CN116332770A - Spiro compound and application thereof in organic photoelectric device - Google Patents

Spiro compound and application thereof in organic photoelectric device Download PDF

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CN116332770A
CN116332770A CN202310337165.7A CN202310337165A CN116332770A CN 116332770 A CN116332770 A CN 116332770A CN 202310337165 A CN202310337165 A CN 202310337165A CN 116332770 A CN116332770 A CN 116332770A
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王鹏
王湘成
何睦
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Shanghai Yaoyi Electronic Technology Co ltd
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Shanghai Yaoyi Electronic Technology Co ltd
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Abstract

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

Description

Spiro compound and application thereof in organic photoelectric device
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to a fluorene spiro 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.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a spiro compound and its application in an organic optoelectronic device for solving the problems in the prior art.
To achieve the above and other related objects, according to one aspect of the present invention, there is provided a spiro compound having a chemical structure represented by formula (i):
Figure BDA0004156775850000021
wherein: r is R a1 、R a2 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-C30 heteroaryl; m is selected from 1 to 4; when m is greater than 1, each R a1 The same or different;
X 1 ，X 2 identical or different, each independently selected from single bonds, -O-, -S-, -C (R) b1 )(R b2 )、-N(R b3 )、-Si(R b4 )(R b5 )-、-B(R b6 ) -, or a group as follows:
Figure BDA0004156775850000022
Y 1 ～Y 11 each independently selected from-C (R) 1 )(R 2 )-、-N(R 3 )-、-Si(R 4 )(R 5 )-、-B(R 6 ) -, -O-or-S-;
the group G is selected from one or more of the following groups:
Figure BDA0004156775850000023
Ar 3 selected from substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C3 to C30 heteroaryl; z is Z 1 -
Z 12 Each independently selected from-C (R) 7 )(R 8 )-、-N(R 9 )-、-Si(R 10 )(R 11 )-、-B(R 12 ) -, -O-or-S-;
R b1～ R b6 、R 1 ～R 12 the same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl; substitution ofOr 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-C30 heteroaryl;
n is selected from 1 to 2, and when n is 2, each G is the same or different;
E 1 ～E 3 the same or different, each independently selected from a single bond, a substituted or unsubstituted C6 to C30 arylene, or a substituted or unsubstituted C3 to C30 heteroarylene;
Ar 1 and Ar is a group 2 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.
In another aspect, the present invention provides an organic layer comprising the spiro compound as described above.
In another aspect, the present invention provides the use of a spiro compound as described above and/or an organic layer as described above in an organic optoelectronic device.
In another aspect, the present invention provides an organic optoelectronic device, which includes a first electrode, a second electrode, and an organic layer as described above, 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 as hereinbefore described.
Compared with the prior art, the invention has the beneficial effects that:
the spiro compound provided by the invention not only introduces benzo alkane, but also introduces a spiro fluorene structure, so that the stacking degree of molecules is reduced, and the unnecessary transmission of electrons among the molecules is reduced. In addition, compared with the introduction of aliphatic groups, alkane and spiro ring, the electron transport capacity is enhanced, so that the hole transport performance of the whole compound is improved. Meanwhile, the spiro compound provided by the invention is applied to an organic device, can increase the hole mobility of the device, can effectively block electrons and excitons from entering a hole transport layer, improves the efficiency of the device, and meanwhile, has higher stability, and can further improve the luminous efficiency and the service life of the device.
Detailed Description
The following words, phrases and symbols used in the present specification have the meanings as described below in general unless otherwise indicated.
Generally, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including those used in cell culture, organic chemistry, analytical chemistry, pharmacology, and the like) are those well known and commonly employed in the art. Unless defined otherwise, all scientific and technical terms used herein in connection with the disclosure described herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, in the claims and/or the specification, the terms "a" or "an" when used in conjunction with the term "comprising" or noun may have the meaning of "one" but are also consistent with the meaning of "one or more", "at least one", and "one or more". Similarly, the term "another" or "other" may mean at least a second or more.
It will be understood that whenever aspects are described herein by the terms "comprising" or "including," other similar aspects are provided as described by "consisting of …" and/or "consisting essentially of ….
In this context, the term "single bond" means that the group referred to is a bond linker, with the two groups adjacent to the group being directly linked. For example, the term "E 2 Is a single bond "means E 2 Is a bond linkage. In other words, when E 2 In the absence, the radical N of the compound of formula I is directly linked to the radical Ar 1 。
In this context, bonds broken by wavy lines
Figure BDA0004156775850000041
The points of attachment of the depicted groups to other parts of the molecule are shown. For example, G represents a group shown below
Figure BDA0004156775850000042
Represents said group and a compound of formula I
Figure BDA0004156775850000043
Carbon linkage on the benzene ring on the right side of the middle.
Herein, represents a point of attachment corresponding to other parts of the molecule. For example
Figure BDA0004156775850000044
Wherein represents X 1 Or X 2 Middle and main body unit->
Figure BDA0004156775850000045
At the corresponding connection point by X 1 By way of example, i.e. formed after joining
Figure BDA0004156775850000046
For another example, a +>
Figure BDA0004156775850000047
Can be combined with Ar 3 Combine to form a group G, formed as +.>
Figure BDA0004156775850000048
For example two +.>
Figure BDA0004156775850000049
Can be respectively with Ar 3 Combine to form a group G, formed as +.>
Figure BDA00041567758500000410
Examples of the substituents in the present invention are described below, but the substituents are not limited thereto:
The term "substituted or unsubstituted", used herein, alone or in combination, refers to substitution with one or more substituents selected from the group consisting of: deuterium, halogen, cyano, nitro, hydroxy, mercapto, carbonyl, ester, imide, amino, phosphine oxide, alkoxy, deuteroalkoxy, trifluoromethoxy, aryloxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, silyl, boron, alkyl, deuteroalkyl, haloalkyl, amino-substituted alkylene, alkyl-NHC (O) -, alkyl-C (O) NH-, cycloalkyl, deuteroalkyl, alkenyl, aryl, aralkyl, aralkenyl, alkylaryl, alkylamino, aralkylamino, heteroarylamino, arylamino, arylphosphino, heteroaryl, acenaphthenyl, oxo, or unsubstituted; 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 term "optionally substituted with … …" is used interchangeably herein with "unsubstituted or substituted. The term "substituted" generally means that one or more hydrogens in the structure referred to are replaced with a specific substituent, either the same or different.
Herein, the term "alkyl" may be straight-chain or branched, and the number of carbon atoms is not particularly limited. For example, a C1-C60 alkyl group is possible. More examples thereof include C1 to C30, C1 to C25, C1 to C20, C1 to C15, C1 to C10, and C1 to C5. In some embodiments, alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, 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, or 5-methylhexyl, and the like.
The above description of alkyl groups also applies to alkyl groups in aralkyl groups, aralkylamine groups, alkylaryl groups, and alkylamino groups.
Herein, the term "heteroalkyl" may be a straight-chain or branched-chain alkyl group containing a heteroatom, and the number of carbon atoms is not particularly limited. For example, a C1-C60 heteroalkyl group is possible. 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.
Herein, the term "cycloalkyl" may be cyclic, and the number of carbon atoms is not particularly limited. For example, a C3-C60 cycloalkyl group is used. Which in some embodiments has 3 to 20 carbon atoms (i.e., C 3-20 Cycloalkyl), or 3 to 15 carbon atoms (i.e., C 3-15 Cycloalkyl) 3 to 12 carbon atoms (i.e. C 3-12 Cycloalkyl), or 3 to 11 carbon atoms (i.e., C 3-11 Cycloalkyl), or 3 to 10 carbon atoms (i.e., C 3-10 Cycloalkyl), or 3 to 8 carbon atoms (i.e., C 3-8 Cycloalkyl), or 3 to 7 carbon atoms (i.e., C 3-7 Cycloalkyl), or 3 to 6 carbon atoms (i.e., C 3-6 Cycloalkyl). 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.
Herein, the term "heterocycloalkyl" may be a cycloalkyl group containing a heteroatom, and the number of carbon atoms is not particularly limited. For example, a C3-C60 heterocycloalkyl group may be used. In some embodiments, heterocycloalkyl includes, but is not limited to
Figure BDA0004156775850000061
Figure BDA0004156775850000062
Etc.
Herein, the term "aryl" is not particularly limited and refers to a monovalent carbocyclic aromatic radical containing 5 to 60 ring atoms and optionally containing one or more fused rings, such as C5 to C30, C5 to C25, C5 to C20, C5 to C15, C6 to C30, C6 to C25, C6 to C20, C6 to C15, C6 to C10 aryl, and the like. Aryl groups may be monocyclic arylene groups or polycyclic arylene groups. 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.
The term "heteroaryl" as used herein refers to a monovalent heteroaryl group that contains at least one C3-C30 (optionally C3-C20, C3-C15, C3-C10) single ring or two or more (e.g., 1 to 6, or 1 to 5, or 1 to 4, or 1 to 3) aromatic rings having heteroatoms independently selected from oxygen, nitrogen, and sulfur. Bicyclic or polycyclic heteroaryl groups include bicyclic, tricyclic or tetracyclic heteroaryl groups in which one ring is an aromatic ring having one or more heteroatoms independently selected from O, S and N, and the other rings may be saturated, partially unsaturated or aromatic and may be carbocyclic or contain one or more heteroatoms independently selected from O, S and N. Heteroaryl groups include, but are not limited to, pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, pyridazinyl, thiazinyl, dioxanyl, triazinyl, tetrazinyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, quinoxalinyl, cinnolinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, indolizinyl, phthalazinyl, pyrazolopyridinyl, pyrazolopyrimidinyl, pyridopyrimidinyl a pyridylpyrazinyl group, pyrazinylpyrazinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothienyl group, benzofuranyl group, isobenzofuranyl group, dibenzothienyl group, dibenzofuranyl group, indazolyl group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, indolocarbazolyl group, indenocarbazolyl group, phenazinyl group, imidazopyridinyl group, phenazinyl group, phenanthridinyl group, phenanthrolinyl group, phenothiazinyl group, imidazopyridinyl group, imidazophenanthridinyl group, benzimidazole quinazoline group, benzimidazole benzophenanthridinyl group, pyrrolopyridinyl group, pyrrolothiazolyl group, imidazothiazolyl group, benzobinaphthyl group, dinaphthofuranyl group, naphthaphthiothienyl group, or naphthabenzothienyl group, 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 compound provided by the invention not only introduces benzo alkane, but also introduces a spiro fluorene structure, so that the stacking degree of molecules is reduced, and the unnecessary transmission of electrons among the molecules is reduced. In addition, compared with the introduction of aliphatic groups, alkane and spiro ring, the electron transport capacity is enhanced, so that the hole transport performance of the whole compound is improved. Meanwhile, the compound provided by the invention is applied to an organic device, can increase the hole mobility of the device, can effectively block electrons and excitons from entering a hole transport layer, improves the efficiency of the device, and meanwhile, the molecule provided by the invention has higher stability, and can further improve the luminous efficiency and the service life of the device.
In one aspect, the invention provides a spiro compound, wherein the chemical structure of the spiro compound is shown as a formula (I):
Figure BDA0004156775850000071
wherein: r is R a1 、R a2 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-C30 heteroaryl; m is selected from 1 to 4; when m is greater than 1, each R a1 The same or different;
X 1 ，X 2 identical or different, each independently selected from single bonds, -O-, -S-, -C (R) b1 )(R b2 )-、-N(R b3 )-、-Si(R b4 )(R b5 )-、-B(R b6 ) -, or a group as follows:
Figure BDA0004156775850000081
Y 1 ～Y 11 each independently selected from-C (R) 1 )(R 2 )-、-N(R 3 )-、-Si(R 4 )(R 5 )-、-B(R 6 ) -, -O-or-S-;
the group G is selected from one or more of the following groups:
Figure BDA0004156775850000082
Ar 3 a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; z is Z 1 -Z 12 Each independently selected from-C (R) 7 )(R 8 )-、-N(R 9 )-、-Si(R 10 )(R 11 )-、-B(R 12 ) -, -O-or-S-;
R b1～ R b6 、R 1 ～R 12 the same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl; a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C3-C30 heteroaryl group;
n is selected from 1 to 2, and when n is 2, each G is the same or different;
E 1 ～E 3 the same or different, each independently selected from a single bond, a substituted or unsubstituted C6 to C30 arylene, or a substituted or unsubstituted C3 to C30 heteroarylene;
Ar 1 and Ar is a group 2 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.
In the spiro compound provided by the invention, R is a1 、R a2 Each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched chain 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, or substituted or unsubstituted C3-C20 heteroaryl. Further, the R a1 、R a2 Each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C6 alkyl; substituted or unsubstituted C1-C6 heteroalkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C3-C6 heterocycloalkyl, substituted or unsubstituted C6-C10 aryl,Or a substituted or unsubstituted C3 to C10 heteroaryl group. Further preferably, said R a1 、R a2 Each independently selected from hydrogen, or deuterium.
In the spiro compound provided by the invention, m is selected from 1, 2, 3 or 4; when m is greater than 1, each R a1 The same or different. Each R is a1 Is selected from the same group as before. And will not be described in detail herein. n is selected from 1 or 2.
In the spiro compound provided by the invention, when X 1 ，X 2 Identical or different, each independently selected from single bonds, -O-, -S-, -C (R) b1 )(R b2 )-、-N(R b3 )-、-Si(R b4 )(R b5 )-、-B(R b6 ) -when R b1 -R b6 The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C10 alkyl; an alkoxy group of a substituted or unsubstituted C1 to C12, an alkylthio group of a substituted or unsubstituted C1 to C12, a cycloalkyl group of a substituted or unsubstituted C3 to C10, a heterocycloalkyl group of a substituted or unsubstituted C3 to C10, an aryl group of a substituted or unsubstituted C6 to C30, or a heteroaryl group of a substituted or unsubstituted C3 to C20. Alternatively, R b1 -R b6 The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C6 alkyl; an alkoxy group of a substituted or unsubstituted C1 to C6, an alkylthio group of a substituted or unsubstituted C1 to C6, a cycloalkyl group of a substituted or unsubstituted C3 to C6, a heterocycloalkyl group of a substituted or unsubstituted C3 to C6, an aryl group of a substituted or unsubstituted C6 to C10, or a heteroaryl group of a substituted or unsubstituted C3 to C10. Preferably, R b1 -R b6 The same or different, each independently selected from hydrogen, deuterium, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, naphthyl, biphenyl, or the like.
In the spiro compound provided by the invention, Y 1 ～Y 11 Each independently selected from-C (R) 1 )(R 2 )-、-N(R 3 )-、-Si(R 4 )(R 5 )-、-B(R 6 ) -, -O-or-S-; r is R 1 -R 6 Identical or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C10, a substituted or unsubstituted C1-C10 heteroalkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C3-C10 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C3-C20 heteroaryl group. Alternatively, Y 1 ～Y 11 Each independently selected from-C (R) 1 )(R 2 )-、-N(R 3 )-、-Si(R 4 )(R 5 )-、-B(R 6 ) -, -O-or-S-; r is R 1 -R 6 The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C6 alkyl; a substituted or unsubstituted C1-C6 heteroalkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C3-C6 heterocycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted C3-C10 heteroaryl group. Further preferably, R 1 -R 6 The same or different, each independently selected from hydrogen, deuterium, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, naphthyl, biphenyl, or the like.
In the spiro compound provided by the invention, Z 1 -Z 12 Each independently selected from-C (R) 7 )(R 8 )-、-N(R 9 )-、-Si(R 10 )(R 11 )-、-B(R 12 ) -, -O-or-S-. R is R 7 -R 12 The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C10 alkyl; an alkoxy group of a substituted or unsubstituted C1 to C12, an alkylthio group of a substituted or unsubstituted C1 to C12, a cycloalkyl group of a substituted or unsubstituted C3 to C10, a heterocycloalkyl group of a substituted or unsubstituted C3 to C10, an aryl group of a substituted or unsubstituted C6 to C30, or a heteroaryl group of a substituted or unsubstituted C3 to C20. Alternatively, R 7 -R 12 The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C6 alkyl; an alkoxy group of a substituted or unsubstituted C1 to C6, an alkylthio group of a substituted or unsubstituted C1 to C6, a cycloalkyl group of a substituted or unsubstituted C3 to C6, a heterocycloalkyl group of a substituted or unsubstituted C3 to C6, an aryl group of a substituted or unsubstituted C6 to C10, or a heteroaryl group of a substituted or unsubstituted C3 to C10.Preferably, R 7 -R 12 The same or different, each independently selected from hydrogen, deuterium, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, naphthyl, biphenyl, or the like.
In the spiro compound provided by the invention, in a specific embodiment, X 1 、X 2 Each independently selected from any one of the following structures:
Figure BDA0004156775850000101
in a specific embodiment of the invention, X 1 、X 2 Each independently selected from single bond, -O-, -S-, -CH 2 -、-C(CH 3 ) 2 -、-NH-、-N(CH 3 )-、-N(Ph)-、-Si(H 2 )-、-Si(CH 3 ) 2 、-B(H)-、-B(CH 3 ) -, or-B (Ph) -and the like.
In the embodiment of the invention, X is 1
Figure BDA0004156775850000102
X 2 Selected from the group consisting of-O-by way of example, compounds forming the structure:
Figure BDA0004156775850000111
the following groups are used:
Figure BDA0004156775850000112
Ar 3 the groups attached to the left and right are not limited to specific substitution positions. For example, e.g. when Ar 3 When phenyl, it may be
Figure BDA0004156775850000113
Figure BDA0004156775850000114
Etc.
In the spiro compound provided by the invention, the group G is selected from any one or more of the following groups:
Figure BDA0004156775850000115
wherein Z is 1 -Z 12 As defined for compound (I) of the present invention.
In a specific embodiment of the present invention, further, the group G is selected from any one of the following groups: the group G is selected from any one of the following groups:
Figure BDA0004156775850000116
Figure BDA0004156775850000121
wherein:
R 13 -R 22 each independently selected from one or more of a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C3-C60 cycloalkyl group, a substituted or unsubstituted C1-C60 heteroalkyl group, a substituted or unsubstituted C3-C60 heterocycloalkyl group, a substituted or unsubstituted C5-C60 aryl group, or a substituted or unsubstituted C3-C60 heteroaryl group.
Alternatively, R 13 -R 22 Each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C30 heteroaryl. Further alternatively, each is independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1 to 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, or substituted or unsubstituted C3 over-the-counterHeteroaryl of C20. Alternatively, R 13 -R 22 Each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C6 alkyl; a substituted or unsubstituted C1-C6 heteroalkyl group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C3-C6 heterocycloalkyl group, a substituted or unsubstituted C6-C10 aryl group, or a substituted or unsubstituted C3-C10 heteroaryl group. Further preferably, R 13 -R 22 The same or different, each independently selected from hydrogen, deuterium, methyl, ethyl, methoxy, trifluoromethyl, trifluoromethoxy, phenyl, naphthyl, biphenyl, or the like.
In the spiro compound provided by the invention, ar is 3 The groups forming the merging ring are selected from any one or more of the following structures, any one or more of which may be bonded to Ar 3 Bonding to form a group G;
Figure BDA0004156775850000122
/>
Figure BDA0004156775850000131
wherein R is C Selected from C1-C10 alkyl, C6-C30 aryl or C5-C30 heteroaryl. Alternatively, R C Selected from C1-C8 alkyl, C6-C20 aryl, or C3-C20 heteroaryl. Alternatively, R C Selected from C1-C6 alkyl, C6-C10 aryl, or C5-C10 heteroaryl. Further alternatively, R 13 -R 22 The same or different, each independently selected from hydrogen, deuterium, methyl, ethyl, phenyl, naphthyl, biphenyl, and the like.
The above-mentioned groups are described below,
Figure BDA0004156775850000132
can be combined with Ar 3 Combine to form a group G, formed as +.>
Figure BDA0004156775850000133
For example two +.>
Figure BDA0004156775850000134
Can be respectively with Ar 3 Combine to form a group G, formed as +.>
Figure BDA0004156775850000135
Other explanations are the same as before and will not be repeated.
In some embodiments, the group G is selected from any one of the following groups:
Figure BDA0004156775850000136
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Figure BDA0004156775850000141
in the spiro compound provided by the invention, the E 1 ～E 3 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 phenanthrylene group, a,
Figure BDA0004156775850000142
In the spiro compound provided by the invention, ar is as follows 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, and,
Figure BDA0004156775850000151
In a preferred embodiment, the chemical structure of the compound is represented by formula (II):
Figure BDA0004156775850000152
wherein Ra is 1 、Ra 2 Each independently selected from hydrogen, deuterium;
R b1 and R is b2 Independently selected from substituted or unsubstituted straight or branched chain C1-C30 alkyl groups; an alkoxy group of a substituted or unsubstituted C1 to C12, an alkylthio group of a substituted or unsubstituted C1 to C12, a cycloalkyl group of a substituted or unsubstituted C3 to C30, a heterocycloalkyl group of a substituted or unsubstituted C3 to C30, an aryl group of a substituted or unsubstituted C6 to C30, or a heteroaryl group of a substituted or unsubstituted C6 to C30; or bonded to an adjacent group to form a ring;
e1 is a single bond or phenyl.
A、E 2 、E 2 、Ar 1 、Ar 2 As defined in claim 1.
In a preferred embodiment, the chemical structure of the compound is represented by the formulas (III) to (VI):
Figure BDA0004156775850000153
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Figure BDA0004156775850000161
Ra 1 、Ra 2 、G、E 2 、E 3 、Ar 1 、Ar 2 as defined for the compounds of formula (II).
In the spiro compounds provided by the invention, the compound is selected from any one or more of the following chemical structures:
Figure BDA0004156775850000162
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Figure BDA0004156775850000171
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Figure BDA0004156775850000181
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Figure BDA0004156775850000191
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Figure BDA0004156775850000201
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Figure BDA0004156775850000211
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Figure BDA0004156775850000221
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Figure BDA0004156775850000231
Figure BDA0004156775850000241
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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 spiro compound as described above.
In another aspect, the present invention provides the use of a spiro 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 adopts the spiro 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.
In another aspect, the invention provides a display or lighting device comprising an organic optoelectronic device according to the invention.
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, solvents, 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 were determined using a JEOL (400 MHz) nuclear magnetic resonance apparatus; HPLC data were determined using a Shimadzu LC-20AD high performance liquid meter.
The materials used in the examples are:
Figure BDA0004156775850000251
Figure BDA0004156775850000261
example 1
Synthesis of Compound 1
Figure BDA0004156775850000262
1) Synthesis of intermediate 1-1
To a reaction vessel were charged 32.4 g (100 mmol) of compound 1-A, 46.6 g (200 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) 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 50.3 g of compound 1-1, 99.4% pure by HPLC, yield 80%. LC MS: M/Z627.27 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.09–1.22(m,2H),1.18–1.27(m,1H),1.27–1.37(m,1H),1.33–1.47(m,2H),1.49–1.69(m,4H),1.81–1.89(m,1H),1.90–2.02(m,1H),2.05–2.13(m,1H),2.15–2.27(m,1H),6.92(s,1H),7.30–7.58(m,17H),7.69–7.77(m,4H),7.81(d,1H),7.88(m,1H)。
2) Synthesis of Compound 1
To the reaction vessel was added under argon atmosphere 1-1.8G (100 mmol) of compound 1-C16.2G (100 mmol) of XPhos Pd G3 787 mg (1 mmol%), 50ml (300 mmol) of 1.5M potassium phosphate and 1000ml (THF) of tetrahydrofuran, and the mixture was stirred under reflux for one night. 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 56.1 g of compound 1 in 79% yield and 99.9% purity by HPLC. LC-MS: M/Z709.37 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.08–1.27(m,3H),1.27–1.37(m,1H),1.33–1.46(m,2H),1.48–1.69(m,4H),1.81–1.89(m,1H),1.90–2.08(m,3H),2.03–2.14(m,1H),2.15–2.27(m,1H),2.63–2.74(m,1H),2.70–2.80(m,1H),2.80–2.89(m,2H),7.17(s,1H),7.30–7.59(m,20H),7.69–7.77(m,4H),7.84–7.92(m,1H),8.14(s,1H)。
Example 2
Synthesis of Compound 9
Figure BDA0004156775850000271
1) Synthesis of intermediate 9-1
To a reaction vessel were charged 35.2 g (100 mmol) of compound 9-A, 25.7 g (100 mmol) of compound 20-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 39.6 g of compound 9-1, 99.3% pure by HPLC, yield 75%. LC MS: M/Z527.24 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.15–1.25(m,4H),1.27–1.39(m,3H),1.35–1.43(m,3H),1.39–1.48(m,3H),1.43–1.55(m,2H),1.90(m,2H),2.15(m,2H),6.92(s,1H),7.35(m,1H),7.46(m,1H),7.53(m,1H),7.56–7.72(m,3H),7.75(d,1H),7.78–7.94(m,4H),8.03(m,1H),8.27(d,1H),8.73–8.81(m,1H)。
2) Synthesis of intermediate 9-2
To a reaction vessel were charged under argon atmosphere 9-1.8 g (100 mmol) of compound 9-C23.3 g (100 mmol), 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) and stirred with heating 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 54.3 g of compound 9-2, 99.5% pure by HPLC, yield 80%. LC MS: M/Z567.26 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.15–1.25(m,4H),1.27–1.55(m,10H),1.90(m,2H),2.15(m,2H),6.92(s,1H),7.30–7.43(m,4H),7.38–7.57(m,6H),7.57–7.73(m,3H),7.69–7.78(m,3H),7.78–7.94(m,4H),7.99–8.07(m,1H),8.27(d,1H),8.73–8.81(m,1H)。
3) Synthesis of Compound 9
To the reaction vessel was added, under argon atmosphere, 9-2.0G (100 mmol) of compound, 9-D16.2G (100 mmol), 787 mg (1 mmol%) of XPhos Pd G3, 50ml (300 mmol) of 1.5M potassium phosphate and 1000ml (THF) of tetrahydrofuran, and the mixture was stirred under reflux for one night. 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 54.1 g of compound 9 in 71% yield and 99.9% purity by HPLC. LC MS: M/Z697.33 (M+).
1H NMR(400MHz,DMSO-d6)δ1.15–1.25(m,4H),1.27–1.55(m,11H),1.90(m,2H),1.93–2.08(m,2H),2.15(m,2H),2.63–2.74(m,1H),2.70–2.80(m,1H),2.80–2.89(m,2H),7.17(s,1H),7.30–7.43(m,5H),7.38–7.53(m,3H),7.48–7.58(m,4H),7.54–7.73(m,3H),7.69–
7.79(m,3H),7.84(m,1H),7.84–7.94(m,2H),7.99–8.07(m,1H),8.14(s,1H),8.27(d,1H),8.73–8.81(m,1H)。
Example 3
Synthesis of Compound 15
Figure BDA0004156775850000281
The procedure of example 2 was repeated except that the starting materials were changed to 15-A, 15-B, 15-C and 15-D. LCMS: M/Z808.33 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.93–2.08(m,2H),2.63–2.79(m,2H),2.76–2.89(m,2H),3.70–3.81(m,2H),3.81–3.92(m,2H),4.36(d,1H),4.61(d,1H),7.00(m,2H),7.04–7.14(m,8H),7.14–7.24(m,1H),7.19–7.29(m,5H),7.30–7.63(m,14H),7.77(t,1H),7.84–7.92(m,1H)。
Example 4
Synthesis of Compound 34
Figure BDA0004156775850000282
The procedure of example 2 was repeated except that the starting materials were changed to 34-A, 34-B, 34-C and 34-D. LCMS: M/Z773.40 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.06–1.23(m,6H),1.33–1.89(m,17H),2.37–2.45(m,2H),2.65–2.75(m,2H),6.67(m,1H),7.05–7.14(m,2H),7.21(m,1H),7.27(t,1H),7.31–7.39(m,2H),7.39–7.50(m,4H),7.50–7.60(m,3H),7.66–7.83(m,7H),7.88(m,1H),8.26(m,2H)。
Example 5
Synthesis of Compound 46
Figure BDA0004156775850000291
The procedure of example 2 was repeated except that the starting materials were changed to 46-A, 46-B, 46-C and 46-D. LCMS: M/Z787.38 (M+). Total synthesis yield: 53%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.42–1.96(m,15H),2.31(m,1H),2.52–2.62(m,1H),2.78–2.89(m,4H),7.08(d,1H),7.23(m,1H),7.30–7.63(m,14H),7.63–7.74(m,2H),7.73(m,3H),7.79–7.92(m,2H),7.99–8.10(m,4H),8.30(m,1H)。
Example 6
Synthesis of Compound 56
Figure BDA0004156775850000292
The procedure of example 2 was repeated except that the starting materials were changed to 56-A, 56-B, 56-C and 56-D. LCMS: M/Z783.32 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.48–1.63(m,2H),1.61(s,1H),1.58–1.70(m,2H),1.67(s,4H),1.68–1.75(m,1H),1.71(s,3H),1.73–1.85(m,1H),1.80–1.97(m,2H),2.34(m,1H),2.55–2.65(m,1H),3.23(m,2H),4.57–4.65(m,2H),6.87–6.95(m,2H),6.95–7.01(m,1H),7.17(s,1H),7.26–7.41(m,4H),7.41–7.58(m,8H),7.68(m,1H),7.82–7.92(m,3H),7.94–8.01(m,1H),8.03(m,1H),8.14(s,1H)。
Example 7
Synthesis of Compound 59
Figure BDA0004156775850000293
The procedure of example 2 was repeated except that the starting materials were changed to 59-A, 59-B, 59-C and 59-D. LCMS: M/Z761.34 (M+). Total synthesis yield: 38%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.20–1.36(m,2H),1.41–1.72(m,2H),1.90(m,1H),2.02(d,1H),2.15(m,1H),2.27(d,1H),2.36–2.46(m,2H),2.46–2.56(m,2H),2.63(s,5H),3.23(m,2H),4.53–4.69(m,2H),6.00(d,1H),6.93(d,1H),7.08(d,1H),7.30–7.61(m,15H),7.57–7.66(m,2H),7.69–7.77(m,3H),7.77–7.86(m,2H),7.86–7.92(m,1H)。
Example 8
Synthesis of Compound 79
Figure BDA0004156775850000301
The procedure of example 2 was repeated except that the starting materials were changed to 79-A, 79-B, 79-C and 79-D. LCMS: M/Z898.36 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.09–1.22(m,2H),1.34–1.72(m,9H),1.77(d,1H),1.84–
1.96(m,1H),2.02(d,1H),2.09–2.22(m,1H),5.75(d,1H),6.33(s,2H),6.54(d,1H),7.03–7.13(m,3H),7.30–7.67(m,19H),7.69–7.77(m,3H),7.84–7.96(m,3H),8.17–8.26(m,2H),8.45(m,1H)。
Example 9
Synthesis of Compound 92
Figure BDA0004156775850000302
The procedure of example 2 was repeated except that the starting materials were changed to 92-A, 92-B, 92-C and 92-D. LCMS: M/Z851.42 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.06–1.20(m,4H),1.24(m,6H),1.32–1.66(m,8H),1.59(s,5H),1.69(s,5H),1.90(m,2H),2.15(m,2H),3.03–3.13(m,1H),3.22–3.32(m,1H),6.91(m,1H),6.95–7.01(m,1H),7.17(s,1H),7.31(m,1H),7.31–7.39(m,2H),7.35–7.41(m,1H),7.46(m,3H),7.50–7.58(m,5H),7.68(m,1H),7.79(m,1H),7.82–7.92(m,3H),7.94–8.01(m,1H),8.03(m,1H),8.14(s,1H)。
Example 10
Synthesis of Compound 127
Figure BDA0004156775850000311
The procedure of example 1 was repeated except that the starting materials were changed to 127-A, 127-B and 127-C. LC MS: M/Z793.46 (M+). Total synthesis yield: 45%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.22(d,12H),1.31–1.57(m,16H),1.90(m,2H),2.15(m,2H),6.67(m,1H),7.10–7.20(m,2H),7.27(m,1H),7.33(s,1H),7.32–7.43(m,6H),7.43–7.51(m,4H),7.47–7.58(m,6H),7.69–7.77(m,4H),7.84–7.92(m,1H),8.14(s,1H)。
Example 11
Synthesis of Compound 143
Figure BDA0004156775850000312
The procedure of example 2 was repeated except that the starting materials were changed to 143-A, 143-B, 143-C and 143-D. LCMS: M/Z891.48 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.22(d,12H),1.31–1.57(m,16H),1.90(m,2H),2.15(m,2H),6.67(m,1H),7.10–7.21(m,3H),7.27(m,1H),7.31–7.43(m,4H),7.43–7.50(m,4H),7.45–7.58(m,6H),7.62–7.69(m,3H),7.69–7.77(m,2H),7.84–7.92(m,1H),8.14(s,1H),8.17–8.24(m,3H)。
Example 12
Synthesis of Compound 168
Figure BDA0004156775850000313
The procedure of example 2 was repeated except that the starting materials were changed to 168-A, 168-B, 168-C and 168-D. LCMS: M/Z762.36 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.09–1.23(m,2H),1.32–1.71(m,11H),1.84–1.96(m,1H),2.08–2.21(m,1H),6.95–7.03(m,2H),7.08(d,1H),7.30–7.67(m,20H),7.68–7.77(m,3H),7.82–7.92(m,2H),8.16–8.28(m,2H),8.64(d,1H)。
Example 13
Synthesis of Compound 188
Figure BDA0004156775850000321
The procedure of example 2 was repeated except that the starting materials were changed to 188-A, 188-B, 188-C and 188-D. LCMS: M/Z660.31 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.09–1.22(m,2H),1.32–1.71(m,11H),1.90(m,1H),2.08–2.21(m,1H),2.85(s,3H),2.98(m,2H),3.61(t,2H),7.04(m,1H),7.08–7.15(m,1H),7.17(s,2H),7.23–7.60(m,18H),7.69–7.77(m,4H),7.80–7.92(m,2H),8.00(m,1H),8.14(s,1H)。
Example 14
Synthesis of Compound 206
Figure BDA0004156775850000322
The procedure of example 2 was repeated except that the starting materials were changed to 206-A, 206-B, 206-C and 206-D. LCMS: M/Z850.43 (M+). Total synthesis yield: 38%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.15(m,2H),1.17–1.27(m,1H),1.27–1.38(m,1H),1.34–1.47(m,2H),1.49–1.69(m,4H),1.81–1.89(m,1H),1.90–2.02(m,1H),2.04–2.11(m,1H),2.07–2.20(m,2H),2.15–2.27(m,1H),2.60–2.81(m,2H),3.52(m,2H),7.01–7.14(m,2H),7.17(s,2H),7.14–7.22(m,1H),7.29–7.63(m,21H),7.69–7.77(m,4H),7.80–7.92(m,2H),8.10–8.18(m,2H)。
Example 15
Synthesis of Compound 227
Figure BDA0004156775850000331
The procedure of example 2 was repeated except that the starting materials were changed to 227-A, 227-B, 228-C and 227-D. LCMS: M/Z791.42 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.07–1.21(m,4H),1.34–1.46(m,2H),1.48–1.80(m,6H,),1.71(s,2H),1.75–1.86(m,2H),1.80–1.88(m,1H),3.79(t,2H),4.11(t,2H),4.38(s,2H),7.05–7.14(m,2H),7.18(m,1H),7.30–7.58(m,16H),7.59–7.69(m,3H),7.69–7.80(m,4H),7.88(m,1H)。
Example 16
Synthesis of Compound 243
Figure BDA0004156775850000332
The procedure of example 2 was repeated except that the starting materials were changed to 243-A, 243-B, 243-C and 243-D. LCMS: M/Z762.40 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.09–1.22(m,2H),1.34–1.72(m,9H),1.77(d,1H),1.84–
1.96(m,1H),2.02(d,1H),2.10(s,3H),2.09–2.22(m,1H),3.62(d,4H),7.17(s,1H),7.30–7.51(m,8H),7.47–7.98(m,15H),7.99–8.07(m,1H),8.14(s,1H),8.27(d,1H),8.73–8.81(m,1H)。
Example 17
Synthesis of Compound 279
Figure BDA0004156775850000333
The procedure of example 2 was repeated except that the starting materials were changed to 279-A, 279-B, 279-C and 279-D. LCMS: M/Z787.42 (M+). Total synthesis yield: 37%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.31–1.58(m,12H),1.84–2.08(m,6H),2.15(m,2H),2.63–2.89(m,9H),7.17(s,1H),7.30–7.79(m,16H),7.84(m,1H),7.89(m,2H),7.99–8.07(m,1H),8.14(s,1H),8.27(d,1H),8.73–8.81(m,1H)。
Example 18
Synthesis of Compound 300
Figure BDA0004156775850000341
The procedure of example 2 was repeated except that the starting materials were changed to 300-A, 300-B, 300-C and 300-D. LCMS: M/Z854.46 (M+). Total synthesis yield: 41%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.31–1.58(m,14H),1.66–1.76(m,1H),1.71–1.81(m,1H),1.76–1.86(m,2H),1.82–1.90(m,2H),1.86–1.96(m,3H),2.15(m,2H),2.41(d,1H),2.65(s,1H),2.64–2.75(m,5H),7.04(m,1H),7.05–7.17(m,3H),7.19(t,1H),7.30–7.40(m,5H),7.40–7.50(m,5H),7.50–7.58(m,2H),7.58–7.67(m,2H),7.67–7.78(m,3H),7.73–7.83(m,1H),7.88(m,1H),8.15–8.25(m,2H)。
Example 19
Synthesis of Compound 318
Figure BDA0004156775850000342
The procedure of example 2 was repeated except that the starting materials were changed to 318-A, 318-B, 318-C and 318-D. LCMS: M/Z954.47 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.31–1.45(m,6H),1.41–1.57(m,6H),1.90(m,2H),2.15(m,2H),3.29(s,4H),7.00–7.11(m,4H),7.08–7.17(m,2H),7.20(m,1H),7.26–7.50(m,19H),7.50–7.58(m,2H),7.58–7.67(m,2H),7.67–7.79(m,4H),7.74–7.83(m,1H),7.88(m,1H),8.15–8.25(m,2H)。
Example 20
Synthesis of Compound 338
Figure BDA0004156775850000343
The procedure of example 2 was repeated except that the starting materials were changed to 338-A, 338-B, 338-C and 338-D. LCMS: M/Z796.44 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.02(s,8H),1.09–1.48(m,6H),1.49–1.70(m,3H),1.81–
1.89(m,1H),1.96(m,1H),2.05–2.13(m,1H),2.15–2.27(m,1H),2.75–2.91(m,2H),3.26(m,1H),3.48(m,1H),4.34(m,1H),4.50(m,1H),6.44(m,1H),6.80(m,1H),6.87(t,1H),6.99–7.07(m,2H),7.09–7.27(m,5H),7.30–7.40(m,2H),7.36–7.44(m,4H),7.40–7.53(m,7H),7.53(m,1H),7.59(d,1H),7.71–7.80(m,2H),7.82–7.92(m,2H)。
Example 21
Synthesis of Compound 356
Figure BDA0004156775850000351
The procedure of example 2 was repeated except that the starting materials were changed to 356-A, 356-B, 356-C and 356-D. LCMS: M/Z869.48 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.00(m,2H),1.25(m,2H),1.35–1.96(m,19H),2.02(d,1H),2.09–2.22(m,1H),2.57–2.65(m,3H),6.44(m,1H),6.80(m,1H),6.87(t,1H),6.99–7.07(m,2H),7.09–7.27(m,5H),7.30–7.63(m,16H),7.68(m,1H),7.71–7.79(m,3H),7.79–7.92(m,2H)。
Example 22
Synthesis of Compound 378
Figure BDA0004156775850000352
The procedure of example 2 was repeated except that the starting materials were changed to 378-A, 378-B, 378-C and 378-D. LCMS: M/Z954.45 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.09–1.21(m,2H),1.32–1.48(m,3H),1.48(m,2H),1.48–
1.69(m,9H),1.71(s,3H),1.84–1.96(m,1H),2.15(m,1H),4.59(d,2H),5.14(s,2H),6.95–7.01(m,1H),7.06(m,1H),7.14–7.21(m,2H),7.29–7.57(m,17H),7.58–7.70(m,4H),7.82–7.92(m,3H),8.14(s,1H),8.17–8.25(m,4H)。
Example 23
Synthesis of Compound 399
Figure BDA0004156775850000361
The procedure of example 2 was repeated except that the starting materials were changed to 399-A, 399-B, 399-C and 399-D. LCMS: M/Z893.43 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.09–1.23(m,2H),1.32–1.72(m,10H),1.84–1.96(m,1H),2.08–2.22(m,1H),3.08(t,2H),3.68(t,2H),6.00(s,2H),6.88(m,1H),6.98–7.14(m,5H),7.15–7.67(m,23H),7.67–7.83(m,3H),7.88(m,1H),8.16–8.27(m,2H)。
Example 24
Synthesis of Compound 420
Figure BDA0004156775850000362
The procedure of example 2 was repeated except that the starting materials were changed to 420-A, 420-B, 420-C and 420-D. LCMS: M/Z968.45 (M+). Total synthesis yield: 40%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.15–1.25(m,4H),1.27–1.55(m,11H),1.90(m,2H),2.15(m,2H),5.12(d,1H),7.00(d,1H),7.05–7.11(m,2H),7.30–7.66(m,22H),7.66–7.79(m,7H),7.88(m,1H),7.96(t,1H),8.16–8.28(m,2H),8.64(d,1H)。
Example 25
Synthesis of Compound 450
Figure BDA0004156775850000363
The procedure of example 2 was repeated except that the starting materials were changed to 450-A, 450-B, 450-C and 450-D. LCMS: M/Z1068.56 (M+). Total synthesis yield: 39%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ0.87(s,6H),1.20(s,8H),1.43(m,4H),1.60(m,2H),1.69(s,6H),1.90(m,2H),2.15(m,2H),3.10(m,2H),6.95–7.01(m,1H),7.06(m,1H),7.13–7.24(m,3H),7.29–7.61(m,18H),7.62–7.70(m,3H),7.71–7.78(m,2H),7.78–7.92(m,4H),8.14(s,1H),8.17–8.28(m,4H)。
Device example 1: preparation of organic electroluminescent device
Figure BDA0004156775850000371
The preparation process comprises the following steps: a transparent anode ITO film layer (thickness 150 nm) was formed on a glass substrate to obtain a first electrode as an anode. Then, a mixed material of the compound T-1 and the compound T-2 is evaporated on the surface of the anode by a vacuum evaporation method to serve as a hole injection layer, wherein the mixing ratio is 3:97 (mass ratio), and the thickness is 10nm. And evaporating a compound T-2 with the thickness of 100nm on the hole injection layer to obtain a first layer of hole transport layer. Then, the compound 1 of the present invention was evaporated on the first hole transport layer to a thickness of 10nm to obtain a second hole transport layer. On the second hole transport layer, the compound T-3 and the compound T-4 were co-evaporated at a mass ratio of 95:5 to form an organic light emitting layer having a thickness of 40 nm. Then, on the organic light-emitting layer, a hole blocking layer (thickness 10 nm) was formed by vapor deposition of the compound T-5 in this order, and an electron transport layer (thickness 30 nm) was formed by mixing the compound T-6 and LiQ in a ratio of 4:6 (mass ratio). Finally, magnesium (Mg) and silver (Ag) are mixed at an evaporation rate of 1:9, and vacuum evaporation is performed on the electron injection layer to form a second electrode 109, thereby completing the manufacture of the organic light-emitting device.
Device examples 2 to 25
An organic electroluminescent device was fabricated in the same manner as in device example 1, except that compound 9, 15, 34, 46, 56, 59, 79, 92, 127, 143, 168, 188, 206, 227, 243, 279, 300, 318, 338, 356, 378, 399, 420, and 450 was used instead of compound 1 in forming the second hole transport layer, respectively.
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 1, respectively, in forming the second hole transport layer.
The operating voltage and efficiency of the organic electroluminescent device prepared above were calculated by a computer-controlled Keithley 2400 test system. The device lifetime in dark conditions was obtained using a polar onix (McScience co.) lifetime measurement system equipped with a power supply and a photodiode as detection units. Each set of devices example and device comparative example 1 were produced and tested in the same batch as the devices of device comparative example 2, the operating voltage, efficiency and lifetime of the devices of device comparative example 1 were each noted as 1, and the ratios of the corresponding indices of device examples 1 to 25, device comparative example 2 and device comparative example 1 were calculated, respectively, as shown in table 1.
Table 1 test results for device examples 1 to 25 and device comparative examples 1 to 2
A second hole transport layer Relative operating voltage Relative efficiency Relative life span
Device comparative example 1 HT-1 1 1 1
Device comparative example 2 HT-2 1.042 1.021 1.181
Device example 1 Compound 1 0.973 1.152 1.615
Device example 2 Compound 9 0.964 1.131 1.416
Device example 3 Compound 15 0.952 1.145 1.367
Device example 4 Compound 34 0.965 1.161 1.710
Device example 5 Compound 46 0.947 1.134 1.756
Device example 6 Compound 56 0.958 1.127 1.546
Device example 7 Compound 59 0.932 1.167 1.681
Device example 8 Compound 79 0.967 1.153 1.371
Device example 9 Compound 92 0.937 1.132 1.657
Device example 10 Compound 127 0.942 1.169 1.543
Device example 11 Compound 143 0.957 1.124 1.448
Device example 12 Compound 168 0.938 1.097 1.687
Device example 13 Compound 188 0.956 1.096 1.357
Device example 14 Compound 206 0.971 1.145 1.268
Device example 15 Compound 227 0.965 1.176 1.701
Device example 16 Compound 243 0.973 1.156 1.281
Device example 17 Compound 279 0.938 1.131 1.564
Device example 18 Compound 300 0.945 1.151 1.813
Device example 19 Compound 318 0.987 1.167 1.562
Device example 20 Compound 338 0.937 1.158 1.754
Device example 21 Compound 356 0.945 1.168 1.435
Device example 22 Compound 378 0.966 1.101 1.587
Device example 23 Compound 399 0.953 1.173 1.548
Device example 24 Compound 420 0.969 1.134 1.690
Device example 25 Compound 450 0.941 1.137 1.312
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 25 all had lower voltages, improved luminous efficiency (up to 20%) and improved lifetime by 40% or more, as compared with the devices formed from the compounds used in device comparative examples 1 to 2.
Therefore, the compound disclosed by the invention is applied to an organic device, so that the device has higher hole mobility, electrons and excitons can be effectively blocked from entering a hole transport layer, the efficiency of the device is improved, meanwhile, molecules have high stability, and the luminous efficiency and the service life of the device can be further improved.
In conclusion, the compound has great application value in organic photoelectric devices.
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 (17)

1. A spiro compound having a chemical structure represented by formula (i):
Figure FDA0004156775840000011
wherein: r is R a1 、R a2 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-C30 heteroaryl; m is selected from 1 to 4; when m is greater than 1, each R a1 The same or different;
X 1 ，X 2 identical or different, each independently selected from single bonds, -O-, -S-, -C (R) b1 )(R b2 )-、-N(R b3 )-、-Si(R b4 )(R b5 )-、-B(R b6 ) -, or a group as follows:
Figure FDA0004156775840000012
Y 1 ～Y 11 each independently selected from-C (R) 1 )(R 2 )-、-N(R 3 )-、-Si(R 4 )(R 5 )-、-B(R 6 ) -, -O-or-S-;
the group G is selected from one or more of the following groups:
Figure FDA0004156775840000013
Ar 3 selected from substituted or unsubstituted C6 to C30 aryl, or substituted or unsubstituted C3 to C30 heteroaryl; z is Z 1 -Z 12 Each independently selected from-C (R) 7 )(R 8 )-、-N(R 9 )-、-Si(R 10 )(R 11 )-、-B(R 12 ) -, -O-or-S-;
R b1～ R b6 、R 1 ～R 12 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-C30 heteroaryl;
n is selected from 1 to 2, and when n is 2, each G is the same or different;
E 1 ～E 3 the same or different, each independently selected from a single bond, a substituted or unsubstituted C6 to C30 arylene, or a substituted or unsubstituted C3 to C30 heteroarylene;
Ar 1 and Ar is a group 2 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.
2. The spiro compound according to claim 1, wherein R is a1 、R a2 Each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched chain C1-C10 alkyl; a substituted or unsubstituted C1-C10 heteroalkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C3-C10 heterocycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C3-C20 heteroaryl group; preferably, said R a1 、R a2 Each independently selected from hydrogen, or deuterium;
and/or m is selected from 1, 2, 3 or 4; when m is greater than 1, each R a1 The same or different;
and/or R b1～ R b6 Identical or differentAnd, independently, hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C10 alkyl; an alkoxy group of a substituted or unsubstituted C1 to C12, an alkylthio group of a substituted or unsubstituted C1 to C12, a cycloalkyl group of a substituted or unsubstituted C3 to C10, a heterocycloalkyl group of a substituted or unsubstituted C3 to C10, an aryl group of a substituted or unsubstituted C6 to C30, or a heteroaryl group of a substituted or unsubstituted C3 to C20;
and/or R 7 -R 12 The same or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C10 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C3-C10 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, or substituted or unsubstituted C3-C20 heteroaryl;
And/or n is selected from 1 or 2.
3. The spiro compound of claim 1, wherein Y 1 ～Y 11 Each independently selected from-C (R) 1 )(R 2 )-、-N(R 3 )-、-Si(R 4 )(R 5 )-、-B(R 6 ) -, -O-or-S-; r is R 1 -R 6 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, or substituted or unsubstituted C3-C20 heteroaryl.
4. The spiro compound according to claim 1, wherein X is 1 、X 2 Each independently selected from any one of the following structures:
Figure FDA0004156775840000031
and/or X 1 、X 2 Each independently selected from single bond, -O-, -S-, -CH 2 -、-C(CH 3 ) 2 -、-NH-、-N(CH 3 )-、-
N(Ph)-、-Si(H 2 )-、-Si(CH 3 ) 2 -、-B(H)-、-B(CH 3 )-、-B(Ph)-。
5. The spiro compound of claim 1, wherein said group G is selected from any one of the following groups:
Figure FDA0004156775840000032
wherein Z is 1 -Z 12 As defined in claim 1.
6. The spiro compound of claim 1, wherein said group G is selected from any one of the following groups:
Figure FDA0004156775840000033
Figure FDA0004156775840000041
wherein:
R 13 -R 22 each independently selected from one or more of hydrogen, deuterium, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C3-C60 cycloalkyl, substituted or unsubstituted C1-C60 heteroalkyl, substituted or unsubstituted C3-C60 heterocycloalkyl, substituted or unsubstituted C5-C60 aryl, or substituted or unsubstituted C3-C60 heteroaryl.
7. The spiro compound according to claim 1, further characterized by Ar 3 The radical forming the merging ring is selected from any one or more of the following structuresAny one or more of the following groups may be substituted with Ar 3 Bonding to form a group G;
Figure FDA0004156775840000042
Figure FDA0004156775840000051
wherein R is C Selected from C1-C10 alkyl, C6-C30 aryl or C5-C30 heteroaryl.
8. The spiro compound according to claim 1, wherein E 1 ～E 3 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 phenanthrylene group, a,
Figure FDA0004156775840000052
Figure FDA0004156775840000053
9. The spiro compound according to claim 1, wherein Ar 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, and,
Figure FDA0004156775840000054
Figure FDA0004156775840000055
10. The spiro compound according to any one of claims 1-9, wherein the chemical structure of the compound is represented by formula (ii):
Figure FDA0004156775840000056
wherein Ra is 1 、Ra 2 Each independently selected from hydrogen, deuterium;
R b1 and R is b2 Independently selected from substituted or unsubstituted straight or branched chain C1-C30 alkyl groups; an alkoxy group of a substituted or unsubstituted C1 to C12, an alkylthio group of a substituted or unsubstituted C1 to C12, a cycloalkyl group of a substituted or unsubstituted C3 to C30, a heterocycloalkyl group of a substituted or unsubstituted C3 to C30, an aryl group of a substituted or unsubstituted C6 to C30, or a heteroaryl group of a substituted or unsubstituted C6 to C30; or bonded to an adjacent group to form a ring;
E1 is a single bond or phenyl;
A、E 2 、E 2 、Ar 1 、Ar 2 as defined in claim 1.
11. The compound of claim 8, wherein the chemical structure of the compound is represented by formulas (iii) to (vi):
Figure FDA0004156775840000061
Ra 1 、Ra 2 、G、E 2 、E 3 、Ar 1 、Ar 2 as defined in claim 10.
12. The spiro compound according to any one of claims 1-11, wherein said spiro compound is selected from any one or more of the following chemical structures:
Figure FDA0004156775840000062
Figure FDA0004156775840000071
Figure FDA0004156775840000081
Figure FDA0004156775840000091
Figure FDA0004156775840000101
/>
Figure FDA0004156775840000111
/>
Figure FDA0004156775840000121
/>
Figure FDA0004156775840000131
/>
Figure FDA0004156775840000141
13. an organic layer comprising the spiro compound of any one of claims 1-12.
14. Use of the spiro compound according to any one of claims 1 to 12 and/or the organic layer according to claim 13 in an organic optoelectronic device.
15. An organic optoelectronic device comprising a first electrode, a second electrode, and the organic layer of claim 13, 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.
16. The organic optoelectronic device according to claim 15, 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.
17. A display or lighting device comprising an organic optoelectronic device according to any one of claims 15 to 16.
CN202310337165.7A 2023-03-31 2023-03-31 Spiro compound and application thereof in organic photoelectric device Pending CN116332770A (en)

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