Patent Application
20220089610
The present specification relates to a multicyclic compound, and an organic light emitting device including the same.
The present specification claims priority to and the benefits of Korean Patent Application No. 10-2018-0170110, filed with the Korean Intellectual Property Office on Dec. 27, 2018, the entire contents of which are incorporated herein by reference.
An electroluminescent device is one type of self-emissive display devices, and has an advantage of having a wide viewing angle, and a high response speed as well as having an excellent contrast.
An organic light emitting device has a structure disposing an organic thin film between two electrodes. When a voltage is applied to an organic light emitting device having such a structure, electrons and holes injected from the two electrodes bind and pair in the organic thin film, and light emits as these annihilate. The organic thin film may be formed in a single layer or a multilayer as necessary.
A material of the organic thin film may have a light emitting function as necessary. For example, as a material of the organic thin film, compounds capable of forming a light emitting layer themselves alone may be used, or compounds capable of performing a role of a host or a dopant of a host-dopant-based light emitting layer may also be used. In addition thereto, compounds capable of performing roles of hole injection, hole transfer, electron blocking, hole blocking, electron transfer, electron injection and the like may also be used as a material of the organic thin film.
Development of an organic thin film material has been continuously required for enhancing performance, lifetime or efficiency of an organic light emitting device.
The present specification is directed to providing a multicyclic compound, and an organic light emitting device including the same.
One embodiment of the present specification provides a multicyclic compound represented by the following Chemical Formula 1.
In Chemical Formula 1,
X is O; S; or NR21,
L1 and L2 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted arylene group,
Ar is a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; or a substituted or unsubstituted amine group,
N-Het is a monocyclic or multicyclic heteroaryl group substituted or unsubstituted and including one or more Ns, and when L1 is a direct bond, the N-Het is a tricyclic or lower heteroaryl group substituted or unsubstituted and including one or more Ns,
R1 to R3 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring,
R21 is a phenyl group; or a naphthyl group,
m and n are each an integer of 1 to 5,
r1 is an integer of 1 to 4,
r2 is an integer of 0 to 2,
r3 is an integer of 1 to 4, and
when r2 is 2 and m, n, r1 and r3 are an integer of 2 or greater, substituents in the parentheses are the same as or different from each other.
Another embodiment of the present application provides an organic light emitting device including a first electrode; a second electrode provided opposite to the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include one or more types of the multicyclic compound represented by Chemical Formula 1.
A compound described in the present specification can be used as a material of an organic material layer of an organic light emitting device. The compound is capable of performing a role of a hole injection material, a hole transfer material, a light emitting material, an electron transfer material, an electron injection material and the like. Particularly, the compound can be used as a light emitting layer material of an organic light emitting device. For example, the compound can be used alone as a light emitting material, or can be used as a host material of a light emitting layer.
Particularly, by introducing naphthobenzofuran, naphthobenzothiophene or benzocarbazole structure between an electron accepting substituent containing Nitrogen and an electron donating substituent, Chemical Formula 1 has a proper band gap (2.7 eV to 3.3 eV) suitable for an application as a host, and has a structure inducing a decrease in the T1 energy caused by an expansion of conjugation and an expansion of planarity of the molecular structure. The value of T1 energy decreased as above is identified to be between 2.18 eV to 2.48 eV from a measurement result, which is between T1 energy (2.0 eV to 2.10 eV) of a generally used red dopant and T1 energy (2.5 eV to 2.7 eV) of a host adjacent layer (electron blocking layer, hole transfer layer) enabling efficient energy transfer to a dopant. In addition, the increase in the planarity of the molecular structure increases intermolecular overlap, which is important in lowering a driving voltage by facilitating electron inflow and transfer.
Specifically, when using the multicyclic compound represented by Chemical Formula 1 in an organic material layer, a device driving voltage can be lowered, light efficiency can be enhanced, and device lifetime properties can be enhanced.
Hereinafter, the present specification will be described in more detail.
In the present specification, a certain part “including” certain constituents means capable of further including other constituents, and does not exclude other constituents unless particularly stated on the contrary.
In the present specification, T1 energy means an energy level value in a triple state.
In the present specification, * of a structural formula means a bonding position.
A term “substitution” means a hydrogen atom bonding to a carbon atom of a compound being changed to another substituent, and the position of substitution is not limited as long as it is a position at which the hydrogen atom is substituted, that is, a position at which a substituent can substitute, and when two or more substituents substitute, the two or more substituents may be the same as or different from each other.
In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.
In the present specification, the alkyl group includes linear or branched having 1 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkyl group may be from 1 to 60, specifically from 1 to 40 and more specifically from 1 to 20. Specific examples thereof may include a methyl group, an ethyl group, a propyl group, an n-propyl group, an isopropyl group, a butyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group, a 1-methyl-butyl group, a 1-ethyl-butyl group, a pentyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 4-methyl-2-pentyl group, a 3,3-dimethylbutyl group, a 2-ethylbutyl group, a heptyl group, an n-heptyl group, a 1-methylhexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, an octyl group, an n-octyl group, a tert-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, an n-nonyl group, a 2,2-dimethylheptyl group, a 1-ethyl-propyl group, a 1,1-dimethyl-propyl group, an isohexyl group, a 2-methylpentyl group, a 4-methylhexyl group, a 5-methylhexyl group and the like, but are not limited thereto.
In the present specification, the alkenyl group includes linear or branched having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkenyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 2 to 20. Specific examples thereof may include a vinyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 3-methyl-1-butenyl group, a 1,3-butadienyl group, an allyl group, a 1-phenylvinyl-1-yl group, a 2-phenylvinyl-1-yl group, a 2,2-diphenylvinyl-1-yl group, a 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl group, a 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, a stilbenyl group, a styrenyl group and the like, but are not limited thereto.
In the present specification, the alkynyl group includes linear or branched having 2 to 60 carbon atoms, and may be further substituted with other substituents. The number of carbon atoms of the alkynyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 2 to 20.
In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably from 1 to 20. Specific examples thereof may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like, but are not limited thereto.
In the present specification, the cycloalkyl group includes monocyclic or multicyclic having 3 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the cycloalkyl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a cycloalkyl group, but may also be different types of cyclic groups such as a heterocycloalkyl group, an aryl group and a heteroaryl group. The number of carbon groups of the cycloalkyl group may be from 3 to 60, specifically from 3 to 40 and more specifically from 5 to 20. Specific examples thereof may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a 3-methylcyclopentyl group, a 2,3-dimethylcyclopentyl group, a cyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 3,4,5-trimethylcyclohexyl group, a 4-tert-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group and the like, but are not limited thereto.
In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a heteroatom, includes monocyclic or multicyclic having 2 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the heterocycloalkyl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a heterocycloalkyl group, but may also be different types of cyclic groups such as a cycloalkyl group, an aryl group and a heteroaryl group. The number of carbon atoms of the heterocycloalkyl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 3 to 20.
In the present specification, the aryl group includes monocyclic or multicyclic having 6 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the aryl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be an aryl group, but may also be different types of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group and a heteroaryl group. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be from 6 to 60, specifically from 6 to 40 and more specifically from 6 to 25. Specific examples of the aryl group may include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, an anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a fluorenyl group, an indenyl group, an acenaphthylenyl group, a benzofluorenyl group, a spirobifluorenyl group, a 2,3-dihydro-1H-indenyl group, a fused ring thereof, and the like, but are not limited thereto.
In the present specification, the fluorenyl group may be substituted, and adjacent substituents may bond to each other to form a ring.
When the fluorenyl group is substituted,
and the like may be included, however, the structure is not limited thereto.
In the present specification, the heteroaryl group includes 0, S, Se, N or Si as a heteroatom, includes monocyclic or multicyclic having 2 to 60 carbon atoms, and may be further substituted with other substituents. Herein, the multicyclic means a group in which the heteroaryl group is directly linked to or fused with other cyclic groups. Herein, the other cyclic groups may be a heteroaryl group, but may also be different types of cyclic groups such as a cycloalkyl group, a heterocycloalkyl group and an aryl group. The number of carbon atoms of the heteroaryl group may be from 2 to 60, specifically from 2 to 40 and more specifically from 3 to 25. Specific examples of the heteroaryl group may include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, a triazolyl group, a furazanyl group, an oxadiazolyl group, a thiadiazolyl group, a dithiazolyl group, a tetrazolyl group, a pyranyl group, a thiopyranyl group, a diazinyl group, an oxazinyl group, a thiazinyl group, a dioxynyl group, a triazinyl group, a tetrazinyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, an isoquinazolinyl group, a qninozolinyl group, a naphthyridyl group, an acridinyl group, a phenanthridinyl group, an imidazopyridinyl group, a diazanaphthalenyl group, a triazaindene group, an indolyl group, an indolizinyl group, a benzothiazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiophene group, a benzofuran group, a dibenzothiophene group, a dibenzofuran group, a carbazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a phenazinyl group, a dibenzosilole group, spirobi(dibenzosilole), a dihydrophenazinyl group, a phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, a 10,11-dihydro-dibenzo[b,f]azepine group, a 9,10-dihydroacridinyl group, a phenanthrazinyl group, a phenothiathiazinyl group, a phthalazinyl group, a naphthylidinyl group, a phenanthrolinyl group, a benzo[c][1,2,5]thiadiazolyl group, a 2,3-dihydrobenzo[b]thiophene group, a 2,3-dihydrobenzofuran group, a 5,10-dihydrobenzo[b,e][1,4]azasilinyl group, a pyrazolo[1,5-c]quinazolinyl group, a pyrido[1,2-b]indazolyl group, a pyrido[1,2-a]imidazo[1,2-e]indolinyl group, a 5,11-dihydroindeno[1,2-b]carbazolyl group and the like, but are not limited thereto.
In the present specification, the phosphine oxide group may be specifically substituted with an aryl group, and as the aryl group, examples described above may be used. Examples of the phosphine oxide group may include a diphenylphosphine oxide group, a dinaphthylphosphine oxide group and the like, but are not limited thereto.
In the present specification, the amine group may be selected from the group consisting of a monoalkylamine group; a monoarylamine group; a monoheteroarylamine group; —NH2; a dialkylamine group; a diarylamine group; a diheteroarylamine group; an alkylarylamine group; an alkylheteroarylamine group; and an arylheteroarylamine group, and although not particularly limited thereto, the number of carbon atoms is preferably from 1 to 30. Specific examples of the amine group may include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, a 9-methyl-anthracenylamine group, a diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, a biphenylnaphthylamine group, a phenylbiphenylamine group, a biphenylfluorenylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group and the like, but are not limited thereto.
In the present specification, an “adjacent” group may mean a substituent substituting an atom directly linked to an atom substituted by the corresponding substituent, a substituent sterically most closely positioned to the corresponding substituent, or another substituent substituting an atom substituted by the corresponding substituent. For example, two substituents substituting ortho positions in a benzene ring, and two substituents substituting the same carbon in an aliphatic ring may be interpreted as groups “adjacent” to each other.
As the aliphatic hydrocarbon ring, the aromatic hydrocarbon ring, the aliphatic heteroring or the aromatic heteroring that the adjacent groups may form, the structures illustrated above as the cycloalkyl group, the aryl group, the heterocycloalkyl group and the heteroaryl group may be used except for those that are not monovalent.
In the present specification, “substituted or unsubstituted” means being substituted with one or more substituents selected from the group consisting of C1 to C60 linear or branched alkyl; C2 to C60 linear or branched alkenyl; C2 to C60 linear or branched alkynyl; C3 to C60 monocyclic or multicyclic cycloalkyl; C2 to C60 monocyclic or multicyclic heterocycloalkyl; C6 to C60 monocyclic or multicyclic aryl; C2 to C60 monocyclic or multicyclic heteroaryl; —SiRR′R″; —P(═O)RR′; C1 to C20 alkylamine; C6 to C60 monocyclic or multicyclic arylamine; and C2 to C60 monocyclic or multicyclic heteroarylamine, or being unsubstituted, or being substituted with a substituent linking two or more substituents selected from among the substituents illustrated above, or being unsubstituted. R, R′ and R″ are the same as or different from each other, and each independently hydrogen; deuterium; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
One embodiment of the present specification provides a multicyclic compound represented by Chemical Formula 1.
Particularly, by introducing naphthobenzofuran, naphthobenzothiophene or benzocarbazole structure between an electron accepting substituent containing Nitrogen and an electron donating substituent, Chemical Formula 1 has a proper band gap (2.7 eV to 3.3 eV) suitable for an application as a host, and has a structure inducing a decrease in the T1 energy caused by an expansion of conjugation and an expansion of planarity of the molecular structure. The value of T1 energy decreased as above is identified to be between 2.18 eV to 2.48 eV from a measurement result, which is between T1 energy (2.0 eV to 2.10 eV) of a generally used red dopant and T1 energy (2.5 eV to 2.7 eV) of a host adjacent layer (electron blocking layer, hole transfer layer) enabling efficient energy transfer to a dopant. In addition, the increase in the planarity of the molecular structure increases intermolecular overlap, which is important in lowering a driving voltage by facilitating electron inflow and transfer.
In one embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; or a substituted or unsubstituted arylene group.
In another embodiment, L1 and L2 are the same as or different from each other, and may be each independently a direct bond; or a substituted or unsubstituted C6 to C60 arylene group.
In another embodiment, L1 and L2 are the same as or different from each other, and may be each independently a direct bond; or a substituted or unsubstituted C6 to C40 arylene group.
In another embodiment, L1 and L2 are the same as or different from each other, and may be each independently a direct bond; or a substituted or unsubstituted C6 to C20 arylene group.
In another embodiment, L1 and L2 are the same as or different from each other, and may be each independently a direct bond; or a C6 to C20 arylene group.
In another embodiment, L1 and L2 are the same as or different from each other, and may be each independently a direct bond; a phenylene group; a biphenylene group; or a naphthylene group.
In one embodiment of the present specification, Ar is a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; or a substituted or unsubstituted amine group.
In another embodiment, Ar may be a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; or a substituted or unsubstituted C1 to C30 amine group.
In another embodiment, Ar may be a substituted or unsubstituted C6 to C60 aryl group; a substituted or unsubstituted C2 to C60 heteroaryl group; or a C1 to C30 amine group unsubstituted or substituted with an aryl group.
In another embodiment, Ar may be a substituted or unsubstituted C6 to C40 aryl group; a substituted or unsubstituted C2 to C40 heteroaryl group; or a substituted or unsubstituted C1 to C30 arylamine group.
In one embodiment of the present specification, Ar may be selected from among the following structural formulae.
In the structural formulae,
Y1 to Y6 are the same as or different from each other, and each independently a direct bond; O; S; or NR22,
Z1 is N or CR31,
R5 to R15, R13 and R31 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group,
R4, R16 and R17 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or bond to adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring,
R22 is a substituted or unsubstituted aryl group,
r4, r6 and r7 are each an integer of 1 to 10,
r5 is an integer of 1 to 7,
r8, r13, r15 and r18 are each an integer of 1 to 4,
r9 to r12, r14 and r17 are each an integer of 1 to 6,
r16 is an integer of 1 to 5, and
when r4 to r18 are an integer of 2 or greater, substituents in the parentheses are the same as or different from each other.
In one embodiment of the present specification, any one of Y1 and Y2 is a direct bond, and the other one may be O; S; or NR22.
In one embodiment of the present specification, any one of Y3 and Y4 is a direct bond, and the other one may be O; S; or NR22.
In one embodiment of the present specification, any one of Y5 and Y6 is a direct bond, and the other one may be O; S; or NR22.
In one embodiment of the present specification, R5 to R15 and R13 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; and a substituted or unsubstituted aryl group.
In another embodiment, R5 to R15 and R13 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; and a substituted or unsubstituted C6 to C40 aryl group.
In another embodiment, R5 to R15 and R13 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; and a substituted or unsubstituted C6 to C20 aryl group.
In another embodiment, R5 to R15 and R13 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; and a substituted or unsubstituted naphthyl group.
In another embodiment, R5 to R15 and R13 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a phenyl group; a biphenyl group; and a naphthyl group.
In one embodiment of the present specification, R5 and R7 to R9 may be hydrogen; or a phenyl group.
In one embodiment of the present specification, R6, R10 to R15 and R13 may be hydrogen.
In one embodiment of the present specification, R4, R16 and R17 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, or may bond to adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In one embodiment of the present specification, R4, R16 and R17 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group.
In one embodiment of the present specification, R4, R16 and R17 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group.
In one embodiment of the present specification, R4, R16 and R17 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C40 aryl group; and a substituted or unsubstituted C2 to C40 heteroaryl group.
In one embodiment of the present specification, R4, R16 and R17 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted fluorenyl group; a substituted or unsubstituted carbazole group; a substituted or unsubstituted benzocarbazole group; a substituted or unsubstituted dibenzofuran group; and a substituted or unsubstituted dibenzothiophene group.
In another embodiment, R4, R16 and R17 may bond to adjacent groups to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In one embodiment of the present specification, R4, R16 and R17 may bond to each other to form a ring of the following structures.
In one embodiment of the present specification, R31 may be hydrogen.
In one embodiment of the present specification, the N-Het is a monocyclic or multicyclic heteroaryl group substituted or unsubstituted and including one or more Ns, and when L1 is a direct bond, the N-Het is a tricyclic or lower heteroaryl group substituted or unsubstituted and including one or more Ns.
In one embodiment of the present specification, the N-Het may be selected from among the following structural formulae.
In the structural formulae,
Y7 to Y10 are the same as or different from each other, and each a direct bond; O; S; or NR23,
Z2 and Z3 are each N or CR32,
R101 to R104 and R32 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring,
R23 is a substituted or unsubstituted aryl group,
r101 is 1 or 2,
r102 to r104 are each an integer of 1 to 5, and
when r101 is 2 and r102 to r104 are an integer of 2 or greater, substituents in the parentheses are the same as or different from each other.
In one embodiment of the present specification, any one of Y7 and Y8 is a direct bond, and the other one may be O; S; or NR23.
In one embodiment of the present specification, any one of Y9 and Y10 is a direct bond, and the other one may be O; S; or NR23.
In one embodiment of the present specification, Z2 and Z3 are each N or CR32, and at least one thereof may be N.
In another embodiment, Z2 and Z3 may be N.
In one embodiment of the present specification, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted aryl group; and a substituted or unsubstituted heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C40 aryl group; and a substituted or unsubstituted C2 to C40 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C2 to C20 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C6 to C60 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C40 aryl group; and a substituted or unsubstituted C6 to C40 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C6 to C20 heteroaryl group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; a substituted or unsubstituted terphenyl group; a substituted or unsubstituted naphthyl group; a substituted or unsubstituted dibenzofuran group; a substituted or unsubstituted dibenzothiophene group; a substituted or unsubstituted carbazole group; a substituted or unsubstituted benzocarbazole group; and a substituted or unsubstituted fluorene group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In another embodiment, R101 to R104 are the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; a phenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; a biphenyl group; a naphthyl group unsubstituted or substituted with an aryl group; a dibenzofuran group; a dibenzothiophene group; a carbazole group unsubstituted or substituted with an aryl group; a benzocarbazole group; a dimethylfluorene group; a diphenylfluorene group; and 9,9′-spirobi[fluorene], or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In one embodiment of the present specification, R101 to R104 are the same as or different from each other, and may be each independently selected from the group consisting of hydrogen; deuterium; a phenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; a biphenyl group; a naphthyl group unsubstituted or substituted with an aryl group; a dibenzofuran group; a dibenzothiophene group; a carbazole group unsubstituted or substituted with an aryl group; a benzocarbazole group; a dimethylfluorene group; a diphenylfluorene group; and 9,9′-spirobi[fluorene].
In one embodiment of the present specification, when the substituent is a substituted or unsubstituted carbazole group; or a substituted or unsubstituted benzocarbazole group, the bonding position may be N of the pyrrole ring, or C of the benzene ring.
In one embodiment of the present specification, R32 may be hydrogen.
In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently selected from the group consisting of hydrogen;
deuterium; a halogen group; a cyano group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted alkynyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted heterocycloalkyl group; a substituted or unsubstituted aryl group; a substituted or unsubstituted heteroaryl group; a substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other may bond to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; deuterium; or a substituted or unsubstituted aryl group.
In one embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently hydrogen; deuterium; a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; or a substituted or unsubstituted naphthyl group.
In another embodiment, R1 to R3 are hydrogen; a phenyl group; a biphenyl group; or a naphthyl group.
In one embodiment of the present specification, R21 is a phenyl group; or a naphthyl group.
In one embodiment of the present specification, R21 is a phenyl group.
In the multicyclic compound provided in one embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 2 or 3.
In Chemical Formulae 2 and 3,
r21 is an integer of 1 to 3,
when r21 is an integer of 2 or greater, substituents in the parentheses are the same as or different from each other, and
the remaining substituents have the same definitions as in Chemical Formula 1.
In one embodiment of the present specification, Chemical Formula 1 may be represented by any one of the following compounds, but is not limited thereto.
In addition, by introducing various substituents to the structure of Chemical Formula 1, compounds having unique properties of the introduced substituents may be synthesized. For example, by introducing substituents normally used as hole injection layer materials, hole transfer layer materials, light emitting layer materials, electron transfer layer materials and charge generation layer materials used for manufacturing an organic light emitting device to the core structure, materials satisfying conditions required for each organic material layer may be synthesized.
In addition, by introducing various substituents to the structure of Chemical Formula 1, the energy band gap may be finely controlled, and meanwhile, properties at interfaces between organic materials are enhanced, and material applications may become diverse.
One embodiment of the present specification provides an organic light emitting device including a first electrode; a second electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include one or more types of the multicyclic compound represented by Chemical Formula 1.
In one embodiment of the present specification, the organic material layer may include two types of the multicyclic compound represented by Chemical Formula 1.
In the organic light emitting device provided in one embodiment of the present specification, the organic material layer further includes a compound represented by the following Chemical Formula 4.
In Chemical Formula 4,
R24 is a substituted or unsubstituted aryl group,
R41 is hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted amine group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group, or groups adjacent to each other may bond to form a substituted or unsubstituted ring,
r41 is an integer of 1 to 8, and
when r41 is an integer of 2 or greater, substituents in the parentheses are the same as or different from each other.
In one embodiment of the present specification, R24 is a substituted or unsubstituted C6 to C30 aryl group.
In one embodiment of the present specification, R24 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; or a substituted or unsubstituted naphthyl group.
In one embodiment of the present specification, R24 is a phenyl group unsubstituted or substituted with an aryl group; a biphenyl group; or a naphthyl group unsubstituted or substituted with an aryl group.
In one embodiment of the present specification, R24 is a substituted or unsubstituted phenyl group.
In one embodiment of the present specification, the substituted or unsubstituted ring formed by R41 bonding to groups adjacent to each other may be a substituted or unsubstituted aliphatic hydrocarbon ring, a substituted or unsubstituted aromatic hydrocarbon ring, a substituted or unsubstituted aliphatic heteroring, or a substituted or unsubstituted aromatic heteroring.
In one embodiment of the present specification, the compound represented by Chemical Formula 4 is represented by the following Chemical Formula 4-1 or Chemical Formula 4-2.
In Chemical Formulae 4-1 and 4-2,
R24 has the same definition as in Chemical Formula 4,
Z4 and Z5 are each independently a direct bond; NR27; or CR23R29,
R25 is a substituted or unsubstituted aryl group, and
R26 to R29 are each independently hydrogen; deuterium; a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In one embodiment of the present specification, R25 is a substituted or unsubstituted phenyl group; or a substituted or unsubstituted biphenyl group.
In one embodiment of the present specification, R27 is a substituted or unsubstituted phenyl group; a substituted or unsubstituted biphenyl group; or a substituted or unsubstituted naphthyl group.
In one embodiment of the present specification, R27 is a phenyl group unsubstituted or substituted with an aryl group; a biphenyl group; or a naphthyl group unsubstituted or substituted with an aryl group.
In one embodiment of the present specification, Chemical Formula 4 is represented by any one of the following compounds.
In the organic light emitting device provided in one embodiment of the present specification, the organic material layer further includes a compound represented by the following Chemical Formula 5.
In Chemical Formula 5,
R42 to R44 are each independently a substituted or unsubstituted aryl group; or a substituted or unsubstituted heteroaryl group.
In one embodiment of the present specification, R42 to R44 are each independently a substituted or unsubstituted C6 to C30 aryl group; or a substituted or unsubstituted C2 to C30 heteroaryl group.
In one embodiment of the present specification, Chemical Formula 5 is represented by any one of the following compounds.
In one embodiment of the present specification, the first electrode may be an anode, and the second electrode may be a cathode.
In another embodiment of the present specification, the first electrode may be a cathode, and the second electrode may be an anode.
In one embodiment of the present specification, the organic light emitting device may be a blue organic light emitting device, and the multicyclic compound according to Chemical Formula 1 may be used as a material of the blue organic light emitting device. For example, the multicyclic compound according to Chemical Formula 1 may be included in a host material of a red light emitting layer of the blue organic light emitting device.
In another embodiment of the present specification, the organic light emitting device may be a green organic light emitting device, and the multicyclic compound according to Chemical Formula 1 may be used as a material of the green organic light emitting device. For example, the multicyclic compound according to Chemical Formula 1 may be included in a host material of a red light emitting layer of the green organic light emitting device.
In another embodiment of the present specification, the organic light emitting device may be a red organic light emitting device, and the multicyclic compound according to Chemical Formula 1 may be used as a material of the red organic light emitting device. For example, the multicyclic compound according to Chemical Formula 1 may be included in a host material of a red light emitting layer of the red organic light emitting device.
Specific details on the multicyclic compound represented by Chemical Formula 1 are the same as the descriptions provided above.
The organic light emitting device of the present specification may be manufactured using common organic light emitting device manufacturing methods and materials except that one or more organic material layers are formed using the multicyclic compound described above.
The multicyclic compound may be formed into an organic material layer through a solution coating method as well as a vacuum deposition method when manufacturing the organic light emitting device. Herein, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, a spray method, roll coating and the like, but is not limited thereto.
The organic material layer of the organic light emitting device of the present specification may be formed in a single layer structure, or may also be formed in a multilayer structure in which two or more organic material layers are laminated. For example, the organic light emitting device according to one embodiment of the present disclosure may have a structure including a hole injection layer, a hole transfer layer, a light emitting layer, an electron transfer layer, an electron injection layer and the like as the organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic material layers.
In the organic light emitting device of the present specification, the organic material layer includes a light emitting layer, and the light emitting layer may include the multicyclic compound.
In another organic light emitting device, the organic material layer includes a light emitting layer, the light emitting layer includes a host, and the host may include one or more types of the multicyclic compound. For example, the host may include two types of the multicyclic compound.
When forming a host by combining two types of the multicyclic compound, more favorable efficiency and lifetime are obtained compared to when using one host. Each host has physical properties of relatively faster electron migration or faster hole migration in one device. Such properties become a problem in controlling a charge balance in a light emitting layer using one type of host. However, by mixing two hosts, such relative properties of a single host may be compensated, and driving, lifetime and efficiency of a device may be improved. Accordingly, values of lifetime, efficiency and driving results change depending on the changes in the ratio when using two types of hosts, and how to combine different hosts is the most important challenge.
In another organic light emitting device, the organic material layer includes a light emitting layer, the light emitting layer includes a host, and the host includes two types of the multicyclic compound and may include two types of the compound in a weight ratio of 1:5 to 5:1 or 1:3 to 3:1.
In another organic light emitting device, the organic material layer includes a light emitting layer, the light emitting layer includes a host, and the host may include one type of the multicyclic compound and one type of the compound of Chemical Formula 4 or 5.
In another organic light emitting device, the organic material layer includes a light emitting layer, the light emitting layer includes a host, and the host may include one type of the multicyclic compound and one type of the compound of Chemical Formula 4 or 5 in a weight ratio of 1:5 to 5:1 or 1:3 to 3:1.
The organic light emitting device of the present disclosure may further include one, two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transfer layer, an electron injection layer, an electron transfer layer, an electron blocking layer and a hole blocking layer.
The organic material layer including the multicyclic compound represented by Chemical Formula 1 may further include other materials as necessary.
In the organic light emitting device according to one embodiment of the present specification, materials other than the multicyclic compound represented by Chemical Formula 1 are illustrated below, however, these are for illustrative purposes only and not for limiting the scope of the present application, and may be replaced by materials known in the 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. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc and gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.
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. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; multilayer structure materials such as LiF/Al or LiO2/Al, and the like, but are not limited thereto.
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 starburst-type amine derivatives such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4′,4″-tri[phenyl(m-tolyl)amino]triphenylamine (m-MTDATA) or 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB) described in the literature [Advanced Material, 6, p. 677 (1994)], polyaniline/dodecylbenzene sulfonic acid, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate), polyaniline/camphor sulfonic acid or polyaniline/poly(4-styrene-sulfonate) that are conductive polymers having solubility, and the like, may be used.
As the hole transfer material, pyrazoline derivatives, arylamine-based derivatives, stilbene derivatives, triphenyldiamine derivatives and the like may be used, and low molecular or high molecular materials may also be used.
As the electron transfer material, metal complexes of oxadiazole derivatives, anthraquinodimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, 8-hydroxyquinoline and derivatives thereof, and the like, may be used, and high molecular materials may also be used as well as low molecular materials.
As examples of the electron injection material, LiF is typically used in the art, however, the present application is not limited thereto.
As the light emitting material, red, green or blue light emitting materials may be used, and as necessary, two or more light emitting materials may be mixed and used. Herein, two or more light emitting materials may be used by being deposited as individual sources of supply or by being premixed and deposited as one source of supply. In addition, fluorescent materials may also be used as the light emitting material, however, phosphorescent materials may also be used. As the light emitting material, materials emitting light by bonding electrons and holes injected from an anode and a cathode, respectively, may be used alone, however, materials having a host material and a dopant material involving in light emission together may also be used.
When mixing light emitting material hosts, same series hosts may be mixed, or different series hosts may be mixed.
For example, any two or more types of materials among n-type host materials or p-type host materials may be selected, and used as a host material of a light emitting layer.
The organic light emitting device according to one embodiment of the present specification may be a top-emission type, a bottom-emission type or a dual-emission type depending on the materials used.
The multicyclic compound according to one embodiment of the present specification may also be used in an organic electronic device including an organic solar cell, an organic photo conductor, an organic transistor and the like under a similar principle used in the organic light emitting device.
Hereinafter, the present specification will be described in more detail with reference to examples, however, these are for illustrative purposes only, and the scope of the present application is not limited thereto.
Structures of Compounds A1 to A7 used in the following preparation examples are as follows.
Structures of Compounds B1 to B42 used in the following preparation examples are as follows.
Structures of Compounds E1 to E19 used in the following preparation examples are as follows.
As the compounds, commercially available reagents were used for the compounds other than E10 to E15, and Compounds E10 to E15 were synthesized as follows.
Synthesis of Compound E
<Compounds E10 to E13>
2,4-Dichloro-6-phenyl-1,3,5-triazine (15 g, 66.4 mmol), dibenzo[b,d]furan-3-ylboronic acid (16.9 g, 79.6 mmol), Pd(PPh3)4 (3.8 g, 3.32 mmol) and K2CO3 (18.3 g, 132.8 mmol) were introduced to a 500 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, THF (200 mL) and H2O (40 mL) were introduced thereto, and the result was stirred for 5 hours at 80° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4, and then concentrated. The result was silica gel columned and recrystallized to obtain white solid Compound E10 (6.3 g, 9.8 mmol, yield 69%).
Compounds E11 to E13 were synthesized in a similar manner as in the above-described synthesis method using starting materials of the following Table 1.
<Compounds E14 and E15>
2,4-Dichloroquinazoline (15 g, 50.2 mmol) and KOtBu (5.6 g, 50.2 mmol) were introduced to a 250 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, CHCl3 (150 mL) was introduced thereto, the result was stirred for 30 minutes at 0° C., and Compound B4 (10.9 g, 50.2 mmol) was slowly added dropwise thereto. After the reaction was terminated in 1 hour, the reaction was terminated by introducing methanol (50 mL) thereto, and the result was washed with water and then extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain white solid Compound E14 (17 g, 45 mmol, yield 69%).
White solid Compound E15 (7 g, yield 80%) was obtained in a similar manner as above using 2,4-dichloro-6-(naphthalen-2-yl)-1,3,5-triazine and B1 as starting materials.
Synthesis of Compound C
Compound A1 (20 g, 79.1 mmol), Compound B1 (15.8 g, 94.92 mmol), Pd2dba3 (3.6 g, 3.95 mmol), P(t-Bu)3 (3.2 g, 15.8 mmol) and NaOH (6.3 g, 158 mmol) were introduced to a 500 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, xylene (300 mL) was introduced thereto, and the result was stirred for 12 hours at 160° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain Compound C1 (26.7 g, 70 mmol, yield 89%).
Compounds C2 to C27 were synthesized in the same manner as in the above-described synthesis method of Synthesis Example 1-1 using Compounds A and B of the following Table 2 instead of Compounds A1 and B1.
Compound A1 (20 g, 79.1 mmol), Compound B18 (15.8 g, 94.92 mmol), Pd(PPh3)4 (4.5 g, 3.95 mmol) and K2CO3 (21.8 g, 158 mmol) were introduced to a 500 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (250 mL) and H2O (50 mL) were introduced thereto, and the result was stirred for 4 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain Compound C28 (33 g, 72 mmol, yield 91%).
Compounds C29 to C31 were synthesized in the same manner as in the above-described synthesis method of Synthesis Example 1-2 using Compound A of the following Table 3 instead of Compound A1.
Synthesis of Compound D
Compound C1 (26 g, 67.8 mmol) was introduced to a 250 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, THF (250 mL) was introduced thereto, and the inner temperature of the reaction vessel was calibrated to −78° C. 2.5 M (in hexane) n-BuLi (29.8 mL) was slowly added dropwise thereto, and after stirring the result for 2 hours, B(OMe)3 (9.8 mL, 101.7 mmol) was slowly added dropwise thereto at room temperature. After the reaction was terminated in 2 hours, the reaction was completely terminated using ethanol (20 mL), and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned to obtain white solid Compound D1 (23.8 g, 55.6 mmol, yield 82%).
Compounds D2 to D31 were synthesized in the same manner as in the above-described synthesis method using Compound C of the following Table 4 instead of C1.
Synthesis of Compound F
Compound D2 (5 g, 10.5 mmol), Compound E5 (3.7 g, 12.6 mmol), Pd(PPh3)4 (0.6 g, 0.53 mmol) and K2CO3 (2.9 g, 21 mmol) were introduced to a 250 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (80 mL) and H2O (20 mL) were introduced thereto, and the result was stirred for 3 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain yellow solid Compound F5 (6.1 g, 8.8 mmol, yield 84%).
Compound F of the following Table 5 was synthesized in the same manner as in the above-described synthesis method using Compounds D and E of the following Table 5 instead of Compounds D2 and E5.
Synthesis of Compound G
Compound A1 (25 g, 98.9 mmol) was introduced to a 1 L round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, CHCl3 (300 mL) was introduced thereto, and the result was stirred for 30 minutes at 0° C. The inner temperature was calibrated to 0° C., and then Br2 (5.35 mL, 104 mmol) was slowly added dropwise thereto. After the reaction was terminated, precipitated solids were washed with methanol (150 mL) and then filtered. The filtered white solids were recrystallized to obtain white solid Compound G1 (30.2 g, 90.9 mmol, yield 92%).
Synthesis of Compound H
Compound G1 (30.2 g, 90.9 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (27.7 g, 109 mmol), PdCl2(dppf) (3.3 g, 4.5 mmol) and KOAc (17.8 g, 182 mmol) were introduced to a 500 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (250 mL) was introduced thereto, and the result was stirred for 6 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain white solid Compound H1 (30.2 g, 80 mmol, yield 88%).
Synthesis of Compound I
Compound H1 (5 g, 13.2 mmol), Compound E1 (3.5 g, 13.2 mmol), Pd(PPh3)4 (0.7 g, 0.66 mmol) and K2CO3 (3.7 g, 26.4 mmol) were introduced to a 250 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (80 mL) and H2O (20 mL) were introduced thereto, and the result was stirred for 3 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain yellow solid Compound I1 (5.8 g, 12.1 mmol, 92%).
Synthesis of Compound F (1)
Compound I1 (5 g, 10.4 mmol), Compound B1 (2.3 g, 13.5 mmol), Pd2dba3 (0.47 g, 0.52 mmol), P(t-Bu)3 (0.8 g, 4.16 mmol) and NaOH (0.8 g, 20.8 mmol) were introduced to a 100 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, xylene (50 mL) was introduced thereto, and the result was stirred for 8 hours at 160° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain Compound F37 (5 g, 8.2 mmol, yield 79%).
Compound F of the following Table 6 was synthesized in the same manner as in Syntheses of Compounds G, H, I and F using Compounds A, G, H, E, I and B of the following Table 6 instead of Compounds A1, G1, H1, E1, I1 and B1.
Synthesis of Compound J
Compound G1 (20 g, 60 mmol), Compound B1 (13 g, 78 mmol), Pd2dba3 (2.7 g, 3.0 mmol), P(t-Bu)3 (2.4 g, 12 mmol) and NaOH (4.8 g, 120 mmol) were introduced to a 500 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, xylene (150 mL) was introduced thereto, and the result was stirred for 8 hours at 160° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain Compound J1 (14.2 g, 34.2 mmol, yield 57%).
Synthesis of Compound K
Compound J1 (14.2 g, 34.2 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (11.3 g, 44.5 mmol), PdCl2(dppf) (1.3 g, 1.7 mmol) and KOAc (6.7 g, 68.4 mmol) were introduced to a 250 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (150 mL) was introduced thereto, and the result was stirred for 6 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain white solid Compound K1 (15.5 g, 30.4 mmol, yield 89%).
Synthesis of Compound F (2)
Compounds J and K were synthesized in the same manner as in Synthesis of Compound J and K using Compounds G and B of the following Table 7 instead of Compounds G1 and B1, and Compound F of the following Table 7 was synthesized in the same manner as in Synthesis of Compound F of Preparation Example 1 using Compounds K and E of the following Table 7 instead of Compounds D1 and E5.
Synthesis of Compound L
Compound G7 (26 g, 79.1 mmol), CuI (15 g, 79.1 mmol), iodo-benzene (24 g, 118.6 mmol), (1R,2S)-cyclohexane-1,2-diamine (9 g, 79.1 mmol) and K3PO4 (33.5 g, 158 mmol) were introduced to a 500 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, toluene (300 mL) was introduced thereto, and the result was stirred for 8 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain Compound L1 (29.7 g, 73.5 mmol, yield 93%).
Synthesis of Compound M
Compound L1 (29.7 g, 73.5 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (24 g, 95.5 mmol), PdCl2(dppf) (3.7 g, 7.3 mmol) and KOAc (14.4 g, 147 mmol) were introduced to a 500 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (250 mL) was introduced thereto, and the result was stirred for 6 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain white solid Compound M1 (27 g, 60 mmol, yield 82%).
Synthesis of Compound N
Compound M1 (5.3 g, 11.7 mmol), Compound E7 (4.2 g, 14.04 mmol), Pd(PPh3)4 (0.7 g, 0.59 mmol) and K2CO3 (3.2 g, 23.4 mmol) were introduced to a 250 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (80 mL) and H2O (20 mL) were introduced thereto, and the result was stirred for 3 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain yellow solid Compound N1 (6.3 g, 9.8 mmol, yield 84%).
Synthesis of Compound F
Compound N of the following Table 8 was synthesized in the same manner as in Synthesis of Compound N using Compound E or Compound B of the following Table 8 instead of Compound E7, and Compound F of the following Table 8 was synthesized in the same manner as in Synthesis of Compound F (1) of Preparation Example 2 using Compound B or Compound E of the following Table 8 instead of Compound B1.
Synthesis of Compound O
Compound A1 (52 g, 135.6 mmol) was introduced to a 1 L round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, THF (400 mL) was introduced thereto, and the inner temperature of the reaction vessel was calibrated to −78° C. 2.5 M (in hexane) n-BuLi (59.6 ml) was slowly added dropwise thereto, and after stirring the result for 2 hours at 60° C., B(OMe)3 (19.7 mL, 203.4 mmol) was slowly added dropwise thereto at room temperature. After the reaction was terminated in 2 hours, the reaction was completely terminated using ethanol (60 mL), and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned to obtain white solid Compound 01 (18.4 g, 62.4 mmol, yield 46%).
Synthesis of Compound P
Compound O1 (5 g, 13.5 mmol), 1-(4-bromophenyl)naphthalene (4.6 g, 16.2 mmol), Pd(PPh3)4 (0.8 g, 0.67 mmol) and K2CO3 (3.7 g, 27 mmol) were introduced to a 250 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (80 mL) and H2O (20 mL) were introduced thereto, and the result was stirred for 12 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain white solid Compound P1 (2.9 g, 6.5 mmol, yield 48%).
Synthesis of Compound P-1
Compound P1 (2.9 g, 6.4 mmol), 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (2.5 g, 9.8 mmol), Pd2(dba)3 (0.3 g, 0.3 mmol), XPhos (2,4′,6′-diisopropyl-1,1′-biphenyl-2-yl dicyclohexylphosphine) (1.2 g, 2.6 mmol) and KOAc (1.3 g, 13 mmol) were introduced to a 100 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (50 mL) was introduced thereto, and the result was stirred for 3 hours at 110° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain white solid Compound P1-1 (3.0 g, 5.54 mmol, yield 85%).
Synthesis of Compound F
Compound P1-1 (3.0 g, 5.54 mmol), Compound E19 (1.8 g, 6.6 mmol), Pd(PPh3)4 (0.3 g, 0.27 mmol) and K2CO3 (1.5 g, 11 mmol) were introduced to a 100 mL round bottom flask, and after setting up the flask to be under the nitrogen atmosphere, dioxane (40 mL) and H2O (10 mL) were introduced thereto, and the result was stirred for 4 hours at 120° C. After the reaction was terminated, the reaction temperature was lowered to room temperature, and the result was washed with water and extracted with methylene chloride. The extracted organic layer was dried with Mg2SO4 and then concentrated. The result was silica gel columned and recrystallized to obtain yellow solid Compound F79 (3.1 g, 4.7 mmol, yield 85%).
Compound F of the following Table 9 was synthesized in the same manner as in Syntheses of Compounds 0, P and F using Compounds A, O, SM1, P and E of the following Table 9 instead of Compounds A1, O1, 1-(4-bromophenyl)naphthalene, P1, P1-1 and E19.
Compounds other than the compounds described in Preparation Examples 1 to 4 were also prepared in the same manner as the compounds described in Preparation Examples 1 to 4, and the synthesis identification results are shown in the following Tables 10 and 11.
1H NMR (CDCl3, 200 Mz)
1) Manufacture of Organic Light Emitting Device
A glass substrate on which indium tin oxide (ITO) was coated as a thin film to a thickness of 1500 Å was cleaned with distilled water ultrasonic waves. After the cleaning with distilled water was finished, the substrate was ultrasonic cleaned with solvents such as acetone, methanol and isopropyl alcohol, then dried, and UVO treated for 5 minutes using UV in a UV cleaner. After that, the substrate was transferred to a plasma cleaner (PT), and after conducting plasma treatment under vacuum for ITO work function and residual film removal, the substrate was transferred to a thermal deposition apparatus for organic deposition.
On the transparent ITO electrode (anode), the following 2-TNATA (4,4′,4″-tris[2-naphthyl(phenyl)amino]triphenylamine) as a hole injection layer and the following NPB (N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine) as a hole transfer layer, which are common layers, were formed.
A light emitting layer was thermal vacuum deposited thereon as follows. As the light emitting layer, one or two types of the compound described in the following Table 12 were deposited in one source of supply as a red host, and using the following (piq)2(Ir)(acac) as a red phosphorescent dopant, the (piq)2(Ir)(acac) was 3% doped to the host to be deposited to 500 Å. After that, the following BCP was deposited to 60 Å as a hole blocking layer, Alq3 was deposited to 200 Å thereon as an electron transfer layer. After that, BCP was deposited to 60 Å as a hole blocking layer, and Alq3 was deposited to 200 Å thereon as an electron transfer layer. Lastly, lithium fluoride (LiF) was deposited to a thickness of 10 Å on the electron transfer layer to form an electron injection layer, and on the electron injection layer, an aluminum (Al) cathode was deposited to a thickness of 1,200 Å to form a cathode, and as a result, an organic electroluminescent device was manufactured.
Meanwhile, all the organic compounds required to manufacture the OLED were vacuum sublimation purified under 10−6 torr to 10−8 torr for each material to be used in the organic light emitting device (OLED) manufacture.
2) Driving Voltage and Light Emission Efficiency of Organic Electroluminescent Device
For the organic electroluminescent devices manufactured as above, electroluminescent (EL) properties were measured using M7000 manufactured by McScience Inc., and with the measurement results, T90 was measured when standard luminance was 6,000 cd/m2 using a lifetime measurement system (M6000) manufactured by McScience Inc. Properties of the organic electroluminescent device of the present disclosure are as shown in the following Table 12.
As shown in Table 12, it was identified that, when using the compound represented by Chemical Formula 1 as a light emitting layer of an organic light emitting device, superior effects were obtained in properties of lifetime, efficiency and driving voltage compared to other cases.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0170110 | Dec 2018 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2019/018453 | 12/26/2019 | WO | 00 |
