CN111620890A - Compound, organic electronic device comprising same, and display device or lighting device - Google Patents

Compound, organic electronic device comprising same, and display device or lighting device Download PDF

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CN111620890A
CN111620890A CN202010556648.2A CN202010556648A CN111620890A CN 111620890 A CN111620890 A CN 111620890A CN 202010556648 A CN202010556648 A CN 202010556648A CN 111620890 A CN111620890 A CN 111620890A
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CN111620890B (en
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蒋佐权
廖良生
屈扬坤
郑琦
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Suzhou University
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Abstract

The present invention relates to a compound, an organic electronic device including the same, and a display device and a lighting device, the compound including a compound represented by the following general formula (1):
Figure DSA0000211705160000011
wherein, Y, Z, R1To R18G and A are defined in the specification. The main functional elements of the compound represented by the general formula (1) realize intramolecular interaction through space unconjugated connection, the material has excellent luminous performance, can be used as a material of an organic material layer of an organic light-emitting device, particularly a material of a core light-emitting layer, and realizes high efficiency of an organic light-emitting diode device.

Description

Compound, organic electronic device comprising same, and display device or lighting device
Technical Field
The invention relates to a compound, an organic electronic device containing the compound, and a display device or a lighting device, and belongs to the technical field of organic electronics.
Background
Organic electronic devices are typified by Organic Light Emitting devices, and a typical example of the Organic Light Emitting devices is Organic Light Emitting Diodes (OLEDs). An organic light emitting diode is a current-driven light emitting device using an organic material as an active material, and particularly refers to a technology in which an organic semiconductor material and an organic light emitting material emit light by carrier injection and recombination under the drive of an electric field. Different from inorganic materials, organic materials have the characteristics of low synthesis cost, adjustable functions, flexibility and good film forming property. And the device based on the organic material is generally simple in manufacturing process, easy to prepare in a large area, environment-friendly, and capable of adopting a thin film preparation method with lower operation temperature, so that the device has the advantage of low manufacturing cost, has great application potential and arouses wide attention and research of scholars at home and abroad in the last 30 years. Illumination devices and display devices based on OLEDs lighting technology are currently commercialized.
In order to improve the efficiency of the organic light emitting diode, various organic materials have been developed, such as organic fluorescent materials, organic phosphorescent materials, organic thermally activated delayed fluorescent materials, host materials, hole transport materials, electron transport materials, and the like. Fluorescent materials have good reliability but low efficiency. Phosphorescent and thermally activated delayed fluorescence materials are highly efficient, but the Roll-off effect is significant, limiting their use at high brightness.
It is of great importance to develop new, efficient organic materials that can be used in the OLED field.
Disclosure of Invention
The present invention aims to provide an organic compound having a spiro structure, an organic electronic device including the same, and a display device or a lighting device.
In order to achieve the purpose, the invention provides the following technical scheme: a compound comprising a compound represented by the following general formula (1):
Figure BSA0000211705180000021
wherein Y is selected from a direct bond, O, S, S (═ O)2Either CR 'R' or Se;
z is selected from O, S, or CRaRbAny one of (a);
R1to R18、R′、R″、RaAnd RbEach independently selected from hydrogen, deuterium, halogen groups, nitrile groups; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted alkylA sulfur radical; substituted or unsubstituted arylthio; substituted or unsubstituted alkylsulfonyl; substituted or unsubstituted arylsulfonyl; substituted or unsubstituted alkenyl; substituted or unsubstituted silyl; a substituted or unsubstituted boron group; substituted or unsubstituted amine groups; a substituted or unsubstituted aryl phosphine group; a substituted or unsubstituted phosphine oxide group; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; substituted or unsubstituted heterocyclyl; or may be bonded to an adjacent group to form a ring;
g is selected from a direct bond, a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30;
a is selected from hydrogen, deuterium, a halogen group, a nitrile group, a sulfone group, a carbonyl group, an ester group, a substituted or unsubstituted aliphatic group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aralkenyl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group.
Further, in the compound represented by the general formula (1), a is selected from hydrogen, deuterium, a halogen group; a nitrile group; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio; substituted or unsubstituted arylthio; substituted or unsubstituted alkylsulfonyl; substituted or unsubstituted arylsulfonyl; substituted or unsubstituted alkenyl; substituted or unsubstituted silyl; a substituted or unsubstituted boron group; substituted or unsubstituted amine groups; a substituted or unsubstituted aryl phosphine group; a substituted or unsubstituted phosphine oxide group; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; substituted or unsubstituted heterocyclyl.
The invention also provides an organic light-emitting device which comprises a first electrode and a second electrode which are oppositely arranged, wherein an organic material layer is arranged between the first electrode and the second electrode, the organic material layer comprises a light-emitting layer, and the light-emitting layer contains the compound.
Further, the light emitting layer is composed of a sensitizing material, a light emitting material, and a host material, and the compound is used as any one or more of the sensitizing material, the light emitting material, or the host material.
Further, the organic material layer further comprises a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer and an electron injection layer, and the organic light emitting device is provided with the second electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the electron transport layer and the first electrode in sequence from the height direction.
Further, the compound is contained in one or more layers of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer.
Further, the organic light emitting device referred to in the present specification includes front side light emitting, rear side light emitting, and both side light emitting.
Further, the "front side" in the present specification means the farthest from the substrate, and the "rear side" means the closest to the substrate.
The present invention also provides a display device or a lighting device including the above organic light emitting device.
Compared with the prior art, the invention has the beneficial effects that: the compound of the present invention can be used as a material for an organic material layer in an organic light emitting device. The compound according to at least one exemplary embodiment of the present specification as a host material may realize a high-efficiency organic light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a light emitting material may realize a high efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a sensitizing material can realize a high-efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a hole transport material may realize a high-efficiency light emitting device while realizing a low driving voltage.
The compound described in this specification can be used as a material for hole injection, hole transport, hole injection and hole transport, light emission, electron transport, electron blocking, or electron injection. In addition, the compounds described in the present specification can also be used for materials of organic photovoltaic devices or organic transistors.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood and to be implemented in accordance with the content of the description, the following detailed description is given with reference to the accompanying drawings and preferred exemplary embodiments of the present invention.
Drawings
Fig. 1 shows an example of an organic light emitting device composed of a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4;
fig. 2 shows an example of an organic light emitting device composed of a substrate 1, a first electrode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 8, a light emitting layer 3, an electron transport layer 7, an electron injection layer 9, and a second electrode 4.
Reference numerals
1: substrate
2: a first electrode
3: luminescent layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: electron blocking layer
8: electron transport layer
9: electron injection layer
Detailed Description
The following detailed description of specific embodiments of the invention is provided in connection with the accompanying drawings and the exemplary embodiments. The following exemplary embodiments are provided to illustrate the present invention, but are not intended to limit the scope of the present invention.
The terms in this specification are to be interpreted:
"substituted or unsubstituted" means unsubstituted or substituted with one or more substituents selected from the group consisting of: deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amine group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamino group, an aralkylamino group, a heteroarylamino group, an arylamino group, an arylphosphine group; and a heterocyclic group, or a substituent which is unsubstituted or linked by two or more substituents among the substituents exemplified above. For example, "a substituent to which two or more substituents are attached" may be a biphenyl group. That is, biphenyl can also be an aryl group, and can be interpreted as a substituent with two phenyl groups attached.
In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.
In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40. Specifically, the carbonyl group may be a compound having the following structure, but is not limited thereto.
Figure BSA0000211705180000051
In the present specification, with respect to the ester group, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, the ester group may be a compound having the following structural formula, but is not limited thereto.
Figure BSA0000211705180000052
In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25. Specifically, the imide group may be a compound having the following structure, but is not limited thereto.
Figure BSA0000211705180000053
Figure BSA0000211705180000061
In the present specification, the number of carbon atoms of the amide group is not particularly limited, but is preferably 1 to 25. Specifically, the amide group may be a compound having the following structure, but is not limited thereto.
Figure BSA0000211705180000062
In the present specification, the silyl group may be represented by the formula-SiRaRbRcIs represented by Ra、RbAnd RcMay each be hydrogen; substituted or unsubstituted alkyl; or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, and the like.
In this specification, the boron group may be represented by the formula-BRaRbIs represented by Ra、RbMay each be hydrogen; substituted or unsubstituted alkyl; or a substituted or unsubstituted aryl group. Specific examples of the boron group include a dimethyl boron group, a diethyl boron group, a tert-butyl methyl boron group, a diphenyl boron group, a phenyl boron group and the like, but are not limited thereto.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms of the alkyl group is from 1 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkyl group is from 1 to 10. According to yet another exemplary embodiment, the number of carbon atoms of the alkyl group is from 1 to 6. Specific examples of the alkyl group include 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, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, n-butyl, Isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.
In the present specification, an alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 40. Specific examples thereof include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, isopropyloxy group, n-butoxy group, isobutoxy group, t-butoxy group, sec-butoxy group, n-pentyloxy group, neopentyloxy group, isopentyloxy group, n-hexyloxy group, 3-dimethylbutyloxy group, 2-ethylbutoxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, benzyloxy group, p-methylbenzyloxy group and the like, but are not limited thereto.
Substituents described in this specification that contain alkyl, alkoxy, and other alkyl moieties include both straight chain and branched chain forms.
In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms thereof is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the number of carbon atoms of the alkenyl group is 2 to 20. According to another exemplary embodiment, the number of carbon atoms of the alkenyl group is 2 to 10. According to yet another exemplary embodiment, the number of carbon atoms of the alkenyl group is 2 to 6. Specific examples thereof include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-methyl-1-butenyl, 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-diphenylvinyl-1-yl, 2-phenyl-2- (naphthyl-1-yl) vinyl-1-yl, 2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl, styryl and the like, but are not limited thereto.
In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 40. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is from 3 to 20. According to yet another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3, 4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl and the like, but are not limited thereto.
In the present specification, the number of carbon atoms of the alkylamino group is not particularly limited, but is preferably 1 to 40. Specific examples of the alkylamino group include, but are not limited to, methylamino, dimethylamino, ethylamino, diethylamino, phenylamino, naphthylamino, biphenylamino, anthracylamino, 9-methyl-anthracylamino, diphenylamino, phenylnaphthylamino, ditolylamino, phenyltolylamino, triphenylamino, and the like.
In the present specification, examples of arylamine groups include substituted or unsubstituted monoarylamine groups, substituted or unsubstituted diarylamine groups, or substituted or unsubstituted triarylamine groups. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. An arylamine group comprising two or more aryl groups can comprise a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group.
Specific examples of the arylamine group include a phenylamino group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methyl-phenylamino group, a 4-methyl-naphthylamine group, a 2-methyl-biphenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a carbazolyl group, a triphenylamine group and the like, but are not limited thereto.
In the present specification, examples of heteroarylamino groups include a substituted or unsubstituted monoheteroarylamino group, a substituted or unsubstituted diheteroarylamino group, or a substituted or unsubstituted triheteroarylamino group. The heteroaryl group in the heteroarylamino group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. Heteroaryl amine groups comprising two or more heterocyclic groups may comprise a monocyclic heterocyclic group, a polycyclic heterocyclic group, or both a monocyclic heterocyclic group and a polycyclic heterocyclic group.
In the present specification, examples of the arylphosphino group include a substituted or unsubstituted monoarylphosphino group, a substituted or unsubstituted diarylphosphino group, or a substituted or unsubstituted triarylphosphino group. The aryl group in the arylphosphino group may be a monocyclic aryl group or a polycyclic aryl group. The arylphosphino group comprising two or more aryl groups may comprise a monocyclic aryl group, a polycyclic aryl group, or both a monocyclic aryl group and a polycyclic aryl group.
In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 30. According to an exemplary embodiment, the number of carbon atoms of the aryl group is 6 to 20. When the aryl group is a monocyclic aryl group, examples of the monocyclic aryl group include phenyl, biphenyl, terphenyl, and the like, but are not limited thereto. Examples of polycyclic aryl groups include naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, indenyl, pyrenyl,
Figure BSA0000211705180000082
A fluorenyl group, a triphenylene group, etc., but is not limited thereto.
In the present specification, a fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro ring structure.
When the fluorenyl group is substituted, the fluorenyl group can be
Figure BSA0000211705180000081
Figure BSA0000211705180000091
And
Figure BSA0000211705180000092
however, the fluorenyl group is not limited thereto.
In the present specification, the heterocyclic group is a heterocyclic group containing one or more of N, O, P, S, Si and Se as a heteroatom, and the number of carbon atoms thereof is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the number of carbon atoms of the heterocyclic group is 1 to 30. Examples of heterocyclic groups include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, oxazinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, pyrimidinyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindolyl, noinyl, indolinyl, oxazinyl, phthalazinyl, acridinopyrimidyl, pyridopyrazinyl, pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzoxazolyl carbazolyl, pyrazyl, triazinyl, tetrazinyl, pyridopyrazinyl, pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, quinoxalyl, naphthyryl, benzofuranyl, dibenzofuranyl, dibenzocarbazolyl, indolocarbazolyl, indenocarbazolyl, phenazinyl, imidazopyridinyl, phenoxazinyl, phenanthridinyl, phenanthrolinyl, phenothiazinyl, imidazopyridinyl, imidazophenanthridinyl, benzimidazoloquinazolinyl or benzimidazolophenanthridinyl and the like, but are not limited thereto.
In this specification, the above description of heterocyclyl groups may be applied to heteroaryl groups, with the exception that the heteroaryl groups are aromatic.
In the present specification, the above description of the aryl group can be applied to the aryl group among aryloxy groups, arylthio groups, arylsulfonyl groups, arylphosphino groups, aralkyl groups, aralkylamino groups, aralkenyl groups, alkylaryl groups, arylamino groups, and arylheteroarylamino groups.
In the present specification, the above description of the alkyl group can be applied to the alkyl group among the alkylthio group, the alkylsulfonyl group, the aralkyl group, the aralkylamino group, the alkylaryl group and the alkylamino group.
In this specification, the above description of heterocyclic groups can be applied to heteroaryl groups among heteroaryl, heteroarylamino and arylheteroarylamino groups.
In this specification, the germanium group may be represented by the formula-GeRaRbRcIs represented by Ra、RbAnd RcMay each be hydrogen; substituted or unsubstituted alkyl; or a substituted or unsubstituted aryl group. Specific examples of the germanium group include a trimethylgermanium group, a triethylgermanium group, a t-butyldimethylgermanium group and the like, but are not limited thereto.
In the present specification, the above description of the alkenyl group can be applied to the alkenyl group in the aralkenyl group.
In this specification, the above description of aryl groups applies to arylene groups, except that arylene groups are divalent.
In this specification, the above description of heteroaryl may apply to heteroarylene groups, with the difference that the heteroarylene group is divalent.
In the present specification, the meaning of combining with an adjacent group to form a ring means combining with an adjacent group to form a substituted or unsubstituted aliphatic hydrocarbon ring; a substituted or unsubstituted aromatic hydrocarbon ring; a substituted or unsubstituted aliphatic heterocycle; substituted or unsubstituted aromatic heterocycle; or a fused ring thereof.
In the present specification, an aliphatic hydrocarbon ring means a ring of a non-aromatic group constituted of only carbon atoms and hydrogen atoms as a ring. Specifically, examples of the aliphatic hydrocarbon ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1, 4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, and the like, but are not limited thereto.
In the present specification, the aromatic hydrocarbon ring means an aromatic ring composed of only carbon atoms and hydrogen atoms. Specifically, examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, triphenylene, phenalene, pyrene, tetracene, perylene,
Figure BSA0000211705180000101
Pentacene, fluorene, indene, acenaphthene, benzofluorene, spirofluorene and the likeBut is not limited thereto.
In the present specification, aliphatic heterocyclic ring means an aliphatic ring containing one or more hetero atoms. Specifically, examples of the aliphatic heterocyclic ring include ethylene oxide, tetrahydrofuran, 1, 4-dioxane, pyrrolidine, piperidine, morpholine, oxepane, azocane, thiacyclooctane and the like, but are not limited thereto.
In the present specification, aromatic heterocyclic ring means an aromatic ring comprising one or more heteroatoms. Specifically, examples of the aromatic heterocycle include pyridine, pyrrole, pyrimidine, pyridazine, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, triazine, pyrimidine, tetrazine, isoquinoline, quinoline, quinol, quinazoline, quinoxaline, naphthyridine, acridine, phenanthridine, naphthyridine, triazoline, indole, indolizine, benzothiazole, benzoxazole, benzimidazole, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, carbazole, benzocarbazole, dibenzocarbazole, phenazine, imidazopyridine, phenoxazine, phenanthridine, nocarbazole, indenocarbazole and the like, but are not limited thereto.
In the present specification, the aliphatic hydrocarbon ring, the aromatic hydrocarbon ring, the aliphatic heterocyclic ring and the aromatic heterocyclic ring may be monocyclic or polycyclic.
According to an exemplary embodiment of the present specification, the general formula (1) may be represented by any one of general formulae (2) to (19):
[ general formula (2) ]
Figure BSA0000211705180000111
In the general formula (2), R1To R18Same as defined in said general formula (1),
[ general formula (3) ]
Figure BSA0000211705180000112
In the general formula (3), R1To R18Same as defined in said general formula (1),
[ general formula (4) ]
Figure BSA0000211705180000121
In the general formula (4), R1To R18Same as defined in said general formula (1),
[ general formula (5) ]
Figure BSA0000211705180000122
In the general formula (5), R1To R18Same as defined in said general formula (1),
[ general formula (6) ]
Figure BSA0000211705180000123
In the general formula (6), R1To R18R 'and R' are the same as defined in said general formula (1),
[ general formula (7) ]
Figure BSA0000211705180000131
In the general formula (7), R1To R18Same as defined in said general formula (1),
[ general formula (8) ]
Figure BSA0000211705180000132
In the general formula (8), R1To R18Same as defined in said general formula (1),
[ general formula (9) ]
Figure BSA0000211705180000133
In the general formula (9)，R1To R18Same as defined in said general formula (1),
[ general formula (10) ]
Figure BSA0000211705180000141
In the general formula (10), R1To R18Same as defined in said general formula (1),
[ general formula (11) ]
Figure BSA0000211705180000142
In the general formula (11), R1To R18Same as defined in said general formula (1),
[ general formula (12) ]
Figure BSA0000211705180000143
In the general formula (12), R1To R18R 'and R' are the same as defined in said general formula (1),
[ general formula (13) ]
Figure BSA0000211705180000151
In the general formula (13), R1To R18′、RaAnd RbSame as defined in said general formula (1),
[ general formula (14) ]
Figure BSA0000211705180000152
In the general formula (14), R1To R18、RaAnd RbSame as defined in said general formula (1),
[ general formula (15) ]
Figure BSA0000211705180000153
In the general formula (15), R1To R18、RaAnd RbSame as defined in said general formula (1),
[ general formula (16) ]
Figure BSA0000211705180000161
In the general formula (16), R1To R18、RaAnd RbSame as defined in said general formula (1),
[ general formula (17) ]
Figure BSA0000211705180000162
In the general formula (17), R1To R18、RaAnd RbSame as defined in said general formula (1),
[ general formula (18) ]
Figure BSA0000211705180000163
In the general formula (18), R1To R18、R′、R″、RaAnd RbThe same as defined in said general formula (1), and
[ general formula (19) ]
Figure BSA0000211705180000171
In the general formula (19), R1To R18、RaAnd RbThe same as defined in said general formula (1).
In the structural formula, any one carbon is a linking moiety for forming a monovalent group, and the remaining carbons are hydrogen or a group in which one or two or more groups of substituents (e.g., a halogen group, a nitrile group, an alkyl group, a silyl group, an arylamino group, an arylphosphino group, an aryl group, and a heteroaryl group) are bonded.
According to an exemplary embodiment of the present invention, in the general formulae (2) to (6), G is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group.
According to an exemplary embodiment of the present invention, in the general formulae (2) to (6), G may be selected from a direct bond or the following structural formula.
Figure BSA0000211705180000172
Figure BSA0000211705180000181
Figure BSA0000211705180000191
According to an exemplary embodiment of the present invention, in the general formulae (2) to (6), a is selected from the following structural formulae.
Figure BSA0000211705180000192
Figure BSA0000211705180000201
Figure BSA0000211705180000211
Figure BSA0000211705180000221
Figure BSA0000211705180000231
Figure BSA0000211705180000241
Figure BSA0000211705180000251
Figure BSA0000211705180000261
Figure BSA0000211705180000271
Figure BSA0000211705180000281
Figure BSA0000211705180000291
Figure BSA0000211705180000301
Figure BSA0000211705180000311
Figure BSA0000211705180000321
Figure BSA0000211705180000331
Figure BSA0000211705180000341
According to an exemplary embodiment of the invention, Y is a direct bond, Z is O, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000351
Figure BSA0000211705180000361
Figure BSA0000211705180000371
According to an exemplary embodiment of the invention, Y is a direct bond, Z is S, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000372
Figure BSA0000211705180000381
Figure BSA0000211705180000391
Figure BSA0000211705180000401
According to an exemplary embodiment of the invention, Y is a direct bond and Z is C (CH)3)2，R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000402
Figure BSA0000211705180000411
Figure BSA0000211705180000421
Figure BSA0000211705180000431
According to an exemplary embodiment of the invention, Y is O, Z is O, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000432
Figure BSA0000211705180000441
Figure BSA0000211705180000451
Figure BSA0000211705180000461
According to an exemplary embodiment of the invention, Y is O, Z is S, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000462
Figure BSA0000211705180000471
Figure BSA0000211705180000481
Figure BSA0000211705180000491
According to an exemplary embodiment of the invention, Y is O and Z is C (CH)3)2，R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000492
Figure BSA0000211705180000501
Figure BSA0000211705180000511
Figure BSA0000211705180000521
According to an exemplary embodiment of the invention, Y is S, Z is O, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000531
Figure BSA0000211705180000541
Figure BSA0000211705180000551
Figure BSA0000211705180000561
According to an exemplary embodiment of the invention, Y is S, Z is S, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000562
Figure BSA0000211705180000571
Figure BSA0000211705180000581
Figure BSA0000211705180000591
According to an exemplary embodiment of the invention, Y is S and Z is C (CH)3)2，R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000592
Figure BSA0000211705180000601
Figure BSA0000211705180000611
Figure BSA0000211705180000621
According to an exemplary embodiment of the invention, Y is C (CH)3)2Z is O, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000631
Figure BSA0000211705180000641
Figure BSA0000211705180000651
Figure BSA0000211705180000661
According to an exemplary embodiment of the invention, Y is C (CH)3)2Z is S, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000662
Figure BSA0000211705180000671
Figure BSA0000211705180000681
Figure BSA0000211705180000691
According to the inventionIn an exemplary embodiment, Y is C (CH)3)2Z is C (CH)3)2，R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000692
Figure BSA0000211705180000701
Figure BSA0000211705180000711
Figure BSA0000211705180000721
According to an exemplary embodiment of the invention, Y is S (═ O)2Z is O, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000731
Figure BSA0000211705180000741
Figure BSA0000211705180000751
Figure BSA0000211705180000761
According to an exemplary embodiment of the invention, Y is S (═ O)2Z is S, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000762
Figure BSA0000211705180000771
Figure BSA0000211705180000781
Figure BSA0000211705180000791
According to an exemplary embodiment of the invention, Y is S (═ O)2Z is C (CH)3)2，R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000792
Figure BSA0000211705180000801
Figure BSA0000211705180000811
Figure BSA0000211705180000821
According to an exemplary embodiment of the invention, Y is Se, Z is O, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000822
Figure BSA0000211705180000831
Figure BSA0000211705180000841
Figure BSA0000211705180000851
Figure BSA0000211705180000861
According to an exemplary embodiment of the invention, Y is Se, Z is S, R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000862
Figure BSA0000211705180000871
Figure BSA0000211705180000881
Figure BSA0000211705180000891
According to an exemplary embodiment of the invention, Y is Se and Z is C (CH)3)2，R1To R18Is hydrogen or deuterium.
According to an exemplary embodiment of the present invention, the compound of the general formula (1) may be optionally one of the following compounds.
Figure BSA0000211705180000892
Figure BSA0000211705180000901
Figure BSA0000211705180000911
Figure BSA0000211705180000921
The compound of formula (1) can be prepared by the following reaction scheme.
< reaction formula 1>
Figure BSA0000211705180000922
In reaction formula 1, Y is the same as defined in general formula (1), G is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl.
< general reaction scheme 2>
Figure BSA0000211705180000931
In reaction formula 2, Y, Z is the same as defined in general formula (1), G is a direct bond, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a is a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl.
The reaction formula refers to an example in which a specific substituent is introduced, but if necessary, a person skilled in the art may introduce the substituent without using a technique known in the art, and when the substituent is introduced, the introduction may be performed by changing the kind or number of the substituent. Furthermore, the introduction can be performed by a person skilled in the art by changing the samples, reaction conditions or starting materials of the following reaction formulae using techniques known in the art.
For example, the compound represented by formula (1) may be prepared according to the above reaction formulas 1 to 2, substituents may be bonded thereto using a method known in the art, and the type, position or number of substituents may be changed according to a technique known in the art. The substituents may be bonded according to the above reaction formulae 1 to 2, however, the reaction is not limited thereto.
Figure BSA0000211705180000932
The invention also provides an organic light-emitting device prepared on the basis of the compound of the general formula (1), which comprises a first electrode and a second electrode which are oppositely arranged, wherein one or more organic material layers are arranged between the first electrode and the second electrode, the organic material layers comprise a light-emitting layer, and the light-emitting layer contains the compound. Wherein the light emitting layer is composed of any one or more of a sensitizing material, a light emitting material and a host material, and the compound is used as any one or more of the sensitizing material or the light emitting material. The organic material layer further comprises a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer and an electron injection layer, and the anode, the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode are sequentially arranged on the organic light emitting device in the height direction. Of course, in addition to the above-described compound provided in the light-emitting layer, the compound may be provided in one or more layers of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers.
In the present specification, when one member is provided "on" another member, this includes not only a case where one member is in contact with another member but also a case where another member is present between two members.
In the present specification, when a portion "includes" one constituent element, unless specifically described otherwise, this does not mean that another constituent element is excluded, but means that another constituent element may be further included.
In one exemplary embodiment of the present specification, the organic material layer includes a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, the hole transport layer, or the layer that simultaneously injects and transports holes includes the compound of formula (1).
In one exemplary embodiment of the present specification, the organic material layer includes a light emitting layer composed of a host material and a light emitting material containing a compound of the general formula (1).
In still another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer is composed of a single component of a light emitting material including the compound of formula (1).
In another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer is composed of a host material containing the compound of formula (1) and a light emitting material.
In one exemplary embodiment of the present specification, the organic material layer includes a light emitting layer including the compound of formula (1), and further including a light emitting dopant.
In another exemplary embodiment, the light emitting dopant comprises a fluorescent light emitting material or a phosphorescent light emitting material.
In yet another exemplary embodiment, the phosphorescent light emitting material includes an iridium-based phosphorescent light emitting material.
In yet another exemplary embodiment, the phosphorescent light emitting material comprises Ir (ppy)3Or Ir (MDQ)2acac。
In one exemplary embodiment of the present specification, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound of formula (1).
In one exemplary embodiment of the present specification, the organic material layer includes an electron blocking layer, and the electron blocking layer includes a compound of formula (1).
In one exemplary embodiment of the present specification, the organic material layer includes an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the electron transport layer, the electron injection layer, or the layer that simultaneously transports and injects electrons includes the compound of formula (1).
In another exemplary embodiment, the organic material layer includes a light emitting layer and an electron transport layer, and the electron transport layer includes the compound of formula (1).
In one exemplary embodiment of the present specification, the organic electronic device may be selected from an organic light emitting device, an organic solar cell, an organic photoconductor, and an organic transistor.
The compounds according to the present description may also be applied in organic electronic devices including organic solar cells, organic photoconductors, organic transistors, etc., under similar principles as used in organic light emitting devices. For example, the organic solar cell may have a structure including a first electrode, a second electrode, and a photoactive layer disposed between the first electrode and the second electrode, and the photoactive layer may include the compound.
Hereinafter, an organic light emitting device will be explained.
An exemplary embodiment of the present specification provides an organic light emitting device including: a first electrode; a second electrode disposed to face the first electrode; a light-emitting layer provided between the first electrode and the second electrode; and two or more organic material layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, wherein at least one of the two or more organic material layers contains a heterocyclic compound. In one exemplary embodiment, the two or more organic material layers may be selected from: an electron transport layer, an electron injection layer, a layer that both transports and injects electrons, a hole injection layer, a hole transport layer, and a hole blocking layer.
In one exemplary embodiment of the present specification, the organic material layer includes two or more electron transport layers, and at least one of the two or more electron transport layers includes a heterocyclic compound. Specifically, in one exemplary embodiment of the present specification, the heterocyclic compound may also be included in one layer of two or more electron transport layers, and may be included in each layer of two or more electron transport layers.
Further, in one exemplary embodiment of the present specification, when a heterocyclic compound is included in each of the one or more electron transport layers, other materials than the heterocyclic compound may be the same as or different from each other.
In another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked on a substrate, wherein the first electrode is a positive electrode and the second electrode is a negative electrode, i.e., a normal type organic light emitting device.
In still another exemplary embodiment, the organic light emitting device may be an organic light emitting device having a structure in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked on a substrate, wherein the first electrode is a negative electrode and the second electrode is a positive electrode, i.e., an organic light emitting device having an inverted structure (an inverted type).
For example, the structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in fig. 1 and 2.
Fig. 1 shows an exemplary embodiment of an organic light emitting device composed of a substrate 1, a first electrode 2, a light emitting layer 3, and a second electrode 4. In the structure as described above, the compound may be contained in the light-emitting layer.
Fig. 2 shows an exemplary embodiment of an organic light emitting device composed of a substrate 1, a first electrode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 8, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a second electrode 4. In the structure as described above, the compound may be included in one or more layers of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, and an electron injection layer.
The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that one or more of the organic material layers include the compound of the present specification, i.e., the compound of formula (1).
When the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.
For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. In this case, the organic light emitting device can be manufactured by the following method: a positive electrode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate using a Physical Vapor Deposition (PVD) method such as sputtering or electron beam evaporation, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer is formed on the positive electrode, and then a material that can be used as a negative electrode is deposited on the organic material layer. In addition to the method as described above, the organic light emitting device may be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate.
Further, in manufacturing the organic light emitting device, the compound of formula (1) may be formed into an organic material layer not only by a vacuum deposition method but also by a solution application method. Here, the solution application method means spin coating, dip coating, blade coating, inkjet printing, screen printing, spray coating, roll coating, and the like, but is not limited thereto.
In addition to the methods described above, an organic light emitting device can be manufactured by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate (international publication No. 2003/012890). However, the manufacturing method is not limited thereto.
In one exemplary embodiment of the present description, the first electrode is a positive electrode and the second electrode is a negative electrode.
In another exemplary embodiment of the present description, the first electrode is a negative electrode and the second electrode is a positive electrode.
As the positive electrode material, a material having a large work function is generally preferred to allow holes to be smoothly injected into the organic material layer. Specific examples of positive electrode materials that can be used in the present invention include: metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and oxides, such as ZnO: al or SnO2: sb; conducting polymers, e.g. poly (3-methylthiophene), poly [3, 4- (ethylene-1, 2-dioxy) thiophene](PEDOT), polypyrrole, polyaniline, and the like, but are not limited thereto.
As the negative electrode material, a material having a small work function is generally preferred to allow electrons to be smoothly injected into the organic material layer. Specific examples of the negative electrode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; materials of multilayer construction, e.g. LiF/Al or LiO2Al, etc., but are not limited thereto.
The hole injection layer is a layer that injects holes from the electrode, and the hole injection material is preferably a compound of: it has an ability to transport holes, thus having an effect of injecting holes in the positive electrode, and has an excellent hole injection effect on the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injecting layer or the electron injecting material, and also has an excellent thin film forming ability. It is preferred that the Highest Occupied Molecular Orbital (HOMO) of the hole injecting material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrins, oligothiophenes, arylamine-based organic materials, hexanenitrile-based hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene-based organic materials, anthraquinones, polyaniline-based and polythiophene-based conductive polymers, and the like, but are not limited thereto.
The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and the hole transport material is a suitable material for: it can receive holes from the positive electrode or the hole injection layer, transfer the holes to the light emitting layer, and have high mobility to the holes. Specific examples thereof include arylamine-based organic materials, conductive polymers, block copolymers in which a co-extensive portion and a non-co-extensive portion exist at the same time, and the like, but are not limited thereto.
The electron transporting material is a material that receives electrons from the electron injecting layer and transports the electrons to the light emitting layer, and is suitably a material having a large electron mobility that can skillfully receive electrons from the negative electrode and can transfer the electrons to the light emitting layer. Specific examples thereof include: al complexes of 8-hydroxyquinoline; comprising Alq3The complex of (1); an organic radical compound; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material used according to the prior art. In particular, suitable examples of cathode materials are typical materials with a low work function, followed by an aluminum or silver layer. Specific examples thereof include cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.
The electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound of: it has an ability to transport electrons, has an effect of injecting electrons from a negative electrode and an excellent effect of injecting electrons into a light emitting layer or a light emitting material, prevents excitons generated from the light emitting layer from migrating to a hole injecting layer, and also has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, thiazole, thiadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like and derivatives thereof, metal complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.
The light-emitting layer is preferably a material: which can receive holes and electrons respectively transported by the hole transport layer and the electron transport layer and emit light in the visible light region by combination of the holes and the electrons, andand has good quantum efficiency for fluorescence or phosphorescence. Specific examples thereof include: 8-hydroxy-quinoline aluminum complex (Alq)3) (ii) a A carbazole-based compound; a di-polystyrene based compound; BAlq; 10-hydroxybenzoquinoline-metal compounds; benzoxazole, benzothiazole, and benzimidazole-based compounds; polymers based on poly (p-phenylene vinylene) (PPV); a spiro compound; polyfluorene, rubrene, aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivative is a fused aromatic ring derivative having a substituted or unsubstituted arylamine group, and examples thereof include pyrene, anthracene, naphthalene, diindenopyrene, etc., having an arylamine group, the styrylamine compound is a compound in which the substituted or unsubstituted arylamine group is substituted with at least one arylvinyl group, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamine group are substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styrenediamine, styrenetriamine, styrenetetramine, and the like. Further, examples of the metal complex include iridium complexes, platinum complexes, and the like, but are not limited thereto.
The light emitting layer may include a host material and a light emitting material, and the light emitting material may include a doped light emitting material and a doped sensitizing material. The host material is preferably an organic compound material, and a host material containing a metal complex may be used. Examples of the host material are not particularly limited, and any host material may be used together with any light-emitting material, and examples of the organic compound serving as a host are selected from: a group consisting of aromatic hydrocarbon cyclic compounds of: benzene, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, perylene,
Figure BSA0000211705180000991
Perylene and azulene; a group consisting of the following aromatic heterocyclic compounds: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyridobipyridine, pyridoxineOxazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuropyridine, furobipyridine, benzothienopyridine, thienobipyridine, benzoselenenopyridine, and selenenopyridyl; and a group consisting of 2 to 10 cyclic structural units which are the same type or different type of groups selected from aromatic hydrocarbon ring groups and aromatic heterocyclic groups and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an aliphatic ring group, but not limited thereto. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinato, sulfonato, phosphino, and combinations thereof, but is not limited thereto.
Examples of the metal complex include lithium 8-quinolinolato, zinc bis (8-quinolinolato), copper bis (8-quinolinolato), manganese bis (8-quinolinolato), aluminum tris (2-methyl-8-quinolinolato), gallium tris (8-quinolinolato), beryllium bis (10-hydroxybenzo [ h ] quinoline), zinc bis (10-hydroxybenzo [ h ] quinoline), chlorogallium bis (2-methyl-8-quinolinolato), gallium bis (2-methyl-8-quinolino) (o-cresol), aluminum bis (2-methyl-8-quinolino) (1-naphthalenic acid), gallium bis (2-methyl-8-quinolino) (2-naphthalenic acid), iridium complex, platinum complex, osmium complex and the like, but is not limited thereto.
Depending on the materials used, the organic light emitting device according to the present description includes front side light emitting, back side light emitting and both side light emitting.
The preparation of the compound represented by chemical formula 1 and the organic light emitting device including the same will be described in detail in the following exemplary embodiments. However, the following exemplary embodiments are provided to illustrate the present specification, and the scope of the present specification is not limited thereto.
Preparation example
< Synthesis example >
The reaction formula refers to an example in which a specific substituent is introduced, but if necessary, a person skilled in the art may introduce the substituent without using a technique known in the art, and when the substituent is introduced, the introduction may be performed by changing the kind or number of the substituent. Furthermore, the introduction can be performed by a person skilled in the art by changing the samples, reaction conditions or starting materials of the following reaction formulae using techniques known in the art.
For example, the compound represented by formula 1 has an intermediate unit according to the following synthetic method.
< Synthesis example 1> Synthesis of the following intermediates A-1, B-1, C-1, D-1 and E-1. The qualifiers of Y are the same as in formula 1.
Figure BSA0000211705180001001
Figure BSA0000211705180001011
< Synthesis example 1-1> Synthesis of the following intermediate A-1
Figure BSA0000211705180001012
(9-oxo-9H-fluoren-1-yl) boronic acid (3.36g, 15mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (15mmol), tetrakis (triphenylphosphine) palladium (1.73g, 1.5mmol) and potassium carbonate (4.14g, 30mmol) were dissolved in a mixed solvent of 300mL tetrahydrofuran and 50mL water under nitrogen atmosphere, and heated under reflux for 18 hours. After the reaction was stopped, the reaction mixture was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and the mixture was separated with dichloromethane, and the organic phase was collected, dried by rotary evaporation, and separated by column chromatography to give intermediate a-1(6.23g) in 85% yield.
MS[M+H]+＝489
< Synthesis examples 1-2> Synthesis of the following intermediate B-1
Figure BSA0000211705180001021
(9-oxo-9H-xanthine-1-yl) boronic acid (3.60g, 15mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (15mmol), tetrakis (triphenylphosphine) palladium (1.73g, 1.5mmol) and potassium carbonate (4.14g, 30mmol) were dissolved in a mixed solvent of 300mL tetrahydrofuran and 50mL water under nitrogen atmosphere, and heated under reflux for 18 hours. After the reaction was stopped, the reaction mixture was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and the mixture was separated with dichloromethane, and the organic phase was collected, dried by rotary evaporation, and separated by column chromatography to give intermediate B-1(6.27g) in 83% yield.
MS[M+H]+＝504
< Synthesis examples 1-3> Synthesis of the following intermediate C-1
Figure BSA0000211705180001022
(9-oxo-9H-thioxanth-1-yl) boronic acid (3.84g, 15mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g, 15mmol), tetrakis (triphenylphosphine) palladium (1.73g, 1.5mmol) and potassium carbonate (4.14g, 30mmol) were dissolved in a mixed solvent of 300mL tetrahydrofuran and 50mL water under nitrogen and heated at reflux for 18 hours. After the reaction was stopped, the reaction mixture was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and the mixture was separated with dichloromethane, and the organic phase was collected, dried by rotary evaporation, and separated by column chromatography to give intermediate C-1(6.63g) in 85% yield.
MS[M+H]+＝520
< Synthesis examples 1-4> Synthesis of the following intermediate D-1
Figure BSA0000211705180001031
(10, 10-dimethyl-9-oxo-9, 10-dihydroanthracen-1-yl) boronic acid (3.99g, 15mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g, 15mmol), tetrakis (triphenylphosphine) palladium (1.73g, 1.5mmol) and potassium carbonate (4.14g, 30mmol) were dissolved in a mixed solvent of 300mL tetrahydrofuran and 50mL water under nitrogen atmosphere, and heated under reflux for 18 hours. After the reaction was stopped, the reaction mixture was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and the mixture was separated with dichloromethane, and the organic phase was collected, dried by rotary evaporation, and separated by column chromatography to give intermediate D-1(6.60g) in 83% yield.
MS[M+H]+＝530
< Synthesis examples 1-5> Synthesis of the following intermediate E-1
Figure BSA0000211705180001041
(10, 10-dioxido-9-oxo-9H-thioxanthon-1-yl) boronic acid (4.32g, 15mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g, 15mmol), tetrakis (triphenylphosphine) palladium (1.73g, 1.5mmol) and potassium carbonate (4.14g, 30mmol) were dissolved in a mixed solvent of 300mL of tetrahydrofuran and 50mL of water under nitrogen, and heated under reflux for 18 hours. After the reaction was stopped, the reaction mixture was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and the mixture was separated with dichloromethane, and the organic phase was collected, dried by rotary evaporation, and separated by column chromatography to give intermediate E-1(6.46g) in 78% yield.
MS[M+H]+＝552
< Synthesis examples 1-6> Synthesis of the following intermediate F-1
Figure BSA0000211705180001042
(9-oxo-9H-selenoxaxanthine-1-yl) boronic acid (15mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5.82g, 15mmol), tetrakis (triphenylphosphine) palladium (1.73g, 1.5mmol) and potassium carbonate (30mmol) were dissolved in a mixed solvent of 300mL tetrahydrofuran and 50mL water under nitrogen, and heated under reflux for 18 hours. After the reaction was stopped, the reaction mixture was cooled to room temperature, tetrahydrofuran was removed by rotary evaporation, and the mixture was separated with dichloromethane, and the organic phase was collected, dried by rotary evaporation, and separated by column chromatography to give intermediate F-1(6.8g) in 80% yield.
MS[M+H]+＝567
< Synthesis example 2> Synthesis of the following intermediates A-2, B-2, C-2 and D-2. The qualifiers of Y are the same as in formula 1.
Figure BSA0000211705180001051
Intermediates a-2 to D-2 were prepared in the same manner as the methods for preparing intermediates a-1 to D-1 except that 4- (4-bromophenyl) -2, 6-diphenylpyrimidine was used instead of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine as the starting material in synthesis examples 1-1 to 1-4. MS [ M + H ] of intermediates A-2 to D-2]+The values are shown in table 1 below.
TABLE 1
Figure BSA0000211705180001052
Figure BSA0000211705180001061
< Synthesis example 3> Synthesis of the following intermediates A-3, B-3, C-3, D-3, E-3 and F-3. The qualifiers of Y are the same as in formula 1.
Figure BSA0000211705180001062
Intermediates A-3 to F-3 were prepared in the same manner as in the method for preparing intermediates A-1 to F-1 except that 7-bromo-5, 9-dioxin-13 b-boronaphtho [3, 2, 1-de ] was used]Anthracene was used as a starting material in synthesis examples 1-1 to 1-6 in place of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. MS [ M + H ] of intermediates A-3 to F-3]+The values are shown in table 2 below.
TABLE 2
Compound numbering MS[M+H]+
A-3 449
B-3 465
C-3 481
D-3 491
E-3 513
F-3 528
< Synthesis example 4> Synthesis of the following intermediates A-4, B-4, C-4 and D-4. The qualifiers of Y are the same as in formula 1.
Figure BSA0000211705180001071
Intermediates a-4 to D-4 were prepared in the same manner as the method for preparing intermediates a-1 to D-4 except that 2- bromothioxanthene 5, 5, 10, 10-tetraoxide was used instead of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine as the starting material in synthesis examples 1-1 to 1-4. MS [ M + H ] of intermediates A-4 to D-4]+The values are shown in table 3 below.
TABLE 3
Compound numbering MS[M+H]+
A-4 459
B-4 475
C-4 491
D-4 501
< Synthesis example 5> Synthesis of the following intermediates A-5, B-5, C-5 and C-5. The qualifiers of Y are the same as in formula 1.
Figure BSA0000211705180001081
Figure BSA0000211705180001091
Intermediates A-5 to D-5 were prepared in the same manner as the method for preparing intermediates A-1 to D-5, except that 11- (4-bromophenyl) -6a, 14 a-dihydrodibenzo [ a, j ] was used]Phenazine was used as the starting material in synthesis examples 1-1 to 1-4 instead of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. MS [ M + H ] of intermediates A-5 to D-5]+The values are shown in table 4 below.
TABLE 4
Compound numbering MS[M+H]+
A-5 536
B-5 551
C-5 567
D-5 577
< Synthesis example 6> Synthesis of the following intermediates A-6, B-6, C-6 and D-6. The qualifiers of Y are the same as in formula 1.
Figure BSA0000211705180001101
Intermediates A-6 to D-6 were prepared in the same manner as the method for preparing intermediates A-1 to C-5 except that 17-bromo-5, 9-diphenyl-5, 9-dihydro-5, 9-diaza-13 b-boranaphtho [3, 2, 1-de ] was used]Anthracene was used as a starting material in synthesis examples 1-1 to 1-4 in place of 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine. MS [ M + H ] of intermediates A-5 to D-5]+The values are shown in table 5 below.
TABLE 5
Compound numbering MS[M+H]+
A-6 600
B-6 616
C-6 632
D-6 642
< preparation example 1> Synthesis of the following Compound 1
Figure BSA0000211705180001111
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate A-1(9.36g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 1(10.51g, 14.4mmol, the yield is about 75%).
MS[M+H]+＝730
< preparation example 2> Synthesis of the following Compound 2
Figure BSA0000211705180001112
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate A-2(9.34g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 2(10.92g, 14.98mmol, the yield is about 78%).
MS[M+H]+＝729
< preparation example 3> Synthesis of the following Compound 3
Figure BSA0000211705180001121
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.04g, 17.86mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate A-3(8.01g, 17.86mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 3(8.02g, 11.61mmol, the yield is about 65%).
MS[M+H]+＝691
< preparation example 4> Synthesis of the following Compound 4
Figure BSA0000211705180001131
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.34g, 18.75mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate A-4(8.60g, 18.75mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 3(9.86g, 14.06mmol, the yield is about 75%) is obtained.
MS[M+H]+＝701
< preparation example 5> Synthesis of the following Compound 5
Figure BSA0000211705180001141
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate A-5(9.31g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain a compound 5(9.74g, 12.54mmol, the yield is about 72%).
MS[M+H]+＝777
< preparation example 6> Synthesis of the following Compound 6
Figure BSA0000211705180001142
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate A-6(10.42g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain a compound 6(9.52g, 11.32mmol, the yield is about 65%).
MS[M+H]+＝841
< preparation example 7> Synthesis of the following Compound 7
Figure BSA0000211705180001151
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate B-1(9.67g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain a compound 7(10.37g, 14.21mmol, the yield is about 74%).
MS[M+H]+＝746
< preparation example 7> Synthesis of the following Compound 7
Figure BSA0000211705180001161
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate B-2(9.64g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 8(10.08g, 13,82mmol, yield is about 72%) is obtained.
MS[M+H]+＝745
< preparation example 9> Synthesis of the following Compound 9
Figure BSA0000211705180001171
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.04g, 17.86mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise at-78 ℃, after stirring for 1 hour at-78 ℃, intermediate B-3(8.29g, 17.86mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 9(8.65g, 12.50mmol, the yield is about 70%) is obtained.
MS[M+H]+＝707
< preparation example 10> Synthesis of the following Compound 10
Figure BSA0000211705180001172
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.34g, 18.75mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate B-4(8.90g, 18.75mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction, the temperature was decreased to room temperature, and the reaction mixture was poured into 500mL of ice water to precipitate the product, which was filtered off with a suction and then subjected to silica gel column chromatography using a eluent mixture of dichloromethane and petroleum ether to obtain Compound 10(9.22g, 13.13mmol, yield about 70%).
MS[M+H]+＝717
< preparation example 11> Synthesis of the following Compound 11
Figure BSA0000211705180001181
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate B-5(9.56g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 11(9.21g, 11.84mmol, the yield is about 68%).
MS[M+H]+＝793
< preparation example 12> Synthesis of the following Compound 12
Figure BSA0000211705180001191
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate B-6(10.70g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 12(11.32g, 13.23mmol, the yield is about 76%).
MS[M+H]+＝857
< preparation example 13> Synthesis of the following Compound 13
Figure BSA0000211705180001201
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.49g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate C-1(9.98g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 13(11.78g, 15.74mmol, the yield is about 82%).
MS[M+H]+＝762
< preparation example 14> Synthesis of the following Compound 14
Figure BSA0000211705180001202
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.49g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate C-2(9.96g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 14(10.72g, 14.40mmol, the yield is about 75%).
MS[M+H]+＝761
< preparation example 15> Synthesis of the following Compound 15
Figure BSA0000211705180001211
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.04g, 17.86mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate C-3(8.57g, 17.86mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain a compound 15(10.12g, 14.29mmol, the yield is about 80%).
MS[M+H]+＝722
< preparation example 16> Synthesis of the following Compound 16
Figure BSA0000211705180001221
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.34g, 18.75mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate C-4(9.19g, 18.75mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 16(9.69g, 13.50mmol, the yield is about 72%).
MS[M+H]+＝733
< preparation example 17> Synthesis of the following Compound 17
Figure BSA0000211705180001231
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate C-5(9.86g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction solution is poured into 500mL of ice water, a product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 17(8.97g, 11.32mmol, yield is about 65%) is obtained.
MS[M+H]+＝809
< preparation example 18> Synthesis of the following Compound 18
Figure BSA0000211705180001232
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate C-6(10.98g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 18(12.45g, 14.28mmol, yield is about 82%) is obtained.
MS[M+H]+＝873
< preparation example 19> Synthesis of the following Compound 19
Figure BSA0000211705180001241
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise, the solution is stirred at minus 78 ℃ for 1 hour, then intermediate D-1(10.18g, 19.20mmol) is added, and the mixture is stirred overnight and then 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 19(11.63g, 15.36mmol, the yield is about 80%).
MS[M+H]+＝772
< preparation example 20> Synthesis of the following Compound 20
Figure BSA0000211705180001251
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate D-2(10.15g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 20(17.84g, 15.36mmol, yield is about 80%) is obtained.
MS[M+H]+＝771
< preparation example 21> Synthesis of the following Compound 21
Figure BSA0000211705180001261
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.04g, 17.86mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, the solution is stirred at minus 78 ℃ for 1 hour, then intermediate D-3(8.76g, 17.86mmol) is added, and the mixture is stirred overnight and then 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 21(9.61g, 13.40mmol, the yield is about 75%).
MS[M+H]+＝733
< preparation example 22> Synthesis of the following Compound 22
Figure BSA0000211705180001262
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.34g, 18.75mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate D-4(9.38g, 18.75mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 22(10.64g, 14.62mmol, the yield is about 78%).
MS[M+H]+＝743
< preparation example 23> Synthesis of the following Compound 23
Figure BSA0000211705180001271
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate D-5(10.04g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 23(9.10g, 11.32mmol, the yield is about 65%).
MS[M+H]+＝819
< preparation example 24> Synthesis of the following Compound 24
Figure BSA0000211705180001281
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (5.89g, 17.41mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise, after stirring for 1 hour at minus 78 ℃, intermediate D-6(11.15g, 17.41mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the solution. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain a compound 24(11.75g, 13.23mmol, the yield is about 76%).
MS[M+H]+＝883
< preparation example 25> Synthesis of the following Compound 25
Figure BSA0000211705180001291
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate E-1(10.59g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 25(8.97g, 11.52mmol, the yield is about 60%).
MS[M+H]+＝794
< preparation example 26> Synthesis of the following Compound 26
Figure BSA0000211705180001292
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.50g, 19.20mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.80mL, 21.12mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate E-3(9.84g, 19.20mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction solution is poured into 500mL of ice water, a product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 26(11.08g, 14.98mmol, the yield is about 78%) is obtained.
MS[M+H]+＝755
< preparation example 27> Synthesis of the following Compound 27
Figure BSA0000211705180001301
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.04g, 17.86mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate F-1(9.94g, 17.86mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction solution is poured into 500mL of ice water, a product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether, and the compound 27(14.98g, 11.61mmol, yield is about 65%) is obtained.
MS[M+H]+＝809
< preparation example 28> Synthesis of the following Compound 28
Figure BSA0000211705180001311
Under the protection of nitrogen, 1-bromo-10-phenyl-10H-phenoxazine (6.34g, 18.75mmol) is placed in a 250mL two-neck flask, 77mL of anhydrous tetrahydrofuran is added to dissolve the 1-bromo-10-phenyl-10H-phenoxazine, then a 2.4M n-butyllithium solution (8.18mL, 19.64mmol) is added dropwise at minus 78 ℃, after stirring for 1 hour at minus 78 ℃, intermediate F-3(9.89g, 18.75mmol) is added, and after stirring overnight, 20mL of distilled water is added to quench the mixture. Removing tetrahydrofuran from the reaction solution under reduced pressure, adding 40mL of dichloromethane for extraction for 3 times, removing dichloromethane under reduced pressure, adding ethanol for recrystallization, performing suction filtration and drying to obtain a solid, placing the solid in a 250mL flask, adding 100mL of acetic acid, stirring for 10 minutes, adding 3mL of concentrated hydrochloric acid, and heating to 110 ℃ for reflux for 3 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction liquid is poured into 500mL of ice water, the product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent prepared from dichloromethane and petroleum ether to obtain the compound 28(11.25g, 13.13mmol, the yield is about 75%).
MS[M+H]+＝770
< preparation example 29> Synthesis of the following Compounds 29 to 56
Figure BSA0000211705180001312
Figure BSA0000211705180001321
Compounds 29 to 56 were produced in the same manner as in the process for producing compounds 1 to 28, except that 1-bromo-10-phenyl-10H-phenothiazine was used as a starting material in production examples 1 to 19 in place of 1-bromo-10-phenyl-10H-phenoxazine. MS [ M + H ] of Compounds 29 to 56]+The values are shown in table 6 below.
TABLE 6
Figure BSA0000211705180001322
Figure BSA0000211705180001331
< preparation example 30> Synthesis of the following Compounds 56-84
Figure BSA0000211705180001341
Compounds 56 to 84 were produced in the same manner as in the method for producing compounds 1 to 28, except that 2-bromo-N- (2-thienyl) -N-phenylaniline was used instead of 1-bromo-10-phenyl-10H-phenoxazine as the starting material in production examples 1 to 28. MS [ M + H ] of Compounds 56 to 84]+The values are shown in table 7 below.
TABLE 7
Figure BSA0000211705180001342
Figure BSA0000211705180001351
Figure BSA0000211705180001361
Comparative exemplary embodiment of the preparation method:
by way of comparison, the synthesis of the following route was carried out with the molecule of exemplary embodiment 1
< comparative example 1> Synthesis of the following Compound 1
Figure BSA0000211705180001362
Spiro [ quinolyl [3, 2, 1-kl ] phenoxazine-9, 9 '-xanthine ] -1' -ylboronic acid (10.74g, 22.32mmol), 2- (4-bromo-phenyl) -4, 6-diphenyl-1, 3, 5-triazine (8.67g, 22.32mmol), tetrakis (triphenylphosphine) palladium (773.39mg, 0.67mmol), anhydrous potassium carbonate (6.16g, 44.64mmol) were placed in a 250mL round bottom flask under nitrogen and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction is finished, no new product is obtained by thin plate chromatography detection, and the yield is 0.
< comparative example 2> Synthesis of the following Compound 1
Figure BSA0000211705180001363
Under nitrogen, (S) -1 '-bromospiro [ quinolyl [3, 2, 1-kl ] phenoxazine-9, 9' -xanthene ] (11.52g, 22.32mmol), (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid (7.88g, 22.32mmol), tetrakis (triphenylphosphine) palladium (773.39mg, 0.67mmol), anhydrous potassium carbonate (6.16g, 44.64mmol) were placed in a 250mL round bottom flask and 90mL tetrahydrofuran and 22mL distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction is finished, no new product is obtained by thin plate chromatography detection, and the yield is 0.
Experimental examples 1-1 to 1-32
< Experimental examples 1-1>
The compound of the present invention is purified by high-purity sublimation by a conventional method, and then an organic light-emitting device is manufactured by the following method.
Thinly coated with a thickness of
Figure BSA0000211705180001374
The glass substrate of Indium Tin Oxide (ITO) of (a) was put in distilled water in which a detergent was dissolved and subjected to ultrasonic washing. After washing ITO for 30 minutes, ultrasonic washing was repeatedly performed twice for 10 minutes using distilled water, and then ultrasonic washing was performed using isopropyl alcohol, acetone, and a methanol solvent, and drying was performed. The substrate is then transferred to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to vacuum evaporationA hair-sending device.
2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene (HAT-CN) of the following formula was thermally vacuum deposited on the transparent ITO electrode thus prepared to a thickness of
Figure BSA0000211705180001371
As a hole injection layer.
Figure BSA0000211705180001372
The following compound 4, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)
Figure BSA0000211705180001373
Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Figure BSA0000211705180001381
Subsequently, the following compound 1, 3-di-9-carbazolylbenzene (mCP) as a material for electron blocking was used
Figure BSA0000211705180001382
Figure BSA0000211705180001383
Vacuum depositing on the hole transport layer to form an electron blocking layer.
Figure BSA0000211705180001384
Then, the following compound 1 and bis [2- ((oxo) diphenylphosphino) phenyl group were reacted]Ether (DPEPO) was vacuum deposited on the electron blocking layer at a weight ratio of 3: 7 and a thickness of
Figure BSA0000211705180001385
Thereby forming a light emitting layer.
Figure BSA0000211705180001386
1, 3, 5-tris [ (3-pyridyl) -3-phenyl ] materials which transport electrons]Benzene (TmPyPB)
Figure BSA0000211705180001387
Vacuum deposition is carried out on the luminescent layer to form an electron transport layer.
Figure BSA0000211705180001388
Reacting the compound 8-hydroxyquinoline lithium (Liq)
Figure BSA0000211705180001391
And metallic aluminum
Figure BSA0000211705180001392
And sequentially deposited on the electron transport layer to serve as an electron injection layer and a negative electrode.
Figure BSA0000211705180001393
In the above process, the deposition rate of the hole injection layer material HAT-CN and the electron injection layer material Liq is kept at
Figure BSA0000211705180001394
To
Figure BSA0000211705180001395
The deposition rate of the organic functional layer material, including hole transport layer material, electron barrier layer material, luminescent layer material and electron transport layer material, is maintained at
Figure BSA0000211705180001396
To
Figure BSA0000211705180001397
Figure BSA00002117051800013910
The deposition rate of the electrode material metallic aluminum is kept at
Figure BSA0000211705180001398
To
Figure BSA0000211705180001399
And the vacuum degree during the deposition was maintained at 1 × 10-7Tray to 5 × 10-6And thus an organic light emitting device is manufactured.
< Experimental examples 1 and 2>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 2 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 3>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 3 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 4>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 4 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 5>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 5 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 6>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 6 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 7>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 7 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 8>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 8 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 9>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 9 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 10>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 10 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 11>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 11 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 12>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 12 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 13>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 13 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 14>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 15 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 15>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 18 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 16>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 19 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 17>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 21 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 18>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 25 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 19>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 27 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 20>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 29 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 21>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 31 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 22>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 35 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 23>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 38 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 24>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 41 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 25>
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 47 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 26>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 51 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 27>
An organic light-emitting device was manufactured in the same manner as in experimental example 1-1, except that compound 53 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 28>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 57 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 29>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 61 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 30>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 63 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 31>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 68 was used instead of compound 1 in experimental example 1-1.
< Experimental examples 1 to 32>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that compound 69 was used instead of compound 1 in experimental example 1-1.
< comparative example 1-1>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that comparative compound 1 was used instead of compound 1 in experimental example 1-1.
Figure BSA0000211705180001441
< comparative examples 1 and 2>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that comparative compound 2 was used instead of compound 1 in experimental example 1-1.
Figure BSA0000211705180001442
< comparative examples 1 to 3>
An organic light-emitting device was fabricated in the same manner as in experimental example 1-1, except that comparative compound 3 was used instead of compound 1 in experimental example 1-1.
Figure BSA0000211705180001451
When a current was applied to the organic light emitting diode devices manufactured in experimental examples 1-1 to 1-32 and comparative examples 1-1, 1-2, and 1-3, the results of table 8 below were obtained.
TABLE 8
Figure BSA0000211705180001452
Figure BSA0000211705180001461
Figure BSA0000211705180001471
As shown in the data of Table 8, it can be seen that the 1-substituted materials of hetero-spirofluorene all exhibited high luminous efficiency, while comparative examples 1-1, 1-2 and 1-3 all exhibited low external quantum efficiency.
It was confirmed that the derivative of the compound according to the formula of the present invention has excellent light emitting behavior and thus exhibits high efficiency characteristics, and can be applied to organic light emitting devices.
< Experimental example 2-1>
The compound prepared in the synthesis example was subjected to high-purity sublimation purification by a generally known method, and then a sensitized organic light-emitting device was manufactured by the following method.
Thinly coated with a thickness of
Figure BSA0000211705180001472
By oxidation ofA glass substrate of Indium Tin (ITO) was put in distilled water in which a detergent was dissolved and subjected to ultrasonic washing. After washing ITO for 30 minutes, ultrasonic washing was repeatedly performed twice for 10 minutes using distilled water, and then ultrasonic washing was performed using isopropyl alcohol, acetone, and a methanol solvent, and drying was performed. The substrate is then transferred to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator.
2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene (HAT-CN) of the following formula was thermally vacuum deposited on the transparent ITO electrode thus prepared to a thickness of
Figure BSA0000211705180001473
As a hole injection layer.
Figure BSA0000211705180001481
The following compound 4, 4' -cyclohexyl-bis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)
Figure BSA0000211705180001482
Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Figure BSA0000211705180001483
Subsequently, the following compound 4, 4', 4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA) as a material for electron blocking was caused to react
Figure BSA0000211705180001484
Vacuum depositing on the hole transport layer to form an electron blocking layer.
Figure BSA0000211705180001485
Then, the following 3, 3 '-bis (9H-carbazol-9-yl) -1, 1' -bi-linkedBenzene (mCBP) is used as a main material, a compound 1 is used as a sensitizing material, C545T is used as a luminescent material, the compound 1 is doped with 15 percent by weight, C545T is doped with 1 percent by weight, and the mixture is jointly vacuum-deposited on the electron blocking layer, wherein the thickness of the mixture is
Figure BSA0000211705180001486
Thereby forming a light emitting layer.
Figure BSA0000211705180001491
1, 3, 5-tris [ (3-pyridyl) -3-phenyl ] materials which transport electrons]Benzene (TmPyPB)
Figure BSA0000211705180001492
Vacuum deposition is carried out on the luminescent layer to form an electron transport layer.
Figure BSA0000211705180001493
Reacting the compound 8-hydroxyquinoline lithium (Liq)
Figure BSA0000211705180001494
And metallic aluminum
Figure BSA0000211705180001495
And sequentially deposited on the electron transport layer to serve as an electron injection layer and a negative electrode.
Figure BSA0000211705180001496
In the above process, the deposition rate of the hole injection layer material HAT-CN and the electron injection layer material Liq is kept at
Figure BSA0000211705180001497
To
Figure BSA0000211705180001498
Organic functional layer material including hole transport layer material, electron barrierThe deposition rate of the layer material, the light-emitting layer material, the electron transport layer material is maintained at
Figure BSA0000211705180001499
To
Figure BSA00002117051800014910
Second, the deposition rate of the electrode material metallic aluminum is kept at
Figure BSA00002117051800014911
To
Figure BSA00002117051800014912
And the vacuum degree during the deposition was maintained at 1 × 10-7Tray to 5 × 10-6And thus an organic light emitting device is manufactured.
< Experimental examples 2-2>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 2 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 3>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 3 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 4>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 4 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 5>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 5 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 6>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 6 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 7>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 7 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 8>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 8 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 9>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 9 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 10>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 10 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 11>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 11 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 12>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 12 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 13>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 13 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 14>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 15 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 15>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 18 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 16>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 19 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 17>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 21 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 18>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 25 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 19>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 27 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 20>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 29 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 21>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 31 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 22>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 35 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 23>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 38 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 24>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 41 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 25>
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 47 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 26>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 51 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 27>
An organic light-emitting device was manufactured in the same manner as in experimental example 2-1, except that compound 53 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 28>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 57 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 29>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 61 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 30>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 63 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 31>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 68 was used instead of compound 1 in experimental example 2-1.
< Experimental examples 2 to 32>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that compound 69 was used instead of compound 1 in experimental example 2-1.
< comparative example 2-1>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that comparative compound 1 was used instead of compound 1 in experimental example 2-1.
Figure BSA0000211705180001541
< comparative example 2-2>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that comparative compound 2 was used instead of compound 1 in experimental example 2-1.
Figure BSA0000211705180001551
< comparative examples 2 to 3>
An organic light-emitting device was fabricated in the same manner as in experimental example 2-1, except that comparative compound 3 was used instead of compound 1 in experimental example 2-1.
Figure BSA0000211705180001552
When a current was applied to the organic light emitting diode devices manufactured in experimental examples 2-1 to 2-32 and comparative examples 2-1, 2-2, and 2-3, the results of table 9 below were obtained.
TABLE 9
Figure BSA0000211705180001553
Figure BSA0000211705180001561
Figure BSA0000211705180001571
As shown in the data in table 9, the device efficiency of comparative example 2-1 was only 2.2% without adding the compound material, and comparative examples 2-2 to 2-4 demonstrated that the added material did not have any sensitizing effect and did not improve the device performance. Whereas the green organic light emitting devices of experimental examples 2-1 to 2-32, in which the compound represented by formula 1 according to the present invention was used as a sensitizing material for green fluorescent light emitting molecules, exhibited better performance in both current efficiency and driving voltage.
Experimental example 3-1 to Experimental example 3-32
< Experimental example 3-1>
The compound of the present invention is purified by high-purity sublimation by a conventional method, and then an organic light-emitting device is manufactured by the following method.
Thinly coated with a thickness of
Figure BSA0000211705180001587
The glass substrate of Indium Tin Oxide (ITO) of (a) was put in distilled water in which a detergent was dissolved and subjected to ultrasonic washing. After washing ITO for 30 minutes, ultrasonic washing was repeatedly performed twice for 10 minutes using distilled water, and then ultrasonic washing was performed using isopropyl alcohol, acetone, and a methanol solvent, and drying was performed. The substrate is then transferred to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 6 minutes, and then transferred to a vacuum evaporator.
2, 3, 6, 7, 10, 11-hexacyano-1, 4, 5, 8, 9, 12-hexaazatriphenylene (HAT-CN) of the following formula was thermally vacuum deposited on the transparent ITO electrode thus prepared to a thickness of
Figure BSA0000211705180001581
As a hole injection layer.
Figure BSA0000211705180001582
The following compound 4, 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)
Figure BSA0000211705180001583
Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Figure BSA0000211705180001584
Subsequently, the following compound 1, 3-di-9-carbazolylbenzene (mCP) as a material for electron blocking was used
Figure BSA0000211705180001585
Figure BSA0000211705180001586
Vacuum depositing on the hole transport layer to form an electron blocking layer.
Figure BSA0000211705180001591
Then, the following compound 1 and tris (2-phenylpyridine) iridium (III) were vacuum-deposited on the electron-blocking layer in a weight ratio of 7: 3 to a thickness of
Figure BSA0000211705180001592
Thereby forming a light emitting layer.
Figure BSA0000211705180001593
1, 3, 5-tris [ (3-pyridyl) -3-phenyl ] materials which transport electrons]Benzene (TmPyPB)
Figure BSA0000211705180001594
Vacuum deposition is carried out on the luminescent layer to form an electron transport layer.
Figure BSA0000211705180001595
Reacting the compound 8-hydroxyquinoline lithium (Liq)
Figure BSA0000211705180001596
And metallic aluminum
Figure BSA0000211705180001597
And sequentially deposited on the electron transport layer to serve as an electron injection layer and a negative electrode.
Figure BSA0000211705180001598
In the above process, the deposition rate of the hole injection layer material HAT-CN and the electron injection layer material Liq is kept at
Figure BSA0000211705180001599
To
Figure BSA00002117051800015910
The deposition rate of the organic functional layer material, including hole transport layer material, electron barrier layer material, luminescent layer material and electron transport layer material, is maintained at
Figure BSA00002117051800015911
To
Figure BSA00002117051800015912
Figure BSA0000211705180001603
The deposition rate of the electrode material metallic aluminum is kept at
Figure BSA0000211705180001601
To
Figure BSA0000211705180001602
And the vacuum degree during the deposition was maintained at 1 × 10-7Tray to 5 × 10-6And thus an organic light emitting device is manufactured.
< Experimental example 3-2>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 2 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 3>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 3 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 4>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 4 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 5>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 5 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 6>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 6 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 7>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 7 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 8>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 8 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 9>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 9 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 10>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 10 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 11>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 11 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 12>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 12 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 13>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 13 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 14>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 15 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 15>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 18 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 16>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 19 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 17>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 21 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 18>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 25 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 19>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 27 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 20>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 29 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 21>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 31 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 22>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 35 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 23>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 38 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 24>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 41 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 25>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 47 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 26>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 51 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 27>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 53 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 28>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 57 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 29>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 61 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 30>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 63 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 31>
An organic light-emitting device was manufactured in the same manner as in experimental example 3-1, except that compound 68 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 32>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that compound 69 was used instead of compound 1 in experimental example 3-1.
< comparative example 3-1>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that comparative compound 1 was used instead of compound 1 in experimental example 3-1.
Figure BSA0000211705180001641
< comparative example 3-2>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that comparative compound 2 was used instead of compound 1 in experimental example 3-1.
Figure BSA0000211705180001651
< comparative examples 3 to 3>
An organic light-emitting device was fabricated in the same manner as in experimental example 3-1, except that comparative compound 3 was used instead of compound 1 in experimental example 3-1.
Figure BSA0000211705180001652
When a current was applied to the organic light emitting diode devices manufactured in experimental examples 3-1 to 3-32 and comparative examples 3-1, 3-2, and 3-3, the results of table 10 below were obtained.
Watch 10
Figure BSA0000211705180001661
Figure BSA0000211705180001671
As shown by the data in Table 10, it can be seen that a host material in which the position No. 1 of hetero-spirofluorene is substituted as a host, Ir (ppy)3As a guest material, the green light emitting device has high light emitting efficiency and low driving voltage. While comparative examples 3-1, 3-2 and 3-3 all showed lowerExternal quantum efficiency and higher drive voltage.
In summary, the following steps: the compound of the present invention can be used as a material for an organic material layer in an organic light emitting device. The main functional elements of the compound realize intramolecular interaction through space unconjugated connection, the material has excellent luminous performance, and can be used as a material of an organic material layer of an organic light-emitting device, particularly a material of a core light-emitting layer. The compound according to at least one exemplary embodiment of the present specification as a host material may realize a high-efficiency organic light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a light emitting material may realize a high efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a sensitizing material can realize a high-efficiency light emitting device while realizing a low driving voltage; the compound according to at least one exemplary embodiment of the present specification as a hole transport material may realize a high-efficiency light emitting device while realizing a low driving voltage.
The compound described in this specification can be used as a material for hole injection, hole transport, hole injection and hole transport, light emission, electron transport, electron blocking, or electron injection. In addition, the compounds described in the present specification can also be used for materials of organic photovoltaic devices or organic transistors.
The features of the above-described exemplary embodiments may be arbitrarily combined, and for the sake of brevity, all possible combinations of the features in the above-described exemplary embodiments are not described in detail, but should be construed as falling within the scope of the present description as long as there is no contradiction between the combinations of the features.
The above-described exemplary embodiments merely represent several embodiments of the present invention, which are described in more detail and detail, but are not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. A compound represented by the following general formula (1):
Figure FSA0000211705170000011
wherein Y is a direct bond, O, S, S (═ O)2Either CR 'R' or Se;
z is selected from O, S, or CRaRbAny one of (a);
R1to R18、R′、R″、RaAnd RbEach independently selected from hydrogen, deuterium, halogen groups, nitrile groups; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio; substituted or unsubstituted arylthio; substituted or unsubstituted alkylsulfonyl; substituted or unsubstituted arylsulfonyl; substituted or unsubstituted alkenyl; substituted or unsubstituted silyl; a substituted or unsubstituted boron group; substituted or unsubstituted amine groups; a substituted or unsubstituted aryl phosphine group; a substituted or unsubstituted phosphine oxide group; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; substituted or unsubstituted heterocyclyl;
g is selected from a direct bond, a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30;
a is selected from nitrile group, sulfone group, carbonyl group, ester group, substituted or unsubstituted aliphatic group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aralkyl group, substituted or unsubstituted aralkenyl group, substituted or unsubstituted arylamine group, substituted or unsubstituted aryl group, substituted or unsubstituted heteroaryl group, and substituted or unsubstituted heterocyclic group.
2. The compound according to claim 1, wherein in the compound represented by the general formula (1), Y is selected from a direct bond, O, S (═ O)2Z is selected from any one of O, S, or CR 'R'; wherein the general formula (1) is selected from any one of the following general formulae (2) to (19):
Figure FSA0000211705170000021
in the general formula (2), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000022
in the general formula (3), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000023
in the general formula (4), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000031
in the general formula (5), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000032
in the general formula (6), R1To R18R 'and R' are the same as defined in the general formula (1);
Figure FSA0000211705170000033
in the general formula (7), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000041
in the general formula (8), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000042
in the general formula (9), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000043
in the general formula (10), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000051
in the general formula (11), R1To R18The same as defined in the general formula (1);
Figure FSA0000211705170000052
in the general formula (12), R1To R18R 'and R' are the same as defined in the general formula (1);
Figure FSA0000211705170000053
in the general formula (13), R1To R18′、RaAnd RbThe same as defined in the general formula (1);
Figure FSA0000211705170000061
in the general formula (14), R1To R18、RaAnd RbThe same as defined in the general formula (1);
Figure FSA0000211705170000062
in the general formula (15), R1To R18、RaAnd RbThe same as defined in the general formula (1);
Figure FSA0000211705170000063
in the general formula (16), R1To R18、RaAnd RbThe same as defined in the general formula (1);
Figure FSA0000211705170000071
in the general formula (17), R1To R18、RaAnd RbThe same as defined in the general formula (1);
Figure FSA0000211705170000072
in the general formula (18), R1To R18、R′、R″、RaAnd RbThe same as defined in the general formula (1);
and the number of the first and second groups,
Figure FSA0000211705170000073
in the general formula (19), R1To R18、RaAnd RbThe same as defined in said general formula (1).
3. The compound according to claim 1, wherein in the general formula (1), A is selected from the group consisting of a nitrile group, a sulfone group, a carbonyl group, an ester group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heterocyclic group.
4. The compound of claim 1, wherein in said formula (1), a is selected from the group consisting of hydrogen, deuterium, halogen groups, nitrile groups; a nitro group; a hydroxyl group; a carbonyl group; an ester group; an imide group; an amide group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted aryloxy; substituted or unsubstituted alkylthio; substituted or unsubstituted arylthio; substituted or unsubstituted alkylsulfonyl; substituted or unsubstituted arylsulfonyl; substituted or unsubstituted alkenyl; substituted or unsubstituted silyl; a substituted or unsubstituted boron group; substituted or unsubstituted amine groups; a substituted or unsubstituted aryl phosphine group; a substituted or unsubstituted phosphine oxide group; substituted or unsubstituted aryl; or substituted or unsubstituted heteroaryl; substituted or unsubstituted heterocyclyl.
5. The compound of claim 1, wherein in the general formula (1), G is selected from a direct bond, or a substituted or unsubstituted arylene, substituted or unsubstituted heteroarylene.
6. The compound of claim 1, the compound of formula (1) being selected from any one of the following structural formulae:
Figure FSA0000211705170000081
Figure FSA0000211705170000091
Figure FSA0000211705170000101
Figure FSA0000211705170000111
Figure FSA0000211705170000121
Figure FSA0000211705170000131
Figure FSA0000211705170000141
Figure FSA0000211705170000151
Figure FSA0000211705170000161
Figure FSA0000211705170000171
Figure FSA0000211705170000181
Figure FSA0000211705170000191
Figure FSA0000211705170000201
Figure FSA0000211705170000211
Figure FSA0000211705170000221
Figure FSA0000211705170000231
Figure FSA0000211705170000241
Figure FSA0000211705170000251
Figure FSA0000211705170000261
Figure FSA0000211705170000271
Figure FSA0000211705170000281
Figure FSA0000211705170000291
Figure FSA0000211705170000301
Figure FSA0000211705170000311
Figure FSA0000211705170000321
Figure FSA0000211705170000331
Figure FSA0000211705170000341
Figure FSA0000211705170000351
Figure FSA0000211705170000361
Figure FSA0000211705170000371
Figure FSA0000211705170000381
Figure FSA0000211705170000391
Figure FSA0000211705170000401
Figure FSA0000211705170000411
Figure FSA0000211705170000421
Figure FSA0000211705170000431
Figure FSA0000211705170000441
Figure FSA0000211705170000451
Figure FSA0000211705170000461
Figure FSA0000211705170000471
Figure FSA0000211705170000481
Figure FSA0000211705170000491
Figure FSA0000211705170000501
Figure FSA0000211705170000511
Figure FSA0000211705170000521
Figure FSA0000211705170000531
Figure FSA0000211705170000541
Figure FSA0000211705170000551
Figure FSA0000211705170000561
Figure FSA0000211705170000571
Figure FSA0000211705170000581
Figure FSA0000211705170000591
Figure FSA0000211705170000601
Figure FSA0000211705170000611
Figure FSA0000211705170000621
7. an organic electronic device, characterized by:
comprises a first electrode and a second electrode;
one or more layers of organic material layers are arranged between the first electrode and the second electrode;
wherein the organic material layer contains the compound according to any one of claims 1 to 6.
8. The organic electronic device according to claim 7, wherein the organic material layer is composed of one or more of a light emitting material, a sensitizing material, and a host material, and the compound is any one or more of the light emitting material, the sensitizing material, or the host material.
9. The organic electronic device according to claim 7, wherein the organic material layer comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer, and the compound is contained in a structure of the one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the electron transport layer, and the electron injection layer.
10. A display device or a lighting device comprising an organic electronic device according to any one of claims 7 to 9.
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WO2022131668A1 (en) * 2020-12-16 2022-06-23 주식회사 센텀머티리얼즈 Novel heterocyclic compound and organic light-emitting device comprising same
CN114671888A (en) * 2020-12-25 2022-06-28 佳能株式会社 Organic compound, organic light-emitting element, display device, photoelectric conversion device, electronic device, illumination device, and exposure light source
WO2022211314A1 (en) * 2021-03-31 2022-10-06 엘티소재주식회사 Heterocyclic compound, organic light-emitting device comprising same, manufacturing method therefor, and composition for organic layer
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