching filter cakes with ethanol, and obtaining a compound 75 (63.52 mmol) with the yield of 65%.

Examples 4 to 26

The compounds in Table 1 were synthesized according to the procedure of example 1 except that the raw materials 3c, 3d, 3e and 3f in example 1 were replaced with the raw material Ic, the raw material Id, the raw material Ie and the raw material If, respectively, in Table 1, and the structures, numbers and mass spectrum data of the prepared compounds are shown in Table 1.

TABLE 1

EXAMPLE 27 Synthesis of Compound 208

Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer and a thermometer, raw materials 208a (100 mmol) and DMF (100 mL) are sequentially added, the temperature is reduced to-5 ℃ -0 ℃, the mixture is stirred for reaction, NBS (105 mmol) is added in batches, and after the addition, the heat preservation reaction is continued for 1h. 200.0mL of water was added, the mixture was filtered, and the filter cake was rinsed with ethanol to give intermediate 208b (86.4 mmol), 86.4% yield.

After nitrogen replacement in a three-port reaction bottle with a mechanical stirrer, a thermometer and a condenser, the intermediate 208b (80 mmol), the raw material 208c (800 mmol), potassium carbonate (160 mmol) and cuprous bromide (16 mmol) are sequentially added, the reaction system is heated to 110-120 ℃, and the reaction is carried out for 8 hours under heat preservation. Cooling the reaction solution to room temperature, passing through a silica gel column, leaching with 30mL of bromobenzene, concentrating the organic phase (30 mL of the organic phase is left at (-0.09-0.08MPa, 70-75 ℃), stopping concentration, cooling to 15-20 ℃, separating out a large amount of solids, and filtering to obtain an intermediate 208d (72 mmol) with the yield of 90%.

After nitrogen replacement is carried out on a three-mouth reaction bottle provided with a mechanical stirrer, a thermometer and a constant pressure dropping funnel, the intermediate 208d (70 mmol) and 150mL of THF solvent are sequentially added, the temperature is reduced to-85 to-80 ℃, butyllithium (2.5M THF solution, 84 mmol) is added dropwise, after the dropwise addition is finished, the heat preservation reaction is carried out for 1h, tributyl borate (91 mmol) is added dropwise, the heat preservation is carried out for 1h dropwise, 50mL of petroleum ether and 30mL of 10% diluted hydrochloric acid are added into reaction liquid, liquid separation is carried out, the upper layer of organic liquid is sequentially washed by 100.0mL of water for 3 times, filtering is carried out, and the filter cake is rinsed by the petroleum ether, so that the intermediate 208e (50 mmol) is obtained, and the yield is 71.4%.

Under the protection of nitrogen in a three-mouth reaction bottle with a mechanical stirrer, a thermometer and a condenser, the intermediate 208e (40 mmol), the raw material 208f (40 mmol), tetrabutylammonium bromide (4 mmol), toluene 80mL, ethanol 20.0mL, water 20.0mL and potassium carbonate (80 mmol) are sequentially added, the temperature is raised to 45-50 ℃, palladium tetratriphenylphosphine (0.4 mmol) is added, the temperature is raised continuously to reflux, and the temperature is kept for reaction for 12 hours. Adding 50.0mL of water, separating, extracting a water phase by 50.0mL of toluene, combining organic phases, adding 50mL of water, washing for 2 times, separating, adding 5g of anhydrous sodium sulfate into the organic phase, stirring, drying, filtering, concentrating the organic phase (-0.09-0.08MPa, 55-65 ℃) when 20.0mL of the residual organic phase is left, stopping heating, cooling to room temperature, separating out a solid, and filtering to obtain 208g of an intermediate (32 mmol) with the yield of 80%.

Introducing nitrogen (0.100L/min) into a sealed reaction vessel for replacement for 2min, introducing raw materials of 208h (100 mmol), triethylamine (200 mmol), palladium acetate (1 mmol) and 100mL of toluene into a reaction system, heating to 100-105 ℃, reacting for 12h, adding 50mL of water, separating, and extracting the water phase with 50mL of toluene for 1 time. The combined organic phases were washed 2 times with water, the organic phases were dried over 5g anhydrous sodium sulfate, filtered, the organic phases were concentrated (50-60 ℃ C., -0.09-0.08 MPa) until no droplets were drained, 50mL ethanol was added with stirring, and filtered to give 70.3mmol of intermediate I-3 with a yield of 70.3%.

Introducing nitrogen into a three-neck flask provided with a mechanical stirrer, a thermometer and a condenser for 10min (2000 mL/min), adding an intermediate 208j (60 mmol), a raw material 208k (66 mmol), potassium carbonate (90 mmol), 80.0mL of methanol and 40.0mL of acetonitrile, starting stirring, heating to 40-45 ℃, adding palladium acetate (1.2 mmol), continuously heating to 60-65 ℃ for reaction for 3h, cooling the reaction liquid to 25 ℃, filtering, leaching the solid with ethanol to obtain 50mmol of an intermediate 208m, wherein the yield is 83.3%.

A three-necked flask equipped with a mechanical stirrer, a thermometer and a condenser was purged with nitrogen (0.100L/min) for 15min, and then, intermediate 208m (40 mmol), triphenylphosphine rhodium chloride (0.4 mmol) and 60mL of 1, 4-dioxane were sequentially added thereto. Heating to 85-90 deg.c for reaction for 5 hr, adding 120mL water, filtering, pulping the filter cake with 50mL alcohol for 1 time, filtering to obtain 7.33g intermediate 208n in 85% yield.

LC-MS(ESI,pos.ion)m/z＝215.6(M+H) ⁺ 。

Introducing nitrogen (0.100L/min) into a three-neck flask provided with a mechanical stirrer, a thermometer and a spherical condenser for replacement for 15min, sequentially adding an intermediate 208n (30 mmol), a raw material 208o (33 mmol), potassium carbonate (60 mmol), tetrabutylammonium bromide (3 mmol), 100mL of toluene, 20.0mL of ethanol and 20.0mL of water, starting stirring, heating to 40-45 ℃, adding dichlorodi-tert-butyl- (4-dimethylaminophenyl) phosphine palladium (0.3 mmol), continuously heating to 60-65 ℃, reacting for 1h, adding 20mL of water, separating, and extracting the water phase for 1 time by using 50mL of toluene. The combined organic phases are washed with water for 2 times, dried by 2g of anhydrous sodium sulfate, filtered, concentrated (50-60 ℃ and-0.09-0.08 Mpa) until no liquid drops exist, and filtered by adding 20ml of ethanol to obtain 28.6mmol of an intermediate 208p with the yield of 95.3 percent.

Introducing nitrogen (0.100L/min) into a three-neck flask provided with a mechanical stirring device, a thermometer and a spherical condenser tube for replacement for 15min, sequentially adding an intermediate 114b (20 mmol) and 60mL of tetrahydrofuran, starting stirring, cooling to-65-60 ℃, dropwise adding LDA (24 mmol), continuing to preserve heat for 1h after dropwise adding, dropwise adding a raw material 114c (24 mmol) +20mL of tetrahydrofuran solution, continuing to preserve heat for 1h after dropwise adding, adding 50mL of water, extracting with 50mL of dichloromethane, extracting a water phase with 30mL of dichloromethane, combining organic phases, washing with water for 2 times, drying an organic phase with 2g of anhydrous sodium sulfate, filtering, concentrating the organic phase (40-45 ℃ and-0.06-0.05 Mpa) until no liquid flows out, adding 10mL of petroleum ether, and filtering to obtain 5.56g of a compound 114, wherein the yield is 72.5%, and the total yield is 69.1%. LC-MS (ESI, pos.ion) m/z =681.20

Preparation and evaluation of organic electroluminescent device

Application example 1: red organic electroluminescent device

The anode was prepared by the following procedure: will have a thickness of

The ITO substrate (manufactured by Corning) of (1). />

The substrate was prepared into an experimental substrate having a cathode, an anode and an insulating layer pattern using a photolithography process using ultraviolet ozone and O to have a size of 40mm × 40mm × 0.7mm ₂ :N ₂ Plasma surface treatment to increase the anode (test substrate)) The sum of the work functions of (a) and (b) removes scum.

HAT-CN was vacuum-deposited on an experimental substrate (anode) to a thickness of

And NDDP is evaporated on the hole injection layer to form a thickness ^ H/L>

The hole transport layer of (1).

Vacuum evaporating TPD on the hole transport layer to form a layer with a thickness of

The hole assist layer (second hole transport layer) of (1).

The hole assist layer is vapor-deposited with a compound 3 as a host and doped with DCM2 to a thickness of

The organic light emitting layer (EML).

DBimiBphen and LiQ were mixed at a weight ratio of 1

A thick Electron Transport Layer (ETL), and LiQ is evaporated on the electron transport layer to form a thickness ^ H>

And then magnesium (Mg) and silver (Ag) are mixed at a ratio of 1:9, vacuum evaporating on the electron injection layer to form a film with a thickness of ^ 4>

The cathode of (1).

The thickness of the vapor deposition on the cathode is set to

Forming an organic capping layer (CPL) fromAnd the fabrication of the organic light emitting device is completed, and the fabricated device is denoted as A1.

Application example 2 to application example 27

Organic electroluminescent devices were produced in the same manner as in application example 1 except that the compounds shown in table 2 were used for each of the light-emitting hosts in forming the organic light-emitting layer, and the produced devices were denoted as A2 to a27.

Comparative example 1

An organic electroluminescent device D1 was produced in the same manner as in application example 1, except that the compound a was used as a light-emitting host in forming an organic light-emitting layer.

Comparative example 2

An organic electroluminescent device D2 was produced in the same manner as in application example 1, except that the compound B was used as a light-emitting host in forming an organic light-emitting layer.

Comparative example 3

An organic electroluminescent device D3 was produced in the same manner as in application example 1, except that the compound C was used as a light-emitting host in forming an organic light-emitting layer.

The compounds used in application examples 1 to 27 and comparative examples 1 to 3 are shown in Table 2.

TABLE 2

For the organic electroluminescent devices obtained in the above application examples 1 to 27 and comparative examples 1 to 3, at 15mA/cm ² Test the lifetime of a T95 device at a constant current density of 10mA/cm ² The data voltage, efficiency, color coordinates were measured and the results are shown in table 3.

TABLE 3

The driving voltages of the organic electroluminescent devices A1 to A27 prepared in application examples 1 to 27 and comparative examples 1 to 3 were all between 3.65 and 4.01V, and the driving voltages of the comparative examples D1, D2 and D3 were between 4.04 and 4.10V, and the driving voltages were slightly reduced during the preparation of the compounds of the present application. The luminous efficiency of the devices A1 to A27 is between 32.34 and 37.02Cd/A, and is at least increased by 25.9 percent compared with the D2 with higher luminous efficiency in the comparative examples D1 to D3; the external quantum efficiency of A1 to A27 is between 22.49 and 26.09 percent, and is at least 13.2 percent higher than that of D2 with higher external quantum efficiency in a comparative example. The T95 lifetime of A1 to A27 is 509 to 578h, which is at least 15.4% higher than that of the device D2 with the higher lifetime of the comparative example.

The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims

1. A heterocyclic compound, wherein the heterocyclic compound has the structure consisting of formula I-1 and formula I-2:

wherein formula I-1 and formula I-2 are fused connections, which represents the point of fusion connection in formula I-1 and formula I-2;

Y ₁ and Y ₂ Each independently selected from the group consisting of a single bond, O, S, C (R) ₃ R ₄ ) Or N (R) ₅ ) And Y is ₁ And Y ₂ At most one of which is a single bond; r ₃ ～R ₅ Each independently selected from the group consisting of unsubstituted: methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, dibenzothienyl, dibenzofuranyl;

Ar ₁ selected from the group consisting of substituted or unsubstituted phenyl, unsubstituted biphenylyl, unsubstituted terphenylyl, unsubstituted naphthyl, unsubstituted dibenzothienyl, unsubstituted dibenzofuranyl, unsubstituted anthracenyl, unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, unsubstituted pyridyl, unsubstituted pyrimidyl, unsubstituted quinolyl, unsubstituted benzopyrimidinyl, and unsubstituted pyrazinyl; ar is ₁ The substituents in (1) are selected from methyl;

l is selected from a single bond or an unsubstituted group W selected from the group consisting of:

R ₁ 、R ₂ the same or different and each is independently selected from the group consisting of unsubstituted: phenyl, naphthyl, biphenyl, terphenyl; a is ₁ 、a ₂ Each represents R ₁ 、R ₂ The number of (2); a is a ₁ 、a ₂ Each independently selected from 0 or 1.

2. The heterocyclic compound according to claim 1, wherein the X ₁ 、X ₂ 、X ₃ 、X ₄ One of (1)Or both are N.

3. The heterocyclic compound according to claim 1, wherein L is selected from a single bond or the group consisting of:

4. the heterocyclic compound according to claim 1, wherein Ar is ₁ Selected from the group consisting of unsubstituted V, said unsubstituted V being selected from the group consisting of:

5. the heterocyclic compound according to claim 1, wherein Ar is ₁ Selected from the group consisting of:

6. the heterocyclic compound according to any one of claims 1 to 5, wherein the formula I-2

Selected from unsubstituted groups U selected from the group consisting of:

7. the heterocyclic compound according to claim 1, wherein the heterocyclic compound is selected from the group consisting of:

8. an electronic component comprising an anode and a cathode disposed opposite to each other, and a functional layer disposed between the anode and the cathode; the functional layer comprises the heterocyclic compound according to any one of claims 1 to 7.

9. The electronic element according to claim 8, wherein the functional layer comprises an organic light-emitting layer containing the heterocyclic compound.

10. The electronic element according to claim 8 or 9, wherein the electronic element is an organic electroluminescent device or a photoelectric conversion device.

11. The electronic element of claim 10, wherein the organic electroluminescent device is a red device.

12. An electronic device comprising the electronic component according to any one of claims 8 to 11.