WO2017090919A1 - Compound for organic electronic element, organic electronic element using same, and electronic device comprising same - Google Patents
Compound for organic electronic element, organic electronic element using same, and electronic device comprising same Download PDFInfo
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- WO2017090919A1 WO2017090919A1 PCT/KR2016/012921 KR2016012921W WO2017090919A1 WO 2017090919 A1 WO2017090919 A1 WO 2017090919A1 KR 2016012921 W KR2016012921 W KR 2016012921W WO 2017090919 A1 WO2017090919 A1 WO 2017090919A1
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 240
- 125000003118 aryl group Chemical group 0.000 claims description 73
- 230000005525 hole transport Effects 0.000 claims description 36
- 125000005842 heteroatom Chemical group 0.000 claims description 35
- 239000011368 organic material Substances 0.000 claims description 34
- 125000000623 heterocyclic group Chemical group 0.000 claims description 33
- 125000001931 aliphatic group Chemical group 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 23
- 229910052717 sulfur Inorganic materials 0.000 claims description 23
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- 238000002347 injection Methods 0.000 claims description 21
- 239000007924 injection Substances 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 21
- 125000003545 alkoxy group Chemical group 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 18
- 125000000732 arylene group Chemical group 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 16
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 125000000304 alkynyl group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000004104 aryloxy group Chemical group 0.000 claims description 12
- 229910052805 deuterium Inorganic materials 0.000 claims description 12
- -1 fused ring group Chemical group 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 8
- 125000005567 fluorenylene group Chemical group 0.000 claims description 8
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 238000005401 electroluminescence Methods 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 4
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 139
- 230000015572 biosynthetic process Effects 0.000 description 44
- 238000003786 synthesis reaction Methods 0.000 description 44
- 239000000463 material Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 14
- 238000001308 synthesis method Methods 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229960001866 silicon dioxide Drugs 0.000 description 12
- 229940125904 compound 1 Drugs 0.000 description 11
- 239000007858 starting material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000000434 field desorption mass spectrometry Methods 0.000 description 8
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- ZHQNDEHZACHHTA-UHFFFAOYSA-N 9,9-dimethylfluorene Chemical compound C1=CC=C2C(C)(C)C3=CC=CC=C3C2=C1 ZHQNDEHZACHHTA-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- GWOAJJWBCSUGHH-UHFFFAOYSA-N 1-bromo-4-(4-iodophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(I)C=C1 GWOAJJWBCSUGHH-UHFFFAOYSA-N 0.000 description 4
- LOXUVZPMEXKUEJ-UHFFFAOYSA-N 2-bromo-7-iodo-9,9-dimethylfluorene Chemical compound C1=C(I)C=C2C(C)(C)C3=CC(Br)=CC=C3C2=C1 LOXUVZPMEXKUEJ-UHFFFAOYSA-N 0.000 description 4
- UGFOTZLGPPWNPY-UHFFFAOYSA-N 7h-benzo[c]carbazole Chemical compound C1=CC=CC2=C3C4=CC=CC=C4NC3=CC=C21 UGFOTZLGPPWNPY-UHFFFAOYSA-N 0.000 description 4
- VFUDMQLBKNMONU-UHFFFAOYSA-N 9-[4-(4-carbazol-9-ylphenyl)phenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 VFUDMQLBKNMONU-UHFFFAOYSA-N 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
- KUBSCXXKQGDPPD-UHFFFAOYSA-N 3-bromo-9-phenylcarbazole Chemical compound C12=CC=CC=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 KUBSCXXKQGDPPD-UHFFFAOYSA-N 0.000 description 2
- 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 2
- ROEOVWIEALGNLM-UHFFFAOYSA-N 5h-benzo[b]carbazole Chemical compound C1=CC=C2C=C3C4=CC=CC=C4NC3=CC2=C1 ROEOVWIEALGNLM-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 0 C*N(*[Al])[Al]* Chemical compound C*N(*[Al])[Al]* 0.000 description 2
- GBHIEOBTVZEMQL-UHFFFAOYSA-N CC1(C)c(cc(cc2)N(c3ccccc3)c(cc3)cc4c3[s]c3cc(-c(cc5)cc(c6c(cccc7)c7c(cccc7)c7c66)c5[n]6-c5ccccc5)ccc43)c2-c2ccccc12 Chemical compound CC1(C)c(cc(cc2)N(c3ccccc3)c(cc3)cc4c3[s]c3cc(-c(cc5)cc(c6c(cccc7)c7c(cccc7)c7c66)c5[n]6-c5ccccc5)ccc43)c2-c2ccccc12 GBHIEOBTVZEMQL-UHFFFAOYSA-N 0.000 description 2
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000005129 aryl carbonyl group Chemical group 0.000 description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 2
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- QVHGAIGDBBZLFX-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1N(c1cc(-c2ccccc2C23c4ccccc4-c4ccccc24)c3cc1)c(cc1)cc2c1[s]c1c2ccc(-c(c2c3cccc2)cc(c2ccccc22)c3[n]2-c2ccccc2)c1 Chemical compound c(cc1)ccc1-c(cc1)ccc1N(c1cc(-c2ccccc2C23c4ccccc4-c4ccccc24)c3cc1)c(cc1)cc2c1[s]c1c2ccc(-c(c2c3cccc2)cc(c2ccccc22)c3[n]2-c2ccccc2)c1 QVHGAIGDBBZLFX-UHFFFAOYSA-N 0.000 description 2
- KQKITDIGXRYMAE-UHFFFAOYSA-N c(cc1)ccc1N(c(cc1)cc2c1[o]c1c2ccc(-c(cc2)cc(c3ccccc33)c2[n]3-c2ccc(ccc3ccccc33)c3c2)c1)c1ccccn1 Chemical compound c(cc1)ccc1N(c(cc1)cc2c1[o]c1c2ccc(-c(cc2)cc(c3ccccc33)c2[n]3-c2ccc(ccc3ccccc33)c3c2)c1)c1ccccn1 KQKITDIGXRYMAE-UHFFFAOYSA-N 0.000 description 2
- SIOFOWHAUYFNNZ-UHFFFAOYSA-N c1ccc(C2(c3cccc(N(c4ccccc4)c(cc4)cc5c4[s]c4c5ccc(-c(cc5)cc(c6cc7ccccc7cc66)c5[n]6-c5ccccc5)c4)c3-c3ccccc23)c2ccccc2)cc1 Chemical compound c1ccc(C2(c3cccc(N(c4ccccc4)c(cc4)cc5c4[s]c4c5ccc(-c(cc5)cc(c6cc7ccccc7cc66)c5[n]6-c5ccccc5)c4)c3-c3ccccc23)c2ccccc2)cc1 SIOFOWHAUYFNNZ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004404 heteroalkyl group Chemical group 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 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 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 1
- VXZCZCODBREKPY-UHFFFAOYSA-N 1-bromo-4-(3-iodophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC(I)=C1 VXZCZCODBREKPY-UHFFFAOYSA-N 0.000 description 1
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 1
- JEYLGFCAZBGCMC-UHFFFAOYSA-N 3-(4-bromophenyl)-9-phenylcarbazole Chemical compound C1=CC(Br)=CC=C1C1=CC=C(N(C=2C=CC=CC=2)C=2C3=CC=CC=2)C3=C1 JEYLGFCAZBGCMC-UHFFFAOYSA-N 0.000 description 1
- FDPBPKDNWCZVQR-UHFFFAOYSA-N 3-bromodibenzothiophene Chemical compound C1=CC=C2C3=CC=C(Br)C=C3SC2=C1 FDPBPKDNWCZVQR-UHFFFAOYSA-N 0.000 description 1
- AZFHXIBNMPIGOD-UHFFFAOYSA-N 4-hydroxypent-3-en-2-one iridium Chemical compound [Ir].CC(O)=CC(C)=O.CC(O)=CC(C)=O.CC(O)=CC(C)=O AZFHXIBNMPIGOD-UHFFFAOYSA-N 0.000 description 1
- JAUCIDPGGHZXRP-UHFFFAOYSA-N 4-phenyl-n-(4-phenylphenyl)aniline Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1NC(C=C1)=CC=C1C1=CC=CC=C1 JAUCIDPGGHZXRP-UHFFFAOYSA-N 0.000 description 1
- STJXCDGCXVZHDU-UHFFFAOYSA-N 7H-Dibenzo[c,g]carbazole Chemical compound N1C2=CC=C3C=CC=CC3=C2C2=C1C=CC1=CC=CC=C12 STJXCDGCXVZHDU-UHFFFAOYSA-N 0.000 description 1
- QRMLAMCEPKEKHS-UHFFFAOYSA-N 9,9-dimethyl-n-(4-phenylphenyl)fluoren-2-amine Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1NC(C=C1)=CC=C1C1=CC=CC=C1 QRMLAMCEPKEKHS-UHFFFAOYSA-N 0.000 description 1
- OGENPBMBOLTWLZ-UHFFFAOYSA-N 9-[4-(4-bromophenyl)phenyl]carbazole Chemical compound C1=CC(Br)=CC=C1C1=CC=C(N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 OGENPBMBOLTWLZ-UHFFFAOYSA-N 0.000 description 1
- NXWZNMCQLJIIAK-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1=CC=C(C=C1)I.C1(=CC=CC=C1)NC1=CC=CC2=CC=CC=C12 Chemical group BrC1=CC=C(C=C1)C1=CC=C(C=C1)I.C1(=CC=CC=C1)NC1=CC=CC2=CC=CC=C12 NXWZNMCQLJIIAK-UHFFFAOYSA-N 0.000 description 1
- MSBWQBKHNLKFLS-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1=CC=C(C=C1)I.C1=CC=CC2=C3C(=C4NC=5C=CC=CC5C4=C21)C=CC=C3 Chemical group BrC1=CC=C(C=C1)C1=CC=C(C=C1)I.C1=CC=CC2=C3C(=C4NC=5C=CC=CC5C4=C21)C=CC=C3 MSBWQBKHNLKFLS-UHFFFAOYSA-N 0.000 description 1
- NIGABCGCFFUCGV-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1=CC=C(C=C1)I.C1=CC=CC=2C1=C1NC3=CC=CC=C3C1=CC2 Chemical group BrC1=CC=C(C=C1)C1=CC=C(C=C1)I.C1=CC=CC=2C1=C1NC3=CC=CC=C3C1=CC2 NIGABCGCFFUCGV-UHFFFAOYSA-N 0.000 description 1
- MOCNGNGLTRMQQH-UHFFFAOYSA-N Brc(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-c1ccccc1 Chemical compound Brc(cc1)cc(c2ccccc22)c1[n]2-c(cc1)ccc1-c1ccccc1 MOCNGNGLTRMQQH-UHFFFAOYSA-N 0.000 description 1
- SYKQZBFJTKIGQN-UHFFFAOYSA-N Brc(cc1)ccc1-c1cccc(-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)c1 Chemical compound Brc(cc1)ccc1-c1cccc(-c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)c1 SYKQZBFJTKIGQN-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 1
- ZQVXGZDSERJQTC-UHFFFAOYSA-N CC1(C)OB(c(cc2)cc(c3ccccc33)c2[n]3-c(cc2)ccc2-c2ccccc2)OC1(C)C Chemical compound CC1(C)OB(c(cc2)cc(c3ccccc33)c2[n]3-c(cc2)ccc2-c2ccccc2)OC1(C)C ZQVXGZDSERJQTC-UHFFFAOYSA-N 0.000 description 1
- UBASCOPZFCGGAV-UHFFFAOYSA-N CC1(C)OB(c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)OC1(C)C Chemical compound CC1(C)OB(c(cc2)cc(c3ccccc33)c2[n]3-c2ccccc2)OC1(C)C UBASCOPZFCGGAV-UHFFFAOYSA-N 0.000 description 1
- QUOJYZWVQWDLAU-UHFFFAOYSA-N CC1(C)c(cc(cc2)N(c3ccccc3)c(cc3)cc4c3c3cc(-c(cc5)cc(c6c7c8ccccc8c8ccccc68)c5[n]7-c5ccccc5)ccc3[s]4)c2-c2ccccc12 Chemical compound CC1(C)c(cc(cc2)N(c3ccccc3)c(cc3)cc4c3c3cc(-c(cc5)cc(c6c7c8ccccc8c8ccccc68)c5[n]7-c5ccccc5)ccc3[s]4)c2-c2ccccc12 QUOJYZWVQWDLAU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003302 alkenyloxy 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
- 125000002102 aryl alkyloxo group Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 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
- 239000000872 buffer Substances 0.000 description 1
- ONXLXFJNXCHALX-UHFFFAOYSA-N c(cc1)ccc1-c(cc1)ccc1N(c1ccc(C2(c3ccccc3-c3ccccc23)c2ccccc2-2)c-2c1)c1cc([s]c(c2c3)ccc3-c(cc3)cc(c4ccccc44)c3[n]4-c3ccccc3)c2c2c1cccc2 Chemical compound c(cc1)ccc1-c(cc1)ccc1N(c1ccc(C2(c3ccccc3-c3ccccc23)c2ccccc2-2)c-2c1)c1cc([s]c(c2c3)ccc3-c(cc3)cc(c4ccccc44)c3[n]4-c3ccccc3)c2c2c1cccc2 ONXLXFJNXCHALX-UHFFFAOYSA-N 0.000 description 1
- CZMIKSPXDYGGCY-UHFFFAOYSA-N c(cc1)ccc1N(c(cc1)cc2c1c1cc(-c(cc3)cc(c4ccccc44)c3[n]4-c3ccc(ccc4ccccc44)c4c3)ccc1[o]2)c1ccccn1 Chemical compound c(cc1)ccc1N(c(cc1)cc2c1c1cc(-c(cc3)cc(c4ccccc44)c3[n]4-c3ccc(ccc4ccccc44)c4c3)ccc1[o]2)c1ccccn1 CZMIKSPXDYGGCY-UHFFFAOYSA-N 0.000 description 1
- FUMQCVPJFOROAT-UHFFFAOYSA-N c1ccc(C2(c3cccc(N(c4ccccc4)c(cc4)cc5c4c4cc(-c(cc6)cc(c7cc8ccccc8cc77)c6[n]7-c6ccccc6)ccc4[s]5)c3-c3c2cccc3)c2ccccc2)cc1 Chemical compound c1ccc(C2(c3cccc(N(c4ccccc4)c(cc4)cc5c4c4cc(-c(cc6)cc(c7cc8ccccc8cc77)c6[n]7-c6ccccc6)ccc4[s]5)c3-c3c2cccc3)c2ccccc2)cc1 FUMQCVPJFOROAT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 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
- 230000008021 deposition Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine 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
- 238000005286 illumination Methods 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- JYAVHXABZQYLTH-UHFFFAOYSA-N n-[4-(4-bromophenyl)phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC(Br)=CC=C1C1=CC=C(N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 JYAVHXABZQYLTH-UHFFFAOYSA-N 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
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
-
- 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
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- 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
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/115—Polyfluorene; Derivatives thereof
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.
- Efficiency, lifespan, and driving voltage are related to each other, and as efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Joule heating generated during driving decreases. It shows a tendency to increase the life.
- a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emitting auxiliary according to each light emitting layer (R, G, B). It is time to develop the floor.
- electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.
- the OLED device is mainly formed by a deposition method, which requires development of a material that can withstand a long time during deposition, that is, a material having strong heat resistance.
- the materials constituting 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, a light emitting auxiliary layer material, etc.
- a hole injection material such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a light emitting auxiliary layer material, etc.
- the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials continues to be required, and in particular, the development of materials for the light emitting auxiliary layer and the hole transport layer is urgently required.
- Embodiments of the present invention to solve the problems of the above-described background, the discovery of a compound having a novel structure, and also when the compound is applied to an organic electric device greatly improve the luminous efficiency, stability and life of the device It turns out that you can.
- an object of the present invention is to provide a novel compound, an organic electric device, and an electronic device using the same.
- the present invention provides a compound represented by the following formula (1) and a composition for a hole-passing layer or a light-emitting auxiliary layer comprising the same, and an organic electric device comprising the compound.
- 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.
- heteroalkyl group means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.
- alkenyl group As used herein, the terms “alkenyl group”, “alkenyl group” or “alkynyl group” have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise stated, and include straight or branched chain groups. It is not limited to this.
- 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.
- alkenoxyl group means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.
- 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.
- aryl group and “arylene group” have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.
- an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction.
- the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.
- aryl or "ar” means a radical substituted with an aryl group.
- an arylalkyl group is an alkyl group substituted with an aryl group
- an arylalkenyl group is an alkenyl group substituted with an aryl group
- the radical substituted with an aryl group has the carbon number described herein.
- an arylalkoxy group means an alkoxy group substituted with an aryl group
- an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group
- an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group.
- the arylcarbonyl group is a carbonyl group substituted with an aryl group.
- heteroalkyl means an alkyl including one or more heteroatoms unless otherwise indicated.
- heteroaryl group or “heteroarylene group” means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.
- heterocyclic group includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.
- heteroatom refers to N, O, S, P or Si unless otherwise stated.
- Heterocyclic groups may also include rings comprising SO 2 instead of carbon forming the ring.
- a “heterocyclic group” includes the following compounds.
- aliphatic as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms
- aliphatic ring means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
- ring refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.
- heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
- carbonyl used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
- ether as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.
- substituted in the term “substituted or unsubstituted” as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxyl 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 substituted by deuterium aryl group, a C 8 ⁇ C 20 aryl alkenyl group, a silane group, a boron Group, germanium group, and C 2 ⁇ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of,
- 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.
- the present invention provides a compound represented by the following formula (1).
- a and B are each selected from the group consisting of the following formulas (1-1) and (1-2) and different from each other,
- Ar 1 , Ar 2 and Ar 3 are each independently a C 6 ⁇ C 60 aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; Is selected from the group consisting of
- L 1 and L 2 are each independently a single bond; C 6 ⁇ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; And a C 2 ⁇ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and
- n is an integer from 0 to 4
- m, p, o are integers from 0 to 3 and when m, n, o, p is 1 or more, R 1 , R 2 , R 3 and R 4 are each independently hydrogen.
- the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); 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 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -
- the compound represented by the formula (1) includes a compound represented by the following formula (2) or formula (3).
- R 1 , R 2 , R 3 , R 4 , m, n, o, p, L 1 , L 2 , Ar 1 , Ar 2 , Ar 3 is represented by the formula ( As defined in 1).
- the compound represented by the formula (1) includes a compound represented as follows.
- the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer. It includes, the organic material layer provides an organic electric device comprising a compound represented by the formula (1).
- the present invention is an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, the hole transport layer and the hole transport layer formed between the first electrode and the light emitting layer And a light emitting auxiliary layer formed between the light emitting layer, wherein the light emitting auxiliary layer contains a compound represented by the following Chemical Formula (1), and the hole transport layer contains a compound represented by the following Chemical Formula (5).
- An organic electric device is provided.
- the present invention is an organic electroluminescence comprising a composition in which at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer is a compound of the formula (1) alone or two or more compounds different in structure Provided is an element.
- the hole transport layer or the light emitting auxiliary layer may include a composition in which the compound is mixed alone or in combination of two or more compounds having different structures.
- the present invention provides an organic electroluminescent device comprising the compound of formula (1), wherein the light emitting auxiliary layer, the hole transport layer containing a compound represented by the following formula (5).
- Ar 4 and Ar 5 are independently of each other C 6 ⁇ C 60 An aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; C 1 ⁇ C 50 Alkyl group; C 2 ⁇ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); wherein L 'is a single bond; C 6 ⁇ C 60 arylene group; Fluorenylene group; C 3 ⁇ C 60 A fused ring group of an aliphatic ring and an aromatic ring of C 6 ⁇ C 60 ; and a heterocyclic group of C 2 ⁇ C 60 , wherein R a and R
- Ar 6 is selected from any one of the following formulas (5-a), (5-b) and (5-c).
- a, b, c are integers from 0 to 4, R 5 , R 6 and R 7 are the same as or different from each other, and independently from each other deuterium; halogen; C 6 ⁇ C 60 Aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; C 1 ⁇ C 50 Alkyl group; C 2 ⁇ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); or R 5 , R 6, and R 7 are each the same as or different from each other when a, b, and c are two or more, and A plurality of R 5 or a plurality of R 5
- L 3 and L 5 are each independently a C 6 ⁇ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; And C 2 ⁇ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P;
- L 4 is a single bond of C 6 ⁇ C 60 ; Arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; And C 2 ⁇ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P;
- Ar 7 , Ar 8 and Ar 9 are each independently a C 6 ⁇ C 60 aryl group; Fluorenyl group; C 2 ⁇ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ⁇ C 60 of aliphatic rings and C 6 ⁇ C 60; Is selected from the group consisting of
- the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); 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 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -
- the compound represented by the formula (5) includes a compound represented by the following formula (5-1 to 5-71).
- the organic electric device 100 includes a first electrode 120, a second electrode 180, and a first electrode 120 and a second electrode formed on a substrate 110.
- An organic material layer including a compound represented by Chemical Formula 1 is provided between 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 material layer may sequentially include the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the light emitting auxiliary layer 151, the electron transport layer 160, and the electron injection layer 170 on the first electrode 120. It may include.
- the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.
- the organic electroluminescent device may be manufactured using a PVD method.
- an anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and thereon, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and a light emitting auxiliary layer 151.
- the organic material layer including the electron transport layer 160 and the electron injection layer 170 it can be prepared by depositing a material that can be used as a cathode thereon.
- the present invention includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer includes a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer, and the organic material layer is represented by Chemical Formula (1).
- the organic material layer includes a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer, and the organic material layer is represented by Chemical Formula (1).
- an organic electroluminescent device comprising a compound contained in).
- the present invention includes a compound according to the formula (1) in at least one layer of the hole injection layer, hole transport layer, light emitting auxiliary layer, light emitting layer, the compound is one or a mixture of two or more compounds It provides an organic electric device comprising the composition.
- the present invention provides an organic electroluminescent device comprising at least one kind of the compound in the light emitting auxiliary layer.
- the present invention may further include an optical efficiency improvement layer formed on at least one of 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 device.
- the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process, the organic layer is an electron transport material containing the compound It provides an organic electric element, characterized in that.
- the present invention provides an organic electric device, characterized in that the same or different compounds of the compound represented by the formula (1) are mixed and used in the organic material layer.
- the present invention also provides an organic electroluminescent device comprising a hole transport layer and a light emitting auxiliary layer comprising a compound represented by the formula (1), in another aspect a hole transport layer comprising a compound represented by the formula (1) or An organic electric device comprising a light emitting auxiliary layer is provided.
- the present invention is a display device comprising the above-mentioned organic electric element; And a controller for driving the display device.
- the organic electronic device provides an electronic device according to the present invention, wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochromatic or white illumination 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.
- Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2, but is not limited thereto.
- Sub 1-I 73.92 g, 200.2 mmol
- Sub 1-2-2 112.0 g, 300.3 mmol
- Sub 1-II (93.9 g, 200.2 mmol) and Sub 1-2-3 (116.8 g, 300.3 mmol) were obtained using the synthesis method of Sub 1-1 to obtain 90.8 g (yield: 75%) of the product.
- Sub 1-III (74.1 g, 200.2 mmol) and Sub 1-2-4 (112.0 g, 300.3 mmol) were obtained using the synthesis method of Sub 1-1 to obtain 70.5 g (yield: 72%) of the product.
- Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3, but is not limited thereto.
- Bromobenzene (37.1 g, 236.2 mmol) was added to a round bottom flask and dissolved with toluene (2200 mL), followed by aniline (20 g, 214.8 mmol), Pd 2 (dba) 3 (9.83 g, 10.7 mmol), P ( t -Bu ) 3 (4.34 g, 21.5 mmol) and NaO t -Bu (62 g, 644.3 mmol) were added in this order and stirred at 100 ° C.
- Sub 2 is as follows, but is not limited thereto.
- Sub 2-1 (8.0 g, 47.3 mmol) was added to a round bottom flask and dissolved with toluene (500 mL), then Sub 1-1 (26.2 g, 52.0 mmol), Pd 2 (dba) 3 (2.2 g, 2.4 mmol) ), P ( t -Bu) 3 (1 g, 4.73 mmol) and NaO t -Bu (13.6 g, 141.8 mmol) were added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 25.0g (yield: 81%).
- L is L 3 or L 5 as defined in formula (2-a), formula (2-b), formula (2-c).
- N-phenylnaphthalen-1-amine 4 -bromo-4'-iodo-1,1'-biphenyl in (65.8 g, 300 mmol) ( 129.2 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 89.2 g (yield: 66%) of the product.
- Sub 4 of Scheme 4 may be synthesized by the reaction route of Scheme 5 below.
- N- (4'-bromo- [1,1'-biphenyl] -4-yl) -N-phenylnaphthalen-1-amine (10.8 g, 24 mmol) is dissolved in toluene, followed by N-phenylnaphthalen-1-amine (4.4 g, 20 mmol), Pd 2 (dba) 3 (0.05 equiv), PPh 3 (0.1 equiv) and NaO t -Bu (3 equiv) were then added, and the mixture was stirred and refluxed at 100 ° C. for 24 hours.
- N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N 1 -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm.
- 2,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm as a hole transporting compound on the membrane to form a hole transport layer.
- inventive compounds and Comparative Examples were vacuum-deposited to a thickness of 20 nm as a light emission auxiliary layer material to form a light emission auxiliary layer.
- CBP 4,4'-N, N'-dicarbazole-biphenyl
- Ir (ppy) 3 tris (2-phenylpyridine) -iridium] as a host.
- the light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping at 95: 5 weight.
- BAlq (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum
- BAlq the electron transport layer Tris (8-quinolinol) aluminum
- Alq3 the electron transport layer Tris (8-quinolinol) aluminum
- the electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement result was measured at a luminance of 5000 cd / m2.
- the T95 life was measured using a life measurement instrument manufactured by McScience.
- the following table shows the results of device fabrication and evaluation.
- An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light emitting auxiliary layer was not used.
- An organic electroluminescent device was manufactured in the same manner as in Example 1, except that a light emitting auxiliary layer was formed using Comparative Compound 1 instead of the compound of the present invention.
- Example 1 Compound Voltage Current density Brightness (cd / m2) Efficiency LifetimeT (95) CIE (x, y) Comparative Example (1) - 6.0 21.7 5000.0 23.0 61.8 (0.31, 0.61) Comparative Example (2) Comparative Compound 1 6.2 14.3 5000.0 35.0 94..5 (0.31, 0.60) Example (1) Compound (1-1) 5.6 10.9 5000.0 45.8 118.1 (0.31, 0.60) Example (2) Compound (1-2) 5.5 11.3 5000.0 44.3 114.2 (0.32, 0.61) Example (3) Compound (1-3) 5.6 11.2 5000.0 44.7 117.7 (0.31, 0.61) Example (4) Compound (1-4) 5.7 10.7 5000.0 46.7 114.1 (0.33, 0.60) Example (5) Compound (1-6) 5.7 10.8 5000.0 46.4 113.6 (0.31, 0.60) Example (6) Compound (1-7) 5.5 11.5 5000.0 43.4 119.9 (0.32, 0.61) Example (7) Compound (1-8) 5.5 11.5 5000.0 43.5 113.8 (0.32, 0.61)
- Comparative Example 1 using the light emitting auxiliary layer and Comparative Examples 1 to 20 using the compound of the present invention were superior to Comparative Example 1, which did not use the light emitting auxiliary layer.
- Inventive compounds substituted with positions 2 and 3 asymmetrically to dibenzotiophen or dibenzofuran showed the best results, compared to Comparative Compound 1, in which both carbazole and amine groups were substituted at position 2.
- N 1 - (naphthalen-2- yl) -N 4 N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N 1 -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm.
- the above-mentioned compound represented by the formula (13) as a hole transport compound was vacuum deposited to a thickness of 60 nm on this film to form a hole transport layer.
- the inventive compound represented by the formula (1) was vacuum deposited to a thickness of 20 nm as a light emitting auxiliary layer material to form a light emitting auxiliary layer.
- CBP 4,4'-N, N'-dicarbazole-biphenyl
- piq 2 Ir (acac)
- bis- A light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping 1-phenylisoquinolyl) iridium (III) acetylacetonate] at a weight of 95: 5.
- BAlq (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum
- BAlq the electron transport layer Tris (8-quinolinol) aluminum
- Alq3 the electron transport layer Tris (8-quinolinol) aluminum
- the electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage.
- the T95 life was measured using a life measurement instrument manufactured by McScience.
- the following table shows the results of device fabrication and evaluation.
- An organic electroluminescent device was manufactured in the same manner as in Example 2, except that Comparative Compound 1 was used as the light emitting auxiliary layer.
- the examples using the compound represented by the formula (5) as the hole transport layer and the compound represented by the formula (1) as the light emitting auxiliary layer are the same under different conditions, but the comparative compound 1 It can be seen that the driving voltage, lifespan, and especially luminous efficiency of the organic electroluminescent device are significantly improved than the comparative example used as the light emitting auxiliary layer. This is because when the physical and chemical properties of the compound represented by Formula 1 described in Table 5 together with the compound represented by Formula 5 constitute a device, the combination improves the performance of the device as a whole by synergistically synergistic action. It is feed.
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Abstract
The present invention provides a novel compound capable of improving the luminous efficiency, stability, and life of an element, an organic electronic element using same, and an electronic device comprising same.
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.
유기 전기 발광소자에 있어 가장 문제시되는 것은 수명과 효율인데, 디스플레이가 대면적화되면서 이러한 효율이나 수명 문제는 반드시 해결해야 되는 상황이다.The biggest problem for organic electroluminescent devices is life and efficiency. As the display becomes larger, such efficiency and life problems must be solved.
효율과 수명, 구동전압 등은 서로 연관이 있으며, 효율이 증가되면 상대적으로 구동전압이 떨어지고, 구동전압이 떨어지면서 구동시 발생되는 주울열(Joule heating)에 의한 유기물질의 결정화가 적어져 결과적으로 수명이 높아지는 경향을 나타낸다.Efficiency, lifespan, and driving voltage are related to each other, and as efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Joule heating generated during driving decreases. It shows a tendency to increase the life.
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.However, simply improving the organic material layer does not maximize the efficiency. This is because a long life and high efficiency can be achieved at the same time when an optimal combination of energy level, T1 value, and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.
또한, 최근 유기 전기 발광소자에 있어 정공수송층에서의 발광 문제를 해결하기 위해서는 반드시 정공수송층과 발광층 사이에 발광보조층이 존재하여야 하며, 각각의 발광층(R, G, B)에 따른 서로 다른 발광보조층의 개발이 필요한 시점이다.In addition, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emitting auxiliary according to each light emitting layer (R, G, B). It is time to develop the floor.
일반적으로 전자수송층에서 발광층으로 전자(electron)가 전달되고 정공(hole)이 정공수송층에서 발광층으로 전달되어 재조합(recombination)에 의해 엑시톤(exciton)이 생성된다. In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.
하지만 정공수송층에 사용되는 물질의 경우 낮은 HOMO 값을 가져야 하기 때문에 대부분 낮은 T1 값을 가지며, 이로 인해 발광층에서 생성된 엑시톤(exciton)이 정공수송층으로 넘어가게 되어 결과적으로 발광층 내 전하 불균형(charge unbalance)을 초래하여 정공수송층 계면에서 발광하게 된다.However, in the case of the material used in the hole transport layer, since it has to have a low HOMO value, most have a low T1 value, which causes the exciton generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. This causes light emission at the hole transport layer interface.
정공수송층 계면에서 발광될 경우, 유기전기소자의 색순도 및 효율이 저하되고 수명이 짧아지는 문제점이 발생하게 된다. 따라서 높은 T1 값을 가지며, 정공 수송층 HOMO 에너지 준위와 발광층의 HOMO 에너지 준위 사이의 HOMO 준위를 갖는 발광보조층이 개발이 절실히 요구된다.When emitting light at the hole transport layer interface, the color purity and efficiency of the organic electric element is reduced and the life is shortened. Therefore, the development of a light emitting auxiliary layer having a high T1 value and a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level is urgently required.
한편, 유기전기소자의 수명단축 원인 중 하나인 양극전극(ITO)으로부터 금속 산화물이 유기층으로 침투확산되는 것을 지연시키면서, 소자 구동시 발생되는 주울열(Joule heating)에 대해서도 안정된 특성, 즉 높은 유리 전이온도를 갖는 정공 주입층 재료에 대한 개발이 필요하다. 정공수송층 재료의 낮은 유리전이 온도는 소자 구동시, 박막 표면의 균일도를 저하시키는 특성이 있는바, 이는 소자수명에 큰 영향을 미치는 것으로 보고되고 있다. 또한, OLED 소자는 주로 증착 방법에 의해 형성되는데, 증착시 오랫동안 견딜 수 있는 재료, 즉 내열특성이 강한 재료 개발이 필요한 실정이다.On the other hand, while delaying the penetration of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has the property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the device life. In addition, the OLED device is mainly formed by a deposition method, which requires development of a material that can withstand a long time during deposition, that is, a material having strong heat resistance.
즉, 유기전기소자가 갖는 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 유기물층을 이루는 물질, 예컨대 정공주입 물질, 정공수송 물질, 발광 물질, 전자수송 물질, 전자주입 물질, 발광보조층 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 발광보조층과 정공수송층의 재료에 대한 개발이 절실히 요구되고 있다.That is, in order to fully exhibit the excellent characteristics of the organic electric device, the materials constituting 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, a light emitting auxiliary layer material, etc., are stable and efficient. Supported by the material should be preceded, but development of a stable and efficient organic material layer for an organic electric device has not been made yet. Therefore, the development of new materials continues to be required, and in particular, the development of materials for the light emitting auxiliary layer and the hole transport layer is urgently required.
참고한 선행문헌으로는 KR1020130076842 A가 있다. As a reference document, there is KR1020130076842 A.
상술한 배경기술의 문제점을 해결하기 위한 본 발명의 실시예는, 신규한 구조를 갖는 화합물을 밝혀내었으며, 또한 이 화합물을 유기전기소자에 적용시 소자의 발광효율, 안정성 및 수명을 크게 향상시킬 수 있다는 사실을 밝혀내었다.Embodiments of the present invention to solve the problems of the above-described background, the discovery of a compound having a novel structure, and also when the compound is applied to an organic electric device greatly improve the luminous efficiency, stability and life of the device It turns out that you can.
이에 본 발명은 신규한 화합물 및 이를 이용한 유기전기소자, 전자장치를 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a novel compound, an organic electric device, and an electronic device using the same.
본 발명은 하기 화학식 (1)로 표시되는 화합물 및 이를 포함하는 정공수승층 또는 발광보조층용 조성물과 상기 화합물을 함유하는 것을 특징으로 하는 유기전기소자를 제공한다.The present invention provides a compound represented by the following formula (1) and a composition for a hole-passing layer or a light-emitting auxiliary layer comprising the same, and an organic electric device comprising the compound.
화학식 (1)Formula (1)
본 발명에 따른 화합물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 고내열성을 달성할 수 있고, 소자의 색순도 및 수명을 크게 향상시킬 수 있다.By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and life of the device can be greatly improved.
본 발명에 따른 화합물을 이용함으로써 소자의 높은 발광효율, 낮은 구동전압, 고내열성을 달성할 수 있고, 소자의 색순도 및 수명을 크게 향상시킬 수 있다.By using the compound according to the present invention, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and life of the device can be greatly improved.
100 : 유기전기소자 110 : 기판100: organic electric element 110: substrate
120 : 제 1전극(양극) 130 : 정공주입층120: first electrode (anode) 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 2전극(음극)180: second electrode (cathode)
이하, 본 발명의 실시예를 참조하여 상세하게 설명한다. 본 발명을 설명함에 있어, 관련된 공지 구성 또는 기능에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명은 생략한다.Hereinafter, with reference to the embodiment of the present invention will be described in detail. 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.
또한, 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 구성요소와 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 addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only to distinguish 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".
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 "헤테로알킬기"는 알킬기를 구성하는 탄소원자 중 하나 이상이 헤테로원자로 대체된 것을 의미한다.The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.
본 발명에 사용된 용어 "알켄일기", "알케닐기" 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 terms "alkenyl group", "alkenyl group" or "alkynyl group" have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise stated, and include straight or branched chain groups. It is not limited to this.
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 "알켄옥실기", "알켄옥시기", "알켄일옥실기", 또는 "알켄일옥시기"는 산소 라디칼이 부착된 알켄일기를 의미하며, 다른 설명이 없는 한 2 내지 60의 탄소수를 가지며, 여기에 제한되는 것은 아니다.As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.
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 "아릴기" 및 "아릴렌기"는 다른 설명이 없는 한 각각 6 내지 60의 탄소수를 가지며, 이에 제한되는 것은 아니다. 본 발명에서 아릴기 또는 아릴렌기는 단일 고리 또는 다중 고리의 방향족을 의미하며, 이웃한 치환기가 결합 또는 반응에 참여하여 형성된 방향족 고리를 포함한다. 예컨대, 아릴기는 페닐기, 비페닐기, 플루오렌기, 스파이로플루오렌기일 수 있다.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, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirofluorene group.
접두사 "아릴" 또는 "아르"는 아릴기로 치환된 라디칼을 의미한다. 예를 들어 아릴알킬기는 아릴기로 치환된 알킬기이며, 아릴알켄일기는 아릴기로 치환된 알켄일기이며, 아릴기로 치환된 라디칼은 본 명세서에서 설명한 탄소수를 가진다. The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, an arylalkyl group is an alkyl group substituted with an aryl group, an arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described herein.
또한 접두사가 연속으로 명명되는 경우 먼저 기재된 순서대로 치환기가 나열되는 것을 의미한다. 예를 들어, 아릴알콕시기의 경우 아릴기로 치환된 알콕시기를 의미하며, 알콕실카르보닐기의 경우 알콕실기로 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 alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.
본 명세서에서 사용된 용어 "헤테로알킬"은 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하는 알킬을 의미한다. 본 발명에 사용된 용어 "헤테로아릴기" 또는 "헤테로아릴렌기"는 다른 설명이 없는 한 각각 하나 이상의 헤테로원자를 포함하는 탄소수 2 내지 60의 아릴기 또는 아릴렌기를 의미하며, 여기에 제한되는 것은 아니며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 이웃한 작용기기가 결합하여 형성될 수도 있다.As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms, each containing one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.
본 발명에 사용된 용어 "헤테로고리기"는 다른 설명이 없는 한 하나 이상의 헤테로원자를 포함하고, 2 내지 60의 탄소수를 가지며, 단일 고리 및 다중 고리 중 적어도 하나를 포함하며, 헤테로지방족 고리 및 헤테로방향족 고리를 포함한다. 이웃한 작용기가 결합하여 형성될 수도 있다.As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.
본 명세서에서 사용된 용어 "헤테로원자"는 다른 설명이 없는 한 N, O, S, P 또는 Si를 나타낸다.The term "heteroatom" as used herein refers to N, O, S, P or Si unless otherwise stated.
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 instead of carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.
다른 설명이 없는 한, 본 발명에 사용된 용어 "지방족"은 탄소수 1 내지 60의 지방족 탄화수소를 의미하며, "지방족고리"는 탄소수 3 내지 60의 지방족 탄화수소 고리를 의미한다.Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "고리"는 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화고리를 포함한다.Unless otherwise stated, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof. Saturated or unsaturated rings.
전술한 헤테로화합물 이외의 그 밖의 다른 헤테로화합물 또는 헤테로라디칼은 하나 이상의 헤테로원자를 포함하며, 여기에 제한되는 것은 아니다.Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.
다른 설명이 없는 한, 본 발명에 사용된 용어 "카르보닐"이란 -COR'로 표시되는 것이며, 여기서 R'은 수소, 탄소수 1 내지 20 의 알킬기, 탄소수 6 내지 30 의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise stated, the term "carbonyl" used in the present invention is represented by -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. Cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.
다른 설명이 없는 한, 본 발명에 사용된 용어 "에테르"란 -R-O-R'로 표시되는 것이며, 여기서 R 또는 R'은 각각 서로 독립적으로 수소, 탄소수 1 내지 20의 알킬기, 탄소수 6 내지 30의 아릴기, 탄소수 3 내지 30의 사이클로알킬기, 탄소수 2 내지 20의 알켄일기, 탄소수 2 내지 20의 알킨일기, 또는 이들의 조합인 것이다.Unless otherwise specified, the term "ether" as used herein is represented by -RO-R ', wherein R or R' are each independently of each other hydrogen, an alkyl group having 1 to 20 carbon atoms, It is an aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.
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 알콕실기, 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 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" as used herein refers to deuterium, halogen, amino, nitrile, nitro, C 1 -C 20 alkyl, C 1 -C 20 alkoxyl 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 substituted by deuterium aryl group, a C 8 ~ C 20 aryl alkenyl group, a silane group, a boron Group, germanium group, and C 2 ~ C 20 It is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.
또한 명시적인 설명이 없는 한, 본 발명에서 사용되는 화학식은 하기 화학식의 지수 정의에 의한 치환기 정의와 동일하게 적용된다.In addition, unless otherwise specified, the formulas used in the present invention apply in the same manner as the substituent definitions by the exponential definition of the following formula.
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.
이하, 본 발명의 일 측면에 따른 화합물 및 이를 포함하는 유기전기소자에 대하여 설명한다. Hereinafter, a compound according to an aspect of the present invention and an organic electric element including the same will be described.
본 발명은 하기 화학식(1)로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (1).
화학식 (1) Formula (1)
{상기 화학식 (1)에서, {In the above formula (1),
1) A 및 B는 각각 하기 화학식 (1-1), (1-2)로 이루어진 군에서 선택되고 서로 상이하며, 1) A and B are each selected from the group consisting of the following formulas (1-1) and (1-2) and different from each other,
화학식 (1-1) 화학식 (1-2) Chemical Formula (1-1) Chemical Formula (1-2)
2) Ar1, Ar2 및 Ar3은 각각 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 로 이루어진 군에서 선택되고,2) Ar 1 , Ar 2 and Ar 3 are each independently a C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; Is selected from the group consisting of
3) X는 O 또는 S이고,3) X is O or S,
4) L1 및 L2는 각각 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며,4) L 1 and L 2 are each independently a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And a C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and
5) n은 0~4의 정수이고, m, p, o는 0~3의 정수이며 m, n, o, p가 1이상일 경우 R1, R2, R3 및 R4는 각각 독립적으로 수소; 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되고,(여기서 상기 L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며, 상기 Ra 및 Rb은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택됨) 또는 이웃한 복수의 R1끼리, 혹은 복수의 R2끼리, 혹은 복수의 R3끼리, 혹은 복수의 R4끼리는 서로 결합하여 방향족 또는 헤테로방향족 고리를 형성 할 수 있고, 5) n is an integer from 0 to 4, m, p, o are integers from 0 to 3, and when m, n, o, p is 1 or more, R 1 , R 2 , R 3 and R 4 are each independently hydrogen. ; heavy hydrogen; halogen; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); (wherein L 'is a single bond; C 6 ~ C 60 arylene group; Fluoryleneylene; C 3 ~ C 60 A fused ring group of an aliphatic ring and a C 6 ~ C 60 aromatic ring; and a hetero ring group of C 2 ~ C 60 ; wherein R a and R b are independently of each other C 6 ~ C 60 Aryl group; fluorenyl group; C 3 ~ C 60 alicyclic ring and C 6 ~ C 60 Aromatic ring fused ring group; and O, N, S, Si and P containing at least one heteroatom 2 to C 60 heterocyclic group; selected from the group consisting of; or a plurality of adjacent R 1 or a plurality of R 2 , or a plurality of R 3 or a plurality of R 4 are bonded to each other aromatic or hetero Can form an aromatic ring,
여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알콕시기, 아릴옥시기는 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(Ra)(Rb); C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); 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 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; It may be further substituted with one or more substituents selected from the group consisting of C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group, and these substituents may also be bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof, and includes a saturated or unsaturated ring.}
또한 본 발명의 일실시예로, 상기 화학식 (1)로 나타낸 화합물은 하기 화학식 (2) 또는 화학식 (3)으로 표시되는 화합물을 포함한다.In addition, in one embodiment of the present invention, the compound represented by the formula (1) includes a compound represented by the following formula (2) or formula (3).
화학식 (2) 화학식 (3) Formula (2) Formula (3)
(상기 화학식 (2) 또는 (3)에서, R1, R2, R3, R4, m, n, o, p, L1, L2, Ar1, Ar2, Ar3는 상기 화학식 (1)에서 정의한 바와 같다.)(In the formula (2) or (3), R 1 , R 2 , R 3 , R 4 , m, n, o, p, L 1 , L 2 , Ar 1 , Ar 2 , Ar 3 is represented by the formula ( As defined in 1).
본 발명에서 구체적인 화합물을 예로 들자면, 상기 화학식 (1)로 나타낸 화합물은 하기와 같이 표시되는 화합물을 포함한다.To give a specific compound in the present invention, for example, the compound represented by the formula (1) includes a compound represented as follows.
본 발명은 제 1전극, 제 2 전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은 정공주입층, 정공수송층, 발광보조층, 발광층을 포함하고, 상기 유기물층은 상기 화학식 (1)로 표시되는 화합물을 포함하는 유기전기소자를 제공한다.The present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer. It includes, the organic material layer provides an organic electric device comprising a compound represented by the formula (1).
또한 본 발명은 제 1전극, 제 2 전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자로서, 상기 제 1전극과 발광층 사이에 형성되는 정공수송층과 상기 정공수송층과 상기 발광층 사이에 형성되는 발광보조층을 포함하며, 상기 발광보조층은 하기 화학식 (1)로 나타나는 화합물을 함유하고, 상기 정공수송층은 하기 화학식 (5)로 나타낸 화합물을 함유하는 것을 특징으로 하는 유기전기소자를 제공한다.In another aspect, the present invention is an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, the hole transport layer and the hole transport layer formed between the first electrode and the light emitting layer And a light emitting auxiliary layer formed between the light emitting layer, wherein the light emitting auxiliary layer contains a compound represented by the following Chemical Formula (1), and the hole transport layer contains a compound represented by the following Chemical Formula (5). An organic electric device is provided.
또한 본 발명은 상기 정공주입층, 정공수송층, 발광보조층, 발광층 중 적어도 하나의 층에 상기 화학식 (1) 화합물이 1종 단독 또는 구조가 상이한 2종 이상의 화합물이 혼합된 조성물을 포함하는 유기전기소자를 제공한다. 구체적으로 상기 정공수송층 또는 상기 발광보조층에 상기 화합물이 1종 단독 또는 구조가 상이한 2종 이상의 화합물이 혼합된 조성물을 포함한다.In another aspect, the present invention is an organic electroluminescence comprising a composition in which at least one of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer is a compound of the formula (1) alone or two or more compounds different in structure Provided is an element. Specifically, the hole transport layer or the light emitting auxiliary layer may include a composition in which the compound is mixed alone or in combination of two or more compounds having different structures.
또한 본 발명은, 상기 발광보조층은 상기 화학식 (1)의 화합물을 포함하고, 상기 정공수송층은 하기 화학식 (5)로 나타낸 화합물을 함유하는 유기전기소자를 제공한다.In another aspect, the present invention provides an organic electroluminescent device comprising the compound of formula (1), wherein the light emitting auxiliary layer, the hole transport layer containing a compound represented by the following formula (5).
화학식 (5)Formula (5)
{상기 화학식 (5)에서, {In the above formula (5),
1) Ar4 및 Ar5는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되며(여기서 상기 L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며, 상기 Ra 및 Rb은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택됨), 또는 Ar4와 Ar5는 서로 결합하여 고리를 형성할 수 있고,1) Ar 4 and Ar 5 are independently of each other C 6 ~ C 60 An aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); wherein L 'is a single bond; C 6 ~ C 60 arylene group; Fluorenylene group; C 3 ~ C 60 A fused ring group of an aliphatic ring and an aromatic ring of C 6 ~ C 60 ; and a heterocyclic group of C 2 ~ C 60 , wherein R a and R b are each independently selected from C 6 ~ C 60 an aryl group; fluorene group; C 3 ~ fused ring group of an aromatic ring of C 60 of aliphatic rings and C 6 ~ C 60; and O, N, S, Si, and C 2, comprising at least one hetero atom of the P Heterocyclic group of ~ C 60 ; or Ar 4 And Ar 5 It may be bonded to each other to form a ring,
2) Ar6은 하기 화학식 (5-a), (5-b), (5-c) 중 어느 하나로 선택되고, .2) Ar 6 is selected from any one of the following formulas (5-a), (5-b) and (5-c).
화학식 (5-a) 화학식 (5-b) 화학식 (5-c)Formula (5-a) Formula (5-b) Formula (5-c)
3) a, b, c는 0~4의 정수이며, R5, R6 및 R7은 서로 동일하거나 상이하며, 서로 독립적으로 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되고, 또는 R5, R6 및 R7은 상기 a, b, c가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며 복수의 R5끼리 혹은 복수의 R6끼리 혹은 복수의 R7끼리 서로 결합하여 고리를 형성할 수 있고,3) a, b, c are integers from 0 to 4, R 5 , R 6 and R 7 are the same as or different from each other, and independently from each other deuterium; halogen; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); or R 5 , R 6, and R 7 are each the same as or different from each other when a, b, and c are two or more, and A plurality of R 5 or a plurality of R 6 or a plurality of R 7 may combine with each other to form a ring,
4) L3 및 L5는 서로 독립적으로 C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고,4) L 3 and L 5 are each independently a C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P;
5) L4은 C6~C60의 단일결합; 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고,5) L 4 is a single bond of C 6 ~ C 60 ; Arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P;
6) Ar7, Ar8 및 Ar9은 각각 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 로 이루어진 군에서 선택되고,6) Ar 7 , Ar 8 and Ar 9 are each independently a C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; Is selected from the group consisting of
여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알콕시기, 아릴옥시기는 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(Ra)(Rb); C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); 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 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; It may be further substituted with one or more substituents selected from the group consisting of C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group, and these substituents may also be bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof, and includes a saturated or unsaturated ring.}
본 발명에서, 상기 화학식 (5)로 나타낸 화합물은 하기 화학식 5-1 내지 5-71로 표시되는 화합물을 포함한다.In the present invention, the compound represented by the formula (5) includes a compound represented by the following formula (5-1 to 5-71).
도 1을 참조하여 설명하면, 본 발명에 따른 유기전기소자(100)는 기판(110) 상에 형성된 제 1전극(120), 제 2전극(180) 및 제 1전극(120)과 제 2전극(180) 사이에 화학식 1로 표시되는 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, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 120 and a second electrode formed on a substrate 110. An organic material layer including a compound represented by Chemical Formula 1 is provided between 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), 발광보조층(151), 전자수송층(160) 및 전자주입층(170)을 포함할 수 있다. The organic material layer may sequentially include the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, the light emitting auxiliary layer 151, the electron transport layer 160, and the electron injection layer 170 on the first electrode 120. It may include.
또한, 미도시하였지만 본 발명에 따른 유기전기소자는 제 1전극과 제 2전극중 적어도 일면 중 상기 유기물층과 반대되는 일면에 형성된 보호층을 더 포함할 수 있다.In addition, although not shown, the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.
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 조합도 아주 중요하며, 특히 각 유기물층 간의 에너지 level 및 T1 값, 물질의 고유특성(mobility, 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 cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.
본 발명의 일 실시예에 따른 유기전기발광소자는 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예컨대, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층(130), 정공수송층(140), 발광층(150), 발광보조층(151), 전자수송층(160) 및 전자주입층(170)을 포함하는 유기물층을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다.The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, an anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on a substrate, and thereon, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and a light emitting auxiliary layer 151. After forming the organic material layer including the electron transport layer 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as a cathode thereon.
이에 따라, 본 발명은 제 1전극; 제 2전극; 및 상기 제 1전극과 제 2전극 사이에 위치하는 유기물층;을 포함하는 유기전기소자에 있어서, 상기 유기물층은 정공주입층, 정공수송층, 발광보조층, 발광층을 포함하고, 상기 유기물층은 상기 화학식 (1)에 포함되는 화합물을 함유하는 것을 특징으로 하는 유기전기소자를 제공한다.Accordingly, the present invention includes a first electrode; Second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer includes a hole injection layer, a hole transport layer, a light emitting auxiliary layer, and a light emitting layer, and the organic material layer is represented by Chemical Formula (1). Provided is an organic electroluminescent device comprising a compound contained in).
또한, 본 발명은 상기 정공주입층, 정공수송층, 발광보조층, 발광층 중 적어도 하나의 층에 상기 화학식 (1)에 따른 화합물이 포함되며, 상기 화합물은 1종 단독 또는 2종 이상의 화합물이 혼합된 조성물을 포함하는 유기전기소자를 제공한다.In addition, the present invention includes a compound according to the formula (1) in at least one layer of the hole injection layer, hole transport layer, light emitting auxiliary layer, light emitting layer, the compound is one or a mixture of two or more compounds It provides an organic electric device comprising the composition.
또한, 본 발명은 상기 발광보조층에 상기 화합물이 1종 단독 또는 2종 이상 포함하는 유기전기소자를 제공한다.In addition, the present invention provides an organic electroluminescent device comprising at least one kind of the compound in the light emitting auxiliary layer.
또한 본 발명은 상기 유기전기소자에서 상기 제 1전극의 일측면 중 상기 유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율개선층을 더 포함하는 유기전기소자를 제공한다.The present invention may further include an optical efficiency improvement layer formed on at least one of 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 device.
또한 본 발명에서 상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 및 롤투롤 공정 중 어느 하나에 의해 형성되며, 상기 유기물층은 전자수송재료로 상기 화합물을 포함하는 것을 특징으로 하는 유기전기소자를 제공한다.In the present invention, the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll-to-roll process, the organic layer is an electron transport material containing the compound It provides an organic electric element, characterized in that.
또 다른 구체적인 예로서, 본 발명은 상기 유기물층에 상기 화학식 (1)로 표시되는 화합물의 동종 또는 이종의 화합물이 혼합되어 사용되는 것을 특징으로 하는 유기전기소자를 제공한다.As another specific example, the present invention provides an organic electric device, characterized in that the same or different compounds of the compound represented by the formula (1) are mixed and used in the organic material layer.
또한, 본 발명은 화학식 (1)로 표시되는 화합물을 포함하는 정공수송층 및 발광보조층을 포함하는 유기전기소자를 제공하며, 또 다른 측면에서 화학식 (1)로 표시되는 화합물을 포함하는 정공수송층 또는 발광보조층을 포함하는 유기전기소자를 제공한다.The present invention also provides an organic electroluminescent device comprising a hole transport layer and a light emitting auxiliary layer comprising a compound represented by the formula (1), in another aspect a hole transport layer comprising a compound represented by the formula (1) or An organic electric device comprising a light emitting auxiliary layer is provided.
또한 본 발명은 상기한 유기전기소자를 포함하는 디스플레이장치 ; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치를 제공한다. In another aspect, the present invention is a display device comprising the above-mentioned organic electric element; And a controller for driving the display device.
또 다른 측면에서 상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용 소자 중 적어도 하나인 것을 특징으로 하는 전자장치를 본 발명에서 제공한다. 이때, 전자장치는 현재 또는 장래의 유무선 통신단말기일 수 있으며, 휴대폰 등의 이동 통신 단말기, PDA, 전자사전, PMP, 리모콘, 네비게이션, 게임기, 각종 TV, 각종 컴퓨터 등 모든 전자장치를 포함한다.In another aspect, the organic electronic device provides an electronic device according to the present invention, wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochromatic or white illumination 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.
이하에서, 본 발명의 상기 화학식 1로 표시되는 화합물의 합성예 및 본 발명의 유기전기소자의 제조예에 관하여 실시예를 들어 구체적으로 설명하지만, 본 발명의 하기 실시예로 한정되는 것은 아니다.Hereinafter, the synthesis examples of the compound represented by Chemical Formula 1 of the present invention and the production examples of the organic electric device of the present invention will be described in detail with reference to Examples, but are not limited to the following Examples of the present invention.
[[
합성예Synthesis Example
1] One]
본 발명에 따른 화학식 (1)로 표시되는 화합물(final product 1)은 하기 반응식 1과 같이 Sub 1 또는 Sub 2가 Sub3가 반응하여 제조된다.Compound represented by the formula (1) according to the present invention (final product 1) is prepared by the reaction of Sub 1 or Sub 2 Sub 3 or Sub 2 as shown in Scheme 1.
<반응식 1><Scheme 1>
(1) e가 1일 경우 f, h는 0이고 g는 1이다 (1) When e is 1, f and h are 0 and g is 1.
(2) h가 1일 경우, g, e는 0이고 f는 1이다(2) When h is 1, g and e are 0 and f is 1.
Sub Sub
1합성1 Synthesis
예시 example
반응식 1의 Sub 1은 하기 반응식 2의 반응경로에 의해 합성될 수 있으며 이에 한정된 것은 아니다. Sub 1 of Scheme 1 may be synthesized by the reaction route of Scheme 2, but is not limited thereto.
<반응식 2><Scheme 2>
Sub 1- I의 합성예시Synthesis Example of Sub 1- I
3-bromo-9-phenyl-9H-carbazole (76.78 g, 238.3 mmol)를 둥근바닥플라스크에 DMF로 녹인 후에, Bis(pinacolato)diboron (66.57 g, 262.1 mmol), Pd(dppf)Cl2
(5.84 g, 7.1 mmol), KOAc (70.16 g, 714.9 mmol)를 첨가하고 90 ℃에서 교반하였다. 반응이 완료되면 증류를 통해 DMF를 제거하고 CH2Cl2와 물로 추출하였다. 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 73.92 g (수율: 84%)를 얻었다.3-bromo-9-phenyl-9H-carbazole (76.78 g, 238.3 mmol) was dissolved in DMF in a round bottom flask, followed by Bis (pinacolato) diboron (66.57 g, 262.1 mmol), Pd (dppf) Cl 2 (5.84 g, 7.1 mmol), KOAc (70.16 g, 714.9 mmol) was added and stirred at 90 ° C. After the reaction was completed, DMF was removed by distillation and extracted with CH 2 Cl 2 and water. The organic layer was dried over MgSO 4 , concentrated and the resulting compound was silicagel column and recrystallized to give 73.92 g (yield: 84%) of the product.
Sub 1의 합성예시 1)Synthesis Example of Sub 1 1)
상기 합성에서 얻어진 Sub 1-I (73.92g, 200.2 mmol)를 둥근바닥플라스크에 THF 880 mL로 녹인 후에, Sub 1-2-1 (116.8g, 300.3 mmol), Pd(PPh3)4
(11.6g, 10 mmol), K2CO3 (83g, 600.6 mmol), 물 440 mL을 첨가하고 80 ℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 81.8g (수율: 81%)를 얻었다.Sub 1-I (73.92 g, 200.2 mmol) obtained in the above synthesis was dissolved in 880 mL of THF in a round bottom flask, and then Sub 1-2-1 (116.8 g, 300.3 mmol), Pd (PPh 3 ) 4 (11.6 g, 10 mmol), K 2 CO 3 (83 g, 600.6 mmol), 440 mL of water were added and stirred at 80 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 81.8g (yield: 81%).
Sub 1의 합성예시 2)Synthesis Example of Sub 1 2)
Sub 1-I(73.92g, 200.2 mmol)과 Sub 1-2-2 (112.0g, 300.3 mmol)을 상기 Sub 1-1의 합성법을 이용하여 생성물 76.3g (수율: 78%)를 얻었다.Sub 1-I (73.92 g, 200.2 mmol) and Sub 1-2-2 (112.0 g, 300.3 mmol) were obtained by using the synthesis method of Sub 1-1, 76.3 g (yield: 78%).
Sub 1의 합성예시 3)Synthesis Example of Sub 1 3)
Sub 1-Ⅱ(93.9g, 200.2 mmol)과 Sub 1-2-3 (116.8g, 300.3 mmol)을 상기 Sub 1-1의 합성법을 이용하여 생성물 90.8g (수율: 75%)를 얻었다.Sub 1-II (93.9 g, 200.2 mmol) and Sub 1-2-3 (116.8 g, 300.3 mmol) were obtained using the synthesis method of Sub 1-1 to obtain 90.8 g (yield: 75%) of the product.
Sub 1의 합성예시 4)Synthesis Example of Sub 1 4)
Sub 1-Ⅲ (74.1g, 200.2 mmol)과 Sub 1-2-4 (112.0g, 300.3 mmol)을 상기 Sub 1-1의 합성법을 이용하여 생성물 70.5g (수율: 72%)를 얻었다.Sub 1-III (74.1 g, 200.2 mmol) and Sub 1-2-4 (112.0 g, 300.3 mmol) were obtained using the synthesis method of Sub 1-1 to obtain 70.5 g (yield: 72%) of the product.
Sub 1 의 예시는 다음과 같으나, 이에 한정되는 것은 아니다. Examples of Sub 1 are as follows, but are not limited thereto.
| 화합물compound | FD-MSFD-MS | 화합물compound | FD-MSFD-MS |
| Sub 1-1Sub 1-1 | m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) | Sub 1-2Sub 1-2 | m/z=503.03(C30H18BrNS=504.44)m / z = 503.03 (C 30 H 18 BrNS = 504.44) |
| Sub 1-3Sub 1-3 | m/z=487.06(C30H18BrNO=488.37)m / z = 487.06 (C 30 H 18 BrNO = 488.37) | Sub 1-4Sub 1-4 | m/z=487.06(C30H18BrNO=488.37)m / z = 487.06 (C 30 H 18 BrNO = 488.37) |
| Sub 1-5Sub 1-5 | m/z=537.07(C34H20BrNO=538.44)m / z = 537.07 (C 34 H 20 BrNO = 538.44) | Sub 1-6Sub 1-6 | m/z=537.07(C34H20BrNO=538.43)m / z = 537.07 (C 34 H 20 BrNO = 538.43) |
| Sub 1-7Sub 1-7 | m/z=603.07(C38H22BrNS=604.56)m / z = 603.07 (C 38 H 22 BrNS = 604.56) | Sub 1-8Sub 1-8 | m/z=579.07(C36H22BrNS=580.54)m / z = 579.07 (C 36 H 22 BrNS = 580.54) |
| Sub 1-9Sub 1-9 | m/z=603.12(C39H26BrNO=604.53)m / z = 603.12 (C 39 H 26 BrNO = 604.53) | Sub 1-10Sub 1-10 | m/z=603.07(C38H22BrNS=604.56)m / z = 603.07 (C 38 H 22 BrNS = 604.56) |
| Sub 1-11Sub 1-11 | m/z=579.07(C36H22BrNS=580.54)m / z = 579.07 (C 36 H 22 BrNS = 580.54) | Sub 1-12Sub 1-12 | m/z=488.05(C29H17BrN2O=489.36)m / z = 488.05 (C 29 H 17 BrN 2 O = 489.36) |
| Sub 1-13Sub 1-13 | m/z=579.07(C36H22BrNS=580.54)m / z = 579.07 (C 36 H 22 BrNS = 580.54) | Sub 1-14Sub 1-14 | m/z=579.07(C36H22BrNS=580.54)m / z = 579.07 (C 36 H 22 BrNS = 580.54) |
| Sub 1-15Sub 1-15 | m/z=639.12(C42H26BrNO=640.57)m / z = 639.12 (C 42 H 26 BrNO = 640.57) | Sub 1-16Sub 1-16 | m/z=715.15(C48H30BrNO=716.66)m / z = 715.15 (C 48 H 30 BrNO = 716.66) |
Sub Sub
2합성2 synthetic
예시 example
반응식 1의 Sub 2은 하기 반응식 3의 반응경로에 의해 합성될 수 있으며 이에 한정된 것은 아니다. Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3, but is not limited thereto.
<반응식 3><Scheme 3>
Sub 2-1의 합성예시Synthesis Example of Sub 2-1
둥근바닥 플라스크에 bromobenzene (37.1 g, 236.2 mmol)을 넣고 toluene (2200 mL)으로 녹인 후 aniline (20 g, 214.8 mmol), Pd2(dba)3 (9.83 g, 10.7 mmol), P(t-Bu)3 (4.34 g, 21.5 mmol), NaOt-Bu (62 g, 644.3 mmol) 을 순서대로 첨가하고 100 ℃에서 교반하였다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 28 g (수율: 77%)를 얻었다.Bromobenzene (37.1 g, 236.2 mmol) was added to a round bottom flask and dissolved with toluene (2200 mL), followed by aniline (20 g, 214.8 mmol), Pd 2 (dba) 3 (9.83 g, 10.7 mmol), P ( t -Bu ) 3 (4.34 g, 21.5 mmol) and NaO t -Bu (62 g, 644.3 mmol) were added in this order and stirred at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 28 g (yield: 77%) of the product.
Sub 2-13의 합성예시Synthesis Example of Sub 2-13
3-bromodibenzo[b,d]thiophene (42.8 g, 162.5 mmol), toluene(1550 mL), [1,1'-biphenyl]-4-amine (25 g, 147.7 mmol), Pd2(dba)3 (6.76 g, 162.5 mmol), P(t-Bu)3 (3 g, 14.8 mmol), NaOt-Bu (42.6 g, 443.2 mmol) 을 상기 실시예 2의 Sub 2-1 합성법을 사용하여 생성물 37.9 g (수율: 73%)를 얻었다3-bromodibenzo [b, d] thiophene (42.8 g, 162.5 mmol), toluene (1550 mL), [1,1'-biphenyl] -4-amine (25 g, 147.7 mmol), Pd 2 (dba) 3 ( 6.76 g, 162.5 mmol), P ( t -Bu) 3 (3 g, 14.8 mmol), NaO t -Bu (42.6 g, 443.2 mmol) were obtained using the Sub 2-1 synthesis of Example 2 above, 37.9 g of the product. (Yield: 73%) was obtained.
Sub 2의 예시는 다음과 같으나, 이에 한정되는 것은 아니다. An example of Sub 2 is as follows, but is not limited thereto.
| 화합물compound | FD-MSFD-MS | 화합물compound | FD-MSFD-MS |
| Sub 2-1Sub 2-1 | m/z=169.09(C12H11N=169.22)m / z = 169.09 (C 12 H 11 N = 169.22) | Sub 2-2Sub 2-2 | m/z=245.12(C18H15N=245.32)m / z = 245.12 (C 18 H 15 N = 245.32) |
| Sub 2-3Sub 2-3 | m/z=245.12(C18H15N=245.32)m / z = 245.12 (C 18 H 15 N = 245.32) | Sub 2-4Sub 2-4 | m/z=321.15(C24H19N= 321.41)m / z = 321.15 (C 24 H 19 N = 321.41) |
| Sub 2-5Sub 2-5 | m/z=321.15 (C24H19N=321.41)m / z = 321.15 (C 24 H 19 N = 321.41) | Sub 2-6Sub 2-6 | m/z=269.12(C20H15N=269.34)m / z = 269.12 (C 20 H 15 N = 269.34) |
| Sub 2-7Sub 2-7 | m/z=269.12(C20H15N=269.34)m / z = 269.12 (C 20 H 15 N = 269.34) | Sub 2-8Sub 2-8 | m/z=295.14(C22H17N=295.38)m / z = 295.14 (C 22 H 17 N = 295.38) |
| Sub 2-9Sub 2-9 | m/z=409.18(C31H23N=409.52)m / z = 409.18 (C 31 H 23 N = 409.52) | Sub 2-10Sub 2-10 | m/z=483.20(C37H25N=483.60)m / z = 483.20 (C 37 H 25 N = 483.60) |
| Sub 2-11Sub 2-11 | m/z=459.20(C35H25N=459.58)m / z = 459.20 (C 35 H 25 N = 459.58) | Sub 2-12Sub 2-12 | m/z=485.21(C37H27N=485.62)m / z = 485.21 (C 37 H 27 N = 485.62) |
| Sub 2-13Sub 2-13 | m/z=275.08(C18H13NS=275.37)m / z = 275.08 (C 18 H 13 NS = 275.37) | Sub 2-14Sub 2-14 | m/z=335.13(C24H17NO=335.40)m / z = 335.13 (C 24 H 17 NO = 335.40) |
| Sub 2-15Sub 2-15 | m/z=297.13(C20H15N3=297.35)m / z = 297.13 (C 20 H 15 N 3 = 297.35) | Sub 2-16Sub 2-16 | m/z=219.10(C16H13N=219.28)m / z = 219.10 (C 16 H 13 N = 219.28) |
| Sub 2-17Sub 2-17 | m/z=249.12(C17H15NO=249.31)m / z = 249.12 (C 17 H 15 NO = 249.31) | Sub 2-18Sub 2-18 | m/z=197.12(C14H15N=197.28)m / z = 197.12 (C 14 H 15 N = 197.28) |
| Sub 2-19Sub 2-19 | m/z=229.11(C14H15NO2=229.27)m / z = 229.11 (C 14 H 15 NO 2 = 229.27) | Sub 2-20Sub 2-20 | m/z=174.12(C12H6D5N=174.25)m / z = 174.12 (C 12 H 6 D 5 N = 174.25) |
| Sub 2-21Sub 2-21 | m/z=281.21(C20H27N=281.44)m / z = 281.21 (C 20 H 27 N = 281.44) | Sub 2-22Sub 2-22 | m/z=321.15(C24H19N=321.41)m / z = 321.15 (C 24 H 19 N = 321.41) |
| Sub 2-23Sub 2-23 | m/z=321.15(C24H19N=321.41)m / z = 321.15 (C 24 H 19 N = 321.41) | Sub 2-24Sub 2-24 | m/z=321.15(C24H19N=321.41)m / z = 321.15 (C 24 H 19 N = 321.41) |
| Sub 2-25Sub 2-25 | m/z=321.15(C24H19N=321.41)m / z = 321.15 (C 24 H 19 N = 321.41) | Sub 2-26Sub 2-26 | m/z=321.15(C24H19N=321.41)m / z = 321.15 (C 24 H 19 N = 321.41) |
| Sub 2-27Sub 2-27 | m/z=297.13(C20H15N3=297.35)m / z = 297.13 (C 20 H 15 N 3 = 297.35) | Sub 2-28Sub 2-28 | m/z=499.20(C36H25N3=499.60)m / z = 499.20 (C 36 H 25 N 3 = 499.60) |
| Sub 2-29Sub 2-29 | m/z=499.20(C36H22N2=410.51)m / z = 499.20 (C 36 H 22 N 2 = 410.51) | Sub 2-30Sub 2-30 | m/z=424.16(C30H20N2O=424.49)m / z = 424.16 (C 30 H 20 N 2 O = 424.49) |
| Sub 2-31Sub 2-31 | m/z=440.13(C30H20N2S=440.56)m / z = 440.13 (C 30 H 20 N 2 S = 440.56) | Sub 2-32Sub 2-32 | m/z=384.16(C28H20N2=384.47)m / z = 384.16 (C 28 H 20 N 2 = 384.47) |
| Sub 2-33Sub 2-33 | m/z=334.15(C24H18N2=334.41)m / z = 334.15 (C 24 H 18 N 2 = 334.41) | Sub 2-34Sub 2-34 | m/z=450.21(C33H26N2=450.57)m / z = 450.21 (C 33 H 26 N 2 = 450.57) |
| Sub 2-35Sub 2-35 | m/z=410.18(C30H22N2=410.51)m / z = 410.18 (C 30 H 22 N 2 = 410.51) | Sub 2-36Sub 2-36 | m/z=410.18(C30H22N2=410.51)m / z = 410.18 (C 30 H 22 N 2 = 410.51) |
| Sub 2-37Sub 2-37 | m/z=575.24(C42H29N3=575.70)m / z = 575.24 (C 42 H 29 N 3 = 575.70) | Sub 2-38Sub 2-38 | m/z=574.24(C43H30N2=574.71)m / z = 574.24 (C 43 H 30 N 2 = 574.71) |
| Sub 2-39Sub 2-39 | m/z=460.19(C34H24N2=460.57)m / z = 460.19 (C 34 H 24 N 2 = 460.57) | Sub 2-40Sub 2-40 | m/z=460.19(C34H24N2=460.57)m / z = 460.19 (C 34 H 24 N 2 = 460.57) |
| Sub 2-41Sub 2-41 | m/z=461.19(C33H23N3=461.56)m / z = 461.19 (C 33 H 23 N 3 = 461.56) | Sub 2-42Sub 2-42 | m/z=626.27(C47H34N2=626.79)m / z = 626.27 (C 47 H 34 N 2 = 626.79) |
| Sub 2-43Sub 2-43 | m/z=565.23(C39H27N5=565.67)m / z = 565.23 (C 39 H 27 N 5 = 565.67) | Sub 2-44Sub 2-44 | m/z=415.21(C30H17D5N2=415.54)m / z = 415.21 (C 30 H 17 D 5 N 2 = 415.54) |
| Sub 2-45Sub 2-45 | m/z=486.21(C36H26N2=486.61)m / z = 486.21 (C 36 H 26 N 2 = 486.61) | Sub 2-46Sub 2-46 | m/z=415.21(C30H17D5N2=415.54)m / z = 415.21 (C 30 H 17 D 5 N 2 = 415.54) |
Final products Final products
1합성1 Synthesis
예시 example
1-1 합성예시1-1 Synthesis Example
Sub 2-1 (8.0g, 47.3 mmol)을 둥근바닥 플라스크에 넣고 toluene (500 mL)으로 녹인 후에, Sub 1-1 (26.2g, 52.0 mmol), Pd2(dba)3 (2.2 g, 2.4 mmol), P(t-Bu)3 (1 g, 4.73 mmol), NaOt-Bu (13.6 g, 141.8 mmol)을 첨가하고 100 ℃에서 교반하였다. 반응이 완료되면 CH2Cl2와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 생성물 25.0g (수율: 81%)를 얻었다.Sub 2-1 (8.0 g, 47.3 mmol) was added to a round bottom flask and dissolved with toluene (500 mL), then Sub 1-1 (26.2 g, 52.0 mmol), Pd 2 (dba) 3 (2.2 g, 2.4 mmol) ), P ( t -Bu) 3 (1 g, 4.73 mmol) and NaO t -Bu (13.6 g, 141.8 mmol) were added and stirred at 100 ° C. After the reaction was completed, the mixture was extracted with CH 2 Cl 2 and water, the organic layer was dried over MgSO 4 and concentrated, and the resulting compound was purified by silicagel column and recrystallized to give the product 25.0g (yield: 81%).
1-12 합성예시1-12 Synthesis Example
Sub 2-47 (16.3g, 47.3 mmol), Sub 1-4 (25.4g, 52.0 mmol)을 상기 1-1과 동일한 합성법을 이용하여 생성물 30.5g (수율: 78%)를 얻었다.Sub 2-47 (16.3 g, 47.3 mmol) and Sub 1-4 (25.4 g, 52.0 mmol) were obtained using the same synthesis method as in 1-1, to obtain 30.5 g (yield: 78%) of the product.
1-20 합성예시1-20 Synthesis Example
Sub 2-48 (22.9g, 47.3 mmol), Sub 1-17 (28.8g, 52.0 mmol)을 상기 1-1과 동일한 합성법을 이용하여 생성물 35.8g (수율: 72%)를 얻었다.Sub 2-48 (22.9 g, 47.3 mmol) and Sub 1-17 (28.8 g, 52.0 mmol) were obtained in the same manner as in 1-1, to obtain 35.8 g (yield: 72%) of the product.
2-5 합성예시2-5 Synthesis Example
Sub 2-49 (8.1g, 47.3 mmol), Sub 1-2 (26.2g, 52.0 mmol)을 상기 1-1과 동일한 합성법을 이용하여 생성물 23.5g (수율: 76%)를 얻었다. Sub 2-49 (8.1 g, 47.3 mmol) and Sub 1-2 (26.2 g, 52.0 mmol) were obtained in the same manner as in 1-1, to obtain 23.5 g (yield: 76%) of the product.
2-16 합성예시2-16 Synthesis Example
Sub 2-4 (15.2g, 47.3 mmol), Sub 1-18 (32.9g, 52.0 mmol)을 상기 1-1과 동일한 합성법을 이용하여 생성물 35.9g (수율: 79%)를 얻었다.Sub 2-4 (15.2 g, 47.3 mmol) and Sub 1-18 (32.9 g, 52.0 mmol) were obtained in the same manner as in 1-1, to obtain 35.9 g (yield: 79%) of the product.
2-21 합성예시2-21 Synthesis Example
Sub 2-50 (18.2g, 47.3 mmol), Sub 1-5 (28.0g, 52.0 mmol)을 상기 1-1과 동일한 합성법을 이용하여 생성물 35.5g (수율: 81%)를 얻었다. Sub 2-50 (18.2 g, 47.3 mmol) and Sub 1-5 (28.0 g, 52.0 mmol) were obtained in the same manner as in 1-1, to obtain 35.5 g (yield: 81%) of the product.
| 화합물compound | FD-MSFD-MS | 화합물compound | FD-MSFD-MS |
| 1-11-1 | m/z=592.20(C42H28N2S=592.76)m / z = 592.20 (C 42 H 28 N 2 S = 592.76) | 1-21-2 | m/z=626.24(C46H30N2O=626.76)m / z = 626.24 (C 46 H 30 N 2 O = 626.76) |
| 1-31-3 | m/z=626.24(C46H30N2O=626.76)m / z = 626.24 (C 46 H 30 N 2 O = 626.76) | 1-41-4 | m/z=744.26(C54H36N2S=744.96)m / z = 744.26 (C 54 H 36 N 2 S = 744.96) |
| 1-51-5 | m/z=593.19(C41H27N3S=593.75)m / z = 593.19 (C 41 H 27 N 3 S = 593.75) | 1-61-6 | m/z=708.26(C51H36N2S=708.92)m / z = 708.26 (C 51 H 36 N 2 S = 708.92) |
| 1-71-7 | m/z=816.31(C61H40N2O=817.00)m / z = 816.31 (C 61 H 40 N 2 O = 817.00) | 1-81-8 | m/z=890.33(C67H42N2O=891.09)m / z = 890.33 (C 67 H 42 N 2 O = 891.09) |
| 1-91-9 | m/z=807.27(C58H37N3S=808.02)m / z = 807.27 (C 58 H 37 N 3 S = 808.02) | 1-101-10 | m/z=774.22(C54H34N2S2=775.00)m / z = 774.22 (C 54 H 34 N 2 S 2 = 775.00) |
| 1-111-11 | m/z=682.21(C48H30N2OS=682.84)m / z = 682.21 (C 48 H 30 N 2 OS = 682.84) | 1-121-12 | m/z=752.28(C56H36N2O=752.92)m / z = 752.28 (C 56 H 36 N 2 O = 752.92) |
| 1-131-13 | m/z=626.24(C46H30N2O=626.76)m / z = 626.24 (C 46 H 30 N 2 O = 626.76) | 1-141-14 | m/z=692.23(C50H32N2S=692.88)m / z = 692.23 (C 50 H 32 N 2 S = 692.88) |
| 1-151-15 | m/z=718.24(C52H34N2S=718.92) m / z = 718.24 (C 52 H 34 N 2 S = 718.92) | 1-161-16 | m/z=872.30(C62H40N4S=873.09)m / z = 872.30 (C 62 H 40 N 4 S = 873.09) |
| 1-171-17 | m/z=677.25(C49H31N3O=677.81)m / z = 677.25 (C 49 H 31 N 3 O = 677.81) | 1-181-18 | m/z=808.29(C59H40N2S=809.04)m / z = 808.29 (C 59 H 40 N 2 S = 809.04) |
| 1-191-19 | m/z=882.31(C65H42N2S=883.13)m / z = 882.31 (C 65 H 42 N 2 S = 883.13) | 1-201-20 | m/z=956.32(C71H44N2S=957.21)m / z = 956.32 (C 71 H 44 N 2 S = 957.21) |
| 1-211-21 | m/z=841.31(C62H39N3O=842.01)m / z = 841.31 (C 62 H 39 N 3 O = 842.01) | 1-221-22 | m/z=824.23(C58H36N2S2=825.06)m / z = 824.23 (C 58 H 36 N 2 S 2 = 825.06) |
| 1-231-23 | m/z=716.25(C52H32N2O2=716.84)m / z = 716.25 (C 52 H 32 N 2 O 2 = 716.84) | 1-241-24 | m/z=868.29(C64H40N2S=869.10)m / z = 868.29 (C 64 H 40 N 2 S = 869.10) |
| 2-12-1 | m/z=592.20(C42H28N2S=592.76)m / z = 592.20 (C 42 H 28 N 2 S = 592.76) | 2-22-2 | m/z=626.24(C46H30N2O=626.76)m / z = 626.24 (C 46 H 30 N 2 O = 626.76) |
| 2-32-3 | m/z=626.24(C46H30N2O=626.76)m / z = 626.24 (C 46 H 30 N 2 O = 626.76) | 2-42-4 | m/z=744.26(C54H36N2S=744.96)m / z = 744.26 (C 54 H 36 N 2 S = 744.96) |
| 2-52-5 | m/z=593.19(C41H27N3S=593.75) m / z = 593.19 (C 41 H 27 N 3 S = 593.75) | 2-62-6 | m/z=708.26(C51H36N2S=708.92)m / z = 708.26 (C 51 H 36 N 2 S = 708.92) |
| 2-72-7 | m/z=816.31(C61H40N2O=817.00)m / z = 816.31 (C 61 H 40 N 2 O = 817.00) | 2-82-8 | m/z=890.33(C67H42N2O=891.09)m / z = 890.33 (C 67 H 42 N 2 O = 891.09) |
| 2-92-9 | m/z=807.27(C58H37N3S=808.02)m / z = 807.27 (C 58 H 37 N 3 S = 808.02) | 2-102-10 | m/z=774.22(C54H34N2S2=775.00)m / z = 774.22 (C 54 H 34 N 2 S 2 = 775.00) |
| 2-112-11 | m/z=682.21(C48H30N2OS=682.84)m / z = 682.21 (C 48 H 30 N 2 OS = 682.84) | 2-122-12 | m/z=752.28(C56H36N2O=752.92)m / z = 752.28 (C 56 H 36 N 2 O = 752.92) |
| 2-132-13 | m/z=626.24(C46H30N2O=626.76)m / z = 626.24 (C 46 H 30 N 2 O = 626.76) | 2-142-14 | m/z=692.23(C50H32N2S=692.88)m / z = 692.23 (C 50 H 32 N 2 S = 692.88) |
| 2-152-15 | m/z=718.24(C52H34N2S=718.92)m / z = 718.24 (C 52 H 34 N 2 S = 718.92) | 2-162-16 | m/z=872.30(C62H40N4S=873.09) m / z = 872.30 (C 62 H 40 N 4 S = 873.09) |
| 2-172-17 | m/z=677.25(C49H31N3O=677.81)m / z = 677.25 (C 49 H 31 N 3 O = 677.81) | 2-182-18 | m/z=808.29(C59H40N2S=809.04)m / z = 808.29 (C 59 H 40 N 2 S = 809.04) |
| 2-192-19 | m/z=882.31(C65H42N2S=883.13)m / z = 882.31 (C 65 H 42 N 2 S = 883.13) | 2-202-20 | m/z=956.32(C71H44N2S=957.21)m / z = 956.32 (C 71 H 44 N 2 S = 957.21) |
| 2-212-21 | m/z=841.31(C62H39N3O=842.01)m / z = 841.31 (C 62 H 39 N 3 O = 842.01) | 2-222-22 | m/z=824.23(C58H36N2S2=825.06)m / z = 824.23 (C 58 H 36 N 2 S 2 = 825.06) |
| 2-232-23 | m/z=716.25(C52H32N2O2=716.84)m / z = 716.25 (C 52 H 32 N 2 O 2 = 716.84) | 2-242-24 | m/z=868.29(C64H40N2S=869.10)m / z = 868.29 (C 64 H 40 N 2 S = 869.10) |
[[
합성예Synthesis Example
2] 2]
본 발명에 따른 화학식 (13)으로 표시되는 화합물(final product 2)은 하기 반응식 4와 같이 Sub 3 또는 Sub 4가 Sub 5가 반응하여 제조된다.Compound represented by the formula (13) according to the present invention (final product 2) is prepared by the reaction of Sub 3 or Sub 4 Sub 5, as shown in Scheme 4.
<반응식 4><Scheme 4>
1. Sub 3의 합성 예시1. Synthesis Example of Sub 3
*L은 화학식 (2-a), 화학식 (2-b), 화학식 (2-c)에서 정의된 L3 또는 L5이다.* L is L 3 or L 5 as defined in formula (2-a), formula (2-b), formula (2-c).
1) Sub 3-1-1 합성 예 (L=biphenyl)1) Synthesis Example of Sub 3-1-1 (L = biphenyl)
출발물질인 9H-carbazole (50.16 g, 300 mmol)에 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 80.05 g (수율: 67%)를 얻었다.Starter 9H-carbazole (50.16 g, 300 mmol) in 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to yield 80.05 g (yield: 67%) of the product.
2) Sub 3-1-2 합성 예 (L=9,9-2) Synthesis Example of Sub 3-1-2 (L = 9,9-
dimethyldimethyl
-9H--9H-
fluorenefluorene
) )
출발물질인 9H-carbazole (50.16 g, 300 mmol)에 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 88.11 g (수율: 67%)를 얻었다.Starting material 9H-carbazole (50.16 g, 300 mmol) in 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 88.11 g (yield: 67%) of the product.
3) Sub 3-1-3 합성 예 (L=9,9-3) Synthesis Example of Sub 3-1-3 (L = 9,9-
dimethyldimethyl
-9H--9H-
fluorenefluorene
) )
출발물질인 7H-benzo[c]carbazole (65.18 g, 300 mmol)에 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 92.8 g (수율: 69%)를 얻었다.Starting material, 7H-benzo [c] carbazole (65.18 g, 300 mmol), 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 92.8 g (yield: 69%) of the product.
4) Sub 3-1-4 합성 예 (L=9,9-4) Synthesis Example of Sub 3-1-4 (L = 9,9-
dimethyldimethyl
-9H--9H-
fluorenefluorene
) )
출발물질인 7H-benzo[c]carbazole (65.18 g, 300 mmol)에 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 95.24 g (수율: 65%)를 얻었다.Starting material, 7H-benzo [c] carbazole (65.18 g, 300 mmol), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 95.24 g (yield: 65%) of the product.
5) Sub 3-1-5 합성 예 (L=biphenyl )5) Sub 3-1-5 Synthesis Example (L = biphenyl)
출발물질인 11H-benzo[a]carbazole (65.18 g, 300 mmol)에 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 80.05 g (수율: 62%)를 얻었다.The starting material, 11H-benzo [a] carbazole 4 -bromo-4'-iodo-1,1'-biphenyl in (65.18 g, 300 mmol) ( 129.2 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to yield 80.05 g (yield: 62%) of the product.
**
6) Sub 3-1-6 합성 예 (L=9,9-6) Sub 3-1-6 Synthesis Example (L = 9,9-
dimethyldimethyl
-9H--9H-
fluorenefluorene
) )
출발물질인 5H-benzo[b]carbazole (65.18 g, 300 mmol)에 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 93.78 g (수율: 64%)를 얻었다.Starter, 5H-benzo [b] carbazole (65.18 g, 300 mmol), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 93.78 g (yield: 64%) of product.
7) Sub 3-1-7 합성 예 (L=biphenyl )7) Synthesis Example of Sub 3-1-7 (L = biphenyl)
출발물질인 9H-dibenzo[a,c]carbazole (80.2 g, 300 mmol)에 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 98.7 g (수율: 66%)를 얻었다.The starting material, 9H-dibenzo [a, c] carbazole 4-bromo-4'-iodo-1,1'-biphenyl in (80.2 g, 300 mmol) ( 129.2 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 98.7 g (yield: 66%) of the product.
8) Sub 3-1-8 합성 예 (L=biphenyl )8) Synthesis Example of Sub 3-1-8 (L = biphenyl)
출발물질인 N-phenylnaphthalen-1-amine (65.8 g, 300 mmol)에 4-bromo-4'-iodo-1,1'-biphenyl (129.2 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3
(41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 89.2 g (수율: 66%)를 얻었다.The starting material, N-phenylnaphthalen-1-amine 4 -bromo-4'-iodo-1,1'-biphenyl in (65.8 g, 300 mmol) ( 129.2 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 89.2 g (yield: 66%) of the product.
9) Sub 3-1-9 합성 예 (L=9,9-9) Synthesis Example of Sub 3-1-9 (L = 9,9-
dimethyldimethyl
-9H--9H-
fluorenefluorene
) )
출발물질인 7H-dibenzo[c,g]carbazole (80.2 g, 300 mmol)에 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na2SO4
(42.6 g, 300 mmol), K2CO3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol), nitrobenzene을 상기 합성법을 사용하여 생성물 98.5g (수율: 61%)를 얻었다.Starting material, 7H-dibenzo [c, g] carbazole (80.2 g, 300 mmol), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (143.7 g, 360 mmol), Na 2 SO 4 (42.6 g, 300 mmol), K 2 CO 3 (41.4 g, 300 mmol), Cu (5.72 g, 90 mmol) and nitrobenzene were obtained using the above synthesis method to give 98.5 g (yield: 61%) of the product.
2. Sub 4의 합성 예시2. Synthesis Example of Sub 4
반응식 4의 Sub 4는 하기 반응식 5의 반응경로에 의해 합성될 수 있다.Sub 4 of Scheme 4 may be synthesized by the reaction route of Scheme 5 below.
<반응식 5>Scheme 5
1) M4-2-1 합성 예1) M4-2-1 Synthesis Example
3-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) 을 DMF 980mL 에 녹인 후에, Bispinacolborate (39.1 g, 154 mmol), PdCl2(dppf) 촉매 (3.43 g, 4.2 mmol), KOAc (41.3 g, 420 mmol)을 순서대로 첨가한후 24 시간 교반하여 보레이트 화합물을 합성한 후에, 얻어진 화합물을 silicagel column 및 재결정을 걸쳐서 분리한후 보레이트 화합물을 35.2 g (68 %)얻었다. After dissolving 3-bromo-9-phenyl-9H-carbazole (45.1 g, 140 mmol) in 980 mL of DMF, Bispinacolborate (39.1 g, 154 mmol), PdCl 2 (dppf) catalyst (3.43 g, 4.2 mmol), KOAc ( 41.3 g, 420 mmol) was added sequentially, followed by stirring for 24 hours to synthesize the borate compound. The obtained compound was separated through a silicagel column and recrystallization to obtain 35.2 g (68%) of the borate compound.
2) M4-2-2 합성 예 2) Synthesis Example of M4-2-2
상기 M2-2-1과 동일한 실험방법을 통해서 40 g (64%)을 얻었다. 40 g (64%) was obtained through the same experimental method as the M2-2-1.
3) Sub 4-1-1 합성 예 3) Sub 4-1-1 Synthesis Example
*M2-2-1 (29.5 g, 80 mmol) 을 THF 360 mL 에 녹인후에, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd(PPh3)4 (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 물 180 mL 을 첨가한 후, 교반 환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 26.56 g (70 %) 얻었다.* M2-2-1 (29.5 g, 80 mmol) in THF 360 mL, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh 3 ) 4 (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and 180 mL of water were added, followed by stirring under reflux. 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 give 26.56 g (70%).
4) Sub 4-1-2 합성 예4) Synthesis Example of Sub 4-1-2
M2-2-1 (29.5 g, 80 mmol), THF 360 mL, 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd(PPh3)4 (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 물 180 mL 을 을 첨가한후, 교반 환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 22.9 g (72 %) 얻었다.M2-2-1 (29.5 g, 80 mmol), THF 360 mL, 1-bromo-4-iodobenzene (23.8 g, 84 mmol), Pd (PPh 3 ) 4 (2.8 g, 2.4 mmol), NaOH (9.6 g , 240 mmol) and 180 mL of water were added, followed by stirring under reflux. After completion of reaction, drying the ether was extracted with water and the organic layer is MgSO 4 and the organic material was concentrated and then generates silicagel column and recrystallized to give the product 22.9 g (72%).
5) Sub 4-1-3 합성 예 5) Sub 4-1-3 Synthesis Example
M2-2-1 (29.5 g, 80 mmol) 을 THF 360 mL 에 녹인후에, 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd(PPh3)4 (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 물 180 mL 을 첨가한 후, 교반 환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 24.7 g (65 %) 얻었다.After dissolving M2-2-1 (29.5 g, 80 mmol) in 360 mL of THF, 4'-bromo-3-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh 3 ) 4 ( 2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and 180 mL of water were added, followed by stirring under reflux. 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 give 24.7 g (65%).
6) Sub 4-1-4 합성 예 6) Synthesis Example of Sub 4-1-4
상기 합성에서 얻어진 M2-2-2 (35.63 g, 80 mmol) 을 THF 360 mL 에 녹인후에, 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd(PPh3)4 (2.8 g, 2.4mmol), NaOH (9.6 g, 240mmol), 물 180 mL 을 첨가한 후, 교반 환류 시킨다. 반응이 완료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 생성물을 29.51 g (67 %) 얻었다.M2-2-2 (35.63 g, 80 mmol) obtained in the above synthesis was dissolved in 360 mL of THF, followed by 4-bromo-4'-iodo-1,1'-biphenyl (30.16 g, 84 mmol), Pd (PPh 3 ) 4 (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) and 180 mL of water were added, followed by stirring under reflux. 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 substance was purified by silicagel column and recrystallized to obtain 29.51 g (67%).
3. Sub 5의 합성 예시3. Synthesis Example of Sub 5
반응식 4의 Sub 5는 하기 반응식 3의 Sub 2의 합성예시와 동일하다.Sub 5 of Scheme 4 is the same as the synthesis example of Sub 2 of Scheme 3.
화학식 (Chemical formula (
2)의2)
Final Product의 합성 Synthesis of Final Product
5-17의 합성예시Synthesis Example of 5-17
9-(4'-bromo-[1,1'-biphenyl]-4-yl)-9H-carbazole(9.6g, 24mmol)을 톨루엔에 녹인 후에, di([1,1'-biphenyl]-4-yl)amine(6.4g, 20mmol), Pd2(dba)3
(0.05당량), PPh3 (0.1당량), NaOt-Bu (3당량)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류 시킨다. 반응이 종료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 최종화합물을 12.9g (수율: 84%)을 얻었다. 9- (4'-bromo- [1,1'-biphenyl] -4-yl) -9H-carbazole (9.6 g, 24 mmol) was dissolved in toluene and then di ([1,1'-biphenyl] -4- yl) amine (6.4g, 20mmol), Pd 2 (dba) 3 (0.05 equiv), PPh 3 (0.1 equiv) and NaO t —Bu (3 equiv) were then added, and the mixture was stirred and refluxed at 100 ° C. for 24 hours. When the reaction was completed by drying the ether was extracted with water and the organic layer is MgSO 4 and the organic material was concentrated and then generates silicagel column and recrystallized from 12.9g of the final compound (yield: 84%) was obtained.
*5-32의 합성예시
* Synthesis Example of 5-32
3-(4-bromophenyl)-9-phenyl-9H-carbazole (9.6g, 24mmol)을 톨루엔에 녹인 후에, N-([1,1'-biphenyl]-4-yl)-9,9-dimethyl-9H-fluoren-2-amine (7.2g, 20mmol), Pd2(dba)3
(0.05당량), PPh3
(0.1당량), NaOt-Bu (3당량)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류 시킨다. 반응이 종료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 최종화합물을 13.8g (수율: 85%)을 얻었다. 3- (4-bromophenyl) -9-phenyl-9H-carbazole (9.6 g, 24 mmol) was dissolved in toluene, followed by N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl- 9H-fluoren-2-amine (7.2 g, 20 mmol), Pd 2 (dba) 3 (0.05 equiv), PPh 3 (0.1 eq.), Then the addition of NaO t -Bu (3 equiv), respectively, is refluxed at 100 ℃ stirred for 24 hours. 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 substance was purified by silicagel column and recrystallized to obtain 13.8 g (yield: 85%) of the final compound.
*5-61의 합성예시
* Synthesis Example of 5-61
N-(4'-bromo-[1,1'-biphenyl]-4-yl)-N-phenylnaphthalen-1-amine (10.8g, 24mmol)을 톨루엔에 녹인 후에, N-phenylnaphthalen-1-amine (4.4g, 20mmol), Pd2(dba)3 (0.05당량), PPh3
(0.1당량), NaOt-Bu (3당량)을 각각 첨가한 뒤, 100℃ 에서 24시간 교반 환류 시킨다. 반응이 종료되면 ether와 물로 추출한 후 유기층을 MgSO4로 건조하고 농축한 후 생성된 유기물을 silicagel column 및 재결정하여 최종화합물을 11.4g (수율: 81%)을 얻었다. N- (4'-bromo- [1,1'-biphenyl] -4-yl) -N-phenylnaphthalen-1-amine (10.8 g, 24 mmol) is dissolved in toluene, followed by N-phenylnaphthalen-1-amine (4.4 g, 20 mmol), Pd 2 (dba) 3 (0.05 equiv), PPh 3 (0.1 equiv) and NaO t -Bu (3 equiv) were then added, and the mixture was stirred and refluxed at 100 ° C. for 24 hours. 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 substance was purified by silicagel column and recrystallized to obtain 11.4 g (yield: 81%) of the final compound.
*상기에서 얻은 Product 중 일부분을 하기와 같이 Mass Data로 확인하였다. * Part of the product obtained above was confirmed by the Mass Data as follows.
| 화합물compound | FD-MSFD-MS | 화합물compound | FD-MSFD-MS |
| 5-175-17 | m/z=638.27 (C48H34N2=638.80)m / z = 638.27 (C 48 H 34 N 2 = 638.80) | 5-205-20 | m/z=678.30 (C51H38N2=678.86)m / z = 678.30 (C 51 H 38 N 2 = 678.86) |
| 5-215-21 | m/z=802.33 (C61H42N2=803.00) m / z = 802.33 (C 61 H 42 N 2 = 803.00) | 5-225-22 | m/z=800.32 (C61H40N2=800.98)m / z = 800.32 (C 61 H 40 N 2 = 800.98) |
| 5-325-32 | m/z=678.30 (C51H38N2=678.86)m / z = 678.30 (C 51 H 38 N 2 = 678.86) | 5-335-33 | m/z=802.33 (C61H42N2=803.00)m / z = 802.33 (C 61 H 42 N 2 = 803.00) |
| 5-345-34 | m/z=800.32 (C61H40N2=800.98)m / z = 800.32 (C 61 H 40 N 2 = 800.98) | 5-435-43 | m/z=714.30 (C54H38N2=714.89)m / z = 714.30 (C 54 H 38 N 2 = 714.89) |
| 5-445-44 | m/z=754.33 (C57H42N2=754.96)m / z = 754.33 (C 57 H 42 N 2 = 754.96) | 5-455-45 | m/z=878.37 (C67H46N2=879.10)m / z = 878.37 (C 67 H 46 N 2 = 879.10) |
| 5-465-46 | m/z=876.35 (C67H44N2=877.08)m / z = 876.35 (C 67 H 44 N 2 = 877.08) | 5-475-47 | m/z=744.26 (C54H36N2S=744.94)m / z = 744.26 (C 54 H 36 N 2 S = 744.94) |
| 5-525-52 | m/z=826.33 (C63H42N2=827.02)m / z = 826.33 (C 63 H 42 N 2 = 827.02) | 5-535-53 | m/z=824.32 (C63H40N2=825.01)m / z = 824.32 (C 63 H 40 N 2 = 825.01) |
| 5-545-54 | m/z=688.29 (C52H36N2=688.86)m / z = 688.29 (C 52 H 36 N 2 = 688.86) | 5-555-55 | m/z=728.32 (C55H40N2=728.92)m / z = 728.32 (C 55 H 40 N 2 = 728.92) |
| 5-575-57 | m/z=778.33 (C59H42N2=778.98)m / z = 778.33 (C 59 H 42 N 2 = 778.98) | 5-585-58 | m/z=902.37 (C69H46N2=903.12)m / z = 902.37 (C 69 H 46 N 2 = 903.12) |
| 5-595-59 | m/z=900.35 (C69H44N2=901.10) m / z = 900.35 (C 69 H 44 N 2 = 901.10) | 5-605-60 | m/z=538.24 (C40H30N2=538.68)m / z = 538.24 (C 40 H 30 N 2 = 538.68) |
| 5-615-61 | m/z=588.26 (C44H32N2=588.74) m / z = 588.26 (C 44 H 32 N 2 = 588.74) | 5-625-62 | m/z=588.26 (C44H32N2=588.74)m / z = 588.26 (C 44 H 32 N 2 = 588.74) |
| 5-635-63 | m/z=614.27 (C46H34N2=614.78)m / z = 614.27 (C 46 H 34 N 2 = 614.78) |
유기전기소자의 제조평가Manufacturing Evaluation of Organic Electrical Device
실시 예 1) 그린 유기 발광 소자의 제작 및 시험 Example 1 Fabrication and Test of Green Organic Light Emitting Diode
먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께로 형성하였다. 이어서, 이 막 상에 정공수송 화합물로서 4,4-비스[N-(1-나프틸)-N-페닐아미노]비페닐 (이하 -NPD로 약기함)를 60 nm 두께로 진공증착하여 홀 수송층을 형성하였다. 이어서, 발광 보조층 재료로서 상기 발명 화합물들과 비교예를 20nm의 두께로 진공증착하여 발광 보조층을 형성하였다. 발광 보조층을 형성한 후, 발광 보조층 상부에 호스트로서는 CBP[4,4'-N,N'-dicarbazole-biphenyl], 도판트로서는 Ir(ppy)3 [tris(2-phenylpyridine)-iridium]을 95:5 중량으로 도핑함으로써 상기 발광 보조층 위에 30nm 두께의 발광층을 증착하였다. 홀 저지층으로 (1,1'-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하고, 전자수송층으로 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 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 유기전계 발광소자를 제조하였다.First, on the ITO layer (anode) formed on the glass substrate, N 1- (naphthalen-2-yl) -N 4 , N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N 1 -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum-deposited to a thickness of 60 nm as a hole transporting compound on the membrane to form a hole transport layer. Formed. Subsequently, the inventive compounds and Comparative Examples were vacuum-deposited to a thickness of 20 nm as a light emission auxiliary layer material to form a light emission auxiliary layer. After forming the light emission auxiliary layer, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host and Ir (ppy) 3 [tris (2-phenylpyridine) -iridium] as a host. The light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping at 95: 5 weight. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a 40 nm thick film. Thereafter, LiF, 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 use an organic light emitting device.
이와 같이 제조된 실시예 및 비교예 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 5000cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 하기표는 소자제작 및 평가한 결과를 나타낸다.The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measurement result was measured at a luminance of 5000 cd / m2. The T95 life was measured using a life measurement instrument manufactured by McScience. The following table shows the results of device fabrication and evaluation.
[[
비교예Comparative example
1] One]
발광보조층을 사용하지 않은 것을 제외하고는 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다. An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the light emitting auxiliary layer was not used.
[[
비교예Comparative example
2] 2]
본 발명의 화합물 대신 비교 화합물 1을 이용하여 발광보조층을 형성하는 점을 제외하고 상기 실시예 1과 동일한 방법으로 유기전기발광소자를 제작하였다.An organic electroluminescent device was manufactured in the same manner as in Example 1, except that a light emitting auxiliary layer was formed using Comparative Compound 1 instead of the compound of the present invention.
비교화합물 1 Comparative Compound 1
| 화합물compound | VoltageVoltage | Current DensityCurrent density | Brightness(cd/m2)Brightness (cd / m2) | EfficiencyEfficiency | LifetimeT(95)LifetimeT (95) | CIE(x, y)CIE (x, y) | |
| 비교예(1)Comparative Example (1) | - - | 6.06.0 | 21.7 21.7 | 5000.0 5000.0 | 23.0 23.0 | 61.8 61.8 | (0.31, 0.61)(0.31, 0.61) |
| 비교예(2)Comparative Example (2) | 비교화합물 1 Comparative Compound 1 | 6.26.2 | 14.3 14.3 | 5000.0 5000.0 | 35.0 35.0 | 94..5 94..5 | (0.31, 0.60)(0.31, 0.60) |
| 실시예(1)Example (1) | 화합물(1-1)Compound (1-1) | 5.6 5.6 | 10.9 10.9 | 5000.0 5000.0 | 45.8 45.8 | 118.1 118.1 | (0.31, 0.60)(0.31, 0.60) |
| 실시예(2)Example (2) | 화합물(1-2)Compound (1-2) | 5.5 5.5 | 11.3 11.3 | 5000.0 5000.0 | 44.3 44.3 | 114.2 114.2 | (0.32, 0.61)(0.32, 0.61) |
| 실시예(3)Example (3) | 화합물(1-3)Compound (1-3) | 5.6 5.6 | 11.2 11.2 | 5000.0 5000.0 | 44.7 44.7 | 117.7 117.7 | (0.31, 0.61)(0.31, 0.61) |
| 실시예(4)Example (4) | 화합물(1-4)Compound (1-4) | 5.7 5.7 | 10.7 10.7 | 5000.0 5000.0 | 46.7 46.7 | 114.1 114.1 | (0.33, 0.60)(0.33, 0.60) |
| 실시예(5)Example (5) | 화합물(1-6)Compound (1-6) | 5.7 5.7 | 10.8 10.8 | 5000.0 5000.0 | 46.4 46.4 | 113.6 113.6 | (0.31, 0.60)(0.31, 0.60) |
| 실시예(6)Example (6) | 화합물(1-7)Compound (1-7) | 5.5 5.5 | 11.5 11.5 | 5000.0 5000.0 | 43.4 43.4 | 119.9 119.9 | (0.32, 0.61)(0.32, 0.61) |
| 실시예(7)Example (7) | 화합물(1-8)Compound (1-8) | 5.5 5.5 | 11.5 11.5 | 5000.0 5000.0 | 43.5 43.5 | 113.8 113.8 | (0.32, 0.61)(0.32, 0.61) |
| 실시예(8)Example (8) | 화합물(1-13)Compound (1-13) | 5.6 5.6 | 11.6 11.6 | 5000.0 5000.0 | 43.1 43.1 | 116.6 116.6 | (0.33, 0.60)(0.33, 0.60) |
| 실시예(9)Example (9) | 화합물(1-14)Compound (1-14) | 5.6 5.6 | 11.1 11.1 | 5000.0 5000.0 | 45.1 45.1 | 119.0 119.0 | (0.30, 0.61)(0.30, 0.61) |
| 실시예(10)Example (10) | 화합물(1-15)Compound (1-15) | 5.7 5.7 | 10.6 10.6 | 5000.0 5000.0 | 47.1 47.1 | 119.2 119.2 | (0.31, 0.61)(0.31, 0.61) |
| 실시예(11)Example (11) | 화합물(2-1)Compound (2-1) | 5.6 5.6 | 10.5 10.5 | 5000.0 5000.0 | 47.5 47.5 | 118.1 118.1 | (0.30, 0.60)(0.30, 0.60) |
| 실시예(12)Example (12) | 화합물(2-2)Compound (2-2) | 5.5 5.5 | 11.8 11.8 | 5000.0 5000.0 | 42.2 42.2 | 116.0 116.0 | (0.33, 0.61)(0.33, 0.61) |
| 실시예(13)Example (13) | 화합물(2-3)Compound (2-3) | 5.5 5.5 | 11.9 11.9 | 5000.0 5000.0 | 42.0 42.0 | 113.8 113.8 | (0.32, 0.61)(0.32, 0.61) |
| 실시예(14)Example (14) | 화합물(2-4)Compound (2-4) | 5.6 5.6 | 11.0 11.0 | 5000.0 5000.0 | 45.5 45.5 | 118.3 118.3 | (0.33, 0.60)(0.33, 0.60) |
| 실시예(15)Example (15) | 화합물(2-6)Compound (2-6) | 5.6 5.6 | 10.8 10.8 | 5000.0 5000.0 | 46.4 46.4 | 111.9 111.9 | (0.30, 0.61)(0.30, 0.61) |
| 실시예(16)Example (16) | 화합물(2-7)Compound (2-7) | 5.6 5.6 | 11.4 11.4 | 5000.0 5000.0 | 43.7 43.7 | 114.6 114.6 | (0.31, 0.61)(0.31, 0.61) |
| 실시예(17)Example (17) | 화합물(2-8)Compound (2-8) | 5.6 5.6 | 11.7 11.7 | 5000.0 5000.0 | 42.7 42.7 | 117.5 117.5 | (0.31, 0.60)(0.31, 0.60) |
| 실시예(18)Example (18) | 화합물(2-13)Compound (2-13) | 5.6 5.6 | 11.4 11.4 | 5000.0 5000.0 | 43.7 43.7 | 119.8 119.8 | (0.33, 0.61)(0.33, 0.61) |
| 실시예(19)Example (19) | 화합물(2-14)Compound (2-14) | 5.7 5.7 | 10.9 10.9 | 5000.0 5000.0 | 45.9 45.9 | 117.5 117.5 | (0.32, 0.60)(0.32, 0.60) |
| 실시예(20)Example (20) | 화합물(2-15)Compound (2-15) | 5.7 5.7 | 10.7 10.7 | 5000.0 5000.0 | 46.7 46.7 | 114.0 114.0 | (0.32, 0.61)(0.32, 0.61) |
상기 표 5의 결과로부터 알 수 있듯이, 본 발명의 유기전기발광소자용 재료를 발광보조층 재료로 사용하여 그린 유기전기발광소자를 제작한 경우, 발광보조층을 사용하지 않거나 비교화합물 1을 사용한 비교예 보다 유기전기발광소자의 구동전압을 낮출 수 있을 뿐만 아니라 발광 효율과 수명을 현저히 개선시킬 수 있음을 알 수 있다. As can be seen from the results of Table 5, when the green organic electroluminescent device was manufactured using the organic electroluminescent device material of the present invention as a light emitting auxiliary layer material, the comparison was made without using the light emitting auxiliary layer or using Comparative Compound 1. It can be seen that not only the driving voltage of the organic electroluminescent device can be lowered but also the light emission efficiency and lifespan are significantly improved.
다시 말해, 발광보조층을 사용하지 않은 비교예 1 보다는 비교화합물을 발광보조층을 사용한 비교예 1, 그리고 본 발명 화합물을 사용한 실시예 1~20의 결과가 우수했으며, 발명화합물과 유사하나 dibenzotiophen에 2번 위치로 carbazole과 아민기가 모두 치환된 비교화합물 1 보다는 dibenzotiophen 또는 dibenzofuran에 비대칭적으로 2번과 3번 위치로 한정돼서 치환된 발명화합물이 가장 우수한 결과를 나타내었다. In other words, the comparative compounds of Comparative Example 1 using the light emitting auxiliary layer and Comparative Examples 1 to 20 using the compound of the present invention were superior to Comparative Example 1, which did not use the light emitting auxiliary layer. Inventive compounds substituted with positions 2 and 3 asymmetrically to dibenzotiophen or dibenzofuran showed the best results, compared to Comparative Compound 1, in which both carbazole and amine groups were substituted at position 2.
이는 하기의 표 6과 같이 비교화합물 1과 발명화합물의 전자 구름도가 상이함을 확인할 수 있고, 특히 LUMO에서 큰 차이를 확인할 수 있었다. 다시 말해, LUMO의 전자구름도를 보면 비교화합물 1의 전자구름도는 dibenzothiophen에 집중되는 것을 볼 수 있지만, 발명화합물은 dibenzothiophen 및 아민기까지 모두 전자구름이 형성되어 있는 것을 확인할 수 있다. This can be confirmed that the electron cloud degree of Comparative Compound 1 and the inventive compound are different, as shown in Table 6 below, in particular, it was confirmed a large difference in LUMO. In other words, when looking at the electron cloud diagram of LUMO, it can be seen that the electron cloud diagram of Comparative Compound 1 is concentrated in dibenzothiophen, but the inventive compound has an electron cloud formed in both dibenzothiophen and amine groups.
따라서 상기의 결과를 설명한 바와 같이 동일한 코어 및 치환기일지라도 치환기의 위치에 따라 화합물의 물성이 바뀌고 이것이 소자 성능향상에 주요 인자로 작용하여 상이한 결과가 도출됨을 확인할 수 있다. 즉, dibenzotiophen 또는 dibenzofuran에 비대칭적으로 2번과 3번 위치에 치환기가 치환됨에 따라 화합물의 물성 및 소자의 결과가 현저히 달라짐을 시사하고 있다. Therefore, as described above, even though the same core and the substituent, the physical properties of the compound change depending on the position of the substituent, and this can be confirmed that different results are obtained by acting as a major factor in improving device performance. In other words, the substitution of substituents at positions 2 and 3 asymmetrically to dibenzotiophen or dibenzofuran suggests that the physical properties of the compound and the results of the device are significantly different.
실시 예 2) Example 2)
레드Red
유기 발광 소자의 제작 및 시험 Fabrication and Test of Organic Light-Emitting Device
먼저, 유리 기판에 형성된 ITO층(양극) 위에 우선 홀 주입층으로서 N1-(naphthalen-2-yl)-N4,N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (2-TNATA로 약기함) 막을 진공증착하여 60 nm 두께로 형성하였다. 이어서, 이 막 상에 정공수송 화합물로서 화학식 (13)로 표시되는 상기 발명화합물을 60 nm 두께로 진공증착하여 홀 수송층을 형성하였다. 이어서, 발광 보조층 재료로서 화학식 (1)로 표시되는 상기 발명 화합물을 20nm의 두께로 진공증착하여 발광 보조층을 형성하였다. 발광 보조층을 형성한 후, 발광 보조층 상부에 호스트로서는 CBP[4,4'-N,N'-dicarbazole-biphenyl]를 사용하였으며, 도판트로서는 (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(Ⅲ)acetylacetonate] 을 95:5 중량으로 도핑함으로써 상기 발광 보조층 위에 30nm 두께의 발광층을 증착하였다. 홀 저지층으로 (1,1'-비스페닐)-4-올레이토)비스(2-메틸-8-퀴놀린올레이토)알루미늄(이하 BAlq로 약기함)을 10 nm 두께로 진공증착하고, 전자수송층으로 트리스(8-퀴놀리놀)알루미늄(이하 Alq3로 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 제조하였다.First, as a first hole-injecting layer on the ITO layer (anode) formed on the glass substrate N 1 - (naphthalen-2- yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl ) -N 1 -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) membrane was vacuum deposited to form a thickness of 60 nm. Subsequently, the above-mentioned compound represented by the formula (13) as a hole transport compound was vacuum deposited to a thickness of 60 nm on this film to form a hole transport layer. Subsequently, the inventive compound represented by the formula (1) was vacuum deposited to a thickness of 20 nm as a light emitting auxiliary layer material to form a light emitting auxiliary layer. After the emission auxiliary layer was formed, CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a host on the emission auxiliary layer, and as a dopant, (piq) 2 Ir (acac) [bis- ( A light emitting layer having a thickness of 30 nm was deposited on the light emitting auxiliary layer by doping 1-phenylisoquinolyl) iridium (III) acetylacetonate] at a weight of 95: 5. As a hole blocking layer, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm, and the electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was formed into a 40 nm thick film. Subsequently, 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.
이와 같이 제조된 실시예 및 비교예 유기전기발광소자들에 순바이어스 직류전압을 가하여 포토리서치(photoresearch)사의 PR-650으로 전기발광(EL) 특성을 측정하였으며, 그 측정 결과 2500cd/m2 기준 휘도에서 맥사이언스사에서 제조된 수명 측정 장비를 통해 T95 수명을 측정하였다. 하기 표는 소자제작 및 평가한 결과를 나타낸다.The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices manufactured as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage. The T95 life was measured using a life measurement instrument manufactured by McScience. The following table shows the results of device fabrication and evaluation.
비교예 3,4,5)Comparative Example 3, 4, 5)
발광보조층으로 비교화합물 1을 사용한 것을 제외하고는 상기 실시예 2와 동일한 방법으로 유기전기발광소자를 제작하였다. An organic electroluminescent device was manufactured in the same manner as in Example 2, except that Comparative Compound 1 was used as the light emitting auxiliary layer.
| 정공수송층 화합물Hole transport layer compound | 발광보조층 화합물Light emitting auxiliary compound | VoltageVoltage | Current DensityCurrent density | Brightness(cd/m2)Brightness (cd / m2) | EfficiencyEfficiency | LifetimeT(95)LifetimeT (95) | |
| 비교예(3)Comparative Example (3) | 화합물(5-17)Compound (5-17) | 비교화합물 1Comparative Compound 1 | 5.7 5.7 | 27.2 27.2 | 2500.0 2500.0 | 9.2 9.2 | 85.3 85.3 |
| 비교예(4)Comparative Example (4) | 화합물(5-32)Compound (5-32) | 비교화합물 1Comparative Compound 1 | 5.25.2 | 23.1 23.1 | 2500.0 2500.0 | 10.8 10.8 | 87.7 87.7 |
| 비교예(5)Comparative Example (5) | 화합물(5-61)Compound (5-61) | 비교화합물 1Comparative Compound 1 | 5.45.4 | 25.5 25.5 | 2500.0 2500.0 | 9.8 9.8 | 82.9 82.9 |
| 실시예(21)Example (21) | 화합물(5-17)Compound (5-17) | 화합물(1-1)Compound (1-1) | 5.1 5.1 | 20.7 20.7 | 2500.0 2500.0 | 12.1 12.1 | 108.4 108.4 |
| 실시예(22)Example (22) | 화합물(5-17)Compound (5-17) | 화합물(1-2)Compound (1-2) | 5.3 5.3 | 24.1 24.1 | 2500.0 2500.0 | 10.4 10.4 | 106.5 106.5 |
| 실시예(23)Example (23) | 화합물(5-17)Compound (5-17) | 화합물(1-3)Compound (1-3) | 5.4 5.4 | 21.8 21.8 | 2500.0 2500.0 | 11.5 11.5 | 106.8 106.8 |
| 실시예(24)Example (24) | 화합물(5-17)Compound (5-17) | 화합물(1-4)Compound (1-4) | 5.1 5.1 | 19.2 19.2 | 2500.0 2500.0 | 13.0 13.0 | 112.2 112.2 |
| 실시예(25)Example (25) | 화합물(5-17)Compound (5-17) | 화합물(1-6)Compound (1-6) | 5.2 5.2 | 18.2 18.2 | 2500.0 2500.0 | 13.7 13.7 | 101.8 101.8 |
| 실시예(26)Example (26) | 화합물(5-17)Compound (5-17) | 화합물(1-7)Compound (1-7) | 5.4 5.4 | 24.7 24.7 | 2500.0 2500.0 | 10.1 10.1 | 103.7 103.7 |
| 실시예(27)Example (27) | 화합물(5-17)Compound (5-17) | 화합물(1-8)Compound (1-8) | 5.4 5.4 | 23.7 23.7 | 2500.0 2500.0 | 10.5 10.5 | 109.9 109.9 |
| 실시예(28)Example (28) | 화합물(5-17)Compound (5-17) | 화합물(1-13)Compound (1-13) | 5.4 5.4 | 21.1 21.1 | 2500.0 2500.0 | 11.8 11.8 | 102.8 102.8 |
| 실시예(29)Example (29) | 화합물(5-17)Compound (5-17) | 화합물(1-14)Compound (1-14) | 5.2 5.2 | 19.1 19.1 | 2500.0 2500.0 | 13.1 13.1 | 106.9 106.9 |
| 실시예(30)Example (30) | 화합물(5-17)Compound (5-17) | 화합물(1-15)Compound (1-15) | 5.1 5.1 | 17.9 17.9 | 2500.0 2500.0 | 14.0 14.0 | 113.2 113.2 |
| 실시예(31)Example (31) | 화합물(5-17)Compound (5-17) | 화합물(2-1)Compound (2-1) | 5.1 5.1 | 18.3 18.3 | 2500.0 2500.0 | 13.7 13.7 | 118.3 118.3 |
| 실시예(32)Example (32) | 화합물(5-17)Compound (5-17) | 화합물(2-2)Compound (2-2) | 5.4 5.4 | 22.2 22.2 | 2500.0 2500.0 | 11.2 11.2 | 109.7 109.7 |
| 실시예(33)Example (33) | 화합물(5-17)Compound (5-17) | 화합물(2-3)Compound (2-3) | 5.3 5.3 | 23.4 23.4 | 2500.0 2500.0 | 10.7 10.7 | 101.5 101.5 |
| 실시예(34)Example (34) | 화합물(5-17)Compound (5-17) | 화합물(2-4)Compound (2-4) | 5.1 5.1 | 18.7 18.7 | 2500.0 2500.0 | 13.4 13.4 | 114.1 114.1 |
| 실시예(35)Example (35) | 화합물(5-17)Compound (5-17) | 화합물(2-6)Compound (2-6) | 5.2 5.2 | 18.1 18.1 | 2500.0 2500.0 | 13.8 13.8 | 116.7 116.7 |
| 실시예(36)Example (36) | 화합물(5-17)Compound (5-17) | 화합물(2-7)Compound (2-7) | 5.5 5.5 | 24.7 24.7 | 2500.0 2500.0 | 10.1 10.1 | 101.4 101.4 |
| 실시예(37)Example (37) | 화합물(5-17)Compound (5-17) | 화합물(2-8)Compound (2-8) | 5.4 5.4 | 24.2 24.2 | 2500.0 2500.0 | 10.3 10.3 | 109.2 109.2 |
| 실시예(38)Example (38) | 화합물(5-17)Compound (5-17) | 화합물(2-13)Compound (2-13) | 5.3 5.3 | 21.5 21.5 | 2500.0 2500.0 | 11.6 11.6 | 114.1 114.1 |
| 실시예(39)Example (39) | 화합물(5-17)Compound (5-17) | 화합물(2-14)Compound (2-14) | 5.3 5.3 | 18.1 18.1 | 2500.0 2500.0 | 13.8 13.8 | 117.1 117.1 |
| 실시예(40)Example (40) | 화합물(5-17)Compound (5-17) | 화합물(2-15)Compound (2-15) | 5.2 5.2 | 18.8 18.8 | 2500.0 2500.0 | 13.3 13.3 | 103.7 103.7 |
| 실시예(41)Example (41) | 화합물(5-32)Compound (5-32) | 화합물(1-1)Compound (1-1) | 4.5 4.5 | 15.1 15.1 | 2500.0 2500.0 | 16.5 16.5 | 113.4 113.4 |
| 실시예(42)Example (42) | 화합물(5-32)Compound (5-32) | 화합물(1-2)Compound (1-2) | 5.0 5.0 | 19.1 19.1 | 2500.0 2500.0 | 13.1 13.1 | 102.7 102.7 |
| 실시예(43)Example (43) | 화합물(5-32)Compound (5-32) | 화합물(1-3)Compound (1-3) | 5.0 5.0 | 17.2 17.2 | 2500.0 2500.0 | 14.6 14.6 | 116.7 116.7 |
| 실시예(44)Example (44) | 화합물(5-32)Compound (5-32) | 화합물(1-4)Compound (1-4) | 4.8 4.8 | 14.9 14.9 | 2500.0 2500.0 | 16.8 16.8 | 106.6 106.6 |
| 실시예(45)Example (45) | 화합물(5-32)Compound (5-32) | 화합물(1-6)Compound (1-6) | 4.8 4.8 | 15.1 15.1 | 2500.0 2500.0 | 16.5 16.5 | 110.0 110.0 |
| 실시예(46)Example (46) | 화합물(5-32)Compound (5-32) | 화합물(1-7)Compound (1-7) | 4.9 4.9 | 18.3 18.3 | 2500.0 2500.0 | 13.7 13.7 | 101.2 101.2 |
| 실시예(47)Example (47) | 화합물(5-32)Compound (5-32) | 화합물(1-8)Compound (1-8) | 5.0 5.0 | 16.9 16.9 | 2500.0 2500.0 | 14.8 14.8 | 116.7 116.7 |
| 실시예(48)Example (48) | 화합물(5-32)Compound (5-32) | 화합물(1-13)Compound (1-13) | 5.0 5.0 | 18.0 18.0 | 2500.0 2500.0 | 13.9 13.9 | 116.0 116.0 |
| 실시예(49)Example (49) | 화합물(5-32)Compound (5-32) | 화합물(1-14)Compound (1-14) | 4.6 4.6 | 15.7 15.7 | 2500.0 2500.0 | 15.9 15.9 | 114.8 114.8 |
| 실시예(50)Example (50) | 화합물(5-32)Compound (5-32) | 화합물(1-15)Compound (1-15) | 4.7 4.7 | 14.9 14.9 | 2500.0 2500.0 | 16.7 16.7 | 102.2 102.2 |
| 실시예(51)Example (51) | 화합물(5-32)Compound (5-32) | 화합물(2-1)Compound (2-1) | 4.5 4.5 | 15.2 15.2 | 2500.0 2500.0 | 16.5 16.5 | 105.1 105.1 |
| 실시예(52)Example (52) | 화합물(5-32)Compound (5-32) | 화합물(2-2)Compound (2-2) | 5.0 5.0 | 18.1 18.1 | 2500.0 2500.0 | 13.8 13.8 | 114.3 114.3 |
| 실시예(53)Example (53) | 화합물(5-32)Compound (5-32) | 화합물(2-3)Compound (2-3) | 4.9 4.9 | 18.1 18.1 | 2500.0 2500.0 | 13.8 13.8 | 115.5 115.5 |
| 실시예(54)Example (54) | 화합물(5-32)Compound (5-32) | 화합물(2-4)Compound (2-4) | 4.8 4.8 | 15.8 15.8 | 2500.0 2500.0 | 15.9 15.9 | 110.3 110.3 |
| 실시예(55)Example (55) | 화합물(5-32)Compound (5-32) | 화합물(2-6)Compound (2-6) | 4.6 4.6 | 15.1 15.1 | 2500.0 2500.0 | 16.5 16.5 | 118.4 118.4 |
| 실시예(56)Example (56) | 화합물(5-32)Compound (5-32) | 화합물(2-7)Compound (2-7) | 5.0 5.0 | 17.7 17.7 | 2500.0 2500.0 | 14.1 14.1 | 106.5 106.5 |
| 실시예(57)Example (57) | 화합물(5-32)Compound (5-32) | 화합물(2-8)Compound (2-8) | 4.9 4.9 | 19.2 19.2 | 2500.0 2500.0 | 13.1 13.1 | 109.4 109.4 |
| 실시예(58)Example (58) | 화합물(5-32)Compound (5-32) | 화합물(2-13)Compound (2-13) | 4.9 4.9 | 19.2 19.2 | 2500.0 2500.0 | 13.0 13.0 | 100.9 100.9 |
| 실시예(59)Example (59) | 화합물(5-32)Compound (5-32) | 화합물(2-14)Compound (2-14) | 4.6 4.6 | 15.7 15.7 | 2500.0 2500.0 | 15.9 15.9 | 107.1 107.1 |
| 실시예(60)Example (60) | 화합물(5-32)Compound (5-32) | 화합물(2-15)Compound (2-15) | 4.8 4.8 | 15.5 15.5 | 2500.0 2500.0 | 16.1 16.1 | 109.1 109.1 |
| 실시예(61)Example (61) | 화합물(5-61)Compound (5-61) | 화합물(1-1)Compound (1-1) | 4.8 4.8 | 17.1 17.1 | 2500.0 2500.0 | 14.6 14.6 | 113.4 113.4 |
| 실시예(62)Example (62) | 화합물(5-61)Compound (5-61) | 화합물(1-2)Compound (1-2) | 5.0 5.0 | 20.1 20.1 | 2500.0 2500.0 | 12.4 12.4 | 115.8 115.8 |
| 실시예(63)Example (63) | 화합물(5-61)Compound (5-61) | 화합물(1-3)Compound (1-3) | 5.1 5.1 | 19.7 19.7 | 2500.0 2500.0 | 12.7 12.7 | 103.3 103.3 |
| 실시예(64)Example (64) | 화합물(5-61)Compound (5-61) | 화합물(1-4)Compound (1-4) | 4.8 4.8 | 16.8 16.8 | 2500.0 2500.0 | 14.9 14.9 | 100.7 100.7 |
| 실시예(65)Example (65) | 화합물(5-61)Compound (5-61) | 화합물(1-6)Compound (1-6) | 4.8 4.8 | 17.0 17.0 | 2500.0 2500.0 | 14.7 14.7 | 109.0 109.0 |
| 실시예(66)Example (66) | 화합물(5-61)Compound (5-61) | 화합물(1-7)Compound (1-7) | 4.9 4.9 | 20.6 20.6 | 2500.0 2500.0 | 12.1 12.1 | 110.0 110.0 |
| 실시예(67)Example (67) | 화합물(5-61)Compound (5-61) | 화합물(1-8)Compound (1-8) | 5.0 5.0 | 19.7 19.7 | 2500.0 2500.0 | 12.7 12.7 | 100.1 100.1 |
| 실시예(68)Example (68) | 화합물(5-61)Compound (5-61) | 화합물(1-13)Compound (1-13) | 5.1 5.1 | 18.1 18.1 | 2500.0 2500.0 | 13.8 13.8 | 117.9 117.9 |
| 실시예(69)Example (69) | 화합물(5-61)Compound (5-61) | 화합물(1-14)Compound (1-14) | 4.6 4.6 | 16.3 16.3 | 2500.0 2500.0 | 15.4 15.4 | 104.8 104.8 |
| 실시예(70)Example (70) | 화합물(5-61)Compound (5-61) | 화합물(1-15)Compound (1-15) | 4.6 4.6 | 16.2 16.2 | 2500.0 2500.0 | 15.5 15.5 | 110.9 110.9 |
| 실시예(71)Example (71) | 화합물(5-61)Compound (5-61) | 화합물(2-1)Compound (2-1) | 4.6 4.6 | 17.3 17.3 | 2500.0 2500.0 | 14.5 14.5 | 111.2 111.2 |
| 실시예(72)Example (72) | 화합물(5-61)Compound (5-61) | 화합물(2-2)Compound (2-2) | 5.0 5.0 | 20.1 20.1 | 2500.0 2500.0 | 12.5 12.5 | 117.4 117.4 |
| 실시예(73)Example (73) | 화합물(5-61)Compound (5-61) | 화합물(2-3)Compound (2-3) | 4.9 4.9 | 18.9 18.9 | 2500.0 2500.0 | 13.2 13.2 | 116.9 116.9 |
| 실시예(74)Example (74) | 화합물(5-61)Compound (5-61) | 화합물(2-4)Compound (2-4) | 4.8 4.8 | 17.0 17.0 | 2500.0 2500.0 | 14.7 14.7 | 119.6 119.6 |
| 실시예(75)Example (75) | 화합물(5-61)Compound (5-61) | 화합물(2-6)Compound (2-6) | 4.6 4.6 | 17.3 17.3 | 2500.0 2500.0 | 14.4 14.4 | 107.7 107.7 |
| 실시예(76)Example (76) | 화합물(5-61)Compound (5-61) | 화합물(2-7)Compound (2-7) | 5.1 5.1 | 17.9 17.9 | 2500.0 2500.0 | 14.0 14.0 | 107.6 107.6 |
| 실시예(77)Example (77) | 화합물(5-61)Compound (5-61) | 화합물(2-8)Compound (2-8) | 4.9 4.9 | 20.8 20.8 | 2500.0 2500.0 | 12.0 12.0 | 115.2 115.2 |
| 실시예(78)Example (78) | 화합물(5-61)Compound (5-61) | 화합물(2-13)Compound (2-13) | 5.0 5.0 | 18.1 18.1 | 2500.0 2500.0 | 13.8 13.8 | 103.8 103.8 |
| 실시예(79)Example (79) | 화합물(5-61)Compound (5-61) | 화합물(2-14)Compound (2-14) | 4.7 4.7 | 17.3 17.3 | 2500.0 2500.0 | 14.5 14.5 | 102.0 102.0 |
| 실시예(80)Example (80) | 화합물(5-61)Compound (5-61) | 화합물(2-15)Compound (2-15) | 4.8 4.8 | 15.7 15.7 | 2500.0 2500.0 | 16.0 16.0 | 104.7 104.7 |
상기 표 7의 결과로부터 알 수 있듯이, 화학식 (5)로 나타내지는 화합물을 정공수송층으로 사용하고, 화학식 (1)로 나타내지는 화합물을 발광보조층으로 사용한 실시예가 다른 조건은 동일하지만 비교화합물 1을 발광보조층으로 사용한 비교예보다 유기전기발광소자의 구동전압, 수명 특히 발광효율을 현저히 개선시킴을 알 수 있다. 이는 표 5에서 설명한 화학식 1로 표시되는 발명화합물의 물리적, 화학적 특성이 화학식 5로 나타내지는 화합물과 함께 소자를 구성하였을 경우, 이 조합이 전기 화학적으로 시너지 작용을 하여 소자 전체의 성능을 향상시킨 것으로 사료된다. As can be seen from the results of Table 7, the examples using the compound represented by the formula (5) as the hole transport layer and the compound represented by the formula (1) as the light emitting auxiliary layer are the same under different conditions, but the comparative compound 1 It can be seen that the driving voltage, lifespan, and especially luminous efficiency of the organic electroluminescent device are significantly improved than the comparative example used as the light emitting auxiliary layer. This is because when the physical and chemical properties of the compound represented by Formula 1 described in Table 5 together with the compound represented by Formula 5 constitute a device, the combination improves the performance of the device as a whole by synergistically synergistic action. It is feed.
이상, 본 발명을 예시적으로 설명하였으며, 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 의해서 해석되어야 하며, 그와 동등한 범위 내에 있는 모든 기술은 본 발명의 권리범위에 포함하는 것으로 해석되어야 할 것이다.The present invention has been described above by way of example, and those skilled in the art will appreciate that various modifications may be made 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.
Claims (13)
- 하기 화학식 (1)로 표시되는 화합물Compound represented by the following formula (1)화학식 (1) Formula (1)
{상기 화학식 (1)에서, {In the above formula (1),1) A 및 B는 각각 하기 화학식 (1-1) 또는 (1-2)로 이루어진 군에서 선택되고 서로 상이하며, 1) A and B are each selected from the group consisting of the following general formula (1-1) or (1-2) and different from each other,화학식 (1-1) 화학식 (1-2) Chemical Formula (1-1) Chemical Formula (1-2)
2) Ar1, Ar2 및 Ar3은 각각 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 로 이루어진 군에서 선택되고,2) Ar 1 , Ar 2 and Ar 3 are each independently a C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; Is selected from the group consisting of3) X는 O 또는 S이고,3) X is O or S,4) L1 및 L2는 각각 독립적으로 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며,4) L 1 and L 2 are each independently a single bond; C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And a C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P, and5) n은 0~4의 정수이고, m, p, o는 0~3의 정수이며 m, n, o, p가 1이상일 경우 R1, R2, R3 및 R4는 각각 독립적으로 수소; 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되고,(여기서 상기 L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며, 상기 Ra 및 Rb은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택됨) 또는 이웃한 복수의 R1끼리, 혹은 복수의 R2끼리, 혹은 복수의 R3끼리, 혹은 복수의 R4끼리는 서로 결합하여 방향족 또는 헤테로방향족 고리를 형성 할 수 있고,5) n is an integer from 0 to 4, m, p, o are integers from 0 to 3, and when m, n, o, p is 1 or more, R 1 , R 2 , R 3 and R 4 are each independently hydrogen. ; heavy hydrogen; halogen; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); (wherein L 'is a single bond; C 6 ~ C 60 arylene group; Fluoryleneylene; C 3 ~ C 60 A fused ring group of an aliphatic ring and a C 6 ~ C 60 aromatic ring; and a hetero ring group of C 2 ~ C 60 ; wherein R a and R b are independently of each other C 6 ~ C 60 Aryl group; fluorenyl group; C 3 ~ C 60 alicyclic ring and C 6 ~ C 60 Aromatic ring fused ring group; and O, N, S, Si and P containing at least one heteroatom 2 to C 60 heterocyclic group; selected from the group consisting of; or a plurality of adjacent R 1 or a plurality of R 2 , or a plurality of R 3 or a plurality of R 4 are bonded to each other aromatic or hetero Can form an aromatic ring,여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알콕시기, 아릴옥시기는 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(Ra)(Rb); C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); 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 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; It may be further substituted with one or more substituents selected from the group consisting of C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group, and these substituents may also be bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof, and includes a saturated or unsaturated ring.} - 제 1항에 있어서, 상기 화학식 (1)로 나타낸 화합물이 하기 화학식 (2) 또는 화학식 (3)으로 표시되는 것을 특징으로 하는 화합물The compound according to claim 1, wherein the compound represented by the formula (1) is represented by the following formula (2) or formula (3)화학식 (2) 화학식 (3) Formula (2) Formula (3)
(상기 화학식 (2) 또는 (3)에서, R1, R2, R3, R4, m, n, o, p, L1, L2, Ar1, Ar2, Ar3는 상기 청구항 1에서 정의한 바와 같다.)(In the formula (2) or (3), R 1 , R 2 , R 3 , R 4 , m, n, o, p, L 1 , L 2 , Ar 1 , Ar 2 , Ar 3 is the claim 1 As defined in.) - 제 1항에 있어서, 상기 화학식 (1)로 나타낸 화합물이 하기와 같이 표시되는 것 중 어느 하나인 화합물.The compound according to claim 1, wherein the compound represented by the formula (1) is any one of the following compounds.
- 제 1전극, 제 2 전극, 및 상기 제 1전극과 상기 제 2전극 사이에 형성된 유기물층을 포함하는 유기전기소자에 있어서, 상기 유기물층은 정공주입층, 정공수송층, 발광보조층, 발광층을 포함하고, 상기 유기물층은 제 1항 내지 3항 중 어느 한 항의 화합물을 포함하는 것을 특징으로 하는 유기전기소자.In an organic electric device comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, the organic material layer includes a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, The organic material layer is an organic electric device, characterized in that it comprises a compound of any one of claims 1 to 3.
- 제 4항에 있어서, 상기 정공주입층, 정공수송층, 발광보조층, 발광층 중 적어도 하나의 층에 상기 화합물은 1종 단독 또는 구조가 상이한 2종 이상의 화합물이 혼합된 조성물을 포함하는 것을 특징으로 하는 유기전기소자.The method of claim 4, wherein the compound comprises at least one layer of the hole injection layer, the hole transport layer, the light emitting auxiliary layer, the light emitting layer comprises a composition in which at least one compound or two or more compounds having different structures are mixed. Organic electrical devices.
- 제 5항에 있어서, 상기 정공수송층 또는 상기 발광보조층에 상기 화합물이 1종 단독 또는 구조가 상이한 2종 이상의 화합물이 혼합된 조성물을 포함하는 것을 특징으로 하는 유기전기소자.The organic electroluminescence device according to claim 5, wherein the hole transport layer or the light emitting auxiliary layer comprises a composition in which the compound is mixed singly or in combination of two or more compounds having different structures.
- 제 4항에 있어서, 상기 발광보조층은 상기 화합물을 포함하고, 상기 정공수송층은 하기 화학식 (5)로 나타낸 화합물을 함유하는 것을 특징으로 하는 유기전기소자.The organic electroluminescence device according to claim 4, wherein the light emitting auxiliary layer comprises the compound, and the hole transport layer contains a compound represented by the following formula (5).화학식 (5)Formula (5)
{상기 화학식 (5)에서, {In the above formula (5),1) Ar4, Ar5는 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되며(여기서 상기 L'은 단일결합; C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되며, 상기 Ra 및 Rb은 서로 독립적으로 C6~C60의 아릴기; 플루오렌일기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택됨), 또는 Ar4와 Ar5는 서로 결합하여 고리를 형성할 수 있고,1) Ar 4 , Ar 5 are independently of each other a C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); wherein L 'is a single bond; C 6 ~ C 60 arylene group; Fluorenylene group; C 3 ~ C 60 A fused ring group of an aliphatic ring and an aromatic ring of C 6 ~ C 60 ; and a heterocyclic group of C 2 ~ C 60 , wherein R a and R b are each independently selected from C 6 ~ C 60 an aryl group; fluorene group; C 3 ~ fused ring group of an aromatic ring of C 60 of aliphatic rings and C 6 ~ C 60; and O, N, S, Si, and C 2, comprising at least one hetero atom of the P Heterocyclic group of ~ C 60 ; or Ar 4 And Ar 5 It may be bonded to each other to form a ring,2) Ar6은 하기 화학식 (5-a), (5-b), (5-c) 중 어느 하나로 선택되고, .2) Ar 6 is selected from any one of the following formulas (5-a), (5-b) and (5-c).화학식 (5-a) 화학식 (5-b) 화학식 (5-c)Formula (5-a) Formula (5-b) Formula (5-c)
3) a, b, c는 0~4의 정수이며, R5, R6 및 R7은 서로 동일하거나 상이하며, 서로 독립적으로 중수소; 할로겐; C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; C1~C50의 알킬기; C2~C20의 알켄일기; C2~C20의 알킨일기; C1~C30의 알콕실기; C6~C30의 아릴옥시기; 및 -L'-N(Ra)(Rb);로 이루어진 군에서 선택되고, 또는 R5, R6 및 R7은 상기 a, b, c가 2 이상인 경우 각각 복수로서 서로 동일하거나 상이하며 복수의 R5끼리 혹은 복수의 R6끼리 혹은 복수의 R7끼리 서로 결합하여 고리를 형성할 수 있고,3) a, b, c are integers from 0 to 4, R 5 , R 6 and R 7 are the same as or different from each other, and independently from each other deuterium; halogen; C 6 ~ C 60 Aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; C 1 ~ C 50 Alkyl group; C 2 ~ C 20 Alkenyl group; Alkynyl groups of C 2 to C 20 ; C 1 -C 30 alkoxyl group; C 6 -C 30 aryloxy group; And -L'-N (R a ) (R b ); or R 5 , R 6, and R 7 are each the same as or different from each other when a, b, and c are two or more, and A plurality of R 5 or a plurality of R 6 or a plurality of R 7 may combine with each other to form a ring,4) L3 및 L5는 서로 독립적으로 C6~C60의 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고,4) L 3 and L 5 are each independently a C 6 ~ C 60 arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P;5) L4은 C6~C60의 단일결합; 아릴렌기; 플루오렌일렌기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 및 O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기;로 이루어진 군에서 선택되고,5) L 4 is a single bond of C 6 ~ C 60 ; Arylene group; Fluorenylene groups; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; And C 2 ~ C 60 heterocyclic group including at least one heteroatom of O, N, S, Si, and P;6) Ar7, Ar8 및 Ar9은 각각 독립적으로 C6~C60의 아릴기; 플루오렌일기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C2~C60의 헤테로고리기; C3~C60의 지방족고리와 C6~C60의 방향족고리의 융합고리기; 로 이루어진 군에서 선택되고,6) Ar 7 , Ar 8 and Ar 9 are each independently a C 6 ~ C 60 aryl group; Fluorenyl group; C 2 ~ C 60 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; Fused ring group of an aromatic ring of C 3 ~ C 60 of aliphatic rings and C 6 ~ C 60; Is selected from the group consisting of여기서, 상기 아릴기, 플루오렌닐기, 아릴렌기, 헤테로고리기, 융합고리기, 알킬기, 알켄일기, 알콕시기, 아릴옥시기는 각각 중수소; 할로겐; C1-C20의 알킬기 또는 C6-C20의 아릴기로 치환 또는 비치환된 실란기; 실록산기; 붕소기; 게르마늄기; 시아노기; 니트로기; -L'-N(Ra)(Rb); C1-C20의 알킬싸이오기; C1-C20의 알콕실기; C1-C20의 알킬기; C2-C20의 알켄일기; C2-C20의 알킨일기; C6-C20의 아릴기; 중수소로 치환된 C6-C20의 아릴기; 플루오렌일기; C2-C20의 헤테로고리기; C3-C20의 시클로알킬기; C7-C20의 아릴알킬기 및 C8-C20의 아릴알켄일기로 이루어진 군에서 선택된 하나 이상의 치환기로 더욱 치환될 수 있으며, 또한 이들 치환기들은 서로 결합하여 고리를 형성할 수도 있으며, 여기서 '고리'란 탄소수 3 내지 60의 지방족고리 또는 탄소수 6 내지 60의 방향족고리 또는 탄소수 2 내지 60의 헤테로고리 또는 이들의 조합으로 이루어진 융합 고리를 말하며, 포화 또는 불포화 고리를 포함한다.}Here, the aryl group, fluorenyl group, arylene group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkoxy group, aryloxy group are each deuterium; halogen; A silane group unsubstituted or substituted with a C 1 -C 20 alkyl group or a C 6 -C 20 aryl group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; -L'-N (R a ) (R b ); 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 ; Aryl group of C 6 -C 20 ; C 6 -C 20 aryl group substituted with deuterium; Fluorenyl group; C 2 -C 20 heterocyclic group; A cycloalkyl group of C 3 -C 20 ; It may be further substituted with one or more substituents selected from the group consisting of C 7 -C 20 arylalkyl group and C 8 -C 20 arylalkenyl group, and these substituents may also be bonded to each other to form a ring, Refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof, and includes a saturated or unsaturated ring.} - 제 7항에 있어서, The method of claim 7, wherein상기 화학식 (5)로 나타낸 화합물은 하기 화학식 5-1 내지 5-71로 표시되는 화합물 중 어느 하나인 것을 특징으로 하는 유기전기소자.The compound represented by Chemical Formula (5) is any one of the compounds represented by the following Chemical Formulas 5-1 to 5-71.
- 제 7항에 있어서, 상기 발광보조층에 포함되는 상기 화합물이 1종 단독 또는 구조가 상이한 2종 이상의 화합물이 혼합된 조성물을 포함하는 것을 특징으로 하는 유기전기소자.The organic electroluminescence device according to claim 7, wherein the compound included in the light emitting auxiliary layer comprises a composition in which one or more compounds having different structures are mixed.
- 제 4항에 있어서, 상기 제 1전극의 일측면 중 상기 유기물층과 반대되는 일측 또는 상기 제 2전극의 일측면 중 상기 유기물층과 반대되는 일측 중 적어도 하나에 형성되는 광효율개선층을 더 포함하는 유기전기소자.The organic electroluminescence device of claim 4, further comprising a light efficiency improvement layer formed on at least one of 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. device.
- 제 4항에 있어서, 상기 유기물층은 스핀코팅 공정, 노즐 프린팅 공정, 잉크젯 프린팅 공정, 슬롯코팅 공정, 딥코팅 공정 및 롤투롤 공정 중 어느 하나에 의해 형성되는 것을 특징으로 하는 유기전기소자.The organic electronic device of claim 4, wherein the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process.
- 제 4 항의 유기전기소자를 포함하는 디스플레이장치; 및 상기 디스플레이장치를 구동하는 제어부;를 포함하는 전자장치A display device comprising the organic electroluminescent element of claim 4; And a controller for driving the display device.
- 제 12 항에 있어서, 상기 유기전기소자는 유기전기발광소자, 유기태양전지, 유기감광체, 유기트랜지스터, 및 단색 또는 백색 조명용소자 중 적어도 하나인 것을 특징으로 하는 전자장치The electronic device of claim 12, wherein the organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoconductor, an organic transistor, and a monochrome or white lighting device.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117543A (en) * | 2016-11-29 | 2018-06-05 | 东进世美肯株式会社 | Compounds and the organic electroluminescence device for including it |
| CN112125872A (en) * | 2019-06-24 | 2020-12-25 | Lt素材株式会社 | Heterocyclic compound and organic light-emitting device using the same |
| JP2021504352A (en) * | 2017-11-24 | 2021-02-15 | メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ | Materials for OLED devices |
| CN114464759A (en) * | 2020-11-09 | 2022-05-10 | 三星Sdi株式会社 | Organic optoelectronic device and display device |
| JP2022545596A (en) * | 2019-09-27 | 2022-10-28 | エルティー・マテリアルズ・カンパニー・リミテッド | Heterocyclic compound and organic light-emitting device containing the same |
| EP4043449A4 (en) * | 2019-10-11 | 2023-12-20 | Idemitsu Kosan Co., Ltd | Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140035737A (en) * | 2012-09-14 | 2014-03-24 | 롬엔드하스전자재료코리아유한회사 | Novel organic electroluminescence compounds and organic electroluminescence device containing the same |
| KR20150001101A (en) * | 2013-06-26 | 2015-01-06 | 덕산하이메탈(주) | An organic electronic element using compound for organic electronic element, and an electronic device thereof |
| KR20150006199A (en) * | 2013-07-08 | 2015-01-16 | 덕산하이메탈(주) | An organic electronic element using compound for organic electronic element, and an electronic device thereof |
| KR20150031892A (en) * | 2013-09-17 | 2015-03-25 | 덕산네오룩스 주식회사 | Organic electronic element using a compound for organic electronic element, and an electronic device thereof |
| KR20150033082A (en) * | 2013-09-23 | 2015-04-01 | 에스케이케미칼주식회사 | Compound for organic electroluminescent device and organic electroluminescent device comprising the same |
| KR20160037059A (en) * | 2014-09-25 | 2016-04-05 | 삼성디스플레이 주식회사 | Material for organic electroluminescent device and organic electroluminescent device using the same |
-
2016
- 2016-11-10 WO PCT/KR2016/012921 patent/WO2017090919A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140035737A (en) * | 2012-09-14 | 2014-03-24 | 롬엔드하스전자재료코리아유한회사 | Novel organic electroluminescence compounds and organic electroluminescence device containing the same |
| KR20150001101A (en) * | 2013-06-26 | 2015-01-06 | 덕산하이메탈(주) | An organic electronic element using compound for organic electronic element, and an electronic device thereof |
| KR20150006199A (en) * | 2013-07-08 | 2015-01-16 | 덕산하이메탈(주) | An organic electronic element using compound for organic electronic element, and an electronic device thereof |
| KR20150031892A (en) * | 2013-09-17 | 2015-03-25 | 덕산네오룩스 주식회사 | Organic electronic element using a compound for organic electronic element, and an electronic device thereof |
| KR20150033082A (en) * | 2013-09-23 | 2015-04-01 | 에스케이케미칼주식회사 | Compound for organic electroluminescent device and organic electroluminescent device comprising the same |
| KR20160037059A (en) * | 2014-09-25 | 2016-04-05 | 삼성디스플레이 주식회사 | Material for organic electroluminescent device and organic electroluminescent device using the same |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108117543A (en) * | 2016-11-29 | 2018-06-05 | 东进世美肯株式会社 | Compounds and the organic electroluminescence device for including it |
| CN108117543B (en) * | 2016-11-29 | 2023-09-12 | 东进世美肯株式会社 | Novel compound and organic electroluminescent device comprising the same |
| US11939339B2 (en) | 2017-11-24 | 2024-03-26 | Merck Patent Gmbh | Materials for organic electroluminescent devices |
| JP2021504352A (en) * | 2017-11-24 | 2021-02-15 | メルク、パテント、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ ＧｍｂＨ | Materials for OLED devices |
| JP7226817B2 (en) | 2019-06-24 | 2023-02-21 | エルティー・マテリアルズ・カンパニー・リミテッド | Heterocyclic compound and organic light-emitting device using the same |
| JP2021001169A (en) * | 2019-06-24 | 2021-01-07 | エルティー・マテリアルズ・カンパニー・リミテッドＬＴ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． | Hetero-cyclic compound and organic light emitting device using the same |
| US11812623B2 (en) | 2019-06-24 | 2023-11-07 | Lt Materials Co., Ltd. | Hetero-cyclic compound and organic light emitting device using the same |
| CN112125872B (en) * | 2019-06-24 | 2023-11-10 | Lt素材株式会社 | Heterocyclic compound and organic light-emitting device using same |
| CN112125872A (en) * | 2019-06-24 | 2020-12-25 | Lt素材株式会社 | Heterocyclic compound and organic light-emitting device using the same |
| JP2022545596A (en) * | 2019-09-27 | 2022-10-28 | エルティー・マテリアルズ・カンパニー・リミテッド | Heterocyclic compound and organic light-emitting device containing the same |
| JP7298947B2 (en) | 2019-09-27 | 2023-06-27 | エルティー・マテリアルズ・カンパニー・リミテッド | Heterocyclic compound and organic light-emitting device containing the same |
| EP4043449A4 (en) * | 2019-10-11 | 2023-12-20 | Idemitsu Kosan Co., Ltd | Compound, material for organic electroluminescent element, organic electroluminescent element, and electronic device |
| CN114464759A (en) * | 2020-11-09 | 2022-05-10 | 三星Sdi株式会社 | Organic optoelectronic device and display device |
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