CN110452239B - Nitrogen-containing heterocyclic compound, application thereof and organic electroluminescent device - Google Patents

Nitrogen-containing heterocyclic compound, application thereof and organic electroluminescent device Download PDF

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CN110452239B
CN110452239B CN201810432859.8A CN201810432859A CN110452239B CN 110452239 B CN110452239 B CN 110452239B CN 201810432859 A CN201810432859 A CN 201810432859A CN 110452239 B CN110452239 B CN 110452239B
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李国孟
高文正
魏金贝
代志宏
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Beijing Eternal Material Technology Co Ltd
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Abstract

The present disclosure relates to a nitrogen-containing heterocyclic compound having a structure represented by the following formula (1):

Description

Nitrogen-containing heterocyclic compound, application thereof and organic electroluminescent device
Technical Field
The disclosure relates to the field of organic electroluminescent materials, in particular to a nitrogen-containing heterocyclic compound, application thereof and an organic electroluminescent device.
Background
The research on organic electroluminescent materials and devices began in the 60's of the 20 th century. Organic electroluminescence can be classified into two major categories, electroluminescence and electrophosphorescence, according to the principle of luminescence. Triplet excitons of fluorescent materials undergo spin-forbidden effects and can only generate photons in a non-radiative form back to the ground state, resulting in the internal quantum efficiency of electroluminescence being limited to within 25%. The energy of singlet excitons and triplet excitons can be fully utilized by the electrophosphorescence, so that the internal quantum efficiency of the phosphorescent device can reach 100% in theory. In 1998, Ma et al, hong Kong university and Forrest et al, Princeton university, USA, respectively report electrophosphorescent materials and devices with a theoretical quantum efficiency of 100%. These important research works have greatly pushed the development of organic electroluminescent devices, making the research of organic electroluminescence an international hot spot.
Fluorescent OLED devices that can achieve a breakthrough of the 25% internal quantum efficiency limit mainly use the Thermally Activated Delayed Fluorescence (TADF) mechanism. The TADF mechanism utilizes a TAD having a small singlet-triplet energy level difference (Δ E)ST) The triplet excitons of the organic small molecule material can be converted into singlet excitons through a reverse system cross-over (RISC) process under the condition of absorbing environmental heat energy, and theoretically, the quantum efficiency in the device can reach 100 percent. However, the TADF materials reported at present have large roll-off efficiency at high brightness and short lifetime, which limits their application in full color display and white light illumination. Currently, a hypersensitive fluorescent system using TADF material as a host material to improve the exciton utilization rate is a focus of attention. In a thermal activation delayed fluorescence light-emitting system, a triplet state of a Thermal Activation Delayed Fluorescence (TADF) material serving as a host material returns to a singlet state through a reverse inter-system cross-over (RISC) process, and then energy is transferred to an object material to emit light, so that complete energy transfer can be realized at low concentration, concentration quenching can be reduced, and the cost of a device is reduced.
However, the current Thermal Activation Delayed Fluorescence (TADF) material has the situation that the hole transport capability and the electron transport capability are not matched, and the reverse system cross-over rate (k)RISC) Lower triplet-polaron annihilation (TPA) is more serious and the like.
In addition, in the organic electroluminescent material, the hole transport capability is often better than the electron transport capability, which results in unbalanced electron and hole transport and affects the luminous efficiency of the electroluminescent device.
Disclosure of Invention
The purpose of the present disclosure is to reduce the driving voltage of an organic electroluminescent device and improve the luminous efficiency.
In order to achieve the above object, a first aspect of the present disclosure provides a nitrogen-containing heterocyclic compound having a structure represented by the following formula (1):
Figure BDA0001653859880000021
wherein Z is1、Z2、Z3、Z4、Z5And Z6Are respectively selected from C atom and CR9And N atom, and Z1、Z2、Z3、Z4、Z5And Z6Wherein the number of N atoms is 0, 1 or 2;
X1、X2、X3and X4Are respectively selected from CR9’Or an N atom, and X1、X2、X3And X4At least one of them is an N atom;
R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9and R9’Each independently selected from hydrogen atom, C1～C10Alkyl radical, C1～C10Cycloalkyl, substituted or unsubstituted C6～C30Aryl and substituted or unsubstituted C3～C30At least one of heteroaryl;
l is respectively and independently selected from single bond, substituted or unsubstituted C6～C30Arylene of (a), substituted or unsubstituted C3～C30M is 0, 1 or 2;
when Z is1、Z2、Z3、Z4、Z5And Z6When the number of N atoms is 0, Ar is selected from one of structures represented by S2-S6; z1、Z2、Z3、Z4、Z5And Z6When the number of N atoms is 1 or 2, Ar is selected from one of structures shown by S1-S6, whereinA locus;
Figure BDA0001653859880000022
said substituted C6～C30Arylene, substituted C3～C30Heteroarylene, substituted C6～C30Aryl, substituted C3～C30The substituents in the heteroaryl are each independently selected from halogen, C1～C10Alkyl of (C)3～C10Cycloalkyl of, C2～C6Alkenyl of, C2～C6Cycloalkenyl group of (A), C1～C6Alkoxy group of (C)1～C6Thioalkoxy of, C6～C30Aryl and C3～C30At least one of heteroaryl groups of (a).
A second aspect of the present disclosure provides a use of the nitrogen-containing heterocyclic compound according to the first aspect of the present disclosure in the preparation of an organic electroluminescent device.
A third aspect of the present disclosure provides an organic electroluminescent device, including a substrate, an anode layer, a cathode layer, and at least one organic layer interposed between the anode layer and the cathode layer, where the organic layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer, and the organic light emitting layer contains the nitrogen-containing heterocyclic compound according to the first aspect of the present disclosure.
Through the technical scheme, the nitrogen-containing heterocyclic compound disclosed by the invention comprises carboline with better electron migration capability and a carbazole group with excellent hole transmission capability, and the asymmetric structure enables molecules to have excellent hole and electron transmission performance; because the hole transmission capacity of the organic electroluminescent molecules is often better than the electron transmission capacity of the organic electroluminescent molecules, the molecular structure of the nitrogen-containing heterocyclic compound disclosed by the invention is introduced with bridging N heterocycles and triazine, benzene cyano, pyrazine, pyridine cyano and other electron-withdrawing groups, so that the improvement of the electron transmission capacity of the molecules is facilitated. The nitrogen-containing heterocyclic compound has excellent bipolar transmission capability, can widen a charge recombination region and reduce the efficiency roll-off; and the energy levels of the compound can be regulated and controlled by introducing different carboline groups and changing the relative substitution positions of the carbazole groups and/or the carboline groups, so that materials with different energy levels are screened, and the materials of devices can be easily selected and matched.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present disclosure. 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.
The present disclosure provides, in a first aspect, a nitrogen-containing heterocyclic compound having a structure represented by the following formula (1):
Figure BDA0001653859880000031
wherein Z is1、Z2、Z3、Z4、Z5And Z6Are respectively selected from C atom and CR9And N atom, and Z1、Z2、Z3、Z4、Z5And Z6Wherein the number of N atoms is 0, 1 or 2;
X1、X2、X3and X4Are respectively selected from CR9’Or an N atom, and X1、X2、X3And X4At least one of them is an N atom;
R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9and R9’Each independently selected from hydrogen atom, C1～C10Alkyl radical, C1～C10Cycloalkyl, substituted or unsubstituted C6～C30Aryl and substituted or unsubstituted C3～C30At least one of heteroaryl;
l is respectively and independently selected from single bond, substituted or unsubstituted C6～C30Arylene of (a), substituted or unsubstituted C3～C30M is 0, 1 or 2;
when Z is1、Z2、Z3、Z4、Z5And Z6When the number of N atoms is 0, Ar is selected from one of structures represented by S2-S6; z1、Z2、Z3、Z4、Z5And Z6When the number of N atoms is 1 or 2, Ar is selected from one of structures shown by S1-S6, wherein, is a connecting site;
Figure BDA0001653859880000041
said substituted C6～C30Arylene, substituted C3～C30Heteroarylene, substituted C6～C30Aryl, substituted C3～C30The substituents in the heteroaryl are each independently selected from halogen, C1～C10Alkyl of (C)3～C10Cycloalkyl of, C2～C6Alkenyl of, C2～C6Cycloalkenyl group of (A), C1～C6Alkoxy group of (C)1～C6Thioalkoxy of, C6～C30Aryl and C3～C30At least one of heteroaryl groups of (a).
The innovation points of the invention are as follows:
carbazole has excellent hole transport capacity, carboline has better hole transport capacity and also has stronger electron transfer capacity, and the molecular structure of the nitrogen-containing heterocyclic compound asymmetrically comprises the two groups, so that molecules have excellent hole and electron transport performances;
because the hole transmission capacity of the organic electroluminescent molecules is often superior to the electron transmission capacity of the organic electroluminescent molecules, the bridged N heterocycle and electron-withdrawing groups such as triazine, benzonitrile, pyrazine, pyridine cyano and the like are introduced into the nitrogen-containing heterocyclic compound molecules, so that the electron transmission capacity of the molecules is promoted, the compound has excellent bipolar transmission capacity, the charge recombination area can be widened, and the efficiency roll-off is reduced;
and the energy levels of the compounds can be regulated and controlled by introducing different carboline groups and changing the relative substitution positions of the carbazole carboline groups and matching asymmetric carbazole carboline substitution structures, so that materials with different energy levels are screened, and the materials of devices can be easily selected and matched.
In one embodiment of the present disclosure, in the nitrogen-containing heterocyclic compound having a structure represented by formula (1), Z1、Z2、Z3、Z4、Z5And Z6The number of N atoms in the group may be 0, i.e. Z1、Z2、Z3、Z4、Z5And Z6Are independently selected from C atom or CR9In this case, the nitrogen-containing heterocyclic compound may have a structure represented by formula (2):
Figure BDA0001653859880000042
wherein Ar can be one selected from structures shown as S2-S6, L, m and X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’May have the same selection ranges as described above.
In another embodiment, in the nitrogen-containing heterocyclic compound having a structure represented by formula (1), Z1、Z2、Z3、Z4、Z5And Z6The number of N atoms in the group may be 1, i.e. Z1、Z2、Z3、Z4、Z5And Z6One of them is N atom, the others are independently selected from C atom or CR9At this time, theThe nitrogen-containing heterocyclic compound may have a structure represented by formula (3):
Figure BDA0001653859880000051
wherein Ar can be one selected from structures shown as S1-S6, L, m and X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’May have the same selection ranges as described above.
In a third embodiment, in the nitrogen-containing heterocyclic compound having a structure represented by formula (1), Z1、Z2、Z3、Z4、Z5And Z6The number of N atoms in the group may be 2, i.e. Z1、Z2、Z3、Z4、Z5And Z6Two of the N atoms, the remainder being independently selected from C atoms or CR9In this case, the nitrogen-containing heterocyclic compound may have a structure represented by formula (4):
Figure BDA0001653859880000052
wherein Ar can be one selected from structures shown as S1-S6, L, m and X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’May have the same selection ranges as described above.
According to the disclosure, X1、X2、X3And X4The number of N atoms in the nitrogen-containing compound is 1 to 3, preferably 1 to 2. To further enhance the electron transport ability of heterocyclic compounds, the disclosure providesIn a most preferred embodiment, X1、X2、X3And X4One of them may be an N atom, the others may be the same or different, and may each independently be CR9’，R9’May have the same definition as above, i.e. selected from hydrogen atom, C1～C10Alkyl radical, C1～C10Cycloalkyl, substituted or unsubstituted C6～C30Aryl and substituted or unsubstituted C3～C30At least one heteroaryl group.
Further preferably, R9’Can be H, i.e. X1、X2、X3And X4One of the groups is N atom, the others are CH, carboline ring is formed in the molecular structure, the electron transmission capability is obviously improved, and the carboline ring has no substituent and small steric hindrance, and is easy to prepare.
In another embodiment of the present disclosure, X1And/or X4May be a N atom, X2And X3May each independently be CR9’，X2And X3Which may be the same or different, R9’Can be independently selected from hydrogen atom and C1～C10Alkyl radical, C1～C10Cycloalkyl, substituted or unsubstituted C6～C30Aryl and substituted or unsubstituted C3～C30At least one of heteroaryl, wherein X2And X3May be interconnected to form a ring.
According to the present disclosure, in the structure shown in formula (1)
Figure BDA0001653859880000061
The position of the three linking sites on the loop is not particularly limited, and may be, for example, 1,3, 5-triple linkage, 1,2, 3-triple linkage or 1,2, 4-triple linkage, preferably 1,3, 5-triple linkage or 1,2, 4-triple linkage, i.e., preferably having a structure represented by formula (5) or formula (6):
Figure BDA0001653859880000062
wherein, is the attachment site.
According to the disclosure, C above6～C30Arylene radical, C3～C30Heteroarylene group, C6～C30Aryl or C3～C30When the heteroaryl groups each have a substituent, each of the substituents is preferably independently halogen or C1～C4Alkyl of (C)3～C6Cycloalkyl of, C1～C4At least one of alkoxy, phenyl, biphenyl, and pyridyl; wherein the halogen can be at least one of-F, -Cl, -Br and-I, C1～C4Is preferably at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, C1～C4The alkoxy group (b) is preferably at least one of methoxy, ethoxy, n-propoxy, isopropoxy and n-butoxy, C3～C6The cycloalkyl group of (b) is preferably a cyclopentyl group or a cyclohexyl group. Wherein the substituents may be further substituted, for example when the substituents are phenyl or pyridyl, the phenyl or pyridyl may be further substituted by halogen or C1～C4Alkyl groups of (2), and the like.
According to the disclosure, C6～C30The aryl group of (A) is well known to those skilled in the art, i.e., an aryl group having 6 to 30 skeletal carbon atoms, preferably an aryl group having 6 to 15 skeletal carbon atoms, and may be selected from, for example, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, indenyl, fluorenyl, benzofluorenyl, 9 '-dialkylfluorenyl, 9' -spirobifluorenyl, indenofluorenyl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl,
Figure BDA0001653859880000063
Radical and tetracenyl
Figure BDA0001653859880000064
At least one of the groups; wherein the biphenyl group may include a biphenyl group selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group may include p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-ylAnd m-terphenyl-2-yl, the naphthyl group may include 1-naphthyl group or 2-naphthyl group, the anthracenyl group may include at least one of 1-anthracenyl group, 2-anthracenyl group and 9-anthracenyl group, and the pyrenyl group may include at least one selected from 1-pyrenyl group, 2-pyrenyl group and 4-pyrenyl group. According to the disclosure, C6～C30The arylene group is well known to those skilled in the art, i.e., an arylene group having 6 to 30 skeletal carbon atoms, and further, may be C of the above-mentioned kind6～C30The aryl group of (a) is an arylene group formed by losing one hydrogen atom, and is preferably a phenylene group.
According to the present disclosure, heteroaryl refers to a monocyclic or fused ring aromatic group having at least one heteroatom, which may comprise one or more heteroatoms selected from B, N, O, S, P (═ O), Si, and P, and having a number of ring backbone atoms; preferably, the heteroatoms may comprise one or more heteroatoms selected from O, S and N. C3～C30The heteroaryl group has 3 to 30 skeletal carbon atoms, preferably 3 to 15 skeletal carbon atoms, and may be at least one selected from the group consisting of thienyl, furyl, dibenzofuryl, azabicyclohefuryl, azabicyclohethienyl, dibenzothienyl, dibenzoselenophenyl, carbazolyl, carbolinyl, pyrrolyl, imidazolyl, benzimidazolyl, indolyl, pyridyl, oxazolyl, oxadiazolyl, benzoxazolyl, triazinyl, pyrimidinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, phenazinyl, phenanthrolinyl, benzimidazolyl and indolocarbazolyl; at least one of pyridyl, bipyridyl and phenylpyridyl is preferable. According to the disclosure, C3～C30Heteroarylene groups are well known to those skilled in the art, i.e., heteroarylene groups having 3 to 30 skeletal carbon atoms, and further, may be C of the above kind3～C30Heteroarylene group, which is a heteroarylene group having one hydrogen atom missing, is preferably phenylene or pyridylene.
According to the disclosure, C1～C10The alkyl group of (A) is well known to those skilled in the art, i.e., an aliphatic alkyl group having 1 to 10 carbon atoms, and may be selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptylAnd at least one of octyl, nonyl and decyl, wherein the alkyl group may be a straight-chain alkyl group or an alkyl group having a branched chain, and is more preferably at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl.
According to the disclosure, C1～C6The alkoxy group of (2) is well known to those skilled in the art, i.e., an alkoxy group having 1 to 6 carbon atoms, and may be at least one selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, and n-hexoxy.
According to the disclosure, C3～C10Cycloalkyl groups of (2) are well known to those skilled in the art, i.e. cycloalkyl groups having 3 to 10 carbon atoms, preferably cyclopentyl or cyclohexyl.
According to the disclosure, C2～C6The alkenyl group of (a) is well known to those skilled in the art, i.e., an alkenyl group having 2 to 6 carbon atoms, and may include a group formed of a mono-alkenyl group or a polyene, and may be, for example, one selected from the group consisting of a vinyl group, a propenyl group, a butenyl group, and a1, 3-butadienyl group.
According to the disclosure, C1～C6The thioalkoxy group of (a) is well known to those skilled in the art, i.e., a thioalkoxy group having 1 to 6 carbon atoms, which may be a group in which an oxygen atom in the alkoxy group is replaced by a sulfur atom, and is selected from methylthio or ethylthio, for example.
According to the present disclosure, the number of substituents on the carboline group is not limited, and in order to further improve the electron transport ability of the heterocyclic compound, the number of substituents on the carboline group may be 0 to 4, preferably 0 to 1, that is, in a preferred embodiment, R is5、R6、R7And R8One of them may be C1～C10Alkyl, substituted or unsubstituted C6～C30Aryl and substituted or unsubstituted C3～C30One of the heteroaryl groups and the others are each a hydrogen atom. In another preferred embodiment, the carboline group is unsubstituted, i.e. has no substituents thereonR5、R6、R7And R8Are all hydrogen atoms.
According to the disclosure, the number of the substituents on the carbazole group is also not limited, and in order to further improve the hole transport capability of the heterocyclic compound, the number of the substituents on the carbazole group may be 0 to 8, preferably 0 to 6. The number and the kind of the substituents on the two benzene rings of the carbazole group may be the same or different, and preferably the same number and the same kind. In preferred embodiments of the present disclosure, to further balance the hole transporting ability and electron transporting ability of the compound, both phenyl rings of the carbazole group may be unsubstituted, i.e., R1、R2、R3、R4、R1’、R2’、R3’And R4’Are all hydrogen atoms.
In another embodiment, the carbazole group may have 2 substituents, the positions of the substituents are not limited, and preferably, two substituents are respectively located on two benzene rings of the carbazole group, and the substitution positions are symmetric; further, R2And R2’Can be respectively selected from C1～C10Alkyl, substituted or unsubstituted C6～C30Aryl and substituted or unsubstituted C3～C30One of the heteroaryl groups, preferably at least one of methyl, isopropyl and tert-butyl, R1、R3、R4、R1’、R3’And R4’May be divided into hydrogen atoms; or, R3And R3’Can be respectively selected from C1～C10Alkyl, substituted or unsubstituted C6～C30Aryl and substituted or unsubstituted C3～C30One of the heteroaryl groups, preferably at least one of methyl, isopropyl and tert-butyl, R1、R2、R4、R1’、R2’And R4’May be divided into hydrogen atoms.
Further, to improve the electron transport properties of the heterocyclic compounds of the present disclosure while facilitating synthesis, neither the carbazole group nor the carboline group includes a substituent, i.e., R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’And R4’Are all hydrogen atoms.
According to the present disclosure, in the structure represented by formula (1), when m is 2, the groups represented by L may be the same or different, and preferably, each L is independently a single bond, a substituted or unsubstituted C6～C15Arylene of (a), substituted or unsubstituted C3～C15Further preferably one of a single bond, phenylene, pyridylene, biphenylene, phenanthrylene, naphthylene and anthracenylene; wherein the phenylene group can comprise one of 1, 2-phenylene, 1, 3-phenylene and 1, 4-phenylene, the naphthylene group can comprise 1, 4-naphthylene or 1, 5-naphthylene, and the anthrylene group can comprise 9, 10-anthrylene.
According to the present disclosure, the nitrogen-containing heterocyclic compound may be selected from one of the following structural formulas:
Figure BDA0001653859880000081
Figure BDA0001653859880000091
Figure BDA0001653859880000101
Figure BDA0001653859880000111
Figure BDA0001653859880000121
Figure BDA0001653859880000131
Figure BDA0001653859880000141
a second aspect of the present disclosure provides a use of the nitrogen-containing heterocyclic compound according to the first aspect of the present disclosure in the preparation of an organic electroluminescent device.
According to the present disclosure, the nitrogen-containing heterocyclic compound has good electron transport properties and appropriate energy levels, and can be used as a host material and/or a guest material of a light-emitting layer of the organic electroluminescent device.
The third aspect of the present disclosure provides an organic electroluminescent device, including a substrate, an anode layer, a cathode layer, and at least one organic layer interposed between the anode layer and the cathode layer, where the organic layer includes a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and an electron injection layer, the hole transport layer, the organic light emitting layer, the electron transport layer, and the electron injection layer are sequentially formed on the anode layer, and a host material and/or a guest material of the organic light emitting layer contains the nitrogen-containing heterocyclic compound described in the first aspect, and preferably contains at least one of compounds P1 to P138.
The organic electroluminescent device disclosed by the invention can reduce the starting voltage of the device, improve the luminous efficiency and reduce the efficiency roll-off based on the excellent performance of the compound disclosed by the invention.
Compounds of synthetic methods not mentioned in the present invention are all starting products obtained commercially. Basic chemical raw materials such as petroleum ether, ethyl acetate, N-dimethylformamide, toluene, dioxane, methylene chloride, 2, 5-difluorobromobenzene, CuI, pinacol ester diborate, sodium carbonate, potassium phosphate, 4-bromoisophthalonitrile, potassium acetate, [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium, tetrakis (triphenylphosphine) palladium, carbazole, 3, 6-di-tert-butylcarbazole, 4-bromo-2, 6-difluoropyridine, 5-bromo-1, 3-benzenedinitrile, 2,4, 6-tribromopyrimidine, sodium hydride, α -carboline and β -carboline used in the examples are commercially available in domestic chemical products.
Sodium tert-butoxide, 1-bromo-2-methylnaphthalene, o-dibromobenzene, butyl lithium, dibromoethane, o-dibromobenzene, N-bromosuccinimide, methoxymethyl trimethyl phosphonium chloride.
Analytical testing of intermediates and compounds in the present invention used an ABCIEX mass spectrometer (4000QTRAP) and Brookfield nuclear magnetic resonance spectrometer (400M Hz).
The above synthetic route will be specifically described below in conjunction with synthetic examples 1 to 10.
Synthesis example 1: synthesis of Compound P37
Figure BDA0001653859880000151
Preparation of intermediate M1:
13.5g (70mmol, 1eq) of 2, 5-difluorobromobenzene, 35.4g (140mmol, 2eq) of pinacol diboron, 68g (697mmol, 20% eq) of potassium acetate, 6.1g (8.4mmol, 12% eq) of [1,1' -bis (diphenylphosphino) ferrocene ] dichloropalladium (ll) and 1000mL of dioxane as a solvent were placed in a 3000mL three-necked flask with magnetic stirring at room temperature, and nitrogen was replaced 3 times. The oil bath was warmed to 100 ℃ and reacted overnight. (PE: EA is 10: 1, product Rf is 0.5, 2, 5-difluorobromobenzene Rf is 1.0)
Cooling the reaction liquid to room temperature, extracting with ethyl acetate, taking an upper layer, spin-drying the reaction liquid, and mixing PE (polyethylene) EA (30: column chromatography of 1 gave a white solid, intermediate M1, 13 g.
Preparation of intermediate M2:
500mL of toluene, intermediate M120 g (83.3mmol, 1.2eq), 14.3g (70mmol, 1eq) of 4-bromoisophthalonitrile, an aqueous solution of sodium carbonate (22.3 g, 210mmol, 3eq, 105mL of water, 2M) and 4.04g (3.5mmol, 0.05eq) of palladium tetratriphenylphosphine were placed in a 1000mL single-neck flask equipped with magnetic stirring at room temperature, and the mixture was stirred, purged with nitrogen 3 times, warmed to 100 ℃ and reacted overnight. (PE: DCM ═ 20: 1, product Rf ═ 0.7, intermediate M1Rf ═ 0.2)
Cooling the reaction liquid to room temperature, extracting with ethyl acetate, taking an upper layer, spin-drying the reaction liquid, and mixing PE, DCM: 1 column chromatography gave a white solid, intermediate M1, 16 g.
Preparation of intermediate M3:
adding 100mL of N, N-dimethylformamide into a 500mL single-neck flask with magnetic stirring at room temperature, adding 1.2g (30mmol, 0.8eq) of NaH (60% content) and 5.2g (30mmol, 0.8eq) of alpha-carboline, reacting for half an hour at zero temperature, adding 20mL of N, N-dimethylformamide solution in which an intermediate M29 g (37.5mmol, 1eq) is dissolved dropwise, starting stirring, replacing nitrogen for 3 times, and reacting for 1h at room temperature. The reaction mixture was quenched by adding ethanol, and after spin-drying, the PE: AE ═ 1:1 was passed through a silica gel column to give 7g of M3 as a white solid.
Preparation of compound P37:
100mL of N, N-dimethylformamide and 4.5g (27mmol, 1.5eq) of carbazole are added into a 500mL single-neck flask with magnetic stirring at room temperature, after reaction for half an hour, 20mL of N, N-dimethylformamide solution in which an intermediate M37 g (18mmol, 1eq) is dissolved is added dropwise, stirring is started, nitrogen is replaced for 3 times, the temperature is raised to 80 ℃, and the reaction is carried out overnight. The reaction mixture was cooled to room temperature, ethanol was added to the reaction mixture to quench the reaction, and the mixture was dried and passed through a silica gel column at PE: AE 1:2 to obtain 8g of P37 as a white solid. Dissolving the product in toluene, and eluting with toluene as eluent to obtain silica gel column; boiling and washing with ethanol to remove impurities to obtain a crude product with the purity of 99.1 percent; the crude product was then boiled with toluene to give 6.2g of a white solid.
The mass spectrum molecular weight theory value is 535.6, and the molecular weight detection value is 535.3. Theoretical value of elemental analysis C, 82.97%; h, 3.95%; n, 13.08%, and an elemental analysis detection value C, 82.77%; h, 3.98%; and N,13.18 percent.
Synthesis example 2
Synthesis of compound P66:
Figure BDA0001653859880000161
preparation of intermediate M4:
the reaction conditions were identical to those for the preparation of intermediate M1, using 13.6g (70mmol, 1eq) of 4-bromo-2, 6-difluoropyridine instead of 13.5g (70mmol, 1eq) of 2, 5-difluorobromobenzene. And stopping the reaction after the point plate detects that the 4-bromo-2, 6-difluoropyridine is completely reacted. (PE: EA ═ 5: 1, product Rf ═ 0.5, 4-bromo-2, 6-difluoropyridine Rf ═ 0.7)
Cooling the reaction liquid to room temperature, extracting with ethyl acetate, taking an upper layer, and spin-drying the reaction liquid, wherein the PE is that EA is 10: 1, column chromatography was carried out to give intermediate M4 as a white solid, 11 g.
Preparation of intermediate M5:
the reaction conditions were identical to those for the preparation of intermediate M2, using 18.7g (70mmol, 1eq) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine instead of 4-bromoisophthalonitrile. Intermediate M1 was replaced with intermediate M420.2 g (83.3mmol, 1.2eq), and the reaction was stopped after completion of the reaction was detected. (PE: EA ═ 3: 1, product Rf ═ 0.5, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine Rf ═ 1)
Cooling the reaction liquid to room temperature, extracting with ethyl acetate, taking an upper layer, spin-drying the reaction liquid, and mixing PE (polyethylene), EA (5: 1 column chromatography gave intermediate M5 as a white solid, 17.3 g.
Preparation of intermediate M6:
100mL of N, N-dimethylformamide is added into a 500mL single-neck flask with magnetic stirring at room temperature, 1.2g (30mmol, 0.8eq) of NaH (60% content) and 5g (30mmol, 0.8eq) of carbazole are added, 20mL of N, N-dimethylformamide solution dissolved with intermediate M513 g (37.5mmol, 1eq) is added dropwise after reaction for half an hour, stirring is started, nitrogen is replaced for 3 times, and the reaction is carried out for 1 hour at room temperature. The reaction was quenched by addition of ethanol and dried, DCM: AE 1:1, and passed through a silica gel column to give 9.2g of M6 as a white solid.
Preparation of compound P66:
100mL of N, N-dimethylformamide and 4.5g (27mmol, 1.5eq) of beta-carboline are added into a 500mL single-neck flask with magnetic stirring at room temperature, 20mL of N, N-dimethylformamide solution in which the intermediate M38.9g (18mmol, 1eq) is dissolved is added dropwise after reaction for half an hour, stirring is started, nitrogen is replaced for 3 times, the temperature is raised to 90 ℃, and the reaction is carried out overnight. Cooling the reaction solution to room temperature, adding ethanol into the reaction solution to quench the reaction, and performing spin drying on the reaction solution, wherein DCM (percent by weight) AE (percent by weight) 1:2 to pass through a silica gel column. Then boiling and washing the product with ethanol to remove impurities to obtain a crude product, and boiling and washing the obtained crude product with toluene to obtain 7.1g of white solid P66 with the purity of 99.7%;
the mass spectrum has a molecular weight theoretical value of 641.7 and a molecular weight detection value of 641.2. Theoretical value of elemental analysis C, 80.48%; h, 4.24%; n, 15.28%, elemental analysis test value C, 80.57%; h, 4.33%; n,14.98 percent.
Synthesis example 3
Synthesis of compound P83:
Figure BDA0001653859880000171
preparation of intermediate M7:
the reaction conditions were identical to those for the preparation of intermediate M1, using 14.5g (70mmol, 1eq) of 5-bromo-1, 3-benzenedinitrile instead of 13.5g (70mmol, 1eq) of 2, 5-difluorobromobenzene. And stopping the reaction after the point plate detects that the 5-bromine-1, 3-benzene dinitrile is completely reacted. (PE: EA is 10: 1, product Rf is 0.4, 5-bromo-1, 3-benzenedinitrile Rf is 0.8)
Cooling the reaction liquid to room temperature, extracting with dichloromethane, taking the lower layer, spin-drying the reaction liquid, and mixing PE (polyethylene) EA 15: 1 column chromatography gave 12.2g M7 as a white solid.
Preparation of intermediate M8:
the reaction conditions were identical to those for the preparation of intermediate M2, using 22.1g (70mmol, 1eq) of 2,4, 6-tribromopyrimidine instead of 4-bromoisophthalonitrile. Intermediate M1 was replaced with intermediate M721.1g (37.5mmol, 1.2eq) and the reaction was stopped after completion of the reaction was detected. (PE: EA is 6: 1, product Rf is 0.6, 2,4, 6-tribromopyrimidine Rf is 0.9)
Cooling the reaction liquid to room temperature, extracting with ethyl acetate, taking an upper layer, spin-drying the reaction liquid, and mixing PE (polyethylene), EA is 3: 1 through the column to give 18.8g M8 as a white solid.
Preparation of intermediate M9:
400mL of xylene, 4g (24mmol, 0.8eq) of intermediate M810.85g (30mmol, 1eq), 4g (24mmol, 0.8eq) of carbazole, 5.36g (30mmol, 1eq) of cuprous iodide, 29.3g (90mmol, 3eq) of cesium carbonate and 1.75g (30mmol, 1eq) of ethylenediamine are placed in a 1000mL single-neck flask with magnetic stirring at room temperature, nitrogen is replaced for 3 times, the temperature is raised to reflux, and the reaction is carried out for 24 hours. The reaction mixture was cooled to room temperature, filtered with suction, and the filtrate was spin-dried over silica gel column (PE: DCM: 1) to give 7.2g of M9 as an off-white solid.
Preparation of compound P83:
400mL of xylene, 96.75g (15mmol, 1eq) of intermediate, 4.5g (27mmol, 1.8eq) of beta-carboline, 5.36g (30mmol, 2eq) of cuprous iodide, 29.3g (90mmol, 6eq) of cesium carbonate and 1.75g (30mmol, 2eq) of ethylenediamine are added into a 1000mL single-neck flask with magnetic stirring at room temperature, nitrogen is replaced for 3 times, and the mixture is heated to reflux and reacted for 24 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was spin-dried, and DCM AE 1:1 was passed through a silica gel column to give 6.3g of an off-white solid. Then boiling and washing the product with ethanol to remove impurities to obtain a crude product, and boiling and washing the obtained crude product with toluene to obtain 5.5g of white solid P83 with the purity of 98.6%;
mass spectrum molecular weight theoretical value 537.5, molecular weight detection value 537.2. Theoretical value of elemental analysis C, 78.20%; h, 3.56%; n, 18.24%, and the elemental analysis detection value C, 78.57%; h, 3.33%; n,18.28 percent.
The compound of the present invention can be obtained by the above-described synthesis method, but is not limited to these methods. Other methods known to those skilled in the art, such as Stille coupling, Grignard, Kumada-Tamao, etc., can be selected by those skilled in the art, and any equivalent synthetic method can be used as desired for the purpose of achieving the desired compound.
The light-emitting layer of the organic electroluminescent device and the organic electroluminescent device of the present invention will be explained below.
The light-emitting layer of the organic electroluminescent device comprises a host material and a dye. The compound of the present invention can be used as a host material or as a dye.
The organic light emitting diode comprises a first electrode and a second electrode which are arranged on a substrate, and an organic material arranged between the electrodes, wherein a hole transport layer, a light emitting layer and an electron transport layer are arranged between the first electrode and the second electrode.
As the substrate, a substrate for an organic light emitting display is used, for example: glass, polymer materials, glass with TFT components, polymer materials, and the like.
The functional layer can comprise a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light emitting layer is arranged between the hole transport layer and the electron transport layer; the light-emitting layer is the light-emitting layer of the organic electroluminescent device.
Specifically, the anode material may be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO)2) Transparent conductive materials such as zinc oxide (ZnO), metal materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT, and multilayer structures of these materials.
The hole injection layer material may include at least one of the following compounds HI-1 to HI-3:
Figure BDA0001653859880000191
the hole transport layer material may include at least one of the compounds HT-1-HT-31:
Figure BDA0001653859880000192
Figure BDA0001653859880000201
Figure BDA0001653859880000211
the device light emitting layer host material may include at least one of the compounds TDH1-TDH 24.
Figure BDA0001653859880000212
Figure BDA0001653859880000221
The dye material of the light emitting layer may include at least one of F-1 to F-24:
Figure BDA0001653859880000222
Figure BDA0001653859880000231
the electron transport layer material may include at least one of the compounds ET-1 to ET-57:
Figure BDA0001653859880000241
Figure BDA0001653859880000251
Figure BDA0001653859880000261
an electron injection layer may also be included in the device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following:
LiQ，LiF，NaCl，CsF，Li2O，Cs2CO3，BaO，Na，Li，Ca。
the cathode can comprise magnesium silver mixture, metal such as LiF/Al, ITO and the like, metal mixture and oxide.
Device examples 1 to 7 the nitrogen-containing heterocyclic compound of the present disclosure was used as a dye for an organic electroluminescent device.
Device example 1:
the device structure is as follows:
ITO (150nm)/HI-2(10nm)/HT-2(40nm)/TDH10: 30% P8(30nm)/ET34(20nm)/LiF (0.5nm)/Al (150 nm). (wherein 30% means that the weight ratio of P8 to TDH10 is 30%, which is also expressed in the following examples)
The preparation process of the organic electroluminescent device is as follows: the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 10 DEG-5Pa, performing vacuum evaporation on the anode layer film to obtain HI-2 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
evaporating HT-2 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
a luminescent layer of the device is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material TDH10 is adjusted to be 0.1nm/s by using a multi-source co-evaporation method, the evaporation rate of the dye P8 is set at a ratio of 30%, and the total film thickness of the evaporation is 30 nm;
vacuum evaporating an electron transport layer material ET-34 of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
Device embodiments 2 to 7: the method of device example 1 was employed except that the host material compound P8 was replaced with P28, P82, P12, P66, P83, and P99, respectively.
Device example 2:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％P28(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 3:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％P82(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 4:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％P12(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 5:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％P66(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 6:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％P83(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 7:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％P99(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 8:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％P120(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device comparative example 1: a material different from the present disclosure is used as a dye of the organic electroluminescent device.
The method of device example 1 was used except that the guest dye was replaced with a 129.
The device structure is as follows: ITO (150nm)/HI-2(10nm)/HT-2(40nm)/TDH10 30% A129(30nm)/ET-34(20nm)/LiF (0.5nm)/Al (150 nm).
Device comparative example 2:
the method of device example 1 was used, except that the guest dye was replaced with a130, and the device structure was:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10:30％A130(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
Figure BDA0001653859880000281
the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
at the same brightness, using digital source meter and brightness meter measuring deviceThe organic electroluminescent devices prepared in examples 1 to 7 and device comparative examples 1 to 2 had driving voltage and current efficiency and device life. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density was the current efficiency, and the results are shown in tables 1 and 2, respectively.
TABLE 1
Example numbering Dye material Required luminance (cd/m)2) Operating voltage (V) Current efficiency (cd/A)
Device example 1 P8 1000 6.2 15.1
Device example 2 P28 1000 6.4 14.2
Device example 3 P82 1000 5.9 15.9
Device example 4 P12 1000 6.0 15.8
Device example 5 P66 1000 6.3 16.3
Device example 6 P83 1000 6.1 13.4
Device example 7 P99 1000 6.3 14.3
Device example 8 P120 1000 6.7 12.5
Comparative device example 1 A129 1000 7.2 11.2
Comparative device example 2 A130 1000 7.0 12.2
From the above table data it can be seen that:
example 2 the organic electroluminescent property of the OLED using the compound P28 of the present invention as a dye was superior to that of the OLED using a129 as a dye of comparative example 1, and P28 achieved higher current efficiency and lower driving voltage; the asymmetric carbazole carboline group is introduced into the dye to prepare the organic electroluminescent device, so that the advantages of obviously reducing the driving voltage and improving the luminous efficiency are achieved.
Meanwhile, the organic electroluminescence performance of the OLED adopting the compound P66 of the invention as the dye in the embodiment 5 is better than that of the OLED adopting A130 as the dye in the comparative example 2, and the P66 also obtains higher current efficiency and lower driving voltage; this shows that the carboline group and the bridged pyridine group are introduced into the molecule, which can significantly reduce the driving voltage and improve the luminous efficiency.
The results show that the novel organic material provided by the invention is used for an organic electroluminescent device, can effectively reduce the take-off and landing voltage and improve the current efficiency, has good stability and is a blue dye material with good performance.
Device examples 9 to 12 use the nitrogen-containing heterocyclic compound of the present disclosure as a host material of a light-emitting layer of an organic electroluminescent device.
Device example 9:
the preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 10 DEG-5Pa, performing vacuum evaporation on the anode layer film to obtain HI-2 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
evaporating HT-2 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
a luminescent layer of the device is evaporated on the hole transport layer in vacuum, the luminescent layer comprises a main material and a dye material, the evaporation rate of the main material P8 is adjusted to be 0.1nm/s, the evaporation rate of the dye F8 is set in a proportion of 30%, and the total film thickness of evaporation is 30nm by using a multi-source co-evaporation method;
vacuum evaporating an electron transport layer material ET-34 of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
The following devices were prepared according to the method described above, having the following structures:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/P8:30％F8(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
wherein 30% represents a weight ratio of P8 relative to TDH10 of 20%, also expressed in this way in the following examples.
Device example 10:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/P28:30％F8(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 11:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/P82:30％F8(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device example 12:
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/P12:30％F8(30nm)/ET-34(20nm)/LiF(0.5nm)/Al(150nm)。
device comparative example 3: a material different from the present disclosure is used as a dye of the organic electroluminescent device.
The method of device example 9 was used except that the host material was replaced with CBP.
Figure BDA0001653859880000291
The device structure is as follows: ITO (150nm)/HI-2(10nm)/HT-2(40nm)/CBP 30% F8(30nm)/ET-34(20nm)/LiF (0.5nm)/Al (150 nm).
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage and current efficiency and the lifetime of the organic electroluminescent devices prepared in examples 9 to 18 and comparative example 3 were measured at the same luminance using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 10000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density was the current efficiency, and the results are shown in Table 1.
TABLE 2
Example numbering Host material Required luminance (cd/m)2) Operating voltage (V) Current efficiency (cd/A)
Device example 9 P8 10000 5.1 48.8
Device example 10 P28 10000 5.5 39.1
Device example 11 P82 10000 5.2 49.1
Device example 12 P12 10000 4.9 53.4
Comparative device example 3 CBP 10000 6.6 23.5
From the above table data it can be seen that:
example 9 the organic electroluminescent performance of the OLED using compound P8 of the present invention as host is better than that of the OLED using CBP as host in comparative example 3, and the device in example 9 achieves higher current efficiency and lower driving voltage; the result shows that the material based on the asymmetric carbazole carboline group is used as a main body to prepare the organic electroluminescent device, and the advantages of obviously reducing the driving voltage and improving the luminous efficiency can be achieved.
Meanwhile, the organic electroluminescence performance of the OLED adopting the compound P82 of the invention as a dye in the embodiment 11 is better than that of the OLED adopting P8 as a main body in the embodiment 9, and the P82 obtains higher current efficiency and lower driving voltage; this shows the advantage that the driving voltage can be significantly reduced and the luminous efficiency can be improved when the host material uses a bridged pyridine group.
The results show that when the novel organic material is used for the main body of the organic electroluminescent device, the novel organic material can effectively reduce the take-off and landing voltage, improve the current efficiency and have good stability.
The preferred embodiments of the present disclosure have been described in detail above, 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 fall within the protection scope of the present disclosure.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.
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 (9)

1. A nitrogen-containing heterocyclic compound characterized by having a structure represented by the following formula (1):
Figure FDA0003473949880000011
wherein Z is1、Z2、Z3、Z4、Z5And Z6Are respectively selected from C atom and CR9And N atom, and Z1、Z2、Z3、Z4、Z5And Z6Wherein the number of N atoms is 0, 1 or 2;
X1、X2、X3and X4Are respectively selected from CR9’Or an N atom, and X1、X2、X3And X4At least one of them is an N atom;
R1、R2、R4、R5、R6、R8、R1’、R2’、R4’、R9and R9’Is a hydrogen atom, R3And R3’At least one member selected from the group consisting of a hydrogen atom, a methyl group, an isopropyl group and a tert-butyl group, R7At least one member selected from the group consisting of a hydrogen atom and an isopropyl group;
l is selected from one of single bond, phenylene, pyridylene, biphenylene, phenanthrylene, naphthylene and anthrylene, and m is 0, 1 or 2; and when Z is1、Z2、Z3、Z4、Z5And Z6Wherein L is not a substituted or unsubstituted phenylene, biphenylene, phenanthrylene, naphthylene, or anthracenylene group, when the number of N atoms is 1;
when Z is1、Z2、Z3、Z4、Z5And Z6When the number of N atoms is 0, Ar is selected from one of structures represented by S2-S6; z1、Z2、Z3、Z4、Z5And Z6When the number of N atoms is 1 or 2, Ar is selected from one of structures shown by S1-S6, wherein, is a connecting site;
Figure FDA0003473949880000021
2. the nitrogen-containing heterocyclic compound according to claim 1, characterized in that the heterocyclic compound has a structure represented by the following formula (2):
Figure FDA0003473949880000022
wherein Ar is selected from one of structures shown as S2-S6, L, m and X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’Have the same definition as in claim 1.
3. The nitrogen-containing heterocyclic compound according to claim 1, characterized in that the heterocyclic compound has a structure represented by the following formula (3) or formula (4):
Figure FDA0003473949880000031
wherein Ar is1One selected from structures S1-S6, L, m, X1、X2、X3、X4、R1、R2、R3、R4、R5、R6、R7、R8、R1’、R2’、R3’、R4’、R9And R9’Have the same definition as in claim 1.
4. The nitrogen-containing heterocyclic compound according to any one of claims 1 to 3, wherein X is1、X2、X3And X4One of them being an N atom and the others being CR9’，R9’Have the same definitions as in claim 1。
5. The nitrogen-containing heterocyclic compound according to claim 1, characterized in that the heterocyclic compound is selected from one of the following structural formulae:
Figure FDA0003473949880000032
Figure FDA0003473949880000041
Figure FDA0003473949880000051
Figure FDA0003473949880000061
Figure FDA0003473949880000071
Figure FDA0003473949880000081
Figure FDA0003473949880000091
6. use of the nitrogen-containing heterocyclic compound according to any one of claims 1 to 5 in an organic electroluminescent device.
7. The use according to claim 6, wherein the nitrogen-containing heterocyclic compound is used as a host material and/or a guest material of a light-emitting layer of the organic electroluminescent device.
8. An organic electroluminescent device comprising a substrate, an anode layer, a cathode layer, and at least one organic layer interposed between the anode layer and the cathode layer, wherein the organic layer comprises a hole injection layer, a hole transport layer, an organic light-emitting layer, an electron transport layer, and an electron injection layer, and wherein the organic light-emitting layer contains the nitrogen-containing heterocyclic compound according to any one of claims 1 to 5.
9. The organic electroluminescent device according to claim 8, wherein the host material and/or the guest material of the organic light-emitting layer contains the nitrogen-containing heterocyclic compound according to any one of claims 1 to 5.
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