CN111440122A - Thermally activated delayed fluorescence material and organic light emitting device - Google Patents

Thermally activated delayed fluorescence material and organic light emitting device Download PDF

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CN111440122A
CN111440122A CN202010369434.4A CN202010369434A CN111440122A CN 111440122 A CN111440122 A CN 111440122A CN 202010369434 A CN202010369434 A CN 202010369434A CN 111440122 A CN111440122 A CN 111440122A
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compound
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emitting device
organic light
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蒋佐权
廖良生
屈扬坤
李虹成
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Suzhou University
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Abstract

The invention relates to a thermal activation delayed fluorescent material and an organic light-emitting device, wherein the thermal activation delayed fluorescent material comprises a compound represented by the following general formula (1):
Figure DDA0002476786080000011
wherein R is0、R1、R2And R3Each independently selected from hydrogen, deuterium, halogen groups, or any of substituted or unsubstituted C6-C30 aryl groups, C1-C20 aliphatic groups; r is selected from any one of substituted or unsubstituted aliphatic group of C1-C10, aryl group of C6-C30 and heteroaryl group of C4-C30; g is selected from a direct bond, or any of a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30; a is a group having electron-deficient properties. The main functional elements of the thermal activation delayed fluorescence material are close in space, can realize the function of space non-conjugated charge transfer, has high thermal stability, high glass transition temperature and excellent luminescence property, and canTo be efficiently applied to the organic light emitting device.

Description

Thermally activated delayed fluorescence material and organic light emitting device
Technical Field
The invention relates to a thermal activation delayed fluorescent material and an organic light-emitting device, belonging to the technical field of organic light-emitting.
Background
Unlike inorganic materials, Organic materials have the characteristics of low synthesis cost, adjustable function, flexibility and good film forming property, and devices based on Organic materials are generally simple in manufacturing process, easy to prepare in large area, environment-friendly and capable of adopting a thin film preparation method with lower operating temperature, so that the Organic light Emitting Diode (Organic L light Emitting Diode, O L ED for short) has the advantage of low manufacturing cost, has huge application potential and causes wide attention and research of domestic and foreign students in the last 30 years.
The Chihaya Adachi professor of Kyushu university in 2009 has found that Thermally Activated Delayed Fluorescence (TADF) materials based on triplet-singlet transition can also achieve 100% internal quantum efficiency, and such materials are mostly pure organic materials and have low cost, so the materials are called the third generation O L ED luminescent materials.
Based on three important papers published by Adachi professor (Nature 2012,492,234-ST) The reverse intersystem crossing condition of the triplet-singlet excitons is met, and finally the high efficiency of the material is achieved.
However, the TADF material constructed by the method still has many problems, the material with higher efficiency is still relatively scarce, the material shows higher efficiency roll-off in the device, the service life of the material is shorter, and the improvement from the molecular construction basis is needed.
Disclosure of Invention
The invention aims to provide a thermal activation delayed fluorescent material and an organic light-emitting device, wherein the main functional elements of the thermal activation delayed fluorescent material realize intramolecular charge interaction through space unconjugated connection, and the thermal activation delayed fluorescent material is completely different from a classical mechanism. Has high thermal stability, high glass transition temperature and excellent luminescence property, and can be efficiently applied to organic light-emitting devices.
In order to achieve the purpose, the invention provides the following technical scheme: a heat-activated delayed fluorescent material comprising a compound represented by the following general formula (1):
Figure BDA0002476786060000021
wherein R is0、R1、R2And R3Each independently selected from hydrogen, deuterium, halogen groups, or any of substituted or unsubstituted C6-C30 aryl groups, C1-C20 aliphatic groups; r is selected from any one of substituted or unsubstituted aliphatic group of C1-C10, aryl group of C6-C30 and heteroaryl group of C4-C30; g is selected from a direct bond, or any of a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30; a is a group having electron-deficient properties.
Further, the thermally activated delayed fluorescence material is selected from the following general formulae (2), (3), (4), (5):
Figure BDA0002476786060000031
wherein, R0, R1, R2 and R3 are respectively and independently selected from hydrogen, deuterium and halogen groups, or any one of substituted or unsubstituted C6-C30 aryl and C1-C20 aliphatic groups; g is selected from any one of a direct bond, a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30; r4 is selected from substituted or unsubstituted C1-C6 aliphatic; a is a group having electron-deficient properties.
Further, in the compound represented by the general formula (1), a is selected from any one of a nitrile group, a sulfone group, a carbonyl group, an ester group, a nitrile group aromatic ring, a sulfone group aromatic ring, a carbonyl aromatic ring, an ester group aromatic ring, a heteroaryl group, or an aromatic boron group.
Further, in the compound represented by the general formula (1), G is selected from a substituted or unsubstituted C6-C30 arylene group, or, a C4-C30 heteroarylene group
Further, in the compound represented by the general formula (1), -G-A is selected from the following arbitrary combinations of G groups and A groups,
a G group:
Figure BDA0002476786060000032
Figure BDA0002476786060000041
Figure BDA0002476786060000051
group A:
Figure BDA0002476786060000052
Figure BDA0002476786060000061
Figure BDA0002476786060000071
Figure BDA0002476786060000081
Figure BDA0002476786060000091
Figure BDA0002476786060000101
Figure BDA0002476786060000111
Figure BDA0002476786060000121
wherein R5 at each position is independently selected from hydrogen, cyano, or any one of substituted or unsubstituted aliphatic group of C1-C10, arylamine group of C6-C24, aryl group of C6-C24, heteroaryl group of C4-C24, pyridine and thiophene.
Further, in the compound represented by the general formula (1), G is a direct bond; a is selected from any one of nitrile group, sulfone group, carbonyl group, ester group, nitrile group aromatic ring, sulfone group aromatic ring, carbonyl aromatic ring, ester group aromatic ring, heteroaryl group or aromatic boron group.
Further, in the compound represented by the general formula (1), G-A is selected from the following arbitrary combinations of G groups and A groups: a direct bond;
group A:
Figure BDA0002476786060000122
Figure BDA0002476786060000131
Figure BDA0002476786060000141
Figure BDA0002476786060000151
Figure BDA0002476786060000161
Figure BDA0002476786060000171
Figure BDA0002476786060000181
Figure BDA0002476786060000191
wherein R5 at each position is independently selected from hydrogen, cyano, or any one of substituted or unsubstituted aliphatic group of C1-C10, arylamine group of C6-C24, aryl group of C6-C24, heteroaryl group of C4-C24, pyridine and thiophene.
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 thermal activation delayed fluorescence material.
Further, the light emitting layer contains a sensitizing material, a light emitting material, and a host material, and the heat-activated delayed fluorescence material is used as the sensitizing material, and/or the light emitting 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 thermally activated delayed fluorescence material is contained in any 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.
Compared with the prior art, the invention has the beneficial effects that: the main functional elements of the thermal activation delay fluorescent material realize a intramolecular space charge transfer mechanism through space unconjugated connection. The material has high thermal stability, high glass transition temperature and excellent luminescence property, and can be used as the material of an organic material layer of an organic light-emitting device, in particular the material of a luminescent layer. The compound according to at least one exemplary embodiment of the present specification may achieve high efficiency thermally activated delayed fluorescence and achieve high efficiency of an organic light emitting device while achieving a low driving voltage; the compound according to at least one exemplary embodiment of the present specification may realize a highly efficient fluorescence-sensitized light emitting device; compounds according to at least one exemplary embodiment of the present description exhibit transient luminescence lifetimes in the order of microseconds. In particular, the compounds described in the present specification can be used as materials for light emission and fluorescence sensitization.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 shows an example of an organic light-emitting device composed of a substrate 1, a positive electrode 2, a light-emitting layer 3, and a negative electrode 4.
Fig. 2 shows an example of an organic light-emitting device composed of a substrate 1, a positive electrode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, and a negative electrode 7.
Reference numerals
1: substrate
2: positive electrode
3: hole injection layer
4: hole transport layer
5: luminescent layer
6: electron transport layer
7: negative electrode
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
A heat-activated delayed fluorescent material comprising a compound represented by the following general formula (1):
Figure BDA0002476786060000211
wherein R is0、R1、R2、R3Each independently selected from hydrogen, deuterium, halogen groups, or any of substituted or unsubstituted C6-C30 aryl groups, C1-C20 aliphatic groups; r is selected from any one of substituted or unsubstituted aliphatic group of C1-C10, aryl group of C6-C30 and heteroaryl group of C4-C30; g is selected from a direct bond, or any of a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30; a is a group having electron-deficient properties.
Preferably, the thermally activated delayed fluorescence material is selected from the following general formula (2), (3), (4) or (5):
Figure BDA0002476786060000212
wherein R is0、R1、R2、R3Each independently selected from hydrogen, deuterium, halogen groups, or any of substituted or unsubstituted C6-C30 aryl groups, C1-C20 aliphatic groups; g is selected from a direct bond, or any of a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30; a is a group with electron-deficient properties; preferably, a is selected from any one of a nitrile group, a sulfone group, a carbonyl group, an ester group, a nitrile group aromatic ring, a sulfone group aromatic ring, a carbonyl group aromatic ring, an ester group aromatic ring, a heteroaryl group, and an aromatic boron group.
Specifically, in the compound represented by the general formula (1), when G is a structure with a benzene bridge, G is selected from any one of substituted or unsubstituted arylene groups of C6-C30 and heteroarylene groups of C4-C30; a is selected from any one of nitrile group, sulfone group, carbonyl group, ester group, nitrile group aromatic ring, sulfone group aromatic ring, carbonyl aromatic ring, ester group aromatic ring, heteroaryl group and aromatic boron group. Preferably, G-A is selected from any combination of the following G groups and A groups,
a G group:
Figure BDA0002476786060000221
Figure BDA0002476786060000231
group A:
Figure BDA0002476786060000241
Figure BDA0002476786060000251
Figure BDA0002476786060000261
Figure BDA0002476786060000271
Figure BDA0002476786060000281
Figure BDA0002476786060000291
Figure BDA0002476786060000301
wherein R at each position5Each independently selected from hydrogen, cyano, or any one of substituted or unsubstituted aliphatic group of C1-C10, arylamine group of C6-C24, aryl group of C6-C24, heteroaryl group of C4-C24, pyridine and thiophene.
Specifically, in the compound represented by the general formula (1), when G is a structure without a benzene bridge, G is a direct bond; a is selected from any one of substituted or unsubstituted aralkyl, aralkenyl, aryl and heteroaryl. Preferably, G-A is selected from any combination of the following G groups and A groups,
a G group: a direct bond;
group A:
Figure BDA0002476786060000311
Figure BDA0002476786060000321
Figure BDA0002476786060000331
Figure BDA0002476786060000341
Figure BDA0002476786060000351
Figure BDA0002476786060000361
Figure BDA0002476786060000371
Figure BDA0002476786060000381
wherein R at each position5Each independently selected from hydrogen, cyano, or any one of substituted or unsubstituted aliphatic group of C1-C10, arylamine group of C6-C24, aryl group of C6-C24, heteroaryl group of C4-C24, pyridine and thiophene.
Preferably, the heat-activated delayed fluorescence material is preferably a compound of the following formulae 1-1 to 1-124, 2-1 to 2-124, 3-1 to 3-124, and 4-1 to 4-124:
Figure BDA0002476786060000382
Figure BDA0002476786060000391
Figure BDA0002476786060000401
Figure BDA0002476786060000411
Figure BDA0002476786060000421
2-1 to 2-124, 3-1 to 3-124 and 4-1 to 4-124 are the substitutions of the general formula (2) in the formulae 1-1 to 1-124 to the general formula (3), the general formula (4) and the general formula (5).
Figure BDA0002476786060000422
Figure BDA0002476786060000431
Figure BDA0002476786060000441
Figure BDA0002476786060000451
Figure BDA0002476786060000461
Figure BDA0002476786060000471
Figure BDA0002476786060000481
Figure BDA0002476786060000491
Figure BDA0002476786060000501
Figure BDA0002476786060000511
Figure BDA0002476786060000521
Figure BDA0002476786060000531
Figure BDA0002476786060000541
Among them, the compounds represented by the above structural formula may be substituted at each carbon atom, and preferably, hydrogen, cyano, or a substituted or unsubstituted aliphatic group of C1-C10, an arylamine group of C6-C24, an aryl group of C6-C24, a heteroaryl group of C4-C24, pyridine, thiophene, etc.
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 BDA0002476786060000551
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 BDA0002476786060000552
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 BDA0002476786060000553
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 BDA0002476786060000561
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 beMonocyclic aryl or polycyclic aryl. 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 BDA0002476786060000584
Fluorenyl, triphenylene, and the like, but are 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 BDA0002476786060000581
Figure BDA0002476786060000582
And
Figure BDA0002476786060000583
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 BDA0002476786060000601
Pentacene, fluorene, indene, acenaphthene, benzofluorene, spirofluorene, etc., but 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, 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.
The compound of chemical formula 1 may be prepared by the following reaction scheme.
[ reaction formula 1]
Figure BDA0002476786060000611
[ reaction formula 2]
Figure BDA0002476786060000612
[ reaction formula 3]
Figure BDA0002476786060000613
[ reaction formula 4]
Figure BDA0002476786060000614
Figure BDA0002476786060000621
[ reaction formula 1]
Figure BDA0002476786060000622
[ reaction formula 2]
Figure BDA0002476786060000623
[ reaction formula 3]
Figure BDA0002476786060000624
Figure BDA0002476786060000631
[ reaction formula 4]
Figure BDA0002476786060000632
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 formulae 1 to 5, 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 formulas 1 to 5, however, the reaction is not limited thereto.
Figure BDA0002476786060000641
The invention also provides an organic electroluminescent device prepared on the basis of the thermal activation delayed fluorescence material, which comprises an anode and a cathode which are oppositely arranged, wherein one or more organic material layers are arranged between the anode and the cathode, the organic material layers comprise a light-emitting layer, and the light-emitting layer contains the thermal activation delayed fluorescence material. Wherein the luminescent layer is composed of a sensitizing material, a luminescent material and a host material, and the thermally activated delayed fluorescence material is used as any one or more of the sensitizing material or the luminescent 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 thermally activated delayed fluorescent material provided in the light emitting layer, the thermally activated delayed fluorescent material 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 light emitting layer composed of a host material and a guest light emitting material, a doping ratio of the guest material is preferably in a range of 10% to 70%, and the guest light emitting material includes a compound of the general formula (1).
In 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 of the present specification, the organic material layer includes a light emitting layer composed of a host material, a guest light emitting material, and a sensitizing material, and the light emitting layer includes a compound represented by general formula (1) as a doping sensitizing material.
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 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 the group consisting of an organic light emitting device, an organic phosphorescent device, an organic solar cell, an organic photoconductor, and an organic transistor.
Hereinafter, an organic light emitting device will be explained.
An exemplary embodiment of the present specification provides an organic light emitting device including a cathode; an anode disposed to face the cathode; a light emitting layer disposed between the cathode and the anode; and two or more organic material layers disposed between the light emitting layer and the cathode or between the light emitting layer and the anode, 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 two or more electron transport layers, materials other 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 (normal type) having a structure in which a positive electrode, one or more organic material layers, and a negative electrode are sequentially stacked on a substrate.
In still another exemplary embodiment, the organic light emitting device may be an organic light emitting device (an inverted type) having an inverted structure in which a negative electrode, one or more organic material layers, and a positive electrode are sequentially stacked on a substrate.
For example, the structure of the organic light emitting device according to 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 positive electrode 2, a light emitting layer 3, and a negative 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 positive electrode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a negative electrode 7. In the structure as described above, the compound may be included in one or more layers of the hole injection layer, the hole transport layer, the light emitting layer, and the electron transport 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.
In addition, in manufacturing the organic light emitting device, the compound of chemical 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, e.g. ZnO: Al or SnO2Sb; 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.
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, and multilayer structure materials such as L iFAl or L iO2Al, 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 that can receive holes from the positive electrode or the hole injection layer, transfer the holes to the light emitting layer, and have a high transfer rate for 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 light emitting layer may include a host material and a dopant material, and the dopant 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 metal complex or organic compound may be used as long as the triplet energy of the host is larger than that of the dopant. Any host material may be used with any dopant, provided that the triplet criteria is met primarily.
Examples of the organic compound host material include a fused aromatic ring derivative, a heterocyclic ring-containing compound, or the like. Specific examples of the fused aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but the examples thereof are not limited thereto.
Examples of organic compounds used as hosts 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 BDA0002476786060000671
Perylene and azulene; a group consisting of the following aromatic heterocyclic compounds: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyridobipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, 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 selenenopyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types 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. 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, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid,Ethers, esters, nitriles, isonitriles, thio, sulfinato, sulfophthalo, phosphino and combinations thereof.
According to one exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by formula 1 as a doped light emitting material.
Figure BDA0002476786060000681
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is a methyl group, G is a single bond, A is 4, 6- diphenyl 1,3, 5-triazine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is hydrogen atom, R is phenyl, G is single bond, A is 4, 6- diphenyl 1,3, 5-triazine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is a phenyl group, G is a phenyl group, and A is 4, 6-diphenyl-1, 3, 5-triazine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is a methyl group, G is a phenyl group, and A is 4, 6-diphenyl-1, 3, 5-triazine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is pyridine, G is phenyl, A is 4, 6- diphenyl 1,3, 5-triazine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is thiophene, G is phenyl, and A is 4, 6-diphenyl-1, 3, 5-triazine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is furan, G is phenyl, A is 4, 6-diphenyl-1, 3, 5-triazine.
In one exemplary implementation of the present descriptionIn the examples, R0、R1、R2、R3Is a hydrogen atom, R is a phenyl group, G is a phenyl group, and A is 4, 6-diphenyl-1, 3, 5-triazine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is a methyl group, G is a phenyl group, and A is 2, 6-diphenylpyrimidine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is a phenyl group, G is a phenyl group, and A is 2, 6-diphenylpyrimidine.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is hydrogen atom, R is methyl, G is single bond, A is diphenyl sulfone.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is hydrogen atom, R is phenyl, G is single bond, A is diphenyl sulfone.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is hydrogen atom, R is methyl, G is phenyl, A is benzophenone oxide.
In one exemplary embodiment of the present specification, R0、R1、R2、R3Is a hydrogen atom, R is a methyl group, G is a single bond, and A is benzonitrile.
According to another exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by formula 1 as a dopant sensitizing material.
The light emitting layer may include a host material, a dopant light emitting material, and a dopant sensitizing material. The luminescent material is preferably a material: which can receive holes and electrons respectively transported by a hole transport layer and an electron transport layer and combine the holes and the electrons to emit light in a visible light region, and 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; di-polystyrene vinylationA 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, and the like, but are not limited thereto.
The organic light emitting device of the present specification can be manufactured by materials and methods known in the art, except that one or more of the organic material layers contains the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by the general 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.
The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and the electron transport material is a suitable material for: it can inject electrons from the negative electrode well and transfer the electrons to the light-emitting layer, and has a high mobility for electrons. Specific examples thereof include: al complex of 8-hydroxyquinoline comprising Alq3The complex of (a), an organic radical compound, a hydroxyflavone-metal complex, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used according to the related art. Suitable examples of cathode materials are in particular typical materials having 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 or 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 has an excellent electron injection effect on a light emitting layer or a light emitting material, prevents excitons generated in the light emitting layer from moving to a hole injection layer, and also has an excellent thin film forming ability. Specific examples thereof include fluorenone, anthraquinone dimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthrone, and the like, and derivatives thereof, metal complex compounds, nitrogen-containing 5-membered ring derivatives thereof, and the like, but are not limited thereto.
In another exemplary embodiment of the present description, the organic material layer includes a host material and a dopant material. Examples of the organic compound host material include a fused aromatic ring derivative or a heterocyclic ring-containing compound and the like. The dopant light emitting material comprises a compound of the general formula (1), and the organic material layer is subjected to transient light emission spectroscopy. Transient lifetime with duration of nanosecond and delayed lifetime with duration of microsecond are observed simultaneously in transient luminescence spectrum test, and the fact that the compound of the general formula (1) has delayed fluorescence behavior is proved to be capable of effectively utilizing triplet excitons. The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a dual emission type, depending on the material used.
In one exemplary embodiment of the present specification, the compound of formula (1) may be included in an organic solar cell or an organic transistor, in addition to an organic light emitting device.
The preparation of the compound represented by the general formula (1) and the organic light emitting device comprising the same will be specifically described in the following examples. However, the following examples are provided to illustrate the present specification, and the scope of the present specification is not limited thereby.
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.
< preparation example 1> Synthesis of the following Compound 1
Figure BDA0002476786060000711
9-Fluorenone-1-boronic acid (5.0g,22.32mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.98g,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 blanket and 90ml tetrahydrofuran and 22ml distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction product is filtered by suction, washed by a large amount of distilled water and then recrystallized by dichloromethane/ethanol to obtain an intermediate 1(7.89g, the yield of 19.20mmol is about 86 percent) which is dried for later use. Under the protection of nitrogen, 2-bromo-N-methyl-N-phenylaniline (5.03g,19.20mmol) was placed in a 250ml two-necked flask, 77ml of anhydrous tetrahydrofuran was added to dissolve the 2-bromo-N-methyl-N-phenylaniline, then the solution was placed at minus 78 ℃ and a 2.4M N-butyllithium solution (8.80ml,21.12mmol) was added dropwise thereto, and after stirring at minus 78 ℃ for 1 hour, intermediate 1(7.90g,19.20mmol) was added, and after stirring overnight, the mixture was quenched by adding 20ml of distilled water. 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 1(8.20g,14.21mmol, the yield is about 74%) is obtained.
MS[M+H]+＝576
< preparation example 2> Synthesis of the following Compound 2
Figure BDA0002476786060000721
Under the protection of nitrogen, 2-bromotriphenylamine (6.22g,19.20mmol) is placed in a 250ml two-neck flask, 77ml of anhydrous tetrahydrofuran is added to dissolve the 2-bromotriphenylamine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.80ml,21.12mmol) is added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 1(7.89g,19.20mmol) is added, and after stirring overnight, 20ml of distilled water is added for quenching. 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 with the mixture of dichloromethane and petroleum ether, and the compound 2(9.81g,15.35mmol, the yield is about 80%) is obtained.
MS[M+H]+＝638
< preparation example 3> Synthesis of the following Compound 3
Figure BDA0002476786060000731
9-fluorenone-1-boronic acid (5.0g,22.32mmol), 2- (4-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (8.66g,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 blanket and 90ml tetrahydrofuran and 22ml distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction product is filtered, washed by a large amount of distilled water and then recrystallized and purified by dichloromethane/ethanol to obtain an intermediate 2(8.70g, the yield is about 80 percent), and the intermediate is dried for later use. Under the protection of nitrogen, 2-bromo-triphenylamine (5.79g,17.86mmol) is placed in a 250ml two-neck flask, 77ml of anhydrous tetrahydrofuran is added to dissolve the 2-bromo-triphenylamine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18ml,19.64mmol) is added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 2(8.72g,17.86mmol) is added, and after stirring overnight, 20ml of distilled water is added for quenching. 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 with the mixture of dichloromethane and petroleum ether, and the compound 3(10.22g,14.29mmol, the yield is about 80%) is obtained.
MS[M+H]+＝714
< preparation example 4> Synthesis of the following Compound 4
Figure BDA0002476786060000741
Under the protection of nitrogen, 2-bromo-diphenylamine (5.79g,17.86mmol) was placed in a 250ml two-necked flask, 77ml of anhydrous tetrahydrofuran was added to dissolve the 2-bromo-diphenylamine, then the flask was placed at-78 ℃, a 2.4M n-butyllithium solution (16.36ml,39.26mmol) was added dropwise, after stirring at-78 ℃ for 1 hour, intermediate 2(8.72g,17.86mmol) was added, and after stirring overnight, 20ml of distilled water was added to quench the flask. 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 eluent with the mixture ratio of dichloromethane and petroleum ether, and then the intermediate 3(7.11g,11.13mmol) is obtained. This intermediate 3 was redissolved in 50ml of DMF, and iodomethane (4.26g, 30mmol) and potassium carbonate (8.28g, 60mmol) were added thereto, and the mixture was stirred under heating for 3 hours, and the reaction liquid was poured into 500ml of ice water to precipitate a product, which was then filtered off with suction and recrystallized from ethyl acetate to obtain compound 4(6.95g, 10.64mmol, yield about 60%).
MS[M+H]+＝652
< preparation example 5> Synthesis of the following Compound 5
Figure BDA0002476786060000751
Intermediate 3(7.99g,12.50mmol), 4-bromopyridine (2.17g,13.75mmol), palladium acetate (140.30mg,0.625mmol), tri-tert-butylphosphine (126.45mg,0.625mmol), sodium tert-butoxide (2.40g,25mmol) were added to a 100ml round bottom flask under nitrogen protection, and 50ml of toluene were added and the mixture heated under reflux for 24 hours. After the reaction, the temperature was decreased to room temperature, toluene was removed under reduced pressure, 20ml of water and 40ml of dichloromethane were added to extract 3 times, the organic layers were combined, dichloromethane was removed under reduced pressure, and silica gel column chromatography was performed using an eluent mixture of dichloromethane and petroleum ether to obtain compound 5(5.82g, yield about 65%).
MS[M+H]+＝715
< preparation example 6> Synthesis of the following Compound 6
Figure BDA0002476786060000752
Under nitrogen protection, intermediate 3(7.99g,12.50mmol), 2-bromothiophene (2.24g,13.75mmol), palladium acetate (140.30mg,0.625mmol), tri-tert-butylphosphine (126.45mg,0.625mmol), sodium tert-butoxide (2.40g,25mmol) were added to a 100ml round-bottomed flask, and 50ml of toluene were added, and the mixture was heated under reflux for 24 hours. After the reaction, the temperature was decreased to room temperature, toluene was removed under reduced pressure, 20ml of water and 40ml of dichloromethane were added to extract 3 times, then the organic layers were combined, dichloromethane was removed under reduced pressure, and silica gel column chromatography was performed using an eluent mixture of dichloromethane and petroleum ether to obtain compound 6(6.72g, yield about 75%).
MS[M+H]+＝720
< preparation example 7> Synthesis of the following Compound 7
Figure BDA0002476786060000761
Under nitrogen protection, intermediate 3(7.99g,12.50mmol), 2-bromofuran (2.02g,13.75mmol), palladium acetate (140.30mg,0.625mmol), tri-tert-butylphosphine (126.45mg,0.625mmol), sodium tert-butoxide (2.40g,25mmol) were added to a 100ml round-bottomed flask, and 50ml of toluene were added, and the mixture was heated under reflux for 24 hours. After the reaction, the temperature was decreased to room temperature, toluene was removed under reduced pressure, 20ml of water and 40ml of dichloromethane were added to extract 3 times, the organic layers were combined, dichloromethane was removed under reduced pressure, and silica gel column chromatography was performed using an eluent mixture of dichloromethane and petroleum ether to obtain compound 7(5.38g, yield about 61%).
MS[M+H]+＝704
< preparation example 8> Synthesis of the following Compound 8
Figure BDA0002476786060000771
9-fluorenone-1-boronic acid (5.0g,22.32mmol), 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (8.66g,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 blanket and 90ml tetrahydrofuran and 22ml distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction product is filtered, washed by a large amount of distilled water and then recrystallized and purified by dichloromethane/ethanol to obtain an intermediate 4(8.70g, the yield is about 80 percent) which is dried for later use. Under the protection of nitrogen, 2-bromo-triphenylamine (5.79g,17.86mmol) is placed in a 250ml two-neck flask, 77ml of anhydrous tetrahydrofuran is added to dissolve the 2-bromo-triphenylamine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18ml,19.64mmol) is added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 4(8.70g,17.86mmol) is added, and after stirring overnight, 20ml of distilled water is added for quenching. 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(11.00g,15.38mmol, yield is about 86%) is obtained.
MS[M+H]+＝714
< preparation example 9> Synthesis of the following Compound 9
Figure BDA0002476786060000781
9-fluorenone-1-boronic acid (5.0g,22.32mmol), 4- (4-bromophenyl) -2, 6-diphenylpyrimidine (8.64g,22.32mmol), tetrakis (triphenylphosphine) palladium (773.39mg,0.67mmol), and anhydrous potassium carbonate (6.16g,44.64mmol) were placed in a 250ml round bottom flask under nitrogen, and 90ml of tetrahydrofuran and 22ml of distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction, the temperature was reduced to room temperature, filtered, washed with a large amount of distilled water, and then recrystallized from dichloromethane/ethanol to purify intermediate 5(8.70g, yield about 80%) which was then dried for further use. Under the protection of nitrogen, 2-bromo-N-methyl-N-phenylaniline (4.68g,17.86mmol) was placed in a 250ml two-necked flask, 77ml of anhydrous tetrahydrofuran was added to dissolve the solution, then the solution was placed at minus 78 ℃, a 2.4M N-butyllithium solution (8.18ml,19.64mmol) was added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 5(8.70g,17.86mmol) was added, and after stirring overnight, 20ml of distilled water was 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, 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 9(8.87g,13.60mmol, the yield is about 76%) is obtained.
MS[M+H]+＝651
< preparation example 10> Synthesis of the following Compound 10
Figure BDA0002476786060000791
Under the protection of nitrogen, 2-bromo-triphenylamine (5.79g,17.86mmol) is placed in a 250ml two-neck flask, 77ml of anhydrous tetrahydrofuran is added to dissolve the 2-bromo-triphenylamine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18ml,19.63mmol) is added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 5(8.70g,17.86mmol) is added, and after stirring overnight, 20ml of distilled water is added for quenching. 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 reduced to room temperature, and the reaction mixture was poured into 500ml of ice water to precipitate the product, which was then filtered off with a suction and subjected to silica gel column chromatography using a eluent mixture of dichloromethane and petroleum ether to obtain compound 10(10.20g,14.29mmol, yield about 80%).
MS[M+H]+＝713
< preparation example 11> Synthesis of the following Compound 11
Figure BDA0002476786060000801
9-fluorenone-1-boronic acid (5.0g,22.32mmol), 1-bromo-4- (phenylsulfonyl) benzene (6.63g,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, the temperature is reduced to room temperature, the reaction solution is filtered by suction, washed by a large amount of distilled water and then recrystallized by dichloromethane/ethanol to obtain an intermediate 6(6.63g,16.74mmol, the yield is about 75 percent) which is dried for later use. Under the protection of nitrogen, 2-bromo-N-methyl-N-phenylaniline (4.39g,16.74mmol) was placed in a 250ml two-necked flask, 77ml of anhydrous tetrahydrofuran was added to dissolve the solution, then the solution was placed at minus 78 ℃, a 2.4M N-butyllithium solution (7.67ml,18.41mmol) was added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 6(6.63g,16.74mmol) was added, and after stirring overnight, 20ml of distilled water was 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, 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 11(7.64g,13.60mmol, the yield is about 81%) is obtained.
MS[M+H]+＝561
< preparation example 12> Synthesis of the following Compound 12
Figure BDA0002476786060000811
Under the protection of nitrogen, 2-bromo-triphenylamine (5.79g,17.86mmol) is placed in a 250ml two-neck flask, 77ml of anhydrous tetrahydrofuran is added to dissolve the 2-bromo-triphenylamine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18ml,19.63mmol) is added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 6(7.07g,17.86mmol) is added, and after stirring overnight, 20ml of distilled water is added for quenching. 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 with the mixture of dichloromethane and petroleum ether, and the compound 12(7.10g,11.38mmol, the yield is about 64%) is obtained.
MS[M+H]+＝623
< preparation example 13> Synthesis of the following Compound 13
Figure BDA0002476786060000821
9-fluorenone-1-boronic acid (5.0g,22.32mmol), p-bromoiodobenzene (11.49g,40.60mmol), tetrakis (triphenylphosphine) palladium (773.39mg,0.67mmol), anhydrous potassium carbonate (6.17g,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, the temperature was reduced to room temperature, filtered, washed with a large amount of distilled water, and then purified by recrystallization from methylene chloride/ethanol to give intermediate 7(6.73g,20.10mmol, yield about 90%), which was dried for use. Under the protection of nitrogen, 2-bromo-N-methyl-N-phenylaniline (4.68g,17.86mmol) was placed in a 250ml two-necked flask, 77ml of anhydrous tetrahydrofuran was added to dissolve the solution, then the solution was placed at minus 78 ℃, a 2.4M N-butyllithium solution (8.18ml,19.63mmol) was added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 7(5.98g,17.86mmol) was added, and after stirring overnight, 20ml of distilled water was 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 with the mixture of dichloromethane and petroleum ether, and then the intermediate 8(6.53g,13.06mmol, the yield is about 76%) is obtained. 9, 10-anthraquinone-2-pinacol boronate (3.34g,10.00mmol), intermediate 8(5.00g,10.00mmol), tetrakis (triphenylphosphine) palladium (346.50mg,0.30mmol), anhydrous potassium carbonate (2.76g,20.00mmol) were placed in a 250ml round bottom flask under nitrogen and 40ml tetrahydrofuran and 20ml distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, and the reaction mixture was filtered, washed with distilled water, and then purified by recrystallization from methylene chloride/ethanol to obtain compound 13(5.15g, yield about 82%).
MS[M+H]+＝627
< preparation example 14> Synthesis of the following Compound 14
Figure BDA0002476786060000831
Placing intermediate 8(5.47g,10.93mmol) and cuprous cyanide (3.92g,43.72mmol) in a 100ml two-neck round-bottom flask under nitrogen protection, adding 50ml of DMF (with water and oxygen removed), heating and refluxing the mixture for 24 hours, finishing the reaction, cooling to room temperature, adding 40ml of 1M sodium hydroxide solution, pouring the mixture into 200ml of ice water, precipitating the product, performing suction filtration, and performing silica gel column chromatography by using dichloromethane and petroleum ether ratio eluent to obtain compound 14(4.64g, 10.38mmol, the yield is about 95%).
MS[M+H]+＝446
< preparation example 15> Synthesis of the following Compound 15
Figure BDA0002476786060000841
Under the protection of nitrogen, placing the intermediate 8(5.47g,10.93mmol) in a 250ml two-neck bottle, adding 50ml of anhydrous tetrahydrofuran for dissolving, then placing at minus 78 ℃, dropwise adding a 2.4M n-butyllithium solution (5.01ml,12.02mmol), stirring at minus 78 ℃ for 1 hour, adding bis (mesitylene) boron fluoride (3.51g,13.12mmol), stirring overnight, and adding 10ml of distilled water for quenching. The reaction mixture was subjected to removal of tetrahydrofuran under reduced pressure, extracted 3 times with 40ml of dichloromethane, subjected to removal of dichloromethane under reduced pressure, and subjected to silica gel column chromatography using a eluent comprising dichloromethane and petroleum ether to give compound 15(4.76g, 7.10mmol, yield: 65%).
MS[M+H]+＝669
< preparation example 16> Synthesis of the following Compound 16
Figure BDA0002476786060000842
9-fluorenone-1-boronic acid (5.0g,22.32mmol), m-bromoiodobenzene (11.49g,40.60mmol), tetrakis (triphenylphosphine) palladium (773.39mg,0.67mmol), anhydrous potassium carbonate (6.17g,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, the temperature was reduced to room temperature, filtered, washed with a large amount of distilled water, and then purified by recrystallization from dichloromethane/ethanol to give intermediate 9(6.73g,20.10mmol, yield about 90%), which was dried for use. Under the protection of nitrogen, 2-bromo-triphenylamine (5.79g,17.86mmol) is placed in a 250ml two-neck flask, 77ml of anhydrous tetrahydrofuran is added to dissolve the 2-bromo-triphenylamine, then the solution is placed at minus 78 ℃, a 2.4M n-butyllithium solution (8.18ml,19.63mmol) is added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 9(5.98g,17.86mmol) is added, and after stirring overnight, 20ml of distilled water is added for quenching. 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 with the mixture ratio of dichloromethane and petroleum ether, and the intermediate 10(6.78g,12.06mmol, the yield is about 68%) is obtained. Under the protection of nitrogen, placing the intermediate 10(6.14g,10.93mmol) in a 250ml two-neck bottle, adding 50ml of anhydrous tetrahydrofuran for dissolving, then placing at minus 78 ℃, dropwise adding a 2.4M n-butyllithium solution (5.01ml,12.02mmol), stirring at minus 78 ℃ for 1 hour, adding bis (mesitylene) boron fluoride (3.51g,13.12mmol), stirring overnight, and adding 10ml of distilled water for quenching. The reaction mixture was subjected to removal of tetrahydrofuran under reduced pressure, extracted 3 times with 40ml of dichloromethane, subjected to removal of dichloromethane under reduced pressure, and subjected to silica gel column chromatography using a eluent comprising dichloromethane and petroleum ether to give compound 16(4.80g, 6.56mmol, yield about 60%).
MS[M+H]+＝731
< preparation example 17> Synthesis of the following Compound 17
Figure BDA0002476786060000861
9-fluorenone-1-boronic acid (5.0g,22.32mmol), symtribromobenzene (12.79g,40.60mmol), tetrakis (triphenylphosphine) palladium (773.39mg,0.67mmol), anhydrous potassium carbonate (6.17g,44.64mmol) were placed in a 250ml round bottom flask under nitrogen protection and 90ml tetrahydrofuran and 22ml distilled water were added. The above mixture was heated to reflux for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, the reaction product is filtered by suction, washed by a large amount of distilled water and then recrystallized by dichloromethane/ethanol to obtain an intermediate 11(8.16g,19.70mmol, the yield is about 88 percent) which is dried for later use. Under the protection of nitrogen, 2-bromo-N-methyl-N-phenylaniline (4.68g,17.86mmol) was placed in a 250ml two-necked flask, 77ml of anhydrous tetrahydrofuran was added to dissolve the solution, then the solution was placed at minus 78 ℃, a 2.4M N-butyllithium solution (8.18ml,19.63mmol) was added dropwise, after stirring at minus 78 ℃ for 1 hour, intermediate 11(5.98g,17.86mmol) was added, and after stirring overnight, 20ml of distilled water was 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 with the mixture of dichloromethane and petroleum ether, and the intermediate 12(8.13g,14.05mmol, the yield is about 79%) is obtained. Placing intermediate 12(6.33g,10.93mmol) and cuprous cyanide (3.92g,43.72mmol) in a 100ml two-neck round-bottom flask under nitrogen protection, adding 50ml of DMF (with water and oxygen removed), heating and refluxing the mixture for 24 hours, ending the reaction, cooling to room temperature, adding 40ml of 1M sodium hydroxide solution, pouring the mixture into 200ml of ice water, precipitating the product, performing suction filtration, and performing silica gel column chromatography by using dichloromethane-petroleum ether ratio eluent to obtain compound 17(3.41g, 7.23mmol, the yield is about 66%).
MS[M+H]+＝471
< preparation example 18> Synthesis of the following Compound 18
Figure BDA0002476786060000871
Under the protection of nitrogen, 2-bromo-diphenylamine (4.43g,17.86mmol) was placed in a 250ml two-necked flask, 77ml of anhydrous tetrahydrofuran was added to dissolve the 2-bromo-diphenylamine, then the flask was placed at-78 ℃, a 2.4M n-butyllithium solution (16.36ml,39.26mmol) was added dropwise, after stirring at-78 ℃ for 1 hour, intermediate 11(5.98g,17.86mmol) was added, and after stirring overnight, 20ml of distilled water was 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, a product is separated out, after suction filtration, silica gel column chromatography is carried out by using eluent with the mixture of dichloromethane and petroleum ether, and then the intermediate 13(6.29g,9.8mmol, the yield is about 55%) is obtained. Intermediate 13(5.09g,9.00mmol), 4-bromopyridine (1.56g,9.90mmol), palladium acetate (101.02mg,0.45mmol), tri-tert-butylphosphine (91.04mg,0.45mmol), sodium tert-butoxide (1.73g,18mmol) were added to a 100ml round bottom flask under nitrogen protection, and 36ml of toluene were added and the mixture was heated under reflux for 24 hours. After the reaction, the temperature was decreased to room temperature, toluene was removed under reduced pressure, 20ml of water and 40ml of dichloromethane were added to extract for 3 times, the organic layers were combined, dichloromethane was removed under reduced pressure, and silica gel column chromatography was performed using a eluent mixture of dichloromethane and petroleum ether to obtain intermediate 14(5.02g,7.82mmol, yield about 87%).
Placing intermediate 14(5.02g,7.82mmol) and cuprous cyanide (2.80g,31.28mmol) in a 100ml two-neck round-bottom flask under nitrogen protection, adding 36ml of DMF (with water and oxygen removed), heating and refluxing the mixture for 24 hours, cooling to room temperature, adding 30ml of 1M sodium hydroxide solution, pouring the mixture into 200ml of ice water, precipitating the product, performing suction filtration, and performing silica gel column chromatography by using dichloromethane-petroleum ether ratio eluent to obtain compound 18(2.64g, 4.93mmol, yield about 63%).
MS[M+H]+＝534
Figure BDA0002476786060000891
One exemplary example a comparative example of the preparation method:
for comparison, the molecule of example 1 was synthesized as follows
< comparative example 1> Synthesis of the following Compound 1
10-methyl-10-hydro-spiroacridine-9, 9 '-fluorenyl-1' -boronic acid (8.68g,22.32mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (5.98g,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 protection, and 90ml of tetrahydrofuran and 22ml of 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.
Figure BDA0002476786060000901
< comparative example 2> Synthesis of the following Compound 1
Figure BDA0002476786060000902
1 '-bromo-10-methyl-10-hydro-spiroacridine-9, 9' -fluorene (9.47g,22.32mmol), 4, 6-diphenyl-1, 3, 5-triazine-2-boronic acid (6.18g,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 protection 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.
Examples 1-1 to 1-18 (Compounds as luminescent Material)
Experimental example 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 BDA0002476786060000903
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 chemical formula is heated in vacuumOn the transparent ITO electrode thus prepared to a thickness of
Figure BDA0002476786060000905
As a hole injection layer.
Figure BDA0002476786060000904
The following compound 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)
Figure BDA0002476786060000911
Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Figure BDA0002476786060000912
Subsequently, the following compound 1, 3-di-9-carbazolylbenzene (mCP) as a material for electron blocking was used
Figure BDA0002476786060000913
Figure BDA0002476786060000914
Vacuum depositing on the hole transport layer to form an electron blocking layer.
Figure BDA0002476786060000915
Then, the following compound 1 and bis [2- ((oxo) diphenylphosphino) phenyl group were reacted]Ether (DPEPO) was vacuum deposited on the exciton blocking layer at a weight ratio of 3:7 and a thickness of
Figure BDA0002476786060000916
Thereby forming a light emitting layer.
Figure BDA0002476786060000917
Make the following electrons transmitThe material 1,3, 5-tri [ (3-pyridyl) -3-phenyl ] is transported]Benzene (TmPyPB)
Figure BDA0002476786060000918
Vacuum deposition is carried out on the luminescent layer to form an electron transport layer.
Figure BDA0002476786060000919
Reacting the compound 8-hydroxyquinoline lithium (L iq)
Figure BDA0002476786060000921
And metallic aluminum
Figure BDA0002476786060000922
And sequentially deposited on the electron transport layer to serve as an electron injection layer and a negative electrode.
Figure BDA0002476786060000923
In the above process, the deposition rates of the hole injection layer material HAT-CN and the electron injection layer material L iq are kept at
Figure BDA0002476786060000924
To
Figure BDA0002476786060000925
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 BDA0002476786060000926
To
Figure BDA0002476786060000927
Figure BDA0002476786060000928
The deposition rate of the electrode material metallic aluminum is kept at
Figure BDA0002476786060000929
To
Figure BDA00024767860600009210
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 14 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 15 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 16 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 17 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 18 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 BDA0002476786060000941
< 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 BDA0002476786060000951
< 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 BDA0002476786060000952
When a current was applied to the organic light emitting diode devices manufactured in experimental examples 1-1 to 1-14 and comparative examples 1-1, 1-2, and 1-3, the results of table 1 below were obtained.
TABLE 1
Figure BDA0002476786060000953
Figure BDA0002476786060000961
As shown in the data in table 1, it can be seen that the materials in which the electron withdrawing substituent is connected to the position 1 of fluorene all exhibit high luminous efficiency, and the efficiencies both greatly exceed 5% of the theoretical external quantum efficiency limit of the common fluorescent materials, indicating the existence of the delayed fluorescence emission phenomenon. While comparative examples 1-1, 1-2 and 1-3 all showed lower external quantum efficiencies.
It was confirmed that the derivative of the compound according to the formula of the present invention has excellent thermally activated delayed luminescence 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 BDA0002476786060000974
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.
A hot vacuum press of 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HAT-CN) of the following formula is applied to the transparent ITO electrode thus prepared to a thickness of
Figure BDA0002476786060000975
As a hole injection layer.
Figure BDA0002476786060000971
The following compound 4,4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline was used as a material for transporting holes](TAPC)
Figure BDA0002476786060000972
Vacuum deposition is performed on the hole injection layer, thereby forming a hole transport layer.
Figure BDA0002476786060000973
Subsequently, the following compound 4,4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA) as a material for electron blocking was allowed to stand
Figure BDA0002476786060000981
Vacuum depositing on the hole transport layer to form an electron blocking layer.
Figure BDA0002476786060000982
Then, the following 3,3 '-bis (9H-carbazol-9-yl) -1,1' -biphenyl (mCBP) is used as a main body material, a compound 1 is used as a sensitizing material, C545T is used as a luminescent material, the compound 1 is doped according to the weight proportion of 15 percent, C545T is doped according to the weight proportion of 1 percent, and the mixture is jointly vacuum-deposited on an exciton blocking layer with the thickness of
Figure BDA0002476786060000983
Thereby forming a light emitting layer.
Figure BDA0002476786060000984
1,3, 5-tris [ (3-pyridyl) -3-phenyl ] materials which transport electrons]Benzene (TmPyPB)
Figure BDA0002476786060000985
Vacuum deposition is carried out on the luminescent layer to form an electron transport layer.
Figure BDA0002476786060000986
Reacting the compound 8-hydroxyquinoline lithium (L iq)
Figure BDA0002476786060000987
And metallic aluminum
Figure BDA0002476786060000988
Sequential depositionAnd the electron transport layer is used as an electron injection layer and a negative electrode.
Figure BDA0002476786060000991
In the above process, the deposition rates of the hole injection layer material HAT-CN and the electron injection layer material L iq are kept at
Figure BDA0002476786060000992
To
Figure BDA0002476786060000993
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 BDA0002476786060000994
To
Figure BDA0002476786060000995
Figure BDA0002476786060000996
The deposition rate of the electrode material metallic aluminum is kept at
Figure BDA0002476786060000997
To
Figure BDA0002476786060000998
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 14 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 15 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 16 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 17 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 18 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 BDA0002476786060001011
< 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 BDA0002476786060001021
< 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 BDA0002476786060001022
When a current was applied to the organic light emitting diode devices manufactured in experimental examples 2-1 to 2-14 and comparative examples 2-1, 2-2, and 2-3, the results of table 2 below were obtained.
TABLE 2
Figure BDA0002476786060001023
Figure BDA0002476786060001031
As shown in the data in Table 2, the device efficiency of comparative example 2-1 was only 2.6% without adding the thermal activation delayed fluorescence sensitizing material, and comparative examples 2-2 and 2-3 demonstrated that the added material did not have the thermal activation delay characteristic and 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 2-14, in which the compound represented by chemical 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>
The compound 1(2 mg) and polymethyl methacrylate (PMMA) PMMA (8 mg) were mixed and dissolved in 1ml of chlorobenzene, shaken up, transferred and spread evenly on a glass slide of a vacuum spin coater by a pipette, and rotated at a rotation speed of 200-.
< Experimental example 3-2>
An organic thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced 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 thin film was produced in the same manner as in experimental example 3-1, except that compound 14 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 15>
An organic thin film was produced 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 16>
An organic thin film was produced in the same manner as in experimental example 3-1, except that compound 16 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 17>
An organic thin film was produced in the same manner as in experimental example 3-1, except that compound 17 was used instead of compound 1 in experimental example 3-1.
< Experimental examples 3 to 18>
An organic thin film was produced 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.
< comparative example 3-1>
An organic thin film was produced 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 BDA0002476786060001061
< comparative example 3-2>
An organic thin film was produced 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 BDA0002476786060001071
< comparative examples 3 to 3>
An organic thin film was produced 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 BDA0002476786060001072
When laser pulses were input to the organic thin films manufactured in experimental examples 3-1 to 3-14 and comparative examples 3-1, 3-2 and 3-3, emission photon lifetime signals were collected, and the results of table 3 below were obtained.
TABLE 3
Figure BDA0002476786060001073
Figure BDA0002476786060001081
It can be seen that the materials in which the electron pulling substituent is attached to the position No. 1 of fluorene all exhibit fluorescence lifetimes in the order of microseconds, corresponding to delayed fluorescence behavior. While comparative examples 3-1, 3-2 and 3-3 all obtained only nanosecond-level lifetimes, corresponding to common fluorescent behavior, and failed to achieve utilization of triplet excitons.
In summary, the following steps: the main functional elements of the thermal activation delayed fluorescence material realize intramolecular interaction through space unconjugated connection, and a space charge transfer mechanism is realized. The material has high thermal stability, high glass transition temperature and excellent luminescence property, and can be used as the material of an organic material layer of an organic light-emitting device, in particular the material of a core light-emitting layer. The compound according to at least one exemplary embodiment of the present specification may achieve high efficiency thermally activated delayed fluorescence and achieve a high efficiency organic light emitting device, while achieving a low driving voltage and a lower efficiency roll-off. In particular, the compounds described in the present specification can be used as materials for light emission and thermally activated delayed fluorescence sensitization.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not 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 heat-activated delayed fluorescent material comprising a compound represented by the following general formula (1):
Figure FDA0002476786050000011
wherein R is0、R1、R2And R3Each independently selected from hydrogen, deuterium, halogen groups, or any of substituted or unsubstituted C6-C30 aryl groups, C1-C20 aliphatic groups; r is selected from any one of substituted or unsubstituted aliphatic group of C1-C10, aryl group of C6-C30 and heteroaryl group of C4-C30; g is selected from a direct bond, or any of a substituted or unsubstituted arylene group of C6-C30, a heteroarylene group of C4-C30; a is a group having electron-deficient properties.
2. The thermally activated delayed fluorescence material according to claim 1, wherein in the compound represented by the general formula (1), a is selected from any one of a nitrile group, a sulfone group, a carbonyl group, an ester group, a nitrile group aromatic ring, a sulfone group aromatic ring, a carbonyl aromatic ring, an ester group aromatic ring, a heteroaryl group, or an aromatic boron group.
3. The thermally activated delayed fluorescence material according to claim 1 or 2, wherein in the general formula (1), G is selected from any one of substituted or unsubstituted arylene and heteroarylene groups of C6 to C30.
4. The thermally activated delayed fluorescence material of claim 3, wherein in the general formula (1), G-A is selected from the following group consisting of any combination of G group and A group,
a G group:
Figure FDA0002476786050000012
Figure FDA0002476786050000021
Figure FDA0002476786050000031
group A:
Figure FDA0002476786050000032
Figure FDA0002476786050000041
Figure FDA0002476786050000051
Figure FDA0002476786050000061
Figure FDA0002476786050000071
Figure FDA0002476786050000081
Figure FDA0002476786050000091
Figure FDA0002476786050000101
wherein R5 at each position is independently selected from hydrogen, cyano, or any one of substituted or unsubstituted aliphatic group of C1-C10, arylamine group of C6-C24, aryl group of C6-C24, heteroaryl group of C4-C24, pyridine and thiophene.
5. The heat-activated delayed fluorescence material according to claim 1 or 2, wherein in the general formula (1), G is a direct bond.
6. The thermally activated delayed fluorescence material of claim 5, wherein in the general formula (1), G-A is selected from the following group consisting of any combination of G group and A group,
a G group: a direct bond;
group A:
Figure FDA0002476786050000102
Figure FDA0002476786050000111
Figure FDA0002476786050000121
Figure FDA0002476786050000131
Figure FDA0002476786050000141
Figure FDA0002476786050000151
Figure FDA0002476786050000161
Figure FDA0002476786050000171
wherein R5 at each position is independently selected from hydrogen, cyano, or any one of substituted or unsubstituted aliphatic group of C1-C10, arylamine group of C6-C24, aryl group of C6-C24, heteroaryl group of C4-C24, pyridine and thiophene.
7. An organic light-emitting device comprising a first electrode and a second electrode disposed opposite to each other with an organic material layer interposed therebetween, the organic material layer comprising a light-emitting layer containing the thermally activated delayed fluorescence material according to any one of claims 1 to 6.
8. The organic light-emitting device according to claim 7, wherein the light-emitting layer contains a sensitizing material, a light-emitting material, and a host material, and the thermally activated delayed fluorescence material serves as the sensitizing material, and/or the light-emitting material.
9. The organic light-emitting device according to claim 7, wherein the organic material layer further comprises one or more layers of 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 this order from a height direction.
10. The organic light emitting device according to claim 9, wherein the thermally activated delayed fluorescence material is contained in any 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.
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111848556A (en) * 2020-07-31 2020-10-30 上海天马有机发光显示技术有限公司 Compound, display panel and display device
CN113150019A (en) * 2021-03-11 2021-07-23 上海和辉光电股份有限公司 Compound for organic electroluminescent device and application thereof
CN113185550A (en) * 2021-05-13 2021-07-30 井冈山大学 Fluorescent sensor for detecting gelation degree of Pickering emulsion and preparation and application thereof
CN113956235A (en) * 2021-11-23 2022-01-21 京东方科技集团股份有限公司 Thermally activated delayed fluorescence material, application thereof, electroluminescent device and display device
CN114105955A (en) * 2021-12-18 2022-03-01 广东工业大学 Fluorospirotriphenylamine derivative compound and preparation method and application thereof
CN114716376A (en) * 2022-05-05 2022-07-08 广东工业大学 Derivative compound based on sulfone electron acceptor and preparation method and application thereof
CN115232110A (en) * 2022-07-18 2022-10-25 广东工业大学 Fluorenone derivative with sandwich structure, preparation method thereof and organic light-emitting device
CN115716852A (en) * 2022-05-13 2023-02-28 黑龙江大学 Sulfur-phosphorus heterocyclic receptor and nitrogen-containing heterocyclic donor compound, and synthesis method and application thereof
CN115894436A (en) * 2022-11-07 2023-04-04 西北工业大学 Organic photoelectric material based on 4-substituted dibenzothiophene sulfone, host-guest room temperature phosphorescent material, preparation method and application
EP4291000A4 (en) * 2021-11-26 2024-10-09 Kunshan Go Visionox Opto Electronics Co Ltd Organic electroluminescent device and display apparatus

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406391A (en) * 2015-09-30 2017-11-28 株式会社Lg化学 Spiro-compound and the organic illuminating element for including it
CN111057005A (en) * 2019-11-04 2020-04-24 苏州久显新材料有限公司 Fluorene derivative and electronic device
CN111056959A (en) * 2019-11-04 2020-04-24 苏州久显新材料有限公司 Fluorene derivative and electronic device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107406391A (en) * 2015-09-30 2017-11-28 株式会社Lg化学 Spiro-compound and the organic illuminating element for including it
CN111057005A (en) * 2019-11-04 2020-04-24 苏州久显新材料有限公司 Fluorene derivative and electronic device
CN111056959A (en) * 2019-11-04 2020-04-24 苏州久显新材料有限公司 Fluorene derivative and electronic device

Cited By (13)

* Cited by examiner, † Cited by third party
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CN113150019B (en) * 2021-03-11 2023-10-17 上海和辉光电股份有限公司 Compound for organic electroluminescent device and application thereof
CN113150019A (en) * 2021-03-11 2021-07-23 上海和辉光电股份有限公司 Compound for organic electroluminescent device and application thereof
CN113185550A (en) * 2021-05-13 2021-07-30 井冈山大学 Fluorescent sensor for detecting gelation degree of Pickering emulsion and preparation and application thereof
CN113185550B (en) * 2021-05-13 2022-04-19 井冈山大学 Fluorescent sensor for detecting gelation degree of Pickering emulsion and preparation and application thereof
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EP4291000A4 (en) * 2021-11-26 2024-10-09 Kunshan Go Visionox Opto Electronics Co Ltd Organic electroluminescent device and display apparatus
CN114105955A (en) * 2021-12-18 2022-03-01 广东工业大学 Fluorospirotriphenylamine derivative compound and preparation method and application thereof
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CN115716852A (en) * 2022-05-13 2023-02-28 黑龙江大学 Sulfur-phosphorus heterocyclic receptor and nitrogen-containing heterocyclic donor compound, and synthesis method and application thereof
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