Patent Application
20140197393
The present invention relates to a novel hydrocarbon-based fused ring compound and an organic light emitting device including the same.
An electroluminescent device is one type of self-luminescent-type display devices, and has advantages in that the device has a wide viewing angle, an excellent contrast, and quick response time.
An organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When voltage is applied to an organic light emitting device having such a structure, light emits by electrons and holes injected from the two electrodes being dissipated after the electrons and holes are bonded and make a pair in the organic thin film. The organic thin film may be formed as a monolayer or a multilayer as necessary.
Materials of an organic thin film may have a light emitting function when necessary. For example, as the material of an organic thin film, compounds capable of forming a light emitting layer alone may be used, or compounds capable of performing as a host or a dopant of a host-dopant-based light emitting layer may also be used. In addition to these, compounds capable of performing hole injection, hole transfer, electron blocking, hole blocking, electron transfer, electron injection, or the like, may also be used as the material of an organic thin film.
There have been continuous demands for the development of organic thin film materials in order to improve the performance, life span or efficiency of an organic light emitting device.
The present invention provides a novel hydrocarbon-based fused ring compound and an organic light emitting device including the same.
The present invention provides a compound of the following Chemical Formula 1:
In Chemical Formula 1,
R1 to R8 are selected from the group consisting of hydrogen; halogen; substituted or unsubstituted linear or branched C1 to C60 alkyl; substituted or unsubstituted linear or branched C2 to C60 alkenyl; substituted or unsubstituted linear or branched C2 to C60 alkynyl; substituted or unsubstituted linear or branched C1 to C60 alkoxy; substituted or unsubstituted monocyclic or multicyclic C3 to C60 cycloalkyl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; and amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or form a substituted or unsubstituted monocyclic or multicyclic aliphatic or aromatic hydrocarbon ring, or a substituted or unsubstituted monocyclic or multicyclic aliphatic or aromatic heteroring, by being linked to an adjacent group.
In addition, the present invention provides an organic light emitting device that includes an anode, a cathode and one or more organic material layers provided between the anode and the cathode, wherein one or more layers of the organic material layers include the compound of Chemical Formula 1.
Compounds described in the present specification may be used as the material of an organic material layer of an organic light emitting device. The compound may be used as a hole injection material, a hole transfer material, a light emitting material, an electron transfer material, an electron injection material, or the like, in an organic light emitting device. In particular, the compound may be used as the material of a light emitting layer of an organic light emitting device. Specifically, the compound may be used alone as a light emitting material, or as a host material or a dopant material of a light emitting layer.
Hereinafter, the present invention will be described in detail.
A compound described in the present specification may be represented by Chemical Formula 1. The compound according to the present invention may be used as the material of an organic material layer of an organic light emitting device depending on the structural and physical properties of a core structure.
In the present specification, halogen includes F, Cl, Br and I.
In the present specification, alkyl includes linear or branched alkyl having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkyl may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20.
In the present specification, alkenyl includes linear or branched alkenyl having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkenyl may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.
In the present specification, alkynyl includes linear or branched alkynyl having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkynyl may be 2 to 60, specifically 2 to 40, and more specifically 2 to 20.
In the present specification, alkoxy includes linear or branched alkoxy having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkoxy may be 1 to 60, specifically 1 to 40, and more specifically 1 to 20.
In the present specification, cycloalkyl includes monocyclic or multicyclic cycloalkyl having 3 to 60 carbon atoms, and may be further substituted with other substituents. Herein, multicyclic means a group in which cycloalkyl is directly bonded to or fused with other ring groups. Herein, the other ring groups may be cycloalkyl, but may also be other types of ring groups, for example, heterocycloalkyl, aryl, heteroaryl or the like. The number of carbon atoms of the cycloalkyl may be 3 to 60, specifically 3 to 40, and more specifically 5 to 20.
In the present specification, heterocycloalkyl includes S, O or N as a heteroatom, includes monocyclic or multicyclic heterocycloalkyl having 2 to 60 carbon atoms, and may be further substituted with other substituents. Herein, multicyclic means a group in which heterocycloalkyl is directly bonded to or fused with other ring groups. Herein, the other ring groups may be heterocycloalkyl, but may also be other types of ring groups, for example, cycloalkyl, aryl, heteroaryl or the like. The number of carbon atoms of the heterocycloalkyl may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20. As one example, the heterocycloalkyl group includes a 10,11-dihydro-dibenzo[b,f]azepin group, indolinyl, or a 9,10-dihydroacridine group.
In the present specification, aryl includes monocyclic or multicyclic aryl having 6 to 60 carbon atoms, and may be further substituted with other substituents. Herein, multicyclic means a group in which aryl is directly bonded to or fused with other ring groups. Herein, the other ring groups may be aryl, but may also be other types of ring groups, for example, cycloalkyl, heterocycloalkyl, heteroaryl or the like. The number of carbon atoms of the aryl may be 6 to 60, specifically 6 to 40, and more specifically 6 to 20. Specific examples of the aryl include phenyl, biphenyl, triphenyl, naphthyl, anthryl, chrysenyl, phenanthrenyl, perylenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrenyl, tetracenyl, pentacenyl, fluorenyl, indenyl, acenaphthylenyl or the like, or fused rings thereof, but are not limited thereto.
In the present specification, heteroaryl includes S, O or N as a heteroatom, includes monocyclic or multicyclic heteroaryl having 2 to 60 carbon atoms, and may be further substituted with other substituents. Herein, multicyclic means a group in which heteroaryl is directly bonded to or fused with other ring groups. Herein, the other ring groups may be heteroaryl, but may also be other types of ring groups, for example, cycloalkyl, heterocycloalkyl, aryl or the like. The number of carbon atoms of the heterocycloalkyl may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20. Specific examples of the heteroaryl include pyridyl, pyrolyl, pyrimidyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, furazanyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, diazinyl, oxazinyl, thiazinyl, dioxynyl, triazinyl, tetrazinyl, quinolyl, isoquinolyl, quinazolinyl, isoquinazolinyl, acridinyl, phenanthridinyl, imidazopyridinyl, diazanaphthalenyl, triazaindene, indolyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, a benzothiophene group, a benzofuran group, a dibenzothiophene group, a dibenzofuran group, carbazolyl, benzocarbazolyl, phenazinyl or the like, or fused rings thereof, but are not limited thereto.
In the present specification, the spiro group is a group including a spiro structure, and may have 10 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro-bonded to a fluorene group. Specifically, the spiro group includes a group of the following structural formulae.
In the present specification, “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of halogen; cyano; linear or branched C1 to C60 alkyl; linear or branched C2 to C60 alkenyl; linear or branched C2 to C60 alkynyl; linear or branched C1 to C60 haloalkyl; linear or branched C2 to C60 haloalkenyl; linear or branched C2 to C60 haloalkynyl; linear or branched C1 to C60 alkoxy; linear or branched C2 to C60 alkenyloxy; linear or branched C2 to C60 alkynyloxy; monocyclic or multicyclic C3 to C60 cycloalkyl; monocyclic or multicyclic C2 to C60 heterocycloalkyl; monocyclic or multicyclic C6 to C60 aryl; monocyclic or multicyclic C2 to C60 heteroaryl; monocyclic or multicyclic C2 to C60 heterocycloalkyl; monocyclic or multicyclic C6 to C60 aryloxy; monocyclic or multicyclic C2 to C60 heteroaryloxy; an acetophenone group; a benzophenone group; a C10 to C60 spiro group; and amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or being unsubstituted. These additional substituents may be further substituted additionally.
According to one embodiment of the present invention, in Chemical Formula 1, R1 to R8 are the same as or different from each other, and each is selected from the group consisting of hydrogen; halogen; substituted or unsubstituted linear or branched C1 to C60 alkyl; substituted or unsubstituted linear or branched C2 to C60 alkenyl; substituted or unsubstituted linear or branched C2 to C60 alkynyl; substituted or unsubstituted linear or branched C1 to C60 alkoxy; substituted or unsubstituted monocyclic or multicyclic C3 to C60 cycloalkyl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; and amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or forms a substituted or unsubstituted monocyclic or multicyclic aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted monocyclic or multicyclic aliphatic or aromatic heteroring, by being linked to an adjacent group, however, not all of R1 to R8 are hydrogen.
According to one embodiment of the present invention, in Chemical Formula 1, at least one of R1 to R8 is substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or forms a substituted or unsubstituted monocyclic or multicyclic aromatic hydrocarbon ring, or a substituted or unsubstituted monocyclic or multicyclic aromatic heteroring, by being linked to an adjacent group.
According to one embodiment of the present invention, in Chemical Formula 1, R1 to R3 are the same as or different from each other, and each is substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or forms a substituted or unsubstituted monocyclic or multicyclic aromatic hydrocarbon ring, or a substituted or unsubstituted monocyclic or multicyclic aromatic heteroring, by being linked to an adjacent group.
According to one embodiment of the present invention, in Chemical Formula 1, R1 to R3 are the same as or different from each other, each is substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C60 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1, R2 and R3 are the same as each other, and are substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1, R1 is the same as R2 and R3, and is substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1, R1 is different from R2 and R3, and is substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1, R4 is selected from the group consisting of hydrogen; substituted or unsubstituted linear or branched C1 to C60 alkyl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; and amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1, R4 is selected from the group consisting of hydrogen; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted C10 to C60 spiro group; and amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1, at least one of R6 and R7 is substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or forms a substituted or unsubstituted monocyclic or multicyclic aromatic hydrocarbon ring, or a substituted or unsubstituted monocyclic or multicyclic aromatic heteroring, by being linked to an adjacent group.
According to one embodiment of the present invention, in Chemical Formula 1, R6 and R7 are the same as or different from each other, and each is substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or forms a substituted or unsubstituted monocyclic or multicyclic aromatic hydrocarbon ring, or a substituted or unsubstituted monocyclic or multicyclic aromatic heteroring, by being linked to an adjacent group.
According to one embodiment of the present invention, in Chemical Formula 1, R6 and R7 are the same as each other, and are substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1, R5 and R8 are hydrogen; substituted or unsubstituted linear or branched C1 to C60 alkyl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted acetophenone group; a substituted or unsubstituted benzophenone group; a substituted or unsubstituted C10 to C60 spiro group; or amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, Chemical Formula 1 may be represented by any one of the following Chemical Formulae 1a to 1g.
In Chemical Formulae 1a to 1g,
R1 to R8 are the same as or different from each other, each independently selected from the group consisting of halogen; substituted or unsubstituted linear or branched C1 to C60 alkyl; substituted or unsubstituted linear or branched C2 to C60 alkenyl; substituted or unsubstituted linear or branched C2 to C60 alkynyl; substituted or unsubstituted linear or branched C1 to C60 alkoxy; substituted or unsubstituted monocyclic or multicyclic C3 to C60 cycloalkyl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; and amine unsubstituted or substituted with C1 to C60 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl,
R9 to R28 are selected from the group consisting of hydrogen; halogen; substituted or unsubstituted linear or branched C1 to C60 alkyl; substituted or unsubstituted linear or branched C2 to C60 alkenyl; substituted or unsubstituted linear or branched C2 to C60 alkynyl; substituted or unsubstituted linear or branched C1 to C60 alkoxy; substituted or unsubstituted monocyclic or multicyclic C3 to C60 cycloalkyl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; and amine unsubstituted or substituted with C1 to C60 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl, or form a substituted or unsubstituted monocyclic or multicyclic aliphatic or aromatic hydrocarbon ring, or a substituted or unsubstituted monocyclic or multicyclic aliphatic or aromatic heteroring, by being linked to an adjacent group.
According to one embodiment of the present invention, in Chemical Formulae 1a to 1g, R1 to R8 are the same as or different from each other, and each is substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted triphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted indenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted acenaphthalenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted phenalenyl, substituted or unsubstituted pyrrole, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted thienyl, substituted or unsubstituted furanyl, substituted or unsubstituted benzothiazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted indolyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzocarbazolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, a substituted or unsubstituted dibenzothiophene group, a substituted or unsubstituted dibenzofuran group, substituted or unsubstituted indolinyl, a substituted or unsubstituted 10,11-dihydro-dibenzo[b,f]azepine group, a substituted or unsubstituted 9,10-dihydroacridine group, a substituted or unsubstituted spiro group in which 2,3-dihydro-1H-indene or cyclohexane is spiro-bonded to fluorene, substituted or unsubstituted dialkylamine, substituted or unsubstituted diarylamine, substituted or unsubstituted alkylarylamine, a substituted or unsubstituted acetophenone group, or a substituted or unsubstituted benzophenone group.
In Chemical Formulae 1a to 1g, R1 to R8 may have one or more additional substituents, and at this time, the additional substituents are linear or branched C1 to C20 alkyl, phenyl, biphenyl, triphenyl, naphthyl, anthryl, phenanthrenyl, indenyl, perylenyl, pyrenyl, acenaphthalenyl, fluorenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrrole, pyridyl, pyrimidyl, pyridazinyl, triazinyl, thienyl, furanyl, benzothiazole, benzoxazole, indolyl, carbazolyl, benzocarbazolyl, quinolyl, isoquinolyl, a dibenzothiopen group, a dibenzofuran group, indolinyl, a 10,11-dihydro-dibenzo[b,f]azepine group, a 9,10-dihydroacridine group, a spiro group in which 2,3-dihydro-1H-indene or cyclohexane is spiro-bonded to fluorene, dialkylamine, diarylamine, or alkylarylamine. These additional substituents may be unsubstituted or additionally substituted with linear or branched C1 to C20 alkyl, phenyl, biphenyl, triphenyl, naphthyl, anthryl, phenanthrenyl, indenyl, perylenyl, pyrenyl, acenaphthalenyl, fluorenyl, fluoranthenyl, triphenylenyl, phenalenyl, pyrrole, pyridyl, pyrimidyl, pyridazinyl, triazinyl, thienyl, furanyl, benzothiazole, benzoxazole, indolyl, carbazolyl, benzocarbazolyl, quinolyl, isoquinolyl, a dibenzothiopen group, a dibenzofuran group, indolinyl, a 10,11-dihydro-dibenzo[b,f]azepine group, a 9,10-dihydroacridine group, a spiro group in which 2,3-dihydro-1H-indene or cyclohexane is spiro-bonded to fluorene, dialkylamine, diarylamine, or alkylarylamine.
According to one embodiment of the present invention, in Chemical Formula 1e, R9 to R16 are hydrogen.
According to one embodiment of the present invention, in Chemical Formula 1f, R17 to R26 are hydrogen.
According to one embodiment of the present invention, in Chemical Formula 1g, R17 and R18 are hydrogen.
According to one embodiment of the present invention, in Chemical Formula 1g, R27 and R28 are selected from the group consisting of hydrogen; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heterocycloalkyl; substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl; a substituted or unsubstituted C10 to C60 spiro group; and amine unsubstituted or substituted with C1 to C20 alkyl, substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl, or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
According to one embodiment of the present invention, in Chemical Formula 1g, R27 and R28 are substituted or unsubstituted monocyclic or multicyclic C6 to C60 aryl; or substituted or unsubstituted monocyclic or multicyclic C2 to C60 heteroaryl.
Specific examples of the compound of Chemical Formula 1 are represented by the following structural formulae, but the compound is not limited thereto.
The compounds described above may be prepared based on the preparation examples described later. For example, the compound of Chemical Formula 1 may be prepared using methods such as Reaction Equation 1. As necessary, substituents may be added or excluded. In addition, based on technologies known in the related art, starting materials, reactants, reaction conditions and the like may be changed.
Another embodiment of the present invention provides an organic light emitting device that includes the compound of Chemical Formula 1 described above. Specifically, an organic light emitting device according to the present invention includes an anode, a cathode, and one or more layers of organic material layers provided between the anode and the cathode, and one or more layers of the organic material layers include the compound of Chemical Formula 1.
The laminating order of the electrodes and the organic material layers of an organic light emitting device according to embodiments of the present invention is illustrated in
According to
An organic light emitting device according to the present invention may be prepared using materials and methods known in the related art except that the compound of Chemical Formula 1 is included in one or more layers of the organic material layers.
The compound of Chemical Formula 1 may form one or more layers of the organic material layers alone in an organic light emitting device. However, when necessary, the compound of Chemical Formula 1 may be mixed with other materials to form the organic material layers.
The compound of Chemical Formula 1 may be used as a hole injection material, a hole transfer material, a light emitting material, an electron transfer material, an electron injection material, or the like, in an organic light emitting device. Particularly, the compound of Chemical Formula 1 may be used as the material of a light emitting layer of an organic light emitting device. Specifically, the compound of Chemical Formula 1 may be used as the light emitting material of a light emitting layer. In addition, the compound of Chemical Formula 1 may be used as a host material or a dopant material of the light emitting layer. The compound of Chemical Formula 1 may be used either alone or as a mixture of two or more types. In addition, the compound of Chemical Formula 1 may be used by being mixed with other types of compounds.
As one example, the organic material layer that includes the compound of Chemical Formula 1 is a light emitting layer.
As another example, the organic material layer that includes the compound of Chemical Formula 1 is a light emitting layer, and this light emitting layer further includes a dopant material.
As another example, the organic material layer that includes the compound of Chemical Formula 1 is a fluorescent blue light emitting layer, and this light emitting layer further includes a fluorescent blue dopant material.
The dopant material is not particularly limited, and examples thereof include TBP (2,5,8,11-tetra-tert-butylperylene), DSAPh (p-bis(p-N,N-diphenyl-aminostyryl)-benzene), DPAVBi (4,4-bis[4-(di-p-tolylamino)styryl]biphenyl), BCzVBi (4,4′-(bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl), DPVBi (1,4-bis(2,2-diphenylvinyl)biphenyl), TBPe (2,5,8,11-tetra-tert-butylperylene), N-BDAVBi (N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine), or the like.
In the organic light emitting device according to the present invention, materials other than the compound of Chemical Formula 1 are illustrated below, however, these are for illustrative purposes only, and do not intend to limit the scope of the present invention, and these materials may be substituted with materials known in the related art.
As the anode material, materials having relatively large work function may be used, and transparent conductive oxides, metals, conductive polymers or the like may be used.
As the cathode material, materials having relatively small work function may be used, and metals, metal oxides, conductive polymers or the like may be used.
As the hole injection material, known hole injection materials may be used, and for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Pat. No. 4,356,429, or starbust-type amine derivatives disclosed in a literature [Advanced Material, 6, p. 677 (1994)], such as TCTA, m-MTDATA, m-MTDAPB, Pani/DBSA (polyaniline/dodecylbenzenesulfonic acid) or PEDOT/PSS (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate)), Pani/CSA (polyaniline/camphor sulfonic acid) or PANI/PSS (polyaniline/poly(4-styrene-sulfonate), which is a conductive polymer having solubility, or the like, may be used.
As the hole transfer material, a pyrazoline derivative, an arylamine-based derivative, a stilbene derivative, a triphenyldiamine derivative or the like may be used, and a low molecular or high molecular material may also be used.
As the electron transfer material, an oxadiazole derivative, anthraquinodimethane and a derivative thereof, benzoquinone and a derivative thereof, naphthoquinone and a derivative thereof, anthraquinone and a derivative thereof, tetracyanoanthraquinodimethane and a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene and a derivative thereof, a diphenoquinone derivative, 8-hydroxyquinoline and a metal complex of a derivative thereof, or the like, may be used, and a high molecular material as well as a low molecular material may also be used.
As the electron injection material, for example, LiF is typically used in the related industry, however, the present invention is not limited thereto.
As the light emitting material, a red, green or blue light emitting material may be used, and when necessary, two or more light emitting materials may be mixed and used. In addition, as the light emitting material, a fluorescent material may be used, but a phosphorescent material may also be used. As the light emitting material, materials that emit light alone by bonding the holes and the electrons injected from an anode and a cathode, respectively, may be used, however, materials in which a host material and a dopant material are both involved in light emitting may also be used.
Hereinafter, the present invention will be described in more detail with reference to examples, however, it is to be understood that these are for illustrative purposes only, and are not intended to limit the scope of the present invention.
After 1 g (2.97 mmol) of Compound SM and 363 mg (3.6 mmol) of ethynylbenzene were dissolved in 22 ml of TEA, 28 mg (0.15 mmol) of CuI and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 862 mg (81%) of target Compound 1-1 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1 g (2.8 mmol) of Compound 1-1 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.15 g (80%) of target Compound 2-1 was obtained.
After 1 g (1.9 mmol) of Compound 2-1, 6.9 g (38.8 mmol) of 1,2-diphenylethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 620 mg (60%) of target Compound 301 was obtained.
After 1 g (1.9 mmol) of Compound 301 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.9 g (95%) of target Compound 4-1 was obtained.
After 1 g (1.6 mmol) of Compound 4-1, 219 mg (1.8 mmol) of phenylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 740 mg (76%) of target Compound 1 was obtained.
After 1 g (2.97 mmol) of Compound SM and 542 mg (3.6 mmol) of ethynylnaphthalene were dissolved in 22 ml of TEA, mg (0.15 mmol) of CuI and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 983 mg (81%) of target Compound 1-2 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.1 g (2.8 mmol) of Compound 1-2 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.26 g (80%) of target Compound 2-2 was obtained.
After 1 g (1.8 mmol) of Compound 2-2, 6.3 g (35 mmol) of 1,2-diphenylethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 118 mg (1.8 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 629 mg (60%) of target Compound 302 was obtained.
After 1.1 g (1.9 mmol) of Compound 302 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.2 g (95%) of target Compound 4-2 was obtained.
After 1.06 g (1.6 mmol) of Compound 4-2, 219 mg (1.8 mmol) of phenylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 801 mg (76%) of target Compound 2 was obtained.
After 1 g (1.9 mmol) of Compound 2-1, 10.8 g (38.8 mmol) of 1,2-di(naphthalen-1-yl)ethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 721 mg (60%) of target Compound 303 was obtained.
After 1.2 g (1.9 mmol) of Compound 303 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.3 g (95%) of target Compound 4-11 was obtained.
After 1.14 g (1.6 mmol) of Compound 4-11, 219 mg (1.8 mmol) of phenylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 862 mg (76%) of target Compound 11 was obtained.
After 1 g (5.4 mmol) of Compound SM and 662 mg (6.48 mmol) of ethynylbenzene were dissolved in 22 ml of TEA, 10.3 mg (0.05 mmol) of CuI and 701.9 mg (0.1 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 913 mg (82%) of target Compound 1-18 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 577 mg (2.8 mmol) of Compound 1-18 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 811 mg (80%) of target Compound 2-18 was obtained.
After 688 mg (1.9 mmol) of Compound 2-18, 10.8 g (38.8 mmol) of 1,2-di(naphthalen-1-yl)ethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 548 mg (60%) of target Compound 304 was obtained.
After 910 mg (1.9 mmol) of Compound 304 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1 g (94%) of target Compound 4-1 was obtained.
After 895 mg (1.6 mmol) of Compound 4-18, 219 mg (1.8 mmol) of phenylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 677 mg (76%) of target Compound 18 was obtained.
After 1.3 g (2.97 mmol) of Compound SM and 363 mg (3.6 mmol) of ethynylbenzene were dissolved in 22 ml of TEA, 28 mg (0.15 mmol) of CuI and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.13 g (83%) of target Compound 1-109 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.3 g (2.8 mmol) of Compound 1-109 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.29 g (75%) of target Compound 2-109 was obtained.
After 1.17 g (1.9 mmol) of Compound 2-109, 10.8 g (38.8 mmol) of 1,2-di(naphthalen-2-yl)ethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 891 mg (64%) of target Compound 305 was obtained.
After 1.39 g (1.9 mmol) of Compound 305 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.4 g (92%) of target Compound 4-109 was obtained.
After 1.3 g (1.6 mmol) of Compound 4-109, 219 mg (1.8 mmol) of phenylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1 g (73%) of target Compound 109 was obtained.
After 1 g (1.9 mmol) of Compound 2-1, 9.8 g (38.8 mmol) of 1,2-di(1H-inden-5-yl)ethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 752 mg (65%) of target Compound 306 was obtained.
After 1.16 g (1.9 mmol) of Compound 306 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.2 g (92%) of target Compound 4-129 was obtained.
After 1.1 g (1.6 mmol) of Compound 4-18, 288 mg (1.8 mmol) of (1H-inden-5-yl)boronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 578 mg (80%) of target Compound 129 was obtained.
After 1.4 g (2.97 mmol) of Compound SM and 363 mg (3.6 mmol) of ethynylbenzene were dissolved in 22 ml of TEA, 28 mg (0.15 mmol) of CuI and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.3 g (86%) of target Compound 1-199 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.4 g (2.8 mmol) of Compound 1-199 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.3 g (70%) of target Compound 2-199 was obtained.
After 1.26 g (1.9 mmol) of Compound 2-199, 9.8 g (38.8 mmol) of 1,2-di(1H-inden-5-yl)ethyne, 70 mg (0.1 mmol) of Pd (PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 951 mg (66%) of target Compound 307 was obtained.
After 1.4 g (1.9 mmol) of Compound 307 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.4 g (90%) of target Compound 4-199 was obtained.
After 1.3 g (1.6 mmol) of Compound 4-199, 287 mg (1.8 mmol) of 1H-inden-5-ylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1 g (73%) of target Compound 199 was obtained.
After 1.48 g (2.97 mmol) of Compound SM and 542 mg (3.6 mmol) of 1-ethynylnaphthalene were dissolved in 22 ml of TEA, 28 mg (0.15 mmol) of CuI and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.3 g (82%) of target Compound 1-203 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.57 g (2.8 mmol) of Compound 1-203 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.38 g (69%) of target Compound 2-203 was obtained.
After 2 g (1.9 mmol) of Compound 2-203, 9.8 g (38.8 mmol) of 1,2-di(1H-inden-5-yl)ethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 940 mg (69%) of target Compound 308 was obtained.
After 1.4 g (1.9 mmol) of Compound 308 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.4 g (90%) of target Compound 4-203 was obtained.
After 1.3 g (1.6 mmol) of Compound 4-203, 219 mg (1.8 mmol) of phenylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 973 mg (75%) of target Compound 203 was obtained.
After 1.08 g (2.97 mmol) of Compound SM and 641 mg (3.6 mmol) of 4-ethynylbiphenyl were dissolved in 22 ml of TEA, 28 mg (0.15 mmol) of CuI and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.1 g (81%) of target Compound 1-231 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.3 g (2.8 mmol) of Compound 1-231 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.2 g (70%) of target Compound 2-231 was obtained.
After 1.2 g (1.9 mmol) of Compound 2-231, 9.8 g (38.8 mmol) of 1,2-di(1H-inden-5-yl)ethyne, 70 mg (0.1 mmol) of Pd (PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 834 mg (69%) of target Compound 309 was obtained.
After 1.2 g (1.9 mmol) of Compound 309 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.2 g (90%) of target Compound 4-231 was obtained.
After 1.1 g (1.6 mmol) of Compound 4-231, 356 mg (1.8 mmol) of biphenyl-4-ylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 946 mg (75%) of target Compound 231 was obtained.
After 1.1 g (2.97 mmol) of Compound SM and 688 mg (3.6 mmol) of 9-ethynyl-9H-carbazole were dissolved in 22 ml of TEA, 28 mg (0.15 mmol) of CuI and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.1 g (82%) of target Compound 1-280 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.33 g (2.8 mmol) of Compound 1-280 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.3 g (74%) of target Compound 2-280 was obtained.
After 1.2 g (1.9 mmol) of Compound 2-280, 7 g (38.8 mmol) of 1,2-di(pyridazin-3-yl)ethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 887 mg (71%) of target Compound 310 was obtained.
After 1.2 g (1.9 mmol) of Compound 310 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.2 g (90%) of target Compound 4-280 was obtained.
After 1.18 g (1.6 mmol) of Compound 4-280, 380 mg (1.8 mmol) of 9H-carbazol-9-ylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1 g (78%) of target Compound 280 was obtained.
3 g (4.9 mmol) of Compound 1 was dissolved in 60 ml of MC. After 15.9 g (98 mmol) of anhydrous ferric chloride was dissolved in 675 ml of nitromethane, it was quickly added to Compound 1, and the mixture was shaken for 15 seconds. After the result was immersed in a sonicator for 30 minutes, it was stirred for 2 days at room temperature. After the reaction completed, the result was washed with a 0.1M HCl solution, and then with a 0.1M NH4OH solution. After the result was extracted with ethyl acetate and water, the organic layer was dried using anhydrous sodium sulfate and filtered. After the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 2.26 g (76%) of target Compound 321 was obtained.
After 1 g (2.6 mmol) of Compound SM and 315 mg (3.1 mmol) of ethynylbenzene were dissolved in 22 ml of TEA, 24 mg (0.13 mmol) of Cur and 211 mg (0.3 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 956 mg (90%) of target Compound 1-331 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.14 g (2.8 mmol) of Compound 1-331 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.2 g (79%) of target Compound 2-331 was obtained.
After 1 g (1.9 mmol) of Compound 2-331, 6.9 g (38.8 mmol) of 1,2-diphenylethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 686 mg (62%) of target Compound 351 was obtained.
After 1 g (1.9 mmol) of Compound 351 and 368 mg (2 mmol) of NBS were dissolved in DMF, the mixture was stirred for 6 hours at room temperature. The result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.15 g (92%) of target Compound 3-331 was obtained.
After 1.2 g (1.6 mmol) of Compound 3-331, 219 mg (1.8 mmol) of phenylboronic acid and 663 mg (4.8 mmol) of K2CO3 were dissolved in 15 ml/3 ml/3 ml of toluene/H2O/EtOH, 92 mg (0.08 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 811 mg (77%) of target Compound 352 was obtained.
3.2 g (4.9 mmol) of Compound 352 was dissolved in 60 ml of MC. After 15.9 g (98 mmol) of anhydrous ferric chloride was dissolved in 675 ml of nitromethane, it was quickly added to Compound 352, and the mixture was shaken for 15 seconds. After the result was immersed in a sonicator for 30 minutes, it was stirred for 2 days at room temperature. After the reaction completed, the result was washed with a 0.1M HCl solution, and then with a 0.1M NH4OH solution. After the result was extracted with ethyl acetate and water, the organic layer was dried using anhydrous sodium sulfate and filtered. After the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 2.47 g (77%) of target Compound 331 was obtained.
After 1.2 g (4.1 mmol) of 1-bromo-3-iodobenzene, 1 g (3.4 mmol) of (10-phenylanthracen-9-yl)boronic acid and 939 mg (6.8 mmol) of K2CO3 were dissolved in 20 ml/4 ml/4 ml of toluene/H2O/EtOH, 195 mg (0.17 mmol) of Pd(PPh3)4 was added dropwise thereto, and the mixture was vacuum distilled for one day. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.1 g (80%) of target Compound 5-353 was obtained.
After 1 g (2.6 mmol) of Compound 5-353 and 281 mg (2.9 mmol) of ethynyltrimethylsilane were dissolved in 22 ml of TEA, 24 mg (0.13 mmol) of CuI and 42 mg (0.06 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 776 mg (70%) of target Compound 4-353 was obtained.
After 1 g (2.3 mmol) of Compound 4-353 and 28 mg (0.2 mmol) of K2CO3 were dissolved in 20 ml of MeOH, the mixture was stirred for 4 hours at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 587 mg (72%) of target Compound 3-353 was obtained.
After 1 g (2.9 mmol) of Compound 3-353 and 592 mg (3.2 mmol) of 2-bromobenzaldehyde were dissolved in 22 ml of TEA, 28 mg (0.15 mmol) of CuI and 42 mg (0.06 mmol) of (Ph3P)2PdCl2 were added dropwise thereto. The mixture was stirred for 3 hours at 50° C. After the reaction completed, the result was extracted with ethyl acetate (EA) and water, and the EA layer was washed with 1N—HCl. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 930 mg (70%) of target Compound 2-353 was obtained.
After 5.9 g (22 mmol) of PPh3 and 1.5 g (22 mmol) of zinc powder were dissolved in 22 ml of dichloromethane at 0° C., 7.4 g (22 mmol) of CBr4 compound was added thereto in small fractions for 30 minutes while stirring. The mixture was further stirred for 1 hour at room temperature. The temperature was lowered to 0° C., and then 1.28 g (2.8 mmol) of Compound 2-353 was added thereto in small fractions for 30 minutes. After that, the result was stirred for one day at room temperature. After the reaction completed, the result was extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 1.3 g (75%) of target Compound 1-353 was obtained.
After 1.2 g (1.9 mmol) of Compound 1-353, 6.9 g (38.8 mmol) of 1,2-diphenylethyne, 70 mg (0.1 mmol) of Pd(PPh3)2Cl2 and 127 mg (1.9 mmol) of zinc powder were dissolved in toluene, the mixture was vacuum distilled for one day. After the reaction completed, the result was cooled and filtered using florisil/silica, and extracted with ethyl acetate and water. The organic layer was dried using anhydrous sodium sulfate and filtered, and after the solvent was removed by vacuum distillation again, the result was separated and purified using column chromatography, and 480 mg (40%) of target Compound 353 was obtained.
UV data of Compound 353 are shown by a diagram in
The HOMO, the LUMO, and the band gap of Compound 353 are shown in the following Table 1.
The compounds were prepared using the methods of the preparation examples, and identification results of the synthesis are shown in Table 2.
1H NMR (CDCl3, 200 MHz)
First, a transparent electrode ITO thin film obtained from an OLED glass (manufactured by Samsung Corning Co. Ltd.) was ultrasonic cleaned using trichloroethylene, acetone, ethanol and distilled water in consecutive order, and was used after being cleaned using isopropyl alcohol.
Next, after an ITO substrate was installed on the substrate folder of vacuum deposition apparatus, and was exhausted until the degree of vacuum within the vacuum deposition apparatus reaches 10−7 torr, a hole injection layer having a thickness of 600 Å was deposited on the ITO substrate by vapor depositing the following 4,4′,4″-tris(N,N-(2-naphthyl)-phenylamino)triphenyl amine (2-TNATA).
Subsequently, a hole transfer layer having a thickness of 250 Å was deposited on the hole injection layer by placing the following N,N′-bis(α-naphthyl)-N,N′-diphenyl-4,4′-diamine (NPB) in another cell within the vacuum deposition apparatus, and evaporating NPB through the application of current to the cell.
After the hole injection layer and the hole transfer layer were formed, a light emitting layer was deposited thereon as follows. In one cell within the vacuum deposition apparatus, the following host was placed as a light emitting material, and the following dopant was placed in another cell.
Subsequently, a light emitting layer was deposited to a thickness of 200 Å on the hole transfer layer by heating the two cells together, and depositing with the deposition rate ratio of the dopant to be 5% by weight (host:dopant=95:5). Next, the following tris(8-hydroxyquinoline)aluminum(III) (Alq) was deposited to a thickness of 200 Å as an electron transfer layer.
After that, lithium fluoride (LiF) was deposited to a thickness of 10 Å as an electron injection layer. Next, an OLED was manufactured by depositing an Al cathode to a thickness of 1200 Å.
Meanwhile, each of all the organic compound materials necessary for the manufacture of an OLED device was vacuumed, sublimed, and purified under 10−6 to 10−8 torr, and used in the manufacture.
The OLED was manufactured using the same method as in a comparative example except that the compounds on the following table 3 were used as the material of the light emitting layer instead of α-AND in the comparative example.
Driving voltage (V), power efficiency (cd/A) and driving life span of the OLED device manufactured as describe above were measured at 1,000 cd/m2, and as the time taken for the efficiency to drop to 50%, and the results are shown in the following Table 3.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2013-0005100 | Jan 2013 | KR | national |
| 10-2013-0141774 | Nov 2013 | KR | national |
