CN113735780B - Benzo five-membered heterocyclic derivative and organic electroluminescent device thereof - Google Patents

Benzo five-membered heterocyclic derivative and organic electroluminescent device thereof Download PDF

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CN113735780B
CN113735780B CN202111131169.7A CN202111131169A CN113735780B CN 113735780 B CN113735780 B CN 113735780B CN 202111131169 A CN202111131169 A CN 202111131169A CN 113735780 B CN113735780 B CN 113735780B
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benzo
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CN113735780A (en
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苗玉鹤
陆影
孙月
刘小婷
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Changchun Hyperions Technology Co Ltd
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Abstract

The invention provides a benzo five-membered heterocyclic derivative and an organic electroluminescent device thereof, and relates to the technical field of organic photoelectric materials. The benzo five-membered heterocyclic derivative provided by the invention has good electron mobility, can effectively promote the transmission balance of holes and electrons, has good hole blocking capability, can effectively block holes in a luminescent layer, increases the recombination probability of the holes and the electrons, and can effectively improve the luminous efficiency and the service life of the device when applied to a hole blocking layer or an electron transmission layer of an organic electroluminescent device; in addition, the benzo five-membered heterocyclic derivative is used as a light extraction material in an organic electroluminescent device, so that the total emission of an interface between an electrode film and a glass substrate and an interface between the glass substrate and air can be effectively solved, the light extraction efficiency is improved, and the luminous efficiency and the service life of the organic electroluminescent device are improved.

Description

Benzo five-membered heterocyclic derivative and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a benzo five-membered heterocyclic derivative and an organic electroluminescent device thereof.
Background
The development of display technology has mainly undergone three stages of Cathode Ray Tube (CRT), liquid crystal display (Liquid Crystal Display, LCD) and organic electroluminescent display (Organic LightEmitting Diode, OLED). The CRT which is applied to television and computer display at the earliest adopts a display of a green display and a single display kinescope, but the display has the defects of high power consumption, large volume, radiation, incapability of realizing large screen, insufficient high definition of pixels and the like, and gradually exits from a history stage. Later LCDs have become the mainstream technology in the display field instead of CRT technology, and sales share is also surpassed CRT, but LCD display technology needs to rely on backlight to emit light, and cannot simultaneously meet the requirements of fast response speed, wide color gamut, low power consumption, large screen and even flexible display. Based on this series of demands, the organic light emitting technology OLED of the third generation flat panel display technology should be developed.
The OLED technology refers to a technology that an organic material emits light under the action of an electric field, and a typical structure is that an organic functional layer is inserted between a cathode and an anode to form a sandwich-like structure, wherein the organic functional layer can be divided into a single-layer structure, a double-layer structure, a three-layer structure and a multi-layer structure according to the design requirements of a device. The initial device is the simplest structure comprising a single organic functional layer which bears the responsibility of both electron transport and hole transport, so the bipolar requirement on the material is high; on the other hand, the light-emitting layer is in direct contact with the cathode and the anode, so that the recombination probability of excitons is reduced to a great extent, and the light-emitting efficiency of the device is low. In order to improve the recombination probability of excitons and realize high-efficiency luminescence, the number of layers of the organic functional layers is gradually increased, and the functions exerted by the functional layers tend to be single, and the current organic functional layers can be divided into a hole injection layer, a hole transport layer, an electron blocking layer, a luminescent layer, a hole blocking layer, an electron transport layer, an electron injection layer, a light extraction layer and the like.
The functional layer of an organic electroluminescent device is advantageous over the good properties of the material, so the choice of material is very critical in the fabrication of the device. From the structural point of view of the device, organic electroluminescent materials can be broadly classified into three types: electrode material, electrode modifying material, carrier transporting material, and light-emitting material. While the properties of the light-emitting material and the electrode material are very important for the organic electroluminescent device, the device performance is improved comprehensively, and many auxiliary materials such as a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, an electron transport material, an electron injection material, a light extraction material, etc. having excellent properties are required. The improvement of the material performance is beneficial to the improvement of the performance of the organic electroluminescent device, so that the research and development of a new auxiliary material has important significance.
Disclosure of Invention
The invention provides a benzo five-membered heterocyclic derivative and an organic electroluminescent device thereof aiming at the problems existing in the prior art.
The invention provides a benzo five-membered heterocyclic derivative which has a structure shown as a formula (I),
Said n is selected from 3, 4 or 5; ar (Ar) 1 Independently selected from the structures shown below,
the X is 1 Selected from O, S, NR 1 Any one of them;
the R is 1 Any one selected from the group consisting of a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, and a substituted or unsubstituted C6-C30 aryl group;
the R is 2 Any one selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; m is selected from 0, 1, 2, 3 or4, when m is greater than 1, a plurality of R 2 Are identical or different from each other, or adjacent two R 2 Can be connected into a ring;
the Y is 1 ～Y 4 Independently selected from N or C;
the L is 1 ～L 3 Independently selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, and substituted or unsubstituted C3-C30 heteroarylene;
the Ar is as follows 2 Is of a structure shown in a formula (III),
the X is 2 Selected from O, S, N (R) 3 )、C(R 3 R 4 ) One of R 3 、R 4 Independently selected from any one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylthio, substituted or unsubstituted C6-C20 arylamino, or R 3 、R 4 Can be connected into a ring;
the R is 5 、R 6 Independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or adjacent two R 5 Or R is 6 Can be connected into a ring;
the p, q are independently selected from 0, 1, 2, 3 or 4;
the above-mentioned "substituted or unsubstituted alkyl group", "substituted or unsubstituted cycloalkyl group", "substituted or unsubstituted alkenyl group", "substituted or unsubstituted cycloalkenyl group", "substituted or unsubstituted aryl group", "substituted or unsubstituted heteroaryl group", "substituted or unsubstituted aryloxy group", "substituted or unsubstituted arylthio group", "substituted or unsubstituted arylamino group", "substituted or unsubstituted arylene group", "substituted or unsubstituted heteroarylene group" is substituted or unsubstituted by one or more substituents selected from the group consisting of deuterium, halogen, cyano, nitro, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, respectively, and when substituted by a plurality of substituents, the plurality of substituents are the same or different from each other; or when the substituents are plural, adjacent substituents may be linked to form a ring.
The invention also provides an organic electroluminescent device, which comprises an anode, an organic layer and a cathode, wherein the organic layer comprises the benzo five-membered heterocyclic derivative.
The beneficial effects are that: the benzo five-membered heterocyclic derivative provided by the invention has better electron mobility, provides assistance in the electron transmission process, can effectively promote the transmission balance of holes and electrons, has deeper HOMO energy level, thus having better hole blocking capability, can effectively block holes in a luminescent layer, increases the recombination probability of the holes and electrons, and can effectively improve the luminous efficiency of the device and prolong the service life when being applied to a hole blocking layer or an electron transmission layer of an organic electroluminescent device; in addition, the benzo five-membered heterocyclic derivative is used as a light extraction material in an organic electroluminescent device, so that the total emission of an interface between an electrode film and a glass substrate and an interface between the glass substrate and air can be effectively solved, the total reflection loss and waveguide loss of light in the device are reduced, the light extraction efficiency is improved, and the luminous efficiency of the organic electroluminescent device is improved.
Detailed Description
The present invention is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are meant to be illustrative of the invention and not limiting the scope of the invention, and that modifications of the invention, which are all within the scope of the invention as claimed by those skilled in the art after reading the present invention.
The alkyl group in the present invention refers to a group obtained by removing one hydrogen atom from an alkane molecule, and includes a straight-chain alkyl group and a branched-chain alkyl group. The number of carbon atoms of the alkyl group is not particularly limited, and is preferably C1 to C60, more preferably C1 to C30, still more preferably C1 to C15, and most preferably C1 to C10. Examples of alkyl groups include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, 2-ethylbutyl, 3-dimethylbutyl, 4-methyl-2-pentyl, 1-methylheptyl, and the like, but are not limited thereto.
The cycloalkyl group in the present invention is a group obtained by removing one hydrogen atom from a cycloalkyl molecule, and the number of carbon atoms of the cycloalkyl group is not particularly limited, and is preferably from 3 to 60, more preferably from 3 to 30, even more preferably from 3 to 15, and most preferably from 3 to 10. Examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctane, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, adamantyl, camphene, norbornyl, cubane and the like, but are not limited thereto.
The alkenyl group in the present invention means a group obtained by removing one hydrogen atom from an olefin molecule, and includes a straight-chain alkenyl group and a branched-chain alkenyl group, and the number of carbon atoms of the alkenyl group is not particularly limited, and is preferably C2 to C60, more preferably C2 to C30, still more preferably C2 to C15, and most preferably C2 to C10. Examples of alkenyl groups include: vinyl, vinyl chloride, styrene, acryl, etc., but is not limited thereto.
The cycloalkenyl group in the present invention is a group obtained by removing one hydrogen atom from a cycloolefin molecule, and the number of carbon atoms of the cycloalkenyl group is not particularly limited, and is preferably from 3 to 60, more preferably from 3 to 20, even more preferably from 3 to 15, and most preferably from 3 to 10. Examples of cycloalkenyl groups include: cyclopropene, cyclobutene, cyclopentene, cyclohexene, cyclobutene, cyclopentadiene, cycloheptene, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, and the like, but are not limited thereto.
The aryl group in the present invention means a group obtained by removing one hydrogen atom from the aromatic nucleus of an aromatic hydrocarbon molecule, and includes monocyclic aryl groups, polycyclic aryl groups and condensed ring aryl groups, and the number of carbon atoms of the aryl groups is not particularly limited, and is preferably from C6 to C60, more preferably from C6 to C30, still more preferably from C6 to C18, most preferably from C6 to C12. Examples of aryl groups include: phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, anthryl, benzanthrenyl, phenanthryl, triphenylenyl, pyrenyl, benzopyrenyl, perylene, fluoranthenyl, indenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, spirobifluorenyl, benzospirobifluorenyl, dibenzospirobifluorenyl, and the like, but are not limited thereto.
Heteroaryl as used herein refers to a group obtained by removing a hydrogen from the aromatic nucleus of a heterocyclic aromatic hydrocarbon molecule, and includes, but is not limited to: o, S, N, si, B, P, se. Heteroaryl groups include monocyclic heteroaryl, polycyclic heteroaryl, and fused ring heteroaryl, and the number of carbon atoms of the heteroaryl group is not particularly limited, and is preferably from C3 to C60, more preferably from C3 to C30, still more preferably from C3 to C15, and most preferably from C3 to C8. Examples of heteroaryl groups include: pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, phenanthroline, oxadiazolyl, oxazolyl, benzoxazolyl, naphthazolyl, phenanthrooxazolyl, thiazolyl, benzothiazolyl, naphthazolyl, imidazolyl, benzimidazolyl, naphthazolyl, phenanthroimidazolyl, furanyl, benzofuranyl, dibenzofuranyl, benzodibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, benzodibenzothiophenyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, acridinyl, and the like, but are not limited thereto.
The arylene group according to the present invention is a group obtained by removing two hydrogen atoms from an aromatic nucleus in an aromatic hydrocarbon molecule, and includes monocyclic arylene, polycyclic arylene, condensed ring arylene, or a combination thereof, and the number of carbon atoms of the arylene group is not particularly limited, and is preferably from C6 to C60, more preferably from C6 to C30, even more preferably from C6 to C18, and most preferably from C6 to C12. Examples of arylene groups include: phenylene, biphenylene, terphenylene, tetrabiphenyl, naphthylene, phenanthrylene, anthracenylene, triphenylene, pyrenylene, fluorenylene, benzofluorenylene, spirobifluorenylene, benzospirobifluorenylene, and the like, but are not limited thereto.
The heteroarylene group according to the present invention refers to a group obtained by removing two hydrogen atoms from the aromatic nucleus of a heterocyclic aromatic hydrocarbon molecule, and hetero atoms in the heteroarylene group include, but are not limited to: o, S, N, si, B, P, se. Heteroarylene includes monocyclic heteroarylene, polycyclic heteroarylene and fused ring heteroarylene, and the polycyclic heteroarylene may have only one heteroatom-substituted benzene ring or may have a plurality of heteroatom-substituted benzene rings. The number of carbon atoms of the heteroarylene group is not particularly limited, but is preferably from C6 to C60, more preferably from C6 to C30, still more preferably from C3 to C15, and most preferably from C3 to C8. Examples of heteroarylenes include: a pyridylene group, a pyrimidylene group, a pyrazinylene group, a pyridazinylene group, a triazinylene group, a furanylene group, a thienyl group, a quinolinylene group, an isoquinolinyl group, a quinoxalinylene group, a quinazolinylene group, a phenanthroline group, a benzofuranylene group, a dibenzofuranylene group, a benzodibenzofuranylene group, a benzothienyl group, a dibenzothiophenylene group, a benzodibenzothiophenylene group, a carbazolylene group, a benzocarbazolylene group, and the like, but are not limited thereto.
"substituted or unsubstituted" as used herein means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium, halogen, amino, cyano, nitro, acyl, ester, carbonyl, haloalkyl, haloalkoxy, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C6-C30 aryloxy, preferably deuterium, cyano, halogen, C1-C10 alkyl, C3-C12 cycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, specific examples may include deuterium, cyano, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclohexyl Group, adamantyl, phenyl, tolyl, mesityl, pentadeuterated phenyl, biphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, pyrenyl, triphenylenyl,a group, perylene group, spirobifluorenyl group, carbazole indolyl group, pyrrolyl group, carbazole group, furanyl group, benzofuranyl group, dibenzofuranyl group, thienyl group, benzothienyl group, benzimidazolyl group, pyridoxazole, pyridothiazole, pyridoimidazole, naphthyridine benzoxazole, naphthyridine benzothiazole, naphthyridine imidazole, quinolinyl group, isoquinolinyl group, phenothiazinyl group, phenoxazinyl group, acridinyl group, dibenzothienyl group, pyridyl group, pyrimidinyl group, pyridazinyl group, pyrazinyl group, triazinyl group, oxazolyl group, thiazolyl group, benzoxazolyl group, benzothiazolyl group, benzotriazolyl group, and the like, but is not limited thereto.
The "×" on the substituents described herein represents the attachment site.
The "halogen" as used herein includes fluorine, chlorine, bromine, iodine.
The term "attached ring" as used herein means that two groups are attached to each other by a chemical bond and optionally aromatized. As exemplified below:
in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, for example, a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, a dibenzofuran ring, a dibenzothiophene ring, a phenanthrene ring, a pyrene ring, or the like, but is not limited thereto.
In the present invention, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional sites of the aromatic ring. For example, the number of the cells to be processed,can indicate->And so on.
The invention provides a benzo five-membered heterocyclic derivative which has a structure shown as a formula (I),
said n is selected from 3, 4 or 5; ar (Ar) 1 Independently selected from the structures shown below,
the X is 1 Selected from O, S, NR 1 One of the following;
the R is 1 Any one selected from the group consisting of a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, and a substituted or unsubstituted C6-C30 aryl group;
the R is 2 Any one selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; m is selected from 0, 1, 2, 3 or 4, when m is greater than 1, a plurality of R 2 Are identical or different from each other, or adjacent two R 2 Can be connected into a ring;
the Y is 1 ～Y 4 Independently selected from N or C;
the L is 1 ～L 3 Independently selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, and substituted or unsubstituted C3-C30 heteroarylene;
The Ar is as follows 2 Is of a structure shown in a formula (III),
the X is 2 Selected from O, S, N (R) 3 )、C(R 3 R 4 ) Any one of R 3 、R 4 Independently selected from any one of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C6-C30 arylthio, substituted or unsubstituted C6-C20 arylamino, or R 3 、R 4 Can be connected into a ring;
the R is 5 、R 6 Independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 cycloalkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or adjacent two R 5 Or R is 6 Can be connected into a ring;
the p, q are independently selected from 0, 1, 2, 3 or 4;
the above-mentioned "substituted or unsubstituted alkyl group", "substituted or unsubstituted cycloalkyl group", "substituted or unsubstituted alkenyl group", "substituted or unsubstituted cycloalkenyl group", "substituted or unsubstituted aryl group", "substituted or unsubstituted heteroaryl group", "substituted or unsubstituted aryloxy group", "substituted or unsubstituted arylthio group", "substituted or unsubstituted arylamino group", "substituted or unsubstituted arylene group", "substituted or unsubstituted heteroarylene group" is substituted or unsubstituted by one or more substituents selected from the group consisting of deuterium, halogen, cyano, nitro, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 heteroaryl group, respectively, and when substituted by a plurality of substituents, the plurality of substituents are the same or different from each other; or when the substituents are plural, adjacent substituents may be linked to form a ring.
Preferably, the benzo five-membered heterocyclic derivative is selected from any one of the following chemical formulas:
the X is 1 Selected from O, S, NR 1 Any one of them;
the R is 1 Any one selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C20 aryl;
the R is 2 Any one selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C20 aryl and substituted or unsubstituted C3-C20 heteroaryl; m is selected from 0, 1, 2, 3 or 4, when m is greater than 1, a plurality of R 2 Are identical or different from each other, or adjacent two R 2 Can be connected into a ring;
the Y is 1 ～Y 4 Independently selected from N or C;
the L is 1 ～L 3 Independently selected from any one of single bond, substituted or unsubstituted C6-C20 arylene, and substituted or unsubstituted C3-C20 heteroarylene;
the X is 2 Selected from O, S, N (R) 3 )、C(R 3 R 4 ) One of R 3 、R 4 Independently selected from one of a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 cycloalkenyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20 heteroaryl group, a substituted or unsubstituted C6-C20 aryloxy group, a substituted or unsubstituted C6-C20 arylthio group, a substituted or unsubstituted C6-C20 arylamino group, or R 3 、R 4 Can be connected into a ring;
the saidR 5 、R 6 Independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, or adjacent two R 5 Or R is 6 Can be connected into a ring;
the p, q are independently selected from 0, 1, 2, 3 or 4.
Preferably, the Ar 1 Any one selected from the following groups:
preferably, the Ar 2 Any one selected from the following groups:
the R is 7 、R 8 、R 9 、R 10 、R 11 Independently selected from any one of hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 cycloalkenyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, or a ring can be formed between adjacent two substituents;
the a 1 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; a, a 2 Selected from 0, 1, 2, 3, 4 or 5; a, a 3 Selected from 0, 1, 2, 3 or 4; a, a 4 Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; a, a 5 Selected from the group consisting of0. 1, 2 or 3;
the R is a Selected from any one of substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C12 cycloalkyl and substituted or unsubstituted C6-C20 aryl.
Preferably, the Ar 2 Any one selected from the following groups:
preferably, the L 1 ～L 3 Independently selected from a single bond or any one of the following groups,
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preferably, the heterocyclic derivative is selected from any one of the structures shown below,
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the specific chemical structures of the benzo five-membered heterocyclic derivatives shown in the formula I are listed above, but the invention is not limited to the chemical structures listed, and substituents are all included on the basis of the structures shown in the formula I.
Furthermore, the invention also provides an organic electroluminescent device which comprises an anode, a cathode and an organic layer, wherein the organic layer comprises the benzo five-membered heterocyclic derivative.
Preferably, the organic layer is located between the anode and the cathode, and the organic layer comprises a hole blocking layer and/or an electron transporting layer, and the hole blocking layer and/or the electron transporting layer comprises the benzo-five-membered heterocyclic derivative of the present invention.
Preferably, the organic layer is located on the side of the cathode facing away from the anode, and the organic layer comprises a cover layer comprising the benzo-five-membered heterocyclic derivative of the present invention.
The organic layer in the organic electroluminescent device of the present invention may include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, etc., as described below. Each functional layer may be formed of a single layer or a plurality of layers, and each layer may contain one material or a plurality of materials. The material of each layer in the organic electroluminescent device is not particularly limited, and materials known in the art may be used in addition to the benzo-five-membered heterocyclic derivative represented by the above formula (I) of the present invention. The materials in the organic functional layers of the above-mentioned organic electroluminescent device and the electrode materials of the device are respectively described as follows:
the anode material is preferably a material having a high work function and also having excellent light transmitting properties, and the anode material includes a metal, a metal oxide, a metal alloy, a combination of a metal and an oxide, a conductive polymer, and the like. Specific examples include: gold, vanadium, chromium, copper, palladium, nickel, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), zinc oxide, indium oxide, tin oxide, antimony (SnO) 2 Sb), polypyrrole, etc., but is not limited thereto.
The hole injection material is preferably a material capable of lowering the hole injection energy barrier, and includes metal oxides, phthalocyanine compounds, arylamine compounds, polycyano-containing conjugated organic materials, polymer materials, and the like, and specific examples include: molybdenum trioxide (MoO) 3 ) Copper phthalocyanine (CuPc), 4' -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), 4', 4' -tris [ 2-naphthylphenylamino ]]Triphenylamine (2T-NATA), 1,4,5,8,9,11-hexaazabenzonitrile (HAT-CN), (2E, 2'E,2 "E) -2,2' - (cyclopropane-1, 2, 3-triyl) tris (2- (perfluorophenyl) -acetonitrile), poly (3, 4-ethylenedioxythiophene)/poly (styrenesulfonic acid) (PEDOT/PSS), and the like, but are not limited thereto.
The hole transport material is a compound having a strong electron donating property, including aromatic amine compounds, carbazole compounds, and the like, and specific examples include: n, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), N4, N4, N4', N4' -tetra ([ 1,1' -biphenyl ] -4-yl) - [1,1' -biphenyl ] -4,4' -diamine, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TAPC), N, N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (TPD), 2, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (spira-TAD), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), and the like, but are not limited thereto.
The electron blocking material has an effect of blocking electrons in the light emitting layer, including aromatic amine compounds and the like. Examples of the electron blocking material include: 4,4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), and the like, but is not limited thereto.
Luminescent materials having the ability to accept holes and electrons include fluorescent luminescent materials and phosphorescent luminescent materials, and specific examples of the fluorescent luminescent materials include: 9, 10-bis (2-naphthyl) Anthracene (ADN), 9, 10-bis (1-naphthyl) anthracene (α -ADN), and the like, but are not limited thereto; specific examples of phosphorescent materials include: 4, 4-bis (9-Carbazolyl) Biphenyl (CBP), 9'- (1, 3-phenyl) bis-9H-carbazole (MCP), 4',4 "-tris (carbazol-9-yl) triphenylamine (TCTA), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like, but are not limited thereto.
The hole blocking material has the function of blocking holes in the light-emitting layer and comprises heterocyclic compounds such as imidazole compounds, phenanthroline compounds and the like. Specific examples include, in addition to the benzo five-membered heterocyclic derivative represented by formula (I) of the present invention: 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1, 1' -biphenyl-4-hydroxy) aluminum (BAlq), and the like, but are not limited thereto. Preferably, the benzo five-membered heterocyclic derivative represented by formula (I) of the present invention.
The electron transport material has high electron accepting capability and high electron transport capability, has the functions of injecting electrons and balancing carriers, and comprises benzo five-membered heterocyclic derivatives, metal complexes and the like, such as pyridine compounds, imidazole compounds, oxadiazole compounds, triazole compounds, phenanthroline compounds and the like. Specific examples include, in addition to the benzo five-membered heterocyclic derivative represented by formula (I) of the present invention: tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) 3,3'- [5' - [3- (3-pyridyl) phenyl ]](TmPyPB), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), 2- (4-biphenyl) -5- (4-t-butylphenyl) -1,3, 4-oxadiazole (PBD), 3- (biphenyl-4-yl) -4-phenyl-5- (4-t-butylphenyl) -1,2, 4-Triazole (TAZ), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), and the like, but are not limited thereto. Preferably, the benzo five-membered heterocyclic derivative represented by formula (I) of the present invention.
The electron injection material can improve electronsThe injectability in the device, including inorganic salts of alkali metals, alkali metal oxides, organic salts of alkali metals, alkali metal fluorides, alkali metal complexes, and the like, and specific examples include: cesium carbonate (Cs) 2 CO 3 ) Lithium oxide (Li) 2 O), potassium acetate (CH) 3 COOK), lithium fluoride (LiF), lithium 8-hydroxyquinoline (Liq), and the like, but is not limited thereto.
The cathode material is preferably a material having a low work function so that electrons are efficiently injected into the organic layer, and the cathode material includes metals, metal alloys, and the like, and specific examples include: aluminum, silver, magnesium, calcium, magnesium silver alloy, and the like, but is not limited thereto.
The cover layer material is preferably a material having a high glass transition temperature. In addition to the benzo-five membered heterocyclic derivatives of formula (I) of the present invention, cover materials that can be used in the present invention include, but are not limited to: thiophene, furan, pyrrole, pyrene, anthracene, and the like. Preferably, the benzo five-membered heterocyclic derivative represented by formula (I) of the present invention.
The organic electroluminescent device is mainly applied to the technical field of information display, and is widely applied to various information displays in the aspect of information display, such as a tablet personal computer, a flat television, a mobile phone, a smart watch, a digital camera, VR, a vehicle-mounted system, wearable equipment and the like.
Synthetic examples
The method for producing the benzo five-membered heterocyclic derivative represented by formula (I) of the present invention is not particularly limited, and conventional methods known to those skilled in the art can be employed. For example, carbon-carbon coupling reaction and the like, the benzo five-membered heterocyclic derivative of formula (I) of the present invention can be prepared by the synthetic route shown below.
Wherein Ar is 1 、Ar 2 、L 1 ～L 3 、R 2 、X 1 、Y 1 ～Y 4 The definition of m and n is the same as the definition, and Xa-Xe are any one of I, br and Cl independentlyMeaning one.
The method for producing the triarylamine compound represented by formula II of the present invention is not particularly limited, and conventional methods known to those skilled in the art can be employed. For example, carbon-nitrogen coupling reaction and the like, more specifically, a Buch-Ward reaction, an Ullman reaction and the like can be employed.
Raw materials and reagents: the raw materials and the reagents used in the invention are all reagent pure. The starting materials or reagents used in the following synthetic examples are not particularly limited and may be commercially available products or prepared by methods well known to those skilled in the art.
Instrument: (1) G2—si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); (2) Vario EL cube organic element analyzer (Elementar, germany); (3) Bruker-510 nuclear magnetic resonance spectrometer (Bruker, germany).
Synthesis example 1: synthesis of Compound 1
Preparation of intermediate 1-1:
a-1 (54.63 g,200.00 mmol), b-1 (31.90 g,204.00 mmol), potassium acetate (39.26 g,400.00 mmol), pd (PPh) 3 ) 4 (4.62 g,4.00 mmol) was mixed with 600mL toluene, 200mL ethanol, 200mL water and added to the reaction flask. Heating and refluxing for 2 hours under the protection of nitrogen; after the reaction, cooling the reaction mixture to room temperature, suction filtering to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene/ethanol=7:2 to obtain intermediate 1-1 (50.60 g, yield 83%); HPLC purity is more than or equal to 99.41%; mass spectrum m/z:304.1001 (theory: 304.1019).
Preparation of intermediate 1-2:
intermediate 1-1 (44.38 g,145.60 mmol), c-1 (40.67 g,160.16 mmol), KOAc (42.87 g,436.80 mmol), pd (dppf) Cl 2 (3.20 g,4.37 mmol), 1, 4-dioxane (700 mL) were added in a mixture to the reaction flask. Heating and refluxing for reaction for 5 hours under the protection of nitrogen; reaction junctionAfter the completion of the reaction, the reaction mixture was cooled to room temperature, water was then added thereto, followed by extraction with ethyl acetate, and the organic layer was dried over anhydrous MgSO 4 Drying, rotary evaporation of ethyl acetate followed by recrystallisation from toluene afforded intermediate 1-2 (48.47 g, 84% yield); HPLC purity is more than or equal to 99.50%; mass spectrum m/z:396.2280 (theory: 396.2261).
Preparation of intermediates 1-3:
d-1 (26.03 g,100.00 mmol), intermediate 1-2 (40.43 g,102.00 mmol), K 2 CO 3 (27.64g，200.00mmol)、Pd(dppf)Cl 2 (1.46 g,2.00 mmol) was mixed with 300mL toluene, 100mL ethanol, 100mL water and added to the reaction flask. Heating and refluxing for reaction for 3 hours under the protection of nitrogen; after the reaction was completed, the reaction mixture was cooled to room temperature, suction filtered to obtain a cake, and the cake was rinsed with ethanol, and finally the cake was washed with toluene/ethanol=20: 3 to give intermediate 1-3 (34.18 g, 76% yield); HPLC purity is more than or equal to 99.54%; mass spectrum m/z:448.0539 (theory: 448.0552).
Preparation of intermediates 1-4:
intermediate 1-3 (29.24 g,65.00 mmol), c-1 (54.47 g,214.50 mmol), KOAc (57.41 g,585.00 mmol), pd (dppf) Cl 2 (4.28 g,5.85 mmol), 1, 4-dioxane (450 mL) were added to the reaction flask with mixing. Heating and refluxing for reaction for 7 hours under the protection of nitrogen; after the reaction was completed, after the reaction mixture was cooled to room temperature, water was added thereto, followed by extraction with ethyl acetate, and the organic layer was dried over anhydrous MgSO 4 Drying, rotary evaporation of ethyl acetate followed by recrystallisation from toluene afforded intermediate 1-4 (34.37 g, 73% yield); HPLC purity is more than or equal to 99.62%; mass spectrum m/z:724.4293 (theory: 724.4278).
Preparation of Compound 1:
intermediate 1-4 (28.97 g,40.00 mmol), e-1 (24.32 g,122.80 mmol), cs 2 CO 3 (78.20g，240.00mmol)、Pd 2 (dba) 3 (1.10g，1.20mmol)、P(t-Bu) 3 (1.94 g,9.60 mmol) was mixed with 200ml tetrahydrofuran and added to the reaction flask. Heating and refluxing for reaction for 5 hours under the protection of nitrogen; after the reaction is completed, the reaction mixture is cooled toSuction filtration at room temperature to obtain a filter cake, flushing the filter cake with ethanol, and finally recrystallizing the filter cake with toluene to obtain the compound 1 (18.70 g, 67% yield), wherein the HPLC purity is more than or equal to 99.77%. Mass spectrum m/z:697.2381 (theory: 697.2365). Theoretical element content (%) C 48 H 31 N 3 O 3 : c,82.62; h,4.48; n,6.02. Measured element content (%): c,82.58; h,4.51; n,5.97.
Synthesis example 2: synthesis of Compound 3
The same preparation as in Synthesis example 1 was repeated except for substituting a-1 for equimolar a-3 to obtain Compound 3 (19.74 g); the HPLC purity is more than or equal to 99.69 percent. Mass spectrum m/z:747.2511 (theory: 747.2522). Theoretical element content (%) C 52 H 33 N 3 O 3 : c,83.52; h,4.45; n,5.62. Measured element content (%): c,83.49; h,4.50; n,5.59.
Synthesis example 3: synthesis of Compound 5
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-5 to give Compound 5 (20.04 g) with an HPLC purity of 99.76%. Mass spectrum m/z:747.2507 (theory: 747.2522). Theoretical element content (%) C 52 H 33 N 3 O 3 : c,83.52; h,4.45; n,5.62. Measured element content (%): c,83.48; h,4.46; n,5.67.
Synthesis example 4: synthesis of Compound 15
The a-1 in synthesis example 1 was replaced by equimolar a-15, as followsThe same preparation as in Synthesis example 1 was repeated to obtain Compound 15 (20.15 g), with an HPLC purity of 99.73% or more. Mass spectrum m/z:774.2644 (theory: 774.2631). Theoretical element content (%) C 53 H 34 N 4 O 3 : c,82.15; h,4.42; n,7.23. Measured element content (%): c,82.19; h,4.37; n,7.21.
Synthesis example 5: synthesis of Compound 20
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-20 to give Compound 20 (19.37 g) with an HPLC purity of not less than 99.72%. Mass spectrum m/z:722.2302 (theory: 722.2318). Theoretical element content (%) C 49 H 30 N 4 O 3 : c,81.42; h,4.18; n,7.75. Measured element content (%): c,81.37; h,4.22; n,7.70.
Synthesis example 6: synthesis of Compound 25
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-25 to give Compound 25 (20.54 g) with an HPLC purity of 99.70%. Mass spectrum m/z:789.2977 (theory: 789.2991). Theoretical element content (%) C 55 H 39 N 3 O 3 : c,83.63; h,4.98; n,5.32. Measured element content (%): c,83.59; h,4.99; n,5.29.
Synthesis example 7: synthesis of Compound 27
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The same preparation as in Synthesis example 1 was conducted except that a-1 in Synthesis example 1 was replaced with equimolar a-27 to obtainCompound 27 (20.06 g) with HPLC purity greater than or equal to 99.76%. Mass spectrum m/z:759.2505 (theory: 759.2522). Theoretical element content (%) C 53 H 33 N 3 O 3 : c,83.78; h,4.38; n,5.53. Measured element content (%): c,83.82; h,4.40; n,5.49.
Synthesis example 8: synthesis of Compound 36
The same procedures as in Synthesis example 1 were repeated except for using a-1 instead of a-36 in equimolar amounts to give Compound 36 (21.37 g) having an HPLC purity of 99.75%. Mass spectrum m/z:821.2696 (theory: 821.2678). Theoretical element content (%) C 58 H 35 N 3 O 3 : c,84.76; h,4.29; n,5.11. Measured element content (%): c,84.81; h,4.32; n,5.09.
Synthesis example 9: synthesis of Compound 47
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-47 to give Compound 47 (21.09 g) with an HPLC purity of 99.74%. Mass spectrum m/z:823.2567 (theory: 823.2583). Theoretical element content (%) C 56 H 33 N 5 O 3 : c,81.64; h,4.04; n,8.50. Measured element content (%): c,81.60; h,4.07; n,8.49.
Synthesis example 10: synthesis of Compound 56
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-56 to give Compound 56 (21.40 g) having an HPLC purity of 99.65%. Quality of the bodySpectrum m/z:835.2456 (theory: 835.2471). Theoretical element content (%) C 58 H 33 N 3 O 4 : c,83.34; h,3.98; n,5.03. Measured element content (%): c,83.29; h,4.03; n,5.00.
Synthesis example 11: synthesis of Compound 63
The same preparation as in Synthesis example 1 was repeated except for substituting a-1 for equimolar a-63 to obtain Compound 63 (21.47 g), with an HPLC purity of 99.69%. Mass spectrum m/z:851.2234 (theory: 851.2243). Theoretical element content (%) C 58 H 33 N 3 O 3 S: c,81.77; h,3.90; n,4.93. Measured element content (%): c,81.82; h,3.88; n,4.87.
Synthesis example 12: synthesis of Compound 71
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-71 to give compound 71 (22.25 g) having an HPLC purity of 99.67%. Mass spectrum m/z:896.2799 (theory: 896.2787). Theoretical element content (%) C 63 H 36 N 4 O 3 : c,84.36; h,4.05; n,6.25. Measured element content (%): c,84.41; h,4.01; n,6.28.
Synthesis example 13: synthesis of Compound 83
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-83 to give Compound 83 (22.35 g) with an HPLC purity of 99.63%. Mass spectrum m/z:886.2931 (theory: 886.2944). Theory of Elemental content (%) C 62 H 38 N 4 O 3 : c,83.95; h,4.32; n,6.32. Measured element content (%): c,83.90; h,4.34; n,6.31.
Synthesis example 14: synthesis of Compound 84
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-84 to give Compound 84 (22.23 g) with an HPLC purity of 99.59%. Mass spectrum m/z:910.2959 (theory: 910.2944). Theoretical element content (%) C 64 H 38 N 4 O 3 : c,84.38; h,4.20; n,6.15. Measured element content (%): c,84.41; h,4.16; n,6.22.
Synthesis example 15: synthesis of Compound 89
The same preparation as in Synthesis example 1 was repeated except for substituting a-1 for equimolar a-89 to obtain Compound 89 (18.27 g) having an HPLC purity of 99.79%. Mass spectrum m/z:671.1834 (theory: 671.1845). Theoretical element content (%) C 45 H 25 N 3 O 4 : c,80.47; h,3.75; n,6.26. Measured element content (%): c,80.50; h,3.71; n,6.31.
Synthesis example 16: synthesis of Compound 90
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-90 to give Compound 90 (18.43 g) with an HPLC purity of 99.77%. Mass spectrum m/z:687.1601 (theory: 687.1617). Theoretical element content (%) C 45 H 25 N 3 O 3 S: c,78.59; h,3.66; n,6.11. Measured element content (%): c,78.62; h,3.65; n,6.09.
Synthesis example 17: synthesis of Compound 91
The same procedure as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-91 to give Compound 91 (19.72 g) having an HPLC purity of 99.69%. Mass spectrum m/z:746.2335 (theory: 746.2318). Theoretical element content (%) C 51 H 30 N 4 O 3 : c,82.02; h,4.05; n,7.50. Measured element content (%): c,81.98; h,4.10; n,7.47.
Synthesis example 18: synthesis of Compound 96
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-96 and b-1 was replaced with equimolar b-96 to give Compound 96 (18.73 g) having an HPLC purity of 99.75%. Mass spectrum m/z:698.2330 (theory: 698.2318). Theoretical element content (%) C 47 H 30 N 4 O 3 : c,80.79; h,4.33; n,8.02. Measured element content (%): c,80.74; h,4.40; n,7.96.
Synthesis example 19: synthesis of Compound 113
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-113 and b-1 was replaced with equimolar b-113 to give Compound 113 (20.09 g) having an HPLC purity of 99.67% or more. Mass spectrum m/z:760.2466 (theory: 760.2474).
Theoretical element content (%) C 52 H 32 N 4 O 3 : c,82.09; h,4.24; n,7.36. Measured element content (%): c,82.13; h,4.19; n,7.40.
Synthesis example 20: synthesis of Compound 144
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-144 and b-1 was replaced with equimolar b-144 to obtain Compound 144 (22.12 g) having an HPLC purity of 99.68%. Mass spectrum m/z:863.2886 (theory: 863.2896). Theoretical element content (%) C 59 H 37 N 5 O 3 : c,82.02; h,4.32; n,8.11. Measured element content (%): c,81.99; h,4.33; n,8.08.
Synthesis example 21: synthesis of Compound 240
The same procedure as in Synthesis example 1 was followed except that b-1 was replaced with equimolar b-240 to give compound 240 (18.53 g) having an HPLC purity of 99.73% or more. Mass spectrum m/z:701.2603 (theory: 701.2616). Theoretical element content (%) C 48 H 27 D 4 N 3 O 3 : c,82.15; h,5.03; n,5.99. Measured element content (%): c,82.19; h,4.98; n,6.02.
Synthesis example 22: synthesis of Compound 247
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-247 and b-1 was replaced with equimolar b-247 to give Compound 247 (20.48 g) having an HPLC purity of 99.69%. Quality of the body Spectrum m/z:787.2460 (theory: 787.2471). Theoretical element content (%) C 54 H 33 N 3 O 4 : c,82.32; h,4.22; n,5.33. Measured element content (%): c,82.28; h,4.19; n,5.29.
Synthesis example 23: synthesis of Compound 256
The same procedure as in Synthesis example 1 was followed except that e-1 was replaced with equimolar e-256 to give 256 (22.97 g) as a compound having an HPLC purity of 99.74%. Mass spectrum m/z:925.3324 (theory: 925.3304). Theoretical element content (%) C 66 H 43 N 3 O 3 : c,85.60; h,4.68; n,4.54. Measured element content (%): c,85.58; h,4.72; n,4.49.
Synthesis example 24: synthesis of Compound 278
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-278, b-1 was replaced with equimolar b-113, and e-1 was replaced with equimolar e-256, to obtain Compound 278 (24.14 g) having an HPLC purity of not less than 99.72%. Mass spectrum m/z:988.3401 (theory: 988.3413). Theoretical element content (%) C 70 H 44 N 4 O 3 : c,85.00; h,4.48; n,5.66. Measured element content (%): c,84.97; h,4.53; n,5.67.
Synthesis example 25: synthesis of Compound 304
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The same procedures as in Synthesis example 1 were followed except that e-1 was replaced with equimolar e-304 to give Compound 304 (18.50 g), HPLC The purity is more than or equal to 99.74 percent. Mass spectrum m/z:700.2216 (theory: 700.2223). Theoretical element content (%) C 45 H 28 N 6 O 3 : c,77.13; h,4.03; n,11.99. Measured element content (%): c,77.09; h,3.98; n,12.02.
Synthesis example 26: synthesis of Compound 313
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-313, b-1 was replaced with equimolar b-113, and e-1 was replaced with equimolar e-313 to obtain compound 313 (20.22 g) having an HPLC purity of 99.68%. Mass spectrum m/z:777.2472 (theory: 777.2488). Theoretical element content (%) C 50 H 31 N 7 O 3 : c,77.21; h,4.02; n,12.61. Measured element content (%): c,77.17; h,3.99; n,12.67.
Synthesis example 27: synthesis of Compound 340
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-340, b-1 was replaced with equimolar b-340 and e-1 was replaced with equimolar e-340 to obtain Compound 340 (21.50 g) having an HPLC purity of 99.63%. Mass spectrum m/z:839.2945 (theory: 839.2926). Theoretical element content (%) C 50 H 17 D 10 N 11 O 3 : c,71.50; h,4.44; n,18.34. Measured element content (%): c,71.47; h,4.38; n,18.29.
Synthesis example 28: synthesis of Compound 354
A-1 in Synthesis example 1Replacement with equimolar a-247 and replacement with equimolar e-354 gave compound 354 (23.11 g) with an HPLC purity of 99.68% or more in the same manner as in Synthesis example 1. Mass spectrum m/z:931.3011 (theory: 931.3019). Theoretical element content (%) C 60 H 37 N 9 O 3 : c,77.32; h,4.00; n,13.53. Measured element content (%): c,77.29; h,3.97; n,13.49.
Synthesis example 29: synthesis of Compound 364
The same procedure as in Synthesis example 1 was followed except that e-1 was replaced with equimolar e-364 to give compound 364 (22.97 g) having an HPLC purity of 99.77%. Mass spectrum m/z:925.3320 (theory: 925.3304). Theoretical element content (%) C 66 H 43 N 3 O 3 : c,85.60; h,4.68; n,4.54. Measured element content (%): c,85.56; h,4.70; n,4.49.
Synthesis example 30: synthesis of Compound 384
The same production method as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-96, b-1 was replaced with equimolar b-384, and d-1 was replaced with equimolar d-384, to obtain compound 384 (18.42 g) having an HPLC purity of 99.75%. Mass spectrum m/z:697.2375 (theory: 697.2365). Theoretical element content (%) C 48 H 31 N 3 O 3 : c,82.62; h,4.48; n,6.02. Measured element content (%): c,82.59; h,4.52; n,5.98.
Synthesis example 31: synthesis of Compound 410
The same preparation method as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-278, b-1 was replaced with equimolar b-384, d-1 was replaced with equimolar d-384, and e-1 was replaced with equimolar e-410, to obtain Compound 410 (21.01 g) with an HPLC purity of 99.73%. Mass spectrum m/z:807.1824 (theory: 807.1837). Theoretical element content (%) C 53 H 33 N 3 S 3 : c,78.78; h,4.12; n,5.20. Measured element content (%): c,78.80; h,4.08; n,5.17.
Synthesis example 32: synthesis of Compound 414
The same preparation method as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-247, b-1 was replaced with equimolar b-384, d-1 was replaced with equimolar d-384, and e-1 was replaced with equimolar e-414, to give Compound 414 (22.22 g) with an HPLC purity of 99.70%. Mass spectrum m/z:895.2136 (theory: 895.2150). Theoretical element content (%) C 60 H 37 N 3 S 3 : c,80.42; h,4.16; n,4.69. Measured element content (%): c,80.37; h,4.20; n,4.72.
Synthesis example 33: synthesis of Compound 437
The same production method as in Synthesis example 1 was followed except that a-1 was replaced with equimolar a-437, b-1 was replaced with equimolar b-340, and e-1 was replaced with equimolar e-410, whereby Compound 437 (21.93 g) was obtained with an HPLC purity of 99.68%. Mass spectrum m/z:869.1731 (theory: 869.1742). Theoretical element content (%) C 56 H 31 N 5 S 3 : c,77.31; h,3.59; n,8.05. Measured element content (%): c,77.27; h,3.61; n,8.08.
Synthesis example 34: synthesis of Compound 460
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-460 and e-1 was replaced with equimolar e-460 to obtain Compound 460 (24.06 g) having an HPLC purity of not less than 99.62%. Mass spectrum m/z:985.2817 (theory: 985.2804). Theoretical element content (%) C 60 H 43 N 9 S 3 : c,73.07; h,4.39; n,12.78. Measured element content (%): c,73.11; h,4.41; n,12.80.
Synthesis example 35: synthesis of Compound 486
The same preparation as in Synthesis example 1 was repeated except that a-1 was replaced with equimolar a-247, b-1 was replaced with equimolar b-486, and e-1 was replaced with equimolar e-486, to obtain compound 486 (23.89 g), which had an HPLC purity of 99.68%. Mass spectrum m/z:978.2363 (theory: 978.2382). Theoretical element content (%) C 61 H 38 N 8 S 3 : c,74.82; h,3.91; n,11.44. Measured element content (%): c,74.79; h,3.88; n,11.39.
Synthesis example 36: synthesis of Compound 498
The same procedure as in Synthesis example 1 was followed except that e-1 in Synthesis example 1 was replaced with equimolar e-498 to give Compound 498 (22.89 g) with an HPLC purity of 99.73% or more. Mass spectrum m/z:922.3793 (theory: 922.3784). Theoretical element content (%) C 66 H 46 N 6 : c,85.87; h,5.02; n,9.10. Measured element content (%): c,85.90; h,4.97; n,9.08.
Device example 1
Firstly, an ITO glass substrate is placed in distilled water for 2 times of washing, ultrasonic washing is carried out for 30 minutes, then the distilled water is used for repeatedly washing for 2 times, ultrasonic washing is carried out for 10 minutes, after the distilled water washing is finished, isopropanol, acetone and methanol solvents are adopted for ultrasonic washing in sequence, drying is carried out on a hot plate heated to 120 ℃, the dried substrate is transferred into a plasma washing machine, and after washing for 5 minutes, the substrate is transferred into an evaporation machine.
Evaporating HI-1 with the thickness of 50nm on the cleaned ITO substrate to be used as a hole injection layer material; evaporating HT-1 with the thickness of 40nm on the hole injection layer as a hole transport layer material; vacuum evaporating a main material RH-1 and a doping material RD-1 on the hole transport layer to form a luminescent layer with a doping ratio of 96:4, wherein the evaporating thickness is 25nm; evaporating the compound 1 as a hole blocking layer on the light-emitting layer, wherein the evaporation thickness is 10nm; evaporating ET-1 on the hole blocking layer as an electron transport layer, wherein the evaporating thickness is 35nm; evaporating LiF as an electron injection layer on the electron transport layer, wherein the evaporating thickness is 0.5nm; then, al (110 nm) was evaporated on the electron injection layer as a cathode, thereby preparing an organic electroluminescent device.
The compounds involved in the device examples and comparative examples of the present invention are shown below:
device examples 2 to 15
An organic electroluminescent device was manufactured by the same manufacturing method as in device example 1, except that compound 1 in device example 1 was replaced with compound 3, compound 15, compound 25, compound 47, compound 56, compound 89, compound 113, compound 144, compound 240, compound 304, compound 354, compound 364, compound 460 and compound 498 according to the present invention, respectively.
Comparative device examples 1 to 4
An organic electroluminescent device was manufactured by the same manufacturing method as device example 1, except that the compound 1 in device example 1 was replaced with the comparative compound 1, the comparative compound 2, and the comparative compound 3 as a hole blocking layer.
Test software, a computer, a K2400 digital source list manufactured by Keithley company in U.S. and a PR788 spectrum scanning luminance meter manufactured by Photo Research company in U.S. are combined into a combined IVL test system to test the driving voltage and luminous efficiency of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature. The results of testing the light emitting characteristics of the devices 1 to 15 in the device examples according to the present invention and the organic electroluminescent devices obtained in the comparative examples 1 to 4 are shown in the following table 1.
Table 1: light emitting characteristic test of organic electroluminescent device
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As shown by the test results in Table 1, compared with comparative device examples 1-3, the benzo five-membered heterocyclic derivative provided by the invention is applied to an organic electroluminescent device as a hole blocking layer material, and can effectively block holes in a luminescent layer, so that the recombination rate of holes and electrons is improved, the luminescent efficiency of the device is improved, and the service life of the device is prolonged.
Device example 16
Firstly, an ITO glass substrate is placed in distilled water for 2 times of washing, ultrasonic washing is carried out for 30 minutes, then the distilled water is used for repeatedly washing for 2 times, ultrasonic washing is carried out for 10 minutes, after the distilled water washing is finished, isopropanol, acetone and methanol solvents are adopted for ultrasonic washing in sequence, drying is carried out on a hot plate heated to 120 ℃, the dried substrate is transferred into a plasma washing machine, and after washing for 5 minutes, the substrate is transferred into an evaporation machine.
Evaporating HI-1 with the thickness of 50nm on the cleaned ITO substrate to be used as a hole injection layer material; evaporating HT-1 with the thickness of 40nm on the hole injection layer as a hole transport layer material; vacuum evaporating a main material RH-1 and a doping material RD-1 on the hole transport layer to form a luminescent layer with a doping ratio of 96:4, wherein the evaporating thickness is 25nm; evaporating the compound 5 of the invention on the light-emitting layer as an electron transport layer, wherein the evaporation thickness is 35nm; evaporating LiF as an electron injection layer on the electron transport layer, wherein the evaporating thickness is 0.5nm; then, al (110 nm) was evaporated on the electron injection layer as a cathode, thereby preparing an organic electroluminescent device.
Device examples 17 to 30
An organic electroluminescent device was produced by the same production method as in device example 16, except that compound 5 in device example 16 was replaced with compound 15, compound 20, compound 27, compound 36, compound 71, compound 83, compound 90, compound 96, compound 144, compound 278, compound 304, compound 313, compound 384 and compound 486 according to the invention, respectively, as an electron transport layer.
Comparative device examples 5 to 8
An organic electroluminescent device was manufactured by the same manufacturing method as device example 16, except that the compound 5 in device example 16 was replaced with the comparative compound 1, the comparative compound 2, and the comparative compound 3 as the electron transport layer. The test results are shown in table 2 below.
Table 2: light emitting characteristic test of organic electroluminescent device
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As shown by the test results in Table 2, the benzo five-membered heterocyclic derivative provided by the invention has better electron migration efficiency compared with comparative examples 4-6 as an electron transport layer material, can effectively improve the injection balance of holes and electrons, and has high luminous efficiency and long service life when applied to an organic electroluminescent device.
Device example 31
Firstly, placing an ITO/Ag/ITO glass substrate in distilled water for cleaning for 2 times, washing for 30 minutes by ultrasonic waves, repeatedly cleaning for 2 times by using distilled water, washing by ultrasonic waves for 10 minutes, after the distilled water is cleaned, sequentially washing by using isopropanol, acetone and methanol solvents by ultrasonic waves, drying on a hot plate heated to 120 ℃, transferring the dried substrate into a plasma cleaner, and transferring the substrate into an evaporation machine after washing for 5 minutes.
Evaporating HI-1 with the thickness of 50nm on the cleaned ITO/Ag/ITO substrate to be used as a hole injection layer material; evaporating HT-1 with the thickness of 40nm on the hole injection layer as a hole transport layer material; vacuum evaporating a main material RH-1 and a doping material RD-1 on the hole transport layer to form a luminescent layer with a doping ratio of 96:4, wherein the evaporating thickness is 25nm; evaporating ET-1 on the light-emitting layer as an electron transport layer, wherein the evaporating thickness is 35nm; evaporating LiF as an electron injection layer on the electron transport layer, wherein the evaporating thickness is 1nm; then, mg/Ag is evaporated on the electron injection layer to serve as a cathode, the evaporation thickness is 12nm, and finally, the compound 1 is evaporated on the cathode to serve as a covering layer, and the evaporation thickness is 70nm, so that the organic electroluminescent device is prepared.
Device examples 32 to 45
An organic electroluminescent device was produced by the same production method as in device example 31, except that compound 1 in device example 31 was replaced with compound 47, compound 63, compound 71, compound 84, compound 91, compound 247, compound 256, compound 304, compound 313, compound 340, compound 384, compound 410, compound 414 and compound 437 according to the invention, respectively, as a cap layer.
Comparative device examples 9 to 10
An organic electroluminescent device was manufactured by the same manufacturing method as that of device example 31, except that the compound 1 in device example 31 was replaced with the comparative compound 1, comparative compound 2 as a cover layer. The test results are shown in table 3 below.
Table 3: light emitting characteristic test of organic electroluminescent device
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As can be seen from the test results in Table 3, the use of the nitrogen-containing heterocyclic derivative provided by the invention as a coating material in an organic electroluminescent device can effectively improve the light extraction efficiency of the device and thus the luminous efficiency of the device, compared with comparative example 7; in addition, the lifetime of the device can be significantly improved.
The result shows that the heterocyclic compound provided by the invention can be used as an electron transport layer material, a hole blocking layer material or a cover layer material when applied to an organic light-emitting device, has higher luminous efficiency and service life, and is an organic light-emitting material with good performance.
It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.

Claims (7)

1. A benzo five-membered heterocyclic derivative is characterized by having a structure represented by formula (I),
said n is selected from 3; the Ar is as follows 1 Independently selected from any one of the following groups:
the L is 1 Independently selected from a single bond or any one of the following groups,
the L is 2 Selected from single bonds;
the L is 3 Selected from a single bond or any one of the following groups,
the Ar is as follows 2 Any one selected from the following groups:
the R is 7 、R 9 、R 10 、R 11 Independently selected from any one of hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, or between two adjacent substituentsCan be linked to form a benzene ring;
the R is 8 、R 9a 、R 11a Independently selected from hydrogen, deuterium;
the a 1 Selected from 0, 1, 2, 3, 4, 5, 6 or 7; a, a 2 Selected from 0, 1, 2, 3, 4 or 5; a, a 3 Selected from 0, 1, 2, 3 or 4; a, a 4 Selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; a, a 5 Selected from 0, 1, 2 or 3;
the R is a Any one selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl and substituted or unsubstituted naphthyl;
the above-mentioned "substituted or unsubstituted methyl group", "substituted or unsubstituted ethyl group", "substituted or unsubstituted propyl group", "substituted or unsubstituted butyl group", "substituted or unsubstituted pentyl group", "substituted or unsubstituted hexyl group", "substituted or unsubstituted phenyl group", "substituted or unsubstituted pyridyl group", "substituted or unsubstituted biphenyl group", "substituted or unsubstituted naphthyl group" is substituted or unsubstituted by deuterium;
provided that the compound is not
2. The benzo five membered heterocyclic derivative according to claim 1, wherein Ar is 1 Any one selected from the following groups:
3. the benzo five membered heterocyclic derivative according to claim 1, wherein Ar is 2 Selected from the group consisting ofAny one of the groups:
4. a heterocyclic derivative, characterized in that the heterocyclic derivative is selected from any one of the structures shown below,
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5. An organic electroluminescent device comprising an anode, a cathode, and an organic layer, wherein the organic layer comprises the benzo-five-membered heterocyclic derivative according to any one of claims 1-4.
6. An organic electroluminescent device as claimed in claim 5, characterized in that the organic layer is located between the anode and the cathode, the organic layer comprising a hole blocking layer and/or an electron transporting layer comprising a benzo-five membered heterocyclic derivative according to any one of claims 1 to 4.
7. An organic electroluminescent device as claimed in claim 5, wherein the organic layer is located on the side of the cathode facing away from the anode, the organic layer comprising a capping layer comprising a benzo-five membered heterocyclic derivative as claimed in any one of claims 1 to 4.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112442023A (en) * 2020-11-30 2021-03-05 长春海谱润斯科技股份有限公司 Heterocyclic derivative and organic electroluminescent device thereof
CN112661714A (en) * 2020-12-22 2021-04-16 长春海谱润斯科技股份有限公司 Heterocyclic compound and organic electroluminescent device containing same
CN113336744A (en) * 2021-06-23 2021-09-03 长春海谱润斯科技股份有限公司 Heterocyclic derivative and organic electroluminescent device thereof
CN113717122A (en) * 2021-09-17 2021-11-30 长春海谱润斯科技股份有限公司 Adamantane spirofluorene derivative and organic electroluminescent device thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112442023A (en) * 2020-11-30 2021-03-05 长春海谱润斯科技股份有限公司 Heterocyclic derivative and organic electroluminescent device thereof
CN112661714A (en) * 2020-12-22 2021-04-16 长春海谱润斯科技股份有限公司 Heterocyclic compound and organic electroluminescent device containing same
CN113336744A (en) * 2021-06-23 2021-09-03 长春海谱润斯科技股份有限公司 Heterocyclic derivative and organic electroluminescent device thereof
CN113717122A (en) * 2021-09-17 2021-11-30 长春海谱润斯科技股份有限公司 Adamantane spirofluorene derivative and organic electroluminescent device thereof

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