CN112898322A - Organic compound, application thereof and organic electroluminescent device containing organic compound - Google Patents

Organic compound, application thereof and organic electroluminescent device containing organic compound Download PDF

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CN112898322A
CN112898322A CN201911218859.9A CN201911218859A CN112898322A CN 112898322 A CN112898322 A CN 112898322A CN 201911218859 A CN201911218859 A CN 201911218859A CN 112898322 A CN112898322 A CN 112898322A
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substituted
unsubstituted
chain alkyl
deuterated
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魏金贝
曾礼昌
李国孟
李熠烺
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Beijing Eternal Material Technology Co Ltd
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Abstract

The invention relates to a novel organic compound having the following structure:
Figure DDA0002300234920000011
wherein: ra、Rb、RcAnd RnEach independently selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstitutedOne of substituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; x1Selected from NR1、CR2R3、SiR19R20Any one of S and O; at least one hydrogen in the structure of formula (1) is deuterated. The compound of the invention shows excellent device performance and stability when used as a light-emitting layer material in an OLED device. The invention also protects the organic electroluminescent device adopting the compound with the general formula.

Description

Organic compound, application thereof and organic electroluminescent device containing organic compound
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to a novel organic compound, in particular to a thermal activation delayed fluorescent material for an organic electroluminescent device and application of the thermal activation delayed fluorescent material in the organic electroluminescent device.
Background
At present, optoelectronic devices employing organic materials are becoming increasingly popular for a number of reasons. Many of the materials used to make such devices are relatively inexpensive, and optoelectronic devices have potential cost advantages over inorganic devices. In the organic electroluminescent device structure in the display and illumination field, blue fluorescence is generally used in combination with red and green phosphorescent materials. Recently, ultra-pure blue fluorescent dye B-N compounds based on TADF (Thermally Activated Delayed Fluorescence) have been reported in the literature, which are based on triphenylboron and contain two nitrogen atoms and form a rigid polycyclic aromatic skeleton. The nitrogen atom has an opposite resonance effect to that of the boron atom, and the opposite resonance effect is enhanced at the position para thereto. This effect therefore clearly separates the HOMO and LUMO orbitals, and the calculated molecular orbital of DABNA-1 indicates that the LUMO orbitals are distributed in the ortho and para positions relative to the boron atom and to the nitrogen atom and to the meta position relative to the boron atom.
Figure BDA0002300234910000011
B-N compounds, which are based on triphenylboron and contain two nitrogen atoms, form a rigid polycyclic aromatic skeleton. The nitrogen atom has an opposite resonance effect to that of the boron atom, and the opposite resonance effect is enhanced at the position para thereto. This effect can therefore clearly separate the HOMO and LUMO orbitals.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel compound, in particular to a thermal activation delayed fluorescent material which can be used for an organic electroluminescent device, and also provides an application of the compound in the organic electroluminescent device.
The novel compound of the present invention has a structure represented by general formula (1):
Figure BDA0002300234910000021
in formula (1): ra、Rb、RcAnd RnEach independently represents a single substituent to the maximum permissible substituent, and each independently is one selected from the group consisting of hydrogen, substituted or unsubstituted C1 to C12 chain alkyl, substituted or unsubstituted C3 to C12 cycloalkyl, substituted or unsubstituted C1 to C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6 to C30 arylamino, substituted or unsubstituted C3 to C30 heteroarylamino, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C3 to C30 heteroaryl;
X1selected from NR1、CR2R3、SiR19R20Any one of S and O, R1、R2、R3、R19And R20Each independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; and when said X is1Is NR1When R is1With ring 1 and/or RaConnected to form a ring or not connected to form a ring;
and at least one hydrogen in the structure of the compound represented by formula (1) is deuterated.
When each of the substituted or unsubstituted groups has a substituent, the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl or fused ring aryl of C6-C30, and monocyclic heteroaryl or fused ring heteroaryl of C3-C30.
More preferably, in the formula (1), R isa、RbAnd RcIs deuterium.
More preferably, in the formula (1), R isa、RbAnd RcAt least one of which is a deuterated C1-C12 chain alkyl group or a deuterated C3-C12 cycloalkyl group.
More preferably, in the formula (1), R isnIs a substituted C6-C30 aryl group having at least one substituent group, or a substituted C3-C30 heteroaryl group having at least one substituent group selected from deuterium, a deuterated C1-C12 chain alkyl group, or a deuterated C3-C12 cycloalkyl group.
More preferably, in the above formula (1), when X is1Is NR1When R is1Selected from C which is substituted or unsubstituted6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl; the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, arylamino of C6-C30 and heteroarylamino of C3-C30.
More preferably, in the above formula (1), when X is1Selected from NR1When R is in the above-mentioned range1Is a substituted C6-C30 aryl group having at least one substituent group, or is a substituted C having at least one substituent group3～C30Heteroaryl, wherein the substituent group is selected from deuterium, deuterated C1-C12 chain alkyl or deuterated C3-C12 cycloalkyl;
or when X is1Selected from the group consisting of CR2R3When R is in the above-mentioned range2Or R3At least one of which is a substituted C6-C30 aryl group having at least one substituent group, or a substituted C having at least one substituent group3～C30Heteroaryl, wherein the substituent group is selected from deuterium, deuterated C1-C12 chain alkyl or deuterated C3-C12 cycloalkyl;
or when X is1Selected from SiR19R20When R is in the above-mentioned range19Or R20At least one of which is a toolA substituted C6-C30 aryl group having at least one substituent group, or a substituted C having at least one substituent group3～C30Heteroaryl, wherein the substituent group is selected from deuterium, deuterated C1-C12 chain alkyl or deuterated C3-C12 cycloalkyl.
Further preferably, the compound of the present invention has the following structural formulae (2-1) to (2-5):
Figure BDA0002300234910000031
in the formulae (2-1) to (2-5), Ra、Rb、Rc、Rn、R1、R2、R3、R19And R20Is the same as that in formula (1), and at least one hydrogen in each of the compound structures represented by formulae (2-1) to (2-5) is deuterated;
preferably, in the formulae (2-1) to (2-5), R isa、RbAnd RcAt least one of which is deuterium;
preferably, in the formulae (2-1) to (2-5), R isa、RbAnd RcAt least one of which is a deuterated C1-C12 chain alkyl group or a deuterated C3-C12 cycloalkyl group.
Still further preferably, the compound of the present invention has the following structural formulae (3-1) and (3-2):
Figure BDA0002300234910000032
in the formula (3-1) or (3-2), Ra、Rb、Rc、RnIs the same as defined in formula (1);
Rdand Rd’Each independently represents a single substituent to the maximum permissible substituent, and each independently is selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstitutedThe substituted or unsubstituted C3-C30 heteroaryl amino group, the substituted or unsubstituted C6-C30 aryl group and the substituted or unsubstituted C3-C30 heteroaryl group, wherein the substituent is one or more of deuterium, halogen, chain alkyl of C1-C12, chain alkyl of C3-C12, chain alkyl of deuterated C1-C12, chain cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, C6-30 arylamino, C3-C30 heteroaryl amino group, monocyclic aryl or fused ring aryl of C6-C30, monocyclic aryl or fused ring heteroaryl of C3-C30;
and at least one hydrogen in each of the compound structures represented by the formulae (3-1) or (3-2) is deuterated;
preferably, RdAnd Rd’Each independently selected from one of hydrogen, deuterium, C1-C12 chain alkyl, C3-C12 cycloalkyl, deuterated C1-C12 chain alkyl and deuterated C3-C12 cycloalkyl;
preferably, in the formula (3-1) or (3-2), said Ra、RbAnd RcAt least one of which is deuterium;
preferably, in the formula (3-1) or (3-2), said Ra、RbAnd RcAt least one of which is a deuterated C1-C12 chain alkyl group or a deuterated C3-C12 cycloalkyl group.
Further preferably, in the above-mentioned formula (1), formulae (2-1) to (2-5), formula (3-1) and formula (3-2), at least one R isnIs nitrogen-containing substituted or unsubstituted C4-C30 electron-donating heteroaryl;
more preferably, in the above-mentioned formulae (1), (2-1) to (2-5), (3-1) and (3-2), RnOnly one is a nitrogen-containing substituted or unsubstituted C4-C30 electron donating heteroaryl group.
Still more preferably, the compound of the present invention has a structural formula as shown in the following (4):
Figure BDA0002300234910000041
wherein R isn1、Rn2And Rn3Each independently selected from hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkylOne of C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, arylamino of C6-C30, heteroaryl amino of C3-C30, monocyclic aryl or fused ring aryl of C6-C30, monocyclic heteroaryl or fused ring heteroaryl of C3-C30;
preferably, said R isn1、Rn2And Rn3Only one of the substituents is nitrogen-containing substituted or unsubstituted C4-C30 electron-donating heteroaryl, wherein the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, and cycloalkyl of deuterated C3-C12;
more preferably, said Rn2The nitrogen-containing substituted or unsubstituted C4-C30 electron-donating heteroaryl is provided, and the substituent is one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12 and cycloalkyl of deuterated C3-C12.
More preferably, in the above-mentioned formula (1), formulae (2-1) to (2-5), formulae (3-1), (3-2) and formula (4) of the present invention, R isa、RbAnd RcEach independently selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; more preferably, Ra、RbAnd RcEach independently selected from one of hydrogen, C1-C12 chain alkyl and C3-C12 naphthenic base.
More preferably, R in the above-mentioned formula (1), formulae (2-1) to (2-5), formula (3-1) and formula (3-2) of the present inventionnAnd R in the formula (4)n1、Rn2And Rn3Each independently selected from Hy1～Hy3The structure of (1):
Figure BDA0002300234910000051
wherein denotes the attachment site to the parent nucleus;
said Hy1Wherein n is 0 or 1, and when n is 0, it represents a single bond; e1Selected from the group consisting of CR4R5、NR6O, S or SiR13R14One of (1);
said Hy2In, E2Selected from the group consisting of CR7R8、NR9O, S or SiR15R16One of (1);
said Hy3In, E3And E4Each independently selected from the group consisting of a single bond, CR10R11、NR12O, S or SiR17R18And E is one of3And E4At least one term of (a) is NR12；
Said Hy1、Hy2Or Hy3In, Re、Rf、Rh、Rg、Ri、RjAnd RkEach independently represents a single substituent to the maximum permissible substituent, and each independently is selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C10 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or Re、Rf、Rh、Rg、Ri、RjAnd RkEach independently is fused with the aromatic ring connected with the aromatic ring to form one of substituted or unsubstituted C9-C30 aryl or substituted or unsubstituted C9-C30 heteroaryl; preferably, Re、Rf、Rg、Rh、Ri、RjAnd RkEach independently selected from one of hydrogen, C1-C12 chain alkyl and C3-C12 naphthenic base;
the substituted or unsubstituted C9 to C30 aryl or substituted or unsubstituted C9 to C30 heteroaryl may specifically include: c9 to C30 aryl or heteroaryl optionally substituted with 0 to 5 groups each independently of the others: substituted or unsubstituted C1-C12 chain alkyl, C3-C12 cycloalkyl, halogen, C1-C6 alkoxy or thioalkoxy, C6-C30 monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon group, and C3-C30 monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon group.
Said Hy1、Hy2Or Hy3In (1), the R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17And R18Each independently selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; preferably, R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17And R18Each independently selected from one of chain alkyl of C1-C12, C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl.
Still more preferably, R in the above-mentioned formula (1), formulae (2-1) to (2-5), formula (3-1) and formula (3-2) of the present inventionnAnd R in the formula (4)n1、Rn2And Rn3Each independently at least one item selected from the group consisting of (Hy)1-1)-(Hy3Any one of the structures of-6):
Figure BDA0002300234910000061
the R ise、Rf、Rh、Ri、Rg、Rj、Rk、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17And R18Independently of each other and in Hy1、Hy2Or Hy3The same as defined in (1).
Still more preferably, R in the above-mentioned formula (1), formulae (2-1) to (2-5), formula (3-1) and formula (3-2) of the present inventionnAnd R in the formula (4)n1、Rn2And Rn3Each independently at least one member selected from the group consisting of (Hy)1-1)-(Hy3Any one of-6):
Figure BDA0002300234910000071
the R ise、Rf、Rh、Rg、Ri、Rj、Rk、R7、R8、R9、R15、R16、R10、R11、R12、R17And R18Independently of each other and in Hy1、Hy2Or Hy3The same as defined in (1).
Still more preferably, R is as defined above in the invention4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh、Ri、RjAnd RkWhen the alkyl is selected from C1-C12 chain alkyl or C3-C12 cycloalkyl, the structure is as follows:
Figure BDA0002300234910000072
in the present invention, the maximum permissible substituent means the number of the substituentThe number is the maximum number of substitutions provided that the substituted group satisfies the bond requirement, illustratively, R to which ring 1 can be attachedaThe number of (A) may be one or more, but at most, it is only up to the maximum permissible substituents (i.e. 4).
In the present specification, the expression of Ca to Cb means that the group has carbon atoms of a to b, and the carbon atoms do not generally include the carbon atoms of the substituents unless otherwise specified.
In the present specification, the expression of the "-" underlined loop structure indicates that the linking site is located at an arbitrary position on the loop structure where the linking site can form a bond.
In the present specification, the substituted or unsubstituted C6-C30 aryl group is preferably a C6-C20 aryl group, and more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, a fluorenyl group and derivatives thereof, a fluoranthyl group, a triphenylene group, a pyrenyl group, a perylenyl group, a triphenylene group, a triphenyl,
Figure BDA0002300234910000082
A group of the group consisting of a phenyl group and a tetracenyl group. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl; terphenyl includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes a 1-naphthyl group and a 2-naphthyl group; the anthracene group is selected from 1-anthracene group, 2-anthracene group and 9-anthracene group; the fluorenyl is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from 9,9 '-dimethylfluorene, 9' -spirobifluorene and benzofluorene; the pyrenyl is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetracenyl group is selected from the group consisting of 1-tetracenyl, 2-tetracenyl, and 9-tetracenyl.
The hetero atom in the present invention generally refers to an atom or group of atoms selected from N, O, S, P, Si and Se, preferably N, O, S.
In the present specification, the substituted or unsubstituted heteroaryl group having C3 to C30 is preferably a heteroaryl group having C4 to C20, more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, and the like, and specific examples thereof include: furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole, or indolocarbazole.
In the present specification, the chain alkyl group having from C1 to C20 is preferably a chain alkyl group having from C1 to C10, more preferably a chain alkyl group having from C1 to C6, and examples thereof include: methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, isopropyl, isobutyl, tert-butyl and the like.
In the present specification, the cycloalkyl group of C3 to C12 includes monocycloalkyl and polycycloalkyl groups, preferably alkyl groups of C1 to C10 and cycloalkyl groups of C3 to C10.
Further, the compound represented by the general formula (1) of the present invention may preferably be one of the compounds represented by the following specific structures:
Figure BDA0002300234910000081
Figure BDA0002300234910000091
Figure BDA0002300234910000101
Figure BDA0002300234910000111
Figure BDA0002300234910000121
Figure BDA0002300234910000131
Figure BDA0002300234910000141
the C1-C10 may be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, etc.
The C1-C6 may be C1, C2, C3, C4, C5, C6, etc.
The C3-C10 may be C3, C4, C5, C6, C7, C8, C9, C10, etc.
The C1 to C12 may be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, etc., preferably C1 to C10.
The value ranges of C1-C10, C1-C6, C3-C10 and C1-C12 which are related subsequently in the invention are the same as the value ranges described above.
In the present invention, Rn1、Rn2And Rn3Only one of which is a nitrogen-containing electron-donating heteroaryl group, preferably Rn2Is a nitrogen-containing electron donating heteroaryl due to Rn2The spatial repulsive force with the groups on two sides is minimum, and the stability is higher.
In the invention, Rn1、Rn2And Rn3At least one of the nitrogen-containing electron-donating heteroaryl groups is selected from a specific class, has higher conjugation strength than other electron-donating heteroaryl groups, can effectively improve the LUMO orbital level of the compound, and can effectively reduce direct injection of electrons.
The invention also discloses a thermally activated delayed fluorescent material, which comprises the compound.
The invention also discloses an application of the thermal activation delayed fluorescence material in an organic electroluminescent device, preferably an application as a luminescent layer in the organic electroluminescent device, and more preferably an application as a luminescent dye and/or a sensitizer in the luminescent layer of the organic electroluminescent device.
The compounds of the invention have heat-activated delayed fluorescence properties.
The invention also discloses an application of the compound in an organic electroluminescent device. The above-described compounds of the present invention are suitable for use as a material for a light-emitting layer in an organic electroluminescent device, and more preferably for use as a light-emitting dye and/or sensitizer in the light-emitting layer of the organic electroluminescent device.
The application field of the compound of the present invention is not limited to the organic electroluminescent material, and the compound can be applied to the technical fields of optical sensors, solar cells, lighting devices, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information tags, electronic artificial skin sheets, large-area sensors such as sheet-type scanners, electronic paper, and the like.
The present invention also provides an organic electroluminescent device comprising a substrate including a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by any one of the above general formula (1), formulae (2-1) to (2-5), formula (3-1), (3-2), and formula (4).
Specifically, one embodiment of the present invention provides an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is arranged between the hole transport layer and the electron transport layer; wherein the light-emitting layer contains the compound of the present invention represented by any one of the above formulae (1), (2-1) to (2-5), (3-1), (3-2) and (4).
The specific reason why the above-mentioned compound of the present invention is excellent as a material for a light-emitting layer in an organic electroluminescent device is not clear, and the following reason is presumed:
1. the boron atom contained in the molecular structure of the compound of the present invention has a resonance effect with a nitrogen atom in the same ring, and the opposite resonance effect is enhanced at the position para to the boron atom. Therefore, the effect can separate HOMO and LUMO orbitals of molecules obviously, and the compound has the property of heat-activated delayed fluorescence;
2. rigid carbazole groups are introduced into the molecular structure of the compound, so that the regulation of the charge distribution of the compound is facilitated, the further delocalized distribution of electrons is facilitated, the fluorescence quantum yield of the compound is improved, and the compound is favorably used as a dye;
3. at least one hydrogen atom in the molecular structure of the compound is replaced by deuterium, so that the compound is beneficial to prolonging the service life of a device after being applied to an organic electroluminescent device;
4. compared with the device prepared by the compound in the prior art, the organic electroluminescent device prepared by adopting the compound as the luminescent dye has the advantages that the voltage of the device prepared by adopting the compound is relatively reduced, the efficiency and the service life are relatively improved, and the excellent device performance is shown.
Detailed Description
The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples. The method and materials for obtaining the compound are not limited to the synthetic methods and materials used in the invention, and other methods or routes can be selected by those skilled in the art to obtain the novel compound provided by the invention. The compounds of the present invention, for which no synthetic method is mentioned, are commercially available starting products or are prepared by the starting products according to known methods.
Solvents and reagents used in the synthesis examples, such as methylene chloride, petroleum ether, ethanol, tetrahydrofuran, N-dimethylacetamide, anhydrous magnesium sulfate, carbazole, and other chemical reagents, can be purchased from domestic chemical product markets, such as reagents from national drug group, TCI, shanghai Bide medicine, Bailingwei reagents, and the like. In addition, they can be synthesized by a known method by those skilled in the art.
Analytical testing of synthetic examples intermediates and compounds an abciex mass spectrometer (4000QTRAP) was used.
The synthesis of the compounds of the present invention is briefly described below.
Synthetic examples
Representative synthetic route:
Figure BDA0002300234910000161
more specifically, the following gives synthetic methods of representative compounds of the present invention.
Synthetic examples
Synthesis example 1: synthesis of S5
Figure BDA0002300234910000171
Synthesis of intermediate S5-1:
to a 1L single-necked flask was added 3, 5-dibromofluorobenzene (50g, 197mmol), 3, 6-di-tert-butylcarbazole (66.1g, 236mmol), cesium carbonate (56.9g, 295mmol), DMF (500ml) at room temperature for reaction overnight at 120 ℃. The heating was stopped, after cooling to room temperature 500ml water was added, extraction was carried out with 500ml dichloromethane, drying was carried out with anhydrous sodium sulfate, and silica gel column chromatography (PE) was carried out to obtain 99.50g of a white solid product with a yield of 98%. Mass spectrometric analysis determined molecular ion mass: 512.33 (theoretical value: 513.32).
Synthesis of intermediate S5-2:
s5-1(50g, 83.1mmol), 4, 5-deuterocarbazole (15.47g, 91.4mmol), Pd were added at room temperature2(dba)3(7.61g, 8.3mmol), tri-tert-butylphosphine (3.94g, 19.5mmol), sodium tert-butoxide (18.72g, 194.8mmol), xylene (500ml) were added to a 1L one-necked flask, and nitrogen was purged three times and heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 60g of crude product, which was recrystallized from toluene/ethanol to give 50g of white solid in 85% yield. Mass spectrometric analysis determined molecular ion mass: 602.63 (theoretical value: 601.63).
Synthesis of intermediate S5-3:
at room temperature, S5-2(50g, 97.4mmol), diphenylamine (I)18.13g，107.1mmol)，Pd2(dba)3(8.92g, 9.7mmol), tri-tert-butylphosphine (3.36g, 16.6mmol), sodium tert-butoxide (15.97g, 166.2mmol), xylene (500ml) were added to a 1L one-necked flask, and nitrogen was purged three times and heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 60g of crude product, which was recrystallized from toluene/ethanol to give 47g of white solid in 82% yield. Mass spectrometric analysis determined molecular ion mass: 689.93 (theoretical value: 689.94).
Synthesis of compound S5:
s5-3(20.00g, 28.9mmol) was added to a 1000ml three-necked flask, o-dichlorobenzene (200ml), N, N-diisopropylethylamine (7.49g, 57.9mmol) was added, nitrogen was pumped three times, boron tribromide (36.31g, 144.9mol) was added to the three-necked flask by rapidly withdrawing with a coarse needle, the flask was heated to reflux, and the reaction was refluxed for 3 h. After the system is cooled to room temperature, water (200ml) is added for quenching, and when the system does not smoke, quenching is finished. The organic phase was separated, the lower organic phase was extracted three times with ethyl acetate (200ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase is mixed with silica gel, concentrated and subjected to column chromatography to obtain 10g of crude product, and the crude product is recrystallized by toluene/ethanol to obtain 7g of yellow solid with the yield of 34 percent. Mass spectrometric analysis determined molecular ion mass: 697.01 (theoretical value: 697.73).
Synthesis example 2: synthesis of S25
Figure BDA0002300234910000181
Synthesis of intermediate S25-1:
at room temperature, S5-2(40g, 66.5mmol), diphenylamine (12.23g, 73.1mmol), Pd2(dba)3(6.09g, 6.6mmol), tri-tert-butylphosphine (2.69g, 13.3mmol), sodium tert-butoxide (12.78g, 166.232.9mmol), xylene (500ml) were added to a 1L one-necked flask, and nitrogen was purged three times and heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 50g of crude product, which was recrystallized from toluene/ethanol to give 39g of white solid in 85% yield. Mass spectrometric analysis of determined molecular ionsQuality: 688.93 (theoretical value: 687.93).
Synthesis of compound S25:
s25-1(20.00g, 29.1mmol) was added to a 1000ml three-necked flask, o-dichlorobenzene (200ml), N, N-diisopropylethylamine (7.52g, 58.1mmol) was added, nitrogen was pumped three times, boron tribromide (36.42g, 145.3mol) was added to the three-necked flask by rapidly withdrawing with a coarse needle, the flask was heated to reflux, and the reaction was refluxed for 3 h. After the system is cooled to room temperature, water (200ml) is added for quenching, and when the system does not smoke, quenching is finished. The organic phase was separated, the lower organic phase was extracted three times with ethyl acetate (200ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase is mixed with silica gel, concentrated and subjected to column chromatography to obtain 12g of crude product, and the crude product is recrystallized by toluene/ethanol to obtain 8g of yellow solid with the yield of 40 percent. Mass spectrometric analysis determined molecular ion mass: 695.76 (theoretical value: 695.71).
Synthesis example 3: synthesis of S45
Figure BDA0002300234910000182
Synthesis of intermediate S45-1:
2-chloro-3-isopropylphenyl-5-fluorobromobenzene (50g, 152.6mmol), 3, 6-di-tert-butylcarbazole (51.17g, 183.1mmol), cesium carbonate (44.2g, 228.9mmol), DMF (500ml) was added to a 1L single-neck flask at room temperature and reacted overnight at 120 ℃. Heating was stopped, after cooling to room temperature, 500ml of water was added, extraction was performed with 500ml of dichloromethane, drying was performed with anhydrous sodium sulfate, and silica gel column chromatography (PE) was performed to obtain 81g of a white solid product with a yield of 90%. Mass spectrometric analysis determined molecular ion mass: 586.05 (theoretical value: 587.04).
Synthesis of intermediate S45-2:
s45-1(80g, 66.5mmol), 4, 5-dideuterocarbazole (25.37g, 149.9mmol), Pd were reacted at room temperature2(dba)3(12.48g, 13.63mmol), tri-tert-butylphosphine (5.51g, 27.3mmol), sodium tert-butoxide (26.19g, 272.5mmol), xylene (1000ml) were added to a 2L one-neck flask, and nitrogen was purged three times and heated to 130 ℃ for reaction overnight. The reaction solution is cooled to room temperature, filtered, and the filtrate is mixed with silica gel, concentrated and subjected to column chromatography (PE:EA 100:1) gave 89g of crude product, which was recrystallized from toluene/ethanol to yield 77g of white solid in 84% yield. Mass spectrometric analysis determined molecular ion mass: 675.94 (theoretical value: 675.35).
Synthesis of compound S45:
adding S45-2(20.00g, 29.6mmol) into a 1000ml three-necked bottle, adding o-xylene (300ml), pumping and charging nitrogen for three times, dropwise adding an N-butyllithium solution (21ml, 1.6M, 33mmol) into the three-necked bottle by using a crude needle under an ice-water bath, stirring for 1 hour, pumping boron tribromide (8.16g, 32.5mmol) by using the crude needle under the ice-water bath, adding into the reaction solution, stirring for 30 minutes, heating to 45 ℃, stirring for 50 minutes, pumping N, N-diisopropylethylamine (7.6g, 59.2mmol) into the reaction system under the ice-water bath, stirring for 30 minutes, heating to 120 ℃, and reacting overnight. The heating was stopped and after the system had cooled to room temperature, water (500ml) was added to quench. The organic phase was separated, the lower organic phase was extracted three times with ethyl acetate (500ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase is mixed with silica gel, concentrated and subjected to column chromatography to obtain 8g of crude product, and the crude product is recrystallized by toluene/ethanol to obtain 5g of yellow solid with the yield of 26 percent. Mass spectrometric analysis determined molecular ion mass: 648.73 (theoretical value: 648.71).
Synthesis example 4: synthesis of S65
Figure BDA0002300234910000191
Synthesis of intermediate S65-1:
to a 1L single-necked flask were added 3, 5-difluoro-2-chlorobromobenzene (50g, 220mmol), 3, 6-di-tert-butylcarbazole (61.4g, 220mmol), cesium carbonate (107.4g, 330mmol), DMF (500ml) at room temperature and reacted overnight at 120 ℃. The heating was stopped, after cooling to room temperature 500ml water was added, extraction was performed with 500ml dichloromethane, drying was performed with anhydrous sodium sulfate, and silica gel column chromatography (PE) was performed to obtain 90g of a white solid product with a yield of 90%. Mass spectrometric analysis determined molecular ion mass: 453.40 (theoretical value: 452.41).
Synthesis of intermediate S65-2:
s65-1(90g, 199mmol), 4, 5-dideuterocarbazole (37.03g, 219 mmo) was added at room temperaturel)，Pd2(dba)3(18.22g, 19.89mmol), tri-tert-butylphosphine (8.05g, 39.79mmol), sodium tert-butoxide (38.24g, 398mmol) and xylene (1000ml) were added to a 2L single-neck flask, and the flask was purged with nitrogen three times and heated to 130 ℃ for reaction overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 110g of crude product, which was recrystallized from toluene/ethanol to give 94g of white solid in 82% yield. Mass spectrometric analysis determined molecular ion mass: 575.17 (theoretical value: 575.16).
Synthesis of intermediate S65-3:
s65-2(95g, 156mmol), phenol (16.2g, 172mmol), potassium carbonate (32.44g, 235mmol), DMF (1000ml) were added to a 2L single neck flask at room temperature and reacted overnight at 120 ℃. Heating was stopped, after cooling to room temperature, 500ml of water was added, extraction was performed with 500ml of dichloromethane, drying was performed with anhydrous sodium sulfate, and silica gel column chromatography (PE) was performed to obtain 86g of a white solid product with a yield of 85%. Mass spectrometric analysis determined molecular ion mass: 649.26 (theoretical value: 649.27).
Synthesis of compound S65:
adding S65-3(20.00g, 30.8mmol) into a 1000ml three-necked bottle, adding o-xylene (300ml), pumping and charging nitrogen for three times, dropwise adding an N-butyllithium solution (21ml, 1.6M, 33mmol) into the three-necked bottle by using a crude needle under an ice-water bath, stirring for 1 hour, pumping boron tribromide (8.16g, 32.5mmol) by using the crude needle under the ice-water bath, adding into the reaction solution, stirring for 30 minutes, heating to 45 ℃, stirring for 50 minutes, pumping N, N-diisopropylethylamine (7.96g, 61.6mmol) into the reaction system under the ice-water bath, stirring for 30 minutes, heating to 120 ℃, and reacting overnight. The heating was stopped and after the system had cooled to room temperature, water (500ml) was added to quench. The organic phase was separated, the lower organic phase was extracted three times with ethyl acetate (500ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase is mixed with silica gel, concentrated and subjected to column chromatography to obtain 9g of crude product, and the crude product is recrystallized by toluene/ethanol to obtain 5.5g of yellow solid with the yield of 28 percent. Mass spectrometric analysis determined molecular ion mass: 623.41 (theoretical value: 622.62).
Synthesis example 4: synthesis of S85
Figure BDA0002300234910000201
Synthesis of intermediate S85-1:
phenyl-3-bromo-2-chloro-5-fluorophenyl sulfide (50g, 157mmol), 3, 6-di-tert-butylcarbazole (48.3g, 173mmol), cesium carbonate (76.9g, 236mmol), DMF (500ml) was added to a 1L single-neck flask at room temperature and reacted overnight at 120 ℃. The heating was stopped, after cooling to room temperature 500ml water was added, extraction was carried out with 500ml dichloromethane, drying was carried out with anhydrous sodium sulfate, and silica gel column chromatography (PE) was carried out to obtain 80g of a white solid product with a yield of 94%. Mass spectrometric analysis determined molecular ion mass: 542.59 (theoretical value: 542.58).
Synthesis of intermediate S85-2:
s85-1(80g, 147mmol), 3, 6-dideuterocarbazole (27.45g, 162mmol), Pd was added at room temperature2(dba)3(13.47g, 14.71mmol), tri-tert-butylphosphine (5.97g, 29.49mmol), sodium tert-butoxide (38.24g, 398mmol) and xylene (1000ml) were added to a 2L single-neck flask, and the flask was heated to 130 ℃ under nitrogen and allowed to react overnight. The reaction was cooled to room temperature, filtered, the filtrate was concentrated with silica gel and column chromatographed (PE: EA ═ 100:1) to give 100g of crude product, which was recrystallized from toluene/ethanol to give 83g of white solid in 85% yield. Mass spectrometric analysis determined molecular ion mass: 665.32 (theoretical value: 665.33).
Synthesis of compound S85:
adding S85-2(20.49g, 30.8mmol) into a 1000ml three-necked bottle, adding o-xylene (300ml), pumping and charging nitrogen for three times, dropwise adding an N-butyllithium solution (21ml, 1.6M, 33mmol) into the three-necked bottle by using a crude needle under an ice-water bath, stirring for 1 hour, pumping boron tribromide (8.16g, 32.5mmol) by using the crude needle under the ice-water bath, adding into the reaction solution, stirring for 30 minutes, heating to 45 ℃, stirring for 50 minutes, pumping N, N-diisopropylethylamine (7.96g, 61.6mmol) into the reaction system under the ice-water bath, stirring for 30 minutes, heating to 120 ℃, and reacting overnight. The heating was stopped and after the system had cooled to room temperature, water (500ml) was added to quench. The organic phase was separated, the lower organic phase was extracted three times with ethyl acetate (500ml), and the organic phases were combined and dried over anhydrous sodium sulfate. The organic phase is mixed with silica gel, concentrated and subjected to column chromatography to obtain 11g of crude product, and the crude product is recrystallized by toluene/ethanol to obtain 6.2g of yellow solid with the yield of 31 percent. Mass spectrometric analysis determined molecular ion mass: 638.69 (theoretical value: 638.68).
Next, the application of the compound of the present invention and the organic electroluminescent device prepared by using the compound of the present invention will be described in detail.
The embodiment of the invention also provides an organic electronic light-emitting device containing the compound. An example of an OLED as an organic electroluminescent device is illustrated below, but it is to be understood that the following detailed description is not a limitation of the present invention, and those skilled in the art can expand the following detailed description to be applied to other organic electroluminescent devices.
In an embodiment, the OLED comprises a first electrode and a second electrode, and several layers of organic material between the electrodes. The organic material layer may be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In a specific embodiment, a substrate may be used below the first electrode or above the second electrode. The substrate is a glass or polymer material having excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material used as the first electrode on the substrate. When the first electrode is used as an anode, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO) may be used2) And transparent conductive oxide materials such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as a cathode, a metal or an alloy such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, printing, or the like. The compound used as the organic material layer may be an organic small molecule, an organic large molecule, and a polymer, and a combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives such as compounds shown below in HT-1 to HT-34; or any combination thereof.
Figure BDA0002300234910000211
Figure BDA0002300234910000221
Figure BDA0002300234910000231
The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be a single compound material or a combination of a plurality of compounds. For example, the hole injection layer may employ one or more compounds of HT-1 to HT-34 described above, or one or more compounds of HI-1-HI-3 described below; one or more of the compounds HT-1 to HT-34 may also be used to dope one or more of the compounds HI-1-HI-3 described below.
Figure BDA0002300234910000232
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). In one aspect of the invention, the light-emitting layer employs a fluorescent electroluminescence technique. The luminescent layer fluorescent host material may be selected from, but not limited to, the combination of one or more of BFH-1 through BFH-17 listed below.
Figure BDA0002300234910000233
Figure BDA0002300234910000241
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may have a multilayer structure including at least one of an electron injection layer ((EIL)), an electron transport layer ((ETL)), and a hole blocking layer ((HBL)).
In a specific example, the electron transport layer material may be selected from, but is not limited to, a combination of one or more of ET-1 through ET-57 listed below.
Figure BDA0002300234910000242
Figure BDA0002300234910000251
Figure BDA0002300234910000261
In an example, the device may further include an electron injection layer between the electron transport layer and the cathode, the electron injection layerLayer materials include, but are not limited to, combinations of one or more of the following: LiQ, LiF, NaCl, CsF, Li2O、Cs2CO3BaO, Na, Li and/or Ca.
Device example 1
In example 1, the device structure is as follows:
ITO (150nm)/HI-2(10nm)/HT-4(40nm)/BFH-3: S5(30nm, 5% wt)/ET-46: ET-57 (50% wt: 50% wt) (25nm)/LiF (0.5nm)/Al (150 nm). The preparation process of the organic electroluminescent device is as follows: glass plates coated with ITO (thickness 150nm) transparent conductive layers were sonicated in commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to less than 1 × 10-5Pa, performing vacuum evaporation on the anode layer film to obtain HI-2 and HT-4 which are respectively used as a hole injection layer and a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is respectively 10nm and 40 nm;
and vacuum evaporating BFH-3 on the hole transport layer: s5(30nm, 5% wt)' as the luminescent layer of the organic electroluminescent device, the evaporation rate is 0.1nm/S, and the total film thickness is 30 nm; wherein "5% wt" means the doping ratio of the blue dye, i.e. the weight ratio of the host material to the compound S5 of the present invention is 95: 5.
Vacuum evaporation of ET-46 on the light-emitting layer: ET-57 (50% wt: 50% wt) as an electron transport layer of an organic electroluminescent device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 25 nm;
and (3) evaporating LiF with the thickness of 0.5nm as an electron injection layer and Al with the thickness of 150nm as a cathode on the electron transport layer in vacuum.
Device examples 2-5 and comparative examples 1-2 were fabricated in the same manner as in device example 1, except that the dye S5 was replaced with the compounds S25, S45, S65, S85 of the present invention and the prior art compounds R-1 and R-2, respectively, and the structures of R-1 and R-2 were as follows:
Figure BDA0002300234910000271
the organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 5 and comparative examples 1 to 2 and the lifetime of the devices were measured at the same luminance using a digital source meter and a luminance meter. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the brightness to the current density is the current efficiency; the life test of LT95 is as follows: using a luminance meter at 1000cd/m2The luminance drop of the organic electroluminescent device was measured to 950cd/m by maintaining a constant current at luminance2Time in hours.
Specific performance data of the organic electroluminescent device prepared in each of the above examples of the present invention are detailed in table 1 below, in which the life value of comparative example 1 is standard 1, and the life value in other examples is a ratio thereof.
TABLE 1
Figure BDA0002300234910000272
As can be seen from table 1 above, when the compound of the present invention is used as a dye in a light emitting layer, the voltage is reduced, the efficiency and the lifetime are improved, and excellent device performance is exhibited, as compared to the comparative compound. The compound of the invention increases the molecular rigidity, improves the luminous efficiency, increases the molecular conjugation degree, and replaces hydrogen in the molecule with deuterium to improve the stability of the material and improve the service life of the device.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (18)

1. A compound of the formula (1):
Figure FDA0002300234900000011
wherein: ra、Rb、RcAnd RnEach independently represents a single substituent to the maximum permissible substituent, and each independently is one selected from the group consisting of hydrogen, substituted or unsubstituted C1 to C12 chain alkyl, substituted or unsubstituted C3 to C12 cycloalkyl, substituted or unsubstituted C1 to C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6 to C30 arylamino, substituted or unsubstituted C3 to C30 heteroarylamino, substituted or unsubstituted C6 to C30 aryl, and substituted or unsubstituted C3 to C30 heteroaryl;
X1selected from NR1、CR2R3、SiR19R20Any one of S and O, R1、R2、R3、R19And R20Each independently selected from one of hydrogen, substituted or unsubstituted C1-C12 chain alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; and when said X is1Is NR1When R is1With ring 1 and/or RbConnected to form a ring or not connected to form a ring;
and, at least one hydrogen in the structure of the compound represented by formula (1) is deuterated;
when each of the substituted or unsubstituted groups has a substituent, the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl or fused ring aryl of C6-C30, and monocyclic heteroaryl or fused ring heteroaryl of C3-C30.
2. The compound according to claim 1, wherein R is represented by the formula (1)a、RbAnd RcIs deuterium.
3. The compound according to claim 1, wherein R is represented by the formula (1)a、RbAnd RcAt least one of which is a deuterated C1-C12 chain alkyl group or a deuterated C3-C12 cycloalkyl group.
4. A compound according to claims 1 to 3, wherein in the formula (1), R isnIs a substituted C6-C30 aryl group having at least one substituent group, or a substituted C3-C30 heteroaryl group having at least one substituent group selected from deuterium, a deuterated C1-C12 chain alkyl group, or a deuterated C3-C12 cycloalkyl group.
5. The compound according to any one of claims 1 to 4, wherein in the formula (1), when X is1Is NR1When R is1Selected from substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C3～C30One of heteroaryl;
the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, arylamino of C6-C30 and heteroarylamino of C3-C30.
6. The compound according to any one of claims 1-4, in the formula (1):
when X is present1Selected from NR1When R is in the above-mentioned range1Is a substituted C6-C30 aryl group having at least one substituent group, or is a substituted C3-C30 heteroaryl group having at least one substituent group selected from deuterium, a deuterated C1-C12 chain alkyl group, or a deuterated C3-C12 cycloalkyl group;
or when X is1Selected from the group consisting of CR2R3When R is in the above-mentioned range2Or R3At least one of which is a substituted C6-C30 aryl group having at least one substituent group, or a substituted C having at least one substituent group3～C30Heteroaryl, wherein the substituent group is selected from deuterium, deuterated C1-C12 chain alkyl or deuterated C3-C12 cycloalkyl;
or when X is1Selected from SiR19R20When R is in the above-mentioned range19Or R20At least one of which is a substituted C6-C30 aryl group having at least one substituent group, or a substituted C having at least one substituent group3～C30Heteroaryl, wherein the substituent group is selected from deuterium, deuterated C1-C12 chain alkyl or deuterated C3-C12 cycloalkyl.
7. The compound according to any one of claims 1 to 4, represented by the following formulae (2-1) to (2-5):
Figure FDA0002300234900000021
in the formulae (2-1) to (2-5), Ra、Rb、Rc、Rn、R1、R2、R3、R19And R20Is the same as defined in formula (1), and at least one hydrogen in the structures of the respective compounds represented by formulas (2-1) to (2-5) is substituted withDeuteration;
preferably, in the formulae (2-1) to (2-5), R isa、RbAnd RcAt least one of which is deuterium;
preferably, in the formulae (2-1) to (2-5), R isa、RbAnd RcAt least one of which is a deuterated C1-C12 chain alkyl group or a deuterated C3-C12 cycloalkyl group.
8. The compound according to any one of claims 1 to 4, represented by the following formula (3-1) or (3-2):
Figure FDA0002300234900000031
in the formula (3-1) or (3-2), Ra、Rb、Rc、RnIs the same as defined in formula (1);
Rdand Rd’Each independently represents a single substituent to the maximum permissible substituent, and each independently is one selected from the group consisting of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl, the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, arylamino of C6-C30, heteroaryl amino of C3-C30, monocyclic aryl or fused ring aryl of C6-C30, monocyclic heteroaryl or fused ring heteroaryl of C3-C30;
and at least one hydrogen in each of the compound structures represented by the formulae (3-1) or (3-2) is deuterated;
preferably, RdAnd Rd’Independently selected from hydrogen, deuterium, C1-C12 chain alkyl, C3-C12 cycloalkyl, deuterated C1-C12 chain alkyl and deuterated C3-C12 cycloalkylOne kind of the material is selected;
preferably, in the formula (3-1) or (3-2), said Ra、RbAnd RcAt least one of which is deuterium;
preferably, in the formula (3-1) or (3-2), said Ra、RbAnd RcAt least one of which is a deuterated C1-C12 chain alkyl group or a deuterated C3-C12 cycloalkyl group.
9. The compound of any one of claims 1, 4, 7, or 8, wherein at least one R in formula (1), formulae (2-1) to (2-5), formula (3-1), or (3-2)nIs nitrogen-containing substituted or unsubstituted C4-C30 electron-donating heteroaryl;
preferably, there is only one RnIs nitrogen-containing substituted or unsubstituted C4-C30 electron donating heteroaryl.
10. The compound according to claim 1, represented by the following formula (4):
Figure FDA0002300234900000032
wherein R isn1、Rn2And Rn3Each independently selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroaryl amino, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, cycloalkyl of deuterated C3-C12, alkoxy or thioalkoxy of C1-C12, arylamino of C6-C30, heteroaryl amino of C3-C30, monocyclic aryl or fused ring aryl of C6-C30, monocyclic heteroaryl or fused ring heteroaryl of C3-C30;
preferably, said R isn1、Rn2And Rn3Only one of the substituents is nitrogen-containing substituted or unsubstituted C4-C30 electron-donating heteroaryl, wherein the substituent is selected from one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12, and cycloalkyl of deuterated C3-C12;
more preferably, said Rn2The nitrogen-containing substituted or unsubstituted C4-C30 electron-donating heteroaryl is provided, and the substituent is one or more of deuterium, halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, chain alkyl of deuterated C1-C12 and cycloalkyl of deuterated C3-C12.
11. The compound according to any one of claims 1, 7, 8, 9 or 10, wherein R in formula (1), formulae (2-1) to (2-5), formula (3-1), (3-2) or formula (4)a、RbAnd RcEach independently selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;
preferably, said R isa、RbAnd RcEach independently selected from one of hydrogen, C1-C12 chain alkyl and C3-C12 naphthenic base.
12. The compound according to any one of claims 1, 7, 8, 9 or 10, wherein R in formula (1), formulae (2-1) to (2-5), formula (3-1), formula (3-2)nAnd R in the formula (4)n1、Rn2And Rn3Each independently selected from Hy1～Hy3The structure of (1):
Figure FDA0002300234900000041
wherein denotes the attachment site to the parent nucleus;
formula Hy1Wherein n is 0 or 1, and when n is 0, it represents a single bond; e1Selected from the group consisting of CR4R5、NR6O, S or SiR13R14One of；
Formula Hy2In, E2Selected from the group consisting of CR7R8、NR9O, S or SiR15R16One of (1);
formula Hy3In, E3And E4Each independently selected from the group consisting of a single bond, CR10R11、NR12O, S or SiR17R18And E is one of3And E4At least one term of (a) is NR12；
Said Hy1、Hy2Or Hy3In, Re、Rf、Rh、Rg、Ri、RjAnd RkEach independently represents a single substituent to the maximum permissible substituent, and each independently is selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, C1-C12 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or Re、Rf、Rh、Rg、Ri、RjAnd RkEach independently is fused with the aromatic ring connected with the aromatic ring to form one of substituted or unsubstituted C10-C30 aryl or substituted or unsubstituted C9-C30 heteroaryl; preferably, Re、Rf、Rg、Rh、Ri、RjAnd RkEach independently selected from one of hydrogen, C1-C12 chain alkyl and C3-C12 naphthenic base;
said Hy1、Hy2Or Hy3In, R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17And R18Each independently selected from one of hydrogen, C1-C12 chain alkyl, C3-C12 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl; it is preferable that，R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17And R18Each independently selected from one of chain alkyl of C1-C12, C3-C12 cycloalkyl and substituted or unsubstituted C6-C30 aryl.
13. The compound according to any one of claims 1, 7, 8, 9 or 10, wherein R in formula (1), formulae (2-1) to (2-5), formula (3-1), (3-2)nAnd R in the formula (4)n1、Rn2And Rn3Each independently selected from (Hy)1-1)-(Hy3-6) structure:
Figure FDA0002300234900000051
the R ise、Rf、Rh、Ri、Rg、Rj、Rk、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17And R18Independently of each other and in Hy1、Hy2Or Hy3The same as defined in (1).
14. A compound according to claim 12 or 13, wherein R is4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16、R17、R18、Ra、Rb、Rc、Rd、Re、Rf、Rg、Rh、Ri、RjAnd RkWhen the alkyl is selected from C1-C12 chain alkyl or C3-C12 cycloalkyl,selected from the following structures:
Figure FDA0002300234900000061
15. the compound of claim 1, selected from the compounds of the following structures:
Figure FDA0002300234900000062
Figure FDA0002300234900000071
Figure FDA0002300234900000081
Figure FDA0002300234900000091
Figure FDA0002300234900000101
Figure FDA0002300234900000111
Figure FDA0002300234900000121
16. use of a compound according to any of claims 1 to 15 as a material for a light-emitting layer, preferably as a luminescent dye and/or sensitizer, in an organic electroluminescent device.
17. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound according to any one of claims 1 to 15.
18. An organic electroluminescent device comprising an anode layer, a plurality of light emitting functional layers and a cathode layer; the plurality of light-emitting functional layers comprise at least one of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer and an electron transport layer which are sequentially formed, wherein the hole injection layer is formed on the anode layer, and the cathode layer is formed on the electron transport layer; wherein the light-emitting layer contains the organic compound according to any one of claims 1 to 15.
CN201911218859.9A 2019-12-03 2019-12-03 Organic compound, application thereof and organic electroluminescent device containing organic compound Pending CN112898322A (en)

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