CN116813583A

CN116813583A - Compound and application thereof in organic photoelectric device

Info

Publication number: CN116813583A
Application number: CN202310785333.9A
Authority: CN
Inventors: 王鹏; 王湘成; 何睦
Original assignee: Shanghai Yaoyi Electronic Technology Co ltd
Current assignee: Shanghai Yaoyi Electronic Technology Co ltd
Priority date: 2023-06-29
Filing date: 2023-06-29
Publication date: 2023-09-29

Abstract

The invention relates to the field of organic electroluminescent materials, in particular to a compound and application thereof in an organic photoelectric device. The chemical structure of the compound is shown as a formula (I):

Description

Compound and application thereof in organic photoelectric device

Technical Field

The invention relates to the field of organic electroluminescent materials, in particular to a compound and application thereof in an organic photoelectric device.

Background

An organic electroluminescent (OLED: organic Light Emission Diodes) device is a device with a sandwich-like structure, comprising positive and negative electrode layers and an organic functional material layer sandwiched between the electrode layers. At present, the technology is widely applied to display panels of products such as novel illumination lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with rapid development and high technical requirements. Common functionalized organic materials used in OLED devices are: a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, a light emitting host material, a light emitting guest (dye), and the like. Based on this, the OLED materials community has been striving to develop new organic electroluminescent materials to achieve low starting voltage, high luminous efficiency and better lifetime of the device. The development of the existing OLED photoelectric functional material is far behind the requirement of panel manufacturing enterprises on the OLED material so far, so that the development of the organic functional material with better performance is particularly urgent to meet the development requirement of the current industry. At present, an aromatic amine compound with good hole transport property is mainly adopted as a hole transport material. N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) is widely used in organic electroluminescent devices for multiple colors due to its moderate highest occupied orbital level and good hole mobility. However, the glass transition temperature of the molecules is low (98 ℃), and the devices are easy to change phase under the action of accumulated joule heat when the devices are operated for a long time, so that the service lives of the devices are greatly influenced. Therefore, it is necessary to design a hole transport material having both higher mobility and glass transition temperature. In addition, mobility performance of the electron transport material needs to be further improved, and solubility of the material in a common solvent needs to be improved so as to be suitable for industrial production.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, it is an object of the present invention to provide a compound and its use in an organic optoelectronic device for solving the problems of the prior art.

To achieve the above and other related objects, in one aspect, the present invention provides a compound having a chemical structure as shown in formula (i):

wherein:

the A is selected from CR ₅ R ₆ 、SiR ₇ R ₈ 、NR ₉ 、O、S：

R ₁ -R ₄ The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl; substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C60 heteroaryl, or substituted or unsubstituted aromatic amine, or a ring bonded to an adjacent group;

R ₅ -R ₈ each independently selected from hydrogen, deuterium, C1-C10 alkyl, or C1-C10 deuterated alkyl;

a is selected from CR ₉ R ₁₀ 、SiR ₁₁ R ₁₂ 、NR ₁₃ O, or S: wherein R is ₉ -R ₁₃ Selected from substituted or unsubstitutedC1-C30 alkyl, substituted or unsubstituted C1-C30 deuterated alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 deuterated aryl, substituted or unsubstituted C3-C30 deuterated heteroaryl, or R ₉ 、R ₁₀ Bonded to form a ring, R ₁₁ 、R ₁₂ Bonded to form a ring.

In some cases, a is preferably selected from the following:

wherein R is ₁₃ Aryl of C6-C30 which is substituted or unsubstituted; * Is an atomic attachment site.

In another aspect the invention provides an organic layer comprising a compound according to the first aspect of the invention.

In another aspect, the invention provides the use of the compounds according to the invention and/or the organic layers according to the invention in organic optoelectronic devices.

In another aspect, the present invention provides an organic optoelectronic device, which includes a first electrode, a second electrode, and an organic layer according to the present invention, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, or an electron transport layer.

In another aspect, the invention provides a display or lighting device comprising an organic optoelectronic device according to the invention.

Compared with the prior art, the invention has the beneficial effects that:

according to the compound provided by the invention, as the hetero atom group is introduced into the benzene ring region of fluorene, the LUMO of the molecule is reduced, and the LUMO of the molecule is fixed in the region of fluorene. And the HOMO of the molecule is reduced, so that the HOMO and LUMO energy level requirements of the device are matched. In addition, compared with the compound of the invention, the compound of the invention has moderate power supply effect of aryl and alkyl groups due to the electric absorption effect of hetero atoms, so that the compound of the invention is applied to an organic device, can ensure that the device has higher hole mobility, can effectively block electrons and excitons from entering a hole transport layer, and has higher luminous efficiency and service life.

Detailed Description

Embodiments of the specifically disclosed compounds and their use in organic optoelectronic devices are described in detail below. Other advantages and effects of the present invention will be readily apparent to those skilled in the art from the present disclosure. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.

Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention; in the description and claims of the invention, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.

Through a great deal of research and study, the inventor provides an oxacyclopentane series-based compound, and discovers that a series of hole transport materials and electron transport materials with excellent performance are obtained by introducing oxacyclopentane derivatives into a triarylamine system and combining the oxacyclopentane derivatives with electron withdrawing groups. The introduction of the oxacyclopentane derivative has better electron donating ability of the aliphatic ring relative to the aryl, so that the compound has good hole and electron transport characteristics and thermal stability. Therefore, the compound can provide a longer service life for the organic electroluminescent device. In the oxacyclopentane derivative, due to the electron withdrawing capability of oxygen atoms, when the oxacyclopentane derivative is combined with triazine electron withdrawing groups, the LUMO energy level of the whole molecule can be deepened, so that the electron transporting capability of the molecule can be improved. When oxacyclopent alkyl groups are incorporated into bipolar molecular materials, also exhibit unusual device lifetime and efficiency. On this basis, the present invention has been completed.

Examples of the substituents in the present invention are described below, but the substituents are not limited thereto:

by [ substituted or unsubstituted ] is meant a substitution with one or more substituents selected from the group consisting of: deuterium, halogen groups, nitrile groups, nitro groups, hydroxyl groups, carbonyl groups, ester groups, imide groups, amino groups, phosphine oxide groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups, silyl groups, boron groups, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, aralkenyl groups, alkylaryl groups, alkylamino groups, aralkylamino groups, heteroarylamino groups, arylamino groups, arylphosphine groups, and heteroaryl groups, acenaphthylene groups, compound groups, or unsubstituted groups; or substituted with a substituent linking two or more of the substituents exemplified above, or unsubstituted. For example, "a substituent linking two or more substituents" may include a biphenyl group, i.e., the biphenyl group may be an aryl group, or a substituent linking two phenyl groups.

The "alkyl group" may be linear or branched, and the number of carbon atoms is not particularly limited. In some embodiments, alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl.

The above description of alkyl groups also applies to alkyl groups in aralkyl groups, aralkylamine groups, alkylaryl groups, and alkylamino groups.

The "heteroalkyl" group may be a straight-chain or branched alkyl group containing a heteroatom, and the number of carbon atoms is not particularly limited. In some embodiments, heteroalkyl groups include, but are not limited to, can be alkoxy, alkylthio, alkylsulfonyl, and the like. Alkoxy groups may include, for example, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, t-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzoxy, and the like. Alkylthio groups may include, for example, but are not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, sec-butylthio, n-pentylthio, neopentylthio, isopentylthio, n-hexylthio, 3-dimethylbutylthio, 2-ethylbutylthio, n-octylthio, n-nonylthio, n-decylthio, benzylthio, and the like.

The [ cycloalkyl ] group may be cyclic, and the number of carbon atoms is not particularly limited. In some embodiments, cycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like.

[ heterocycloalkyl ] may be a cycloalkyl group containing a heteroatom, and the number of carbon atoms is not particularly limited. In some embodiments, heterocycloalkyl includes, but is not limited toEtc.

The "aryl" is not particularly limited, and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. In some embodiments, monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, and the like. Polycyclic aryl groups include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, and the like. Fluorenyl groups can be substituted, such as 9,9 '-dimethylfluorenyl, 9' -dibenzofluorenyl, and the like. In addition, two of the substituents may combine with each other to form a spiro structure, for example, 9' -spirobifluorenyl, and the like.

The above description of aryl groups applies to arylene groups, except that arylene groups are divalent.

The above description of aryl groups applies to aryl groups in aryloxy, arylthio, arylsulfonyl, arylphosphinyl, aralkyl, aralkylamino, aralkenyl, alkylaryl, arylamino and arylheteroarylamino groups.

[ heteroaryl ] contains one or more of N, O, P, S, si and Se as heteroatoms. Heteroaryl groups include, but are not limited to, pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, diazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, oxazinyl, thiazinyl, dioxanyl, triazinyl, tetrazinyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothiophenyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl, indenocarbazolyl, phenazinyl, imidazopyridinyl, phenazinyl, phenanthridinyl, phenanthrolinyl, phenothiazinyl, imidazopyridinyl, imidazophenanthridinyl, benzimidazolazolyl, benzimidazolophenidinyl, spiro [ fluorene-9, 9' -xanthene ], benzobinaphthyl, dinaphthyl, naphthyfuranyl, dinaphthylthiophenyl, naphthybenzothiophenyl, triphenylphosphine oxide, triphenylborane, and the like.

The above description of heteroaryl groups applies to heteroaryl groups in heteroaryl amine groups and arylheteroaryl amine groups.

The above description of heteroaryl groups applies to heteroarylene groups, except that the heteroarylene group is divalent.

The term "bond ring" refers to an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, an aliphatic heterocyclic ring, an aromatic heterocyclic ring, or a condensed ring thereof, which are formed by adjacent groups. For example R ₉ 、R ₁₀ Bonded into a ring can formThe combination of the compounds of the formula (I) is +.>And the like, and will not be described in detail.

In one aspect, the invention provides a compound, the chemical structure of which is shown as a formula (I):

R ₁ -R ₄ the same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl; substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted aromatic amine groups, or a bond to an adjacent group. The substituted or unsubstituted heteroaryl group of C3 to C60 may be, for example, a substituted or unsubstituted aryl group containing a nitrogen atom of C3 to C60, a substituted or unsubstituted aryl group containing an oxygen atom of C3 to C60, or a substituted or unsubstituted aryl group containing a sulfur atom of C3 to C60. Or substituted or unsubstituted C3-C60 heteroaryl groups can be substituted or unsubstituted, for example Unsubstituted C3-C30 nitrogen atom-containing aryl, substituted or unsubstituted C3-C30 oxygen atom-containing aryl, and substituted or unsubstituted C3-C30 sulfur atom-containing aryl.

a is selected from CR ₉ R ₁₀ 、SiR ₁₁ R ₁₂ 、NR ₁₃ O, or S: wherein R is ₉ -R ₁₃ Each independently selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 deuterated alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 deuterated aryl, and substituted or unsubstituted C3-C30 deuterated heteroaryl.

In some embodiments, the compounds have the formula

In some embodiments, the aforementioned alkyl groups in formula (I) may also have a number of carbon atoms ranging from 1 to 10, from 1 to 20, from 20 to 30, etc. The number of carbon atoms of the cycloalkyl group may be 3 to 10, 3 to 20, or 3 to 30. The number of carbon atoms of the aforementioned heteroalkyl group may be 3 to 10, 1 to 20, 20 to 30, or the like. The number of carbon atoms of the aforementioned heterocycloalkyl group may be 3 to 10, 3 to 20, 20 to 30, or the like. The number of carbon atoms of the aforementioned aryl group may be 6 to 10, 6 to 20, 20 to 30, or the like. The number of carbon atoms of the heteroaryl group mentioned above may be 6 to 10, 6 to 20, 20 to 30, or the like.

The above description of the number of carbon atoms for aryl and heteroaryl groups applies to arylene and heteroarylene groups referred to in the present invention.

In the compound provided by the invention, R ₁ -R ₄ The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C20 alkyl; substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkylA group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C3 to C60 heteroaryl group, a substituted or unsubstituted aromatic amine group, or a bond to an adjacent group.

Alternatively, R ₁ -R ₄ The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C10 alkyl; substituted or unsubstituted C1-C10 heteroalkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C30 heteroaryl, or substituted or unsubstituted aromatic amine, or a ring bonded to an adjacent group.

In some embodiments, R ₁ -R ₄ At least one selected from the following structures:

The group of formula (II) belongs to one of the substituted or unsubstituted aromatic amine groups. The group of formula (III) belongs to one of the substituted or unsubstituted C3-C30 heteroaryl groups.

Wherein:

L ₁ -L ₆ are identical or different and are each independently selected from single bonds, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C3-C30 heteroaryl groups.

Alternatively, L ₁ -L ₆ Are identical or different and are each independently selected from single bonds, substituted or unsubstituted C6-C20 aryl groups, or substituted or unsubstituted C3-C20 heteroaryl groups.

Further alternatively, the L ₁ ～L ₆ Each independently selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted dibenzofluorenylene group, a,A substituted or unsubstituted phenanthrylene group, or a substituted or unsubstituted triphenylene group.

Preferably L ₁ ～L ₆ Each independently selected from a single bond, phenylene, naphthylene, anthracenylene, dibenzofuranylene, dibenzothiophenylene, or 9-phenylcarbazole, and the like.

Ar ₁ -Ar ₄ Are identical or different and are each independently selected from substituted or unsubstituted C6-C30 aryl groups or substituted or unsubstituted C3-C30 heteroaryl groups.

Alternatively, ar ₁ -Ar ₄ Are identical or different and are each independently selected from substituted or unsubstituted C6-C20 aryl groups or substituted or unsubstituted C3-C20 heteroaryl groups.

Further alternatively, the Ar ₁ ～Ar ₄ Each independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, or substituted or unsubstituted:

e is an electron withdrawing group containing nitrogen atoms, or an electron withdrawing group containing fluorine atoms, or an electron withdrawing group containing phosphorus atoms, or an electron withdrawing group containing oxygen, or an electron withdrawing group containing sulfur.

Alternatively, the E is selected from 1,3, 5-triazine.

When R is ₁ -R ₄ In some embodiments, R is not selected from the group of formula (II) or formula (III) ₁ -R ₄ Each independently selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, or any of the following substituted or unsubstituted groups:

in the compound provided by the invention, R ₅ -R ₈ Each independently selected from hydrogen, deuterium, C1-C10 alkyl, or C1-C10 deuterated alkyl.

Alternatively, in the compounds provided by the present invention, R ₅ -R ₈ Each independently selected from hydrogen, deuterium, C1-C4 alkyl, or C1-C4 deuterated alkyl.

Further alternatively, the R ₅ -R ₈ Each independently selected from methyl or deuterated methyl.

Since the hydrogen atoms are replaced by deuterium atoms, the lifetime of the material is improved. In the compound provided by the invention, R is ₅ -R ₈ Preferably CD ₃ 。

In the compounds provided by the invention, A is selected from CR ₉ R ₁₀ 、SiR ₁₁ R ₁₂ 、NR ₁₃ O, or S: wherein R is ₉ -R ₁₃ Each independently selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 deuterated alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 deuterated aryl, substituted or unsubstituted C3-C30 deuterated heteroaryl, or R ₉ 、R ₁₀ Bonded to form a ring, R ₁₁ 、R ₁₂ Bonded to form a ring.

In some embodiments, A is selected from NR ₁₃ O, or S or any one of the following groups:

wherein R is ₁₃ Aryl of C6-C30 which is substituted or unsubstituted; * Is an atomic attachment site. Alternatively, R ₁₃ Phenyl, naphthyl, and the like.

In some embodiments, A is selected from NR ₁₃ ，R ₁₃ Selected from nitrogen-containing sources Electron withdrawing groups of the electrons; preferably, the nitrogen atom-containing electron withdrawing group is selected from any one of the following groups:

in the compounds provided by the invention, the compounds are selected from any one of the following chemical structures:

/>

specifically, the above structure may be unsubstituted or substituted with one or more substituents selected from the group consisting of. Examples of the group include deuterium, halogen group, nitrile group, nitro group, hydroxyl group, carbonyl group, ester group, imide group, amine group, phosphine oxide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamino group, aralkylamino group, heteroarylamino group, arylamino group, arylheteroarylamino group, arylphosphine group, and heteroaryl group.

In another aspect, the present invention provides an organic layer comprising the compounds of the foregoing invention.

In a further aspect the present invention provides the use of a compound as described above and/or an organic layer as described above in an organic optoelectronic device.

The organic photoelectric device provided by the invention comprises a first electrode, a second electrode and one or more organic layers arranged between the first electrode and the second electrode, wherein the organic layers can be of a single-layer structure or a multi-layer serial structure laminated with two or more organic layers, and the organic layers comprise at least one layer of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer or an electron transport layer. Can be prepared using common methods and materials for preparing organic photovoltaic devices. The organic photoelectric device of the invention adopts the compound as an organic layer of the organic photoelectric device.

In the organic photoelectric device provided by the invention, the first electrode is used as the anode layer, and the anode material can be a material with a large work function, for example, so that holes are smoothly injected into the organic layer. More for example, metals, metal oxides, combinations of metals and oxides, conductive polymers, and the like. The metal oxide may be, for example, indium Tin Oxide (ITO), zinc oxide, indium Zinc Oxide (IZO), or the like.

In the organic photoelectric device provided by the invention, the second electrode is used as the cathode layer, and the cathode material can be a material with a small work function, for example, so that electrons are smoothly injected into the organic layer. The cathode material may be, for example, a metal or a multi-layer structural material. The metal may be, for example, magnesium, silver, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, tin, and lead, or alloys thereof. The cathode material is preferably selected from magnesium and silver.

In the organic photoelectric device provided by the present invention, a material of the hole injection layer, preferably a material having a Highest Occupied Molecular Orbital (HOMO) between a work function of the anode material and a HOMO of the surrounding organic layer, is used as a material that advantageously receives holes from the anode at a low voltage.

In the organic photoelectric device provided by the invention, the material of the hole transport layer is a material having high mobility to holes and is suitable as a material for receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer. The material of the hole transport layer includes, but is not limited to, an organic material of arylamine, a conductive polymer, a block copolymer having both conjugated and non-conjugated portions, and the like.

In the organic photoelectric device provided by the present invention, the material of the light emitting layer may be generally selected from materials having good quantum efficiency for fluorescence or phosphorescence as materials capable of emitting light in the visible light region by receiving holes and electrons from the hole transporting layer and from the electron transporting layer, respectively, and combining the holes and electrons.

In the organic photoelectric device provided by the present invention, the material of the electron transport layer is a material having high mobility to electrons and is suitable as a material that favorably receives electrons from the cathode and transports the electrons to the light emitting layer.

In the organic photoelectric device provided by the invention, the material of the cover layer generally has a high refractive index, so that the light efficiency of the organic light-emitting device can be improved, and the improvement of external light-emitting efficiency is particularly facilitated.

In the organic photoelectric device provided by the invention, the organic photoelectric device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor and the like.

Embodiments of the present invention are described below by way of specific examples.

Synthetic examples:

the synthesis of the compound represented by the above formula (I) can be carried out by a known method. For example, cross-coupling reactions using transition metals such as nickel, palladium, and the like. Other synthetic methods are C-C, C-N coupling reactions using transition metals such as magnesium or zinc. The reaction is limited to mild reaction conditions, excellent selectivity of various functional groups, and the like, and is preferably a Suzuki reaction or a Buchwald reaction. The compounds of the present invention are illustrated by the following examples, but are not limited to the compounds and synthetic methods illustrated by these examples. The initial raw materials, the solvent, some common OLED intermediates and other products are purchased from domestic OLED intermediate manufacturers; various palladium catalysts, ligands, etc. are available from sigma-Aldrich. ¹ H-NMR data Using JEOL (400 MHz) nuclear magnetic resonance; HPLC data were determined using a Shimadzu LC-20AD high performance liquid meter.

The compounds used in the examples are:

example 1

Synthesis of Compound H-6

1) Synthesis of intermediate H-6-1

To the reaction vessel were added 37.1 g (100 mmol) of compound H-6-A, 19.9 g (100 mmol) of compound H-6-B, 23.4 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 1000mL of xylene (xylene) under an argon atmosphere, and the mixture was heated and stirred at 140℃for 15 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 34.3 g of compound H-6-1, purity of HPLC was 99.3%, yield was 70%. LC MS: M/Z489.21 (M+).

¹ H NMR(500MHz,DMSO-d ₆ )δ8.31(m,1H),7.96(d,1H),7.90–7.82(m,2H),7.72(d,1H),7.62–7.57(m,2H),7.49(m,1H),7.46–7.39(m,2H),7.23(m,1H),7.18(m,1H),7.02(d,1H),1.59(s,6H),1.55(s,12H).

2) Synthesis of Compound H-6

To the reaction vessel were added 49.0 g (100 mmol) of Compound H-6-1, 30.7 g (100 mmol) of Compound H-6-C, 23.4 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol%) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 1000mL of xylene (xylene) under an argon atmosphere, and the mixture was heated and stirred at 140℃for 15 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 48.7 g of compound H-6-1, 99.9% purity by HPLC, yield 60%. LC MS: M/Z715.29 (M+).

¹ H NMR(500MHz,DMSO-d6)δ8.33–8.27(m,2H),8.05(d,1H),7.99(m,2H),7.80(m,2H),7.71(d,1H),7.62–7.50(m,9H),7.49(m,1H),7.44–7.37(m,2H),7.29(m,1H),7.25(m,1H),7.15(m,1H),7.05(d,1H),1.60(s,6H),1.56(d,12H).

Example 2

Synthesis of Compound H-11

The procedure of example 1 was repeated except that the starting materials were changed to H-11-A, H-11-B and H-11-C. LCMS: M/Z913.39 (M+). Total synthesis yield: 41%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ7.89–7.82(m,2H),7.69(d,1H),7.55–7.43(m,6H),7.42(s,1H),7.40–7.32(m,2H),7.31–7.18(m,14H),7.16–7.02(m,10H),6.99(m,2H),6.84(d,1H),1.56(s,12H).

Example 3

Synthesis of Compound H-15

The procedure of example 1 was repeated except that the starting materials were changed to H-15-A, H-15-B and H-15-C. LCMS: M/Z747.31 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.

1H NMR(500MHz,DMSO-d6)δ8.01(m,1H),7.92(d,1H),7.84(m,2H),7.71(d,1H),7.69–7.63(m,2H),7.60–7.52(m,3H),7.51–7.24(m,12H),7.20–7.14(m,2H),7.11(d,1H),6.96(d,J＝1.6Hz,1H),6.87(dd,J＝7.4,1.6Hz,1H),6.83–6.77(m,2H),1.56(d,J＝1.1Hz,12H).

Example 4

Synthesis of Compound H-18

The procedure of example 1 was repeated except that the starting materials were changed to H-18-A, H-18-B and H-18-C. LCMS: M/Z913.39 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ7.84(m,1H),7.72(m,2H),7.68–7.63(m,2H),7.57–7.51(m,2H),7.46–7.32(m,7H),7.32–7.10(m,20H),7.04(m,2H),7.01–6.96(m,3H),1.56(d,12H).

Example 5

Synthesis of Compound H-21

The procedure of example 1 was repeated except that the starting materials were changed to H-21-A, H-21-B and H-21-C. LCMS: M/Z865.39 (M+). Total synthesis yield: 38%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ7.90–7.82(m,2H),7.71–7.63(m,3H),7.61(m,1H),7.54(m,4H),7.48(m,1H),7.46–7.31(m,7H),7.31–7.15(m,11H),7.05(m,2H),6.99(m,2H),6.84(d,J＝1.4Hz,1H),1.61(s,6H),1.56(s,12H).

Example 6

Synthesis of Compound H-26

The procedure of example 1 was repeated except that the starting materials were changed to H-26-A, H-26-B and H-26-C. LCMS: M/Z724.31 (M+). Total synthesis yield: 38%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.21(d,1H),8.13(m,1H),7.82(m,1H),7.78(m,2H),7.63–7.40(m,15H),7.40–7.32(m,2H),7.34–7.26(m,2H),7.26–7.20(m,2H),7.20–7.15(m,3H),1.56(s,12H).

Example 7

Synthesis of Compound H-33

The procedure of example 1 was repeated except that the starting materials were changed to H-33-A, H-33-B and H-33-C. LCMS: M/Z747.26 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.30(m,1H),7.98(m,2H),7.84(d,1H),7.81(m,1H),7.75–7.62(m,5H),7.59(d,1H),7.57–7.30(m,8H),7.22–7.15(m,3H),7.18–7.11(m,1H),1.59(s,6H),1.56(s,12H).

Example 8

Synthesis of Compound H-36

The procedure of example 1 was repeated except that the starting materials were changed to H-36-A, H-36-B and H-36-C. LCMS: M/Z929.37 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ7.93(m,1H),7.84(m,3H),7.81–7.76(m,1H),7.75–7.66(m,5H),7.64–7.59(m,1H),7.58(t,1H),7.53(t,1H),7.44(m,2H),7.40–7.25(m,12H),7.22(m,2H),6.94(d,1H),6.85–6.79(m,2H),6.75(m,2H),1.59(s,6H),1.56(s,12H).

Example 9

Synthesis of Compound H-41

The procedure of example 1 was repeated except that the starting materials were changed to H-41-A, H-41-B and H-41-C. LCMS: M/Z740.34 (M+). Total synthesis yield: 38%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.10(m,1H),8.03(m,2H),7.91(d,1H),7.65–7.58(m,2H),7.58–7.38(m,12H),7.37–7.32(m,2H),7.28(m,1H),7.20(m,1H),7.08–6.99(m,2H),6.87(m,1H),2.30–2.13(m,4H),1.94–1.82(m,4H),1.56(s,12H).

Example 10

Synthesis of Compound H-50

The procedure of example 1 was repeated except that the starting materials were changed to H-50-A, H-50-B and H-50-C. LCMS: M/Z1062.46 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.30(m,1H),7.97(d,1H),7.83(m,2H),7.69(d,1H),7.63–7.57(m,3H),7.52–7.45(m,2H),7.47–7.37(m,3H),7.39–7.32(m,2H),7.32–7.03(m,18H),7.00(m,2H),6.85(d,1H),2.90(m,1H),2.44–2.33(m,2H),2.33–2.21(m,2H),2.19(m,1H),1.95–1.86(m,1H),1.75–1.55(m,9H),1.55–1.41(m,10H).

Example 11

Synthesis of Compound H-51

The procedure of example 1 was repeated except that the starting materials were changed to H-51-A, H-51-B and H-51-C. LCMS: M/Z835.29 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.30(m,1H),7.97(d,1H),7.84(m,1H),7.81(m,1H),7.76(d,1H),7.73–7.67(m,3H),7.60(d,1H),7.48(m,2H),7.42(m,1H),7.36(m,1H),7.31–7.17(m,9H),7.05(m,2H),6.98(m,3H),6.84(d,1H),1.56(s,11H),0.47(s,6H).

Example 12

Synthesis of Compound H-54

The procedure of example 1 was repeated except that the starting materials were changed to H-54-A, H-54-B and H-54-C. LCMS: M/Z1000.38 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.10(m,1H),8.04(d,1H),7.92(m,2H),7.84(m,3H),7.78(d,1H),7.75(s,1H),7.73–7.67(m,2H),7.64–7.47(m,6H),7.47–7.19(m,18H),7.16(m,1H),6.87(m,1H),6.85–6.78(m,3H),1.56(s,12H).

Example 13

Synthesis of Compound H-61

The procedure of example 1 was repeated except that the starting materials were changed to H-61-A and H-61-B. LC MS: M/Z610.31 (M+). Total synthesis yield: 60 percent; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ7.84(m,6H),7.71(m,3H),7.58(s,1H),7.40(s,1H),7.38–7.23(m,13H),7.20(m,2H),6.98(d,1H),6.88–6.79(m,8H),3.31(m,2H),2.01–1.89(m,7H),1.75–1.61(m,6H),1.56(s,12H).

Example 14

Synthesis of Compound E-2

37.1 g (100 mmol) of compound E-2-A, 40.3 g (100 mmol) of compound E-2-B, 23.4 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol%) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 1000mL of xylene (xylene) were charged into a reaction vessel under an argon atmosphere, and heated and stirred at 140℃for 15 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 43.5 g of compound E-2, 99.9% pure by HPLC, yield 61%. LC MS: M/Z649.31 (M+).

¹ H NMR(500MHz,DMSO-d6)δ8.38(m,2H),8.08–8.04(m,1H),7.98–7.84(m,5H),7.73–7.64(m,4H),7.62(d,1H),7.54–7.42(m,7H),7.37(s,1H),1.59(s,6H),1.55(d,12H).

Example 15

Synthesis of Compound E-6

The procedure of example 14 was repeated except that the starting materials were changed to E-6-A and E-6-B. LC MS: M/Z599.29 (M+). Total synthesis yield: 59%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.41–8.34(m,4H),7.88–7.80(m,3H),7.70–7.64(m,2H),7.59(m,1H),7.51–7.39(m,10H),1.60(s,6H),1.55(s,12H).

Example 16

Synthesis of Compound E-9

The procedure of example 14 was repeated except that the starting materials were changed to E-9-A and E-9-B. LC MS: M/Z523.26 (M+). Total synthesis yield: 61%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.41–8.34(m,4H),7.74(m,1H),7.62(t,1H),7.52–7.43(m,8H),7.21(s,1H),1.60(s,6H),1.55(s,12H).

Example 17

Synthesis of Compound E-14

The procedure of example 14 was repeated except that the starting materials were changed to E-14-A and E-14-B. LC MS M/Z

787.32 (M+). Total synthesis yield: 59%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.42–8.34(m,2H),8.20(m,1H),8.07(d,1H),7.96–7.88(m,2H),7.82(d,1H),7.71–7.64(m,4H),7.57–7.46(m,3H),7.50–7.39(m,5H),7.31–7.24(m,4H),7.25–7.18(m,2H),7.11–7.05(m,4H),1.56(s,12H).

Example 18

Synthesis of Compound E-21

The procedure of example 1 was repeated except that the starting materials were changed to E-21-A and E-21-B. LC MS: M/Z647.29 (M+). Total synthesis yield: 59%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.38(m,4H),7.72(m,1H),7.63(t,1H),7.49(s,1H),7.49–7.42(m,6H),7.42–7.37(m,2H),7.31–7.24(m,4H),7.27–7.18(m,2H),7.12–7.06(m,4H),1.55(s,12H).

Example 19

Synthesis of Compound E-28

The procedure of example 14 was repeated except that the starting materials were changed to E-28-A and E-28-B. LC MS M/Z

721.31 (M+). Total synthesis yield: 62%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.41–8.34(m,4H),7.89–7.80(m,5H),7.70–7.65(m,2H),7.63(m,1H),7.51(d,1H),7.49–7.40(m,8H),7.36–7.25(m,4H),6.83–6.78(m,2H),1.56(s,12H).

Example 20

Synthesis of Compound E-41

547.23 (M+). Total synthesis yield: 59%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ9.05(t,1H),8.49(m,1H),8.41–8.34(m,2H),8.11(d,1H),8.08–7.97(m,3H),7.89–7.84(m,1H),7.61(s,1H),7.56–7.43(m,7H),7.28(s,1H),1.56(s,12H).

Example 21

Synthesis of Compound E-44

The procedure of example 14 was repeated except that the starting materials were changed to E-44-A and E-44-B. LC MS M/Z

679.23 (M+). Total synthesis yield: 57%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.51(d,1H),8.41–8.34(m,4H),8.12(d,1H),7.94(d,1H),7.89(d,1H),7.73–7.65(m,5H),7.64(d,1H),7.55(m,1H),7.50–7.42(m,6H),1.56(s,12H)

Example 22

Synthesis of Compound E-45

The procedure of example 14 was repeated except that the starting materials were changed to E-45-A and E-45-B. LC MS M/Z

722.30 (M+). Total synthesis yield: 58%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ9.73–9.69(m,1H),8.41–8.34(m,2H),8.30(m,2H),8.10(m,1H),8.02(m,1H),7.97(d,1H),7.90(s,1H),7.82(m,1H),7.73(s,1H),7.65–7.41(m,16H),1.57(s,12H).

Example 23

Synthesis of Compound E-49

The procedure of example 14 was repeated except that the starting materials were changed to E-49-A and E-49-B. LC MS M/Z

773.34 (M+). Total synthesis yield: 58%; HPLC purity: 99.9%.

1H NMR(500MHz,DMSO-d6)δ9.73–9.69(m,1H),8.41–8.34(m,2H),8.30(dd,J＝7.2,1.5Hz,2H),8.10(dd,J＝7.5,1.6Hz,1H),8.02(dd,J＝6.3,2.7Hz,1H),7.97(d,J＝7.5Hz,1H),7.90(s,1H),7.82(dd,J＝7.2,1.8Hz,1H),7.73(s,1H),7.65–7.41(m,16H),1.57(d,J＝2.9Hz,12H).

Example 24

Synthesis of Compound E-57

The procedure of example 1 was repeated except that the starting materials were changed to E-57-A and E-57-B. LC MS: M/Z563.75 (M+). Total synthesis yield: 59%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.42–8.34(m,4H),7.74(m,1H),7.59(t,1H),7.51–7.44(m,7H),7.47–7.39(m,2H),2.26–2.10(m,4H),1.76–1.61(m,4H),1.55(s,12H),1.53–1.37(m,2H).

Example 25

Synthesis of Compound E-60

The procedure of example 14 was repeated except that the starting materials were changed to E-60-A and E-60-B. LC MS M/Z

817.40 (M+). Total synthesis yield: 59%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.41–8.34(m,2H),7.97–7.92(m,2H),7.92–7.83(m,5H),7.87–7.79(m,1H),7.71–7.64(m,5H),7.63(m,1H),7.59–7.50(m,2H),7.50–7.41(m,5H),7.41–7.36(m,2H),3.31(m,2H),2.02–1.86(m,6H),1.69(m,4H),1.64(t,2H),1.56(s,12H)

Example 26

Synthesis of Compound E-69

The procedure of example 14 was repeated except that the starting materials were changed to E-69-A and E-69-B. LC MS M/Z

737.29 (M+). Total synthesis yield: 58%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.42–8.34(m,4H),8.17(m,1H),8.06(m,1H),7.92(m,2H),7.81–7.75(m,2H),7.72(s,1H),7.68(s,1H),7.65–7.52(m,6H),7.48–7.41(m,6H),7.38(m,2H),1.56(s,12H).

Example 27

Synthesis of Compound D-1

1) Synthesis of intermediate D-1-1

To a reaction vessel, 30.0 g (100 mmol) of compound 1-A, 31.2 g (100 mmol) of compound 1-B, 23.4 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol%) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl, and 1000mL of xylene (xylene) were charged under an argon atmosphere, and heated and stirred at 140℃for 15 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 37.1 g of compound D-1, purity of HPLC was 99.1%, yield was 70%. LC MS: M/Z530.19 (M+).

¹ H NMR(500MHz,DMSO-d6)δ8.42–8.34(m,4H),8.10(d,1H),7.93(s,1H),7.80(s,1H),7.51–7.40(m,7H),7.31(d,1H),1.55(s,12H).

2) Synthesis of Compound D-1

To the reaction vessel, 50ml (300 mmol) of 1.5M potassium phosphate and 1000ml (THF) of tetrahydrofuran were added under argon atmosphere, followed by stirring under reflux, and heating overnight, with the addition of 53.1G (100 mmol) of compound D-1, 22.2G (100 mmol) of compound D-1-C, and 787 mg (1 mmol) of XPhos Pd G3. Cooling to room temperature, adding 800ml of water, precipitating a large amount of solid, filtering, stirring and washing the filter cake with water for 3 times, and vacuum drying. The crude product was purified by column chromatography on silica gel (eluent: ethyl acetate/hexane) to give 40.4 g of compound D-1 in 60% yield and 99.9% purity by HPLC. LC-MS: M/Z672.79 (M+).

¹ H NMR(500MHz,DMSO-d6)δ8.44(d,J＝7.5Hz,1H),8.41–8.34(m,4H),8.21(m,1H),8.13(m,1H),8.07–7.99(m,2H),7.95(s,1H),7.83(m,1H),7.81–7.75(m,2H),7.61(m,2H),7.58–7.48(m,3H),7.48–7.40(m,6H),1.56(d,12H).

Example 28

Synthesis of Compound D-8

The procedure of example 27 was repeated except that the starting materials were changed to D-8-A, D-8-B and D-8-C. LCMS: M/Z784.36 (M+). Total synthesis yield: 35%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.44(m,2H),8.41–8.32(m,7H),7.93–7.87(m,2H),7.71(s,1H),7.68–7.61(m,5H),7.60(s,1H),7.52–7.40(m,13H),7.40–7.33(m,1H),1.57(s,12H).

Example 29

Synthesis of Compound D-12

The procedure of example 27 was repeated except that the starting materials were changed to D-12-A, D-12-B and D-12-C. LCMS: M/Z828.97 (M+). Total synthesis yield: 41%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.45–8.34(m,4H),8.04(m,2H),7.97(m,1H),7.96(s,1H),7.88(m,2H),7.81(s,1H),7.74(d,1H),7.68–7.58(m,4H),7.60–7.50(m,3H),7.49–7.42(m,4H),7.46–7.37(m,2H),7.41–7.33(m,3H),1.56(s,12H).

Example 30

Synthesis of Compound D-23

The procedure of example 1 was repeated except that the starting materials were changed to D-23-A, D-23-B and D-23-C. LCMS: M/Z661.31 (M+). Total synthesis yield: 41%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.09(m,1H),7.90(s,1H),7.88–7.82(m,2H),7.80–7.70(m,5H),7.67(m,2H),7.63(m,1H),7.60–7.53(m,2H),7.52–7.39(m,4H),7.43–7.31(m,3H),1.59(s,6H),1.56(s,12H).

Example 31

Synthesis of Compound D-32

The procedure of example 27 was repeated except that the starting materials were changed to D-32-A, D-32-B and D-32-C. LCMS: M/Z633.24 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.19(t,1H),8.14–8.08(m,3H),7.93–7.86(m,3H),7.73–7.68(m,2H),7.67–7.53(m,7H),7.53–7.40(m,3H),1.56(s,12H)

Example 32

Synthesis of Compound D-35

The procedure of example 27 was repeated except that the starting materials were changed to D-35-A, D-35-B and D-35-C. LCMS: M/Z793.31 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ7.98–7.93(m,2H),7.93–7.75(m,8H),7.75–7.68(m,3H),7.68–7.59(m,3H),7.47–7.30(m,8H),7.27(m,1H),1.59(s,6H),1.56(s,12H).

Example 33

Synthesis of Compound D-38

The procedure of example 27 was repeated except that the starting materials were changed to D-38-A, D-38-B and D-38-C. LCMS: M/Z849.34 (M+). Total synthesis yield: 43%. HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.55(m,1H),8.13(d,1H),8.02(m,1H),7.94(s,1H),7.92–7.84(m,3H),7.82–7.74(m,3H),7.69–7.53(m,7H),7.46–7.32(m,4H),7.27(m,4H),7.13(m,2H),7.07–6.96(m,4H),1.56(s,12H).

Example 34

Synthesis of Compound D-39

The procedure of example 1 was repeated except that the starting materials were changed to D-39-A, D-39-B and D-39-C. LCMS: M/Z751.28 (M+). Total synthesis yield: 43%. HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.40(m,1H),8.10–8.01(m,2H),7.94(s,1H),7.89(d,1H),7.83–7.75(m,4H),7.73–7.67(m,2H),7.64–7.52(m,6H),7.52–7.45(m,3H),7.47–7.40(m,2H),7.44–7.37(m,2H),7.40–7.33(m,1H),1.56(s,12H).

Example 35

Synthesis of Compound D-46

The procedure of example 1 was repeated except that the starting materials were changed to D-46-A, D-46-B and D-46-C. LCMS: M/Z707.21 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.37–8.31(m,1H),8.24(d,J＝7.6Hz,1H),8.06–8.02(m,1H),7.98–7.92(m,2H),7.80(s,2H),7.84–7.76(m,2H),7.73(m,1H),7.70–7.62(m,3H),7.50(m,1H),7.46–7.36(m,4H),7.39–7.32(m,1H),7.28(m,1H),1.56(s,12H).

Example 36

Synthesis of Compound D-51

The procedure of example 1 was repeated except that the starting materials were changed to D-51-A, D-51-B and D-51-C. LCMS: M/Z889.33 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.46(d,1H),8.31(d,1H),8.09(m,1H),8.00(m,1H),7.95(s,1H),7.92–7.71(m,7H),7.65(m,1H),7.61–7.52(m,2H),7.52–7.40(m,3H),7.39–7.32(m,2H),7.32–7.22(m,4H),7.13(m,2H),7.07–6.96(m,4H),1.56(s,12H).

Example 37

Synthesis of Compound D-53

The procedure of example 1 was repeated except that the starting materials were changed to D-53-A, D-53-B and D-53-C. LCMS: M/Z710.30 (M+). Total synthesis yield: 43%. HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.41(m,1H),8.12–8.06(m,2H),7.95(s,1H),7.86(m,1H),7.81–7.73(m,5H),7.69–7.38(m,14H),7.32–7.23(m,2H),1.56(s,12H).

Example 38

Synthesis of Compound D-57

The procedure of example 1 was repeated except that the starting materials were changed to D-57-A, D-57-B and D-57-C. LCMS: M/Z707.29 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.15(m,3H),7.87–7.80(m,2H),7.74(s,1H),7.68(m,1H),7.68–7.61(m,2H),7.53(s,1H),7.48(t,1H),7.43(m,1H),7.39(d,1H),7.36(m,1H),7.33–7.19(m,7H),7.17–7.11(m,4H),1.57(s,12H).

Example 39

Synthesis of Compound D-59

The procedure of example 1 was repeated except that the starting materials were changed to D-59-A, D-59-B and D-59-C. LCMS: M/Z924.38 (M+). Total synthesis yield: 43%. HPLC purity: 99.9%.

¹ H NMR(500MHz,DMSO-d6)δ8.57–8.51(m,1H),8.46(d,1H),8.31(d,1H),8.09(m,1H),7.97–7.88(m,2H),7.87–7.82(m,1H),7.82–7.78(m,2H),7.77(d,1H),7.71–7.63(m,3H),7.59(m,1H),7.53–7.44(m,4H),7.44–7.37(m,1H),7.40–7.33(m,1H),7.36–7.25(m,4H),7.27(d,1H),7.28–7.22(m,1H),7.25–7.18(m,2H),7.15–7.04(m,6H),7.03–6.97(m,2H),1.56(s,12H).

Device example 1: preparation of organic electroluminescent device

The preparation process is as follows:

1) A transparent anode ITO film layer (thickness 150 nm) was formed on a glass substrate to obtain a first electrode as an anode.

2) By vacuum evaporation, a mixed material of the compound T-1 and the compound T-2 was evaporated as a hole injection layer on the anode surface at a mixing ratio (mass ratio) of 3:97, thickness 10nm.

3) The compound T-2 having a thickness of 100nm was evaporated on the hole injection layer to obtain a first hole transport layer. Then, the compound H-6 of the present invention having a thickness of 10nm was evaporated on the first hole transport layer to obtain a second hole transport layer.

4) On the second hole transport layer, compound T-3 and compound T-4 were mixed in an amount of 95:5 mass ratio co-evaporation to form an organic light emitting layer with a thickness of 40 nm.

5) On the organic light-emitting layer, the compound T-5 was evaporated in order to form a hole blocking layer (thickness 10 nm) with a mixing ratio of 4: the compound T-6 of 6 (mass ratio) and LiQ form an electron transport layer (thickness 30 nm).

6) Magnesium (Mg) and silver (Ag) were mixed at 1:9, and evaporating the mixture on an electron injection layer serving as a second electrode in vacuum to complete the manufacture of the organic light-emitting device.

Device examples 2 to 13

An organic electroluminescent device was fabricated in the same manner as in device example 1, except that the compounds H-11, H-15, H-18, H-21, H-26, H-33, H-36, H-41, H-50, H-51, H-54 and H-61 were used in place of the compound H-6, respectively, in the formation of the second hole transport layer.

Device comparative examples 1 to 2

An organic electroluminescent device was fabricated in the same manner as in device example 1, except that compound HT-1 and compound HT-2 were used in place of compound H-6, respectively, when forming the second hole transport layer.

Each of the above sets of device examples and device comparative example 1 were produced and tested in the same batch as the device of device comparative example 2, the operating voltage, efficiency and lifetime of the device of device comparative example 1 were each noted as 1, and the ratio of the corresponding indices of device examples 1 to 20, device comparative example and device comparative example 1, respectively, was calculated as shown in table 1.

Table 1 test results for device examples 1 to 13 and device comparative examples 1 to 2

As is clear from the results of table 1, when the second hole transport layer of the light-emitting device was formed, the compounds used in device examples 1 to 13 had lower voltages, improved light-emitting efficiency, and significantly improved lifetime, as compared with the devices formed from the compounds used in device comparative examples 1 to 2.

Device example 14: preparation of organic electroluminescent device

A glass substrate coated with Indium Tin Oxide (ITO) having a thickness of 100nm as a thin film was put into distilled water in which a cleaning agent was dissolved, and ultrasonic cleaning was performed. After washing the ITO for 20 minutes, the ultrasonic washing was repeated twice with distilled water for 10 minutes each. After washing with distilled water, the substrate was washed with isopropyl alcohol, acetone and methanol by ultrasonic waves, and then dried and transferred to a plasma cleaner. In addition, the substrate was cleaned with oxygen plasma for 5 minutes and then transferred to a in-vacuum depositor. On the transparent ITO electrode prepared as above, a hole injection layer was formed by thermally vacuum depositing a compound HI at a deposition rate of 0.04 to 0.09nm/s and a total film thickness of 60 nm.

1) And vacuum evaporating a compound HAT as a first hole transport layer on the hole injection layer, wherein the evaporation speed is 0.04-0.09 nm/s, and the total film thickness of the evaporation is 5nm.

2) And vacuum evaporation HT is carried out on the first hole transport layer to serve as a second hole transport layer. The evaporation rate is 0.04-0.09 nm/s, and the total film thickness of the evaporation is 50nm.

3) A light-emitting layer was formed on the 2 nd hole transport layer by vacuum evaporation of the compound BH and the compound BD at a weight ratio of 25:1. The evaporation rate is 0.04-0.09 nm/s, and the total film thickness of the evaporation is 20nm.

4) On the light-emitting layer, an electron transporting layer and an injection layer were formed by vacuum evaporation of the compound E-2 and the compound LiQ in a weight ratio of 1:1. The vapor deposition rate was 0.1nm/s, and the total vapor deposition film thickness was 35nm.

5) Lithium fluoride (LiF) was deposited on the electron injection and transport layer at a deposition rate of 0.03nm/s and a total film thickness of 1nm, and then aluminum was deposited at a deposition rate of 0.2nm/s and a total film thickness of 100nm to form a cathode.

The vacuum was maintained at 1 x 10 during this process ^-7 To 5 x 10 ^-5 And (5) a bracket.

Device examples 15 to 26

An organic electroluminescent device was fabricated in the same manner as in device example 14, except that compounds E-6, E-9, E-14, E-21, E-28, E-41, E-44, E-45, E-49, E-57, E-60 and E-69 were used in place of compound E-2, respectively, in the formation of the electron transport layer.

Device comparative examples 3 to 4

An organic electroluminescent device was fabricated in the same manner as in device example 14, except that the compounds ET1 and ET2 were used instead of the compound E-2 in forming the light-emitting layer.

Each of the above sets of device examples and device comparative example 3 were produced and tested in the same batch as the device of device comparative example 4, the operating voltage, efficiency and lifetime of the device of device comparative example 3 were each recorded as 1, and the ratio of the corresponding indices of device examples 14-26, device comparative example and device comparative example 1, respectively, was calculated as shown in table 2.

Table 2 test results for device examples 14 to 26 and device comparative examples 3 to 4

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As can be seen from the results of table 2, when the inventive series of compounds were used as electron transport layers of light emitting devices instead of the commercial electron transport materials ET1 and ET2 of device comparative examples 3 and 4, voltage reduction was achieved and current efficiency was improved. The result shows that the novel organic material of the invention is taken as an electron transport material of an organic electroluminescent device, is an organic luminescent functional material with good performance, and is expected to be popularized and applied commercially

Device example 27: preparation of organic electroluminescent device

The basic structural model of the organic photoelectric device is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/EML (compound of the invention): RD (Ir complex) =94:6 (40 nm)/ETL (30 nm)/LiF (1 nm)/Al (80 nm).

The manufacturing method of the organic photoelectric device of the embodiment comprises the following steps:

(1) A transparent anodic Indium Tin Oxide (ITO) 20 (10Ω/sq) glass substrate was subjected to ultrasonic cleaning with acetone, ethanol and distilled water in this order, and then treated with ozone plasma for 15 minutes.

(2) After mounting the ITO substrate on the substrate holder of the vacuum vapor deposition equipment, the system pressure was controlled to 10 ^-6 A HAT-CN with a thickness of 10nm, TAPC with a thickness of 40nm and TCTA with a thickness of 10nm were sequentially deposited on the ITO substrate.

(3) A 40nm thick light emitting layer (EML) was evaporated on the TCTA described above, wherein the mass ratio of the compound D-1 of the present invention to RD was 94:6. the compound D-1 is a host material of the light-emitting layer.

(4) An Electron Transport Layer (ETL) material having a thickness of 30nm was vapor deposited on the light emitting layer.

(5) LiF having a thickness of 1nm was vapor deposited as an electron injection layer on the electron transport layer.

(6) Finally, al with the thickness of 80nm is evaporated on the electron injection layer to be used as a cathode, and the device is packaged by utilizing a glass packaging cover.

Device examples 28 to 39

An organic electroluminescent device was fabricated in the same manner as in device example 25, except that compounds D-8, D-12, D-23, D-32, D-35, D-38, D-39, D-46, D-51, D-53, D-57 and D-59 were used in place of compound D-1, respectively, in the formation of the light-emitting layer.

Device comparative examples 5 to 6

An organic electroluminescent device was fabricated in the same manner as in device example 27, except that compound RH-01 and compound RH-02 were used in place of compound D-1, respectively, in the formation of the light-emitting layer.

Each of the above sets of device examples and device comparative example 5 was produced and tested in the same lot as the device of device comparative example 6, the current efficiency, LT98 (hr) relative values of the devices of device comparative example 5 were each noted as 1, and the ratios of the corresponding indices of device examples 27 to 39, device comparative example and device comparative example 1, respectively, were calculated as shown in table 3.

Table 3 test results for device examples 27 to 39 and device comparative examples 5 to 6

As is clear from the results of table 3, when the compounds used in device examples 27 to 39 were used as the light-emitting layers of the light-emitting devices, the light-emitting efficiency was improved and the lifetime was remarkably improved as compared with the devices formed from the compounds used in device comparative examples 5 to 6.

Accordingly, the device structures in the above embodiment and the comparative example are identical except for the corresponding functional layers, the device performance based on the comparative material is used as a reference, the current efficiency of the device containing the compound of the present invention is remarkably improved, and the service life of the device is also improved.

The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims

1. A compound having a chemical structure according to formula (i):

wherein:

R ₅ -R ₈ each independently selected from hydrogen, deuterium, C1-C10 alkyl, or C1-C10 deuterated alkyl; a is selected from CR ₉ R ₁₀ 、SiR ₁₁ R ₁₂ 、NR ₁₃ O, or S: wherein R is ₉ -R ₁₃ Each independently selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 deuterated alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 Deuterated aryl, substituted or unsubstituted C3-C30 deuterated heteroaryl, or R ₉ 、R ₁₀ Bonded to form a ring, R ₁₁ 、R ₁₂ Bonded to form a ring.

2. The compound of claim 1, wherein R ₁ -R ₄ At least one selected from the following structures:

wherein:

L ₁ -L ₆ the same or different, each independently selected from a single bond, a substituted or unsubstituted C6-C30 aryl, or a substituted or unsubstituted C3-C30 heteroaryl;

Ar ₁ -Ar ₄ the same or different, each independently selected from substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl;

3. The compound of claim 1, wherein a is selected from NR ₁₃ O, or S or any one of the following groups:

4. A compound according to claim 1 wherein a is selected from NR ₁₃ ，R ₁₃ An electron withdrawing group selected from nitrogen atoms; preferably, the electron withdrawing group containing nitrogen atoms is selected from the group consisting ofAny of the groups:

5. The compound of claim 2, wherein L ₁ ～L ₆ Each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted dibenzofluorenyl group, a substituted or unsubstituted phenanthrylene group, or a substituted or unsubstituted triphenylene group.

6. The compound of claim 2, wherein Ar ₁ ～Ar ₄ Each independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, or substituted or unsubstituted:

7. the compound of claim 2, wherein E is selected from 1,3, 5-triazine.

8. The compound of claim 1, wherein R ₁ -R ₄ Each independently selected from hydrogen, substituted or unsubstituted benzeneA group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or any of the following substituted or unsubstituted groups:

9. The compound of claim 1, wherein R ₅ -R ₈ Each independently selected from methyl or deuterated methyl.

10. A compound according to any one of claims 1 to 9, wherein the compound is selected from any one of the following chemical structures:

11. an organic layer comprising a compound according to any one of claims 1 to 10.

12. Use of a compound according to any one of claims 1 to 10 and/or an organic layer according to claim 11 in an organic optoelectronic device.

13. An organic optoelectronic device comprising a first electrode, a second electrode, and the organic layer of claim 11, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, or an electron transport layer.

14. The organic optoelectronic device according to claim 13, wherein the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin film transistor.

15. A display or lighting device comprising an organic optoelectronic device according to any one of claims 13 to 14.