KR20160064432A - Phosphoryl substituted Fluoranthene derivatives and organic electroluminescent device including the same - Google Patents
Phosphoryl substituted Fluoranthene derivatives and organic electroluminescent device including the same Download PDFInfo
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- KR20160064432A KR20160064432A KR1020140168031A KR20140168031A KR20160064432A KR 20160064432 A KR20160064432 A KR 20160064432A KR 1020140168031 A KR1020140168031 A KR 1020140168031A KR 20140168031 A KR20140168031 A KR 20140168031A KR 20160064432 A KR20160064432 A KR 20160064432A
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- 125000003914 fluoranthenyl group Chemical class C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 title claims abstract 8
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 title 1
- -1 phosphoryl group Chemical group 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 89
- 239000010410 layer Substances 0.000 claims description 66
- 239000012044 organic layer Substances 0.000 claims description 30
- 125000003118 aryl group Chemical group 0.000 claims description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000002346 layers by function Substances 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 6
- 230000000903 blocking effect Effects 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 3
- 125000000732 arylene group Chemical group 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 125000001624 naphthyl group Chemical group 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 38
- 238000003786 synthesis reaction Methods 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 239000007787 solid Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 22
- 150000002219 fluoranthenes Chemical class 0.000 description 20
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
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- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 8
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- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 8
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- 239000002904 solvent Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
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- 239000012141 concentrate Substances 0.000 description 6
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- 238000001816 cooling Methods 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
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- 238000010992 reflux Methods 0.000 description 4
- 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 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- UAXIPHOYCGRXPG-UHFFFAOYSA-N 2,5-dibromopyridine Chemical compound BrC1=NC=C(C=C1)Br.BrC1=NC=C(C=C1)Br UAXIPHOYCGRXPG-UHFFFAOYSA-N 0.000 description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- ZKSVYBRJSMBDMV-UHFFFAOYSA-N 1,3-diphenyl-2-benzofuran Chemical compound C1=CC=CC=C1C1=C2C=CC=CC2=C(C=2C=CC=CC=2)O1 ZKSVYBRJSMBDMV-UHFFFAOYSA-N 0.000 description 1
- CTPUUDQIXKUAMO-UHFFFAOYSA-N 1-bromo-3-iodobenzene Chemical compound BrC1=CC=CC(I)=C1 CTPUUDQIXKUAMO-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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- PSRUTZHGMSPRPZ-UHFFFAOYSA-N 5-bromoacenaphthylene Chemical group C1=CC2=CC=CC3=C2C1=CC=C3Br PSRUTZHGMSPRPZ-UHFFFAOYSA-N 0.000 description 1
- 101100096578 Arabidopsis thaliana SQD2 gene Proteins 0.000 description 1
- XQTOKJKFPBUODT-UHFFFAOYSA-N BrC1=NC=CC(=C1)Br.BrC1=NC=CC(=C1)Br Chemical compound BrC1=NC=CC(=C1)Br.BrC1=NC=CC(=C1)Br XQTOKJKFPBUODT-UHFFFAOYSA-N 0.000 description 1
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 150000001204 N-oxides Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-N aluminum;quinolin-8-ol 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-N 0.000 description 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000005874 benzothiadiazolyl group Chemical group 0.000 description 1
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 150000001572 beryllium Chemical class 0.000 description 1
- GQVWHWAWLPCBHB-UHFFFAOYSA-L beryllium;benzo[h]quinolin-10-olate Chemical compound [Be+2].C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21.C1=CC=NC2=C3C([O-])=CC=CC3=CC=C21 GQVWHWAWLPCBHB-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003230 hygroscopic agent Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 description 1
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 125000006413 ring segment Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
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- 125000001544 thienyl group Chemical group 0.000 description 1
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- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/58—Pyridine rings
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- 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
- H10K50/00—Organic light-emitting devices
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
본 발명은 포스포릴기가 결합된 플루오란텐 유도체 및 이를 포함한 유기 전계발광 소자에 관한 것으로, 특히 발광 효율이 높은 유기 전계발광 소자 및 이를 위한 신규한 포스포릴기가 결합된 플루오란텐 유도체에 관한 것이다.The present invention relates to a fluoranthene derivative to which a phospholyl group is bonded and an organic electroluminescent device including the same, and more particularly to an organic electroluminescent device having a high luminous efficiency and a novel phospholy group bonded thereto To a fluoranthene derivative.
초창기의 디스플레이 산업의 주종이었던 CRT(Cathode Ray Tube)에서부터 현재 가장 많이 사용되고 있는 LCD(Liquid Crystal Display)까지 지난 몇 십년간 디스플레이 산업은 눈부시게 발전하였다. From the CRT (Cathode Ray Tube), which was the main market of the early display industry, to the LCD (Liquid Crystal Display) which is the most used now, the display industry has developed remarkably over the past few decades.
그럼에도 불구하고 최근 표시장치의 대형화에 따라 공간 점유가 작은 평면표시소자의 요구가 증대되고 있는데, LCD는 시야각이 제한되고, 자체 발광형이 아니므로 별도의 광원이 필요하다는 단점을 가지고 있다. 이러한 이유로 자기 발광 현상을 이용한 디스플레이로서 OLED(유기발광다이오드, Organic Light Emitting Diodes)가 주목받고 있다.Nevertheless, the demand for a flat display device having a small space occupation has been increased due to the recent enlargement of display devices. However, LCD has a disadvantage that a separate light source is required because the viewing angle is limited and the device is not self-luminous. For this reason, OLEDs (Organic Light Emitting Diodes) are attracting attention as displays using self-emission phenomenon.
OLED는 1963년 Pope 등에 의하여 안트라센(Anthracene) 방향족 탄화수소의 단결정을 이용한 캐리어 주입형 전계발광(Electroluminescence; EL)의 연구가 최초로 시도되었고, 이러한 연구로부터 유기물에서의 전하주입, 재결합, 여기자 생성, 발광 등의 기초적 메커니즘과 전기발광 특성 등에 대한 많은 이해와 연구가 시작되었다.In 1963, OLED was first attempted to study the carrier injection type electroluminescence (EL) using a single crystal of anthracene aromatic hydrocarbons by Pope et al. From these studies, it was found that charge injection, recombination, exciton generation, And the basic mechanism of electroluminescence and electroluminescence characteristics.
또한, 1987년 Tang과 Van Slyke가 유기전계발광소자의 다층 박막 구조를 이용하여 고효율의 특성을 보고한 이후 [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 913 (1987)], OLED는 차세대 디스플레이로서의 우수한 특성뿐만 아니라 LCD 배면광 및 조명 등에 사용가능한 높은 잠재력을 가지고 있어 각광을 받으며 많은 연구가 진행되고 있다[Kido, J., Kimura, M., and Nagai, K., Science 267, 1332 (1995)]. 특히 발광 효율을 높이기 위해 소자의 구조 변화 및 물질 개발 등 다양한 접근이 이루어지고 있다[Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364]. In addition, after Tang and Van Slyke in 1987 reported the characteristics of high efficiency using a multilayer thin film structure of organic electroluminescent devices [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 913 (1987)], OLEDs have a high potential for use in LCD backlighting and illumination as well as excellent characteristics as a next generation display, and many studies have been conducted under the spotlight [Kido, J., Kimura, M., and Nagai, K., Science 267,1332 (1995)]. Especially, in order to increase the luminous efficiency, various approaches such as structural change and material development have been performed [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].
OLED 디스플레이의 기본적 구조는 일반적으로 양극(Anode), 정공주입층(Hole Injection Layer, HIL), 정공수송층(Hole Transporting Layer, HTL), 발광층 (Emission Layer, EML), 전자수송층(Electron Transporting Layer, ETL), 그리고 음극(Cathode)의 다층 구조로 구성되며, 전자 유기 다층막이 양 전극 사이에 형성된 샌드위치 구조로 되어 있다.The basic structure of an OLED display generally includes an anode, a hole injection layer (HIL), a hole transporting layer (HTL), an emission layer (EML), an electron transporting layer (ETL) ), And a cathode (cathode), and the electron-emitting organic multi-layer film has a sandwich structure formed between both electrodes.
OLED가 제대로 빛을 내기 위해서는 유기물질 박막에 음극에서는 전자가 전자수송층의 도움으로 유기물질인 발광층으로 이동하고, 상대적으로 양극에서는 정공이 정공수송층의 도움으로 발광층으로 이동하게 되어 발광층에서 만난 전자와 정공이 재결합하면서 여기자(exciton)를 형성한다. 형성된 여기자가 낮은 에너지 상태로 떨어지면서 에너지가 방출되면서 특정한 파장의 빛이 발생한다. 이때 발광층을 구성하고 있는 유기 물질이 어떤 것이냐에 따라 빛의 색깔이 달라지며, R, G, B를 내는 각각의 유기물질을 이용하여 총천연색을 만들어낼 수가 있다.In order for the OLED to emit light properly, electrons in the organic thin film are transported to the organic light emitting layer with the help of the electron transport layer, and in the anode, holes are transported to the light emitting layer with the help of the hole transport layer, Thereby forming an exciton. The generated excitons drop to a low energy state, and energy is emitted and light of a specific wavelength is generated. At this time, the color of the light changes according to the organic material constituting the light emitting layer, and the organic material of R, G, and B can be used to produce a full color.
기존에 전자수송층에 대표적으로 사용된 예로는 1987년 Kodak이 발표한 다층박막 OLED 이전부터 사용되어진 tris(8-hydroxyquinoline)aluminum(Ⅲ) (Alq3)과 같은 알루미늄 착체와 1990년대 중반 일본에서 발표한 bis(10-hydroxybenzo-[h]quinolinato)beryllium (Bebq2)과 같은 베릴륨 착체[T. Sato et.al. J. Mater. Chem. 10 (2000) 1151] 등이 있다.Aluminum complexes such as tris (8-hydroxyquinoline) aluminum (III) (Alq 3 ), which has been used since before the multilayer thin film OLEDs announced by Kodak in 1987, Beryllium complexes such as bis (10-hydroxybenzo- [h] quinolinato) beryllium (Bebq 2 ) [T. Sato et al. J. Mater. Chem. 10 (2000) 1151).
OLED가 우수한 특징들을 충분히 발휘하기 위해서는 소자 내 물질이 안정적이고 효율적인 재료에 의하여 뒷받침되는 것이 선행되어야 한다. 그러나 기존의 전자 전달 재료는 OLED가 상용화되면서 그 한계가 대두되었고, 현재의 요구를 충분히 만족시키지 못하고 있다. 따라서 새로운 고성능의 전자 전달 재료의 개발이 계속 요구 되고 있다.In order for OLED to fully exhibit excellent features, it must precede that the material in the device is backed by a stable and efficient material. However, the existing electron transport materials have been limited by the commercialization of OLED, and they are not satisfying the current requirements sufficiently. Therefore, the development of new high performance electron transfer materials is continuously required.
본 발명의 과제는 종래의 재료보다 전류 밀도가 우수하고 내구성이 뛰어난 신규한 플루오란텐 유도체를 제공하는 것이며, 또한 상기 플루오란텐 유도체가 유기막에 포함되어 소자의 구동전압을 낮추고 발광 효율이 개선되며 수명이 연장된 유기 전계발광 소자를 제공하는 것이다.The object of the present invention is to provide a novel fluoranthene derivative which is superior in current density and durability to that of the conventional material, and that the fluoranthene derivative is contained in the organic layer to lower the driving voltage of the device and improve the luminous efficiency And to provide an organic electroluminescent device having an extended lifetime.
본 발명의 일 측면에 의하면, 하기 화학식 1로 표시되는 포스포릴기가 결합된 플루오란텐 유도체가 제공된다.According to one aspect of the present invention, there is provided a fluoranthene derivative to which a phosphoryl group is bonded, represented by the following formula (1).
[화학식 1][Chemical Formula 1]
[상기 화학식 1에서,[In the above formula (1)
R1, R2는 서로 결합하여 적어도 하나의 벤젠, 나프탈렌 등과 같은 방향족 고리를 형성하거나, 각각 독립적으로 수소이거나 치환 또는 비치환된 C1~C30의 알킬이며; R 1 and R 2 are bonded to each other to form an aromatic ring such as at least one benzene, naphthalene or the like, or are each independently hydrogen or a substituted or unsubstituted C1-C30 alkyl;
R3 내지 R6는 각각 독립적으로 수소이거나 치환 또는 비치환된 C6~C30의 아릴기이거나 치환 또는 비치환된 C5~C30의 헤테로아릴기이며;R 3 to R 6 are each independently hydrogen or a substituted or unsubstituted C 6 to C 30 aryl group or a substituted or unsubstituted C 5 to C 30 heteroaryl group;
X는 N 또는 CH이며;X is N or CH;
L은 치환 또는 비치환된 아릴렌기이거나 헤테로 아릴렌기이며; L is a substituted or unsubstituted arylene group or a heteroarylene group;
n은 0 또는 1 이다] n is 0 or 1;
본 발명의 다른 측면에 의하면, 상기 포스포릴기가 결합된 플루오란텐 유도체를 포함하는 유기 전계발광 소자가 제공된다.According to another aspect of the present invention, the phosphoryl group is bonded An organic electroluminescent device comprising a fluoranthene derivative is provided.
본 발명의 또 다른 측면에 의하면, 제1 전극, 제2 전극, 및 상기 전극들 사이에 배치된 1층 이상의 유기막을 포함하되, 상기 유기막은 상기 포스포릴기가 결합된 플루오란텐 유도체를 포함하는 유기 전계발광 소자가 제공된다. According to another aspect of the present invention, there is provided a semiconductor device comprising a first electrode, a second electrode, and at least one organic film disposed between the electrodes, An organic electroluminescent device comprising a fluoranthene derivative is provided.
본 발명의 또 다른 측면에 의하면, 상기 포스포릴기가 결합된 플루오란텐 유도체가 상기 유기막을 구성하는 전자저지층, 전자수송층, 전자주입층, 전자수송 기능과 전자주입 기능을 동시에 갖는 기능층 및 발광층으로 이루어진 군 중에서 선택된 어느 1층에 포함되는 것을 특징으로 하는 유기 전계발광 소자가 제공된다.According to still another aspect of the present invention, the fluoranthene derivative to which the phosphoryl group is bonded comprises an electron blocking layer, an electron transporting layer, an electron injecting layer, a functional layer having both an electron transporting function and an electron injecting function, And the organic electroluminescent device is included in any one layer selected from the group consisting of organic electroluminescent devices.
본 발명의 일 실시예에 따른 포스포릴기가 결합된 플루오란텐 유도체는 유기 전계발광 소자의 유기막에 포함되어 소자의 구동전압을 낮추고 발광 효율이 개선되며 수명을 연장할 수 있다.The fluoranthene derivative to which the phospholyl group is bonded according to an embodiment of the present invention is included in the organic layer of the organic electroluminescent device, thereby lowering the driving voltage of the device, improving the luminous efficiency and extending the lifetime.
도 1은 본 발명의 일 실시예에 따른 유기 전계발광 소자의 개략적인 단면도이다.
도 2는 비교시험예 및 시험예 1 내지 3에서 제조된 유기 전계발광 소자의 전류 밀도를 나타내는 그래프이다.1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
2 is a graph showing current densities of organic electroluminescent devices manufactured in Comparative Examples and Test Examples 1 to 3. FIG.
본 명세서에서 용어 "아릴"은 다른 의미로 명시되지 않는 한, 단일 고리이거나 융합 또는 공유 결합된 다중 고리(1개 내지 3개의 고리)일 수 있는 다중불포화 방향족 탄화수소 치환기를 의미한다.As used herein, the term "aryl " means a polyunsaturated aromatic hydrocarbon substituent, which may be a single ring or a multiple ring (1 to 3 rings) fused or covalently bonded unless otherwise specified.
"헤테로아릴"이란 용어는 (다중 고리의 경우 각각의 별도의 고리에서) N, O 및 S로부터 선택되는 1 내지 4개의 이종원자를 포함하는 아릴 기(또는 고리)를 의미하고, 질소 및 황 원자는 경우에 따라 산화되고, 질소 원자(들)은 경우에 따라 4차화된다. 헤테로아릴 기는 탄소 또는 이종원자를 통해 분자의 나머지에 결합될 수 있다.The term "heteroaryl" means an aryl group (or a ring) comprising one to four heteroatoms selected from N, O and S (in each case on a separate ring in the case of multiple rings) Optionally oxidized, and the nitrogen atom (s) are quaternized, as the case may be. Heteroaryl groups can be attached to the remainder of the molecule through carbon or heteroatoms.
상기 아릴은 각 고리에 적절하게는 4 내지 7개, 바람직하게는 5 또는 6개의 고리원자를 포함하는 단일 또는 융합고리계를 포함한다. 또한, 하나 이상의 아릴이 화학결합을 통하여 결합되어 있는 구조도 포함한다. 상기 아릴의 구체적인 예로 페닐, 나프틸, 비페닐, 안트릴, 인데닐, 플루오레닐, 페난트릴, 트라이페닐레닐, 피렌일, 페릴렌일, 크라이세닐, 나프타세닐, 파이렌일, 플루오란텐일 등을 포함하지만, 이에 한정되지 않는다.The aryl includes a single or fused ring system, suitably containing from 4 to 7, preferably 5 or 6, ring atoms in each ring. Also included are structures in which one or more aryls are attached through a chemical bond. Specific examples of the aryl include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, But are not limited thereto.
상기 헤테로아릴은 5 내지 6원 단환 헤테로아릴, 및 하나 이상의 벤젠 환과 융합된 다환식 헤테로아릴을 포함하며, 부분적으로 포화될 수도 있다. 또한, 하나 이상의 헤테로아릴이 화학결합을 통하여 결합되어 있는 구조도 포함된다. 상기 헤테로아릴기는 고리 내 헤테로원자가 산화되거나 사원화되어, 예를 들어 N-옥사이드 또는 4차 염을 형성하는 2가 아릴 그룹을 포함한다.The heteroaryl includes 5- to 6-membered monocyclic heteroaryl and polycyclic heteroaryl fused with one or more benzene rings, and may be partially saturated. Also included are structures in which one or more heteroaryls are attached via a chemical bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt.
상기 헤테로아릴의 구체적인 예로 퓨릴, 티오펜일, 피롤릴, 이미다졸릴, 피라졸릴, 티아졸릴, 티아디아졸릴, 이소티아졸릴, 이속사졸릴, 옥사졸릴, 옥사디아졸릴, 트리아진일, 테트라진일, 트리아졸릴, 테트라졸릴, 퓨라잔일, 피리딜, 피라진일, 피리미딘일, 피리다진일 등의 단환 헤테로아릴, 벤조퓨란일, 벤조티오펜일, 이소벤조퓨란일, 벤조이미다졸릴, 벤조티아졸릴, 벤조이소티아졸릴, 벤조이속사졸릴, 벤조옥사졸릴, 이소인돌릴, 인돌릴, 인다졸릴, 벤조티아디아졸릴, 퀴놀릴, 이소퀴놀릴, 신놀리닐, 퀴나졸리닐, 퀴녹살리닐, 카바졸릴, 페난트리딘일, 벤조디옥솔릴 등의 다환식 헤테로아릴 및 이들의 상응하는 N-옥사이드(예를 들어, 피리딜 N-옥사이드, 퀴놀릴 N-옥사이드), 이들의 4차 염 등을 포함하지만, 이에 한정되지 않는다.Specific examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, Monocyclic heteroaryl such as pyridyl, pyridyl, pyrazinyl, pyridazinyl and the like, benzofuranyl, benzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl , Benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, but are not limited thereto. But is not limited thereto.
본 명세서에 기재된 "치환 또는 비치환된"이라는 표현에서 "치환"은 탄화수소 내의 수소 원자 하나 이상이 각각, 서로 독립적으로, 동일하거나 상이한 치환기로 대체되는 것을 의미한다. 유용한 치환기는 다음을 포함하지만 이에 제한되지 않는다."Substituted" in the expression " substituted or unsubstituted ", as used herein, means that at least one hydrogen atom in the hydrocarbon is each independently replaced with the same or different substituents. Useful substituents include, but are not limited to:
이러한 치환기는, -F; -Cl; -Br; -CN; -NO2; -OH; -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C1~C20 알킬기; -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C1~C20 알콕시기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C6~C30 아릴기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C6~C30 헤테로아릴기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C5~C20 사이클로알킬기; C1~C20 알킬기, C1~C20 알콕시기, -F, -Cl, -Br, -CN, -NO2 또는 -OH로 치환되거나 비치환된 C5~C30 헤테로사이클로알킬기; 및 -N(G1)(G2)으로 표시되는 기로 이루어진 군으로부터 선택된 하나 이상일 수 있다. 이때, 상기 G1 및 G2는 서로 독립적으로 각각 수소; C1~C10 알킬기; 또는 C1~C10 알킬기로 치환되거나 비치환된 C6~C30 아릴기일 수 있다.
Such substituents include, but are not limited to, -F; -Cl; -Br; -CN; -NO 2 ; -OH; A C 1 -C 20 alkyl group which is unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO 2 or -OH; A C 1 -C 20 alkoxy group unsubstituted or substituted by -F, -Cl, -Br, -CN, -NO 2 or -OH; C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN , -NO 2, or substituted by -OH or unsubstituted C 6 ~ C 30 aryl group; C 1 ~ C 20 alkyl group, C 1 ~ C 20 alkoxy group, -F, -Cl, -Br, -CN ,
이하, 본 발명에 대해 상세히 설명하고자 한다.Hereinafter, the present invention will be described in detail.
본 발명의 일 실시예에 따른 포스포릴기가 결합된 플루오란텐 유도체는 하기 화학식 1로 표시될 수 있다.The phosphoryl group according to an embodiment of the present invention is bonded The fluoranthene derivative may be represented by the following formula (1).
[화학식 1][Chemical Formula 1]
상기 화학식 1에서,In Formula 1,
R1, R2는 서로 결합하여 적어도 하나의 벤젠, 나프탈렌 등과 같은 방향족 고리를 형성하거나, 각각 독립적으로 수소이거나 치환 또는 비치환된 C1~C30의 알킬이며; R 1 and R 2 are bonded to each other to form an aromatic ring such as at least one benzene, naphthalene or the like, or are each independently hydrogen or a substituted or unsubstituted C1-C30 alkyl;
R3 내지 R6는 각각 독립적으로 수소이거나 치환 또는 비치환된 C6~C30의 아릴기이거나 치환 또는 비치환된 C5~C30의 헤테로아릴기이며;R 3 to R 6 are each independently hydrogen or a substituted or unsubstituted C 6 to C 30 aryl group or a substituted or unsubstituted C 5 to C 30 heteroaryl group;
X는 N 또는 CH이며;X is N or CH;
L은 치환 또는 비치환된 아릴렌기이거나 헤테로 아릴렌기이며; L is a substituted or unsubstituted arylene group or a heteroarylene group;
n은 0 또는 1 이다.n is 0 or 1;
바람직하게는 R3 내지 R6는 각각 독립적으로 수소, 페닐, 비페닐, 나프틸 및 퀴놀린으로 이루어진 군 중에서 선택되는 것을 특징으로 하는 포스포릴기가 결합된 플루오란텐 유도체.Preferably, R 3 to R 6 are each independently selected from the group consisting of hydrogen, phenyl, biphenyl, naphthyl, and quinoline. The fluoranthene derivative to which the phosphoryl group is bonded.
본 발명의 상기 화학식 1로 표시되는 화합물의 구체적인 예로서, 하기 화학식 2로 표시되는 것들이 있다. 그러나 본 발명의 화학식 1로 표시되는 화합물이 하기 화학식 2의 화합물들로 한정되지 않는다.
Specific examples of the compound represented by the formula (1) of the present invention include those represented by the following formula (2). However, the compound represented by formula (1) of the present invention is not limited to the compounds of formula (2).
[화학식 2](2)
상기 화학식 1로 표시되는 포스포릴기가 결합된 플루오란텐 유도체는 공지의 유기 합성방법을 이용하여 합성가능하다. 상기 포스포릴기가 결합된 플루오란텐 유도체의 합성방법은 후술하는 제조예를 참조하여 당업자에게 용이하게 인식될 수 있다.When the phospholyl group represented by the above formula (1) is bonded The fluoranthene derivative can be synthesized using a known organic synthesis method. When the phosphoryl group is bonded The method of synthesizing the fluoranthene derivative can be easily recognized by those skilled in the art with reference to the following production examples.
또한 본 발명에 따르면, 상기 화학식 1로 표시되는 포스포릴기가 결합된 플루오란텐 유도체를 포함하는 유기 전계발광 소자가 제공된다. Also, according to the present invention, there is provided an organic electroluminescent device comprising a fluoranthene derivative to which a phospholyl group is bonded, represented by the general formula (1).
상기 화학식 1의 포스포릴기가 결합된 플루오란텐 유도체는 전자수송층 재료로 유용하며, 이밖의 여러층의 유기 전계발광 소자의 재료로서 사용될 수 있다.The fluoranthene derivative to which the phospholyl group is bonded is useful as an electron transport layer material and can be used as a material for various other layers of organic electroluminescent devices.
또한 본 발명에 따른 유기 전계발광 소자는 제1 전극, 제2 전극 및 이들 전극 사이에 배치된 1층 이상의 유기막을 포함한다. 상기 유기막은 상기 화학식 1로 표시되는 포스포릴기가 결합된 플루오란텐 유도체를 하나 이상 포함한다.The organic electroluminescent device according to the present invention includes a first electrode, a second electrode, and at least one organic film disposed between the electrodes. The organic layer includes at least one fluoranthene derivative to which the phospholyl group is bonded.
상기 유기막은 정공주입층, 정공수송층, 정공주입 기능과 정공수송 기능을 동시에 갖는 기능층, 버퍼층, 전자저지층, 발광층, 정공저지층, 전자수송층, 전자주입층, 및 전자수송 기능과 전자주입 기능을 동시에 갖는 기능층으로 이루어진 군 중에서 선택되는 1층 이상을 포함할 수 있다.The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one layer selected from the group consisting of functional layers having at the same time.
예를 들어, 상기 포스포릴기가 결합된 플루오란텐 유도체는 발광층, 양극과 발광층 사이에 배치된 유기막 및 발광층과 음극 사이에 배치된 유기막으로 이루어진 군 중에서 선택되는 적어도 어느 하나에 포함될 수 있다. 바람직하게는, 상기 플루오란텐 유도체는 발광층, 정공주입층, 정공수송층, 및 정공주입 기능과 정공수송 기능을 동시에 갖는 기능층으로 이루어진 군 중에서 선택되는 어느 1층 이상에 포함될 수 있다. 상기 플루오란텐 유도체는 단일 물질 또는 서로 다른 물질의 조합으로서 상기 유기막에 포함될 수 있다. 또는 상기 플루오란텐 유도체는 발광층, 정공수송층 및 정공주입층 등에 종래 알려진 화합물과 혼합되어 사용될 수 있다. For example, when the phosphoryl group is bonded The fluoranthene derivative may be contained in at least one selected from the group consisting of a light emitting layer, an organic film disposed between the anode and the light emitting layer, and an organic film disposed between the light emitting layer and the cathode. Preferably, the fluoranthene derivative may be contained in at least one layer selected from the group consisting of a light emitting layer, a hole injecting layer, a hole transporting layer, and a functional layer having both a hole injecting function and a hole transporting function. The fluoranthene derivative may be included in the organic film as a single substance or a combination of different substances. Alternatively, the fluoranthene derivative may be used in combination with a conventionally known compound such as a light emitting layer, a hole transporting layer, and a hole injecting layer.
본 발명에 따른 유기 전계발광소자는 양극/발광층/음극, 양극/정공주입층/발광층/음극, 양극/정공주입층/정공수송층/발광층/전자수송층/음극, 또는 양극/정공주입층/정공수송층/발광층/전자수송층/전자주입층/음극의 구조를 가질 수 있다. 또는 상기 유기 전계발광소자는 양극/정공주입 기능 및 정공수송 기능을 동시에 갖는 기능층/발광층/전자수송층/음극, 또는 양극/정공주입 기능 및 정공 수송 기능을 동시에 갖는 기능층/발광층/전자수송층/전자주입층/음극의 구조를 가질 수 있지만 이에 한정되는 것은 아니다.The organic electroluminescent device according to the present invention can be applied to an organic electroluminescent device including a positive electrode / a light emitting layer / a cathode, a positive electrode / a hole injecting layer / a light emitting layer / a negative electrode, an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / an electron transporting layer / / Light emitting layer / electron transporting layer / electron injecting layer / cathode structure. Alternatively, the organic electroluminescent device may include a functional layer / a light emitting layer / an electron transporting layer / a cathode having both an anode / hole injecting function and a hole transporting function, a functional layer / a light emitting layer / an electron transporting layer / Electron injecting layer / cathode structure, but the present invention is not limited thereto.
도 1은 본 발명의 일 실시예에 따른 유기 전계발광 소자의 개략적인 단면도이다.1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
상기 유기 전계발광 소자는 스퍼터링(sputtering)이나 전자빔 증발(e-beam evaporation)과 같은 PVD(physical vapor deposition) 방법을 이용하여 제조될 수 있다. 예를 들어, 기판 상에 금속 또는 전도성을 가지는 금속 산화물 또는 이들의 합금을 증착시켜 양극을 형성하고, 그 위에 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층을 포함하는 유기막을 형성한 후, 그 위에 음극으로 사용할 수 있는 물질을 증착시킴으로써 제조될 수 있다. 이와 같은 방법 외에도, 기판 상에 음극 물질부터 유기막, 양극 물질을 차례로 증착시켜 유기 전계발광 소자를 만들 수도 있다.The organic electroluminescent device may be manufactured using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. For example, an anode is formed by depositing a metal or a metal oxide having conductivity or an alloy thereof on a substrate, and an organic film including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer is formed thereon And then depositing a material which can be used as a cathode thereon. In addition to such a method, an organic electroluminescent device may be formed by sequentially depositing a cathode material, an organic film, and a cathode material on a substrate.
한편, 상기 유기막은 다양한 고분자 소재를 사용하여 증착법이 아닌 용액 공정(wet process), 예컨대 스핀 코팅, 딥 코팅, 닥터 블레이딩, 스크린 프린팅, 잉크젯 프린팅 또는 열 전사법 등의 방법으로 제조될 수 있다.Meanwhile, the organic layer may be prepared by a wet process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer by using various polymer materials instead of a vapor deposition method.
본 발명에 따른 유기 전계발광 소자는 사용되는 재료에 따라 전면 발광형, 후면 발광형 또는 양면 발광형일 수 있다.
The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.
이하, 다양한 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 하나, 이하의 실시예는 본 발명을 예시하기 위한 것이며, 본 발명의 범위가 이들로 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
[실시예][Example]
합성예Synthetic example 1: 중간체(1)의 합성 1: Synthesis of intermediate (1)
5-브로모아세나프틸렌 (5-bromoacenaphthylene) 20.0 g(0.086 mol), 무수 벤젠 (Benzene) 400 mL에 2,3-다이클로로-5,6-다이사이아노-1,4-벤조퀴논 (2,3-dichloro-5,6-dicyano-1,4-Benzoquinone) 23.4 g(0.103 mol)을 가하고, 가열 환류 하에 12시간 교반했다. 반응 혼합물에 2,3-다이클로로-5,6-다이사이아노-1,4-벤조퀴논 (2,3-dichloro-5,6-dicyano-1,4-Benzoquinone, DDQ) 6.0 g(26.4mmol)을 추가 첨가하고, 4시간 가열 교반 하였다. 반응이 종결되면 상온으로 냉각 후, 침전물을 여과 분리하고, 클로로포름(Chloroform)으로 세정했다. 여액을 모아, 10% NaOH 용액, H2O 차례로 두차례 세정했다. 분액 후, 유기상을 무수 Na2SO4로 건조하고, 감압 하에 증류하여 갈색의 고체 화합물(중간체(1)) 11.0g(수율: 55%)을 얻었다.
20.0 g (0.086 mol) of 5-bromoacenaphthylene and 400 mL of anhydrous benzene were added to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2 , 3-dichloro-5,6-dicyano-1,4-benzoquinone (23.4 g, 0.103 mol) was added and the mixture was stirred under reflux for 12 hours. To the reaction mixture was added 6.0 g (26.4 mmol) of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) ) Was further added, and the mixture was heated and stirred for 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the precipitate was separated by filtration and washed with chloroform. The filtrate was collected, washed twice with 10% NaOH solution and then with H 2 O in that order. After the liquid separation, the organic phase was dried over anhydrous Na 2 SO 4 and distilled under reduced pressure to obtain 11.0 g (yield: 55%) of a brown solid compound (intermediate (1)).
합성예Synthetic example 2: 중간체(2)의 합성 2: Synthesis of intermediate (2)
중간체(1) 11 g (0.048 mol), 1,3-다이페닐아이소벤조퓨란(1,3-diphenylisobenzofuran) 12.8g (0.048 mol)의 톨루엔(Toluene) 43.6 mL 의 혼합물을 가열 환류 하에 16시간 교반 하였다. 용매를 증류 제거 후, 아세트산(Acetic acid) 1000 mL를 가하고, 80로 가열했다. 이 혼합물에, 48% HBr 수용액 132ml를 가하고, 80℃에서 2시간 교반했다. 반응이 종결되면 상온까지 냉각 후, 침전물을 여과하여 취하고, 메탄올로 세정했다. 얻어진 황색 고체를 톨루엔(Toluene) 100 mL로 재결정화 했다. 얻어진 결정을 여과하여 취하여 갈색 고체의 화합물(중간체(2)) 17.5g(수율: 75%)을 얻었다.
A mixture of 11 g (0.048 mol) of Intermediate (1) and 43.6 mL of toluene (Toluene) of 12.8 g (0.048 mol) of 1,3-diphenylisobenzofuran was stirred for 16 hours under reflux . After the solvent was distilled off, 1000 mL of acetic acid was added and the mixture was heated to 80 ° C. To this mixture was added 132 ml of 48% HBr aqueous solution, and the mixture was stirred at 80 占 폚 for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and the precipitate was filtered off and washed with methanol. The resulting yellow solid was recrystallized from toluene (Toluene) to 100 mL. The resulting crystals were collected by filtration to obtain 17.5 g (yield: 75%) of a brown solid compound (intermediate (2)).
합성예Synthetic example 3: 중간체(3)의 합성 3: Synthesis of intermediate (3)
중간체(2) 30g (0.062 mol), PIN2B2 18.9g (0.074 mol), Pd(dppf)Cl2 1.5g (1.86 mmol), KOAc 12.2g (0.124 mol), 디옥산(Dioxane) 310 mL를 같이 넣고 질소 하에서 100~110℃에서 2시간 환류 교반하였다. 반응이 종결되면 온도를 상온으로 내린 후, 용매를 감압 증류하여 제거하였다. 클로로포름(Chloroform) 600 mL를 혼합물에 넣고 용해시킨 후, 실리카겔로 여과한 후 클로로포름(Chloroform)으로 세척한다. 여과액을 증류 제거한 후, 얻어진 고체를 정제하여 갈색 고체의 화합물(중간체(3)) 26 g(수율: 79%)을 얻었다.
A mixture of 30 g (0.062 mol) of Intermediate 2, 18.9 g (0.074 mol) of PIN 2 B 2 , 1.5 g (1.86 mmol) of Pd (dppf) Cl 2 , 12.2 g (0.124 mol) of KOAc, 310 mL of dioxane And the mixture was stirred under reflux at 100 to 110 ° C for 2 hours under nitrogen. When the reaction was completed, the temperature was lowered to room temperature, and the solvent was distilled off under reduced pressure. Dissolve 600 mL of chloroform in the mixture, filter through silica gel, and wash with chloroform. The filtrate was distilled off, and the obtained solid was purified to obtain 26 g (yield: 79%) of a brown solid compound (intermediate (3)).
합성예Synthetic example 4: 중간체(4)의 합성 4: Synthesis of intermediate (4)
3구 1.0 L 플라스크에 1-브로모-4-아이오도벤젠(1-bromo-4-iodobenzene) 20.0 g(70.6 mmol)을 넣고 질소 분위기 하에 THF 500 mL에 용해시킨다. 반응온도를 -78℃로 냉각시킨 후, 2.5M n-BuLi 용액 31 mL (77.7mmol)를 천천히 적가하여 교반하였다. 적가가 종결된 후 -78℃에서 한 시간 교반시킨 후, 클로로디페닐포스핀(chlorodiphenylphosphine) 13.9 mL (77.7mmol)을 천천히 적가하였다. 두시간 교반한 후, H2O 10mL를 첨가하였다. 반응온도를 상온으로 천천히 올려준 후, 반응 혼합물을 감압 농축하였다. 농축액에 메틸렌클로라이드 500 mL와 H2O 500 mL을 넣은 후, 유기층을 분리하고 물과 염수(brine)로 세척하였다. 얻어진 중간체 혼합물의 반응온도를 0℃로 냉각시킨 후, 과산화수소 (H2O2) 85.8 mL (0.988 mol)를 천천히 적가하였다. 반응온도를 상온으로 올린 후, 18시간 교반하였다. 반응이 종결되면 유기층을 분리하여 물로 2회 세척한 후, MgSO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 농축액을 용매로 고체화 정제하여 하얀색 고체의 화합물(중간체(4)) 18g(수율 : 71.4 %)을 얻었다.
20.0 g (70.6 mmol) of 1-bromo-4-iodobenzene is added to a three-necked 1.0 L flask and dissolved in 500 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78 ° C, 31 mL (77.7 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred. After the addition was completed, the mixture was stirred at -78 ° C for one hour, and 13.9 mL (77.7 mmol) of chlorodiphenylphosphine was slowly added dropwise thereto. After stirring for two hours, 10 mL of H 2 O was added. After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure. After adding 500 mL of methylene chloride and 500 mL of H 2 O to the concentrate, the organic layer was separated and washed with water and brine. After cooling the reaction temperature of the obtained intermediate mixture to 0 캜, 85.8 mL (0.988 mol) of hydrogen peroxide (H 2 O 2 ) was slowly added dropwise. The reaction temperature was raised to room temperature and stirred for 18 hours. When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO 4 , filtered, and the filtrate was concentrated under reduced pressure. The obtained concentrate was solidified and purified by using a solvent to obtain 18 g (yield: 71.4%) of a white solid compound (intermediate (4)).
합성예Synthetic example 5: 중간체(5)의 합성 5: Synthesis of intermediate (5)
플라스크에 중간체(4) 12 g(33.6 mmol), PIN2B2 9.40g(37.0mmol), Pd(dppf)Cl2 1.09g(1.34mmol), KOAc 6.6g(67.2mmol) 및 디옥산(Dioxane) 240 mL을 같이 넣고 질소 하에서 75~80℃에서 12시간 환류 교반하였다. 온도를 상온으로 내린 후, 용매를 감압 증류하여 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(중간체(5)) 12.01 g(수율 : 88%)을 얻었다.
To the flask was added 12 g (33.6 mmol) of intermediate (4), PIN 2 B 2 1.09 g (1.34 mmol) of Pd (dppf) Cl 2 , 6.6 g (67.2 mmol) of KOAc and 240 mL of dioxane were added thereto and the mixture was refluxed under stirring at 75 to 80 ° C for 12 hours under nitrogen atmosphere . After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 12.01 g (yield: 88%) of a pale yellow solid compound (Intermediate ( 5 )).
합성예Synthetic example 6: 중간체(6)의 합성 6: Synthesis of intermediate (6)
1구 100 mL 플라스크에 중간체(5) 3.0 g(7.42 mmol), 2,5-디브로모피리딘(2,5-dibromopyridine) 1.76g(7.42 mmol) 및 Pd(PPh3)4 0.25 g(0.22mmol)을 넣고 질소 분위기 하에 톨루엔(Toluene) 20 mL과 에탄올(EtOH) 8 mL에 용해시킨 후, 2M K2CO3 용액 8mL를 첨가하여 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 H2O 50 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 50 mL로 2회 추출 후 추출액을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 백색 고체의 화합물(중간체(6)) 1.76 g(수율 : 54.6 %)을 얻었다.
In 1 100 mL flask, intermediate (5) 3.0 g (7.42 mmol ), 2,5- dibromo-pyridine (2,5-dibromopyridine) 1.76g (7.42 mmol) and Pd (PPh 3) 4 0.25 g (0.22mmol ) Was dissolved in 20 mL of toluene and 8 mL of ethanol (EtOH) under a nitrogen atmosphere, and then 8 mL of 2M K 2 CO 3 solution was added and the mixture was refluxed and stirred. After the reaction was completed, it was cooled to room temperature and 50 mL of H 2 O was added. The mixture was extracted twice with 50 mL of methylene chloride, the extract was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 1.76 g (yield: 54.6%) of a white solid compound (intermediate (6)).
합성예Synthetic example 7: 중간체(7)의 합성 7: Synthesis of intermediate (7)
1구 100 mL 플라스크에 중간체(5) 3.0 g(7.42 mmol), 2,4-디브로모피리딘(2,4-dibromopyridine) 1.76g(7.42 mmol) 및 Pd(PPh3)4 0.25 g(0.22mmol)을 넣고 질소 분위기 하에 톨루엔(Toluene) 20 mL과 에탄올(EtOH) 8 mL에 용해시킨 후, 2M K2CO3 용액 8mL를 첨가하여 환류 교반하였다. 반응이 종결된 후 상온으로 냉각하고 H2O 50 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 50 mL로 2회 추출 후 추출액을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 백색 고체의 화합물(중간체(7)) 1.22 g(수율 : 38 %)을 얻었다.
In 1 100 mL flask, intermediate (5) 3.0 g (7.42 mmol ), 2,4- dibromo-pyridine (2,4-dibromopyridine) 1.76g (7.42 mmol) and Pd (PPh 3) 4 0.25 g (0.22mmol ) Was dissolved in 20 mL of toluene and 8 mL of ethanol (EtOH) under a nitrogen atmosphere, and then 8 mL of 2M K 2 CO 3 solution was added and the mixture was refluxed and stirred. After the reaction was completed, it was cooled to room temperature and 50 mL of H 2 O was added. The mixture was extracted twice with 50 mL of methylene chloride, the extract was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 1.22 g (yield: 38%) of a white solid compound (Intermediate (7)).
합성예Synthetic example 8: 중간체(8)의 합성 8: Synthesis of intermediate (8)
3구 1.0 L 플라스크에 1-브로모-3-아이오도벤젠 (1-bromo-3-iodobenzene) 10.0 g(35.3 mmol) 을 넣고 질소 분위기 하에 THF 300 mL에 용해시킨다. 반응온도를 -78℃로 냉각시킨 후, 2.5M n-BuLi 용액 15.5 mL (38.83mmol)를 천천히 적가하여 교반하였다. 적가가 종결된 후 -78℃에서 한 시간 교반시킨 후, 클로로디페닐포스핀 (chlorodiphenylphosphine) 6.97 mL (38.83mmol)을 천천히 적가하였다. 2시간 교반한 후, H2O 5mL를 첨가하였다. 반응온도를 상온으로 천천히 올려준 후, 반응 혼합물을 감압 농축하였다. 농축액에 메틸렌클로라이드 300 mL와 H2O 100 mL을 넣은 후, 유기층을 분리하고 물과 염수(brine)로 세척하였다. 얻어진 중간체 혼합물의 반응온도를 0℃로 냉각시킨 후, 과산화수소 (H2O2) 42.9 mL (0.494 mol)를 천천히 적가하였다. 반응온도를 상온으로 올린 후, 18시간 교반하였다. 반응이 종결되면 유기층을 분리하여 물로 2회 세척한 후, MgSO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 농축액을 용매로 고체화 정제하여 하얀색 고체의 화합물(중간체(8)) 10.7g(수율 : 85 %)을 얻었다.
10.0 g (35.3 mmol) of 1-bromo-3-iodobenzene is added to a three-necked 1.0 L flask and dissolved in 300 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78 ° C, 15.5 mL (38.83 mmol) of 2.5 M n-BuLi solution was slowly added dropwise and stirred. After the addition was completed, the mixture was stirred at -78 ° C for one hour, and then 6.97 mL (38.83 mmol) of chlorodiphenylphosphine was slowly added dropwise. After stirring for 2 hours, 5 mL of H 2 O was added. After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure. After adding 300 mL of methylene chloride and 100 mL of H 2 O to the concentrate, the organic layer was separated and washed with water and brine. After the reaction mixture was cooled to 0 ° C, 42.9 mL (0.494 mol) of hydrogen peroxide (H 2 O 2 ) was slowly added dropwise. The reaction temperature was raised to room temperature and stirred for 18 hours. When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO 4 , filtered, and the filtrate was concentrated under reduced pressure. The obtained concentrate was solidified and purified by using a solvent to obtain 10.7 g (yield: 85%) of a white solid compound (intermediate (8)).
합성예Synthetic example 9: 중간체(9)의 합성 9: Synthesis of intermediate (9)
3구 1.0 L 플라스크에 2,5-디브로모피리딘 (2,5-dibromopyridine) 7.0 g(29.6 mmol)을 넣고 질소 분위기 하에 THF 350 mL에 용해시킨다. 반응온도를 -78℃로 냉각시킨 후, 2.5M n-BuLi 용액 14.2 mL (35.5mmol)를 천천히 적가하여 교반하였다. 적가가 종결된 후 -78℃에서 한 시간 교반시킨 후, 클로로디페닐포스핀 (chlorodiphenylphosphine) 6.37 mL (35.5mmol)을 천천히 적가하였다. 두시간 교반한 후, NH4OH 70mL를 첨가하였다. 반응온도를 상온으로 천천히 올려준 후, 반응 혼합물을 감압 농축하였다. 농축액에 메틸렌클로라이드 200 mL를 넣은 후, 유기층을 분리하고 물과 염수(brine)로 세척하였다. 얻어진 중간체 혼합물의 반응온도를 0℃로 냉각시킨 후, 과산화수소 (H2O2) 36 mL (0.988 mol)를 천천히 적가하였다. 반응온도를 상온으로 올린 후, 18시간 교반하였다. 반응이 종결되면 유기층을 분리하여 물로 2회 세척한 후, MgSO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 농축액을 용매로 고체화 정제하여 하얀색 고체의 화합물(중간체(9)) 4.8 g(수율 : 45 %)을 얻었다.
7.0 g (29.6 mmol) of 2,5-dibromopyridine is added to a three-necked 1.0 L flask and dissolved in 350 mL of THF under a nitrogen atmosphere. After cooling the reaction temperature to -78 ° C, 14.2 mL (35.5 mmol) of 2.5M n-BuLi solution was slowly added dropwise and stirred. After the addition was completed, the mixture was stirred at -78 ° C for one hour, and then 6.37 mL (35.5 mmol) of chlorodiphenylphosphine was slowly added dropwise thereto. After stirring for two hours, 70 mL of NH 4 OH was added. After the reaction temperature was slowly raised to room temperature, the reaction mixture was concentrated under reduced pressure. After adding 200 mL of methylene chloride to the concentrate, the organic layer was separated and washed with water and brine. After cooling the reaction temperature of the obtained intermediate mixture to 0 캜, 36 mL (0.988 mol) of hydrogen peroxide (H 2 O 2 ) was slowly added dropwise. The reaction temperature was raised to room temperature and stirred for 18 hours. When the reaction was completed, the organic layer was separated, washed twice with water, dried over MgSO 4 , filtered, and the filtrate was concentrated under reduced pressure. The obtained concentrate was solidified and purified by using a solvent to obtain 4.8 g (yield: 45%) of a white solid compound (Intermediate (9)).
합성예Synthetic example 10: 중간체(10)의 합성 10: Synthesis of Intermediate (10)
1구 500 mL 플라스크에 플루오란텐 (fluoranthene) 50 g(0.247 mol)을 넣고 질소 분위기 하에 MeCN 150 mL에 용해시킨다. 상온 하에서 NBS 48.4 g (0.272 mol)를 천천히 넣어준 후, 상온에서 18 시간 교반시킨다. 반응이 종결되면 소량의 MeCN 30 mL을 첨가하여 교반시킨 후, 여과한다. 얻어진 고체를 다시 MeOH (1L) 로 세척하여 노란색 고체의 화합물 (중간체 (10)) 52 g (수율: 75%)을 얻었다.
Add 50 g (0.247 mol) of fluoranthene to a 500 mL flask and dissolve in 150 mL of MeCN under a nitrogen atmosphere. 48.4 g (0.272 mol) of NBS was slowly added at room temperature, and the mixture was stirred at room temperature for 18 hours. When the reaction is completed, 30 mL of a small amount of MeCN is added, stirred, and filtered. The obtained solid was washed again with MeOH (1 L) to obtain 52 g (yield: 75%) of a yellow solid compound (Intermediate (10)).
합성예Synthetic example 11: 중간체(11)의 합성 11: Synthesis of intermediate (11)
플라스크에 중간체(10) 5.0 g(0.018 mol), PIN2B2 4.97 g(0.0196mol), Pd(dppf)Cl2 0.44 g(0.54 mmol), KOAc 3.5 g(0.036 mol) 및 디옥산(Dioxane) 90 mL을 같이 넣고 질소 하에서 75~80℃에서 2시간 환류 교반하였다. 온도를 상온으로 내린 후, 용매를 감압 증류하여 제거하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(중간체(11)) 3.6 g(수율 : 61%)을 얻었다.
To the flask was added 5.0 g (0.018 mol) of intermediate (10), PIN 2 B 2 0.49 g (0.54 mmol) of Pd (dppf) Cl 2 , 3.5 g (0.036 mol) of KOAc and 90 mL of dioxane were added thereto and the mixture was refluxed under stirring at 75 to 80 ° C for 2 hours under nitrogen atmosphere . After the temperature was lowered to room temperature, the solvent was distilled off under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 3.6 g (yield: 61%) of a light yellow solid compound (Intermediate (11)).
상기 합성된 중간체 화합물을 이용하여 이하와 같이 다양한 플루오란텐 유도체 화합물을 합성하였다.
A variety of fluoranthene derivative compounds were synthesized as follows using the synthesized intermediate compounds.
실시예Example 1: 화합물(2-1)의 합성 1: Synthesis of compound (2-1)
화합물(2-1)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-1) is shown below.
1구 100 mL 플라스크에 중간체(3) 0.5 g (0.943 mmol)과 중간체(9) 0.34 g(0.943 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 54 mg(0.047 mmol)과 2M 탄산칼륨 수용액 0.9 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-1) 0.12 g(수율: 19%)을 얻었다.
In a 100 mL flask, add intermediate ( 3 ) 0.5 g (0.943 mmol) and intermediate (9) 0.34 g (0.943 mmol ) in toluene was dissolved in 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 54 mg (0.047 mmol) and 2M 0.9 mL of an aqueous potassium carbonate solution was added, and the mixture was refluxed with stirring for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 0.12 g (yield: 19%) of a pale yellow solid compound (2-1).
실시예Example 2: 화합물(2-2)의 합성 2: Synthesis of compound (2-2)
화합물(2-2)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-2) is shown below.
1구 100 mL 플라스크에 중간체(3) 0.5 g (0.943 mmol)과 중간체(6) 0.41 g(0.943 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 54 mg(0.047 mmol)과 2M 탄산칼륨 수용액 0.9 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-2) 0.16 g(수율: 22%)을 얻었다.
In a 100 mL flask, add intermediate (3) 0.5 g (0.943 mmol) and intermediate (6) 0.41 g (0.943 mmol ) was dissolved in toluene, 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 54 mg (0.047 mmol) and 2M 0.9 mL of an aqueous potassium carbonate solution was added, and the mixture was refluxed with stirring for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 0.16 g (yield: 22%) of a pale yellow solid compound (2-2).
실시예Example 3: 화합물(2-3)의 합성 3: Synthesis of compound (2-3)
화합물(2-3)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-3) is shown below.
1구 100 mL 플라스크에 중간체(3) 0.5 g (0.943 mmol)과 중간체(7) 0.41 g(0.943 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 54 mg(0.047 mmol)과 2M 탄산칼륨 수용액 0.9 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-3) 0.25 g(수율: 35%)을 얻었다.
In a 100 mL flask, add intermediate (3) 0.5 g (0.943 mmol) and intermediate (7) 0.41 g (0.943 mmol ) was dissolved in toluene, 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 54 mg (0.047 mmol) and 2M 0.9 mL of an aqueous potassium carbonate solution was added, and the mixture was refluxed with stirring for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The obtained compound was purified by silica gel column chromatography to obtain 0.25 g (yield: 35%) of a pale yellow solid compound (2-3).
실시예Example 4: 화합물(2-7)의 합성 4: Synthesis of compound (2-7)
화합물(2-7)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-7) is shown below.
1구 100 mL 플라스크에 중간체(3) 0.5 g (0.943 mmol)과 중간체(12) 0.41 g(0.943 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 54 mg(0.047 mmol)과 2M 탄산칼륨 수용액 0.9 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-7) 0.31 g(수율: 43%)을 얻었다.
In a 100 mL flask, add intermediate (3) 0.5 g (0.943 mmol) and intermediate (12) 0.41 g (0.943 mmol ) was dissolved in toluene, 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 54 mg (0.047 mmol) and 2M 0.9 mL of an aqueous potassium carbonate solution was added, and the mixture was refluxed with stirring for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 0.31 g (yield: 43%) of a pale yellow solid compound (2-7).
실시예Example 5: 화합물(2-13)의 합성 5: Synthesis of compound (2-13)
화합물(2-13)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-13) is shown below.
1구 100 mL 플라스크에 중간체(3) 0.5 g (0.943 mmol)과 중간체(4) 0.34 g(0.943 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 54 mg(0.047 mmol)과 2M 탄산칼륨 수용액 0.9 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-13) 0.19 g(수율: 30%)을 얻었다.
In a 100 mL flask, add intermediate (3) 0.5 g (0.943 mmol) and intermediate (4) 0.34 g (0.943 mmol ) in toluene was dissolved in 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 54 mg (0.047 mmol) and 2M 0.9 mL of an aqueous potassium carbonate solution was added, and the mixture was refluxed with stirring for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain a pale yellow solid (2-13) 0.19 g (yield: 30%) was obtained.
실시예 6: 화합물(2-14)의 합성Example 6: Synthesis of compound (2-14)
화합물(2-14)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-14) is shown below.
1구 100 mL 플라스크에 중간체(3) 0.5 g (0.943 mmol)과 중간체(8) 0.34 g(0.943 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 54 mg(0.047 mmol)과 2M 탄산칼륨 수용액 0.9 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-14) 0.18 g(수율: 28%)을 얻었다.
In a 100 mL flask, add intermediate (3) 0.5 g (0.943 mmol) and Intermediate (8) 0.34 g (0.943 mmol) reflux was dissolved in toluene, 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 54 mg (0.047 mmol) and was added 0.9 mL 2M aqueous solution of potassium carbonate for 3 hours Lt; / RTI > When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 0.18 g (yield: 28%) of a pale yellow solid (2-14).
실시예 7: 화합물(2-17)의 합성Example 7: Synthesis of compound (2-17)
화합물(2-17)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-17) is shown below.
1구 100 mL 플라스크에 중간체(3) 0.5 g (0.943 mmol)과 중간체(13) 0.41 g(0.943 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 54 mg(0.047 mmol)과 2M 탄산칼륨 수용액 0.9 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-17) 0.32 g(수율: 45%)을 얻었다.
In a 100 mL flask, add intermediate (3) 0.5 g (0.943 mmol) and intermediate (13) 0.41 g (0.943 mmol ) was dissolved in toluene, 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 54 mg (0.047 mmol) and 2M 0.9 mL of an aqueous potassium carbonate solution was added, and the mixture was refluxed with stirring for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 0.32 g (yield: 45%) of a pale yellow solid (2-17).
실시예 8: 화합물(2-19)의 합성Example 8: Synthesis of compound (2-19)
화합물(2-19)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-19) is shown below.
1구 100 mL 플라스크에 중간체(11) 0.4 g (1.23 mmol)과 중간체(8) 0.4 g(1.12 mmol)을 톨루엔 6 mL와 에탄올 3 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 65 mg(0.056 mmol)과 2M 탄산칼륨 수용액 1 mL를 가하여 1시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-19) 0.29 g(수율: 54%)을 얻었다.
A 1-necked 100 mL flask was charged with intermediate (11) 0.4 g (1.23 mmol) and intermediate (8) 0.4 g (1.12 mmol ) was dissolved in toluene, 6 mL ethanol and 3 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 65 mg (0.056 mmol) and
실시예 9: 화합물(2-20)의 합성Example 9: Synthesis of compound (2-20)
화합물(2-20)의 합성 경로를 이하에 나타낸다.The synthesis route of the compound (2-20) is shown below.
1구 100 mL 플라스크에 중간체(11) 0.44 g (1.34 mmol)과 중간체(9) 0.4 g(1.12 mmol)을 톨루엔 7 mL와 에탄올 4 mL에 녹이고 테트라키스트리페닐포스핀팔라듐(Pd(PPh3)4) 65 mg(0.06 mmol)과 2M 탄산칼륨 수용액 1.0 mL를 가하여 3시간 동안 환류 교반하였다. 반응이 종결되면 상온으로 반응온도를 냉각하고 H2O 5 mL를 첨가하였다. 혼합물에 메틸렌클로라이드 30 mL로 첨가하여 유기층을 분리하였다. 유기층을 Na2SO4로 건조, 여과하고 여액을 감압 농축하였다. 얻어진 화합물을 실리카겔 컬럼 크로마토그래피로 정제하여 미황색 고체의 화합물(2-20) 0.19 g(수율: 35%)을 얻었다.
A 1-necked 100 mL flask was charged with intermediate (11) 0.44 g (1.34 mmol) and intermediate (9) 0.4 g (1.12 mmol ) was dissolved in toluene, 7 mL ethanol and 4 mL of tetrakis (triphenylphosphine) palladium (Pd (PPh 3) 4) 65 mg (0.06 mmol) and 2M 1.0 mL of an aqueous potassium carbonate solution was added, and the mixture was refluxed and stirred for 3 hours. When the reaction was completed, the reaction temperature was cooled to room temperature and 5 mL of H 2 O was added. To the mixture was added 30 mL of methylene chloride and the organic layer was separated. The organic layer was dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting compound was purified by silica gel column chromatography to obtain 0.19 g (yield: 35%) of a pale yellow solid (2-20).
본 발명의 화합물에 대하여 Jasco V-630 기기를 이용하여 UV/VIS 스펙트럼을 측정하고, Jasco FP-8500 기기를 이용하여 PL(photoluminescence) 스펙트럼을 측정하여 하기 표 1에 나타내었다.
The UV / VIS spectra of the compounds of the present invention were measured using a Jasco V-630 instrument and PL (photoluminescence) spectra were measured using a Jasco FP-8500 instrument.
*2: 5.0 x 10-6 M in Methylene Chloride* 1: 1.0 x 10 -5 M in Methylene Chloride
* 2: 5.0 x 10 -6 M in Methylene Chloride
본 발명의 화합물에 대하여 Waters Acquity UPLC H-Class/ SQD2 system 기기를 이용하여 LC-MS를 측정하였으며 그 결과를 하기 표 2에 나타내었다.
The compounds of the present invention were analyzed by LC-MS using a Waters Acquity UPLC H-Class / SQD2 system instrument and the results are shown in Table 2 below.
소자 제작 시험예Device fabrication test example
상기 실시예의 화합물에 대한 전자의 이동도를 확인하기 위하여 EOD(electron only device) 소자를 제작하였다. 소자 제작 시 ITO 및 Al을 전극으로 사용하였고, Liq는 홀의 주입을 막고 전자가 잘 주입되기 위해 사용 되었으며, 두 개의 Liq 사이에 측정하고자 하는 화합물을 증착하였다.
An electron only device (EOD) device was fabricated to confirm the electron mobility for the compounds of the above examples. ITO and Al were used as electrodes in the fabrication of the device. Liq was used to prevent the injection of holes and to inject electrons well, and the compound to be measured was deposited between two Liq.
비교시험예 : ITO / Liq / AlqComparative Test Example: ITO / Liq / Alq 33 / Liq / Al / Liq / Al
EOD 소자는 ITO (180 nm) / Liq (2 nm) / Alq3 (60 nm) / Liq (2 nm) / Al (100 nm) 순으로 증착하여 소자를 제작하였다. 유기물은 9 10-7Torr의 진공도에서 증착하였으며 Liq는 0.1 Å/sec, Alq3는 1 Å/sec, Al은 10 Å/sec의 속도로 증착하였다. 실험에 사용된 비교물질은 Alq3이다. 소자 제작이 끝난 후 소자의 공기 및 수분의 접촉을 막기 위하여 질소 기체로 채워져 있는 글러브 박스 안에서 봉지를 하였다. 3M사의 접착용 테이프로 격벽을 형성 후 수분 등을 제거할 수 있는 흡습제인 바륨산화물(Barium Oxide)을 넣고 유리판을 붙였다.
EOD devices were fabricated by depositing ITO (180 nm) / Liq (2 nm) / Alq 3 (60 nm) / Liq (2 nm) / Al (100 nm) in this order. Organic materials were deposited at a vacuum of 9 10 -7 Torr, and deposited at a rate of 0.1 Å / sec for Liq, 1 Å / sec for Alq 3 , and 10 Å / sec for Al. The comparative material used in the experiment is Alq 3 . After fabricating the device, it was sealed in a glove box filled with nitrogen gas to prevent air and moisture contact of the device. Barium oxide (Barium Oxide), which is a hygroscopic agent capable of removing moisture and so on, was put into a glass plate after 3M's adhesive tape was formed.
시험예Test Example 1 : One : ITOITO / / LiqLiq / 화합물(2-2) / / Compound (2-2) / LiqLiq / / AlAl
상기 비교시험예에서, Alq3을 이용하는 대신 상기 실시예 2에서 제조한 화합물(2-2)을 이용한 것을 제외하고는, 상기 비교시험예와 동일한 방법으로 소자를 제작하였다.
In the comparative test example, a device was fabricated in the same manner as in the comparative test except that the compound (2-2) prepared in Example 2 was used instead of Alq 3 .
시험예Test Example 2 : 2 : ITOITO / / LiqLiq / 화합물(2-3) / / Compound (2-3) / LiqLiq / / AlAl
상기 비교시험예에서, Alq3을 이용하는 대신 상기 실시예 3에서 제조한 화합물(2-3)을 이용한 것을 제외하고는, 상기 비교시험예와 동일한 방법으로 소자를 제작하였다.
In the comparative test example, a device was fabricated in the same manner as in the comparative test except that the compound (2-3) prepared in Example 3 was used instead of Alq 3 .
시험예Test Example 3 : 3: ITOITO / / LiqLiq / 화합물(2-13) / / Compound (2-13) / LiqLiq / / AlAl
상기 비교시험예에서, Alq3을 이용하는 대신 상기 실시예 5에서 제조한 화합물(2-13)을 이용한 것을 제외하고는 상기 비교시험예와 동일한 방법으로 소자를 제작하였다.
In the comparative test example, a device was fabricated in the same manner as in the comparative test except that the compound (2-13) prepared in Example 5 was used instead of Alq 3 .
상기 비교시험예 및 시험예 1 내지 3에서 제조된 EOD 소자에 대한 전기적 특성을 하기 표 3에 나타내고, 비교시험예 및 시험예 1 내지 3에서 제조된 EOD 소자에 대하여 전압에 따른 전류 밀도를 하기 도 2에 나타내었다.
The electrical characteristics of the EOD device manufactured in the comparative test example and the test examples 1 to 3 are shown in the following Table 3, and the current density according to the voltage of the EOD device manufactured in the comparative test example and the test examples 1 to 3 Respectively.
상기 표 3 및 도 2로 확인할 수 있는 바와 같이 본 발명의 화합물들을 EOD 소자로 제작하였을 때 비교시험예 소자보다 시험예 1 내지 3의 소자들이 월등한 전류 밀도를 보이는 것을 확인할 수 있다. 이러한 월등한 전류 밀도의 상승은 OLED 소자를 제작할 때 소자의 구동 전압을 낮추고, 발광 효율 특성 및 수명 특성을 향상시킬 수 있다.As can be seen from Table 3 and FIG. 2, when the compounds of the present invention were fabricated from EOD devices, it was confirmed that the devices of Test Examples 1 to 3 exhibited superior current densities to those of the comparative test devices. Such a superior current density increase can lower the driving voltage of the device when fabricating the OLED device, and improve the light emitting efficiency characteristic and the lifetime characteristic.
Claims (8)
[화학식 1]
[상기 화학식 1에서,
R1, R2는 서로 결합하여 적어도 하나의 벤젠, 나프탈렌 등과 같은 방향족 고리를 형성하거나, 각각 독립적으로 수소이거나 치환 또는 비치환된 C1~C30의 알킬이며;
R3 내지 R6는 각각 독립적으로 수소이거나 치환 또는 비치환된 C6~C30의 아릴기이거나 치환 또는 비치환된 C5~C30의 헤테로아릴기이며;
X는 N 또는 CH이며;
L은 치환 또는 비치환된 아릴렌기이거나 헤테로 아릴렌기이며;
n은 0 또는 1 이다] A fluoranthene derivative having a phosphoryl group bonded thereto represented by the following formula (1).
[Chemical Formula 1]
[In the above formula (1)
R 1 and R 2 are bonded to each other to form an aromatic ring such as at least one benzene, naphthalene or the like, or are each independently hydrogen or a substituted or unsubstituted C1-C30 alkyl;
R 3 to R 6 are each independently hydrogen or a substituted or unsubstituted C 6 to C 30 aryl group or a substituted or unsubstituted C 5 to C 30 heteroaryl group;
X is N or CH;
L is a substituted or unsubstituted arylene group or a heteroarylene group;
n is 0 or 1;
R3 내지 R6는 각각 독립적으로 수소, 페닐, 비페닐, 나프틸 및 퀴놀린으로 이루어진 군 중에서 선택되는 것을 특징으로 하는 포스포릴기가 결합된 플루오란텐 유도체.The method according to claim 1,
R 3 to R 6 are each independently selected from the group consisting of hydrogen, phenyl, biphenyl, naphthyl and quinoline.
상기 화학식 1의 화합물은 하기 화학식 2로 이루어진 군으로부터 선택되는 것을 특징으로 하는 포스포릴기가 결합된 플루오란텐 유도체.
[화학식 2]
Wherein the compound of formula (1) is selected from the group consisting of the following formula (2).
(2)
상기 포스포릴기가 결합된 플루오란텐 유도체가 전자수송층 재료로 사용되는 것을 특징으로 하는 유기 전계발광 소자.5. The method of claim 4,
Wherein the fluoranthene derivative to which the phosphoryl group is bonded is used as an electron transporting layer material.
상기 유기막은 제 1항 내지 3항 중 어느 한 항의 포스포릴기가 결합된 플루오란텐 유도체를 포함하는 유기 전계발광 소자.A first electrode, a second electrode, and at least one organic film disposed between the electrodes,
Wherein the organic film comprises a fluoranthene derivative to which a phospholyl group is bonded according to any one of claims 1 to 3.
상기 유기막은 정공주입층, 정공수송층, 정공주입 기능과 정공수송 기능을 동시에 갖는 기능층, 버퍼층, 전자저지층, 발광층, 정공저지층, 전자수송층, 전자주입층, 및 전자수송 기능과 전자주입 기능을 동시에 갖는 기능층으로 이루어진 군 중에서 선택되는 1층 이상을 포함하는 유기 전계발광 소자.The method according to claim 6,
The organic layer includes a hole injecting layer, a hole transporting layer, a functional layer having both a hole injecting function and a hole transporting function, a buffer layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transporting layer, And at least one functional layer having at least one functional group at the same time.
상기 포스포릴 기가 결합된 플루오란텐 유도체가 상기 유기막을 구성하는 전자저지층, 전자수송층, 전자주입층, 전자수송 기능과 전자주입 기능을 동시에 갖는 기능층 및 발광층으로 이루어진 군 중에서의 선택된 어느 1층에 포함되는 것을 특징으로 하는 유기 전계발광 소자.The method according to claim 6,
When the phosphoryl group is bonded The fluoranthene derivative is contained in any one selected from the group consisting of an electron blocking layer, an electron transporting layer, an electron injecting layer, a functional layer having both an electron transporting function and an electron injecting function, and a light emitting layer constituting the organic film The organic electroluminescent device comprising:
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| KR20140065342A (en) | 2012-11-21 | 2014-05-29 | 주식회사 엘지화학 | Fluoranthene compound and organic electronic device comprising the same |
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| KR20140065342A (en) | 2012-11-21 | 2014-05-29 | 주식회사 엘지화학 | Fluoranthene compound and organic electronic device comprising the same |
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