CN115633513A - Organic electroluminescent device - Google Patents

Organic electroluminescent device Download PDF

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CN115633513A
CN115633513A CN202110804901.6A CN202110804901A CN115633513A CN 115633513 A CN115633513 A CN 115633513A CN 202110804901 A CN202110804901 A CN 202110804901A CN 115633513 A CN115633513 A CN 115633513A
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陈志宽
李祥智
蔡烨
魏定纬
丁欢达
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Ningbo Lumilan Advanced Materials Co Ltd
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Abstract

The present invention provides an organic electroluminescent device characterized by comprising a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a light-emission auxiliary layer between the light-emitting layer and the first electrode, wherein the light-emitting layer comprises a compound having a structure represented by formula (1). The organic electroluminescent device has lower driving voltage, higher current efficiency and longer service life.

Description

Organic electroluminescent device
Technical Field
The invention belongs to the field of electroluminescent devices, and relates to an organic electroluminescent device.
Background
An organic electroluminescent device converts electrical energy into light by injecting charges into an organic light emitting material, and generally includes an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the organic electroluminescent device may be composed of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer (containing a host material and a dopant material), an electron transport layer, an electron injection layer, and the like; materials used in the organic layer are classified into a hole injection material, a hole transport material, an electron blocking material, a light emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, and the like according to functions. In the organic electroluminescent device, holes from an anode and electrons from a cathode are injected into a light emitting layer by a voltage, and excitons having high energy are generated by recombination of the holes and the electrons. The organic light emitting compound moves to an excited state by energy and emits light by the energy when the organic light emitting compound returns to a ground state from the excited state.
The most important factor determining the luminous efficiency in the organic electroluminescent device is the light emitting material. The luminescent material is required to have the following characteristics: high external quantum efficiency, high mobility of electrons and holes, and stability of the formed light emitting material layer. Recently, it is an urgent task to develop an organic electroluminescent device having high efficiency and long life. In particular, in view of the electroluminescent characteristics required for large and medium-sized OLED panels, the development of highly excellent light emitting materials superior to conventional materials is urgently required.
In the organic EL device, the electron transport material actively transports electrons from the cathode to the light emitting layer and suppresses the transport of holes that are not recombined in the light emitting layer to increase the chance of recombination of holes and electrons in the light emitting layer. Organometallic complexes such as Alq3 are excellent in transporting electrons, and thus are conventionally used as electron transporting materials. However, alq3 has a problem in that the lifetime of the fabricated device is short. Therefore, there is a need for a new electron transport material that does not have the above-mentioned problems and rapidly transports electrons in an organic electroluminescent device to provide an organic electroluminescent device having high luminous efficiency.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide an organic electroluminescent device.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a light-emission auxiliary layer between the light-emitting layer and the first electrode, wherein the light-emitting layer comprises a compound having a structure represented by formula (1):
Figure BDA0003166116700000011
R 1 -R 6 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a way that O atoms or S atoms are not adjacent a substituted or unsubstituted C2-C30 alkenyl group, a C2-C30 alkenyl group in which one or more methylene groups are substituted by-O-or-S-in such a manner that O atom or S atom is not adjacent to each other substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl group, substituted or unsubstituted C1-C30 alkoxy group or substituted or unsubstituted C6-C30 aryloxy group,
R 1 -R 6 each independently exists or two adjacent rings are connected to form a ring which is a substituted or unsubstituted benzene ring,
l is selected from a linkage, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C5-C30 heteroarylene,
Ar 1 selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C5-C60 heteroarylamine, substituted or unsubstituted C5-C60 arylheteroarylamine,
n is selected from an integer of 0 to 3 (e.g. may be 0, 1, 2 or 3),
m is an integer from 0 to 5 (e.g., may be 0, 1, 2, 3,4 or 5),
n1 is selected from the integer of 0-1,
m1 is an integer selected from 0 to 1.
Preferably, n1+ m1=1.
Preferably, -L-Ar 1 Is selected from
Figure BDA0003166116700000021
Wherein Ar is 2 、Ar 3 Each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl.
Preferably, ar 2 、Ar 3 Each independently selected from the group consisting of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazolyl, or dibenzocarbazolyl;
preferably, -L-Ar1 is selected from
Figure BDA0003166116700000022
Wherein the dotted line represents L and Ar 3 Forming a ring through chemical bond connection;
more preferably, -L-Ar1 is selected from the group consisting of substituted or unsubstituted:
Figure BDA0003166116700000023
Figure BDA0003166116700000031
preferably, -L-Ar 1 Is selected from
Figure BDA0003166116700000032
Wherein the dotted line represents Ar 2 、Ar 3 Is connected into a ring through chemical bonds,
more preferably, -L-Ar 1 Selected from the group consisting of substituted or unsubstituted
Figure BDA0003166116700000033
Figure BDA0003166116700000041
Preferably, ar 1 Is selected from
Figure BDA0003166116700000042
Wherein X 1 Selected from N or CR X1 ，X 2 Selected from N or CR X2 ，X 3 Selected from N or CR X3 ，X 4 Selected from N or CR X4 ，X 5 Selected from N or CR X5 ，
R X1 、R X2 、R X3 、R X4 、R X5 Each independently selected from hydrogen, deuterium, halogenA cyano group, a substituted or unsubstituted C1-C30 alkyl group, a C1-C30 alkyl group in which one or more methylene groups are substituted by-O-or-S-in such a manner that an O atom or an S atom is not adjacent, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C3-C30 heteroaralkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkoxy group, or a substituted or unsubstituted C6-C30 aryloxy group,
R X1 、R X2 、R X3 、R X4 、R X5 each independently exists or two adjacent rings are connected to form a ring, the ring is a substituted or unsubstituted benzene ring, pyridine ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthooxazole ring, naphthothiazole ring, benzofuran ring or benzothiophene ring,
preferably, ar 1 Is selected from
Figure BDA0003166116700000051
Preferably, ar 1 Is selected from
Figure BDA0003166116700000052
Wherein X 1 、X 2 、X 5 Any two of which are selected from the group consisting of N,
Y 1 selected from N, CR Y1 ，Y 2 Selected from N, CR Y2 ，Y 3 Selected from N, CR Y3 ，Y 4 Selected from N, CR Y4 ，
R Y1 、R Y2 、R Y3 、R Y4 Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a way that the O atom or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 alkyl3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy or substituted or unsubstituted C6-C30 aryloxy,
R Y1 、R Y2 、R Y3 、R Y4 each independently exists, or two adjacent rings are connected to form a ring which is a substituted or unsubstituted benzene ring.
More preferably, X 2 、X 5 Is selected from N.
More preferably, X 1 、X 5 Is selected from N.
More preferably, Y 1 Selected from the group consisting of CR Y1 ，Y 2 Selected from the group consisting of CR Y2 ，Y 3 Selected from the group consisting of CR Y3 ，Y 4 Selected from the group consisting of CR Y4 ，
More preferably, R X1 、R X2 、R X3 、R X4 、R X5 、R Y1 、R Y2 、R Y3 、R Y4 Each independently selected from hydrogen, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, and spirobifluorenyl.
Preferably, each L is independently selected from phenylene, biphenylene, naphthylene,
preferably, R 1 -R 6 Each independently selected from hydrogen, deuterium, cyano, fluorine, methyl, ethyl, tert-butyl, deuterium-substituted methyl, fluorine-substituted methyl, phenyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl,
preferably, ar 1 Selected from phenyl, biphenyl, terphenyl, naphthyl, benzophenanthryl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl,Dibenzofuran-substituted phenyl group, dibenzothiophene-substituted phenyl group, dimethylfluorenyl group, diphenyl-substituted fluorenyl group, spirobifluorenyl group, 2-phenylphenanthrene [3,4-d ]]Oxazolyl, 2-phenylphenanthrene [3,4-d ]]A thiazolyl group;
in the present invention, when the group contains a substituent, the substituents are each independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C6 alkyl, unsubstituted or R ' substituted C6-C12 aryl, unsubstituted or R ' substituted C3-C20 heteroaryl; r' is selected from deuterium, halogen, cyano, deuterium-substituted methyl, halogen-substituted methyl;
more preferably, the C1-C6 alkyl group is selected from methyl, ethyl, tert-butyl;
the aryl of C6-C12 is selected from phenyl, biphenyl and naphthyl;
the heteroaryl of C3-C20 is selected from triazinyl, pyridyl, phenyl-substituted pyridyl, pyridyl-substituted phenyl, dibenzofuranyl and dibenzothiophenyl.
Preferably, the compound having the structure represented by formula (1) is any one of the following compounds:
Figure BDA0003166116700000061
Figure BDA0003166116700000071
Figure BDA0003166116700000081
Figure BDA0003166116700000091
Figure BDA0003166116700000101
Figure BDA0003166116700000111
Figure BDA0003166116700000121
Figure BDA0003166116700000131
Figure BDA0003166116700000141
Figure BDA0003166116700000151
Figure BDA0003166116700000161
Figure BDA0003166116700000171
Figure BDA0003166116700000181
Figure BDA0003166116700000191
Figure BDA0003166116700000201
Figure BDA0003166116700000211
Figure BDA0003166116700000221
Figure BDA0003166116700000231
as used in the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine, preferably fluorine.
As used herein, the term "alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.
As used herein, unless otherwise specified, the term "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 30 carbon atoms. Examples of such cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantane and the like.
Heteroaryl, heteroarylene groups of the present invention include monocyclic, polycyclic or fused ring aryl groups, which rings may be interrupted by short non-aromatic units, including, but not limited to, furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, derivatives thereof, and the like.
Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, 9 '-dimethylfluorenyl, 9' -diphenylfluorenyl, or spirobifluorenyl.
Preferably, the heteroaryl group is selected from dibenzofuranyl, dibenzothienyl, carbazolyl, triazinyl, pyridyl, pyrimidinyl, imidazolyl, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, naphthoimidazolyl, naphthooxazolyl, naphthothiazolyl, phenanthroimidazolyl, phenanthroizooxazolyl, phenanthroizothiazolyl, quinoxalinyl, quinazolinyl, indolocarbazolyl, indolofluorenyl, benzothiophenopyrazinyl, benzothiophenopyrimidinyl, benzofuropyrazinyl, benzofuropyrimidinyl, indolopyrimidyl, indolopyridyl, indenopyridyl, spiro (fluorene-9, 1 '-indene) pyrazinyl, spiro (fluorene-9, 1' -indene) pyrimidyl, benzofurocarbazolyl, or benzothiophenocarbazolyl.
As used herein, the term "aryloxy" refers to a monovalent substituent represented by RO-, wherein R represents an aryl group having 6 to 30 carbon atoms. Examples of such aryloxy groups include, but are not limited to, phenoxy, naphthoxy, diphenoxy, and the like.
As used herein, the term "substituted" means that the hydrogen atom in the compound is replaced with another substituent. The position is not limited to a specific position as long as hydrogen at the position can be substituted by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.
As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium, and tritium.
The term "two adjacent groups are linked to form a ring" as used herein means that 2 substituents at adjacent positions in the same or adjacent rings may be linked to each other via chemical bonds to form a ring, and the present invention is not limited to specific linking and forming methods (for example, linking via single bond, linking via benzene ring, linking via naphthalene ring, etc.)
Figure BDA0003166116700000241
Thickening and passing
Figure BDA0003166116700000242
Thickening and passing
Figure BDA0003166116700000243
Thickening and passing
Figure BDA0003166116700000244
Thickening and passing
Figure BDA0003166116700000245
Thickening; wherein
Figure BDA0003166116700000246
Indicating a thick and dense position) has the same meaning as when the same description is referred to below.
In the present invention, the definition of a group defines a range of carbon numbers, the number of carbon atoms of which is any integer within the defined range, such as a C6-C60 aryl group, and the number of carbon atoms representing an aryl group can be any integer within the range encompassed by 6-60, such as 6, 8, 10, 15, 20, 30, 35, 40, 45, 50, 55, 60, or the like.
In the present invention, the preparation route of the compound having the structure represented by formula (1) is as follows:
Figure BDA0003166116700000251
wherein OTf represents
Figure BDA0003166116700000252
Preferably, a difference between the HOMO level value of the compound having the structure represented by formula (1) and the HOMO level value of the material of the emission assisting layer is less than 0.5eV. In the invention, the difference of the energy level values is controlled to be less than 0.5eV, so that the OLED device can obtain smaller driving voltage.
Preferably, the material of the luminescence auxiliary layer is selected from compounds having a structure represented by formula (2):
Figure BDA0003166116700000253
wherein Y is selected from O, S, NR N1 Or CR Y1 R Y2 ，
The R is N1 Selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl,
the R is Y1 、R Y2 Independently selected from substituted or unsubstituted C1-C30 alkyl or substituted or unsubstituted C6-C30 aryl,
said R is Y1 、R Y2 Independently of or with R 34 Or/and R 34 Are connected to form a ring A,
the R is 21 -R 36 Is independently selected from
Figure BDA0003166116700000261
Hydrogen, deuterium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkyl wherein one or non-adjacent at least two methylene groups are independently replaced by-O-or-S-, a substituted or unsubstituted C2-C30 alkenyl group wherein one or non-adjacent at least two methylene groups are independently replaced by-O-or-S-, any one of a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C7-C30 aralkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroaryl group, a substituted or unsubstituted C3-C30 heteroaralkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C30 arylamino group, a substituted or unsubstituted C1-C30 alkoxy group, or a substituted or unsubstituted C6-C30 aryloxy group,
and R is 21 -R 36 At least one item selected from
Figure BDA0003166116700000262
The R is 21 -R 36 Independently exist or are connected with each other to form a ringB，
The ring A is selected from a substituted or unsubstituted indole ring or a benzene ring,
the ring B is selected from a substituted or unsubstituted benzene ring,
said L 1 、L 2 、L 3 Independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group or a substituted or unsubstituted C2-C30 heteroarylene group,
ar is 1 '、Ar 2 ' is independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C2-C60 heteroaryl.
Preferably, R in formula (2) 27 、R 28 、R 29 、R 30 Any one of them is selected from
Figure BDA0003166116700000263
Preferably, R in the formula (2) 27 、R 29 Any one of them is selected from
Figure BDA0003166116700000264
Preferably, said L 1 、L 2 、L 3 Independently selected from any one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted fluorenylene, a substituted or unsubstituted dibenzofuranylene or a substituted or unsubstituted dibenzothiophenylene;
preferably, ar is 1 '、Ar 2 ' is independently selected from the group consisting of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, benzonaphthothienyl, dinaphthofuranyl, dinaphthothiophenyl, carbazolyl, phenyl-substituted carbazolyl, naphthyl-substituted carbazolyl, pyridyl-substituted carbazolyl.
Preferably, the material of the luminescence auxiliary layer is selected from compounds having structures represented by formulas (2-1) and (2-2):
Figure BDA0003166116700000271
preferably, the compound having the structure represented by formula (2) is any one of the following compounds:
Figure BDA0003166116700000272
Figure BDA0003166116700000281
Figure BDA0003166116700000291
Figure BDA0003166116700000301
Figure BDA0003166116700000311
Figure BDA0003166116700000321
Figure BDA0003166116700000331
Figure BDA0003166116700000341
Figure BDA0003166116700000351
Figure BDA0003166116700000361
Figure BDA0003166116700000371
wherein D represents deuterium.
In the present invention, a compound having a structure represented by formula (2) is prepared by the following preparation method:
reacting a compound H1' with
Figure BDA0003166116700000372
Reacting to obtain a compound (2) according to the following reaction formula:
Figure BDA0003166116700000373
wherein R is 21 -R 36 、Ar 1’ 、Ar 2’ 、L 1 、L 2 、L 3 Y has the same limits as above, and in the compound H1', R 21’ -R 36’ At least one of which is halogen and the remaining radicals are as defined for R 21 -R 36 (e.g. R) 21’ Not halogen, then it is as defined for R 21 )。
In another aspect, the present invention provides an optoelectronic product comprising an organic electroluminescent device as described above.
Compared with the prior art, the invention has the following beneficial effects:
the organic electroluminescent device has lower driving voltage (below 4.02V), higher current efficiency (above 24 Cd/A) and longer service life (above 225 h).
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Synthesis of the Compound of example 1
Figure BDA0003166116700000381
In a 100 ml three-necked flask, nitrogen gas was introduced, and the compound HT-1-A (1 mmol), the compound HT-1-B (1 mmol), sodium tert-butoxide (2 mmol), tris (dibenzylideneacetone) dipalladium (0) (0.05 mmol), a 50% tri-tert-butylphosphine solution (0.08 mmol) and 50ml of toluene were added, followed by stirring under reflux. After cooling to 25 ℃ with ethyl acetate and H 2 O extracts the organic layer. The extracted organic layer was over MgSO 4 Dried and filtered. The filtrate was concentrated under reduced pressure and purified by silica gel column chromatography (DCM/hexane) and then recrystallization purification using DCM/acetone mixed solvent, thereby obtaining compound H-1 (0.54 g, 83% yield).
Elemental analysis: c 49 H 31 NOS theoretical value: c,86.31; h,4.58; n,2.05; s,4.70; measured value: c,86.28; h,4.60; n,2.05; s,4.72; HRMS (ESI) M/z (M +): theoretical value: 681.2126; measured value: 681.2133.
Figure BDA0003166116700000382
h-2 synthesis: the synthesis was identical to that of H-1 except that HT-2-A was used instead of HT-1-A and HT-2-B was used instead of HT-1-B, giving H-2 (0.52 g, 80% yield).
Elemental analysis: c 49 H 33 Theoretical value of NO: c,90.29; h,5.10; n,2.15; measured value: c,90.28; h,5.12; n,2.15; HRMS (ESI) M/z (M +): theoretical value: 651.2562; measured value: 651.2572.
Figure BDA0003166116700000383
synthesis of H-3: the same synthesis as for H-1, except that HT-3-A was used instead of HT-1-A, and HT-3-B was used instead of HT-1-B, gave H-3 (0.56 g, 81% yield).
Elemental analysis: c 52 H 36 N 2 Theoretical value: c,90.67; h,5.27; n,4.07; measured value: c,90.63; h,5.29; n,4.08; HRMS (ESI) M/z (M +): theoretical values are as follows: 688.2878; measured value: 688.2886.
Figure BDA0003166116700000391
h-4: taking a 50ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding compounds H-4-A (1 mmol), H-4-B (1 mmol) and potassium carbonate (K) 2 CO 3 1.5mmol, ethanol (3 ml), water (3 ml), toluene (15 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 0.05 mmol), heated to 60 ℃ and reacted for 12 hours, cooled to room temperature after completion of the reaction, quenched by addition of 20 ml of water, extracted with dichloromethane (3 × 20 ml), the resulting extract was dried over magnesium sulfate in this order, filtered and spin-dried, and the crude product was purified by column chromatography (ethyl acetate/n-hexane: volume ratio 1/10) to obtain H-4 (0.52 g, 72% yield).
Elemental analysis: c 55 H 36 N 2 Theoretical values are as follows: c,91.13; h,5.01; n,3.86; measured value: c,91.16; h,4.99; n,3.85; HRMS (ESI) M/z (M +): theoretical value: 724.2878; measured value: 724.2869.
Figure BDA0003166116700000392
synthesis of H-5: the same synthesis as for H-1, except that HT-5-A was used instead of HT-1-A, and HT-5-B was used instead of HT-1-B, gave H-5 (0.54 g, 79% yield).
Elemental analysis: c 49 H 32 N 2 Theoretical value of S: c,86.44; h,4.74; n,4.11; s,4.71; measured value: c,86.39; h,4.76; n,4.13; s,4.72; HRMS (ESI) M/z (M +): theoretical value: 680.2286; measured value: 680.2277.
Figure BDA0003166116700000401
synthesis of H-6: the same synthesis as for H-1, except that HT-6-A was used instead of HT-1-A and HT-6-B was used instead of HT-1-B, gave H-6 (0.61 g, 85% yield).
Elemental analysis: c 55 H 43 N theoretical value: c,92.01; h,6.04; n,1.95; measured value: c,91.99; h,6.06; n,1.95; HRMS (ESI) M/z (M +): theoretical value: 717.3396; measured value: 717.3403.
Figure BDA0003166116700000402
synthesis of H-7: the same synthesis as for H-1, except that HT-7-A was used instead of HT-1-A, and HT-7-B was used instead of HT-1-B, gave H-7 (0.57 g, 83% yield).
Elemental analysis: c 53 H 35 N theoretical value: c,92.81; h,5.14; n,2.04; measured value: c,92.85; h,5.12; n,2.03; HRMS (ESI) M/z (M +): theoretical values are as follows: 685.2770; measured value: 685.2778.
Figure BDA0003166116700000403
synthesis of H-8: the difference from the synthesis of H-1 was that HT-8-A was used instead of HT-1-A and HT-8-B was used instead of HT-1-B, yielding H-8 (0.62 g, 87% yield).
Elemental analysis: c 54 H 35 Theoretical value of NO: c,90.85; h,4.94; n,1.96; measured value: c,90.84; h,4.96; n,1.96; HRMS (ESI) M/z (M +): theoretical value: 713.2719; measured value: 713.2728.
Figure BDA0003166116700000411
(1) 1-C Synthesis: taking a 50ml double-neck round-bottom flask, putting a stirrer and an upper connecting reflux pipe, filling nitrogen after drying, and dividingAdding 1-A (1 mmol), 1-B (1 mmol) and potassium carbonate (K) 2 CO 3 1.5mmol, ethanol (3 ml), water (3 ml), toluene (15 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh) 3 ) 4 0.05 mmol), heated to 60 ℃ and reacted for 12 hours, cooled to room temperature after completion of the reaction, quenched by addition of 20 ml of water, extracted with dichloromethane (3 × 20 ml), the resulting extract was dried over magnesium sulfate in this order, filtered and spin-dried, and the crude product was purified by column chromatography (ethyl acetate/n-hexane: volume ratio 1/10) to obtain 1-C (0.17 g, yield 54%).
(2) Synthesis of 1-D: a50 ml two-neck round-bottom flask is taken and placed with a stirrer and an upper reflux pipe, nitrogen is filled after drying, 1-C (1 mmol), bis (pinacolato) diboron (1.2 mmol), potassium acetate (2 mmol), 1, 4-dioxane (20 ml) are respectively added, nitrogen protection is carried out, 1-bis (diphenylphosphino) ferrocene ] palladium (II) dichloride (0.05 mmol) is added, reflux is carried out for 12 hours, and after the reaction is finished, a crude product is purified by column chromatography (ethyl acetate/n-hexane: volume ratio is 1/10) to obtain 1-D (0.27 g, yield is 97%).
(3) Synthesis of 1-F: the same as 1-C except that 1-D was used instead of 1-B and 1-E was used instead of 1-A, gave 1-F (0.24 g, 61% yield).
(4) Synthesis of 1-G: taking a 50ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding 1-F (1 mmol) and dichlorobis (tricyclohexylphosphine) palladium (PdCl) 2 (PCy 3 ) 2 0.05 mmol), pivalic acid (t-BuCO) 2 H,2 mmol), cesium carbonate (Cs) 2 CO 3 2 mmol) and dimethylacetamide (20 ml) at 120 ℃ for 10 hours, after the reaction is completed, cooling to room temperature, concentrating the reaction system, and purifying the crude product by column chromatography (ethyl acetate/n-hexane: volume ratio 1/10), to give 1-G (0.17G, 47% yield).
(5) 1-H Synthesis: 1-G (1 mmol), dichloromethane (20 ml) and a solution of boron tribromide (2 mmol) in dichloromethane were added dropwise at 0 ℃ to a 50ml three-necked flask, and after completion of the reaction, the solvent was removed and the crude product was purified by column chromatography (ethyl acetate/n-hexane, 1/10) to give 1-H (0.29G, 84% yield).
(6) 1-J Synthesis: taking a 50ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, adding 1-H (1 mmol), dichloromethane (20 ml) and pyridine (6 mmol), cooling a reaction system to 0 ℃, adding Tf 2 O (1.5 mmol), stirring at room temperature for 30 min, cooling to 0 deg.C, adding 30 ml dichloromethane, 40 ml water, drying the organic phase over anhydrous magnesium sulfate, distilling under reduced pressure to remove the solvent, separating the crude product by column chromatography (ethyl acetate/n-hexane, 1/10) to obtain 1-J (0.42 g, 88% yield)
(7) 1, synthesis: a50-milliliter two-neck round-bottom flask is taken and placed with a stirrer and an upper reflux pipe, nitrogen is introduced after drying, 1-J (1 mmol), 1-K (1 mmol), cesium carbonate (0.012 mol), tris (dibenzylideneacetone) dipalladium (Pd 2 (dba) 3, 0.05mmol) and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl (xphos, 0.055 mmol) are respectively added, then toluene is added, the mixture is refluxed for 24 hours, after reaction, the reaction system is cooled to room temperature after filtration and concentrated, and a crude product is purified by column chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to obtain a compound 1 (0.46 g, the yield is 70%).
Elemental analysis: c 48 H 31 N 3 Theoretical value: c,88.72; h,4.81; n,6.47; measured value: c,88.67; h,4.83; n,6.50; HRMS (ESI) M/z (M +): theoretical value: 649.2518; measured value: 649.2525.
Figure BDA0003166116700000421
(1) Synthesis of 7-C: the same synthesis as 1-C except that 1-A was replaced with 7-A, and 1-B was replaced with 7-B gave 7-C (0.16 g, 51% yield).
(2) Synthesis of 7-D, the same as 1-D except that 1-C was replaced with 7-C, to give 7-D (0.26 g, 94% yield)
(3) Synthesis of 7-F: same as the synthesis of 1-C, except that 1-B was replaced with 7-D, and 1-A was replaced with 7-E, to give 7-F (0.23 g, 58% yield)
(4) Synthesis of 7-G: the same synthesis as 1-G, except that 1-F was replaced with 7-F, gave 7-G (0.2G, 55% yield)
(5) 7-H Synthesis: the same synthesis as 1-H except that 1-G was replaced with 7-G to give 7-H (0.3G, 88% yield)
(6) 7-J Synthesis: same as the synthesis of 1-J except that 1-H was replaced by 7-H to give 7-J (0.41 g, 86% yield)
(7) Synthesis of compound 7: synthesis of Compound 1, except that 1-J was replaced with 7-J and 1-K was replaced with 7-K, compound 7 (0.41 g, 75% yield) was obtained.
Elemental analysis: c 40 H 23 N 3 Theoretical value: c,88.05; h,4.25; n,7.70; measured value: c,88.10; h,4.23; n,7.67; HRMS (ESI) M/z (M +): theoretical value: 545.1892; measured value: 545.1897.
Figure BDA0003166116700000431
(1) Synthesis of 8-C: the same synthesis as 1-C except that 1-B was replaced with 8-B gave 8-C (0.16 g, 51% yield).
(2) Synthesis of 8-D, identical to 1-D except that 1-C was replaced with 8-C, to give 8-D (0.25 g, 90% yield)
(3) Synthesis of 8-F: same as the synthesis of 1-C, except that 1-B and 1-A were replaced with 8-D to give 8-F (0.21 g, 53% yield)
(4) Synthesis of 8-G: same as the synthesis of 1-G except that 1-F was replaced by 8-F to give 8-G (0.18G, 50% yield)
(5) Synthesis of 8-H: the same synthesis as 1-H except that 1-G was replaced with 8-G gave 8-H (0.31G, 89% yield)
(6) Synthesis of 8-J: the same synthesis as 1-J, except that 1-H was replaced by 8-H, gave 8-J (0.41 g, 86% yield)
(7) Synthesis of compound 8: synthesis of Compound 1, except that 1-J was replaced with 8-J and 1-K was replaced with 8-K, compound 8 (0.53 g, 81% yield) was obtained.
Elemental analysis: c 46 H 25 N 3 Theoretical value of S: c,84.77; h,3.87; n,6.45; s,4.92; measured value: c,84.76; h,3.86; n,6.47; s,4.91; HRMS (ii) (ESI) M/z (M +): theoretical value: 651.1769; measured value: 651.1775.
the same preparation method as above was used except that the raw materials as in table 1 below were used to prepare the corresponding products, and the elemental analysis of the products and the HRMS test results are shown in table 2.
TABLE 1
Figure BDA0003166116700000432
Figure BDA0003166116700000441
Figure BDA0003166116700000451
Figure BDA0003166116700000461
Figure BDA0003166116700000471
TABLE 2
Figure BDA0003166116700000472
Device embodiments
The OLED has the following layer structure: a base (indium tin oxide (ITO) coated glass substrate)/a Hole Injection Layer (HIL)/a Hole Transport Layer (HTL)/an emission layer (EML)/an Electron Transport Layer (ETL)/an Electron Injection Layer (EIL), and finally a cathode.
The materials used are specifically shown in table 2, and the materials required to make an OLED are as follows.
Figure BDA0003166116700000481
The preparation of the organic electroluminescent device comprises the following steps:
(1) Substrate cleaning: carrying out ultrasonic treatment on the ITO-coated glass substrate in an aqueous cleaning agent (the components and the concentration of the aqueous cleaning agent are less than or equal to 10wt% of glycol solvent and less than or equal to 1wt% of triethanolamine), washing in deionized water, and carrying out ultrasonic treatment in the following steps of: ultrasonic degreasing is carried out in an ethanol mixed solvent (volume ratio is 1.
(2) Evaporating an organic light-emitting functional layer:
placing the glass substrate with the anode layer in a vacuum chamber, and vacuumizing to 1 × 10 -6 To 2X 10 -4 Pa, evaporating HAT (CN) 6 as a hole injection layer on the anode layer film in vacuum, wherein the evaporation thickness is 5nm;
a hole transport layer is evaporated on the hole injection layer, and the thickness of the evaporated film is 80nm;
evaporating a light-emitting auxiliary layer on the hole transport layer, wherein the evaporation thickness is 20nm;
the luminescent layer is vapor-plated on the hole transport layer, and the specific preparation method comprises the following steps: carrying out vacuum evaporation on a luminescent host material and a guest material in a co-evaporation manner, wherein the total thickness of the evaporation is 30nm;
vacuum evaporating an electron transport layer on the luminescent layer, wherein the preparation method comprises the following steps: carrying out vacuum evaporation on Bphen and LiQ in a co-evaporation mode, wherein the total film thickness of evaporation is 30nm;
vacuum evaporating an electron injection layer on the electron transport layer, wherein the total film thickness of the evaporation is 1nm;
al is evaporated on the electron injection layer, and the total thickness of the evaporated film is 80nm. The parameters of the layers in the device, their materials and thicknesses, etc., are shown in table 3.
TABLE 3
Figure BDA0003166116700000491
Figure BDA0003166116700000501
Testing the performance of the device:
the instrument comprises: the characteristics of the device such as current, voltage, brightness, luminescence spectrum and the like are synchronously tested by adopting a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system;
and (3) testing conditions are as follows: the current density is 20mA/cm 2 Room temperature.
And (3) testing the service life: the time (in hours) was recorded when the device brightness dropped to 98% of the original brightness.
The device performance test results are shown in table 4:
TABLE 4
Driving voltage (V) Current efficiency (Cd/A) Life (h)
1 3.81 26 231
2 3.92 27 225
3 3.89 28 264
4 3.98 26 241
5 3.99 27 250
6 3.96 26 233
7 3.92 27 235
8 3.97 29 267
9 3.83 29 266
10 3.82 30 271
11 3.83 28 277
12 3.98 24 238
13 3.90 26 252
14 3.89 24 244
15 3.92 24 266
16 3.94 26 258
17 4.44 21 131
18 4.35 24 148
As can be seen from Table 4, the compounds of the present invention allow the organic electroluminescent device to have a lower driving voltage (below 4.02V), a higher current efficiency (above 24 Cd/A) and a longer lifetime (above 225 h).
The applicant states that the present invention is illustrated by the above embodiments of the organic electroluminescent device of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. An organic electroluminescent device comprising a first electrode, a second electrode facing the first electrode, a light-emitting layer between the first electrode and the second electrode, and a light-emission auxiliary layer between the light-emitting layer and the first electrode, wherein the light-emitting layer comprises a compound having a structure represented by formula (1):
Figure FDA0003166116690000011
R 1 -R 6 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a way that O atoms or S atoms are not adjacent a substituted or unsubstituted C2-C30 alkenyl group, a C2-C30 alkenyl group in which one or more methylene groups are substituted by-O-or-S-in such a manner that O atom or S atom is not adjacent to each other substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C2-C30 alkynylA substituted or unsubstituted C1-C30 alkoxy group or a substituted or unsubstituted C6-C30 aryloxy group,
R 1 -R 6 each independently exists or two adjacent rings are connected to form a ring which is a substituted or unsubstituted benzene ring,
l is selected from a linkage, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C5-C30 heteroarylene,
Ar 1 selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C5-C60 heteroarylamine, substituted or unsubstituted C5-C60 arylheteroarylamine,
n is an integer selected from 0 to 3,
m is an integer selected from 0 to 5,
n1 is selected from the integer of 0-1,
m1 is an integer selected from 0 to 1.
2. The organic electroluminescent device of claim 1, wherein n1+ m1=1.
3. The organic electroluminescent device of claim 1 or 2, wherein-L-Ar is 1 Is selected from
Figure FDA0003166116690000021
Wherein Ar 2 、Ar 3 Each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl;
preferably, ar 2 、Ar 3 Each is independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, benzonaphthofluorenyl, and benzonaphthofluorenylFuryl, benzonaphthothienyl, benzocarbazolyl, or dibenzocarbazolyl;
preferably, -L-Ar 1 Is selected from
Figure FDA0003166116690000022
Wherein the dotted lines represent L and Ar 3 Is connected into a ring through chemical bond;
more preferably, -L-Ar 1 Selected from the group consisting of substituted or unsubstituted:
Figure FDA0003166116690000031
4. the organic electroluminescent device according to any one of claims 1 to 3, wherein-L-Ar 1 Is selected from
Figure FDA0003166116690000032
Wherein the dotted line represents Ar 2 、Ar 3 Is connected into a ring through chemical bonds,
preferably, -L-Ar 1 Selected from the group consisting of substituted or unsubstituted:
Figure FDA0003166116690000041
preferably, ar 1 Is selected from
Figure FDA0003166116690000051
Wherein X 1 Selected from N or CR X1 ，X 2 Selected from N or CR X2 ，X 3 Selected from N or CR X3 ，X 4 Selected from N or CR X4 ，X 5 Selected from N or CR X5 ，
R X1 、R X2 、R X3 、R X4 、R X5 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstitutedC1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are replaced by-O-or-S-in such a manner that O atoms or S atoms are not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,
R X1 、R X2 、R X3 、R X4 、R X5 independently exist or are connected with each other to form a ring, the ring is a substituted or unsubstituted benzene ring, pyridine ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthooxazole ring, naphthothiazole ring, benzofuran ring or benzothiophene ring,
preferably, ar 1 Is selected from
Figure FDA0003166116690000052
Preferably, ar 1 Is selected from
Figure FDA0003166116690000053
Wherein X 1 、X 2 、X 5 Any two of which are selected from the group consisting of N,
Y 1 selected from N, CR Y1 ，Y 2 Selected from N, CR Y2 ，Y 3 Selected from N, CR Y3 ，Y 4 Selected from N, CR Y4 ，
R Y1 、R Y2 、R Y3 、R Y4 Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a way that the O atom or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C1-C30 cycloalkyl, substituted or unsubstituted C2-C30 heterocycloalkyl, substituted or unsubstituted C2-C30 heteroaryl, and substituted or unsubstituted C3-C30 heteroarylalkyl,Substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,
R Y1 、R Y2 、R Y3 、R Y4 each independently exists or two adjacent rings are connected to form a ring, and the ring is a substituted or unsubstituted benzene ring;
more preferably, Y 1 Selected from the group consisting of CR Y1 ，Y 2 Selected from the group consisting of CR Y2 ，Y 3 Selected from the group consisting of CR Y3 ，Y 4 Selected from the group consisting of CR Y4 ，
More preferably, R X1 、R X2 、R X3 、R X4 、R X5 、R Y1 、R Y2 、R Y3 、R Y4 Each independently selected from hydrogen, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl;
preferably, each of said L is independently selected from phenylene, biphenylene, naphthylene;
preferably, R 1 -R 6 Each independently selected from hydrogen, deuterium, cyano, fluorine, methyl, ethyl, tert-butyl, deuterium-substituted methyl, fluorine-substituted methyl, phenyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl;
preferably, ar 1 Selected from phenyl, biphenyl, terphenyl, naphthyl, benzophenanthryl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, 2-phenylphenanthrene [3,4-d ]]Oxazolyl or 2-phenylphenanthrene [3,4-d]A thiazolyl group;
preferably, when said group contains a substituent, each of said substituents is independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C6 alkyl, unsubstituted or R ' substituted C6-C12 aryl, unsubstituted or R ' substituted C2-C20 heteroaryl; r' is selected from deuterium, halogen, cyano, deuterium substituted methyl, halogen substituted methyl;
more preferably, the C1-C6 alkyl group is selected from methyl, ethyl, tert-butyl;
the aryl of C6-C12 is selected from phenyl, biphenyl and naphthyl;
the heteroaryl of C3-C20 is selected from triazinyl, pyridyl, phenyl-substituted pyridyl, pyridyl-substituted phenyl, dibenzofuranyl or dibenzothiophenyl.
5. The organic electroluminescent device according to any one of claims 1 to 4, wherein the compound having the structure represented by formula (1) is any one of the following compounds:
Figure FDA0003166116690000071
Figure FDA0003166116690000081
Figure FDA0003166116690000091
Figure FDA0003166116690000101
Figure FDA0003166116690000111
Figure FDA0003166116690000121
Figure FDA0003166116690000131
Figure FDA0003166116690000141
Figure FDA0003166116690000151
Figure FDA0003166116690000161
Figure FDA0003166116690000171
Figure FDA0003166116690000181
Figure FDA0003166116690000191
Figure FDA0003166116690000201
Figure FDA0003166116690000211
Figure FDA0003166116690000221
Figure FDA0003166116690000231
Figure FDA0003166116690000241
Figure FDA0003166116690000251
Figure FDA0003166116690000261
6. the organic electroluminescent device according to any one of claims 1 to 5, wherein the difference between the HOMO energy level value of the compound having the structure represented by formula (1) and the HOMO energy level value of the material of the light-emission auxiliary layer is less than 0.5eV.
7. The organic electroluminescent device according to any one of claims 1 to 6, wherein the material of the luminescence auxiliary layer is selected from compounds having a structure represented by formula (2):
Figure FDA0003166116690000262
wherein Y is selected from O, S, NR N1 Or CR Y1 R Y2 ，
Said R is N1 Selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl,
said R is Y1 、R Y2 Independently selected from substituted or unsubstituted C1-C30 alkyl or substituted or unsubstituted C6-C30 aryl,
the R is Y1 、R Y2 Independently of or with R 34 Are connected to form a ring A,
said R is 21 -R 36 Is independently selected from
Figure FDA0003166116690000271
Hydrogen, deuterium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C1-C30 alkyl, wherein one or at least two methylene groups which are not adjacent to each other are independently replaced by-O-or-S-, a substituted or unsubstituted C2-C30 alkenyl group wherein one or non-adjacent at least two methylene groups are independently replaced by-O-or-S-, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkylamino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,
and R is 21 -R 36 At least one item selected from
Figure FDA0003166116690000272
Said R is 21 -R 36 Independently exist or are connected with each other to form a ring B,
the ring A is selected from a substituted or unsubstituted indole ring or a benzene ring,
the ring B is selected from a substituted or unsubstituted benzene ring,
said L is 1 、L 2 、L 3 Independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group or a substituted or unsubstituted C2-C30 heteroarylene group,
ar is 1' 、Ar 2' Independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C2-C60 heteroaryl.
8. The organic electroluminescent device according to any one of claims 1 to 7, wherein R in formula (2) is 27 、R 28 、R 29 、R 30 Any one of them is selected from
Figure FDA0003166116690000281
Preferably, R in said formula (2) 27 、R 29 Any one of them is selected from
Figure FDA0003166116690000282
Preferably, said L 1 、L 2 、L 3 Independently selected from any one of a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted fluorenylene, a substituted or unsubstituted dibenzofuranyl or a substituted or unsubstituted dibenzothiophenyl;
preferably, ar is 1' 、Ar 2' Independently selected from the group consisting of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, pyridyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, dibenzofuranyl, dibenzothienyl, benzonaphthofuranyl, benzonaphthothienyl, dinaphthofuranyl, dinaphthothiophenyl, carbazolyl, phenyl-substituted carbazolyl, naphthyl-substituted carbazolyl, pyridyl-substituted carbazolyl.
9. The organic electroluminescent device according to any one of claims 1 to 8, wherein the compound having the structure represented by formula (2) is any one of the following compounds:
Figure FDA0003166116690000283
Figure FDA0003166116690000291
Figure FDA0003166116690000301
Figure FDA0003166116690000311
Figure FDA0003166116690000321
Figure FDA0003166116690000331
Figure FDA0003166116690000341
Figure FDA0003166116690000351
Figure FDA0003166116690000361
Figure FDA0003166116690000371
Figure FDA0003166116690000381
Figure FDA0003166116690000391
wherein D represents deuterium.
10. An optoelectronic product comprising an organic electroluminescent device according to any one of claims 1 to 9.
CN202110804901.6A 2021-07-16 2021-07-16 Organic electroluminescent device Pending CN115633513A (en)

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