CN114094023B - Organic electroluminescent element containing compound based on tribenzotriindene - Google Patents

Organic electroluminescent element containing compound based on tribenzotriindene Download PDF

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CN114094023B
CN114094023B CN202111353380.3A CN202111353380A CN114094023B CN 114094023 B CN114094023 B CN 114094023B CN 202111353380 A CN202111353380 A CN 202111353380A CN 114094023 B CN114094023 B CN 114094023B
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organic electroluminescent
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CN114094023A (en
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姜卫东
张海威
曹建华
董焕章
唐怡杰
邸庆童
边坤
郭文龙
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Shanghai 800 Million Spacetime Advanced Material Co ltd
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    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes

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  • Electroluminescent Light Sources (AREA)

Abstract

The invention discloses a hole transport layer and a charge blocking layer containing a compound based on a tris-benzotriindene. By using compounds comprising a tris-benzidine group in the hole transport layer, the voltage, efficiency and lifetime of the OLED can be improved. In addition, the voltage, efficiency and lifetime of the OLED can be further improved by using compounds comprising a tris-benzidine-based compound in the charge blocking layer in a tandem OLED structure.

Description

Organic electroluminescent element containing compound based on tribenzotriindene
Technical Field
The present invention relates to a hole injection layer and a charge generation layer of an organic electroluminescent element. And more particularly to a hole injection layer and a charge generation layer comprising a tris-benzindene-based compound.
Background
In general, an organic light emitting phenomenon refers to a phenomenon that emits light when electric energy is applied to an organic substance. That is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode to the organic layer, and electrons are injected from the cathode to the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
As a method for effectively manufacturing an organic electroluminescent element, studies have been made to manufacture an organic layer in an element in a multilayer structure instead of a single layer. In 1987, tang proposed an organic electroluminescent element having a layered structure of a hole layer and a functional layer of a light-emitting layer, and most of the organic electroluminescent elements currently used include: the light emitting device includes a substrate, an anode, a hole injection layer that receives holes from the anode, a hole transport layer that transports holes, a light emitting layer that emits light by recombination of holes and electrons, an electron transport layer that transports electrons, an electron injection layer that receives electrons from a cathode, and a cathode. The reason why the organic electroluminescent device is fabricated in a plurality of layers is that since the movement speeds of holes and electrons are different, if a hole injection layer and a transport layer, an electron transport layer and an electron injection layer are fabricated appropriately, holes and electrons can be efficiently transported, balance between holes and electrons can be achieved in the device, and the exciton utilization ratio can be improved.
In an OLED element, a Hole Injection Layer (HIL) facilitates hole injection from the ITO anode to the organic layer. In order to achieve low element drive voltages, it is important to have a minimum charge injection barrier from the anode. Various HIL materials have been developed, such as triarylamine compounds having a shallow HOMO level, very electron-deficient heterocyclic compounds, and triarylamine compounds doped with P-type conductivity dopants. In order to improve OLED performance, such as longer element lifetime, higher efficiency and lower voltage, it is important to develop HIL materials with better performance.
In order to overcome the above-described problems of the conventional techniques and to further improve the characteristics of the organic electroluminescent element, there is a continuing need for the development of a more stable and effective substance that can be used as a hole injection and transport substance in the organic electroluminescent element.
Disclosure of Invention
The present invention aims to improve the voltage, efficiency and lifetime of an OLED by using a hole injection layer comprising a tris-benzindene-based compound. In addition, a charge injection layer comprising a tris-benzindene-based compound is provided that can be used to series p-type charge generation layers in OLED structures, further improving the voltage, efficiency and lifetime of the OLED.
According to an embodiment of the present invention, an organic electroluminescent element is disclosed, comprising: an anode, a cathode, a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by the general formula (I):
Wherein:
R 0～R11 is each independently selected from the group consisting of hydrogen, deuterium, halogen, nitrile, alkyl of substituted or unsubstituted C 1-C40, alkyl or cycloalkyl of substituted or unsubstituted C 3-C40 with a branched chain, heteroalkyl of substituted or unsubstituted C 1-C40, alkenyl of substituted or unsubstituted C 2-C40, aryl of substituted or unsubstituted C 6-C60, aryloxy of substituted or unsubstituted C 6-C60, aralkyl of substituted or unsubstituted C 7-C60, silyl of substituted or unsubstituted C 3-C40, arylsilane of substituted or unsubstituted C 6-C60, amino of substituted or unsubstituted C 2-C60 heteroaryl of substituted or unsubstituted C 0-C40, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, wherein two or more adjacent groups may optionally be joined or fused to form one or more additional substituted or unsubstituted rings, containing no or one or more heteroatoms N, P, B, O S in the formed ring. Preferably, R 0～R11 is not all hydrogen and deuterium, more preferably, R 0、R1 and R 4～R11 are not all hydrogen and deuterium.
In the present specification, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" means a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring.
According to another embodiment of the present invention, there is also disclosed a tandem organic electroluminescent element including:
An anode, a cathode, a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by the general formula (I):
Wherein:
R 0～R11 is each independently selected from the group consisting of hydrogen, deuterium, halogen, nitrile, alkyl of substituted or unsubstituted C 1-C40, alkyl or cycloalkyl of substituted or unsubstituted C 3-C40 with a branched chain, heteroalkyl of substituted or unsubstituted C 1-C40, alkenyl of substituted or unsubstituted C 2-C40, aryl of substituted or unsubstituted C 6-C60, aryloxy of substituted or unsubstituted C 6-C60, aralkyl of substituted or unsubstituted C 7-C60, silyl of substituted or unsubstituted C 3-C40, arylsilane of substituted or unsubstituted C 6-C60, amino of substituted or unsubstituted C 2-C60 heteroaryl of substituted or unsubstituted C 0-C40, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, wherein two or more adjacent groups may optionally be joined or fused to form one or more additional substituted or unsubstituted rings, containing no or one or more heteroatoms N, P, B, O S in the formed ring. Preferably, R 0～R11 is not all hydrogen or deuterium.
The hole injection layer and the charge generation layer disclosed by the invention comprise or consist of a compound with the tritolyl of tritolyl, so that the voltage of an OLED element can be reduced, and the efficiency and the service life of the element can be improved.
Drawings
Fig. 1 is a schematic diagram of an organic light emitting device that may contain a compound material disclosed herein.
Fig. 2 is a schematic diagram of a tandem organic light emitting device that may contain the compound materials disclosed herein.
Fig. 3 is a schematic diagram of another tandem organic light emitting device that may contain the compound materials disclosed herein.
Detailed Description
The present invention is described in further detail below with reference to specific examples, but is not intended to limit the scope of the present invention.
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically illustrates, without limitation, an organic light-emitting device 100. The drawings are not necessarily to scale, and some of the layer structures in the drawings may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the layers described. The nature and function of the various layers and exemplary materials are described in more detail in U.S. patent US7,279,704B2 at columns 6-10, the entire contents of which are incorporated herein by reference.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is m-MTDATA doped with F4-TCNQ at a molar ratio of 50:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of host materials are disclosed in U.S. patent No. 6,303,238 to thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1 as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of cathodes are disclosed in U.S. Pat. nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, including composite cathodes having a thin layer of metal, such as Mg: ag, with an overlying transparent, electrically conductive, sputter deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.
The above-described hierarchical structure is provided by way of non-limiting example. The function of the OLED may be achieved by combining the various layers described above, or some of the layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sublayers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.
In one embodiment, two or more OLED cells can be connected in series to form a series OLED, as schematically and non-limitingly illustrated in FIG. 2 as a series organic light emitting device 500. The apparatus 500 may include a substrate 101, an anode 110, a first unit 100, a charge generation layer 300, a second unit 200, and a cathode 290. The first unit 100 includes a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light emitting layer 150, a hole blocking layer 160, and an electron transport layer 170, the second unit 200 includes a hole injection layer 220, a hole transport layer 230, an electron blocking layer 240, a light emitting layer 250, a hole blocking layer 260, an electron transport layer 270, and an electron injection layer 280, and the charge generation layer 300 includes an N-type charge generation layer 310 and a P-type charge generation layer 320. The device 500 may be fabricated by sequentially depositing the layers described.
The OLED may also be provided with an encapsulation layer, as schematically and non-limitingly illustrated in fig. 3 an organic light emitting device 600, which, unlike fig. 2, may further comprise an encapsulation layer 102 over the cathode 290 to prevent harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly outside the OLED element. Multilayer film packages are described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.
Elements manufactured in accordance with embodiments of the present invention may be incorporated into a variety of consumer products having one or more electronic component modules (or units) of the element. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, heads-up displays, displays that are fully or partially transparent, flexible displays, smart phones, tablet computers, tablet phones, wearable devices, smart watches, laptop computers, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and taillights.
The materials and structures described herein may also be used in other organic electronic components listed above.
As used herein, "top" means furthest from the substrate and "bottom" means closest to the substrate. In the case where the first layer is described as being "disposed" on "the second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photosensitive" when it is believed that the ligand directly contributes to the photosensitive properties of the emissive material. When it is believed that the ligand does not contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary," but ancillary ligands may alter the properties of the photosensitive ligand.
Definition of terms for substituents
Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.
Alkyl groups include straight and branched chain alkyl groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. In addition, the alkyl group may be optionally substituted. The carbon in the alkyl chain may be substituted with other heteroatoms. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and neopentyl are preferred.
Cycloalkyl as used herein includes cyclic alkyl groups. Preferred cycloalkyl groups are cycloalkyl groups containing 3 to 40 ring carbon atoms, including cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. In addition, cycloalkyl groups may be optionally substituted. The carbon in the ring may be substituted with other heteroatoms.
Alkenyl as used herein, encompasses straight chain, branched, and cyclic alkenyl groups. Preferred alkenyl groups are alkenyl groups containing 2 to 40 carbon atoms. Examples of alkenyl groups include vinyl, allyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, 1-methylvinyl, styryl, 2-diphenylvinyl, 1-methallyl, 1-dimethylallyl, 2-methallyl, 1-phenylallyl, 2-phenylallyl, 3-diphenylallyl, 1, 2-dimethylallyl, 1-phenyl-1-butenyl and 3-phenyl-1-butenyl. In addition, alkenyl groups may be optionally substituted.
Aryl or aromatic groups as used herein, non-fused and fused systems are contemplated. Preferred aryl groups are those containing from 6 to 60 carbon atoms, more preferably from 6 to 20 carbon atoms, and even more preferably from 6 to 12 carbon atoms. Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chicory, perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-yl, p-triphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methylbiphenyl-4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-tetrabiphenyl.
Heterocyclyl or heterocyclo as used herein, aromatic and non-aromatic cyclic groups are contemplated. Heteroaryl also refers to heteroaryl. Preferred non-aromatic heterocyclic groups are those containing 3 to 7 ring atoms, which include at least one heteroatom such as nitrogen, oxygen and sulfur. The heterocyclic group may also be an aromatic heterocyclic group having at least one hetero atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom.
Heteroaryl as used herein, non-fused and fused heteroaromatic groups are contemplated that may contain 1 to 5 heteroatoms. Preferred heteroaryl groups are those containing from 2 to 60 carbon atoms, more preferably from 3 to 20 carbon atoms, and even more preferably from 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzothiophene pyridine, thienodipyridine, benzothiophene bipyridine, benzoselenophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-aza-1, 3-aza-borane, 1-borane, 4-borane, and the like. In addition, heteroaryl groups may be optionally substituted.
Further preferably, the substituted or unsubstituted C 2-C60 heteroaryl groups are each independently selected from one or more of the groups II-1 to II-17:
Wherein,
Each Z 1、Z2 is independently selected from hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1-C60 alkyl, C 2-C60 alkenyl, C 2-C60 alkynyl, C 1-C60 alkoxy, C 3-C60 naphthenyl, C 3-C60 cycloalkenyl, C 6-C60 aryl, C 6-C60 aryl containing at least one-F, -CN or C1-C10 alkyl, substituted or unsubstituted C 6-C60 aryloxy, substituted or unsubstituted C 6-C60 arylthio, or substituted or unsubstituted C 2-C60 heteroaryl;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
t 1 represents an oxygen atom or a sulfur atom;
represents the bond between the substituent and the main structure.
Alkoxy is represented by-O-alkyl, and examples and preferred examples of alkyl are the same as described above. Examples of the alkoxy group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentoxy and hexoxy groups. The alkoxy group having 3 or more carbon atoms may be linear, cyclic or branched.
Aryloxy is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. Examples of the aryloxy group having 6 to 60 carbon atoms include phenoxy and diphenoxy.
Aralkyl as used herein, an alkyl group having an aryl substituent. In addition, aralkyl groups may be optionally substituted. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthyl-ethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthyl-ethyl, 2- β -naphthyl-ethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-chlorophenyl, 1-isopropyl and 1-isopropyl. Among the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl.
In the present specification, the term "substituted or unsubstituted" means that the compound is substituted or unsubstituted with 1 or more substituents selected from hydrogen, deuterium, a halogen atom, a hydroxyl group, a nitrile group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a carboxylate thereof, a sulfonic acid group or a sulfonate thereof, a phosphoric acid group or a phosphate thereof, a C 1-C60 alkyl group, a C 2-C60 alkenyl group, a C 2-C60 alkynyl group, a C 1-C60 alkoxy group, a C 3-C60 cycloalkyl group, a C 3-C60 cycloalkenyl group, a C 6-C60 aryl group, a C 6-C60 aryloxy group, a C 6-C60 arylene sulfide group, and a C 2-C60 heteroaryl group, or a substituent bonded with 2 or more substituents among the above-exemplified substituents.
It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered equivalent.
In the compounds mentioned in this disclosure, the hydrogen atoms may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred due to their enhanced efficiency and stability of the elements.
In the compounds mentioned in this disclosure, multiple substitution is meant to encompass double substitution up to the maximum available substitution range.
According to an embodiment of the present invention, an organic electroluminescent element is disclosed, comprising: an anode, a cathode, a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises a compound represented by the general formula (I):
Wherein:
R 0～R11 is each independently selected from the group consisting of hydrogen, deuterium, halogen, nitrile, alkyl of substituted or unsubstituted C 1-C40, alkyl or cycloalkyl of substituted or unsubstituted C 3-C40 with a branched chain, heteroalkyl of substituted or unsubstituted C 1-C40, alkenyl of substituted or unsubstituted C 2-C40, aryl of substituted or unsubstituted C 6-C60, aryloxy of substituted or unsubstituted C 6-C60, aralkyl of substituted or unsubstituted C 7-C60, silyl of substituted or unsubstituted C 3-C40, arylsilane of substituted or unsubstituted C 6-C60, amino of substituted or unsubstituted C 2-C60 heteroaryl of substituted or unsubstituted C 0-C40, acyl, carbonyl, carboxylic acid, ester, isonitrile, thio, sulfinyl, sulfonyl, phosphino, wherein two or more adjacent groups may optionally be joined or fused to form one or more additional substituted or unsubstituted rings, containing no or one or more heteroatoms N, P, B, O S in the formed ring.
According to another embodiment of the present invention, a hole injection layer comprising a compound of formula I is in contact with the anode.
According to another embodiment of the invention, wherein each R 0～R11 is independently selected from the group consisting of hydrogen, deuterium, nitro, fluoro, nitrile, trifluoromethyl, trifluoromethoxy, or pentafluorosulfide.
According to a preferred embodiment of the present invention, the compound of formula (I) is selected from the group consisting of formulas CJHM-CJHM, 514:
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According to one embodiment of the invention, the hole injection layer is a layer consisting entirely of a compound having the general formula I.
According to one embodiment of the invention, the hole injection layer further comprises an aromatic amine compound.
According to a preferred embodiment of the present invention, wherein the hole injection layer further comprises an aromatic amine compound; preferably, the aromatic amine compound is selected from the group consisting of the following structures:
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the invention also provides a material, the raw material of which comprises the compound taking the trimellitene as the base, and preferably the material is an organic electroluminescent material.
The materials described herein for the specific layers in an organic light emitting element may be used in combination with various other materials present in the element. Combinations of these materials are described in detail in U.S. patent application 2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
Materials described herein as useful for particular layers in an organic light emitting element may be used in combination with a variety of other materials present in the element. For example, the luminescent dopants disclosed herein may be used in combination with a variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in the patent application US2015/0349273A1, paragraph 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
The present invention also provides an organic electroluminescent element comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode; the material of at least one of the organic layers comprises the above-mentioned tris-benzindene-based compound.
The organic electroluminescent element comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers need be present. The organic electroluminescent device described herein may comprise one light emitting layer, or it may comprise a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred is a system with three light-emitting layers, wherein the three layers can display blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises a compound of the invention according to the invention.
Further, the organic electroluminescent element according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light emitting layer is directly adjacent to the hole injection layer or anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent element according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner generally used according to the prior art. A person of ordinary skill in the art will thus be able to use all materials known in relation to organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Furthermore, an organic electroluminescent device is preferred, characterized in that one or more layers are applied by means of a sublimation method, wherein the material is applied by vapor deposition in a vacuum sublimation device at an initial pressure of less than 10 -5 Pa, preferably less than 10 -6 Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa.
Also preferred are organic electroluminescent elements, characterized in that one or more layers are applied by means of an organic vapor deposition method or by means of sublimation of a carrier gas, wherein the material is applied at a pressure between 10 -5 Pa and 1 Pa. A particular example of this method is an organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent elements are preferred, from which one or more layers are produced, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.
These methods are generally known to those of ordinary skill in the art and they can be applied to the organic electroluminescent element comprising the compound according to the present invention without inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent element according to the invention, characterized in that at least one layer is applied by means of a sublimation method, and/or in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to a pharmaceutical composition comprising at least one compound of the invention as indicated above. The same preferable cases as indicated above with respect to the organic electroluminescent element apply to the compound of the present invention. In particular, the compounds may furthermore preferably comprise further compounds. Treatment of the compounds according to the invention from the liquid phase, for example by spin coating or by printing methods, requires preparations of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or mixtures of these solvents.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects obtained by the invention are as follows:
the compound with the tribenzobisindene as the base or the material composed of the compound with the tribenzobisindene as the base, which is shown in the formula I, can reduce the voltage of an OLED element, improve the efficiency of the element and prolong the service life of the element.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description and to simplify the description, and are not indicative or implying that the apparatus or elements in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental materials and related equipment used in the examples below, unless otherwise specified, are all commercially available, and the percentages, such as the percentages without otherwise specified, are all mass percentages.
The following examples are examples of the test apparatus and method for testing the performance of OLED materials and devices as follows:
OLED element performance detection conditions:
luminance and chromaticity coordinates: testing using a spectral scanner PhotoResearch PR-715;
Current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: the NEWPORT 1931-C test was used.
Example 1
A process for preparing compound CJHM383 comprising the steps of:
the first step: preparation of Compound Int-1
20.0Mmol of 4,5,6, 7-tetrafluoro-1H-indene-1, 3 (2H) -dione (CAS: 29045-72-5), 0.1mol of potassium bromide, 0.1mol of 1M dilute hydrochloric acid aqueous solution and 0.4mol of 30% hydrogen peroxide are mixed with 100mL of toluene, stirred at room temperature for reaction for 1 hour, 50mL of 5% sodium thiosulfate aqueous solution and 50mL of saturated sodium bicarbonate aqueous solution are added, extraction is carried out with ethyl acetate, the organic phase is dried, concentrated to dryness under reduced pressure, and the compound Int-1 is obtained by separation and purification by a silica gel column, white solid is obtained, and the yield is 98%.
And a second step of: preparation of Compound Int-2
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20.0Mmol of Int-1 is dissolved in 80mL of dry DMF, 24.0mmol of cuprous cyanide is added in portions under the protection of nitrogen, the temperature is raised to 55 ℃ and the mixture is stirred for reaction for 10 hours, the reaction solution is poured into 150mL of water and filtered, filter cakes are washed with ethyl acetate, the filtrate is collected, an organic phase is separated, the aqueous phase is extracted with ethyl acetate, dried and concentrated to dryness under reduced pressure, and the compound Int-2 is obtained as a white solid with the yield of 88%.
And a third step of: preparation of Compound Int-3
15.0Mmol of Int-2 and 15.1mmol of diphenyl methanol (CAS: 91-01-0) are dispersed in 150mL of toluene, 5.0mmol of p-toluenesulfonic acid is added, the mixture is heated, refluxed and stirred for reaction for 24 hours, water generated by the reaction is removed through a water separator, the mixture is cooled to room temperature, 50mL of saturated aqueous potassium carbonate solution is added, the mixture is extracted with ethyl acetate, the organic phase is dried, concentrated under reduced pressure to dryness, and the compound Int-3 is obtained by separating and purifying with a silica gel column, and is a white solid with the yield of 85%.
Fourth step: preparation of Compound Int-4
42.0Mmol of sodium hydride is dispersed in 20mL of dry DME, the temperature is reduced to 0 ℃, 40.0mmol of tert-butylmalononitrile (CAS: 4210-60-0) solution dissolved in DME is added dropwise, the temperature is raised to room temperature, stirring is carried out for 30 minutes, 19.0mmol of Int-3 solution dissolved in DME is added dropwise, the temperature is raised, reflux stirring is carried out for 24 hours, cooling is carried out to room temperature, 100mL of water is added, filtering is carried out, and the filter cake is washed with water to obtain the compound Int-4 as an off-white solid, and the yield is 80%.
Fifth step: preparation of Compound Int-5
15.0Mmol of Int-4 is dissolved in 50mL of methanol and 50mL of THF, the temperature is reduced to 0 ℃, 30.0mmol of sodium borohydride is added in portions, the mixture is stirred for 2 hours for reaction, 200mL of saturated saline solution is added, the mixture is extracted by ethyl acetate, the organic phase is dried, the organic phase is concentrated to dryness under reduced pressure, and the compound Int-5 is obtained by separating and purifying by a silica gel column, and is a white solid with the yield of 87%.
Sixth step: preparation of Compound Int-6
5.0ML of polyphosphoric acid and 50mL of dried chlorobenzene are mixed, 10.0mmol of Int-5 is added in batches under the protection of nitrogen, the temperature is raised, the reflux and stirring reaction is carried out for 20 hours, the temperature is reduced to room temperature, the reaction solution is poured into 200mL of saturated sodium bicarbonate aqueous solution, an organic phase is separated, the aqueous phase is extracted by ethyl acetate, the organic phases are combined and dried, the filtration is carried out, the filtrate is concentrated to dryness under reduced pressure, and the compound Int-6 is obtained by separating and purifying by a silica gel column, and is a white solid with the yield of 38%.
Seventh step: preparation of Compound Int-7
10.0Mmol of Int-6 is dissolved in 120mL of dry carbon tetrachloride, 31.0mmol of NBS and 1mg of AIBN are added under the protection of nitrogen, the mixture is heated to reflux and stirred for reaction for 5 hours, the temperature is reduced to room temperature, the mixture is filtered, filtrate is washed by saturated aqueous solution of sodium bisulphite, an organic phase is separated, dried, filtered, and the filtrate is concentrated to dryness under reduced pressure, and is separated and purified by a silica gel column to obtain a compound Int-7 as a yellow solid, and the yield is 78%.
Eighth step: preparation of Compound Int-8
10.0Mmol of Int-7 is dissolved in 80mL of dry DMF, 32.0mmol of cuprous cyanide is added, stirring reaction is carried out for 24 hours under the protection of nitrogen, the reaction solution is poured into 150mL of water, filtration is carried out, a filter cake is washed with water, dichloromethane is used for dissolving, filtration is carried out, the filtrate is dried, filtration is carried out, the filtrate is concentrated to dryness under reduced pressure, and the compound Int-8 is obtained, yellow solid is separated and purified by a silica gel column, and the yield is 88%.
Ninth step: preparation of Compound CJHM383
10.0Mmol of Int-8 and 120mL of diphenyl ether are mixed, the mixture is heated to reflux and stirred for reaction for 10 minutes, the temperature is reduced to 40 ℃,120mL of diethyl ether and 120mL of 4% sodium carbonate aqueous solution are added, the upper organic phase is separated, 4% sodium carbonate aqueous solution is used for extraction, the water phase is collected, filtration is carried out, the filtrate is acidified by concentrated hydrochloric acid to obtain white precipitate, bromine water is added dropwise until the water phase is purple, filtration is carried out, a filter cake is washed to be neutral by water to obtain a compound CJHM383, white solid is obtained after sublimation purification, and the yield is 68 percent, MS (TOF-SIMS) m/z is 542.0846.
Example 2
Preparation of Compound CJHM385
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (3, 4-bis (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM385, MS (TOF-SIMS) m/z:878.0138 is prepared.
Example 3
Preparation of Compound CJHM and 3839
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (4-fluorophenyl) methanol is used in place of the diphenyl methanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount to prepare compound CJHM389,383, MS (TOF-SIMS) m/z:578.0644.
Example 4
Preparation of Compound CJHM to 390
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that diphenyl methanol in the third step of example 1 is replaced with bis (3, 4-difluorophenyl) methanol, and the mass amount of the compound is changed according to the molar amount, compound CJHM390,390, MS (TOF-SIMS) m/z:614.0471, is prepared.
Example 5
Preparation of Compound CJHM405,405
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (2-fluorophenyl) methanol is used in place of the diphenyl methanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount to prepare compound CJHM, MS (TOF-SIMS) m/z:578.0658.
Example 6
Preparation of Compound CJHM to 406
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (2-nitrilophenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM406,406, MS (TOF-SIMS) m/z:592.0751 is prepared.
Example 7
Preparation of Compound CJHM-407
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (2- (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM407,407, MS (TOF-SIMS) m/z:710.0494 is prepared.
Example 8
Preparation of Compound CJHM408,408
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (2- (trifluoromethyl) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM408,408, MS (TOF-SIMS) m/z:678.0596 is prepared.
Example 9
Preparation of Compound CJHM409
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (2, 4-bis (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM409,409, MS (TOF-SIMS) m/z:878.0140 is prepared.
Example 10
Preparation of Compound CJHM435,435
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (2, 3, 4-tris (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM435,435, MS (TOF-SIMS) m/z:1045.9784, is prepared.
Example 11
Preparation of Compound CJHM445
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione is used instead of Int-2 in the third step of example 1, di (4- (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, to prepare compound CJHM, MS (TOF-SIMS) m/z:703.0445.
Example 12
Preparation of Compound CJHM A444
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that Int-2 in the third step of example 1 is replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione, and the mass amount of the compound is changed according to the molar amount, compound CJHM444 and MS (TOF-SIMS) m/z:535.0799 are prepared.
Example 13
Preparation of Compound CJHM446
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione is used instead of Int-2 in the third step of example 1, di (3, 4-bis (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM is prepared, MS (TOF-SIMS) m/z:871.0093.
Example 14
Preparation of Compound CJHM A450
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that Int-2 in the third step of example 1 is replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione, diphenyl-methanol in the third step of example 1 is replaced with bis (4-fluorophenyl) methanol, and the mass amount of the compound is changed according to the molar amount, to prepare compound CJHM450, MS (TOF-SIMS) m/z:571.0611.
Example 15
Preparation of Compound CJHM451
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione is used instead of Int-2 in the third step of example 1, di (3, 4-difluorophenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount to prepare compound CJHM, MS (TOF-SIMS) m/z:607.0424.
Example 16
Preparation of Compound CJHM473
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that Int-2 in the third step of example 1 is replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione, diphenyl methanol in the third step of example 1 is replaced with bis (2-fluorophenyl) methanol, and the mass amount of the compound is changed according to the molar amount, to prepare compound CJHM473, MS (TOF-SIMS) m/z:571.0613.
Example 17
Preparation of Compound CJHM474
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that Int-2 in the third step of example 1 is replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione, diphenyl methanol in the third step of example 1 is replaced with bis (2-cyanophenyl) methanol, and the mass amount of the compound is changed according to the molar amount, to prepare compound CJHM474, MS (TOF-SIMS) m/z:585.0704.
Example 18
Preparation of Compound CJHM475
The synthesis method of reference example 1, i.e., the method steps were the same as those of example 1 except that 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione was used instead of Int-2 in the third step of example 1, di (2-trifluoromethoxyphenyl) methanol was used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound was changed according to the molar amount to prepare compound CJHM, MS (TOF-SIMS) m/z:703.0447.
Example 19
Preparation of Compound CJHM476
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that Int-2 in the third step of example 1 is replaced with 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione, diphenyl-methanol in the third step of example 1 is replaced with bis (2-trifluoromethylphenyl) methanol, and the mass amount of the compound is changed according to the molar amount, to prepare a compound CJHM476, MS (TOF-SIMS) m/z:671.0547.
Example 20
Preparation of Compound CJHM and 478
The synthesis method of reference example 1, i.e., the method steps were the same as those of example 1 except that 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione was used instead of Int-2 in the third step of example 1, di (2, 4-bis (trifluoromethoxy) phenyl) methanol was used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound was changed according to the molar amount to prepare compound CJHM478,478, MS (TOF-SIMS) m/z:871.0093.
Example 21
Preparation of Compound CJHM482
The synthesis method of reference example 1, i.e., the method steps were the same as those of example 1 except that 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione was used instead of Int-2 in the third step of example 1, di (2, 5-bis (trifluoromethoxy) phenyl) methanol was used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound was changed depending on the molar amount, to prepare compound CJHM482, MS (TOF-SIMS) m/z:871.0091.
Example 22
Preparation of Compound CJHM to 499
The synthesis method of reference example 1, i.e., the method steps were the same as those of example 1 except that 2,4,5,6, 7-pentafluoro-1H-indene-1, 3 (2H) -dione was used instead of Int-2 in the third step of example 1, di (2, 3, 4-tris (trifluoromethoxy) phenyl) methanol was used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound was changed depending on the molar amount, to prepare compound CJHM499, MS (TOF-SIMS) m/z:1038.9739.
Example 23
Preparation of Compound CJHM515,515
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (2, 5-bis (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, to prepare compound CJHM, MS (TOF-SIMS) m/z:878.0140.
Example 24
Preparation of Compound CJHM516,516
The synthesis method of reference example 1, i.e., the method steps are the same as those of example 1 except that di (3, 4-bis (trifluoromethoxy) phenyl) methanol is used instead of diphenylmethanol in the third step of example 1, and the mass amount of the compound is changed according to the molar amount, compound CJHM516,516, MS (TOF-SIMS) m/z:1006.9904, is prepared.
Those skilled in the art will recognize that the above preparation methods are merely illustrative examples, and that those skilled in the art can modify them to obtain other compound structures of the present invention.
Light-emitting element embodiment
Firstly, ultrasonic treating the glass substrate coated with the ITO conductive layer in a cleaning agent for 30 minutes, flushing in deionized water, ultrasonic treating in an acetone/ethanol mixed solvent for 30 minutes, baking in a clean environment until the glass substrate is completely dried, irradiating for 10 minutes by an ultraviolet cleaning machine, bombarding the surface by a low-energy cation beam, then placing the treated ITO glass substrate on a bracket and filling the bracket into a vacuum cavity, vacuumizing to 1 multiplied by 10 -5～9×10-3 Pa so as to obtain the glass substrateSequentially vacuum evaporating the organic layers specified below,
1) Evaporating the compound (formula I) of the present invention, which is 3% of HT09 by mass, as a Hole Injection Layer (HIL) of the element, as a doping material and HT09 as a host material on the ITO anode layer film, the evaporated film thickness being
2) Continuing to vapor deposit HT09 as a Hole Transport Layer (HTL) on the hole injection layer, wherein the vapor deposition film thickness is
3) Vapor deposition of H01 as a host material and RD as a dopant material on the hole transport layer was continued, RD being 5% by mass of H01, as an organic light-emitting layer of the element, the film thickness of the vapor-deposited organic light-emitting layer was
4) Continuously evaporating a layer of mixture of ET and LiQ on the organic light-emitting layer, wherein the mass ratio of ET to LiQ is 35:65, and the mixture is used as an electron transport layer of the element, and the film thickness of the evaporation film is/>
5) Continuously evaporating a LiF layer on the electron transport layer to form an electron injection layer with an evaporating film thickness of
6) Evaporating metallic aluminum as cathode layer of the element on the electron injection layer, the film thickness of the evaporated film isThe device was then transferred to a glove box and encapsulated with a glass cover plate and desiccant to complete the OLED device provided by the present invention.
Comparative example 1
According to the same procedure as described above, the compound of the invention (formula I) in step 1) is replaced by F4-TCNQ, giving comparative element 1;
Comparative example 2
According to the same procedure as described above, the compound of the invention (formula I) in step 1) is replaced by S01, giving comparative element 2;
The material structure used in the element is as follows:
IVL and lifetime characteristics of the element were measured at different current densities and voltages. The driving voltage, current efficiency, full width at half maximum (FWHM) and emission maximum λmax of the light-emitting element were measured at a luminance of 1000cd/m 2, and data normalization processing was performed with respect to the comparative element 1, and the LT95% lifetime of the element was measured at an initial luminance of 10000cd/m 2, and data normalization processing was performed with respect to the comparative element 1.
TABLE 1 element data
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As can be seen from the data in table1 above, the compounds of the present invention show advantages over the comparative compounds in various respects, such as lower driving voltages for the examples of the present invention relative to the comparative examples, indicating that hole injection using the compounds of the present invention is much more energy efficient than the comparative compounds. The inventive examples also have higher current efficiency and longer element life than the comparative examples. The performance of the compound of the example is far better than that of the compound of the comparative example 2, because the alkyl ring has larger electron pulling substituent, and the oxidation-reduction stability of the material is improved.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (6)

1. A compound containing tris-benzotriindene, characterized in that the general formula (I) of the compound is represented as follows:
Wherein:
r 0 is a nitrile group,
R 1 is nitrile or fluorine, R2 is fluorine, R3 is fluorine,
R 4-R11 is independently selected from hydrogen, cyano, fluoro, trifluoromethyl, trifluoromethoxy, pentafluorosulfide, and R4-R11 are not all hydrogen.
2. The tris-benzidine-containing compound according to claim 1, wherein the compound of formula (I) is selected from the group consisting of formulas CJHM to CJHM:
3. an organic electroluminescent element comprising an anode, a cathode, and a hole injection layer disposed between the anode and the cathode, wherein the hole injection layer comprises the tris-benzidine-containing compound of claim 1.
4. The organic electroluminescent element according to claim 3, wherein the hole injection layer further comprises an aromatic amine compound selected from the group consisting of:
5. An organic electroluminescent material, characterized in that a raw material of the organic electroluminescent material comprises the tris-benzidine-containing compound according to claim 1.
6. A consumer product comprising the organic electroluminescent element of claim 3.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES359987A1 (en) * 1967-11-09 1970-10-01 Ciba Geigy Procedure for obtaining peptides of hypocalcenic effectiveness. (Machine-translation by Google Translate, not legally binding)
CN107353891A (en) * 2017-06-15 2017-11-17 华南理工大学 It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES359987A1 (en) * 1967-11-09 1970-10-01 Ciba Geigy Procedure for obtaining peptides of hypocalcenic effectiveness. (Machine-translation by Google Translate, not legally binding)
CN107353891A (en) * 2017-06-15 2017-11-17 华南理工大学 It is a kind of using three indenes fluorenes units as star-like bipolarity small molecule emitter material of core and preparation method and application

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