WO2017104994A1 - Composition for organic electronic element, organic electronic element using same, and electronic device thereof - Google Patents
Composition for organic electronic element, organic electronic element using same, and electronic device thereof Download PDFInfo
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- WO2017104994A1 WO2017104994A1 PCT/KR2016/013480 KR2016013480W WO2017104994A1 WO 2017104994 A1 WO2017104994 A1 WO 2017104994A1 KR 2016013480 W KR2016013480 W KR 2016013480W WO 2017104994 A1 WO2017104994 A1 WO 2017104994A1
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- 239000000203 mixture Substances 0.000 title claims description 6
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- 239000000126 substance Substances 0.000 claims abstract description 14
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- 125000005842 heteroatom Chemical group 0.000 claims description 37
- 229910052717 sulfur Inorganic materials 0.000 claims description 37
- 125000003118 aryl group Chemical group 0.000 claims description 35
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 33
- 229910052698 phosphorus Inorganic materials 0.000 claims description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 238000002347 injection Methods 0.000 claims description 30
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- 125000001424 substituent group Chemical group 0.000 claims description 21
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- ZMCQQCBOZIGNRV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[2-(1,2,4-triazol-1-yl)ethyl]benzamide Chemical compound NCC1=CC(OC2=CC=CC(=C2)C(=O)NCCN2C=NC=N2)=NC(=C1)C(F)(F)F ZMCQQCBOZIGNRV-UHFFFAOYSA-N 0.000 description 3
- BGEVROQFKHXUQA-UHFFFAOYSA-N 71012-25-4 Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1C1=CC=CC=C1N2 BGEVROQFKHXUQA-UHFFFAOYSA-N 0.000 description 3
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- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 238000003756 stirring Methods 0.000 description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 2
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- RBZACNJDMXNRMU-UHFFFAOYSA-N 4-oxapentacyclo[9.7.1.02,10.03,7.015,19]nonadeca-1(18),2(10),3(7),5,8,11,13,15(19),16-nonaene Chemical compound O1C=CC2=C1C1=C(C=C2)C=2C=CC=C3C=CC=C1C=23 RBZACNJDMXNRMU-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 125000000524 functional group Chemical group 0.000 description 2
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- JWJQEUDGBZMPAX-UHFFFAOYSA-N (9-phenylcarbazol-3-yl)boronic acid Chemical compound C12=CC=CC=C2C2=CC(B(O)O)=CC=C2N1C1=CC=CC=C1 JWJQEUDGBZMPAX-UHFFFAOYSA-N 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
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- VDESPCTYYGQYKU-UHFFFAOYSA-N 18-oxapentacyclo[12.7.0.02,7.08,13.015,19]henicosa-1(14),2,4,6,8,10,12,15(19),16,20-decaene Chemical compound C1=CC=CC2=C3C(C=CO4)=C4C=CC3=C(C=CC=C3)C3=C21 VDESPCTYYGQYKU-UHFFFAOYSA-N 0.000 description 1
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- HGPVPXXVBLDHPA-UHFFFAOYSA-N 2-chloro-4-phenylbenzo[h]quinazoline Chemical compound C1(=NC(C2=CC=CC=C2)=C2C=CC3=CC=CC=C3C2=N1)Cl HGPVPXXVBLDHPA-UHFFFAOYSA-N 0.000 description 1
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
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- OBNRDTOHHATXAN-UHFFFAOYSA-N Brc(c1c2)c(-c3cccc4c3cccc4)[o]c1ccc2-c(cc1)cc2c1[s]c1c2cccc1 Chemical compound Brc(c1c2)c(-c3cccc4c3cccc4)[o]c1ccc2-c(cc1)cc2c1[s]c1c2cccc1 OBNRDTOHHATXAN-UHFFFAOYSA-N 0.000 description 1
- MTWUASFDWBZYKG-UHFFFAOYSA-N Brc(c1cc(-c(cc2)cc3c2[s]c2c3cccc2)ccc1[o]1)c1Br Chemical compound Brc(c1cc(-c(cc2)cc3c2[s]c2c3cccc2)ccc1[o]1)c1Br MTWUASFDWBZYKG-UHFFFAOYSA-N 0.000 description 1
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- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- QLHVRSLENKVAAR-UHFFFAOYSA-N NCCc1c2[s]c(-c3cccc4c3c-3ccc4)c-3c2cc(-c2cc(-c3ccc(c4ccccc4c4ccccc44)c4c3)ccc2)c1 Chemical compound NCCc1c2[s]c(-c3cccc4c3c-3ccc4)c-3c2cc(-c2cc(-c3ccc(c4ccccc4c4ccccc44)c4c3)ccc2)c1 QLHVRSLENKVAAR-UHFFFAOYSA-N 0.000 description 1
- DLGOLDCIEHQIMN-UHFFFAOYSA-N Nc(cccc1)c1C(c1ccccc1)=N Chemical compound Nc(cccc1)c1C(c1ccccc1)=N DLGOLDCIEHQIMN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- PQIUGRLKNKSKTC-UHFFFAOYSA-N benzo[h]quinazoline Chemical compound N1=CN=C2C3=CC=CC=C3C=CC2=C1 PQIUGRLKNKSKTC-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- FSDKEUAGVPSQGW-UHFFFAOYSA-N c1c[s]c(cc2)c1cc2-c1cc(-c(cc2)cc3c2c(cccc2)c2c2ccccc32)ccc1 Chemical compound c1c[s]c(cc2)c1cc2-c1cc(-c(cc2)cc3c2c(cccc2)c2c2ccccc32)ccc1 FSDKEUAGVPSQGW-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005549 heteroarylene group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- BLKGAZMIPRHYHI-UHFFFAOYSA-N iridium(3+) 1-phenylisoquinoline Chemical compound [Ir+3].C1=CC=CC=C1C1=NC=CC2=CC=CC=C12.C1=CC=CC=C1C1=NC=CC2=CC=CC=C12 BLKGAZMIPRHYHI-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical group C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 238000007243 oxidative cyclization reaction Methods 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000005576 pyrimidinylene group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- PXFBSZZEOWJJNL-UHFFFAOYSA-N triphenylen-2-ylboronic acid Chemical compound C1=CC=C2C3=CC(B(O)O)=CC=C3C3=CC=CC=C3C2=C1 PXFBSZZEOWJJNL-UHFFFAOYSA-N 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- SOSIJULCFHJNTI-UHFFFAOYSA-N triphenyleno[2,1-b]thiophene Chemical compound C1=CC=CC2=C3C(C=CS4)=C4C=CC3=C(C=CC=C3)C3=C21 SOSIJULCFHJNTI-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
- organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material.
- An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween.
- the organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
- the material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.
- the light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be.
- the light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting colors.
- a host / dopant system may be used. The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
- Efficiency, lifespan, and driving voltage are related to each other, and as the efficiency increases, the driving voltage is relatively decreased, and as the result, the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. It shows a tendency to increase the life.
- simply improving the organic material layer does not maximize the efficiency. This is because a long lifetime and high efficiency can be simultaneously achieved when an optimal combination of energy level and T 1 value between each organic material layer, intrinsic properties (mobility, interfacial properties, etc.) of the material is achieved. Therefore, there is a need for the development of a light emitting material capable of achieving an efficient charge balance in the light emitting layer.
- a material forming the organic material layer in the device such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc.
- a stable and efficient material is supported by a stable and efficient material. It should be preceded, but the development of a stable and efficient organic material layer for an organic electric device has not been made enough. Therefore, the development of new materials is continuously required, and in particular, the development of the host material of the light emitting layer is urgently required.
- An object of the present invention is to provide a compound capable of lowering the driving voltage of the device and improving the luminous efficiency, color purity and lifetime of the device, an organic electric device using the same, and an electronic device thereof.
- the present invention provides a compound represented by the following formula.
- the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
- the compound according to the embodiment of the present invention not only can the driving voltage of the device be lowered, but the luminous efficiency, color purity, and lifetime of the device can be greatly improved.
- FIG. 1 is an exemplary view of an organic electroluminescent device according to the present invention.
- FIG. 1 is an exemplary view of an organic electroluminescent device according to the present invention.
- first, second, A, B, (a), and (b) can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being “connected”, “coupled” or “connected” to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It should be understood that the elements may be “connected”, “coupled” or “connected”.
- a component such as a layer, film, region, plate, etc.
- it is not only when the other component is “on top of” but also another component in between. It is to be understood that this may also include cases.
- a component is said to be “directly above” another part, it should be understood to mean that there is no other part in the middle.
- halo or halogen as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.
- alkyl or “alkyl group” has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.
- alkenyl group or “alkynyl group”, unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.
- cycloalkyl refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
- alkoxyl group means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.
- aryloxyl group or “aryloxy group” means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.
- fluorenyl group or “fluorenylene group” means a monovalent or divalent functional group in which R, R 'and R “are all hydrogen in the following structures, unless otherwise stated, and" Substituted fluorenyl group “or” substituted fluorenylene group “means that at least one of the substituents R, R ', and R" is a substituent other than hydrogen, and R and R' are bonded to each other to form a carbon It includes the case of forming a compound by spying together.
- aryl group and “arylene group” have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
- the aryl group or arylene group includes monocyclic, ring aggregate, conjugated ring system, spiro compound and the like.
- heterocyclic group includes not only aromatic rings, such as “heteroaryl groups” or “heteroarylene groups,” but also non-aromatic rings, and each carbon number includes one or more heteroatoms unless otherwise specified. It means a ring of 2 to 60, but is not limited thereto.
- heteroatom refers to N, O, S, P or Si unless otherwise indicated, and heterocyclic groups are monocyclic, ring aggregates, conjugated multiple ring systems, spies, including heteroatoms. Means a compound or the like.
- Heterocyclic groups may also include rings comprising SO 2 in place of the carbon forming the ring.
- a “heterocyclic group” includes the following compounds.
- ring includes monocyclic and polycyclic rings, includes hydrocarbon rings as well as heterocycles including at least one heteroatom, and includes aromatic and nonaromatic rings.
- polycyclic includes ring assemblies, fused multiple ring systems and spiro compounds, such as biphenyl, terphenyl, and the like, including aromatics as well as nonaromatics, hydrocarbons
- the ring as well includes heterocycles comprising at least one heteroatom.
- ring assemblies means that two or more ring systems (single or conjugated ring systems) are directly connected to each other through a single bond or a double bond and directly between such rings. It means that the number of linkages is one less than the total number of ring systems in this compound. Ring aggregates may have the same or different ring systems directly connected to each other via a single bond or a double bond.
- conjugated multiple ring systems refers to a covalently fused ring form of at least two atoms, including a ring system in which two or more hydrocarbons are fused together and at least one heteroatom. And heterocyclic systems having at least one conjugated form. These conjugated several ring systems can be aromatic rings, heteroaromatic rings, aliphatic rings or combinations of these rings.
- spiro compound has a "spiro union", and a spiro linkage means a linkage formed by two rings sharing one atom only.
- atoms shared by the two rings are called spiro atoms, and according to the number of spiro atoms in a compound, they are respectively referred to as 'monospyro-', 'diespyro-' and 'trispyro-' It is called a compound.
- an arylalkoxy group means an alkoxy group substituted with an aryl group
- an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group
- an alkenyl group substituted with an arylcarbonyl group is used herein.
- the arylcarbonyl group is a carbonyl group substituted with an aryl group.
- substituted in the term “substituted or unsubstituted” refers to deuterium, halogen, amino groups, nitrile groups, nitro groups, C 1 -C 20 alkyl groups, C 1 -C 20 alkoxy group, C 1 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl group, C 6 -C 20 aryl group, of a C 6 -C 20 aryl group substituted with a heavy hydrogen, C 8 -C 20 aryl alkenyl group, a silane group, a boron Substituted by at least one substituent selected from the group consisting of a group, a germanium group, and a C 2 -C 20
- the group name corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified in each symbol and examples of the substituents in this specification may describe 'the name of the group reflecting the singer', but is described as 'the parent compound name'. You may. For example, in the case of phenanthrene, which is a kind of aryl group, the monovalent group is phenanthryl and the divalent group may be grouped with a singer, such as phenanthryl, to describe the group name. Regardless, it may be described as the parent compound name 'phenanthrene'.
- pyrimidine it may be described as 'pyrimidine' irrespective of the valence, or as the 'name of the group' of the singer, such as pyrimidinyl group in the case of monovalent and pyrimidinylene in the case of divalent. have.
- the substituent R 1 when a is an integer of 0, the substituent R 1 is absent, when a is an integer of 1, one substituent R 1 is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 are each bonded as follows, where R 1 may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.
- FIG. 1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
- an organic electric device 100 may include a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110.
- An organic material layer including the compound according to the present invention is provided between the two electrodes 180.
- the first electrode 120 may be an anode (anode)
- the second electrode 180 may be a cathode (cathode)
- the first electrode may be a cathode and the second electrode may be an anode.
- the organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence.
- at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, and the like. It may also serve as a hole blocking layer.
- the organic electronic device further includes a protective layer or a light efficiency improving layer formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer. can do.
- Compound according to an embodiment of the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport auxiliary layer, an electron transport layer 160, an electron injection layer ( 170, a host or dopant material of the light emitting layer 150, or a material of the light efficiency improving layer.
- the compound of the present invention may be used as the material of the light emitting layer 150, the hole transport layer 140 and / or the light emitting auxiliary layer 151, preferably may be used as a material of the light emitting layer 150.
- the intrinsic properties (mobility, interfacial characteristics, etc.) of the organic organic device can improve the service life and efficiency at the same time.
- the organic electroluminescent device may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD.
- the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130 thereon.
- the organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170 By forming an organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170, and then depositing a material that can be used as the cathode 180 thereon have.
- the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150
- an electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.
- the organic material layer is a solution or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.
- the organic electric element according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.
- WOLED White Organic Light Emitting Device
- Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.
- CCM color conversion material
- the organic electroluminescent device may be one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, a monochromatic or white illumination device.
- Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device.
- the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
- X 1 is S, O, C (R 4 ) (R 5 ) or Si (R ′) (R ′′).
- R 1 to R 3 are each independently hydrogen; heavy hydrogen; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And combinations thereof may be selected from the group.
- R 1 to R 3 is an aryl group, preferably an aryl group of C 6 -C 30 , more preferably an aryl group of C 6 -C 18 , and exemplarily phenyl, biphenyl, naphthyl, triphenyl Ren and the like.
- R 1 to R 3 are heterocyclic groups, preferably C 2 -C 30 heterocyclic group, more preferably C 2 -C 12 It may be a heterocyclic group, for example pyridine, pyrimidine, quinazoline , Benzoquinazolin, carbazole, benzocarbazole, dibenzocarbazole, dibenzofuran, dibenzothiophene, benzofurypyrimidine, benzophenanthrothiophene, benzophenanthrofuran, benzothiopyrimidine, etc. have.
- R 1 to R 3 When R 1 to R 3 is a fluorenyl group, it may be 9,9-dimethyl-9H-fluorene, if halogen may be fluorine, if alkyl group may be tert-butyl group, if it is an alkenyl group ethene It may be a diary or, in the case of an alkoxy group, may be methoxy.
- R 1 to R 3 may independently form neighboring groups or R 2 and R 3 may be bonded to each other to form at least one ring. That is, adjacent R 1 , adjacent R 2 , adjacent R 3 , or R 2 and R 3 may be bonded to each other to form a ring, wherein the formed ring is a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And combinations thereof. For example, they may be bonded to each other to form a ring such as benzene or naphthalene, and in particular, R 2 and R 3 may be bonded to each other to form benzene or naphthalene.
- R ⁇ 1> -R ⁇ 3> may be the same or different, respectively.
- R 4 , R 5 , R 'and R'' Are independently of each other, hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Of C 2 -C 30 Alkenyl groups; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; Silyl groups of C 1 -C 30 ; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; And -L'-N (R a ) (R b ).
- R 4 , R 5 , R 'and R'' Are independently of each other, hydrogen; heavy hydrogen; C 1 -C 30 alkyl group; C 6 -C 30 aryloxy group; Aryl group of C 6 -C 30 ; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl groups; And the like.
- R 4 , R 5 , R 'and R'' May independently be hydrogen, a methyl group, a phenyl group, a fluorenyl group, or the like.
- R 4 and R 5 may be bonded to each other to form a ring, and R ′ and R ′′ may also be bonded to each other to form a ring.
- L ' is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And a C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P.
- R a and R b are each independently a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And an aryloxy group of C 6 -C 30 It can be selected from the group consisting of.
- a ring formed by bonding, and a ring formed by bonding of R 2 and R 3 to each other is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Of C 6 -C 20 Aryl group; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 hetero
- Formula 1 may be represented by the following formula (2) or (3).
- R 1 to R 3 , 1, m, n and X 1 are the same as defined in Chemical Formula 1.
- s and u are each an integer of 0-4, t and v are each an integer of 0-6, s + t is an integer of 1 or more, u + v is an integer of 1 or more.
- L 2 to L 5 are independently of each other, a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And a C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; And combinations thereof may be selected from the group.
- L 2 to L 5 are independently of each other a single bond; C 6 -C 30 arylene group; Fluorenylene groups; And a C 2 -C 30 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; And the like.
- L 2 to L 5 is a single bond, phenyl, biphenyl, fluorene, carbazole, pyridine, pyrimidine, triazine, benzocarbazole, dibenzocarbazole, quinazoline, acenaphthobenzofuran, acenaph Tobenzothiophene and the like.
- X 2 and X 3 may be independently of each other N, NL 1 -Ar 1 , O, S, C (R 10 ) (R 11 ) or Si (R 18 ) (R 19 ).
- X 2 when X 2 is N, it may be connected to L 2
- X 3 when X 3 is N, it may be connected to L 3 .
- R 6 to R 9 , and R 12 to R 17 are each independently hydrogen; heavy hydrogen; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; -L'-N (R a ) (R b ); And combinations thereof may be selected from the group.
- R 6 to R 9 and R 12 to R 17 may combine with each other to form at least one ring.
- a, b, c, d, e, f, o, p, q, and r are each an integer of 0-4.
- L 1 is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And combinations thereof may be selected from the group.
- L 1 is a single bond independently from each other; C 6 -C 30 arylene group; Fluorenylene groups; And a C 2 -C 30 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; And the like.
- L 1 is a single bond, phenyl, biphenyl, fluorene, carbazole, pyridine, pyrimidine, triazine, benzocarbazole, dibenzocarbazole, quinazoline, acenaphthobenzofuran, acenaphthobenzocyse Ore, etc.
- Ar 1 is a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L'-N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And combinations thereof may be selected from the group.
- an aryl group of C 6 -C 30 Fluorenyl group; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; -L'-N (R a ) (R b ); And the like.
- Ar 1 is a phenyl group, biphenyl group, triphenylene group, ferenyl group, phenanthryl group, fluorenyl group, spirofluorenyl group, pyridyl group, pyrimidinyl group, triazinyl group, quinazolyl group, benzoquinazolyl group , Dibenzoquinazolyl group, dibenzothienyl group, dibenzofuryl group, benzofuropyrimidyl group, naphthopuropyrimidyl group, benzothienopyrimidyl group, carbazole group, benzocarbazole group and the like.
- R 10 , R 11 , R 18 and R 19 are each independently hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Of C 2 -C 30 Alkenyl groups; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; Silyl groups of C 1 -C 30 ; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; -L'-N (R a ) (R b ); And combinations thereof may be selected from the group.
- R 10 , R 11 , R 18 and R 19 are, independently from each other, hydrogen; heavy hydrogen; C 1 -C 30 alkyl group; C 6 -C 30 aryloxy group; Aryl group of C 6 -C 30 ; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl groups; And the like.
- R 10 , R 11 , R 18 and R 19 are each independently of the other hydrogen; Methyl group, phenyl group, fluorenyl group and the like.
- R 10 and R 11 may be bonded to each other to form a ring, wherein spiro compounds may be formed together with carbon (C) to which they are bonded.
- R 18 and R 19 may be bonded to each other to form a ring, and at this time, a spiro compound may be formed together with silicon (Si) to which they are bonded.
- L ′, R a and R b are the same as defined in Chemical Formula 1.
- Ar 1 may be one of the following structural formulas Z-1 to Z-8.
- Z 1 to Z 70 may be each independently C, C (R c ) or N, wherein C in Z 1 to Z 70 is bonded to L 1 of Formula 2 Can be.
- one of Z 1 to Z 6 of formula Z-1 may be C, at least the other may be N, one of Z 7 to Z 14 of formula Z-2 is C, and at least the other is N And one of Z 15 to Z 24 of Formula Z-3 may be C, and at least the other may be N, one of Z 25 to Z 34 of Formula Z-4 is C, and at least the other is N And one of Z 35 to Z 44 of Formula Z-5 may be C, and at least the other may be N.
- One of Z 45 to Z 56 of Formula Z-6 is C, and at least the other is N And one of Z 57 to Z 62 of Formula Z-7 may be C, and at least the other may be N.
- One of Z 63 to Z 70 of Formula Z-8 is C, and at least the other is N Can be.
- R c is hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 30 ; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; A silyl group of C 1 -C 30; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; -L'-N (R a ) (R b ); And combinations thereof.
- R c is an aryl group of C 6 -C 30 ; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl groups; And the like.
- R c is a phenyl group, naphthyl group, biphenyl group, pyrenyl group, pyridyl group, pyrimidinyl group, triazineyl group, indole group, dibenzothienyl group, carbazole group, dibenzofuryl group, dibenzoquinazolyl group, benzo Quinazolyl group, fluorenyl group, spirobifluorenyl group, and the like.
- R c may be bonded to each other adjacent groups to form at least one ring selectively.
- W 1 to W 3 may be selected from the group consisting of a single bond, C (R d ) (R e ), N-Ar 2 , O, S, and Si (R f ) (R g ).
- R d to R g are each independently hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 30 ; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; Silyl groups of C 1 -C 30 ; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; -L'-N (R a ) (R b ); And combinations thereof may be selected from the group.
- R d to R g are each independently hydrogen; An alkyl group of C 1 -C 30 ; Aryl group of C 6 -C 30 ; And fluorenyl groups; And the like.
- R d to R g may be each independently hydrogen, a methyl group, a phenyl group, a fluorenyl group, or the like.
- R d and R e may be bonded to each other to form a ring, wherein a spiro compound may be formed together with carbon (C) to which they are bonded.
- R f With R g May be bonded to each other to form a ring, and together with the silicon (Si) to which they are bonded, a spiro compound may be formed.
- L ′, R a , and R b are the same as defined in Formula 1, and Ar 2 may be defined the same as Ar 1 defined in Formula 2.
- the compound represented by Formula 1 may be one of the following compounds.
- the present invention provides a compound for an organic electric device represented by Chemical Formula 1.
- the present invention provides an organic electric device containing the compound represented by the formula (1).
- the organic electric element includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode.
- the organic material layer may include a compound represented by Chemical Formula 1, and Chemical Formula 1 may include a hole injection layer, a hole transport layer, a light emitting auxiliary layer, It may be contained in at least one layer of the light emitting layer, the electron transport auxiliary layer, the electron transport layer, it may be included as a component of one kind of a compound or two or more kinds. That is, the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer and / or an electron transport layer.
- the compound represented by Formula 1 may be used as a phosphorescent host material of the light emitting layer.
- the present invention is an optical efficiency improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer It provides an organic electric element further comprising.
- the compounds (final products) according to the present invention are prepared using Sub 2 as in Scheme 1, but are not limited thereto.
- Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 2, but is not limited thereto.
- Triphenylen-2-ylboronic acid (3.0 g, 11.04 mmol), Sub 2-I-56 (7.80 g, 11.04 mmol), Pd (PPh 3 ) 4 (0.38 g, 0.33 mmol), K 2 CO 3 (4.58 g, 33.11 mmol), THF (49 mL) and water (24 mL) were obtained using 6.79 g of the product using the synthesis method of M 1-I-1 (yield: 72%).
- the compound belonging to Sub 1 may be a compound as follows, but is not limited thereto.
- the compound belonging to Sub 2 may be the following compounds, but is not limited thereto.
- Table 1 shows FD-MS values of some compounds belonging to Sub 2.
- An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer.
- a 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (abbreviated as "2-TNATA”) film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate.
- a 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviated as "NPD”) membrane was formed as a hole transport compound on the hole injection layer to a thickness of 60 nm.
- Vacuum deposition was performed to form a hole transport layer.
- Compound 1-14 of the present invention was used as a host on the hole transport layer, and bis- (1-phenylisoquinoline) iridium (III) acetylacetonate (abbreviated as "(piq) 2 Ir (acac)”) was used as a dopant material.
- the light emitting layer was deposited to a thickness of 30 nm by doping at a weight ratio of 5: 5.
- BAlq (1,1'-biphenyl-4-olato) bis (2-methyl-8-quinolinolato) aluminum
- BAlq 2-methyl-8-quinolinolato
- Alq 3 8-hydroxyquinoline aluminum
- LiF which is an alkali metal halide
- Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.
- Examples 2 to 20 are the same as in Example 1 except that each compound of the present invention shown in Table 3 is used instead of compound 1-14 according to the embodiment of the present invention as a red host material of the emission layer.
- An organic electroluminescent device was manufactured by the method.
- Comparative Examples 1 to 3 are organic in the same manner as in Example 1, except for using the following Comparative Compound 1 to Comparative Compound instead of Compound 1-14 according to the Example of the present invention as a host material of the emission layer. An electroluminescent device was prepared.
- Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared according to Examples 1 to 20 and Comparative Examples 1 to 3 of the present invention
- the T95 lifetime was measured using a McScience Life Measurement Equipment at 2500 cd / m 2 reference luminance, and the measurement results are shown in Table 3 below.
- the organic electroluminescent device using the compound according to an embodiment of the present invention as a phosphorescent host material can significantly improve the luminous efficiency, driving voltage and lifetime.
- a compound having a core having the same structure as that of Comparative Compound 2 or 3 showed better device results than that of Comparative Compound 1, which is CBP, which is used as a general host material.
- Compounds according to an embodiment of the present invention showed the best device results with the lowest driving voltage, maximizing efficiency and lifetime.
- the LUMO energy value is relatively low, thereby easily receiving electrons into the electron transporting layer. It is believed that improving the charge balance results in lower driving voltages, higher efficiency and longer lifetime. Therefore, this suggests that while the heterocyclic group having the ET property is substituted in the core of the present invention, the chemical and physical properties may be significantly changed.
- An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer.
- a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm.
- the NPD film is vacuum-deposited at a thickness of 60 nm as a hole transport compound on the hole injection layer.
- a transport layer was formed.
- Compound 1-1 of the present invention was used as a host on the hole transport layer, and a dopant material was doped with tris (2-phenylpyridine) -iridium (abbreviated as "Ir (ppy) 3 ") at a 95: 5 weight ratio of 30 nm thick.
- the light emitting layer was deposited by.
- BAlq was vacuum-deposited to a thickness of 10 nm with a holdoff layer, and Alq 3 was formed into a thickness of 40 nm with an electron transport layer.
- LiF which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.
- Examples 22 to 38 are the same as in Example 21, except that each compound of the present invention shown in Table 4 was used instead of Compound 1-1 according to the embodiment of the present invention as a green host material of the emission layer.
- An organic electroluminescent device was manufactured by the method.
- Comparative Examples 4 to 6 were organic in the same manner as in Example 21, except that Comparative Compound 1 to Comparative Compound were used instead of Compound 1-1 according to the Example of the present invention, respectively, as a host material of the emission layer.
- An electroluminescent device was prepared.
- Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 21 to 38 and Comparative Examples 4 to 6 of the present invention
- the T95 lifetime was measured using McScience's life measurement equipment at 5000 cd / m 2 reference luminance, and the measurement results are shown in Table 4 below.
- the organic electroluminescent device using the organic light emitting device material of the present invention as a green phosphorescent host material has a lower driving voltage, higher luminous efficiency and longer life than Comparative Examples 4 to 6. I could confirm it.
- Comparative Compound 2 or 3 showed better device results than Comparative Compound 1, which is a CBP used as a general host material, and the present invention is substituted with another substituent on the core of Comparative Compound 2 or 3.
- Compounds according to the embodiment of the present invention showed the best device results with the lowest driving voltage, efficiency and lifetime are maximized.
- the device characteristics were described in terms of the light emitting layer.
- materials generally used as the light emitting layer include organic electron devices such as the electron transport layer, the electron injection layer, the hole injection layer, the hole transport layer, and the light emitting auxiliary layer. It can be used in combination with a single or other material as an organic layer of. Therefore, the compounds of the present invention can be used in a single or other materials mixed with other organic material layers, for example, electron transport layer, electron injection layer, hole injection layer, hole transport layer and light emitting auxiliary layer in addition to the light emitting layer.
- a 2-TNATA film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate as a hole injection layer to form a thickness of 60 nm.
- an NPD film was vacuum deposited to a thickness of 60 nm as a hole transport compound on the hole injection layer to form a hole transport layer.
- the light emitting layer was deposited to a thickness of 30 nm by doping the compound of the present invention as a host material on the hole transport layer with a weight ratio of 95: 5 of Ir (ppy) 3 as a dopant material. 1-44 was used by mixing in 50:50 weight ratio.
- a hole blocking layer was formed by vacuum depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer having a thickness of 40 nm on Alq 3 was formed on the hole blocking layer.
- LiF which is an alkali metal halide
- LiF was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and then, an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.
- Example 40 to [ Example 42] Green Organic Light Emitting Diode ( Light emitting layer Mixed phosphorescent host)
- Examples 40 to 42 are organic electroluminescent in the same manner as in Example 39, except that each compound of the present invention shown in Table 5 is used instead of the compound 1-44 of the present invention as a host material of the emission layer. The device was manufactured.
- Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 39 to 42 of the present invention, 5000cd / m 2
- the T95 life was measured using McScience's life measurement equipment at the reference luminance, and the measurement results are shown in Table 5 below.
- Table 5 shows the results of device measurements using Compound 1-11 of the present invention as two mixed phosphorescent host materials.
- the compound of the present invention of the wide band gap-type of the present invention introduced the compound 1-11 (Example 23) of the low band gap-type and triphenylene group showed the most excellent device measurement results
- the combination of -44, 1-45, 2-38, and 2-39 as two phosphorescent host materials resulted in greater efficiency and lifetime when two mixed host materials were used than when a single host material was used. It can be seen that it can be further improved.
- the band gap and T1 values can be finely adjusted than in the case of a single host material, and thus, electrons and holes are efficiently transferred to the dopant, thereby increasing efficiency.
- the lifespan also increases.
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Abstract
Disclosed are: a compound represented by chemical formula 1; an organic electronic element comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode; and an electronic device comprising the same, wherein the compound represented by chemical formula 1 is contained in the organic layer, thereby enabling the driving voltage of the organic electronic element to decrease and luminous efficiency and lifespan to improve.
Description
본 발명은 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다.The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다.In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다.The material used as the organic material layer in the organic electric element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.
그리고, 상기 발광 재료는 분자량에 따라 고분자형과 저분자형으로 분류될 수 있고, 발광 메커니즘에 따라 전자의 일중항 여기상태로부터 유래되는 형광 재료와 전자의 삼중항 여기상태로부터 유래되는 인광 재료로 분류될 수 있다. 또한, 발광 재료는 발광색에 따라 청색, 녹색, 적색 발광 재료와 보다 나은 천연색을 구현하기 위해 필요한 노란색 및 주황색 발광 재료로 구분될 수 있다.The light emitting material may be classified into a polymer type and a low molecular type according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. In addition, the light emitting materials may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural colors according to the light emitting colors.
한편, 발광 재료로서 하나의 물질만 사용하는 경우 분자간 상호 작용에 의하여 최대 발광 파장이 장파장으로 이동하고 색순도가 떨어지거나 발광 감쇄 효과로 소자의 효율이 감소되는 문제가 발생하므로, 색순도의 증가와 에너지 전이를 통한 발광 효율을 증가시키기 위하여 발광 재료로서 호스트/도판트계를 사용할 수 있다. 그 원리는 발광층을 형성하는 호스트보다 에너지 대역 간극이 작은 도판트를 발광층에 소량 혼합하면, 발광층에서 발생한 엑시톤이 도판트로 수송되어 효율이 높은 빛을 내는 것이다. 이때 호스트의 파장이 도판트의 파장대로 이동하므로, 이용하는 도판트의 종류에 따라 원하는 파장의 빛을 얻을 수 있다.On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. The principle is that when a small amount of dopant having an energy band gap smaller than that of the host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.
현재 휴대용 디스플레이 시장은 대면적 디스플레이로 그 크기가 증가하고 있는 추세이며, 이로 인해 기존 휴대용 디스플레이에서 요구되던 소비적력보다 더 큰 소비전력이 요구되고 있다. 따라서, 배터리라는 제한적인 전력 공급원을 가지고 있는 휴대용 디스플레이 입장에서는 소비전력이 매우 중요한 요소가 되었고, 효율과 수명 문제 또한 반드시 해결해야 하는 상황이다.Currently, the portable display market is increasing in size with large-area displays, which requires more power consumption than is required for conventional portable displays. Therefore, power consumption has become a very important factor for a portable display having a limited power supply such as a battery, and the problem of efficiency and lifespan must also be solved.
효율과 수명, 구동전압 등은 서로 연관이 있으며, 효율이 증가되면 상대적으로 구동전압이 떨어지고, 구동전압이 떨어지면서 구동 시 발생하는 주울열(Joule heating)에 의한 유기물질의 결정화가 적어져 결과적으로 수명이 높아지는 경향을 나타낸다. 하지만 상기 유기물층을 단순히 개선한다고 하여 효율을 극대화시킬 수는 없다. 왜냐하면, 각 유기물층 간의 에너지 준위 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있기 때문이다. 따라서 발광층 내에서 효율적으로 전하 균형(charge balance)을 이룰 수 있는 발광 재료의 개발이 필요한 실정이다.Efficiency, lifespan, and driving voltage are related to each other, and as the efficiency increases, the driving voltage is relatively decreased, and as the result, the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. It shows a tendency to increase the life. However, simply improving the organic material layer does not maximize the efficiency. This is because a long lifetime and high efficiency can be simultaneously achieved when an optimal combination of energy level and T 1 value between each organic material layer, intrinsic properties (mobility, interfacial properties, etc.) of the material is achieved. Therefore, there is a need for the development of a light emitting material capable of achieving an efficient charge balance in the light emitting layer.
즉, 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질 등이 안정하고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 하나, 아직까지 안정되고 효율적인 유기전기소자용 유기물층 재료의 개발이 충분히 이루어지지 않은 상태이다. 따라서, 새로운 재료의 개발이 계속 요구되고 있으며, 특히 발광층의 호스트 물질에 대한 개발이 절실히 요구되고 있다.That is, in order to fully exhibit the excellent characteristics of the organic electric device, a material forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. It should be preceded, but the development of a stable and efficient organic material layer for an organic electric device has not been made enough. Therefore, the development of new materials is continuously required, and in particular, the development of the host material of the light emitting layer is urgently required.
본 발명은 소자의 구동전압을 낮추고, 소자의 발광효율, 색순도 및 수명을 향상시킬 수 있는 화합물, 이를 이용한 유기전기소자 및 그 전자장치를 제공하는 것을 목적으로 한다.An object of the present invention is to provide a compound capable of lowering the driving voltage of the device and improving the luminous efficiency, color purity and lifetime of the device, an organic electric device using the same, and an electronic device thereof.
일 측면에서, 본 발명은 하기 화학식으로 표시되는 화합물을 제공한다.In one aspect, the present invention provides a compound represented by the following formula.
다른 측면에서, 본 발명은 상기 화학식으로 표시되는 화합물을 이용한 유기전기소자 및 그 전자장치를 제공한다.In another aspect, the present invention provides an organic electronic device using the compound represented by the above formula and an electronic device thereof.
본 발명의 실시예에 따른 화합물을 이용함으로써 소자의 구동전압을 낮출 수 있을 뿐만 아니라, 소자의 발광효율, 색순도 및 수명을 크게 향상시킬 수 있다.By using the compound according to the embodiment of the present invention, not only can the driving voltage of the device be lowered, but the luminous efficiency, color purity, and lifetime of the device can be greatly improved.
도 1은 본 발명에 따른 유기전기발광소자의 예시도이다.1 is an exemplary view of an organic electroluminescent device according to the present invention.
[부호의 설명][Description of the code]
100: 유기전기소자 110: 기판100: organic electric element 110: substrate
120: 제 1전극 130: 정공주입층120: first electrode 130: hole injection layer
140: 정공수송층 141: 버퍼층140: hole transport layer 141: buffer layer
150: 발광층 151: 발광보조층150: light emitting layer 151: light emitting auxiliary layer
160: 전자수송층 170: 전자주입층160: electron transport layer 170: electron injection layer
180: 제 2전극180: second electrode
도 1은 본 발명에 따른 유기전기발광소자의 예시도이다.1 is an exemplary view of an organic electroluminescent device according to the present invention.
이하, 본 발명의 실시예를 첨부된 도면을 참조하여 상세하게 설명한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
각 도면의 구성요소들에 참조부호를 부가함에 있어서, 동일한 구성요소들에 대해서는 비록 다른 도면상에 표시되더라도 가능한 한 동일한 부호를 가지도록 하고 있음에 유의해야 한다. 또한, 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.
본 발명의 구성 요소를 설명하는 데 있어서, 제 1, 제 2, A, B, (a), (b) 등의 용어를 사용할 수 있다. 이러한 용어는 그 구성 요소를 다른 구성 요소와 구별하기 위한 것일 뿐, 그 용어에 의해 해당 구성 요소의 본질이나 차례 또는 순서 등이 한정되지 않는다. 어떤 구성 요소가 다른 구성 요소에 "연결", "결합" 또는 "접속"된다고 기재된 경우, 그 구성 요소는 그 다른 구성 요소에 직접적으로 연결되거나 또는 접속될 수 있지만, 각 구성 요소 사이에 또 다른 구성 요소가 "연결", "결합" 또는 "접속"될 수도 있다고 이해되어야 할 것이다.In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It should be understood that the elements may be "connected", "coupled" or "connected".
또한, 층, 막, 영역, 판 등의 구성 요소가 다른 구성 요소 "위에" 또는 "상에" 있다고 하는 경우, 이는 다른 구성 요소 "바로 위에" 있는 경우뿐만 아니라 그 중간에 또 다른 구성 요소가 있는 경우도 포함할 수 있다고 이해되어야 할 것이다. 반대로, 어떤 구성 요소가 다른 부분 "바로 위에" 있다고 하는 경우에는 중간에 또 다른 부분이 없는 것을 뜻한다고 이해되어야 할 것이다.In addition, if a component such as a layer, film, region, plate, etc. is said to be "on" or "on" another component, it is not only when the other component is "on top of" but also another component in between. It is to be understood that this may also include cases. On the contrary, when a component is said to be "directly above" another part, it should be understood to mean that there is no other part in the middle.
본 명세서 및 첨부된 청구의 범위에서 사용된 바와 같이, 달리 언급하지 않는 한, 하기 용어의 의미는 하기와 같다.As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows.
본 명세서에서 사용된 용어 "할로" 또는 "할로겐"은 다른 설명이 없는 한 불소(F), 브롬(Br), 염소(Cl) 또는 요오드(I)이다.The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.
본 발명에 사용된 용어 "알킬" 또는 "알킬기"는 다른 설명이 없는 한 1 내지 60의 탄소수의 단일결합을 가지며, 직쇄 알킬기, 분지쇄 알킬기, 사이클로알킬(지환족)기, 알킬-치환된 사이클로알킬기, 사이클로알킬-치환된 알킬기를 비롯한 포화 지방족 작용기의 라디칼을 의미한다.As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms, unless otherwise indicated, and is a straight chain alkyl group, branched chain alkyl group, cycloalkyl (alicyclic) group, alkyl-substituted cyclo Radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.
본 발명에 사용된 용어 "할로알킬기" 또는 "할로겐알킬기"는 다른 설명이 없는 한 할로겐으로 치환된 알킬기를 의미한다.As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.
본 발명에 사용된 용어 "알켄일기" 또는 "알킨일기"는 다른 설명이 없는 한 각각 2 내지 60의 탄소수의 이중결합 또는 삼중결합을 가지며, 직쇄형 또는 측쇄형 사슬기를 포함하며, 여기에 제한되는 것은 아니다.As used herein, the term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.
본 발명에 사용된 용어 "시클로알킬"은 다른 설명이 없는 한 3 내지 60의 탄소수를 갖는 고리를 형성하는 알킬을 의미하며, 여기에 제한되는 것은 아니다.The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.
본 발명에 사용된 용어 "알콕실기", "알콕시기", 또는 "알킬옥시기"는 산소 라디칼이 부착된 알킬기를 의미하며, 다른 설명이 없는 한 1 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" means an alkyl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 1 to 60, and is limited herein. It is not.
본 발명에 사용된 용어 "아릴옥실기" 또는 "아릴옥시기"는 산소 라디칼이 부착된 아릴기를 의미하며, 다른 설명이 없는 한 6 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "aryloxyl group" or "aryloxy group" means an aryl group to which an oxygen radical is attached, and unless otherwise specified, has a carbon number of 6 to 60, but is not limited thereto.
본 발명에 사용된 용어 "플루오렌일기" 또는 "플루오렌일렌기"는 다른 설명이 없는 한 각각 하기 구조에서 R, R' 및 R"이 모두 수소인 1가 또는 2가 작용기를 의미하며, "치환된 플루오렌일기" 또는 "치환된 플루오렌일렌기"는 치환기 R, R', R" 중 적어도 하나가 수소 이외의 치환기인 것을 의미하며, R과 R'이 서로 결합되어 이들이 결합된 탄소와 함께 스파이로 화합물을 형성한 경우를 포함한다.As used herein, the term "fluorenyl group" or "fluorenylene group" means a monovalent or divalent functional group in which R, R 'and R "are all hydrogen in the following structures, unless otherwise stated, and" Substituted fluorenyl group "or" substituted fluorenylene group "means that at least one of the substituents R, R ', and R" is a substituent other than hydrogen, and R and R' are bonded to each other to form a carbon It includes the case of forming a compound by spying together.
본 발명에 사용된 용어 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. 본 발명에서 아릴기 또는 아릴렌기는 단일고리형, 고리집합체, 접합된 여러 고리계, 스파이로 화합물 등을 포함한다.As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, the aryl group or arylene group includes monocyclic, ring aggregate, conjugated ring system, spiro compound and the like.
본 발명에 사용된 용어 "헤테로고리기"는 "헤테로아릴기" 또는 "헤테로아릴렌기"와 같은 방향족 고리뿐만 아니라 비방향족 고리도 포함하며, 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 2 내지 60의 고리를 의미하나 여기에 제한되는 것은 아니다. 본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타내며, 헤테로고리기는 헤테로원자를 포함하는 단일고리형, 고리집합체, 접합된 여러 고리계, 스파이로 화합물 등을 의미한다.As used herein, the term "heterocyclic group" includes not only aromatic rings, such as "heteroaryl groups" or "heteroarylene groups," but also non-aromatic rings, and each carbon number includes one or more heteroatoms unless otherwise specified. It means a ring of 2 to 60, but is not limited thereto. As used herein, the term “heteroatom” refers to N, O, S, P or Si unless otherwise indicated, and heterocyclic groups are monocyclic, ring aggregates, conjugated multiple ring systems, spies, including heteroatoms. Means a compound or the like.
또한 "헤테로고리기"는, 고리를 형성하는 탄소 대신 SO2를 포함하는 고리도 포함할 수 있다. 예컨대, "헤테로고리기"는 다음 화합물을 포함한다. "Heterocyclic groups" may also include rings comprising SO 2 in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.
본 발명에서 사용된 용어 "고리"는 단일환 및 다환을 포함하며, 탄화수소고리는 물론 적어도 하나의 헤테로원자를 포함하는 헤테로고리를 포함하고, 방향족 및 비방향족 고리를 포함한다.As used herein, the term “ring” includes monocyclic and polycyclic rings, includes hydrocarbon rings as well as heterocycles including at least one heteroatom, and includes aromatic and nonaromatic rings.
본 발명에서 사용된 용어 "다환"은 바이페닐, 터페닐 등과 같은 고리 집합체(ring assemblies), 접합된(fused) 여러 고리계 및 스파이로 화합물을 포함하며, 방향족뿐만 아니라 비방향족도 포함하고, 탄화수소고리는 물론 적어도 하나의 헤테로원자를 포함하는 헤테로고리를 포함한다.As used herein, the term "polycyclic" includes ring assemblies, fused multiple ring systems and spiro compounds, such as biphenyl, terphenyl, and the like, including aromatics as well as nonaromatics, hydrocarbons The ring as well includes heterocycles comprising at least one heteroatom.
본 발명에서 사용된 용어 "고리 집합체(ring assemblies)"는 둘 또는 그 이상의 고리계(단일고리 또는 접합된 고리계)가 단일결합이나 또는 이중결합을 통해서 서로 직접 연결되어 있고 이와 같은 고리 사이의 직접 연결의 수가 이 화합물에 들어 있는 고리계의 총 수보다 1개가 적은 것을 의미한다. 고리 집합체는 동일 또는 상이한 고리계가 단일결합이나 이중결합을 통해 서로 직접 연결될 수 있다.As used herein, the term "ring assemblies" means that two or more ring systems (single or conjugated ring systems) are directly connected to each other through a single bond or a double bond and directly between such rings. It means that the number of linkages is one less than the total number of ring systems in this compound. Ring aggregates may have the same or different ring systems directly connected to each other via a single bond or a double bond.
본 발명에서 사용된 용어 "접합된 여러 고리계"는 적어도 두개의 원자의 공유하는 접합된(fused) 고리 형태를 의미하며, 둘 이상의 탄화수소류의 고리계가 접합된 형태 및 적어도 하나의 헤테로원자를 포함하는 헤테로고리계가 적어도 하나 접합된 형태 등을 포함한다. 이러한 접합된 여러 고리계는 방향족고리, 헤테로방향족고리, 지방족 고리 또는 이들 고리의 조합일 수 있다.As used herein, the term "conjugated multiple ring systems" refers to a covalently fused ring form of at least two atoms, including a ring system in which two or more hydrocarbons are fused together and at least one heteroatom. And heterocyclic systems having at least one conjugated form. These conjugated several ring systems can be aromatic rings, heteroaromatic rings, aliphatic rings or combinations of these rings.
본 발명에서 사용된 용어 "스파이로 화합물"은 '스파이로 연결(spiro union)'을 가지며, 스파이로 연결은 2개의 고리가 오로지 1개의 원자를 공유함으로써 이루어지는 연결을 의미한다. 이때, 두 고리에 공유된 원자를 '스파이로 원자'라 하며, 한 화합물에 들어 있는 스파이로 원자의 수에 따라 이들을 각각 '모노스파이로-', '다이스파이로-', '트라이스파이로-' 화합물이라 한다.As used herein, the term "spiro compound" has a "spiro union", and a spiro linkage means a linkage formed by two rings sharing one atom only. In this case, the atoms shared by the two rings are called spiro atoms, and according to the number of spiro atoms in a compound, they are respectively referred to as 'monospyro-', 'diespyro-' and 'trispyro-' It is called a compound.
또한 접두사가 연속으로 명명되는 경우 먼저 기재된 순서대로 치환기가 나열되는 것을 의미한다. 예를 들어, 아릴알콕시기의 경우 아릴기로 치환된 알콕시기를 의미하며, 알콕시카르보닐기의 경우 알콕시기로 치환된 카르보닐기를 의미하며, 또한 아릴카르보닐알켄일기의 경우 아릴카르보닐기로 치환된 알켄일기를 의미하며 여기서 아릴카르보닐기는 아릴기로 치환된 카르보닐기이다.Also, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxycarbonyl group means a carbonyl group substituted with an alkoxy group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group is used herein. The arylcarbonyl group is a carbonyl group substituted with an aryl group.
또한 명시적인 설명이 없는 한, 본 발명에서 사용된 용어 "치환 또는 비치환된"에서 "치환"은 중수소, 할로겐, 아미노기, 니트릴기, 니트로기, C1-C20의 알킬기, C1-C20의 알콕시기, C1-C20의 알킬아민기, C1-C20의 알킬티오펜기, C6-C20의 아릴티오펜기, C2-C20의 알켄일기, C2-C20의 알킨일기, C3-C20의 시클로알킬기, C6-C20의 아릴기, 중수소로 치환된 C6-C20의 아릴기, C8-C20의 아릴알켄일기, 실란기, 붕소기, 게르마늄기, 및 O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기로 이루어진 군으로부터 선택되는 1개 이상의 치환기로 치환됨을 의미하며, 이들 치환기에 제한되는 것은 아니다.Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" refers to deuterium, halogen, amino groups, nitrile groups, nitro groups, C 1 -C 20 alkyl groups, C 1 -C 20 alkoxy group, C 1 -C 20 alkylamine group, C 1 -C 20 alkylthiophene group, C 6 -C 20 arylthiophene group, C 2 -C 20 alkenyl group, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl group, C 6 -C 20 aryl group, of a C 6 -C 20 aryl group substituted with a heavy hydrogen, C 8 -C 20 aryl alkenyl group, a silane group, a boron Substituted by at least one substituent selected from the group consisting of a group, a germanium group, and a C 2 -C 20 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P It is not limited to these substituents.
본 명세서에서 각 기호 및 그 치환기의 예로 예시되는 아릴기, 아릴렌기, 헤테로고리기 등에 해당하는 '기 이름'은 '가수를 반영한 기의 이름'을 기재할 수도 있지만, '모체화합물 명칭'으로 기재할 수도 있다. 예컨대, 아릴기의 일종인 '페난트렌'의 경우, 1가의 '기'는 '페난트릴'로 2가의 기는 '페난트릴렌' 등과 같이 가수를 구분하여 기의 이름을 기재할 수도 있지만, 가수와 상관없이 모체 화합물 명칭인 '페난트렌'으로 기재할 수도 있다. 유사하게, 피리미딘의 경우에도, 가수와 상관없이 '피리미딘'으로 기재하거나, 1가인 경우에는 피리미딘일기, 2가의 경우에는 피리미딘일렌 등과 같이 해당 가수의 '기의 이름'으로 기재할 수도 있다. The group name corresponding to the aryl group, arylene group, heterocyclic group, etc. exemplified in each symbol and examples of the substituents in this specification may describe 'the name of the group reflecting the singer', but is described as 'the parent compound name'. You may. For example, in the case of phenanthrene, which is a kind of aryl group, the monovalent group is phenanthryl and the divalent group may be grouped with a singer, such as phenanthryl, to describe the group name. Regardless, it may be described as the parent compound name 'phenanthrene'. Similarly, in the case of pyrimidine, it may be described as 'pyrimidine' irrespective of the valence, or as the 'name of the group' of the singer, such as pyrimidinyl group in the case of monovalent and pyrimidinylene in the case of divalent. have.
또한, 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.In addition, unless otherwise stated, the formulas used in the present invention apply equally to the substituent definitions based on the exponential definitions of the following formulas.
여기서, a가 0의 정수인 경우 치환기 R1은 부존재하며, a가 1의 정수인 경우 하나의 치환기 R1은 벤젠 고리를 형성하는 탄소 중 어느 하나의 탄소에 결합하며, a가 2 또는 3의 정수인 경우 각각 다음과 같이 결합하며 이때 R1은 서로 동일하거나 다를 수 있으며, a가 4 내지 6의 정수인 경우 이와 유사한 방식으로 벤젠 고리의 탄소에 결합하며, 한편 벤젠 고리를 형성하는 탄소에 결합된 수소의 표시는 생략한다.Herein, when a is an integer of 0, the substituent R 1 is absent, when a is an integer of 1, one substituent R 1 is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R 1 may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded to the carbon forming the benzene ring Is omitted.
도 1은 본 발명의 일 실시예에 따른 유기전기소자에 대한 예시도이다.1 is an exemplary view of an organic electric device according to an embodiment of the present invention.
도 1을 참조하면, 본 발명의 일 실시예에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(120)과 제 2전극(180) 사이에 본 발명에 따른 화합물을 포함하는 유기물층을 구비한다. 이때, 제 1전극(120)은 애노드(양극)이고, 제 2전극(180)은 캐소드(음극)일 수 있으며, 인버트형의 경우에는 제 1전극이 캐소드이고 제 2전극이 애노드일 수 있다.Referring to FIG. 1, an organic electric device 100 according to an embodiment of the present invention may include a first electrode 120, a second electrode 180, and a first electrode 120 formed on a substrate 110. An organic material layer including the compound according to the present invention is provided between the two electrodes 180. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.
유기물층은 제 1전극(120) 상에 순차적으로 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. 이때, 이들 층 중 적어도 하나가 생략되거나, 정공저지층, 전자저지층, 발광보조층(151), 전자수송보조층, 버퍼층(141) 등을 더 포함할 수도 있고, 전자수송층(160) 등이 정공저지층의 역할을 할 수도 있을 것이다.The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. In this case, at least one of these layers may be omitted, or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transport auxiliary layer, a buffer layer 141, and the like. It may also serve as a hole blocking layer.
또한, 미도시하였지만, 본 발명의 일 실시예에 따른 유기전기소자는 제 1전극과 제 2전극 중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층 또는 광효율 개선층(Capping layer)을 더 포함할 수 있다. In addition, although not shown, the organic electronic device according to an embodiment of the present invention further includes a protective layer or a light efficiency improving layer formed on one surface of the at least one surface of the first electrode and the second electrode opposite to the organic material layer. can do.
상기 유기물층에 적용되는 본 발명의 일 실시예에 따른 화합물은 정공주입층(130), 정공수송층(140), 발광보조층(151), 전자수송보조층, 전자수송층(160), 전자주입층(170) 등의 재료, 발광층(150)의 호스트 또는 도펀트 재료, 또는 광효율 개선층의 재료로 사용될 수 있을 것이다. 예컨대, 본 발명의 화합물은 발광층(150), 정공수송층(140) 및/또는 발광보조층(151) 재료로 사용될 수 있으며, 바람직하게는 발광층(150)의 재료로 사용될 수 있다.Compound according to an embodiment of the present invention applied to the organic layer is a hole injection layer 130, a hole transport layer 140, a light emitting auxiliary layer 151, an electron transport auxiliary layer, an electron transport layer 160, an electron injection layer ( 170, a host or dopant material of the light emitting layer 150, or a material of the light efficiency improving layer. For example, the compound of the present invention may be used as the material of the light emitting layer 150, the hole transport layer 140 and / or the light emitting auxiliary layer 151, preferably may be used as a material of the light emitting layer 150.
한편, 동일한 코어일지라도 어느 위치에 어느 치환기를 결합시키냐에 따라 밴드갭(band gap), 전기적 특성, 계면 특성 등이 달라질 수 있으므로, 코어의 선택 및 이에 결합된 서브(sub)-치환체의 조합에 대한 연구가 필요하며, 특히 각 유기물층 간의 에너지 준위 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등이 최적의 조합을 이루었을 때 긴 수명과 높은 효율을 동시에 달성할 수 있다.Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of the cores and the combination of sub-substituents bonded thereto may be performed. In particular, long life and high efficiency can be simultaneously achieved when an optimal combination of energy level and T 1 value and intrinsic properties (mobility, interfacial properties, etc.) between organic layers is achieved.
따라서, 본 발명에서는 화학식 1로 표시되는 화합물을 사용하여 발광층(150)을 형성함으로써 각 유기물층 간의 에너지 레벨 및 T1 값, 물질의 고유특성(이동도, 계면특성 등) 등을 최적화하여 유기전기소자의 수명 및 효율을 동시에 향상시킬 수 있다.Therefore, in the present invention, by forming the light emitting layer 150 using the compound represented by the formula (1) by optimizing the energy level and T 1 value between each organic material layer, the intrinsic properties (mobility, interfacial characteristics, etc.) of the organic organic device Can improve the service life and efficiency at the same time.
본 발명의 일 실시예에 따른 유기전기발광소자는 다양한 증착법(deposition)을 이용하여 제조될 수 있을 것이다. PVD나 CVD 등의 증착 방법을 사용하여 제조될 수 있는데, 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극(120)을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극(180)으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 또한, 정공수송층(140)과 발광층(150) 사이에 발광보조층(151)을, 발광층(150)과 전자수송층(160) 사이에 전자수송보조층을 추가로 더 형성할 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. It may be manufactured using a deposition method such as PVD or CVD. For example, the anode 120 is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130 thereon. , By forming an organic material layer including a hole transport layer 140, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170, and then depositing a material that can be used as the cathode 180 thereon have. In addition, the light emitting auxiliary layer 151 may be further formed between the hole transport layer 140 and the light emitting layer 150, and an electron transport auxiliary layer may be further formed between the light emitting layer 150 and the electron transport layer 160.
또한, 유기물층은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정 또는 솔벤트 프로세스(solvent process), 예컨대 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정, 롤투롤 공정, 닥터 블레이딩 공정, 스크린 프린팅 공정, 또는 열 전사법 등의 방법에 의하여 더 적은 수의 층으로 제조할 수 있다. 본 발명에 따른 유기물층은 다양한 방법으로 형성될 수 있으므로, 그 형성방법에 의해 본 발명의 권리범위가 제한되는 것은 아니다.In addition, the organic material layer is a solution or solvent process (e.g., spin coating process, nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blading) using various polymer materials. It can be produced in fewer layers by methods such as ding process, screen printing process, or thermal transfer method. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.
본 발명의 일 실시예에 따른 유기전기소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.The organic electric element according to an embodiment of the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to the material used.
WOLED(White Organic Light Emitting Device)는 고해상도 실현이 용이하고 공정성이 우수한 한편, 기존의 LCD의 칼라필터 기술을 이용하여 제조될 수 있는 이점이 있다. 주로 백라이트 장치로 사용되는 백색 유기발광소자에 대한 다양한 구조들이 제안되고 특허화되고 있다. 대표적으로, R(Red), G(Green), B(Blue) 발광부들을 상호평면적으로 병렬배치(side-by-side) 방식, R, G, B 발광층이 상하로 적층되는 적층(stacking) 방식이 있고, 청색(B) 유기발광층에 의한 전계발광과 이로부터의 광을 이용하여 무기형광체의 자발광(photo-luminescence)을 이용하는 색변환물질(color conversion material, CCM) 방식 등이 있는데, 본 발명은 이러한 WOLED에도 적용될 수 있을 것이다.WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.
또한, 본 발명의 일 실시예에 따른 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 단색 또는 백색 조명용 소자 중 하나일 수 있다.In addition, the organic electroluminescent device according to an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, a monochromatic or white illumination device.
본 발명의 다른 실시예는 상술한 본 발명의 유기전기소자를 포함하는 디스플레이장치와, 이 디스플레이장치를 제어하는 제어부를 포함하는 전자장치를 포함할 수 있다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.
이하, 본 발명의 일 측면에 따른 화합물에 대하여 설명한다.Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.
본 발명의 일 측면에 따른 화합물은 하기 화학식 1로 표시된다.Compound according to an aspect of the present invention is represented by the following formula (1).
<화학식 1><Formula 1>
상기 화학식 1에서, 각 기호는 아래와 같이 정의될 수 있다.In Formula 1, each symbol may be defined as follows.
X1은 S, O, C(R4)(R5) 또는 Si(R')(R'')이다.X 1 is S, O, C (R 4 ) (R 5 ) or Si (R ′) (R ″).
R1 내지 R3는 서로 독립적으로 수소; 중수소; 할로겐; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다.R 1 to R 3 are each independently hydrogen; heavy hydrogen; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And combinations thereof may be selected from the group.
R1 내지 R3이 아릴기인 경우, 바람직하게는 C6-C30의 아릴기, 더욱 바람직하게는 C6-C18의 아릴기일 수 있고, 예시적으로 페닐, 바이페닐, 나프틸, 트리페닐렌 등일 수 있다. R1 내지 R3이 헤테로고리기인 경우, 바람직하게는 C2-C30의 헤테로고리기, 더욱 바람직하게는 C2-C12의 헤테로고리기일 수 있고, 예시적으로 피리딘, 피리미딘, 퀴나졸린, 벤조퀴나졸린, 카바졸, 벤조카바졸, 다이벤조카바졸, 다이벤조퓨란, 다이벤조싸이오펜, 벤조퓨로피리미딘, 벤조페난트로싸이오펜, 벤조페난트로퓨란, 벤조싸이오피리미딘 등일 수 있다. R1 내지 R3이 플루오렌일기인 경우, 9,9-다이메틸-9H-플루오렌일 수 있고, 할로겐인 경우 플루오린일 수 있고, 알킬기인 경우 tert-부틸기일 수 있고, 알켄일기인 경우 에텐일기일 수 있고, 알콕시기인 경우 메톡시일 수 있다. When R 1 to R 3 is an aryl group, preferably an aryl group of C 6 -C 30 , more preferably an aryl group of C 6 -C 18 , and exemplarily phenyl, biphenyl, naphthyl, triphenyl Ren and the like. When R 1 to R 3 are heterocyclic groups, preferably C 2 -C 30 heterocyclic group, more preferably C 2 -C 12 It may be a heterocyclic group, for example pyridine, pyrimidine, quinazoline , Benzoquinazolin, carbazole, benzocarbazole, dibenzocarbazole, dibenzofuran, dibenzothiophene, benzofurypyrimidine, benzophenanthrothiophene, benzophenanthrofuran, benzothiopyrimidine, etc. have. When R 1 to R 3 is a fluorenyl group, it may be 9,9-dimethyl-9H-fluorene, if halogen may be fluorine, if alkyl group may be tert-butyl group, if it is an alkenyl group ethene It may be a diary or, in the case of an alkoxy group, may be methoxy.
또한, R1 내지 R3은 서로 독립적으로 이웃한 기끼리 또는 R2와 R3가 서로 결합하여 적어도 하나의 고리를 형성할 수 있다. 즉, 이웃한 R1 끼리, 이웃한 R2끼리, 이웃한 R3끼리, 또는 R2와 R3가 서로 결합하여 고리를 형성할 수 있으며, 이때 형성된 고리는 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 이들의 조합일 수 있다. 예컨대, 이들이 서로 결합하여 벤젠, 나프탈렌 등의 고리를 형성할 수 있으며, 특히 R2와 R3이 서로 결합하여 벤젠이나 나프탈렌 등을 형성할 수 있다.In addition, R 1 to R 3 may independently form neighboring groups or R 2 and R 3 may be bonded to each other to form at least one ring. That is, adjacent R 1 , adjacent R 2 , adjacent R 3 , or R 2 and R 3 may be bonded to each other to form a ring, wherein the formed ring is a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And combinations thereof. For example, they may be bonded to each other to form a ring such as benzene or naphthalene, and in particular, R 2 and R 3 may be bonded to each other to form benzene or naphthalene.
l은 0 내지 4의 정수이고, m 및 n은 각각 0 내지 3의 정수이며, 이들 각각이 2 이상의 정수인 경우, 복수의 R1 내지 R3는 각각 동일하거나 상이할 수 있다.l is an integer of 0-4, m and n are each an integer of 0-3, and when each of these is an integer of 2 or more, some R <1> -R <3> may be the same or different, respectively.
상기 R4, R5, R' 및 R'' 는 서로 독립적으로, 수소; 중수소; C1-C50의 알킬기; C2-C30의 알켄일기; C2-C30의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; C1-C30의 실릴기; C6-C60의 아릴기; O, N, S, Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; 및 -L'-N(Ra)(Rb)로 이루어진 군에서 선택될 수 있다. 바람직하게는, R4, R5, R' 및 R'' 는 서로 독립적으로, 수소; 중수소; C1-C30 알킬기; C6-C30의 아릴옥시기; C6-C30의 아릴기; O, N, S, Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C30의 헤테로고리기; 및 플루오렌일기; 등일 수 있다. 구체적으로 R4, R5, R' 및 R'' 는 서로 독립적으로 수소, 메틸기, 페닐기, 플루오렌일기 등일 수 있다. 또한, R4와 R5가 서로 결합하여 고리를 형성할 수 있으며, R'과 R''도 서로 결합하여 고리를 형성할 수 있다.R 4 , R 5 , R 'and R'' Are independently of each other, hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Of C 2 -C 30 Alkenyl groups; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; Silyl groups of C 1 -C 30 ; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; And -L'-N (R a ) (R b ). Preferably, R 4 , R 5 , R 'and R'' Are independently of each other, hydrogen; heavy hydrogen; C 1 -C 30 alkyl group; C 6 -C 30 aryloxy group; Aryl group of C 6 -C 30 ; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl groups; And the like. Specifically R 4 , R 5 , R 'and R'' May independently be hydrogen, a methyl group, a phenyl group, a fluorenyl group, or the like. In addition, R 4 and R 5 may be bonded to each other to form a ring, and R ′ and R ″ may also be bonded to each other to form a ring.
상기 L'은 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기;로 이루어진 군에서 선택될 수 있다.L 'is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And a C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P.
상기 Ra 및 Rb는 서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로 고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기;로 이루어진 군에서 선택될 수 있다. R a and R b are each independently a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And an aryloxy group of C 6 -C 30 It can be selected from the group consisting of.
상기 아릴기, 플루오렌일기, 헤테로고리기, 알킬기, 융합고리기, 알켄일기, 알킨일기, 알콕실기, 아릴옥시기, 아릴렌기, 플루오렌일렌기, R1 내지 R3 중 이웃한 기끼리 서로 결합하여 형성된 고리, 및 R2와 R3가 서로 결합하여 형성된 고리 각각은 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; C8-C20의 아릴알켄일기; 및 이들의 조합으로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환될 수 있다.Adjacent groups among the aryl group, fluorenyl group, heterocyclic group, alkyl group, fused ring group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group, R 1 to R 3 A ring formed by bonding, and a ring formed by bonding of R 2 and R 3 to each other is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Of C 6 -C 20 Aryl group; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; Arylalkenyl group of C 8 -C 20 ; And one or more substituents selected from the group consisting of a combination thereof.
상기 화학식 1은 하기 화학식 2 또는 3으로 표시될 수 있다.Formula 1 may be represented by the following formula (2) or (3).
<화학식 2> <화학식 3><Formula 2> <Formula 3>
상기 화학식 2 및 3에서, R1 내지 R3, l, m, n 및 X1은 화학식 1에서 정의된 것과 동일하다.In Chemical Formulas 2 and 3, R 1 to R 3 , 1, m, n and X 1 are the same as defined in Chemical Formula 1.
s 및 u는 각각 0 내지 4의 정수이고, t 및 v는 각각 0 내지 6의 정수이며, s+t는 1 이상의 정수이고, u+v는 1 이상의 정수이다. s and u are each an integer of 0-4, t and v are each an integer of 0-6, s + t is an integer of 1 or more, u + v is an integer of 1 or more.
L2 내지 L5는 서로 독립적으로, 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 바람직하게는, L2 내지 L5는 서로 독립적으로 단일결합; C6-C30의 아릴렌기; 플루오렌일렌기; 및 O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C30의 헤테로고리기; 등일 수 있다. 구체적으로 L2 내지 L5는 단일결합, 페닐, 바이페닐, 플루오렌, 카바졸, 피리딘, 피리미딘, 트라아진, 벤조카바졸, 다이벤조카바졸, 퀴나졸린, 아세나프토벤조퓨란, 아세나프토벤조싸이오펜 등일 수 있다.L 2 to L 5 are independently of each other, a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And a C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; And combinations thereof may be selected from the group. Preferably, L 2 to L 5 are independently of each other a single bond; C 6 -C 30 arylene group; Fluorenylene groups; And a C 2 -C 30 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; And the like. Specifically L 2 to L 5 is a single bond, phenyl, biphenyl, fluorene, carbazole, pyridine, pyrimidine, triazine, benzocarbazole, dibenzocarbazole, quinazoline, acenaphthobenzofuran, acenaph Tobenzothiophene and the like.
X2 및 X3는 서로 독립적으로 N, N-L1-Ar1, O, S, C(R10)(R11) 또는 Si(R18)(R19)일 수 있다. 이때, X2가 N일 경우에는 L2와 연결될 수 있고, X3가 N일 경우에는 L3와연결될 수 있다X 2 and X 3 may be independently of each other N, NL 1 -Ar 1 , O, S, C (R 10 ) (R 11 ) or Si (R 18 ) (R 19 ). In this case, when X 2 is N, it may be connected to L 2, and when X 3 is N, it may be connected to L 3 .
R6 내지 R9, 및 R12 내지 R17은 서로 독립적으로 수소; 중수소; 할로겐; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; -L'-N(Ra)(Rb); 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 또한, R6 내지 R9 및 R12 내지 R17는 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 형성할 수 있다.R 6 to R 9 , and R 12 to R 17 are each independently hydrogen; heavy hydrogen; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; -L'-N (R a ) (R b ); And combinations thereof may be selected from the group. In addition, R 6 to R 9 and R 12 to R 17 may combine with each other to form at least one ring.
a, b, c, d, e, f, o, p, q, 및 r은 각각 0 내지 4의 정수이다.a, b, c, d, e, f, o, p, q, and r are each an integer of 0-4.
상기 L1은 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 바람직하게는, L1은 서로 독립적으로 단일결합; C6-C30의 아릴렌기; 플루오렌일렌기; 및 O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C30의 헤테로고리기; 등일 수 있다. 구체적으로 L1은 단일결합, 페닐, 바이페닐, 플루오렌, 카바졸, 피리딘, 피리미딘, 트라아진, 벤조카바졸, 다이벤조카바졸, 퀴나졸린, 아세나프토벤조퓨란, 아세나프토벤조싸이오펜 등일 수 있다. L 1 is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And combinations thereof may be selected from the group. Preferably, L 1 is a single bond independently from each other; C 6 -C 30 arylene group; Fluorenylene groups; And a C 2 -C 30 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P; And the like. Specifically, L 1 is a single bond, phenyl, biphenyl, fluorene, carbazole, pyridine, pyrimidine, triazine, benzocarbazole, dibenzocarbazole, quinazoline, acenaphthobenzofuran, acenaphthobenzocyse Ore, etc.
상기 Ar1은 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; -L'-N(Ra)(Rb); C1-C30의 알콕실기; C6-C30의 아릴옥시기; 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 바람직하게는, C6-C30의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C30의 헤테로고리기; -L'-N(Ra)(Rb); 등일 수 있다. 구체적으로 Ar1은 페닐기, 비페닐기, 트리페닐렌기, 페렌일기, 페난트릴기, 플루오렌일기, 스파이로플루오렌일기, 피리딜기, 피리미딘일기, 트리아진일기, 퀴나졸릴기, 벤조퀴나졸릴기, 디벤조퀴나졸릴기, 디벤조티엔일기, 디벤조퓨릴기, 벤조퓨로피리미딜기, 나프토퓨로피리미딜기, 벤조티에노피리미딜기, 카바졸기, 벤조카바졸기 등일 수 있다.Ar 1 is a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L'-N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And combinations thereof may be selected from the group. Preferably, an aryl group of C 6 -C 30 ; Fluorenyl group; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; -L'-N (R a ) (R b ); And the like. Specifically, Ar 1 is a phenyl group, biphenyl group, triphenylene group, ferenyl group, phenanthryl group, fluorenyl group, spirofluorenyl group, pyridyl group, pyrimidinyl group, triazinyl group, quinazolyl group, benzoquinazolyl group , Dibenzoquinazolyl group, dibenzothienyl group, dibenzofuryl group, benzofuropyrimidyl group, naphthopuropyrimidyl group, benzothienopyrimidyl group, carbazole group, benzocarbazole group and the like.
상기 R10, R11, R18 및 R19는 서로 독립적으로, 수소; 중수소; C1-C50의 알킬기; C2-C30의 알켄일기; C2-C30의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; C1-C30의 실릴기; C6-C60의 아릴기; O, N, S, Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; -L'-N(Ra)(Rb); 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 바람직하게는, R10, R11, R18 및 R19는 서로 독립적으로, 수소; 중수소; C1-C30 알킬기; C6-C30의 아릴옥시기; C6-C30의 아릴기; O, N, S, Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C30의 헤테로고리기; 및 플루오렌일기; 등일 수 있다. 구체적으로 R10, R11, R18 및 R19는 서로 독립적으로, 수소; 메틸기, 페닐기, 플루오렌일기 등일 수 있다. 또한, R10 과 R11은 서로 결합하여 고리를 형성할 수 있는데, 이때 이들이 결합된 탄소(C)와 함께 스파이로화합물이 형성될 수 있다. 또한, R18과 R19도 서로 결합하여 고리를 형성할 수 있으며, 이때 이들이 결합된 규소(Si)와 함께 스파이로(spiro)화합물을 형성될 수 있다. R 10 , R 11 , R 18 and R 19 are each independently hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Of C 2 -C 30 Alkenyl groups; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; Silyl groups of C 1 -C 30 ; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; -L'-N (R a ) (R b ); And combinations thereof may be selected from the group. Preferably, R 10 , R 11 , R 18 and R 19 are, independently from each other, hydrogen; heavy hydrogen; C 1 -C 30 alkyl group; C 6 -C 30 aryloxy group; Aryl group of C 6 -C 30 ; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl groups; And the like. Specifically R 10 , R 11 , R 18 and R 19 are each independently of the other hydrogen; Methyl group, phenyl group, fluorenyl group and the like. In addition, R 10 and R 11 may be bonded to each other to form a ring, wherein spiro compounds may be formed together with carbon (C) to which they are bonded. In addition, R 18 and R 19 may be bonded to each other to form a ring, and at this time, a spiro compound may be formed together with silicon (Si) to which they are bonded.
상기 L', Ra 및 Rb는 상기 화학식 1에서 정의된 것과 동일하다.L ′, R a and R b are the same as defined in Chemical Formula 1.
상기 화학식 2의 X2 및 X3가 N-L1-Ar1 일 때, 상기 Ar1은 하기 구조식 Z-1 내지 화학식 Z-8 중 하나일 수 있다.When X 2 and X 3 of Formula 2 are NL 1 -Ar 1 , Ar 1 may be one of the following structural formulas Z-1 to Z-8.
<화학식 Z-1> <화학식 Z-2> <화학식 Z-3> <화학식 Z-4><Formula Z-1> <Formula Z-2> <Formula Z-3> <Formula Z-4>
<화학식 Z-5> <화학식 Z-6> <화학식 Z-7> <화학식 Z-8><Formula Z-5> <Formula Z-6> <Formula Z-7> <Formula Z-8>
상기 화학식 Z-1 내지 Z-8에서, Z1 내지 Z70은 서로 독립적으로 C, C(Rc) 또는 N일 수 있고, 여기서 Z1 내지 Z70 중 C는 상기 화학식 2의 L1과 결합될 수 있다.In Formulas Z-1 to Z-8, Z 1 to Z 70 may be each independently C, C (R c ) or N, wherein C in Z 1 to Z 70 is bonded to L 1 of Formula 2 Can be.
바람직하게는, 화학식 Z-1의 Z1 내지 Z6 중 하나는 C이고, 적어도 다른 하나는 N일 수 있으며, 화학식 Z-2의 Z7 내지 Z14 중 하나는 C이고, 적어도 다른 하나는 N일 수 있으며, 화학식 Z-3의 Z15 내지 Z24 중 하나는 C이고, 적어도 다른 하나는 N일 수 있으며, 화학식 Z-4의 Z25 내지 Z34 중 하나는 C이고, 적어도 다른 하나는 N일 수 있으며, 화학식 Z-5의 Z35 내지 Z44 중 하나는 C이고, 적어도 다른 하나는 N일 수 있으며, 화학식 Z-6의 Z45 내지 Z56 중 하나는 C이고, 적어도 다른 하나는 N일 수 있으며, 화학식 Z-7의 Z57 내지 Z62 중 하나는 C이고, 적어도 다른 하나는 N일 수 있으며, 화학식 Z-8의 Z63 내지 Z70 중 하나는 C이고, 적어도 다른 하나는 N일 수 있다.Preferably, one of Z 1 to Z 6 of formula Z-1 may be C, at least the other may be N, one of Z 7 to Z 14 of formula Z-2 is C, and at least the other is N And one of Z 15 to Z 24 of Formula Z-3 may be C, and at least the other may be N, one of Z 25 to Z 34 of Formula Z-4 is C, and at least the other is N And one of Z 35 to Z 44 of Formula Z-5 may be C, and at least the other may be N. One of Z 45 to Z 56 of Formula Z-6 is C, and at least the other is N And one of Z 57 to Z 62 of Formula Z-7 may be C, and at least the other may be N. One of Z 63 to Z 70 of Formula Z-8 is C, and at least the other is N Can be.
Rc는 수소; 중수소; C1-C50의 알킬기; C2-C30의 알켄일기; C2-C30의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; C1-C30의 실릴기; C6-C60의 아릴기; O, N, S,Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; -L'-N(Ra)(Rb); 및 이들의 조합으로 이루어진 군에서 선택될 수있다. 바람직하게는, Rc는 C6-C30의 아릴기; O, N, S,Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C30의 헤테로고리기; 및 플루오렌일기; 등일 수 있다. 구체적으로 Rc는 페닐기, 나프틸기, 비페닐기, 피렌일기, 피리딜기, 피리미딘일기, 트리아진일기, 인돌기, 디벤조티엔일기, 카바졸기, 디벤조퓨릴기, 디벤조퀴나졸릴기, 벤조퀴나졸릴기, 플루오렌일기, 스파이로바이플루오렌일기 등일 수 있다. 또한, Rc는 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 선택적으로 형성할 수 있다.R c is hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 30 ; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; A silyl group of C 1 -C 30; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; -L'-N (R a ) (R b ); And combinations thereof. Preferably, R c is an aryl group of C 6 -C 30 ; C 2 -C 30 heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P; And fluorenyl groups; And the like. Specifically, R c is a phenyl group, naphthyl group, biphenyl group, pyrenyl group, pyridyl group, pyrimidinyl group, triazineyl group, indole group, dibenzothienyl group, carbazole group, dibenzofuryl group, dibenzoquinazolyl group, benzo Quinazolyl group, fluorenyl group, spirobifluorenyl group, and the like. In addition, R c may be bonded to each other adjacent groups to form at least one ring selectively.
W1 내지 W3는 단일결합, C(Rd)(Re), N-Ar2, O, S, 및 Si(Rf)(Rg)로 이루어진 군에서 선택될 수 있다.W 1 to W 3 may be selected from the group consisting of a single bond, C (R d ) (R e ), N-Ar 2 , O, S, and Si (R f ) (R g ).
Rd 내지 Rg은 서로 독립적으로, 수소; 중수소; C1-C50의 알킬기; C2-C30의 알켄일기; C2-C30의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; C1-C30의 실릴기; C6-C60의 아릴기; O, N, S,Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; -L'-N(Ra)(Rb); 및 이들의 조합으로 이루어진 군에서 선택될 수 있다. 바람직하게는, Rd 내지 Rg은 서로 독립적으로, 수소; C1-C30의 알킬기; C6-C30의 아릴기; 및 플루오렌일기; 등일 수 있다. 구체적으로, Rd 내지 Rg은 서로 독립적으로 수소, 메틸기, 페닐기, 플루오렌일기 등일 수 있다. 또한, Rd 와 Re는 서로 결합하여 고리를 형성할 수 있으며, 이때 이들이 결합된 탄소(C)와 함께 스파이로 화합물이 형성될 수 있다. 또한, Rf
와 Rg
는 서로 결합하여 고리를 형성할 수 있으며, 이때 이들이 결합된 규소(Si)와 함께 스파이로(spiro)화합물을 형성될 수 있다.R d to R g are each independently hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 30 ; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; Silyl groups of C 1 -C 30 ; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; -L'-N (R a ) (R b ); And combinations thereof may be selected from the group. Preferably, R d to R g are each independently hydrogen; An alkyl group of C 1 -C 30 ; Aryl group of C 6 -C 30 ; And fluorenyl groups; And the like. Specifically, R d to R g may be each independently hydrogen, a methyl group, a phenyl group, a fluorenyl group, or the like. In addition, R d and R e may be bonded to each other to form a ring, wherein a spiro compound may be formed together with carbon (C) to which they are bonded. R f With R g May be bonded to each other to form a ring, and together with the silicon (Si) to which they are bonded, a spiro compound may be formed.
L', Ra, 및 Rb는 화학식 1에서 정의된 것과 동일하며, Ar2는 화학식 2에서 정의된 Ar1과 동일하게 정의될 수 있다.L ′, R a , and R b are the same as defined in Formula 1, and Ar 2 may be defined the same as Ar 1 defined in Formula 2.
구체적으로, 상기 화학식 1로 표시되는 화합물은 하기 화합물 중 하나일 수 있다.Specifically, the compound represented by Formula 1 may be one of the following compounds.
다른 실시예로, 본 발명은 상기화학식 1로 표시되는 유기전기소자용 화합물을 제공한다. In another embodiment, the present invention provides a compound for an organic electric device represented by Chemical Formula 1.
또 다른 실시예로, 본 발명은 상기 화학식 1로 표시되는 화합물을 함유하는 유기전기소자를 제공한다.In another embodiment, the present invention provides an organic electric device containing the compound represented by the formula (1).
이때, 유기전기소자는 제 1전극; 제 2전극; 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층;을 포함할 수 있으며, 상기 유기물층은 화학식 1로 표시되는 화합물을 포함할 수 있으며, 화학식 1은 정공주입층, 정공수송층, 발광보조층, 발광층, 전자수송보조층, 전자수송층 중 적어도 하나의 층에 함유될 수 있으며, 1종 단독 화합물 또는 2종 이상의 혼합물의 성분으로 포함될 수 있다. 즉, 화학식 1로 표시되는 화합물은 정공주입층, 정공수송층, 발광보조층, 발광층, 전자수송보조층 및/또는 전자수송층의 재료로 사용될 수 있다. 바람직하게는, 화학식 1로 표시되는 화합물은 상기 발광층의 인광 호스트 재료로 사용될 수 있다.In this case, the organic electric element includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Chemical Formula 1, and Chemical Formula 1 may include a hole injection layer, a hole transport layer, a light emitting auxiliary layer, It may be contained in at least one layer of the light emitting layer, the electron transport auxiliary layer, the electron transport layer, it may be included as a component of one kind of a compound or two or more kinds. That is, the compound represented by Formula 1 may be used as a material of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer and / or an electron transport layer. Preferably, the compound represented by Formula 1 may be used as a phosphorescent host material of the light emitting layer.
본 발명의 또 다른 실시예로, 본 발명은 상기 제 1전극의 일측면 중 상기유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율 개선층을 더 포함하는 유기전기소자를 제공한다.In another embodiment of the present invention, the present invention is an optical efficiency improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer It provides an organic electric element further comprising.
이하에서, 본 발명에 따른 화학식 1로 표시되는 화합물의 합성예 및 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명이 하기의 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.
합성예Synthesis Example
예시적으로 본 발명에 따른 화합물(final products)은 하기 반응식 1과 같이 Sub 2를 이용하여 제조되나, 이에 한정되는 것은 아니다.By way of example, the compounds (final products) according to the present invention are prepared using Sub 2 as in Scheme 1, but are not limited thereto.
<반응식 1><Scheme 1>
I. Sub 2의 합성I. Synthesis of Sub 2
상기 반응식 1의 Sub 2은 하기 반응식 2의 반응경로에 의해 합성될 수 있으나, 이에 한정되는 것은 아니다.Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 2, but is not limited thereto.
<반응식 2><Scheme 2>
<반응식 3> M 1의 합성Scheme 3 Synthesis of M 1
II. Final Products의 합성II. Synthesis of Final Products
1. 1-49의 합성1.1 Synthesis of 1-49
1) M 1-I-1의 합성1) Synthesis of M 1-I-1
둥근바닥플라스크에 (4-(9H-carbazol-9-yl)phenyl)boronic acid (14.15g, 49.28mmol), 6-bromobenzo[b]thiophene (10.50g, 49.28mmol), Pd(PPh3)4 (1.71g, 1.48mmol), K2CO3 (20.43g, 147.82mmol), THF (217mL), 물 (108mL)을 넣은 후, 80℃ 에서 가열 환류 시켰다. 반응이 완료되면 상온에서 증류수를 넣어 희석시키고 메틸렌클로라이드와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 16.47g 얻었다(수율: 89%). (4- (9H-carbazol-9-yl) phenyl) boronic acid (14.15g, 49.28mmol), 6-bromobenzo [b] thiophene (10.50g, 49.28mmol), Pd (PPh 3 ) 4 ( 1.71 g, 1.48 mmol), K 2 CO 3 (20.43 g, 147.82 mmol), THF (217 mL), and water (108 mL) were added thereto, followed by heating to reflux at 80 ° C. After the reaction was completed, distilled water was diluted at room temperature, and extracted with methylene chloride and water. The organic layer was dried over MgSO 4 , concentrated, and the resulting organics were purified by silicagel column and recrystallized to give 16.47 g of product (yield: 89%).
2) M 1-1의 합성2) Synthesis of M 1-1
둥근바닥플라스크에 CHCl3 (192mL)과 M 1-I-1 (16.40g, 43.68mmol)을 넣은 후, Br2 (4.92ml, 117.14mmol) + CHCl3
(96mL) 혼합 용액을 서서히 적가하고, 상온에서 20시간 동안 교반하였다. 반응이 완료되면 포화 NaHSO3 수용액을 넣어 반응을 종결시킨 후, CHCl3와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 17.00g을 얻었다(수율: 73%).CHCl 3 (192mL) and M 1-I-1 (16.40g, 43.68mmol) were added to a round bottom flask, followed by Br 2 (4.92ml, 117.14mmol) + CHCl 3 (96 mL) mixed solution was slowly added dropwise and stirred at room temperature for 20 hours. After the reaction was completed, the reaction was terminated by adding a saturated NaHSO 3 aqueous solution, and extracted with CHCl 3 and water. The organic layer was dried over MgSO 4 , concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 17.00 g of a product (yield: 73%).
3) Sub 2-47의 합성3) Synthesis of Sub 2-47
Sub1-1 (5.45g, 31.69mmol), THF (139mL), M 1-1 (16.90g, 31.69mmol), Pd(PPh3)4 (0.55g, 0.48mmol), K2CO3 (6.57g, 47.54mmol), 물 (70mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 13.06g 을 얻었다(수율: 71%).Sub1-1 (5.45 g, 31.69 mmol), THF (139 mL), M 1-1 (16.90 g, 31.69 mmol), Pd (PPh 3 ) 4 (0.55 g, 0.48 mmol), K 2 CO 3 (6.57 g, 47.54 mmol) and water (70 mL) were used to obtain 13.06 g of the product using the M 1-I-1 synthesis method (yield: 71%).
6) 1-49 의 합성6) Synthesis of 1-49
상기 합성에서 얻어진 Sub 2-47 (13g, 22.39mmol), Pd(PPh3)2Cl2(1.57g, 2.24mmol),1,8-Diazabicyclo[5.4.0]undec-7-ene(4.77g, 31.35mmol)을 무수 DMF(45mL)에 녹여, 140°C에서 교반하였다. 반응이 완료되면, 톨루엔을 넣어 희석시키고 celite를 이용하여 Pd를 제거하고, 물로 세척한 후, 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 6.60g을 얻었다(수율: 59%). Sub 2-47 (13 g, 22.39 mmol), Pd (PPh 3 ) 2 Cl 2 (1.57 g, 2.24 mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.77 g,) obtained in the above synthesis 31.35 mmol) was dissolved in anhydrous DMF (45 mL) and stirred at 140 ° C. After the reaction was completed, toluene was added, diluted with celite, Pd was removed, washed with water, the organic layer was dried over MgSO 4 , concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 6.60 g of a product (yield). : 59%).
2. 1-14의 합성2. Synthesis of 1-14
1) M 1-I-2의 합성1) Synthesis of M 1-I-2
(9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)boronic acid(6.63g, 15.96mmol), 5-bromobenzo[b]thiophene (3.40g, 15.96mmol), Pd(PPh3)4 (0.55g, 0.48mmol), K2CO3 (6.62g, 47.87mmol), THF (70mL), 물 (35mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 6.67g 얻었다(수율: 83%). (9- (4-phenylquinazolin-2-yl) -9H-carbazol-3-yl) boronic acid (6.63g, 15.96mmol), 5-bromobenzo [b] thiophene (3.40g, 15.96mmol), Pd (PPh 3 6.67g of product ( 4 ) (0.55g, 0.48mmol), K 2 CO 3 (6.62g, 47.87mmol), THF (70mL) and water (35mL) was synthesized using the synthesis method of M 1-I-1. (Yield 83%).
2) M 1-2의 합성2) Synthesis of M 1-2
CHCl3 (162ml)과 M 1-I-2(18.50g, 36.73mmol), Br2 (4.14mL, 80.82mmol) + CHCl3 (81mL) 혼합 용액을 상기 M 1-1의 합성방법을 사용하여 생성물 17.98g을 얻었다(수율: 74%).CHCl 3 (162 ml), M 1-I-2 (18.50 g, 36.73 mmol), Br 2 (4.14 mL, 80.82 mmol) + CHCl 3 (81 mL) mixed solution was prepared using the synthesis method of M 1-1. 17.98 g were obtained (yield 74%).
3) Sub 2-14의 합성3) Synthesis of Sub 2-14
Sub 1-1 (4.65g, 27.06mmol), THF (119ml), M 1-2 (17.90g, 27.06mmol), Pd(PPh3)4 (0.47g, 0.41mmol), K2CO3 (5.61g, 40.59mmol), 물 (60mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 13.43g 을 얻었다(수율: 70%).Sub 1-1 (4.65g, 27.06mmol), THF (119ml), M 1-2 (17.90g, 27.06mmol), Pd (PPh 3 ) 4 (0.47g, 0.41mmol), K 2 CO 3 (5.61g , 40.59 mmol) and water (60 mL) were obtained by 13.43 g of the product using the M 1-I-1 synthesis method (yield: 70%).
4) 1-14의 합성4) Synthesis of 1-14
상기 합성에서 얻어진 Sub 2-14 (13.40g, 18.91mmol), Pd(PPh3)2Cl2
(1.33g, 1.89mmol),1,8-Diazabicyclo[5.4.0]undec-7-ene(4.03g, 26.47mmol), 무수 DMF(38mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.53g(수율: 55%)을 얻었다(수율: 55%).Sub 2-14 (13.40 g, 18.91 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.33g, 1.89mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.03g, 26.47mmol), anhydrous DMF (38mL) using the synthesis method of 1-49 6.53g (Yield 55%) was obtained (Yield 55%).
3. 1-45의 3. 1-45
합성예Synthesis Example
1) M 1-I-3의 합성1) Synthesis of M 1-I-3
(3-(triphenylen-2-yl)phenyl)boronic acid(12.58g, 36.14mmol), 5-bromobenzo[b]thiophene (7.70g, 36.14mmol), Pd(PPh3)4 (1.25g, 1.08mmol), K2CO3 (14.98g, 108.40mmol), THF (159mL), 물 (80mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 13.72g 얻었다(수율: 87%). (3- (triphenylen-2-yl) phenyl) boronic acid (12.58g, 36.14mmol), 5-bromobenzo [b] thiophene (7.70g, 36.14mmol), Pd (PPh 3 ) 4 (1.25g, 1.08mmol) , K 2 CO 3 (14.98 g, 108.40 mmol), THF (159 mL), and water (80 mL) were obtained by 13.72 g of the product using the synthesis method of M 1-I-1 (yield: 87%).
2) M 1-3의 합성2) Synthesis of M 1-3
CHCl3 (136ml)과 M 1-I-3(13.50g, 30.92mmol), Br2(3.49ml, 68.03mmol) + CHCl3(68mL) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 14.15g을 얻었다(수율: 77%).CHCl 3 (136 ml), M 1-I-3 (13.50 g, 30.92 mmol), Br 2 (3.49 ml, 68.03 mmol) + CHCl 3 (68 mL) mixed solution were prepared using the synthesis method of M 1-1. 14.15 g was obtained (yield 77%).
3) Sub 2-43 합성3) Sub 2-43 synthesis
Sub 1-1 (4.08g, 23.72mmol), THF (104mL), M 1-3 (14.10g, 23.72mmol), Pd(PPh3)4 (0.41g, 0.36mmol), K2CO3 (4.92g, 35.58mmol), 물 (52mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 11.57g 을 얻었다(수율: 76%).Sub 1-1 (4.08g, 23.72mmol), THF (104mL), M 1-3 (14.10g, 23.72mmol), Pd (PPh 3 ) 4 (0.41g, 0.36mmol), K 2 CO 3 (4.92g , 35.58 mmol), and water (52 mL) were used to obtain 11.57 g of the product using the M 1-I-1 synthesis method (yield: 76%).
4) 1-45의 합성4) Synthesis of 1-45
상기 합성에서 얻어진 Sub 2-45 (11.5g, 17.92mmol), Pd(PPh3)2Cl2
(1.26g, 1.79mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(3.82g, 25.09mmol), 무수 DMF(36mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.53g을 얻었다(수율: 65%).Sub 2-45 (11.5 g, 17.92 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (1.26g, 1.79mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (3.82g, 25.09mmol), anhydrous DMF (36mL) using the synthesis method of 1-49 6.53g Was obtained (yield: 65%).
4. 1-26의 4. 1-26
합성예Synthesis Example
둥근바닥플라스크에 5-bromobenzo[b]thiophene (1mmol, 1당량)을 넣고 3.5mL의 무수 Ether 녹인 후 반응물의 온도를 -78oC 로 낮추었다. 이 반응액에 n-BuLi (2.5 M , 1.1당량)를 천천히 적가하고 난 후, 상온에서 1시간 더 교반하였다. 그 후 다시 반응물의 온도를 -78oC로 낮추고 Triisopropyl borate(1.5당량)를 적가하였다. 온도를 서서히 올려 상온에서 교반한 뒤 물을 넣어 희석시키고 2N HCl를 넣고 교반한다. 반응이 완료되면 ethyl acetate와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silica column 및 재결정하여 생성물을 얻었다. 5-bromobenzo [b] thiophene (1 mmol, 1 equivalent) was added to a round bottom flask, and 3.5 mL of anhydrous Ether was dissolved, and the temperature of the reaction was lowered to -78 o C. N-BuLi (2.5 M, 1.1 equiv) was slowly added dropwise to the reaction solution, followed by further stirring at room temperature for 1 hour. Then the temperature of the reaction was lowered to -78 o C and Triisopropyl borate (1.5 equiv) was added dropwise. After slowly raising the temperature and stirring at room temperature, dilute with water, add 2N HCl, and stir. After the reaction was completed, the mixture was extracted with ethyl acetate and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was purified by silica column and recrystallization.
1) M 1-I-4의 합성1) Synthesis of M 1-I-4
(9-(4-(dibenzo[b,d]furan-2-yl)benzo[4,5]thieno[3,2-d]pyrimidin-2-yl)-9H-carbazol-3-yl)boronic acid(6.2g, 29.10mmol), 5-bromobenzo[b]thiophene(16.34g, 29.10mmol), Pd(PPh3)4 (1.01g, 0.87mmol), K2CO3 (12.06g, 87.29mmol), THF (128mL), 물 (64mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 14.94g 얻었다.(수율: 79%)(9- (4- (dibenzo [b, d] furan-2-yl) benzo [4,5] thieno [3,2-d] pyrimidin-2-yl) -9H-carbazol-3-yl) boronic acid (6.2 g, 29.10 mmol), 5-bromobenzo [b] thiophene (16.34 g, 29.10 mmol), Pd (PPh 3 ) 4 (1.01 g, 0.87 mmol), K 2 CO 3 (12.06 g, 87.29 mmol), THF (128 mL) and water (64 mL) were used to synthesize 14.94 g of the product using the synthesis method of M 1-I-1. (Yield: 79%)
2) M 1-4의 합성2) Synthesis of M 1-4
CHCl3 (100mL), M 1-I-4 (14.80g, 22.78mmol), Br2 (2.57ml, 50.11mmol) + CHCl3(100 mL) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 12.51g을 얻었다(수율: 68%).CHCl 3 (100 mL), M 1-I-4 (14.80 g, 22.78 mmol), Br 2 (2.57 ml, 50.11 mmol) + CHCl 3 (100 mL) mixed solution was prepared using the synthesis method of M 1-1. 12.51 g of product was obtained (yield: 68%).
3) Sub 2-26 합성3) Sub 2-26 Synthesis
Sub 1-1 (2.66g, 15.48mmol), THF (68ml), M 1-4 (12.50g, 15.48mmol), Pd(PPh3)4 (0.54g, 0.46mmol), K2CO3 (6.42g, 46.44mmol), 물 (34mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 11.11g 을 얻었다(수율: 84%).Sub 1-1 (2.66g, 15.48mmol), THF (68ml), M 1-4 (12.50g, 15.48mmol), Pd (PPh 3 ) 4 (0.54g, 0.46mmol), K 2 CO 3 (6.42g , 46.44 mmol), and water (34 mL) were used to obtain 11.11 g of the product using the M 1-I-1 synthesis method (yield: 84%).
4) 1-26 의 합성4) Synthesis of 1-26
상기 합성에서 얻어진 Sub 2-26 (11.1g, 12.98mmol), Pd(PPh3)2Cl2
(0.91g, 1.30mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(2.77g, 18.18mmol), 무수 DMF(26mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.53g을 얻었다(수율: 62%).Sub 2-26 (11.1 g, 12.98 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (0.91g, 1.30mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (2.77g, 18.18mmol), anhydrous DMF (26mL) using the synthesis method of 1-49 6.53g Obtained (yield: 62%).
5. 1-31의 5. 1-31
합성예Synthesis Example
1) M 1-I-5의 합성1) Synthesis of M 1-I-5
(9-phenyl-9H-carbazol-3-yl)boronic acid(6.87g, 23.93mmol), 6-bromobenzo[b]thiophene (5.10g, 23.93mmol), Pd(PPh3)4 (0.83g, 0.72mmol), K2CO3 (9.92g, 71.80mmol), THF (105mL), 물 (53mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 13.05g 얻었다(수율: 85%). (9-phenyl-9H-carbazol-3-yl) boronic acid (6.87g, 23.93mmol), 6-bromobenzo [b] thiophene (5.10g, 23.93mmol), Pd (PPh 3 ) 4 (0.83g, 0.72mmol ), K 2 CO 3 (9.92 g, 71.80 mmol), THF (105 mL), and water (53 mL) were obtained by 13.05 g of the product using the synthesis method of M 1-I-1 (yield: 85%).
2) M 1-5의 합성2) Synthesis of M 1-5
CHCl3 (152mL), M1-I-5 (13.0g, 34.62mmol), Br2 (3.9ml, 76.17mmol) + CHCl3
(76mL) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 13.48g을 얻었다(수율: 73%).CHCl 3 (152 mL), M1-I-5 (13.0 g, 34.62 mmol), Br 2 (3.9 ml, 76.17 mmol) + CHCl 3 (76 mL) A mixed solution of 13.48 g of product was obtained using the synthesis method of M 1-1 (yield: 73%).
3) Sub 2-31 합성3) Sub 2-31 Synthesis
Sub 1-1 (4.32g, 25.13mmol), THF (111mL), M 1-5(13.40g, 25.13mmol), Pd(PPh3)4 (0.87g, 0.75mmol), K2CO3 (10.42g, 75.38mmol), 물 (55mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 12.55g 을 얻었다(수율: 86%).Sub 1-1 (4.32 g, 25.13 mmol), THF (111 mL), M 1-5 (13.40 g, 25.13 mmol), Pd (PPh 3 ) 4 (0.87 g, 0.75 mmol), K 2 CO 3 (10.42 g , 75.38 mmol) and water (55 mL) were obtained using the M 1-I-1 synthesis method to obtain 12.55 g of the product (yield: 86%).
4) 1-31의 합성4) Synthesis of 1-31
상기 합성에서 얻어진 Sub 2-31 (12.50g, 21.53mmol), Pd(PPh3)2Cl2
(1.51g, 2.15mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(4.59g, 30.14mmol), 무수 DMF(43mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.56g을 얻었다(수율: 61%).Sub 2-31 (12.50 g, 21.53 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.51g, 2.15mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.59g, 30.14mmol), anhydrous DMF (43mL) using the synthesis method of 1-49 6.56g Obtained (yield: 61%).
6. 1-32의 6. 1-32
합성예Synthesis Example
1) M 1-I-6의 합성1) Synthesis of M 1-I-6
(11-(9,9-dimethyl-9H-fluoren-2-yl)-11H-benzo[a]carbazol-8-yl)boronic acid(16.38g, 36.13mmol), 6-bromobenzo[b]thiophene (7.70g, 36.13mmol), Pd(PPh3)4 (1.25g, 1.08mmol), K2CO3 (14.98g, 108.40mmol), THF (159mL), 물 (80mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 16.83g 얻었다(수율: 86%). (11- (9,9-dimethyl-9H-fluoren-2-yl) -11H-benzo [a] carbazol-8-yl) boronic acid (16.38g, 36.13mmol), 6-bromobenzo [b] thiophene (7.70 g, 36.13 mmol), Pd (PPh 3 ) 4 (1.25 g, 1.08 mmol), K 2 CO 3 (14.98 g, 108.40 mmol), THF (159 mL), water (80 mL) of the M 1-I-1 16.83 g of product was obtained using the synthesis method (yield: 86%).
2) M 1-6의 합성2) Synthesis of M 1-6
CHCl3 (136mL), M 1-I-6 (16.70g, 30.83mmol), Br2 (3.48ml, 67.82mmol) + CHCl3(68mL) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 14.88g을 얻었다(수율: 69%).CHCl 3 (136 mL), M 1-I-6 (16.70 g, 30.83 mmol), Br 2 (3.48 mL, 67.82 mmol) + CHCl 3 (68 mL) mixed solution were prepared using the synthesis method of M 1-1. 14.88 g was obtained (yield 69%).
3) Sub 2-32 합성3) Sub 2-32 Synthesis
Sub 1-1 (3.64g, 21.16mmol), THF (93mL), M 1-6 (14.80g, 21.16mmol), Pd(PPh3)4 (0.37g, 0.32mmol), K2CO3 (4.39g, 31.74mmol), 물 (47mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 12.64g 을 얻었다(수율: 80%).Sub 1-1 (3.64 g, 21.16 mmol), THF (93 mL), M 1-6 (14.80 g, 21.16 mmol), Pd (PPh 3 ) 4 (0.37 g, 0.32 mmol), K 2 CO 3 (4.39 g , 31.74 mmol) and water (47 mL) were obtained using the M 1-I-1 synthesis method to obtain 12.64 g of a product (yield: 80%).
4) 1-32 의 합성4) Synthesis of 1-32
상기 합성에서 얻어진 Sub 2-32 (12.6g, 16.87mmol), Pd(PPh3)2Cl2
(1.18g, 1.69mmol),1,8-Diazabicyclo[5.4.0]undec-7-ene(3.60g, 23.62mmol), 무수 DMF(33mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.52g을 얻었다(수율: 58%).Sub 2-32 (12.6 g, 16.87 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.18g, 1.69mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (3.60g, 23.62mmol), anhydrous DMF (33mL) using the synthesis method of 1-49 6.52g Obtained (yield: 58%).
7. 1-13의 7. 1-13
합성예Synthesis Example
1) M 1-I-7의 합성1) Synthesis of M 1-I-7
(11-(9,9-dimethyl-9H-fluoren-2-yl)-11H-benzo[a]carbazol-8-yl)boronic acid (36.42g, 70.39mmol), 6-bromobenzo[b]thiophene(15.00g, 70.39mmol), Pd(PPh3)4 (2.44g, 2.11mmol), K2CO3 (29.19g, 211.18mmol), THF (310mL), 물 (155mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 30.89g 얻었다(수율: 81%). (11- (9,9-dimethyl-9H-fluoren-2-yl) -11H-benzo [a] carbazol-8-yl) boronic acid (36.42 g, 70.39 mmol), 6-bromobenzo [b] thiophene (15.00 g, 70.39 mmol), Pd (PPh 3 ) 4 (2.44 g, 2.11 mmol), K 2 CO 3 (29.19 g, 211.18 mmol), THF (310 mL), water (155 mL) of M 1-I-1 30.89 g of product was obtained using the synthesis method (yield: 81%).
2) M 1-7의 합성2) Synthesis of M 1-7
CHCl3 (224ml)과 M 1-I-7 (30.80g, 50.85mmol), Br2 (5.73mL, 111.86mmol) + CHCl3 (112mL) 혼합 용액을 상기 M 1-1의 합성방법을 사용하여 생성물 24.46g을 얻었다(수율: 63%).CHCl 3 (224 ml), M 1-I-7 (30.80 g, 50.85 mmol), Br 2 (5.73 mL, 111.86 mmol) + CHCl 3 (112 mL) mixed solution were prepared using the synthesis method of M 1-1. 24.46 g were obtained (yield 63%).
3) Sub 2-13 합성3) Sub 2-13 synthesis
Sub 1-1 (5.50g, 31.96mmol), THF (141ml), M 1-7 (24.40g, 31.96mmol), Pd(PPh3)4 (0.55g, 0.48mmol), K2CO3 (6.62g, 47.93mmol), 물 (70ml)을 상기 M 1-I-1 합성방법을 사용하여 생성물 13.21g 을 얻었다(수율: 51%).Sub 1-1 (5.50g, 31.96mmol), THF (141ml), M 1-7 (24.40g, 31.96mmol), Pd (PPh 3 ) 4 (0.55g, 0.48mmol), K 2 CO 3 (6.62g , 47.93 mmol), and water (70 ml) were used to obtain 13.21 g of the product using the M 1-I-1 synthesis method (yield: 51%).
4) 1-13 의 합성4) Synthesis of 1-13
상기 합성에서 얻어진 Sub 2-13 (13.20g, 16.28mmol), Pd(PPh3)2Cl2
(1.14g, 1.63mmol),1,8-Diazabicyclo[5.4.0]undec-7-ene(3.47g, 22.79mmol), 무수 DMF(33ml)을 상기 1-49의 합성방법을 사용하여 생성물 6.54g을 얻었다(수율: 55%).Sub 2-13 (13.20 g, 16.28 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.14g, 1.63mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (3.47g, 22.79mmol), anhydrous DMF (33ml) using the synthesis method of 1-49 6.54g (Yield 55%) was obtained.
8. 1-35의 8. 1-35
합성예Synthesis Example
1) M 1-I-8의 합성1) Synthesis of M 1-I-8
(11-(9,9-dimethyl-9H-fluoren-2-yl)-11H-benzo[a]carbazol-8-yl)boronic acid(17.89g, 40.36mmol), 6-bromobenzo[b]thiophene (8.60g, 40.36mmol), Pd(PPh3)4 (1.40g, 1.21mmol), K2CO3 (16.73g, 121.08mmol), THF (178mL), 물 (89mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 18.02g 얻었다(수율: 84%). (11- (9,9-dimethyl-9H-fluoren-2-yl) -11H-benzo [a] carbazol-8-yl) boronic acid (17.89g, 40.36mmol), 6-bromobenzo [b] thiophene (8.60 g, 40.36 mmol), Pd (PPh 3 ) 4 (1.40 g, 1.21 mmol), K 2 CO 3 (16.73 g, 121.08 mmol), THF (178 mL), water (89 mL) of M 1-I-1 18.02 g of product was obtained using the synthesis method (yield: 84%).
2) M 1-8 합성2) M 1-8 Synthesis
CHCl3 (149mL)과 M 1-I-8(18.0g, 33.85mmol), CHCl3 (75mL) + Br2 (3.82ml, 74.48mmol) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 16.57g을 얻었다(수율: 71%).CHCl 3 (149 mL), M 1-I-8 (18.0 g, 33.85 mmol), CHCl 3 (75 mL) + Br 2 (3.82 mL, 74.48 mmol) mixed solution was prepared using the synthesis method of M 1-1. 16.57 g were obtained (yield 71%).
3) Sub 2-35 합성3) Sub 2-35 Synthesis
Sub 1-1 (4.07g, 23.64mmol), THF (104mL)로 녹인 후에, M 1-8 (16.30g, 23.64mmol), Pd(PPh3)4 (0.41g, 0.36mmol), K2CO3 (4.90g, 35.46mmol), 물 (52mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 11.67g 을 얻었다(수율: 67%).Sub 1-1 (4.07 g, 23.64 mmol), THF (104 mL), then M 1-8 (16.30 g, 23.64 mmol), Pd (PPh 3 ) 4 (0.41 g, 0.36 mmol), K 2 CO 3 (4.90 g, 35.46 mmol) and water (52 mL) were used to obtain the product 11.67 g (yield: 67%) using the M 1-I-1 synthesis method.
4) 1-35 의 합성4) Synthesis of 1-35
상기 합성에서 얻어진 Sub 2-35 (11.6g, 15.74mmol), Pd(PPh3)2Cl2
(1.11g, 1.57mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(3.36g, 22.04mmol), 무수 DMF(31mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.51g을 얻었다(수율: 63%).Sub 2-35 (11.6 g, 15.74 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (1.11g, 1.57mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (3.36g, 22.04mmol), anhydrous DMF (31mL) using the synthesis method of 1-49 6.51g Was obtained (yield 63%).
9. 1-53의 9. 1-53
합성예Synthesis Example
1) Sub 2-54 합성1) Sub 2-54 Synthesis
Sub 1-4 (15.05g, 60.00mmol), 2,3-dibromobenzo[b]thiophene(13.20g, 60.00mmol), Pd(PPh3)4 (0.69g, 0.60mmol), K2CO3 (8.29g, 60.00mmol), THF (264mL), 물 (132mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 8.03g 얻었다(수율: 32%). Sub 1-4 (15.05g, 60.00mmol), 2,3-dibromobenzo [b] thiophene (13.20g, 60.00mmol), Pd (PPh 3 ) 4 (0.69g, 0.60mmol), K 2 CO 3 (8.29g , 60.00 mmol), THF (264 mL), and water (132 mL) were obtained by 8.03 g of the product using the synthesis method of M 1-I-1 (yield: 32%).
2) Sub 2-I-54 합성2) Sub 2-I-54 Synthesis
상기 합성에서 얻어진 Sub 2-54 (8g, 19.13mmol), Pd(PPh3)2Cl2
(1.34g, 1.91mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(4.08g, 26.78mmol), 무수 DMF(38mL)을 상기 1-49의 합성방법을 사용하여 생성물 4.32g을 얻었다(수율: 67%).Sub 2-54 (8 g, 19.13 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (1.34g, 1.91mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.08g, 26.78mmol), anhydrous DMF (38mL) using the synthesis method of 1-49 and 4.32g Was obtained (yield 67%).
3) 1-53 합성3) 1-53 Synthesis
(9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)boronic acid(5.29g, 12.75mmol), THF (56ml), Sub 2-I-54(4.3g, 12.75mmol), Pd(PPh3)4 (0.44g, 0.38mmol), K2CO3 (5.29g, 38.25mmol), 물 (28ml)을 상기 M 1-I-1 합성방법을 사용하여 생성물 6.64g을 얻었다(수율: 83%).(9- (4-phenylquinazolin-2-yl) -9H-carbazol-3-yl) boronic acid (5.29 g, 12.75 mmol), THF (56 ml), Sub 2-I-54 (4.3 g, 12.75 mmol), Pd (PPh 3 ) 4 (0.44 g, 0.38 mmol), K 2 CO 3 (5.29 g, 38.25 mmol), and water (28 mL) were obtained using 6.64 g of the product using the M 1-I-1 synthesis method (yield) : 83%).
10. 1-62의 10. 1-62
합성예Synthesis Example
1)Sub 2-56합성1) Sub 2-56 synthetic
Sub 1-3 (19.46g, 77.56mmol)을 넣고, M 1-2 (51.30g, 77.56mmol), Pd(PPh3)4 (0.90g, 0.78mmol), K2CO3 (10.72g, 77.56mmol), THF (341mL), 물 (171mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 17.10g 얻었다(수율: 28%). Add Sub 1-3 (19.46g, 77.56mmol), M 1-2 (51.30g, 77.56mmol), Pd (PPh 3 ) 4 (0.90g, 0.78mmol), K 2 CO 3 (10.72g, 77.56mmol) ), THF (341 mL) and water (171 mL) were used to synthesize 17.10 g of the product using the synthesis method of M 1-I-1 (yield: 28%).
2) Sub 2-I-56 합성2) Sub 2-I-56 Synthesis
상기 합성에서 얻어진 Sub 2-56 (17.10g, 21.71mmol), Pd(PPh3)2Cl2
(1.52g, 2.17mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(4.63g, 30.40mmol), 무수 DMF(43mL)을 상기 1-49의 합성방법을 사용하여 생성물 7.83g을 얻었다(수율: 51%).Sub 2-56 (17.10 g, 21.71 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.52g, 2.17mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.63g, 30.40mmol), anhydrous DMF (43mL) using the synthesis method of 1-49 7.83g (Yield 51%) was obtained.
3) 1-62 합성3) 1-62 synthetic
Triphenylen-2-ylboronic acid(3.0g, 11.04mmol), Sub 2-I-56 (7.80g, 11.04mmol), Pd(PPh3)4 (0.38g, 0.33mmol), K2CO3 (4.58g, 33.11mmol), THF (49mL), 물 (24mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 6.79g 얻었다(수율: 72%).Triphenylen-2-ylboronic acid (3.0 g, 11.04 mmol), Sub 2-I-56 (7.80 g, 11.04 mmol), Pd (PPh 3 ) 4 (0.38 g, 0.33 mmol), K 2 CO 3 (4.58 g, 33.11 mmol), THF (49 mL) and water (24 mL) were obtained using 6.79 g of the product using the synthesis method of M 1-I-1 (yield: 72%).
11. 2-3의 11. 2-3
합성예Synthesis Example
1) M 1-I-9의 합성1) Synthesis of M 1-I-9
(9-(naphthalen-2-yl-d7)-9H-carbazol-3-yl)boronic acid(16.95g, 49.23mmol), 5-bromobenzofuran(9.70g, 49.23mmol), Pd(PPh3)4 (1.71g, 1.48mmol), K2CO3 (20.41g, 147.69mmol), THF (217mL), 물 (108mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 17.64g 얻었다(수율: 86%).(9- (naphthalen-2-yl-d7) -9H-carbazol-3-yl) boronic acid (16.95g, 49.23mmol), 5-bromobenzofuran (9.70g, 49.23mmol), Pd (PPh 3 ) 4 (1.71 g, 1.48 mmol), K 2 CO 3 (20.41 g, 147.69 mmol), THF (217 mL) and water (108 mL) were obtained using 17.64 g of the product using the synthesis method of M 1-I-1 (Yield: 86 %).
2) M 1-9 합성2) M 1-9 Synthesis
CHCl3 (186ml)과 M 1-I-9(17.60g, 42.25mmol), CHCl3 (93ml) + Br2 (4.76ml, 92.96mmol) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 18.20g을 얻었다(수율: 75%).CHCl 3 (186ml), M 1-I-9 (17.60g, 42.25mmol), CHCl 3 (93ml) + Br 2 (4.76ml, 92.96mmol) mixed solution was prepared using the synthesis method of M 1-1. 18.20 g was obtained (yield: 75%).
3) Sub 2-62 합성3) Sub 2-62 Synthesis
Sub 1-1 (5.42g, 31.52mmol), THF (139mL), M 1-9(18.10g, 31.52mmol), Pd(PPh3)4 (0.55g, 0.47mmol), K2CO3 (6.53g, 47.27mmol), 물 (69mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 12.34g 을 얻었다(수율: 63%).Sub 1-1 (5.42 g, 31.52 mmol), THF (139 mL), M 1-9 (18.10 g, 31.52 mmol), Pd (PPh 3 ) 4 (0.55 g, 0.47 mmol), K 2 CO 3 (6.53 g , 47.27 mmol), and water (69 mL) were obtained using 12.34 g of the product using the M 1-I-1 synthesis method (yield: 63%).
4) 2-3 합성4) 2-3 synthetic
상기 합성에서 얻어진 Sub 2-62 (12.30g, 19.79mmol), Pd(PPh3)2Cl2
(1.39g, 1.98mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(4.22g, 27.70mmol), 무수 DMF(40mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.53g을 얻었다(수율: 61%).Sub 2-62 (12.30 g, 19.79 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.39g, 1.98mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.22g, 27.70mmol), anhydrous DMF (40mL) using the synthesis method of 1-49 6.53g Obtained (yield: 61%).
12. 2-14의 12. 2-14
합성예Synthesis Example
1) M 1-I-10의 합성1) Synthesis of M 1-I-10
(9-(4-([1,1'-biphenyl]-4-yl)benzo[h]quinazolin-2-yl)-9H-carbazol-3-yl)boronic acid(25.56g, 47.20mmol), 5-bromobenzofuran (9.30g, 47.20mmol), Pd(PPh3)4 (1.64g, 1.42mmol), K2CO3 (19.57g, 141.60mmol), THF (208mL), 물 (104mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 23.75g 얻었다(수율: 82%). (9- (4-([1,1'-biphenyl] -4-yl) benzo [h] quinazolin-2-yl) -9H-carbazol-3-yl) boronic acid (25.56g, 47.20mmol), 5 bromobenzofuran (9.30 g, 47.20 mmol), Pd (PPh 3 ) 4 (1.64 g, 1.42 mmol), K 2 CO 3 (19.57 g, 141.60 mmol), THF (208 mL), water (104 mL) 23.75 g of product was obtained using the synthesis method of I-1 (yield: 82%).
2) M 1-10 합성2) M 1-10 Synthesis
CHCl3 (167mL)과 M 1-I-10(23.30g, 37.97mmol)을 넣고, CHCl3 (84mL) + Br2 (4.28mL, 83.52mmol) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 18.75g을 얻었다(수율: 64%).CHCl 3 (167mL) and M 1-I-10 (23.30g, 37.97mmol) were added, and a mixture of CHCl 3 (84mL) + Br 2 (4.28mL, 83.52mmol) was prepared using the synthesis method of M 1-1. This gave 18.75 g of product (yield: 64%).
3) Sub 2-73 합성3) Sub 2-73 synthesis
Sub 1-1 (4.17g, 24.24mmol), THF (107mL), M 1-10(18.70g, 24.24mmol), Pd(PPh3)4 (0.42g, 0.36mmol), K2CO3 (5.02g, 36.36mmol), 물 (53mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 11.71g 을 얻었다(수율: 59%).Sub 1-1 (4.17 g, 24.24 mmol), THF (107 mL), M 1-10 (18.70 g, 24.24 mmol), Pd (PPh 3 ) 4 (0.42 g, 0.36 mmol), K 2 CO 3 (5.02 g , 36.36 mmol), and water (53 mL) were used to obtain 11.71 g of the product using the M 1-I-1 synthesis method (yield: 59%).
4) 2-14합성4) 2-14 Synthesis
상기 합성에서 얻어진 Sub 2-73 (11.70g, 14.29mmol), Pd(PPh3)2Cl2
(1.00g, 1.43mmol),1,8-Diazabicyclo[5.4.0]undec-7-ene(3.05g, 20.01mmol), 무수 DMF(29mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.54g을 얻었다(수율: 62%).Sub 2-73 (11.70 g, 14.29 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (1.00g, 1.43mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (3.05g, 20.01mmol), anhydrous DMF (29mL) using the synthesis method of 1-49 6.54g Obtained (yield: 62%).
13. 2-16의 13. 2-16
합성예Synthesis Example
1) M 1-I-11의 합성1) Synthesis of M 1-I-11
(9-(4-(4-phenyldibenzo[f,h]quinazolin-2-yl)phenyl)-9H-carbazol-3-yl)boronic acid(33.44g, 56.54mmol), 5-bromobenzofuran (11.14g, 56.54mmol), Pd(PPh3)4 (1.96g, 1.70mmol), K2CO3 (23.44g, 169.62mmol), THF (249mL), 물 (124mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 29.27g 얻었다(수율: 78%). (9- (4- (4-phenyldibenzo [f, h] quinazolin-2-yl) phenyl) -9H-carbazol-3-yl) boronic acid (33.44g, 56.54mmol), 5-bromobenzofuran (11.14g, 56.54 mmol), Pd (PPh 3 ) 4 (1.96g, 1.70mmol), K 2 CO 3 (23.44g, 169.62mmol), THF (249mL), water (124mL) were prepared using the synthesis method of M 1-I-1. To give 29.27 g of product (yield: 78%).
2) M 1-11 합성2) M 1-11 Synthesis
CHCl3 (193ml)과 M 1-I-11(29.20g, 43.99mmol)을 넣고, CHCl3 (97mL) + Br2 (4.96mL, 96.78mmol) 혼합용액을 상기 M 1-1의 합성방법을 사용하여 생성물 22.05g을 얻었다(수율: 61%).CHCl 3 (193ml) and M 1-I-11 (29.20g, 43.99mmol) were added, and a mixture of CHCl 3 (97mL) + Br 2 (4.96mL, 96.78mmol) was prepared using the synthesis method of M 1-1. This gave 22.05 g of product (yield: 61%).
3) Sub 2-75 합성3) Sub 2-75 Synthesis
Sub 1-1 (4.61g, 26.78mmol), THF (117ml), M 1-11(22.00g, 26.78mmol), Pd(PPh3)4 (0.46g, 0.40mmol), K2CO3 (5.55g, 40.17mmol), 물 (59mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 12.10g 을 얻었다(수율: 52%).Sub 1-1 (4.61 g, 26.78 mmol), THF (117 ml), M 1-11 (22.00 g, 26.78 mmol), Pd (PPh 3 ) 4 (0.46 g, 0.40 mmol), K 2 CO 3 (5.55 g , 40.17 mmol) and water (59 mL) were obtained using the M 1-I-1 synthesis method to obtain 12.10 g of the product (yield: 52%).
4) 2-16 합성4) 2-16 synthetic
상기 합성에서 얻어진 Sub 2-75 (12g, 13.81mmol), Pd(PPh3)2Cl2
(0.97g, 1.38mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(2.94g, 19.34mmol), 무수 DMF(28mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.53g을 얻었다(수율: 60%).Sub 2-75 (12 g, 13.81 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (0.97g, 1.38mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (2.94g, 19.34mmol), anhydrous DMF (28mL) using the synthesis method of 1-49 6.53g Was obtained (yield: 60%).
14. 2-25의 14. 2-25
합성예Synthesis Example
1) M 1-I-12 합성1) M 1-I-12 Synthesis
(5-(4-phenylbenzo[4,5]thieno[2,3-d]pyrimidin-2-yl)-5H-benzo[b]carbazol-1-yl)boronic acid(28.05g, 53.80mmol), 5-bromobenzofuran (10.60g, 53.80mmol), Pd(PPh3)4 (1.87g, 1.61mmol), K2CO3 (22.31g, 161.40mmol), THF (237mL), 물 (118mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 23.64g 얻었다(수율: 74%). (5- (4-phenylbenzo [4,5] thieno [2,3-d] pyrimidin-2-yl) -5H-benzo [b] carbazol-1-yl) boronic acid (28.05g, 53.80mmol), 5 bromobenzofuran (10.60 g, 53.80 mmol), Pd (PPh 3 ) 4 (1.87 g, 1.61 mmol), K 2 CO 3 (22.31 g, 161.40 mmol), THF (237 mL), water (118 mL) 23.64 g of product was obtained using the synthesis method of I-1 (yield: 74%).
2) M 1-12 합성2) M 1-12 Synthesis
CHCl3 (220ml)과 M 1-I-12(29.70g, 50.03mmol), CHCl3 (110mL) + Br2 (5.64mL, 110.06mmol) 용액을 상기 M 1-1의 합성방법을 사용하여 생성물 19.55g을 얻었다(수율: 52%).CHCl 3 (220 ml), M 1-I-12 (29.70 g, 50.03 mmol), CHCl 3 (110 mL) + Br 2 (5.64 mL, 110.06 mmol) solution was obtained using the synthesis method of M 1-1. g was obtained (yield: 52%).
3) Sub 2-84 합성3) Sub 2-84 Synthesis
Sub 1-2 (6.39g, 25.95mmol), THF (114mL), M 1-12(19.50g, 25.95mmol), Pd(PPh3)4 (0.45g, 0.39mmol), K2CO3 (5.38g, 38.92mmol), 물 (57mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 12.68g 을 얻었다(수율: 56%).Sub 1-2 (6.39 g, 25.95 mmol), THF (114 mL), M 1-12 (19.50 g, 25.95 mmol), Pd (PPh 3 ) 4 (0.45 g, 0.39 mmol), K 2 CO 3 (5.38 g , 38.92 mmol) and water (57 mL) were obtained using the M 1-I-1 synthesis method to obtain 12.68 g of the product (yield: 56%).
4) 2-25 합성4) 2-25 synthetic
상기 합성에서 얻어진 Sub 2-84 (12.6g, 14.44mmol), Pd(PPh3)2Cl2
(1.01g, 1.44mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(3.08g, 20.21mmol), 무수 DMF(29mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.52g을 얻었다(수율: 57%).Sub 2-84 (12.6 g, 14.44 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (1.01g, 1.44mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (3.08g, 20.21mmol), anhydrous DMF (29mL) using the synthesis method of 1-49 6.52g (Yield 57%) was obtained.
15. 2-30의 15. 2-30
합성예Synthesis Example
1) M 1-I-13의 합성1) Synthesis of M 1-I-13
(5-(4-phenylbenzo[4,5]thieno[2,3-d]pyrimidin-2-yl)-5H-benzo[b]carbazol-1-yl)boronic acid(13.31g, 58.37mmol), 5-bromobenzofuran (11.50g, 58.37mmol), Pd(PPh3)4 (2.02g, 1.75mmol), K2CO3 (24.20g, 175.10mmol), THF (257mL), 물 (128mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 15.60g 얻었다(수율: 89%). (5- (4-phenylbenzo [4,5] thieno [2,3-d] pyrimidin-2-yl) -5H-benzo [b] carbazol-1-yl) boronic acid (13.31 g, 58.37 mmol), 5 bromobenzofuran (11.50 g, 58.37 mmol), Pd (PPh 3 ) 4 (2.02 g, 1.75 mmol), K 2 CO 3 (24.20 g, 175.10 mmol), THF (257 mL), water (128 mL) 15.60 g of product was obtained using the synthesis method of I-1 (yield: 89%).
2) M 1-13 합성2) M 1-13 Synthesis
CHCl3 (226mL)과 M 1-I-13(15.43g, 51.37mmol), CHCl3 (113mL) + Br2 (5.79mL, 113mmol) 용액을 상기 M 1-1의 합성방법을 사용하여 생성물 16.71g을 얻었다(수율: 71%).CHCl 3 (226 mL) and M 1-I-13 (15.43 g, 51.37 mmol), CHCl 3 (113 mL) + Br 2 (5.79 mL, 113 mmol) were dissolved in 16.71 g of the product using the synthesis method of M 1-1. Was obtained (yield 71%).
3) Sub 2-88 합성3) Sub 2-88 Synthesis
Sub 1-1 (6.27g, 36.45mmol), THF (160mL), M 1-13 (16.70g, 36.45mmol), Pd(PPh3)4 (0.63g, 0.55mmol), K2CO3 (7.56g, 54.67mmol), 물 (80ml)을 상기 M 1-I-1 합성방법을 사용하여 생성물 11.61g 을 얻었다(수율: 63%).Sub 1-1 (6.27g, 36.45mmol), THF (160mL), M 1-13 (16.70g, 36.45mmol), Pd (PPh 3 ) 4 (0.63g, 0.55mmol), K 2 CO 3 (7.56g , 54.67 mmol), and water (80 ml) were used for the synthesis of M 1-I-1 to give 11.61 g of the product (yield: 63%).
4) 2-30 합성4) 2-30 synthetic
상기 합성에서 얻어진 Sub 2-88 (11.6g, 22.95mmol), Pd(PPh3)2Cl2
(1.61g, 2.30mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(4.89g, 32.13mmol), 무수 DMF(46mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.53g을 얻었다(수율: 67%).Sub 2-88 (11.6 g, 22.95 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (1.61g, 2.30mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.89g, 32.13mmol), anhydrous DMF (46mL) using the synthesis method of 1-49 6.53g Was obtained (yield 67%).
16. 2-35의 16. 2-35
합성예Synthesis Example
1) M 1-I-14의 합성1) Synthesis of M 1-I-14
Benzofuran-5-ylboronic acid(12.37g, 76.39mmol), 2-chloro-4-phenylbenzo[h]quinazoline (22.21g, 76.39mmol), Pd(PPh3)4 (2.65g, 2.29mmol), K2CO3 (31.67g, 229.17mmol), THF (336mL), 물 (168mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 23.61g 얻었다(수율: 83%). Benzofuran-5-ylboronic acid (12.37g, 76.39mmol), 2-chloro-4-phenylbenzo [h] quinazoline (22.21g, 76.39mmol), Pd (PPh 3 ) 4 (2.65g, 2.29mmol), K 2 CO 3 (31.67 g, 229.17 mmol), THF (336 mL), and water (168 mL) were obtained by 23.61 g of the product using the synthesis method of M 1-I-1 (yield: 83%).
2) M 1-14 합성2) M 1-14 Synthesis
CHCl3 (279mL)과 M 1-I-14(23.60g, 63.37mmol), CHCl3 (139ml) + Br2 (7.14g, 139.41mmol) 혼합 용액을 상기 M 1-1의 합성방법을 사용하여 생성물 22.18g을 얻었다(수율: 66%).CHCl 3 (279 mL), M 1-I-14 (23.60 g, 63.37 mmol), CHCl 3 (139 mL) + Br 2 (7.14 g, 139.41 mmol) mixed solution was prepared using the synthesis method of M 1-1. 22.18 g was obtained (yield: 66%).
3) Sub 2-91 합성3) Sub 2-91 synthesis
Sub 1-1 (7.17g, 41.68mmol), THF (183ml), M 1-14(22.10g, 41.68mmol), Pd(PPh3)4 (0.72g, 0.63mmol), K2CO3 (8.64g, 62.52mmol), 물 (92mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 12.52g 을 얻었다(수율: 52%).Sub 1-1 (7.17g, 41.68mmol), THF (183ml), M 1-14 (22.10g, 41.68mmol), Pd (PPh 3 ) 4 (0.72g, 0.63mmol), K 2 CO 3 (8.64g , 62.52 mmol), and water (92 mL) were used to obtain 12.52 g of the product using the M 1-I-1 synthesis method (yield: 52%).
4) 2-35 합성4) 2-35 Synthesis
상기 합성에서 얻어진 Sub 2-91 (12.50g, 21.65mmol), Pd(PPh3)2Cl2
(1.52g, 2.16mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(4.61g, 30.30mmol), 무수 DMF(43mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.56g을 얻었다(수율: 61%).Sub 2-91 (12.50 g, 21.65 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.52g, 2.16mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (4.61g, 30.30mmol), anhydrous DMF (43mL) using the synthesis method of 1-49 6.56g Obtained (yield: 61%).
17. 3-21의 17-21
합성예Synthesis Example
1) M 1-I-15의 합성1) Synthesis of M 1-I-15
((9-(4-phenylquinazolin-2-yl)-9H-carbazol-3-yl)boronic acid(38.90g, 93.68mmol), 6-bromo-1,1-dimethyl-1H-indene(20.90g, 93.68mmol), Pd(PPh3)4 (3.25g, 2.81mmol), K2CO3 (38.84g, 281.03mmol), THF (412mL), 물 (206mL)을 상기 M 1-I-1의 합성방법을 사용하여 생성물을 34.64g 얻었다(수율: 72%). ((9- (4-phenylquinazolin-2-yl) -9H-carbazol-3-yl) boronic acid (38.90g, 93.68mmol), 6-bromo-1,1-dimethyl-1H-indene (20.90g, 93.68 mmol), Pd (PPh 3 ) 4 (3.25 g, 2.81 mmol), K 2 CO 3 (38.84 g, 281.03 mmol), THF (412 mL), water (206 mL). To give 34.64 g of product (yield: 72%).
2) M 1-15 합성2) M 1-15 Synthesis
CHCl3 (296mL)과 M 1-I-15 (34.50g, 67.17mmol)을 넣고, CHCl3 (296mL) + Br2 (7.57mL, 147.77mmol) 용액을 상기 M 1-1의 합성방법을 사용하여 생성물 23.00g을 얻었다(수율: 51%).CHCl 3 (296mL) and M 1-I-15 (34.50g, 67.17mmol) were added, and a solution of CHCl 3 (296mL) + Br 2 (7.57mL, 147.77mmol) was prepared using the synthesis method of M 1-1. 23.00 g of product were obtained (yield 51%).
3) Sub 2-120 합성3) Sub 2-120 Synthesis
Sub 1-1 (5.89g, 34.26mmol), THF (151mL), M 1-15 (23.00g, 34.26mmol), Pd(PPh3)4 (0.59g, 0.51mmol), K2CO3 (7.10g, 51.38mmol), 물 (75mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 13.05g 을 얻었다(수율: 53%).Sub 1-1 (5.89 g, 34.26 mmol), THF (151 mL), M 1-15 (23.00 g, 34.26 mmol), Pd (PPh 3 ) 4 (0.59 g, 0.51 mmol), K 2 CO 3 (7.10 g , 51.38 mmol), and water (75 mL) were obtained by 13.05 g of the product using the M 1-I-1 synthesis method (yield: 53%).
4) 3-21 합성4) 3-21 synthesis
상기 합성에서 얻어진 Sub 2-120 (13g, 18.09mmol), Pd(PPh3)2Cl2
(1.27g, 1.81mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(3.86g, 25.32mmol), 무수 DMF(36mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.46g을 얻었다(수율: 56%).Sub 2-120 (13 g, 18.09 mmol), Pd (PPh 3 ) 2 Cl 2 obtained in the above synthesis (1.27 g, 1.81 mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (3.86 g, 25.32 mmol), and anhydrous DMF (36 mL) using the synthesis method of 1-49 6.46 g Obtained (yield: 56%).
18. 3-25의 18. 3-25
합성예Synthesis Example
1) M 1-I-16의 합성1) Synthesis of M 1-I-16
5-bromo-1,1-dimethyl-1H-indene (26g, 116.53mmol), 9H-carbazole (19.49g, 116.53mmol), Pd2(dba)3 (3.20g, 3.50mmol), P(t-Bu)3 (1.89g, 9.32mmol), NaOt-Bu (33.60g, 349.60mmol), toluene (1223mL)을 넣은 후에 100 에서 반응을 진행한다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축 한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물 30.29g 를 얻었다(수율: 84%). 5-bromo-1,1-dimethyl-1H-indene (26g, 116.53mmol), 9H-carbazole (19.49g, 116.53mmol), Pd 2 (dba) 3 (3.20g, 3.50mmol), P (t-Bu ) 3 (1.89g, 9.32mmol), NaOt-Bu (33.60g, 349.60mmol) and toluene (1223mL) were added, and the reaction was carried out at 100. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain a product 30.29g (yield: 84%).
2) M 1-16 합성2) M 1-16 Synthesis
CHCl3 (429mL)과 M 1-I-16(30.20g, 97.61mmol), CHCl3 (215mL) + Br2 (11mL, 214.73mmol) 용액을 상기 M 1-1의 합성방법을 사용하여 생성물 22.34g을 얻었다(수율: 49%).CHCl 3 (429 mL), M 1-I-16 (30.20 g, 97.61 mmol), CHCl 3 (215 mL) + Br 2 (11 mL, 214.73 mmol) in solution 22.34 g using the synthesis method of M 1-1 Was obtained (yield 49%).
3) Sub 2-123 합성3) Sub 2-123 Synthesis
Sub 1-1 (8.21g, 47.73mmol), THF (210mL), M 1-16(22.30g, 47.73mmol), Pd(PPh3)4 (0.83g, 0.72mmol), K2CO3 (9.90g, 71.60mmol), 물 (105mL)을 상기 M 1-I-1 합성방법을 사용하여 생성물 14.00g 을 얻었다(수율: 57%).Sub 1-1 (8.21 g, 47.73 mmol), THF (210 mL), M 1-16 (22.30 g, 47.73 mmol), Pd (PPh 3 ) 4 (0.83 g, 0.72 mmol), K 2 CO 3 (9.90 g , 71.60 mmol) and water (105 mL) were used to synthesize 14.00 g of the product using the M 1-I-1 synthesis method (yield: 57%).
4) 3-25합성4) 3-25 synthetic
상기 합성에서 얻어진 Sub 2-123 (14g, 27.21mmol), Pd(PPh3)2Cl2
(1.91g, 2.72mmol), 1,8-Diazabicyclo[5.4.0]undec-7-ene(5.80g, 38.10mmol), 무수 DMF(54mL)을 상기 1-49의 합성방법을 사용하여 생성물 6.49g을 얻었다(수율: 55%).Sub 2-123 (14 g, 27.21 mmol) obtained in the above synthesis, Pd (PPh 3 ) 2 Cl 2 (1.91g, 2.72mmol), 1,8-Diazabicyclo [5.4.0] undec-7-ene (5.80g, 38.10mmol), anhydrous DMF (54mL) using the synthesis method of 1-49 6.49g (Yield 55%) was obtained.
Sub 1에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니다.The compound belonging to Sub 1 may be a compound as follows, but is not limited thereto.
또한, Sub 2에 속하는 화합물은 아래와 같은 화합물일 수 있으나, 이에 한정되는 것은 아니며, 표 1은 Sub 2에 속하는 일부 화합물의 FD-MS값을 나타낸 것이다.In addition, the compound belonging to Sub 2 may be the following compounds, but is not limited thereto. Table 1 shows FD-MS values of some compounds belonging to Sub 2.
[표 1] Sub 2의 FD-MS[Table 1] FD-MS of Sub 2
[표 2] Final Product의 FD-MS [Table 2] FD-MS of Final Product
한편, 상기에서는 화학식 1로 표시되는 본 발명의 합성예를 예시적으로 설명하였지만, 이들은 모두 Pd(II)-catalyzed oxidative cyclization 반응 (Org
.
Lett. 2011, 13, 5504), Suzuki cross-coupling 반응 등에 기초한 것으로, 구체적 합성예에 명시된 치환기 이외에 화학식 1에 정의된 다른 치환기 (R1 내지 R3)가 결합되더라도 상기 반응이 진행된다는 것을 당업자라면 쉽게 이해할 수 있을 것이다. 따라서, 본 발명에 구체적으로 명시되지 않은 치환기가 결합되더라도 상기 반응들은 진행할 것이다.On the other hand, the synthesis example of the present invention represented by the formula (1) has been described by way of example, all of these are Pd (II) -catalyzed oxidative cyclization reaction ( Org . Lett . 2011, 13, 5504), Suzuki cross-coupling reaction On the basis of this, it will be readily understood by those skilled in the art that the reaction proceeds even if other substituents (R1 to R3) defined in formula (1) in addition to the substituents specified in the specific synthesis examples are combined. Thus, the reactions will proceed even if substituents not specifically specified in the present invention are combined.
유기전기소자의 제조평가Manufacturing Evaluation of Organic Electrical Device
[[
실시예Example
1] One]
적색유기전기발광소자Red organic electroluminescent device
(인광호스트) Phosphorescent Host
본 발명의 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 상에 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine ("2-TNATA"로 약기함)막을 진공증착하여 60 nm 두께의 정공주입층을 형성한 후, 정공주입층 위에 정공수송 화합물로서 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl ("NPD"로 약기함) 막을 60 nm 두께로 진공증착하여 정공수송층을 형성하였다. 정공수송층 상부에 호스트로서는 상기 본 발명 화합물 1-14을 사용하였으며, 도판트 물질로 bis-(1-phenylisoquinoline)iridium(Ⅲ)acetylacetonate ("(piq)2Ir(acac)"로 약기함)를 95:5 중량비로 도핑하여 30nm 두께로 발광층을 증착하였다. 이어서 홀저지층으로 (1,1'-biphenyl-4-olato)bis(2-methyl-8-quinolinolato)aluminum ("BAlq"로 약기함)을 10nm 두께로 진공증착하고, 전자수송층으로 tris-(8-hydroxyquinoline)aluminum ("Alq3"로 약칭함)을 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로서 유기전기발광소자를 제조하였다An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer. First, a 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (abbreviated as "2-TNATA") film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate. After the hole injection layer was formed, a 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (abbreviated as "NPD") membrane was formed as a hole transport compound on the hole injection layer to a thickness of 60 nm. Vacuum deposition was performed to form a hole transport layer. Compound 1-14 of the present invention was used as a host on the hole transport layer, and bis- (1-phenylisoquinoline) iridium (III) acetylacetonate (abbreviated as "(piq) 2 Ir (acac)") was used as a dopant material. The light emitting layer was deposited to a thickness of 30 nm by doping at a weight ratio of 5: 5. Subsequently, (1,1'-biphenyl-4-olato) bis (2-methyl-8-quinolinolato) aluminum (abbreviated as "BAlq") was vacuum-deposited to a thickness of 10 nm with a holding layer and tris- () as an electron transporting layer. 8-hydroxyquinoline) aluminum (abbreviated as "Alq 3 ") was deposited to a thickness of 40 nm. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.
[[
실시예Example
2] 내지 [ 2] to [
실시예Example
20] 20]
레드유기전기발광소자Red organic electroluminescent device
실시예 2 내지 실시예20은, 발광층의 레드호스트 물질로 본 발명의 실시예에 따른 화합물 1-14 대신 하기 표 3에 기재된 본 발명의 각 화합물을 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.Examples 2 to 20 are the same as in Example 1 except that each compound of the present invention shown in Table 3 is used instead of compound 1-14 according to the embodiment of the present invention as a red host material of the emission layer. An organic electroluminescent device was manufactured by the method.
[[
비교예Comparative example
1] 내지 [ 1] to [
비교예3Comparative Example 3
]]
비교예 1 내지 비교예 3은, 발광층의 호스트 물질로 본 발명의 실시예에 따른 화합물 1-14 대신 각각 하기 비교화합물 1 내지 비교화합물을 사용한 점을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제조하였다.Comparative Examples 1 to 3 are organic in the same manner as in Example 1, except for using the following Comparative Compound 1 to Comparative Compound instead of Compound 1-14 according to the Example of the present invention as a host material of the emission layer. An electroluminescent device was prepared.
<비교화합물 1> <비교화합물 2> <비교화합물 3><Comparative Compound 1> <Comparative Compound 2> <Comparative Compound 3>
본 발명의 실시예 1 내지 실시예 20 및 비교예 1 내지 비교예3에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였고, 2500cd/m2 기준 휘도에서 맥사이언스사의 수명 측정 장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 3과 같다.Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared according to Examples 1 to 20 and Comparative Examples 1 to 3 of the present invention The T95 lifetime was measured using a McScience Life Measurement Equipment at 2500 cd / m 2 reference luminance, and the measurement results are shown in Table 3 below.
[표 3]TABLE 3
상기 표 3의 측정 결과로 알 수 있듯이, 본 발명의 일 실시예에 따른 화합물을 인광호스트 재료로 사용한 유기전기발광소자가 발광효율과 구동전압 그리고 수명을 현저히 개선시킬 수 있음을 확인하였다.As can be seen from the measurement results of Table 3, it was confirmed that the organic electroluminescent device using the compound according to an embodiment of the present invention as a phosphorescent host material can significantly improve the luminous efficiency, driving voltage and lifetime.
즉, 일반적인 호스트물질로 사용되는 CBP인 비교화합물 1 보다는 비교화합물 2 또는 3과 같은 구조의 코어를 가진 화합물이 우수한 소자 결과를 나타내었고, 비교화합물 2 및 3의 코어에 다른 치환기가 치환되어 있는 본 발명의 일 실시예에 따른 화합물들이 구동전압은 가장 낮고, 효율 및 수명은 극대화되는 가장 우수한 소자 결과를 나타내었다.That is, a compound having a core having the same structure as that of Comparative Compound 2 or 3 showed better device results than that of Comparative Compound 1, which is CBP, which is used as a general host material. Compounds according to an embodiment of the present invention showed the best device results with the lowest driving voltage, maximizing efficiency and lifetime.
이는 본 발명의 코어에 ET(Electron Transfer) 특성을 갖는 헤테로고리기 (실시예 1 내지 실시예 20)가 치환되면서 LUMO 에너지 값이 상대적으로 낮아져 전자 수송층으로 전자를 쉽게 받을 수 있고, 이로 인해 발광층 내의 charge balance를 향상시켜 결과적으로 낮은 구동 전압, 높은 효율 및 수명의 결과를 야기시킨 것으로 판단된다. 따라서 이는 본 발명의 코어에 ET 특성을 갖는 헤테로고리기가 치환되면서, 화학적 물리적 특성이 현저히 달라질 수 있음을 시사하고 있다.As the heterocyclic group (Examples 1 to 20) having an ET (Electron Transfer) property is substituted in the core of the present invention, the LUMO energy value is relatively low, thereby easily receiving electrons into the electron transporting layer. It is believed that improving the charge balance results in lower driving voltages, higher efficiency and longer lifetime. Therefore, this suggests that while the heterocyclic group having the ET property is substituted in the core of the present invention, the chemical and physical properties may be significantly changed.
특히, 실시예 2 및 실시예 7처럼 카바졸의 2차치환기로서 헤테로고리기가 치환될 경우에는 효율 및 수명이 더욱 극대화 되는 것을 알 수 있었다.In particular, when the heterocyclic group is substituted as a secondary substituent of carbazole like Example 2 and Example 7, it can be seen that the efficiency and life is further maximized.
이는 동일한 모핵일 지라도 특정 치환기가 도입됨에 따라 화합물의 energy level과 같은 화학적 특성이 달라지고, packing density와 같은 소자적 특성이 달라져 현저히 다른 소자 특성이 나타날 수 있음을 시사하고 있다.This suggests that even in the same parent nucleus, chemical properties such as energy level of the compound may be changed and specific device characteristics, such as packing density, may be different due to the introduction of specific substituents.
특히 인광호스트의 경우, 정공수송층 및 도펀트와의 상호관계를 파악해야 하는 바, 유사한 모핵을 사용하더라도 본 발명의 화합물이 인광호스트에서 나타내는 특징을 유추하기는 매우 어려울 것이다.In particular, in the case of phosphorescent host, it is very difficult to infer the characteristics of the compound of the present invention in the phosphorescent host even if a similar parent nucleus is used to grasp the correlation between the hole transport layer and the dopant.
[[
실시예Example
21] 21]
녹색유기전기발광소자Green Organic Light Emitting Diode
(인광호스트) Phosphorescent Host
본 발명의 화합물을 발광층의 발광 호스트 물질로 사용하여 통상적인 방법에 따라 유기전계 발광소자를 제작하였다. 먼저, 유리 기판에 형성된 ITO층(양극) 상에 2-TNATA막을 진공증착하여 60 nm 두께의 정공주입층을 형성한 후, 정공주입층 위에 정공수송 화합물로서 NPD 막을 60 nm 두께로 진공증착하여 정공수송층을 형성하였다. 정공 수송층 상부에 호스트로서는 본 발명 화합물 1-1을 사용하였으며, 도판트 물질로 tris(2-phenylpyridine)-iridium ("Ir(ppy)3"으로 약기함)을 95:5 중량비로 도핑하여 30nm 두께로 발광층을 증착하였다. 이어서 홀저지층으로 BAlq을 10 nm 두께로 진공증착하고, 전자수송층으로 Alq3 을 40 nm 두께로 성막하였다. 이후, 전자주입층으로 할로젠화 알칼리 금속인 LiF를 0.2 nm 두께로 증착하고, 이어서 Al을 150 nm의 두께로 증착하여 음극으로 사용함으로서 유기전기발광소자를 제조하였다An organic light emitting diode was manufactured according to a conventional method using the compound of the present invention as a light emitting host material of a light emitting layer. First, a 2-TNATA film is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm.Then, the NPD film is vacuum-deposited at a thickness of 60 nm as a hole transport compound on the hole injection layer. A transport layer was formed. Compound 1-1 of the present invention was used as a host on the hole transport layer, and a dopant material was doped with tris (2-phenylpyridine) -iridium (abbreviated as "Ir (ppy) 3 ") at a 95: 5 weight ratio of 30 nm thick. The light emitting layer was deposited by. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm with a holdoff layer, and Alq 3 was formed into a thickness of 40 nm with an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm as an electron injection layer, and then, Al was deposited to a thickness of 150 nm to prepare an organic electroluminescent device.
[[
실시예Example
22] 내지 [ 22] to [
실시예38Example 38
] ]
그린유기전기발광소자Green Organic Light Emitting Diode
실시예 22 내지 실시예38은 각각 발광층의 그린호스트 물질로서 본 발명의 실시예에 따른 화합물 1-1 대신 하기 표 4에 기재된 본 발명의 각 화합물을 사용한 점을 제외하고는 상기 실시예 21과 동일한 방법으로 유기전기발광소자를 제조하였다.Examples 22 to 38 are the same as in Example 21, except that each compound of the present invention shown in Table 4 was used instead of Compound 1-1 according to the embodiment of the present invention as a green host material of the emission layer. An organic electroluminescent device was manufactured by the method.
[[
비교예4Comparative Example 4
] 내지 [] To [
비교예Comparative example
6] 6]
비교예 4 내지 비교예 6은 각각 발광층의 호스트 물질로서 본 발명의 실시예에 따른 화합물 1-1 대신 각각 상기 비교화합물 1 내지 비교화합물을 사용한 점을 제외하고는 상기 실시예 21과 동일한 방법으로 유기전기발광소자를 제조하였다.Comparative Examples 4 to 6 were organic in the same manner as in Example 21, except that Comparative Compound 1 to Comparative Compound were used instead of Compound 1-1 according to the Example of the present invention, respectively, as a host material of the emission layer. An electroluminescent device was prepared.
본 발명의 실시예 21 내지 실시예 38, 비교예 4 내지 비교예 6에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 5000cd/m2 기준 휘도에서 맥사이언스사의 수명 측정 장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 4와 같다.Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 21 to 38 and Comparative Examples 4 to 6 of the present invention The T95 lifetime was measured using McScience's life measurement equipment at 5000 cd / m 2 reference luminance, and the measurement results are shown in Table 4 below.
[표 4]TABLE 4
상기 표 4의 결과로 알 수 있듯이, 본 발명의 유기발광소자용 재료를 그린인광호스트 재료로 사용한 유기전기발광소자는 비교예 4 내지 비교예 6보다 낮은 구동전압과 높은 발광효율 및 장수명을 나타내는 것을 확인할 수 있었다.As can be seen from the results of Table 4, the organic electroluminescent device using the organic light emitting device material of the present invention as a green phosphorescent host material has a lower driving voltage, higher luminous efficiency and longer life than Comparative Examples 4 to 6. I could confirm it.
다시 말해, 일반적인 호스트물질로 사용되는 CBP인 비교화합물 1 보다는 비교화합물 2 또는 3과 같은 코어를 가진 화합물이 우수한 소자 결과를 나타내었고, 비교화합물 2 또는 3의 코어에 다른 치환기가 치환되어 있는 본 발명의 일 실시예에 따른 화합물들이 구동전압은 가장 낮고, 효율 및 수명은 극대화되는 가장 우수한 소자 결과를 나타내었다. In other words, a compound having the same core as Comparative Compound 2 or 3 showed better device results than Comparative Compound 1, which is a CBP used as a general host material, and the present invention is substituted with another substituent on the core of Comparative Compound 2 or 3. Compounds according to the embodiment of the present invention showed the best device results with the lowest driving voltage, efficiency and lifetime are maximized.
이는 본 발명의 코어에 ET 특성을 갖는 헤테로고리기가 치환된 (실시예 21 내지 실시예 38) 경우에, LUMO 에너지 값이 상대적으로 낮아져 전자수송층으로 전자를 쉽게 받을 수 있고 이로 인해 발광층 내 charge balance를 향상시켜 결과적으로 낮은 구동 전압, 높은 효율 및 수명의 결과를 야기시킨 것으로 판단된다.This is because when the heterocyclic group having an ET characteristic is substituted in the core of the present invention (Examples 21 to 38), the LUMO energy value is relatively low, so that electrons can be easily received by the electron transport layer, thereby improving charge balance in the light emitting layer. It is believed that the improvement resulted in the result of low driving voltage, high efficiency and lifetime.
또한, 코어가 카바졸로 1차 치환되고, 이 카바졸에 2차 치환기로서 헤테로고리기가 치환될 경우(실시예 23 및 24, 실시예 30, 32 및 36등)에는 효율 및 수명이 더욱 극대화 되는 것을 알 수 있었다. 특히, 2차 치환기가 4,6-diphenyl-1,3,5-triazine-2-yl기인 화합물들(실시예 23, 30, 및 36)이 효율 및 수명을 가장 극대화 시키는 것으로 확인되었다.In addition, when the core is first substituted with carbazole and the heterocyclic group is substituted as the secondary substituent to the carbazole (Examples 23 and 24, Examples 30, 32 and 36, etc.), efficiency and lifespan are further maximized. Could know. In particular, compounds having secondary substituents of 4,6-diphenyl-1,3,5-triazine-2-yl groups (Examples 23, 30, and 36) have been found to maximize efficiency and longevity.
즉, 이는 동일한 모핵일 지라도 특정 치환기가 도입됨에 따라 화합물의 energy level과 같은 화학적 특성이 달라지고, packing density와 같은 소자적 특성이 달라져 현저히 다른 소자 특성이 나타날 수 있음을 시사하고 있다.That is, even if the same parent nucleus, it is suggested that the chemical properties such as the energy level of the compound and the device properties such as packing density is changed as the specific substituent is introduced, significantly different device properties.
특히 인광호스트의 경우 정공수송층 및 도펀트와의 상호관계를 파악해야 하는 바 유사한 코어를 사용하더라도 본 발명의 화합물이 인광호스트에서 나타내는 특징을 유추하기는 매우 어려울 것이다.In particular, in the case of a phosphorescent host, it is very difficult to infer the characteristics of the compound of the present invention in the phosphorescent host even if a similar core is used to understand the correlation between the hole transport layer and the dopant.
아울러, 전술한 소자 제작의 평가 결과에서는 발광층 관점에서 소자특성을 설명하였으나, 통상적으로 발광층으로 사용되는 재료들은 전술한 전자수송층, 전자주입층, 정공주입층, 정공수송층 및 발광보조층 등 유기전기소자의 유기물층으로 단일 또는 다른 재료와 혼합으로 사용될 수 있다. 따라서 전술한 이유로 본 발명의 화합물은 발광층 이외에 다른 유기물층, 예를 들어 전자수송층, 전자주입층, 정공주입층, 정공수송층 및 발광보조층 등에 단일 또는 다른 재료와 혼합으로 사용될 수 있다.In addition, in the evaluation results of the above-described device fabrication, the device characteristics were described in terms of the light emitting layer. However, materials generally used as the light emitting layer include organic electron devices such as the electron transport layer, the electron injection layer, the hole injection layer, the hole transport layer, and the light emitting auxiliary layer. It can be used in combination with a single or other material as an organic layer of. Therefore, the compounds of the present invention can be used in a single or other materials mixed with other organic material layers, for example, electron transport layer, electron injection layer, hole injection layer, hole transport layer and light emitting auxiliary layer in addition to the light emitting layer.
[[
실시예Example
39] 39]
그린유기전기발광소자Green Organic Light Emitting Diode
( (
발광층Light emitting layer
혼합 인광호스트) Mixed phosphorescent host)
먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 정공 주입층으로서 2-TNATA막을 진공증착하여 60 nm 두께로 형성하였다. 이어서, 상기 정공주입층상에 정공수송 화합물로서 NPD막을 60 nm 두께로 진공 증착하여 정공수송층을 형성하였다. 정공 수송층 상부에 호스트물질로서 본 발명의 화합물을, 도판트 물질로 Ir(ppy)3를 95:5 중량비로 도핑하여 30nm 두께로 발광층을 증착하였는데, 이때 호스트 물질로 본 발명의 화합물 1-11 과 1-44를 50 : 50 중량비로 혼합하여 사용하였다. 이어서, 상기 발광층상에 BAlq를 10nm 두께로 진공증착하여 정공저지층을 형성하고, 상기 정공저지층상에 Alq3을 40nm 두께로 전자수송층을 성막하였다. 이후, 전자수송층상에 할로젠화 알칼리 금속인 LiF를 0.2nm 두께로 증착하여 전자주입층을 형성하고, 이어서 Al을 150nm의 두께로 증착하여 음극을 형성함으로써 유기전기발광소자를 제조하였다.First, a 2-TNATA film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate as a hole injection layer to form a thickness of 60 nm. Subsequently, an NPD film was vacuum deposited to a thickness of 60 nm as a hole transport compound on the hole injection layer to form a hole transport layer. The light emitting layer was deposited to a thickness of 30 nm by doping the compound of the present invention as a host material on the hole transport layer with a weight ratio of 95: 5 of Ir (ppy) 3 as a dopant material. 1-44 was used by mixing in 50:50 weight ratio. Subsequently, a hole blocking layer was formed by vacuum depositing BAlq to a thickness of 10 nm on the light emitting layer, and an electron transport layer having a thickness of 40 nm on Alq 3 was formed on the hole blocking layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and then, an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.
[[
실시예Example
40] 내지 [ 40] to [
실시예Example
42] 42]
그린유기전기발광소자Green Organic Light Emitting Diode
( (
발광층Light emitting layer
혼합 인광호스트) Mixed phosphorescent host)
실시예 40 내지 실시예 42는 각각 발광층의 호스트 물질로 본 발명의 화합물 1-44 대신 하기 표 5에 기재된 본 발명의 각 화합물을 사용한 점을 제외하고는 상시 실시예 39와 동일한 방법으로 유기전기발광소자를 제조하였다.Examples 40 to 42 are organic electroluminescent in the same manner as in Example 39, except that each compound of the present invention shown in Table 5 is used instead of the compound 1-44 of the present invention as a host material of the emission layer. The device was manufactured.
본 발명의 실시예 39 내지 실시예 42에 의해 제조된 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치 (photoresearch) 사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 5000cd/m2 기준휘도에서 맥사이언스사의 수명측정장비를 통해 T95 수명을 측정하였으며, 그 측정 결과는 하기 표 5와 같다.Electroluminescence (EL) characteristics were measured by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared in Examples 39 to 42 of the present invention, 5000cd / m 2 The T95 life was measured using McScience's life measurement equipment at the reference luminance, and the measurement results are shown in Table 5 below.
[표 5]TABLE 5
상기 표 5는, 본 발명의 화합물 1-11을 사용하여 2종의 혼합된 인광 호스트 물질로 사용한 소자 측정 결과를 나타내었다.Table 5 shows the results of device measurements using Compound 1-11 of the present invention as two mixed phosphorescent host materials.
상기 표 5에서 알 수 있듯이, 가장 우수한 소자 측정 결과를 보인, Low band gap-type의 본 발명 화합물 1-11(실시예 23)과 triphenylene group을 도입한 Wide band gap-type의 본 발명 화합물인 1-44, 1-45, 2-38, 및 2-39를 혼합하여 2종의 인광 호스트 물질로 사용한 결과 단일 호스트물질을 사용했을 때보다 두 개의 혼합된 호스트 물질을 사용하였을 때, 효율 및 수명을 더욱 개선 시킬 수 있음을 확인할 수 있다.As can be seen in Table 5, the compound of the present invention of the wide band gap-type of the present invention introduced the compound 1-11 (Example 23) of the low band gap-type and triphenylene group showed the most excellent device measurement results The combination of -44, 1-45, 2-38, and 2-39 as two phosphorescent host materials resulted in greater efficiency and lifetime when two mixed host materials were used than when a single host material was used. It can be seen that it can be further improved.
이는 혼합된 두 개의 호스트 물질의 경우 단일 호스트 물질일 때 보다 band gap 및 T1값의 미세조정이 가능해지고, 이로 인해 도펀트에 전자 및 정공이 효율적으로 전달이 되어 효율이 상승된다고 예측할 수 있다. 또한, 분자 내 exciton(여기자) 발생 확률이 높아짐에 따라 수명도 증가되는 것으로 판단된다. This can be expected that in the case of two mixed host materials, the band gap and T1 values can be finely adjusted than in the case of a single host material, and thus, electrons and holes are efficiently transferred to the dopant, thereby increasing efficiency. In addition, as the probability of occurrence of exciton in the molecule increases, the lifespan also increases.
이상의 설명은 본 발명을 예시적으로 설명한 것에 불과한 것으로, 본 발명이 속하는 기술분야에서 통상의 지식을 가지는 자라면 본 발명의 본질적인 특성에서 벗어나지 않는 범위에서 다양한 변형이 가능할 것이다. 따라서, 본 명세서에 개시된 실시예들은 본 발명을 한정하기 위한 것이 아니라 설명하기 위한 것이고, 이러한 실시예에 의하여 본 발명의 사상과 범위가 한정되는 것은 아니다. 본 발명의 보호범위는 아래의 청구범위에 의하여 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.
CROSS-REFERENCE TO RELATED APPLICATIONCROSS-REFERENCE TO RELATED APPLICATION
본 특허출원은 2015년 12월 16일 한국에 출원한 특허출원번호 제10-2015-0180418호에 대해 미국 특허법 119조 내지 121조, 365조 (35 U.S.C §19조 내지 §121조, §365조)에 따라 우선권을 주장하며, 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다. 아울러, 본 특허출원은 미국 이외에 국가에 대해서도 위와 동일한 이유로 우선권을 주장하면 그 모든 내용은 참고문헌으로 본 특허출원에 병합된다.This patent application is filed with the Korean Patent Application No. 10-2015-0180418 filed on December 16, 2015 in the United States Patent Act, Sections 119 to 121, 365 (35 USC §19 to § 121, §365 ), The contents of which are hereby incorporated by reference in their entirety. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.
Claims (10)
- 하기 화학식 1로 표시되는 화합물:Compound represented by the following formula (1):<화학식 1><Formula 1>
상기 화학식 1에서,In Chemical Formula 1,X1은 S, O, C(R4)(R5) 또는 Si(R')(R'')이고,X 1 is S, O, C (R 4 ) (R 5 ) or Si (R ') (R''),R1 내지 R3은 서로 독립적으로 수소; 중수소; 할로겐; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; 및 이들의 조합으로 이루어진 군에서 선택되며, 이웃한 R1끼리, 이웃한 R2끼리, 이웃한 R3끼리, 또는 R2와 R3끼리 서로 결합하여 적어도 하나의 고리를 형성할 수 있으며, 단, 상기 R1 내지 R3 중 적어도 하나는 C6-C60의 아릴기; 플루오렌일기; 또는 O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기이며,R 1 to R 3 are each independently hydrogen; heavy hydrogen; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And it is selected from the group consisting of, adjacent to each other by R 1, the adjacent R 2 each other, in a small neighborhood to each other by R 3, or R 2 and R 3 bonded to each other may form at least one ring, with the proviso that At least one of R 1 to R 3 is a C 6 -C 60 aryl group; Fluorenyl group; Or a C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P,l는 0 내지 4의 정수이고, m 및 n은 각각 0 내지 3의 정수이며,l is an integer of 0 to 4, m and n are each an integer of 0 to 3,상기 R4, R5, R' 및 R'' 는 서로 독립적으로, 수소; 중수소; C1-C50의 알킬기; C2-C30의 알켄일기; C2-C30의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; C1-C30의 실릴기; C6-C60의 아릴기; O, N, S, Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; 및 -L'-N(Ra)(Rb)로 이루어진 군에서 선택되고, R4와 R5끼리 또는 R'과 R"끼리 서로 결합하여 고리를 형성할 수 있으며,R 4 , R 5 , R 'and R'' Are independently of each other, hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Of C 2 -C 30 Alkenyl groups; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; A silyl group of C 1 -C 30; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; And -L'-N (R a ) (R b ), and R 4 and R 5 or R 'and R "may be bonded to each other to form a ring.상기 L'은 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기;로 이루어진 군에서 선택되며,L 'is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; And C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si, and P,상기 Ra 및 Rb는 서로 독립적으로 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로 고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; 및 C6-C30의 아릴옥시기;로 이루어진 군에서 선택되고,R a and R b are each independently a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; And C 6 -C 30 An aryloxy group; selected from the group consisting of,상기 아릴기, 플루오렌일기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알킨일기, 알콕실기, 아릴옥시기, 아릴렌기, 플루오렌일렌기, R1 내지 R3 중 이웃한 기끼리 서로 결합하여 형성된 고리, 및 R2와 R3가 서로 결합하여 형성된 고리 각각은 중수소; 할로겐; 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기; C8-C20의 아릴알켄일기; 및 이들의 조합으로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환될 수 있다.Adjacent groups among the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, fluorenylene group, R 1 to R 3 A ring formed by bonding, and a ring formed by bonding of R 2 and R 3 to each other is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C 1 -C 20; An alkoxyl group of C 1 -C 20 ; An alkyl group of C 1 -C 20 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; Of C 6 -C 20 Aryl group; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C 3 -C 20 ; C 7 -C 20 arylalkyl group; Arylalkenyl group of C 8 -C 20 ; And one or more substituents selected from the group consisting of a combination thereof. - 제 1항에 있어서,The method of claim 1,상기 화학식 1은 하기 화학식 중 하나로 표시되는 것을 특징으로 하는 화합물:Formula 1 is a compound characterized in that represented by one of the following formula:<화학식 2> <화학식 3><Formula 2> <Formula 3>
상기 화학식 2 및 3에서, In Chemical Formulas 2 and 3,R1 내지 R3, l, m, n 및 X1은 제1항에서 정의된 것과 동일하며,R 1 to R 3 , l, m, n and X 1 are the same as defined in claim 1,s 및 u는 각각 0 내지 4의 정수이고, t 및 v는 각각 0 내지 6의 정수이며, s+t는 1 이상의 정수이고, u+v는 1 이상의 정수이며,s and u are each an integer of 0 to 4, t and v are each an integer of 0 to 6, s + t is an integer of 1 or more, u + v is an integer of 1 or more,L2 내지 L5는 서로 독립적으로, 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 및 이들의 조합으로 이루어진 군에서 선택되며,L 2 to L 5 are independently of each other, a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And combinations thereof.X2 및 X3는 서로 독립적으로 N, N-L1-Ar1, O, S, C(R10)(R11) 또는 Si(R18)(R19)이며, X2가 N일 경우 L2와 연결되고, X3가 N일 경우에는 L3와 연결되며,X 2 and X 3 are independently of each other N, NL 1 -Ar 1 , O, S, C (R 10 ) (R 11 ) or Si (R 18 ) (R 19 ) and L 2 when X 2 is N And if X 3 is N, then L 3 ,a, b, c, d, e, f, o, p, q, 및 r은 서로 독립적으로 0 내지 4의 정수이며, a, b, c, d, e, f, o, p, q, and r are integers from 0 to 4 independently of each other,R6 내지 R9 및 R12 내지 R17은 서로 독립적으로 수소; 중수소; 할로겐; C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C1-C50의 알킬기; C6-C60의 방향족 고리와 C3-C60의 지방족 고리의 융합고리기; C2-C20의 알켄일기; C2-C20의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; -L'-N(Ra)(Rb); 및 이들의 조합으로 이루어진 군에서 선택되며, R6 내지 R9 및 R12 내지 R17은 이웃한 기끼리 서로 결합하여 적어도 하나의 고리를 형성할 수 있고,R 6 to R 9 and R 12 to R 17 are each independently hydrogen; heavy hydrogen; halogen; C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C 1 -C 50 ; A fused ring group of an aromatic ring of C 6 -C 60 and an aliphatic ring of C 3 -C 60 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; -L'-N (R a ) (R b ); And combinations thereof, R 6 to R 9 and R 12 to R 17 may combine with each other to form at least one ring,상기 L1은 단일결합; C6-C60의 아릴렌기; 플루오렌일렌기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 및 이들의 조합으로 이루어진 군에서 선택되며, L 1 is a single bond; C 6 -C 60 arylene group; Fluorenylene groups; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; And combinations thereof.상기 Ar1은 C6-C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; C3-C60의 지방족고리와 C6-C60의 방향족고리의 융합고리기; C1-C50의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; -L'-N(Ra)(Rb); C1-C30의 알콕실기; C6-C30의 아릴옥시기; 및 이들의 조합으로 이루어진 군에서 선택되고,Ar 1 is a C 6 -C 60 aryl group; Fluorenyl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C 3 -C 60 and an aromatic ring of C 6 -C 60 ; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 20 ; An alkynyl group of C 2 -C 20 ; -L'-N (R a ) (R b ); An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; And combinations thereof,상기 R10, R11, R18 및 R19은 서로 독립적으로, 수소; 중수소; C1-C50의 알킬기; C2-C30의 알켄일기; C2-C30의 알킨일기; C1-C30의 알콕실기; C6-C30의 아릴옥시기; C1-C30의 실릴기; C6-C60의 아릴기; O, N, S, Si 및 P 로 이루어진 군에서 선택된 적어도 하나의 헤테로원자를 포함하는 C2-C60의 헤테로고리기; 플루오렌일기; -L'-N(Ra)(Rb); 및 이들의 조합으로 이루어진 군에서 선택되고, R10과 R11끼리 R18과 R19끼리 서로 결합하여 고리를 형성할 수 있으며,R 10 , R 11 , R 18 and R 19 are each independently hydrogen; heavy hydrogen; An alkyl group of C 1 -C 50 ; Alkenyl groups of C 2 -C 30 ; An alkynyl group of C 2 -C 30 ; An alkoxyl group of C 1 -C 30 ; C 6 -C 30 aryloxy group; A silyl group of C 1 -C 30; C 6 -C 60 aryl group; C 2 -C 60 heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; Fluorenyl group; -L'-N (R a ) (R b ); And selected from the group consisting of a combination thereof, R 10 And R 11 And R 18 And R 19 It can combine with each other to form a ring,상기 L', Ra 및 Rb는 제1항에서 정의된 것과 동일하다.L ′, R a and R b are the same as defined in claim 1. - 제 1항에 있어서, The method of claim 1,하기 화합물 중 하나인 것을 특징으로 하는 화합물:Compounds characterized in that one of the following compounds:
.
. - 제 1전극; 제 2전극; 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층;을 포함하는 유기전기소자에 있어서,A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode.상기 유기물층은 제 1항의 화합물을 함유하는 것을 특징으로 하는 유기전기소자.The organic material layer is an organic electroluminescent device comprising the compound of claim 1.
- 제 4항에 있어서,The method of claim 4, wherein상기 유기물층은 상기 유기물층의 정공주입층, 정공수송층, 발광보조층, 발광층, 전자수송보조층 및 전자수송층 중 적어도 하나의 층을 포함하며,The organic material layer includes at least one layer of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport auxiliary layer and an electron transport layer of the organic material layer,상기 유기물층에 함유된 화합물은 1종 단독 화합물 또는 2종 이상의 혼합물로 포함되는 것을 특징으로 하는 유기전기소자.The compound contained in the organic material layer is an organic electric device, characterized in that it comprises a single compound or a mixture of two or more.
- 제 5항에 있어서,The method of claim 5,상기 화합물은 상기 발광층의 인광호스트 물질로 사용되는 것을 특징으로 하는 유기전기소자.The compound is an organic electroluminescent device, characterized in that used as a phosphorescent host material of the light emitting layer.
- 제 4항에 있어서,The method of claim 4, wherein상기 제 1전극과 제 2전극의 일면 중 상기 유기물층과 반대되는 적어도 일면에 형성되는 광효율 개선층을 더 포함하는 유기전기소자.And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
- 제 4항에 있어서,The method of claim 4, wherein상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 또는 롤투롤 공정에 의해 형성되는 것을 특징으로 하는 유기전기소자.The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.
- 제 4항의 유기전기소자를 포함하는 디스플레이장치; 및Claim 4 display device comprising the organic electroluminescent element; And상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치.And a controller for driving the display device.
- 제 9항에 있어서,The method of claim 9,상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치.The organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, and a device for monochrome or white illumination.
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