JP2008247895A - Electron transport material and organic electroluminescent element using the same - Google Patents
Electron transport material and organic electroluminescent element using the same Download PDFInfo
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- JP2008247895A JP2008247895A JP2008053379A JP2008053379A JP2008247895A JP 2008247895 A JP2008247895 A JP 2008247895A JP 2008053379 A JP2008053379 A JP 2008053379A JP 2008053379 A JP2008053379 A JP 2008053379A JP 2008247895 A JP2008247895 A JP 2008247895A
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- 239000000463 material Substances 0.000 title abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 256
- 125000005647 linker group Chemical group 0.000 claims abstract description 101
- YTEIHWVCQJZNEN-UHFFFAOYSA-N 3-pyridin-4-ylpyridine Chemical group C1=CN=CC(C=2C=CN=CC=2)=C1 YTEIHWVCQJZNEN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims description 77
- 229910052739 hydrogen Inorganic materials 0.000 claims description 77
- -1 phosphoryl groups Chemical group 0.000 claims description 70
- 150000002431 hydrogen Chemical class 0.000 claims description 42
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 42
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 40
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 38
- 125000004429 atom Chemical group 0.000 claims description 28
- 125000001424 substituent group Chemical group 0.000 claims description 28
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 26
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 25
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 23
- 239000001963 growth medium Substances 0.000 claims description 23
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 21
- 238000005859 coupling reaction Methods 0.000 claims description 19
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 19
- 125000001624 naphthyl group Chemical group 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Chemical group 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims 17
- 238000010168 coupling process Methods 0.000 claims 17
- 230000009467 reduction Effects 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 93
- 239000010410 layer Substances 0.000 description 69
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 238000007740 vapor deposition Methods 0.000 description 39
- 238000003786 synthesis reaction Methods 0.000 description 37
- 230000015572 biosynthetic process Effects 0.000 description 35
- 239000000243 solution Substances 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 23
- 238000000034 method Methods 0.000 description 20
- 239000012141 concentrate Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000010408 film Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 238000002347 injection Methods 0.000 description 17
- 239000007924 injection Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 13
- 239000012044 organic layer Substances 0.000 description 13
- 238000010898 silica gel chromatography Methods 0.000 description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- 239000012300 argon atmosphere Substances 0.000 description 12
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229910052750 molybdenum Inorganic materials 0.000 description 11
- 239000011733 molybdenum Substances 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 10
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 9
- ZKNBQZBRNLAVHS-UHFFFAOYSA-N 3-bromo-5-pyridin-4-ylpyridine Chemical compound BrC1=CN=CC(C=2C=CN=CC=2)=C1 ZKNBQZBRNLAVHS-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 9
- 239000010409 thin film Substances 0.000 description 8
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000003054 catalyst Substances 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 235000011056 potassium acetate Nutrition 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 5
- 235000019798 tripotassium phosphate Nutrition 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000006411 Negishi coupling reaction Methods 0.000 description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000004866 oxadiazoles Chemical class 0.000 description 4
- 150000003222 pyridines Chemical class 0.000 description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
- GPOMKCKAJSZACG-UHFFFAOYSA-N 2-phenylanthracene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2C(C=CC=C2)=C2)C2=C1 GPOMKCKAJSZACG-UHFFFAOYSA-N 0.000 description 3
- RQHQTFLXMUBQBU-UHFFFAOYSA-N 3,6-dibromo-9-naphthalen-1-ylcarbazole Chemical compound C12=CC=C(Br)C=C2C2=CC(Br)=CC=C2N1C1=CC=CC2=CC=CC=C12 RQHQTFLXMUBQBU-UHFFFAOYSA-N 0.000 description 3
- PGKQJNOISHJIBI-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-[7-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)triphenylen-2-yl]-1,3,2-dioxaborolane Chemical group O1C(C)(C)C(C)(C)OB1C1=CC=C(C=2C(=CC(=CC=2)B2OC(C)(C)C(C)(C)O2)C=2C3=CC=CC=2)C3=C1 PGKQJNOISHJIBI-UHFFFAOYSA-N 0.000 description 3
- JBYBLHYEVCYGME-UHFFFAOYSA-N 9,10-dibromo-2-phenylanthracene Chemical compound C=1C=C2C(Br)=C3C=CC=CC3=C(Br)C2=CC=1C1=CC=CC=C1 JBYBLHYEVCYGME-UHFFFAOYSA-N 0.000 description 3
- BLKLIQJTGNDTOL-UHFFFAOYSA-N 9-phenyl-2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C2C3=CC=C(B4OC(C)(C)C(C)(C)O4)C=C3N(C=3C=CC=CC=3)C2=C1 BLKLIQJTGNDTOL-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- FSSKYZQJNSHRLG-UHFFFAOYSA-N C1=CC=C(C=C1)N2C3=C(C=CC(=C3)OS(=O)(=O)C(F)(F)F)C4=C2C=C(C=C4)OS(=O)(=O)C(F)(F)F Chemical compound C1=CC=C(C=C1)N2C3=C(C=CC(=C3)OS(=O)(=O)C(F)(F)F)C4=C2C=C(C=C4)OS(=O)(=O)C(F)(F)F FSSKYZQJNSHRLG-UHFFFAOYSA-N 0.000 description 3
- PMCOWOCKUQWYRL-UHFFFAOYSA-N Cc1ccnc(C)n1 Chemical compound Cc1ccnc(C)n1 PMCOWOCKUQWYRL-UHFFFAOYSA-N 0.000 description 3
- NSAUQTCATRWAJC-UHFFFAOYSA-N Cc1cnc(C)[o]1 Chemical compound Cc1cnc(C)[o]1 NSAUQTCATRWAJC-UHFFFAOYSA-N 0.000 description 3
- WVUHHPQQQLBMOE-UHFFFAOYSA-N Cc1cnc(C)[s]1 Chemical compound Cc1cnc(C)[s]1 WVUHHPQQQLBMOE-UHFFFAOYSA-N 0.000 description 3
- LCZUOKDVTBMCMX-UHFFFAOYSA-N Cc1cnc(C)cn1 Chemical compound Cc1cnc(C)cn1 LCZUOKDVTBMCMX-UHFFFAOYSA-N 0.000 description 3
- RHOOLJLEYYXKTK-UHFFFAOYSA-N Cc1cnc(C)nc1 Chemical compound Cc1cnc(C)nc1 RHOOLJLEYYXKTK-UHFFFAOYSA-N 0.000 description 3
- HJFZAYHYIWGLNL-UHFFFAOYSA-N Cc1nc(C)cnc1 Chemical compound Cc1nc(C)cnc1 HJFZAYHYIWGLNL-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VVSCYVPRHRQDPS-UHFFFAOYSA-N [7-(trifluoromethylsulfonyloxy)triphenylen-2-yl] trifluoromethanesulfonate Chemical group C1=CC=C2C3=CC(OS(=O)(=O)C(F)(F)F)=CC=C3C3=CC=C(OS(=O)(=O)C(F)(F)F)C=C3C2=C1 VVSCYVPRHRQDPS-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000005504 styryl group Chemical group 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- YXDSQNPTLSHISU-UHFFFAOYSA-N triphenylene-2,7-diol Chemical group C1=CC=C2C3=CC(O)=CC=C3C3=CC=C(O)C=C3C2=C1 YXDSQNPTLSHISU-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- MDILQAKUYPNNON-UHFFFAOYSA-N 2,7-dimethoxytriphenylene Chemical group C1=CC=C2C3=CC(OC)=CC=C3C3=CC=C(OC)C=C3C2=C1 MDILQAKUYPNNON-UHFFFAOYSA-N 0.000 description 2
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 description 2
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 2
- NUUYTGXGPHSYQZ-UHFFFAOYSA-N 3-[2-phenyl-10-(5-pyridin-4-ylpyridin-3-yl)anthracen-9-yl]-5-pyridin-4-ylpyridine Chemical compound C1=CC=CC=C1C1=CC=C(C(C=2C=C(C=NC=2)C=2C=CN=CC=2)=C2C(C=CC=C2)=C2C=3C=C(C=NC=3)C=3C=CN=CC=3)C2=C1 NUUYTGXGPHSYQZ-UHFFFAOYSA-N 0.000 description 2
- UQVQCERBEPZNSK-UHFFFAOYSA-N 3-pyridin-4-yl-5-[7-(5-pyridin-4-ylpyridin-3-yl)triphenylen-2-yl]pyridine Chemical group C1=CC2=C(C=C1)C1=C(C=CC(=C1)C1=CN=CC(=C1)C1=CC=NC=C1)C1=C2C=C(C=C1)C1=CC(=CN=C1)C1=CC=NC=C1 UQVQCERBEPZNSK-UHFFFAOYSA-N 0.000 description 2
- HNILOESMUPGLRZ-UHFFFAOYSA-N 9-naphthalen-1-yl-3,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C3=CC=CC=C3C=CC=2)C=2C3=CC(=CC=2)B2OC(C)(C)C(C)(C)O2)C3=C1 HNILOESMUPGLRZ-UHFFFAOYSA-N 0.000 description 2
- AIVVGIAPEHWVGF-UHFFFAOYSA-N 9-phenyl-2,7-bis(5-pyridin-4-ylpyridin-3-yl)carbazole Chemical compound C1=CC=C(C=C1)N1C2=C(C=CC(=C2)C2=CC(=CN=C2)C2=CC=NC=C2)C2=C1C=C(C=C2)C1=CN=CC(=C1)C1=CC=NC=C1 AIVVGIAPEHWVGF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- JPQDHQFEQPKVIP-UHFFFAOYSA-N C1=CC=C2C(=C1)C(=CC=C2C3=CN=CC(=C3)C4=CC=NC=C4)C5=CN=CC(=C5)C6=CC=NC=C6 Chemical compound C1=CC=C2C(=C1)C(=CC=C2C3=CN=CC(=C3)C4=CC=NC=C4)C5=CN=CC(=C5)C6=CC=NC=C6 JPQDHQFEQPKVIP-UHFFFAOYSA-N 0.000 description 2
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- 125000004986 diarylamino group Chemical group 0.000 description 1
- NNNFHIWKVLLMKH-UHFFFAOYSA-N ditert-butyl-[1-(2-ditert-butylphosphanylnaphthalen-1-yl)naphthalen-2-yl]phosphane Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3P(C(C)(C)C)C(C)(C)C)=C(P(C(C)(C)C)C(C)(C)C)C=CC2=C1 NNNFHIWKVLLMKH-UHFFFAOYSA-N 0.000 description 1
- MUPGNOONALUUNP-UHFFFAOYSA-N ditert-butyl-[1-(2-methoxynaphthalen-1-yl)naphthalen-2-yl]phosphane Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OC)=C(P(C(C)(C)C)C(C)(C)C)C=CC2=C1 MUPGNOONALUUNP-UHFFFAOYSA-N 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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- 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
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 229920000123 polythiophene Chemical class 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- 150000003220 pyrenes Chemical class 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- QLULGIRFKAWHOJ-UHFFFAOYSA-N pyridin-4-ylboronic acid Chemical compound OB(O)C1=CC=NC=C1 QLULGIRFKAWHOJ-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 150000004322 quinolinols Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- 238000005057 refrigeration Methods 0.000 description 1
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- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical class C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical group COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
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- 125000003003 spiro group Chemical group 0.000 description 1
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- 238000000859 sublimation Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Electroluminescent Light Sources (AREA)
- Pyridine Compounds (AREA)
Abstract
Description
本発明は、３，４’−ビピリジル基を有する新規な電子輸送材料、この電子輸送材料を用いた有機電界発光素子（以下、有機ＥＬ素子または単に素子と略記することがある。）等に関する。 The present invention relates to a novel electron transport material having a 3,4'-bipyridyl group, an organic electroluminescence device using the electron transport material (hereinafter, sometimes abbreviated as an organic EL device or simply a device), and the like.
近年、次世代のフルカラーフラットパネルディスプレイとして有機ＥＬ素子が注目され、活発な研究がなされている。有機ＥＬ素子の実用化を促進するには、素子の駆動電圧の低減、長寿命化が不可欠な要素であり、これらを達成するために新しい電子輸送材料の開発がなされてきた。特開２００３−１２３９８３号公報（：特許文献１）には、フェナントロリン誘導体を電子輸送材料に使用することで有機ＥＬ素子を低電圧で駆動させることができると記載されており、更に、フェナントロリンの類似体である２，２’−ビピリジル化合物も同様に、電子輸送材料に使用することで有機ＥＬ素子を低電圧で駆動させることができると記載されている。しかしながらこの文献の実施例に報告されている素子の特性（駆動電圧、発光効率など）は比較例を基準にした相対値のみであり、実用的な値と判断できる実測値は記載されていない。他に、２，２’−ビピリジル化合物を電子輸送材料に使用した例は、Proceedings of the 10th International Workshop on Inorganic and Organic Electroluminescence（：非特許文献１）、特開２００２−１５８０９３号公報（：特許文献２）、および特表平１１−５１４１４３号公報（：特許文献３）に開示されている。非特許文献１に記載されている２，２’−ビピリジル化合物はガラス転移温度（以下、Ｔｇと略記する。）が低く、実用的ではなかった。特許文献３に記載の２，２’−ビピリジル化合物は比較的低電圧で有機ＥＬ素子を駆動させることができるが、実用化には更なる低電圧化が望まれる。特許文献３には、具体的な化合物が示されていない。
本発明は、このような従来技術が有する課題に鑑みてなされたものである。本発明は、有機ＥＬ素子の駆動電圧の低減、長寿命化等に寄与する電子輸送材料を提供することを課題とする。さらに本発明は、この電子輸送材料を用いた有機ＥＬ素子を提供することを課題とする。 The present invention has been made in view of the problems of such conventional techniques. It is an object of the present invention to provide an electron transport material that contributes to reduction in driving voltage and long life of an organic EL element. Furthermore, this invention makes it a subject to provide the organic EL element using this electron transport material.
本発明者らは鋭意検討した結果、３，４’−ビピリジルを有する化合物を有機ＥＬ素子の電子輸送層に用いることにより、高輝度で長寿命、かつ低電圧で駆動できる有機ＥＬ素子が得られることを見出し、この知見に基づいて本発明を完成した。
上記の課題は以下に示す各項によって解決される。
As a result of intensive studies, the present inventors have obtained an organic EL device that can be driven with high brightness, long life, and low voltage by using a compound having 3,4'-bipyridyl for the electron transport layer of the organic EL device. Based on this finding, the present invention has been completed.
Said subject is solved by each item shown below.
［１］下記の式（１）で表される化合物。
Ｒ１〜Ｒ４は独立して水素、１価の基またはＧに結合する遊離原子価であり、Ｒ５〜Ｒ８は独立して水素または１価の基であるが、Ｒ１〜Ｒ４の１つはＧに結合する遊離原子価であり；そして、ｎ個の３，４’−ビピリジル基は同一でもよく、異なっていてもよい。
［２］Ｒ１〜Ｒ４の１つがＧに結合する遊離原子価であり、それ以外が水素であり、Ｒ５〜Ｒ8が水素である、前記［１］項に記載の化合物。
[1] A compound represented by the following formula (1).
R 1 to R 4 are independently hydrogen, a monovalent group or a free valence bonded to G, and R 5 to R 8 are independently hydrogen or a monovalent group, but R 1 to R 4 Is the free valence attached to G; and the n 3,4′-bipyridyl groups may be the same or different.
[2] The compound according to [1], wherein one of R 1 to R 4 is a free valence bonded to G, the other is hydrogen, and R 5 to R 8 are hydrogen.
［３］下記の式（２）で表される、前記［２］項に記載の化合物。
［４］下記の式（２−１）で表される、前記［３］項に記載の化合物。
［５］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ａ−１）〜（Ａ−２１）で表される化合物の群から選択される１つから誘導される２価の基である、前記［４］項に記載の化合物。
［６］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ａ−１）〜（Ａ−４）で表される化合物の群から選択される１つから誘導される２価の基である、前記［４］項に記載の化合物。
［７］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が下記の式（Ｃ−１）〜（Ｃ−１０）で表される２価の基の群から選択される１つである、前記［４］項に記載の化合物。
［８］Ｇが前記の式（Ｇ２）で表される連結基であり、式（Ｇ２）中、Ｇ１が前記の式（Ａ−１）〜（Ａ−２１）および式（Ｂ−１）〜（Ｂ−４１）で表される化合物の群から選択される１つから誘導される同一の２価の基である、前記［４］項に記載の化合物。
［９］Ｇが前記の式（Ｇ２）で表される連結基であり、式（Ｇ２）中、Ｇ１が前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基である、前記［４］項に記載の化合物。
［１０］Ｇが下記の式（Ｇ３−１）〜（Ｇ３−３）で表される連結基の群から選択される１つである、前記［４］項に記載の化合物。
［１１］Ｇが式（Ｇ３−２）で表される連結基であり；Ｇ１Ａが前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基であり、Ｇ１Ｂが下記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される１つである、前記［１０］項に記載の化合物。
［１２］Ｇが式（Ｇ３−３）で表される連結基であり；Ｇ１Ａが前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される１つであり、Ｇ１Ｂが前記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される同一の基である、前記［１０］項に記載の化合物。
［１３］Ｇが下記の式（Ｇ３−４）で表される連結基である、前記［１０］項に記載の化合物。
[5] a linking group G is represented by the formula (G1), from the group of compounds formula (G1) Medium G 1 is represented by the formula (A-1) ~ (A -21) The compound according to [4] above, which is a divalent group derived from one selected.
[6] is a linking group G is represented by the formula (G1), from the group of compounds represented by formula (G1) Medium G 1 is the formula (A-1) ~ (A -4) The compound according to [4] above, which is a divalent group derived from one selected.
[7] G is a linking group represented by the above formula (G1), and G 1 in the formula (G1) is a divalent group represented by the following formulas (C-1) to (C-10): The compound according to [4] above, which is one selected from the group of
[8] G is a linking group represented by the formula (G2), the formula (G2) in, G 1 is the formula (A-1) ~ (A -21) and formula (B-1) The compound according to [4] above, which is the same divalent group derived from one selected from the group of compounds represented by (B-41).
[9] G is a linking group represented by the above formula (G2), and in formula (G2), G 1 is a divalent group represented by the above formulas (C-1) to (C-6). The compound according to item [4], which is the same group selected from the group of groups.
[10] The compound according to [4] above, wherein G is one selected from the group of linking groups represented by the following formulas (G3-1) to (G3-3).
[11] G is a linking group represented by the formula (G3-2); G 1A is selected from the group of divalent groups represented by the formulas (C-1) to (C-6). The same group, and G 1B is one selected from the group of divalent groups represented by the following formulas (D-1) to (D-12): Compound.
[12] G is a linking group represented by the formula (G3-3); G 1A is selected from the group of divalent groups represented by the formulas (C-1) to (C-6). And G 1B is the same group selected from the group of divalent groups represented by the formulas (D-1) to (D-12). Compound.
[13] The compound according to [10], wherein G is a linking group represented by the following formula (G3-4).
［１４］下記の式（２−２）で表される、前記［３］項に記載の化合物。
［１５］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ａ−１）〜（Ａ−２１）で表される化合物の群から選択される１つから誘導される２価の基である、前記［１４］項に記載の化合物。
［１６］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ａ−１）〜（Ａ−４）で表される化合物の群から選択される１つから誘導される２価の基である、前記［１４］項に記載の化合物。
［１７］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ｃ−１）〜（Ｃ−１０）で表される２価の基の群から選択される１つである、前記［１４］項に記載の化合物。
［１８］Ｇが式（Ｇ２）で表される連結基であり、式（Ｇ２）中Ｇ１が前記の式（Ａ−１）〜（Ａ−２１）および式（Ｂ−１）〜（Ｂ−４１）で表される化合物の群から選択される１つから誘導される同一の２価の基である、前記［１４］項に記載の化合物。
［１９］Ｇが前記の式（Ｇ２）で表される連結基であり、式（Ｇ２）中Ｇ１が前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基である、前記［１４］項に記載の化合物。
［２０］Ｇが下記の式（Ｇ３−１）〜（Ｇ３−３）で表される連結基の群から選択される１つである、前記［１４］項に記載の化合物。
［２１］Ｇが式（Ｇ３−２）で表される連結基であり；Ｇ１Ａが前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基であり、Ｇ１Ｂが前記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される１つである、前記［２０］項に記載の化合物。
［２２］Ｇが式（Ｇ３−３）で表される連結基であり；Ｇ１Ａが前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される１つであり、Ｇ１Ｂが前記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される同一の基である、前記［２０］項に記載の化合物。
［２３］Ｇが下記の式（Ｇ３−４）で表される連結基である、前記［２０］項に記載の化合物。
[15] a linking group G is represented by the formula (G1), from the group of compounds formula (G1) Medium G 1 is represented by the formula (A-1) ~ (A -21) The compound according to item [14], which is a divalent group derived from one selected.
[16] a linking group G is represented by the formula (G1), from the group of compounds represented by formula (G1) Medium G 1 is the formula (A-1) ~ (A -4) The compound according to item [14], which is a divalent group derived from one selected.
[17] G is a linking group represented by the formula (G1), and G 1 in the formula (G1) is a divalent group represented by the formulas (C-1) to (C-10). The compound according to the above item [14], which is one selected from the group of [14].
[18] G is a linking group represented by the formula (G2), and G 1 in the formula (G2) is the formula (A-1) to (A-21) and the formula (B-1) to (B -The compound according to item [14], which is the same divalent group derived from one selected from the group of compounds represented by -41).
[19] G is a linking group represented by the formula (G2), and G 1 in the formula (G2) is a divalent group represented by the formulas (C-1) to (C-6). The compound according to the above item [14], which is the same group selected from the group of [14].
[20] The compound according to [14] above, wherein G is one selected from the group of linking groups represented by the following formulas (G3-1) to (G3-3).
[21] G is a linking group represented by the formula (G3-2); G 1A is selected from the group of divalent groups represented by the formulas (C-1) to (C-6). The above-mentioned [20], wherein G 1B is one selected from the group of divalent groups represented by the formulas (D-1) to (D-12). Compound.
[22] G is a linking group represented by the formula (G3-3); G 1A is selected from the group of divalent groups represented by the formulas (C-1) to (C-6). And G 1B is the same group selected from the group of divalent groups represented by the above formulas (D-1) to (D-12). Compound.
[23] The compound according to [20], wherein G is a linking group represented by the following formula (G3-4).
［２４］下記の式（２−３）で表される、前記［３］項に記載の化合物。
［２５］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ａ−１）〜（Ａ−２１）で表される化合物の群から選択される１つから誘導される２価の基である、前記［２４］項に記載の化合物。
［２６］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ａ−１）〜（Ａ−４）で表される化合物の群から選択される１つから誘導される２価の基である、前記［２４］項に記載の化合物。
［２７］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ｃ−１）〜（Ｃ−１０）で表される２価の基の群から選択される１つである、前記［２４］項に記載の化合物。
［２８］Ｇが前記の式（Ｇ２）で表される連結基であり、式（Ｇ２）中Ｇ１が前記の式（Ａ−１）〜（Ａ−２１）および式（Ｂ−１）〜（Ｂ−４１）で表される化合物の群から選択される１つから誘導される同一の２価の基である、前記［２４］項に記載の化合物。
［２９］Ｇが前記の式（Ｇ２）で表される連結基であり、式（Ｇ２）中Ｇ１が前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基である、前記［２４］項に記載の化合物。
［３０］Ｇが下記の式（Ｇ３−１）〜（Ｇ３−３）で表される連結基の群から選択される１つである、前記［２４］項に記載の化合物。
［３１］Ｇが前記の式（Ｇ３−２）で表される連結基であり；Ｇ１Ａが前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基であり、Ｇ１Ｂが前記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される１つである、前記［３０］項に記載の化合物。
［３２］Ｇが式（Ｇ３−３）で表される連結基であり；Ｇ１Ａが前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される１つであり、Ｇ１Ｂが前記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される同一の基である、前記［３０］項に記載の化合物。
［３３］Ｇが下記の式（Ｇ３−４）で表される連結基である、前記［３０］項に記載の化合物。
[25] G is a linking group represented by the above formula (G1), and G 1 in the formula (G1) is selected from the group of compounds represented by the above formulas (A-1) to (A-21). The compound according to the above [24], which is a divalent group derived from one selected.
[26] a linking group G is represented by the formula (G1), from the group of compounds represented by formula (G1) Medium G 1 is the formula (A-1) ~ (A -4) The compound according to the above [24], which is a divalent group derived from one selected.
[27] G is a linking group represented by the above formula (G1), and G 1 in the formula (G1) is a divalent group represented by the above formulas (C-1) to (C-10). The compound according to [24] above, which is one selected from the group of
[28] G is a linking group represented by the formula (G2), the formula (G2) Medium G 1 is of the formula (A-1) ~ (A -21) and formula (B-1) ~ The compound according to [24] above, which is the same divalent group derived from one selected from the group of compounds represented by (B-41).
[29] G is a linking group represented by the above formula (G2), and G 1 in the formula (G2) is a divalent group represented by the above formulas (C-1) to (C-6). The compound according to the above item [24], which is the same group selected from the group of [24].
[30] The compound according to [24] above, wherein G is one selected from the group of linking groups represented by the following formulas (G3-1) to (G3-3).
[31] G is a linking group represented by the above formula (G3-2); G 1A is selected from the group of divalent groups represented by the above formulas (C-1) to (C-6). Item [30], wherein the same group is selected, and G 1B is one selected from the group of divalent groups represented by formulas (D-1) to (D-12). Compound described in 1.
[32] G is a linking group represented by the formula (G3-3); G 1A is selected from the group of divalent groups represented by the formulas (C-1) to (C-6). And G 1B is the same group selected from the group of divalent groups represented by the formulas (D-1) to (D-12). Compound.
[33] The compound according to [30], wherein G is a linking group represented by the following formula (G3-4).
［３４］下記の式（２−４）で表される、前記［３］項に記載の化合物。
［３５］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ａ−１）〜（Ａ−２１）で表される化合物の群から選択される１つから誘導される２価の基である、前記［３４］項に記載の化合物。
［３６］Ｇが前記の式（Ｇ１）で表される連結基であり、式（Ｇ１）中Ｇ１が前記の式（Ｃ−１）〜（Ｃ−１０）で表される２価の基の群から選択される１つである、前記［３４］項に記載の化合物。
[34] The compound according to item [3], represented by the following formula (2-4).
[35] G is a linking group represented by the above formula (G1), and G 1 in the formula (G1) is selected from the group of compounds represented by the above formulas (A-1) to (A-21). The compound according to the above [34], which is a divalent group derived from one selected.
[36] G is a linking group represented by the above formula (G1), and G 1 in the formula (G1) is a divalent group represented by the above formulas (C-1) to (C-10). The compound according to [34] above, which is one selected from the group of
［３７］下記の式（３）で表される、前記[２]項に記載の化合物。
［３８］Ｇが式（Ｇ５）で表される連結基であり、式（Ｇ５）においてＧ１が同一である、前記[３７]項に記載の化合物。
[37] The compound according to item [2], which is represented by the following formula (3).
[38] The compound according to [37], wherein G is a linking group represented by formula (G5), and G 1 is the same in formula (G5).
［３９］下記の式（４）で表される、前記[２]項に記載の化合物。
［４０］Ｇが式（Ｇ７）で表される連結基であり、式（Ｇ７）においてＧ１が同一である、前記[３９]項に記載の化合物。
[39] The compound according to item [2], represented by the following formula (4):
[40] The compound according to [39], wherein G is a linking group represented by formula (G7), and G 1 is the same in formula (G7).
［４１］Ｇが下記の式（５）で表される連結基である、前記[３]項に記載の化合物。
［４２］Ｇが前記の式（５）で表される連結基である、前記[４]項に記載の化合物。
［４３］Ｇが前記の式（５）で表される連結基である、前記[１４]項に記載の化合物。
[41] The compound according to [3], wherein G is a linking group represented by the following formula (5).
[42] The compound according to item [4], wherein G is a linking group represented by the formula (5).
[43] The compound according to [14], wherein G is a linking group represented by the formula (5).
［４４］Ｇが下記の式（６）で表される連結基である、前記［３］項に記載の化合物。
［４５］Ｇが前記の式（６）で表される連結基である、前記［４］項に記載の化合物。
［４６］Ｇが前記の式（６）で表される連結基である、前記［１４］項に記載の化合物。
[44] The compound according to [3], wherein G is a linking group represented by the following formula (6).
[45] The compound according to [4], wherein G is a linking group represented by the formula (6).
[46] The compound according to [14], wherein G is a linking group represented by the formula (6).
［４７］Ｇが下記の式（７）で表される連結基である、前記［３］項に記載の化合物。
［４８］Ｇが前記の式（７）で表される連結基である、前記［４］項に記載の化合物。
［４９］Ｇが前記の式（７）で表される連結基である、前記［１４］項に記載の化合物。
[47] The compound according to [3], wherein G is a linking group represented by the following formula (7).
[48] The compound according to [4], wherein G is a linking group represented by the formula (7).
[49] The compound according to item [14], wherein G is a linking group represented by the formula (7).
［５０］Ｇが下記の式（８）で表される連結基である、前記［３］項に記載の化合物。
［５１］Ｇが前記の式（８）で表される連結基である、前記［４］項に記載の化合物。
［５２］Ｇが前記の式（８）で表される連結基である、前記［１４］項に記載の化合物。
[50] The compound according to [3], wherein G is a linking group represented by the following formula (8).
[51] The compound according to [4], wherein G is a linking group represented by the formula (8).
[52] The compound according to [14], wherein G is a linking group represented by the formula (8).
［５３］Ｇが下記の式（９）で表される連結基である、前記［３］項に記載の化合物。
［５４］Ｇが前記の式（９）で表される連結基である、前記［４］項に記載の化合物。
［５５］Ｇが下記の式（９）で表される連結基である、前記［１４］項に記載の化合物。
[53] The compound according to [3], wherein G is a linking group represented by the following formula (9).
[54] The compound according to [4] above, wherein G is a linking group represented by the formula (9).
[55] The compound according to item [14], wherein G is a linking group represented by the following formula (9).
［５６］前記［１］〜［５５］項のいずれか１項に記載の化合物を含有する有機電界発光素子。
［５７］陽極および陰極により挟持された、少なくとも正孔輸送層、発光層、および電子輸送層を基板上に有する有機電界発光素子であって、該電子輸送層が、前記［１］〜［５５］項のいずれか１項に記載の化合物を含有する有機電界発光素子。
[56] An organic electroluminescence device comprising the compound according to any one of the items [1] to [55].
[57] An organic electroluminescent device having at least a hole transport layer, a light emitting layer, and an electron transport layer sandwiched between an anode and a cathode on the substrate, wherein the electron transport layer is the above [1] to [55] ] The organic electroluminescent element containing the compound of any one of clauses.
本発明の化合物は薄膜状態で電圧を印加しても安定であり、また、電荷の輸送能力が高いという特徴を持つ。本発明の化合物は有機ＥＬ素子における電荷輸送材料として適している。本発明の化合物を有機ＥＬ素子の電子輸送層に用いることで、駆動電圧が低く、長寿命の有機ＥＬ素子を得ることができる。本発明の有機ＥＬ素子を用いることにより、フルカラー表示等の高性能のディスプレイ装置を作成できる。 The compound of the present invention is stable even when a voltage is applied in a thin film state and has a feature of high charge transport capability. The compound of the present invention is suitable as a charge transport material in an organic EL device. By using the compound of the present invention for the electron transport layer of an organic EL device, a long-life organic EL device having a low driving voltage can be obtained. By using the organic EL element of the present invention, a high-performance display device such as full-color display can be created.
以下、本発明をさらに詳細に説明する。
＜化合物の説明＞
本願の第１の発明は、下記の式（１）で表される、３，４’−ビピリジル基を有する化合物である。
<Description of compound>
1st invention of this application is a compound which has a 3,4'- bipyridyl group represented by following formula (1).
本明細書中、Ｒ1〜Ｒ8と３，４’−ビピリジル核で形成される基のことを３，４’−ビピリジル基と称する。３，４’−ビピリジル基におけるＲ1〜Ｒ４の１つはＧに結合する遊離原子価であり、それ以外は独立して水素または１価の基である。Ｒ５〜Ｒ８は独立して水素または１価の基である。ｎ個の３，４’−ビピリジル基は同一でもよく、異なっていてもよいが、同一であることが好ましい。なお、前記の連結基Ｇにおける「ｎ個の遊離原子価」および、３，４’−ビピリジル基における「Ｇに結合する遊離原子価」という表記は、Ｇおよび３，４’−ビピリジル基が遊離基（ラジカル）で存在する事を表すものではない。「遊離原子価」とは、共有結合によって他の基や原子と結合している、いわゆる「結合手」のことを表す。すなわち、「３，４’−ビピリジル基におけるＲ1〜Ｒ４の１つはＧに結合する遊離原子価であり」という表記は、３，４’−ビピリジル基におけるＲ1〜Ｒ４のどれか１つが連結基Ｇの遊離原子価を持つ原子に結合している状態を表すものである。 In the present specification, a group formed by R 1 to R 8 and a 3,4′-bipyridyl nucleus is referred to as a 3,4′-bipyridyl group. One of R 1 to R 4 in the 3,4′-bipyridyl group is a free valence bonded to G, and the others are independently hydrogen or a monovalent group. R 5 to R 8 are independently hydrogen or a monovalent group. The n 3,4′-bipyridyl groups may be the same or different, but are preferably the same. The notations “n free valences” in the linking group G and “free valences bonded to G” in the 3,4′-bipyridyl group indicate that G and 3,4′-bipyridyl groups are free. It does not represent the presence of a group (radical). “Free valence” refers to a so-called “bond” that is bonded to another group or atom by a covalent bond. That is, reference to "3,4' one of R 1 to R 4 in the bipyridyl group is in the free valence which binds to G", any of R 1 to R 4 in the 3,4'-bipyridyl group 1 represents a state in which one is bonded to an atom having a free valence of the linking group G.
Ｒ１〜Ｒ８における１価の基は、ニトロ基、シアノ基、ジメシチルボリル基、炭素数６〜１２のアリール、または炭素数１〜１２のアルキルである。このアルキルは直鎖でも分岐鎖でも環状でもよい。１価の基の具体例はフェニル、２−ビフェニリル、３−ビフェニリル、４−ビフェニリル、１−ナフチル、２−ナフチル、メチル、ｔ−ブチル、シクロヘキシルである。Ｒ５〜Ｒ８は水素が好ましい。 The monovalent group in R 1 to R 8 is a nitro group, a cyano group, a dimesitylboryl group, an aryl having 6 to 12 carbon atoms, or an alkyl having 1 to 12 carbon atoms. The alkyl may be linear, branched or cyclic. Specific examples of the monovalent group are phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, methyl, t-butyl, and cyclohexyl. R 5 to R 8 are preferably hydrogen.
３，４’−ビピリジル基は、Ｒ１、Ｒ２またはＲ３がＧに結合することが好ましい。Ｇとの結合に関与しないＲ１〜Ｒ４は水素であることが好ましい。 In the 3,4'-bipyridyl group, R 1 , R 2 or R 3 is preferably bonded to G. R 1 to R 4 that do not participate in bonding with G are preferably hydrogen.
式（１）において、ｎは２が最も好ましく、次に３が好ましく、その次に４が好ましい。その理由の１つは化合物が製造し易いことである。２つめは、分子量が極端に大きくならず比較的昇華性が高くなると考えられ、有機ＥＬ素子の製造時製膜し易いという利点が見込めることである。 In formula (1), n is most preferably 2, then 3 is preferred, and then 4 is preferred. One reason is that the compound is easy to produce. Secondly, it is considered that the molecular weight does not become extremely large and the sublimation property is relatively high, and an advantage that it is easy to form a film at the time of manufacturing an organic EL element can be expected.
＜ｎ＝２である化合物＞
ｎが２である化合物は、詳しくは下記の式（２）で表される。
The compound in which n is 2 is specifically represented by the following formula (2).
Ｇは下記の式（Ｇ１）〜（Ｇ３）で表される連結基の群から選択される１つである。式（Ｇ２）および（Ｇ３）において、Ｇ１は同一でもよく、異なっていてもよい。
上記の式（Ａ−１）〜（Ａ−２１）および（Ｂ−１）〜（Ｂ−４０）において、Ｒは独立して水素、炭素数１〜８のアルキル、炭素数３〜１０のシクロアルキル、または炭素数６〜２０のアリールである。炭素数１〜８のアルキルは直鎖および分岐鎖どちらでもよく、炭素数１〜８の直鎖アルキルまたは炭素数３〜８の分岐鎖アルキルがあげられる。炭素数１〜８の直鎖アルキルの例はメチル、エチル、ｎ−プロピル、ｎ−ブチル、ｎ−ペンチル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチルである。炭素数３〜８の分岐鎖アルキルの例はイソプロピル、イソブチル、ｓ−ブチル、ｔ−ブチル、イソペンチル、ネオペンチル、ｔ−ペンチル、１−メチルペンチル、４−メチル−２−ペンチル、３，３−ジメチルブチル、２−エチルブチル、１−メチルヘキシル、ｔ−オクチル、１−メチルヘプチル、２−エチルヘキシル、２−プロピルペンチルなどである。炭素数３〜１０のシクロアルキルの例はシクロプロピル、シクロブチル、シクロペンチル、メチルシクロペンチル、シクロヘキシル、メチルシクロヘキシル、ジメチルシクロヘキシル、シクロヘプチル、シクロオクチル、シクロノニル、シクロデシルなどである。炭素数６〜２０のアリールの例はフェニル、トリル、キシリル、ビフェニリル、ナフチル、アントラセニル、フェナントリル、テルフェニリル、フルオレニル、ピレニルなどである。好ましいＲは水素、メチル、エチル、ヘキシル、シクロヘキシル、フェニル、１−ナフチル、および２−ナフチルである。 In the above formulas (A-1) to (A-21) and (B-1) to (B-40), R is independently hydrogen, alkyl having 1 to 8 carbons, or cyclohexane having 3 to 10 carbons. Alkyl or aryl having 6 to 20 carbon atoms. The alkyl having 1 to 8 carbon atoms may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl having 1 to 8 carbon atoms and a branched chain alkyl having 3 to 8 carbon atoms. Examples of linear alkyl having 1 to 8 carbon atoms are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl. Examples of branched alkyl having 3 to 8 carbon atoms are isopropyl, isobutyl, s-butyl, t-butyl, isopentyl, neopentyl, t-pentyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethyl. Butyl, 2-ethylbutyl, 1-methylhexyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl and the like. Examples of cycloalkyl having 3 to 10 carbon atoms are cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like. Examples of aryl having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, biphenylyl, naphthyl, anthracenyl, phenanthryl, terphenylyl, fluorenyl, pyrenyl and the like. Preferred R is hydrogen, methyl, ethyl, hexyl, cyclohexyl, phenyl, 1-naphthyl, and 2-naphthyl.
式（Ａ−１）〜（Ａ−２１）および式（Ｂ−１）〜（Ｂ−４１）で表される化合物から誘導される２価の基は、遊離原子価を持つ原子以外の位置に置換基を有していてもよい。置換基の具体例はフェニル、２−ビフェニリル、３−ビフェニリル、４−ビフェニリル、１−ナフチル、２−ナフチル、メチル、ｔ−ブチル、シクロヘキシル、ｍ−テルフェニル−２’−イル及びｍ−テルフェニル−５’−イルである。 The divalent group derived from the compounds represented by formulas (A-1) to (A-21) and formulas (B-1) to (B-41) is located at a position other than an atom having a free valence. It may have a substituent. Specific examples of the substituent are phenyl, 2-biphenylyl, 3-biphenylyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, methyl, t-butyl, cyclohexyl, m-terphenyl-2′-yl and m-terphenyl. -5'-yl.
＜ｎ＝３である化合物＞
ｎが３である化合物は、詳しくは下記の式（３）で表される。
The compound in which n is 3 is specifically represented by the following formula (3).
Ｇは下記の式（Ｇ４）または（Ｇ５）で表される連結基である。式（Ｇ５）において、Ｇ１は同一でもよく、異なっていてもよいが、同一である方が好ましい。
Ｇ２Ａは、下記の式（Ｅ−１）〜（Ｅ−９）で表される３価の基の群から選択される１つであり、Ｇ２Ｂはホウ素、ホスホリル基、または式（Ｅ−１）〜（Ｅ−９）で表される３価の基の群から選択される１つである。
＜ｎ＝４である化合物＞
ｎが４である化合物は、詳しくは下記の式（４）で表される。
The compound in which n is 4 is specifically represented by the following formula (4).
Ｇは下記の式（Ｇ６）または（Ｇ７）で表される連結基である。式（Ｇ７）において、Ｇ１は同一でもよく、異なっていてもよいが、同一である方が好ましい。
Ｇ３Ａは、下記の式（Ｆ−１）〜（Ｆ−８）で表される４価の基の群から選択される１つであり、Ｇ３Ｂは炭素、ケイ素、または式（Ｆ−１）〜（Ｆ−８）で表される４価の基の群から選択される１つである。
＜ｎ＝２である化合物のさらに詳細な説明＞
ｎが２である好ましい化合物は下記の式（２−１）〜（２−４）で表される。
Preferred compounds in which n is 2 are represented by the following formulas (2-1) to (2-4).
式（２−１）〜（２−４）において、Ｇが式（Ｇ１）であるとき、Ｇ１は前記のＡ群の化合物から選択される１つから誘導される２価の基であることが好ましく、Ａ群の中でも式（Ａ−１）〜（Ａ−４）で表される化合物の群から選択される１つから誘導される２価の基であることがより好ましく、下記の式（Ｃ−１）〜（Ｃ−１０）で表される２価の基の群から選択される１つであることがさらに好ましい。Ｃ群の中では下記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される１つであることが好ましい。
式（２−１）〜（２−３）において、Ｇが式（Ｇ２）であるとき、Ｇ１は前記のＡ群およびＢ群の化合物から選択される１つから誘導される同一の２価の基であることが好ましく、式（Ａ−１）〜（Ａ−４）で表される化合物の群から選択される１つから誘導される同一の２価の基であることがより好ましく、前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基であることがさらに好ましい。 In the formulas (2-1) to (2-3), when G is the formula (G2), G 1 is the same divalent derivative derived from one selected from the group A and B compounds. Are preferably the same divalent group derived from one selected from the group of compounds represented by formulas (A-1) to (A-4), More preferably, they are the same groups selected from the group of divalent groups represented by the above formulas (C-1) to (C-6).
式（２−１）〜（２−３）において、Ｇが式（Ｇ３）であるとき、さらに詳しくは下記の式（Ｇ３−１）〜（Ｇ３−３）で表される連結基であることが好ましい。
式（２−１）〜（２−４）において、Ｇが式（Ｇ３−１）で表される連結基であるとき、Ｇ１Ｂは下記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される同一の基であることが好ましい。
式（２−１）〜（２−３）において、Ｇが式（Ｇ３−２）で表される連結基であるとき、Ｇ１Ａは前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される同一の基であり、Ｇ１Ｂは前記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される１つであることが好ましい。 In Formulas (2-1) to (2-3), when G is a linking group represented by Formula (G3-2), G 1A is represented by Formulas (C-1) to (C-6). And G 1B is selected from the group of divalent groups represented by the above formulas (D-1) to (D-12). One is preferred.
式（２−１）〜（２−３）において、Ｇが式（Ｇ３−３）で表される連結基であるとき、Ｇ１Ａは前記の式（Ｃ−１）〜（Ｃ−６）で表される２価の基の群から選択される１つであり、Ｇ１Ｂは前記の式（Ｄ−１）〜（Ｄ−１２）で表される２価の基の群から選択される同一の基であることが好ましい。 In Formulas (2-1) to (2-3), when G is a linking group represented by Formula (G3-3), G 1A is represented by Formulas (C-1) to (C-6). And G 1B is the same selected from the group of divalent groups represented by the above formulas (D-1) to (D-12). The group is preferably.
式（２−１）〜（２−３）において、Ｇが式（Ｇ３−１）で表される連結基であるとき、Ｇはさらに詳しくは式（Ｇ３−４）で表される連結基であることがより好ましい。
＜化合物の具体例＞
本発明の化合物の具体例は以下に列記する式によって示されるが、本発明はこれらの具体的な構造の開示によって限定されることはない。なお、下記の具体例において、Ｍｅはメチルを示し、ｔ−Ｂｕはｔ−ブチルを示す。
<Specific examples of compounds>
Specific examples of the compounds of the present invention are shown by the formulas listed below, but the present invention is not limited by the disclosure of these specific structures. In the following specific examples, Me represents methyl and t-Bu represents t-butyl.
＜式（２−１）で表される化合物の具体例＞
式（２−１）で表される化合物の具体例は下記の式（２−１−１）〜（２−１−６７）で示される。これらの中で好ましい化合物は式（２−１−１）〜（２−１−２８）で示される。より好ましい化合物は式（２−１−１）〜（２−１−３）、（２−１−８）〜（２−１−１０）、（２−１−１５）、（２−１−２１）および（２−１−２３）で示される。
<Specific Example of Compound Represented by Formula (2-1)>
Specific examples of the compound represented by the formula (2-1) are represented by the following formulas (2-1-1) to (2-1-67). Of these, preferred compounds are represented by formulas (2-1-1) to (2-1-28). More preferred compounds are the formulas (2-1-1) to (2-1-3), (2-1-8) to (2-1-10), (2-1-15), (2-1- 21) and (2-1-23).
＜式（２−２）で表される化合物の具体例＞
式（２−２）で表される化合物の具体例は下記の式（２−２−１）〜（２−２−５１）で示される。これらの中で好ましい化合物は式（２−２−１）〜（２−２−２６）で示される。より好ましい化合物は式（２−２−１）〜（２−２−３）、（２−２−８）〜（２−２−１０）、（２−２−１４）、（２−２−１９）および（２−２−２１）で示される。
<Specific Example of Compound Represented by Formula (2-2)>
Specific examples of the compound represented by the formula (2-2) are represented by the following formulas (2-2-1) to (2-251). Among these, preferred compounds are represented by formulas (2-2-1) to (2-226). More preferred compounds are the formulas (2-2-1) to (2-2-3), (2-2-8) to (2-2-10), (2-2-14), (2-2) 19) and (2-2-21).
＜式（２−３）で表される化合物の具体例＞
式（２−３）で表される化合物の具体例は下記の式（２−３−１）〜（２−３−５１）で示される。これらの中で好ましい化合物は式（２−３−１）〜（２−３−２６）で示される。より好ましい化合物は式（２−３−１）〜（２−３−３）、（２−３−８）〜（２−３−１０）、（２−３−１４）、（２−３−１９）および（２−３−２１）で示される。
<Specific Example of Compound Represented by Formula (2-3)>
Specific examples of the compound represented by the formula (2-3) are represented by the following formulas (2-3-1) to (2-3-51). Among these, preferred compounds are represented by formulas (2-3-1) to (2-3-26). More preferred compounds are the formulas (2-3-1) to (2-3-3), (2-3-8) to (2-3-10), (2-3-14), (2-3- 19) and (2-3-21).
＜式（３）で表される化合物の具体例＞
式（３）で表される化合物の具体例は下記の式（３−１）〜（３−５）で示される。
Specific examples of the compound represented by the formula (3) are represented by the following formulas (3-1) to (3-5).
式（４）で表される化合物の具体例は下記の式（４−１）〜（４−４）で示される。
＜化合物の合成法＞
本発明の化合物は既知の方法、例えば鈴木カップリング反応や根岸カップリング反応を利用して合成することができる。式（２）で表される化合物を、鈴木カップリング反応または根岸カップリング反応で合成するスキームを以下に例示する。
上記式中、Ｇは２価の基または２個の遊離原子価をもつ環系である。Ｒは短鎖のアルキルであり、通常メチル、エチル、イソプロピルなどが好適に用いられる。Ｘは塩素、臭素、ヨウ素、またはトリフラートである。
<Method of compound synthesis>
The compound of the present invention can be synthesized using a known method such as Suzuki coupling reaction or Negishi coupling reaction. A scheme for synthesizing the compound represented by the formula (2) by Suzuki coupling reaction or Negishi coupling reaction is illustrated below.
In the above formula, G is a divalent group or a ring system having two free valences. R is a short-chain alkyl, and usually methyl, ethyl, isopropyl and the like are preferably used. X is chlorine, bromine, iodine, or triflate.
上記式中、Ｇは２価の基または２個の遊離原子価をもつ環系であり、Ｘは塩素、臭素、ヨウ素、またはトリフラートである。
In the above formula, G is a divalent group or a ring system having two free valences, and X is chlorine, bromine, iodine, or triflate.
スキーム１には、２箇所をボロン酸またはボロン酸エステルにしたＧに、パラジウム触媒と塩基の存在下、反応性基を有する３，４’−ビピリジンを２段階に反応させる方法、および２箇所に反応性基を有するＧにパラジウム触媒と塩基の存在下、３，４’−ビピリジンのボロン酸を２段階に反応させる方法を示した。Ｇに同一の３，４’−ビピリジル基を導入する場合、上のプロセスではＧの２倍モルの反応性基を有する３，４’−ビピリジンを一度に反応させてもよいし、下のプロセスではＧの２倍モルの３，４’−ビピリジンのボロン酸を一度に反応させてもよい。 Scheme 1 shows a method of reacting G having boronic acid or boronic acid ester at two sites in a two-step with 3,4'-bipyridine having a reactive group in the presence of a palladium catalyst and a base, and at two sites. A method of reacting G having a reactive group with boronic acid of 3,4'-bipyridine in two steps in the presence of a palladium catalyst and a base was shown. When the same 3,4′-bipyridyl group is introduced into G, in the above process, 3,4′-bipyridine having a reactive group twice the mole of G may be reacted at one time. Then, it is possible to react with boronic acid of 3,4′-bipyridine having 2 moles of G at a time.
スキーム２には、２箇所を亜鉛錯体にしたＧに、パラジウム触媒の存在下、反応性基を有する３，４’−ビピリジンを２段階に反応させる方法、および２箇所に反応性基を有するＧにパラジウム触媒の存在下、３，４’−ビピリジンの亜鉛錯体を２段階に反応させる方法を示した。Ｇに同一の３，４’−ビピリジル基を導入する場合、上のプロセスではＧの２倍モルの反応性基を有する３，４’−ビピリジンを一度に反応させてもよいし、下のプロセスではＧの２倍モルの３，４’−ビピリジンの亜鉛錯体を一度に反応させてもよい。 Scheme 2 includes a method of reacting G having two reactive zinc groups with 3,4'-bipyridine having a reactive group in two steps in the presence of a palladium catalyst, and G having a reactive group at two sites. Shows a method of reacting a zinc complex of 3,4'-bipyridine in two steps in the presence of a palladium catalyst. When the same 3,4′-bipyridyl group is introduced into G, in the above process, 3,4′-bipyridine having a reactive group twice the mole of G may be reacted at one time. Then, a zinc complex of 3,4'-bipyridine having twice the mole of G may be reacted at once.
Ｇが複数の２価の基が連結している場合、または複数の２個の遊離原子価をもつ環系が連結している場合、あるいは２価の基と２個の遊離原子価をもつ環系の組み合わせである場合、たとえば−Ｇ１−Ｇ１−である場合には、それぞれ単体のＧ１に上記のカップリング反応を用いて３，４’−ビピリジル基を連結した後、既知のカップリング反応でＧ１同士を連結して目的の化合物を合成してもよい。このカップリング反応の際にも、鈴木カップリング反応または根岸カップリング反応は好ましく用いられる。 G is connected to a plurality of divalent groups, or is connected to a ring system having a plurality of two free valences, or a ring having a divalent group and two free valences In the case of a combination of systems, for example, -G 1 -G 1- , a 3,4'-bipyridyl group is linked to each single G 1 using the above coupling reaction, and then a known cup The target compound may be synthesized by linking G 1 together in a ring reaction. Also in this coupling reaction, the Suzuki coupling reaction or the Negishi coupling reaction is preferably used.
また、Ｇ１がたとえばオキサジアゾールのようなヘテロ環である場合、共に３，４’−ビピリジル基を有する環系の酸クロリドとヒドラジンを反応させて得たヒドラジドから、分子内環化脱水反応を経て合成するような方法を用いることもできる。 Further, when G 1 is a heterocycle such as oxadiazole, intramolecular cyclization dehydration reaction from hydrazide obtained by reacting a cyclic acid chloride having 3,4'-bipyridyl group with hydrazine. It is also possible to use a method of synthesis via
式（３）で表される化合物または式（４）で表される化合物も、上記の合成法を適宜組み合わせて合成することができる。以上、本発明の化合物の合成法を例示したが、本発明はこれら例示した合成法によって制限されることはない。 The compound represented by Formula (3) or the compound represented by Formula (4) can also be synthesized by appropriately combining the above synthesis methods. As mentioned above, although the synthesis method of the compound of this invention was illustrated, this invention is not restrict | limited by these illustrated synthesis methods.
鈴木カップリング反応で用いられるパラジウム触媒の具体例は、Ｐｄ（ＰＰｈ３）４、ＰｄＣｌ２（ＰＰｈ３）２、Ｐｄ（ＯＡｃ）２、トリス（ジベンジリデンアセトン）二パラジウム（０）、トリス（ジベンジリデンアセトン）二パラジウム（０）クロロホルム錯体、ビス（ジベンジリデンアセトン）パラジウム（０）等である。反応促進するため、場合によりこれらのパラジウム化合物にホスフィン化合物を加えてもよい。そのホスフィン化合物の具体例は、トリ（ｔ−ブチル）ホスフィン、トリシクロヘキシルホスフィン、１−（Ｎ，Ｎ−ジメチルアミノメチル）−２−（ジｔ−ブチルホスフィノ）フェロセン、１−（Ｎ，Ｎ−ジブチルアミノメチル）−２−（ジｔ−ブチルホスフィノ）フェロセン、１−（メトキシメチル）−２−（ジｔ−ブチルホスフィノ）フェロセン、１，１’−ビス（ジｔ−ブチルホスフィノ）フェロセン、２，２’−ビス（ジｔ−ブチルホスフィノ）−１，１’−ビナフチル、２−メトキシ−２’−（ジｔ−ブチルホスフィノ）−１，１’−ビナフチル、２−ジシクロヘキシルホスフィノ−２’，６’−ジメトキシビフェニル等である。この反応で用いられる塩基の具体例は、炭酸ナトリウム、炭酸カリウム、炭酸セシウム、炭酸水素ナトリウム、水酸化ナトリウム、水酸化カリウム、水酸化バリウム、ナトリウムエトキシド、ナトリウムｔ−ブトキシド、酢酸ナトリウム、リン酸三カリウム、フッ化カリウム等である。さらに、この反応で用いられる溶媒の具体例は、ベンゼン、トルエン、キシレン、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロフラン、ジエチルエ−テル、ｔ−ブチルメチルエ−テル、１，４−ジオキサン、メタノ−ル、エタノール、イソプロピルアルコ−ル等である。これらの溶媒は適宜選択でき、単独で用いてもよく、混合溶媒として用いてもよい。 Specific examples of the palladium catalyst used in the Suzuki coupling reaction include Pd (PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , Pd (OAc) 2 , tris (dibenzylideneacetone) dipalladium (0), tris (di) Benzylideneacetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0) and the like. In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (N, N -Dibutylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl) -2- (di-t-butylphosphino) ferrocene, 1,1'-bis (di-t-butylphosphino) ) Ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl, 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, 2- And dicyclohexylphosphino-2 ′, 6′-dimethoxybiphenyl. Specific examples of the base used in this reaction are sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, phosphoric acid. Tripotassium, potassium fluoride and the like. Furthermore, specific examples of the solvent used in this reaction are benzene, toluene, xylene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butylmethyl ether, 1,4-dioxane, methanol, ethanol, Isopropyl alcohol and the like. These solvents can be appropriately selected and may be used alone or as a mixed solvent.
根岸カップリング反応で用いられるパラジウム触媒の具体例は、Ｐｄ（ＰＰｈ３）４、ＰｄＣｌ２（ＰＰｈ３）２、Ｐｄ（ＯＡｃ）２、トリス（ジベンジリデンアセトン）二パラジウム（０）、トリス（ジベンジリデンアセトン）二パラジウム（０）クロロホルム錯体、ビス（ジベンジリデンアセトン）パラジウム（０）、ビス（トリｔ−ブチルホスフィノ）パラジウム（０）、（１，１’−ビス（ジフェニルホスフィノ）フェロセン）ジクロロパラジウム（II）等である。さらに、この反応で用いられる溶媒の具体例は、ベンゼン、トルエン、キシレン、Ｎ，Ｎ−ジメチルホルムアミド、テトラヒドロフラン、ジエチルエ−テル、ｔ−ブチルメチルエ−テル、１，４−ジオキサン等である。これらの溶媒は適宜選択でき、単独で用いてもよく、混合溶媒として用いてもよい。 Specific examples of the palladium catalyst used in the Negishi coupling reaction include Pd (PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , Pd (OAc) 2 , tris (dibenzylideneacetone) dipalladium (0), tris (di) Benzylideneacetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (tri-t-butylphosphino) palladium (0), (1,1′-bis (diphenylphosphino) ferrocene) Such as dichloropalladium (II). Furthermore, specific examples of the solvent used in this reaction are benzene, toluene, xylene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butylmethyl ether, 1,4-dioxane and the like. These solvents can be appropriately selected and may be used alone or as a mixed solvent.
本発明の化合物を、有機ＥＬ素子における、電子注入層または電子輸送層に用いた場合、電界印加時において安定であり、また、低電圧で発光を得ることが可能となる。これらは、本発明の化合物が、電界発光型素子の電子注入材料、または電子輸送材料として優れていることを表す。ここで言う電子注入層とは陰極から有機層へ電子を受け取る層であり、電子輸送層とは注入された電子を発光層へ輸送するための層である。また、電子輸送層が電子注入層を兼ねることも可能である。それぞれの層に用いる材料を、電子注入材料および電子輸送材料という。 When the compound of the present invention is used for an electron injection layer or an electron transport layer in an organic EL device, it is stable when an electric field is applied, and light emission can be obtained at a low voltage. These represent that the compound of the present invention is excellent as an electron injecting material or an electron transporting material for an electroluminescent device. The electron injection layer mentioned here is a layer for receiving electrons from the cathode to the organic layer, and the electron transport layer is a layer for transporting the injected electrons to the light emitting layer. The electron transport layer can also serve as the electron injection layer. The material used for each layer is referred to as an electron injection material and an electron transport material.
＜有機ＥＬ素子の説明＞
本願の第２の発明は、電子注入層、または電子輸送層に、本発明の式（１）で表される化合物を含有する有機ＥＬ素子である。本発明の有機ＥＬ素子は、駆動電圧が低く、駆動時の耐久性が高い。
<Description of organic EL element>
2nd invention of this application is an organic EL element which contains the compound represented by Formula (1) of this invention in an electron injection layer or an electron carrying layer. The organic EL element of the present invention has a low driving voltage and high durability during driving.
本発明の有機ＥＬ素子の構造は各種の態様があるが、基本的には陽極と陰極との間に少なくとも正孔輸送層、発光層、電子輸送層を挟持した多層構造である。素子の具体的な構成の例は、（１）陽極／正孔輸送層／発光層／電子輸送層／陰極、（２）陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／陰極、（３）陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／電子注入層／陰極、等である。 Although the structure of the organic EL device of the present invention has various modes, it is basically a multilayer structure in which at least a hole transport layer, a light emitting layer, and an electron transport layer are sandwiched between an anode and a cathode. Examples of the specific configuration of the device are (1) anode / hole transport layer / light emitting layer / electron transport layer / cathode, (2) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer. / Cathode, (3) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode, etc.
本発明の化合物は、高い電子注入性および電子輸送性を持っているので、単体又は他の材料と併用して電子注入層、または電子輸送層に使用できる。本発明の有機ＥＬ素子は、本発明の電子輸送材料に他の材料を用いた正孔注入層、正孔輸送層、発光層、などを組み合わせることで、青色、緑色、赤色や白色の発光を得ることもできる。 Since the compound of the present invention has high electron injecting property and electron transporting property, it can be used for an electron injecting layer or an electron transporting layer alone or in combination with other materials. The organic EL device of the present invention emits blue, green, red and white light by combining a hole injection layer, a hole transport layer, a light emitting layer, etc. using other materials with the electron transport material of the present invention. It can also be obtained.
本発明の有機ＥＬ素子に使用できる発光材料または発光性ドーパントは、高分子学会編、高分子機能材料シリーズ“光機能材料”、共同出版(１９９１)、Ｐ２３６に記載されているような昼光蛍光材料、蛍光増白剤、レーザー色素、有機シンチレータ、各種の蛍光分析試薬等の発光材料、城戸淳二監修、“有機ＥＬ材料とディスプレイ”シーエムシー社出版（２００１）Ｐ１５５〜１５６に記載されているようなドーパント材料、Ｐ１７０〜１７２に記載されているような３重項材料の発光材料等である。 The light-emitting material or light-emitting dopant that can be used in the organic EL device of the present invention is daylight fluorescence as described in the Polymer Society of Japan, Polymer Functional Materials Series “Optical Functional Materials”, Joint Publication (1991), P236. Materials, fluorescent brighteners, laser dyes, organic scintillators, various fluorescent analysis reagents and other luminescent materials, supervised by Koji Koji, “Organic EL materials and displays” published by CMC Publishing Co., Ltd. (2001) P155-156 And a light emitting material of a triplet material as described in P170 to 172.
発光材料または発光性ドーパントとして使用できる化合物は、多環芳香族化合物、ヘテロ芳香族化合物、有機金属錯体、色素、高分子系発光材料、スチリル誘導体、芳香族アミン誘導体、クマリン誘導体、ボラン誘導体、オキサジン誘導体、スピロ環を有する化合物、オキサジアゾール誘導体、フルオレン誘導体等である。多環芳香族化合物の例は、アントラセン誘導体、フェナントレン誘導体、ナフタセン誘導体、ピレン誘導体、クリセン誘導体、ペリレン誘導体、コロネン誘導体、ルブレン誘導体等である。ヘテロ芳香族化合物の例は、ジアルキルアミノ基またはジアリールアミノ基を有するオキサジアゾール誘導体、ピラゾロキノリン誘導体、ピリジン誘導体、ピラン誘導体、フェナントロリン誘導体、シロール誘導体、トリフェニルアミノ基を有するチオフェン誘導体、キナクリドン誘導体等である。有機金属錯体の例は、亜鉛、アルミニウム、ベリリウム、ユーロピウム、テルビウム、ジスプロシウム、イリジウム、白金、オスミウム、金、等と、キノリノール誘導体、ベンゾキサゾ−ル誘導体、ベンゾチアゾール誘導体、オキサジアゾール誘導体、チアジアゾール誘導体、ベンゾイミダゾール誘導体、ピロール誘導体、ピリジン誘導体、フェナントロリン誘導体等との錯体である。色素の例は、キサンテン誘導体、ポリメチン誘導体、ポルフィリン誘導体、クマリン誘導体、ジシアノメチレンピラン誘導体、ジシアノメチレンチオピラン誘導体、オキソベンズアントラセン誘導体、カルボスチリル誘導体、ペリレン誘導体、ベンゾオキサゾール誘導体、ベンゾチアゾール誘導体、ベンゾイミダゾール誘導体等の色素が挙げられる。高分子系発光材料の例は、ポリパラフェニルビニレン誘導体、ポリチオフェン誘導体、ポリビニルカルバゾ−ル誘導体、ポリシラン誘導体、ポリフルオレン誘導体、ポリパラフェニレン誘導体等である。スチリル誘導体の例は、アミン含有スチリル誘導体、スチリルアリーレン誘導体等である。 The compounds that can be used as the light emitting material or the light emitting dopant are polycyclic aromatic compounds, heteroaromatic compounds, organometallic complexes, dyes, polymer light emitting materials, styryl derivatives, aromatic amine derivatives, coumarin derivatives, borane derivatives, oxazines. Derivatives, compounds having a spiro ring, oxadiazole derivatives, fluorene derivatives and the like. Examples of the polycyclic aromatic compound are anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, pyrene derivatives, chrysene derivatives, perylene derivatives, coronene derivatives, rubrene derivatives, and the like. Examples of heteroaromatic compounds include oxadiazole derivatives, pyrazoloquinoline derivatives, pyridine derivatives, pyran derivatives, phenanthroline derivatives, silole derivatives, thiophene derivatives having a triphenylamino group, quinacridone derivatives having a dialkylamino group or a diarylamino group Etc. Examples of organometallic complexes are zinc, aluminum, beryllium, europium, terbium, dysprosium, iridium, platinum, osmium, gold, etc., quinolinol derivatives, benzoxazole derivatives, benzothiazole derivatives, oxadiazole derivatives, thiadiazole derivatives, A complex with a benzimidazole derivative, a pyrrole derivative, a pyridine derivative, a phenanthroline derivative, or the like. Examples of dyes are xanthene derivatives, polymethine derivatives, porphyrin derivatives, coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, oxobenzanthracene derivatives, carbostyril derivatives, perylene derivatives, benzoxazole derivatives, benzothiazole derivatives, benzimidazoles And pigments such as derivatives. Examples of the polymer light-emitting material include polyparaphenyl vinylene derivatives, polythiophene derivatives, polyvinyl carbazole derivatives, polysilane derivatives, polyfluorene derivatives, polyparaphenylene derivatives, and the like. Examples of styryl derivatives are amine-containing styryl derivatives, styrylarylene derivatives, and the like.
本発明の有機ＥＬ素子に使用される他の電子輸送材料は、光導電材料において電子伝達化合物として使用できる化合物、有機ＥＬ素子の電子輸送層および電子注入層に使用できる化合物の中から任意に選択して用いることができる。 Other electron transport materials used in the organic EL device of the present invention are arbitrarily selected from compounds that can be used as electron transport compounds in photoconductive materials and compounds that can be used in the electron transport layer and electron injection layer of organic EL devices. Can be used.
このような電子輸送材料の具体例は、キノリノール系金属錯体、２，２’−ビピリジル誘導体、フェナントロリン誘導体、ジフェニルキノン誘導体、ペリレン誘導体、オキサジアゾール誘導体、チオフェン誘導体、トリアゾール誘導体、チアジアゾール誘導体、オキシン誘導体の金属錯体、キノキサリン誘導体、キノキサリン誘導体のポリマー、ベンザゾール類化合物、ガリウム錯体、ピラゾール誘導体、パ−フルオロ化フェニレン誘導体、トリアジン誘導体、ピラジン誘導体、ベンゾキノリン誘導体、イミダゾピリジン誘導体、ボラン誘導体等である。 Specific examples of such electron transport materials include quinolinol metal complexes, 2,2′-bipyridyl derivatives, phenanthroline derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, oxine derivatives. Metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives, imidazopyridine derivatives, borane derivatives, and the like.
本発明の有機ＥＬ素子に使用される正孔注入材料および正孔輸送材料については、光導電材料において、正孔の電荷輸送材料として従来から慣用されている化合物や、有機ＥＬ素子の正孔注入層および正孔輸送層に使用されている公知のものの中から任意のものを選択して用いることができる。それらの具体例は、カルバゾ−ル誘導体、トリアリールアミン誘導体、フタロシアニン誘導体等である。 Regarding the hole injection material and the hole transport material used in the organic EL device of the present invention, in a photoconductive material, a compound conventionally used as a charge transport material for holes or a hole injection of an organic EL device is used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof are carbazole derivatives, triarylamine derivatives, phthalocyanine derivatives and the like.
本発明の有機ＥＬ素子を構成する各層は、各層を構成すべき材料を蒸着法、スピンコート法またはキャスト法等の方法で薄膜とすることにより、形成することができる。このようにして形成された各層の膜厚については特に限定はなく、材料の性質に応じて適宜設定することができるが、通常２ｎｍ〜５０００ｎｍの範囲である。なお、発光材料を薄膜化する方法は、均質な膜が得やすく、かつピンホールが生成しにくい等の点から蒸着法を採用するのが好ましい。蒸着法を用いて薄膜化する場合、その蒸着条件は、本発明の発光材料の種類により異なる。蒸着条件は一般的に、ボート加熱温度５０〜４００℃、真空度１０−６〜１０−３Ｐａ、蒸着速度０．０１〜５０ｎｍ／秒、基板温度−１５０〜＋３００℃、膜厚５ｎｍ〜５μｍの範囲で適宜設定することが好ましい。 Each layer constituting the organic EL element of the present invention can be formed by forming a material to constitute each layer into a thin film by a method such as a vapor deposition method, a spin coating method, or a casting method. The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. Note that it is preferable to employ a vapor deposition method as a method of thinning the light emitting material from the standpoint that a homogeneous film can be easily obtained and pinholes are hardly generated. When thinning using the vapor deposition method, the vapor deposition conditions differ depending on the type of the light emitting material of the present invention. Deposition conditions generally include a boat heating temperature of 50 to 400 ° C., a degree of vacuum of 10 −6 to 10 −3 Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −150 to + 300 ° C., and a film thickness of 5 nm to 5 μm. It is preferable to set appropriately within the range.
本発明の有機ＥＬ素子は、前記のいずれの構造であっても、基板に支持されていることが好ましい。基板は機械的強度、熱安定性および透明性を有するものであればよく、ガラス、透明プラスチックフィルム等を用いることができる。陽極物質は４ｅＶより大きな仕事関数を有する金属、合金、電気伝導性化合物およびこれらの混合物を用いることができる。その具体例は、Ａｕ等の金属、ＣｕＩ、インジウムチンオキシド（以下、ＩＴＯと略記する）、ＳｎＯ２、ＺｎＯ等である。 The organic EL device of the present invention is preferably supported by a substrate in any of the structures described above. The substrate only needs to have mechanical strength, thermal stability, and transparency, and glass, a transparent plastic film, and the like can be used. As the anode material, metals, alloys, electrically conductive compounds and mixtures thereof having a work function larger than 4 eV can be used. Specific examples thereof include metals such as Au, CuI, indium tin oxide (hereinafter abbreviated as ITO), SnO 2 , ZnO, and the like.
陰極物質は４ｅＶより小さな仕事関数の金属、合金、電気伝導性化合物、およびこれらの混合物を使用できる。その具体例は、アルミニウム、カルシウム、マグネシウム、リチウム、マグネシウム合金、アルミニウム合金等である。合金の具体例は、アルミニウム／弗化リチウム、アルミニウム／リチウム、マグネシウム／銀、マグネシウム／インジウム等である。有機ＥＬ素子の発光を効率よく取り出すために、電極の少なくとも一方は光透過率を１０％以上にすることが望ましい。電極としてのシート抵抗は数百Ω／□以下にすることが好ましい。なお、膜厚は電極材料の性質にもよるが、通常１０ｎｍ〜１μｍ、好ましくは１０〜４００ｎｍの範囲に設定される。このような電極は、上述の電極物質を使用して、蒸着やスパッタリング等の方法で薄膜を形成させることにより作製することができる。 Cathode materials can use metals, alloys, electrically conductive compounds, and mixtures thereof with work functions of less than 4 eV. Specific examples thereof are aluminum, calcium, magnesium, lithium, magnesium alloy, aluminum alloy and the like. Specific examples of the alloy include aluminum / lithium fluoride, aluminum / lithium, magnesium / silver, and magnesium / indium. In order to efficiently extract light emitted from the organic EL element, it is desirable that at least one of the electrodes has a light transmittance of 10% or more. The sheet resistance as the electrode is preferably several hundred Ω / □ or less. Although the film thickness depends on the properties of the electrode material, it is usually set in the range of 10 nm to 1 μm, preferably 10 to 400 nm. Such an electrode can be produced by forming a thin film by a method such as vapor deposition or sputtering using the electrode material described above.
次に、本発明の発光材料を用いて有機ＥＬ素子を作成する方法の一例として、前述の陽極／正孔注入層／正孔輸送層／発光層／本発明の電子輸送材料／陰極からなる有機ＥＬ素子の作成法について説明する。適当な基板上に、陽極材料の薄膜を蒸着法により形成させて陽極を作製した後、この陽極上に正孔注入層および正孔輸送層の薄膜を形成させる。この上に発光層の薄膜を形成させる。この発光層の上に本発明の電子輸送材料を真空蒸着し、薄膜を形成させ、電子輸送層とする。さらに陰極用物質からなる薄膜を蒸着法により形成させて陰極とすることにより、目的の有機ＥＬ素子が得られる。なお、上述の有機ＥＬ素子の作製においては、作製順序を逆にして、陰極、電子輸送層、発光層、正孔輸送層、正孔注入層、陽極の順に作製することも可能である。 Next, as an example of a method for producing an organic EL device using the light emitting material of the present invention, an organic material comprising the above-mentioned anode / hole injection layer / hole transport layer / light emitting layer / electron transport material of the present invention / cathode is used. A method for creating an EL element will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A light emitting layer thin film is formed thereon. On this light emitting layer, the electron transport material of this invention is vacuum-deposited, a thin film is formed, and it is set as an electron carrying layer. Furthermore, the target organic EL element is obtained by forming the thin film which consists of a substance for cathodes by a vapor deposition method, and making it a cathode. In the production of the organic EL element described above, the production order can be reversed, and the cathode, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode can be produced in this order.
このようにして得られた有機ＥＬ素子に直流電圧を印加する場合には、陽極を＋、陰極を−の極性として印加すればよく、電圧２〜４０Ｖ程度を印加すると、透明又は半透明の電極側（陽極又は陰極、および両方）より発光が観測できる。また、この有機ＥＬ素子は、交流電圧を印加した場合にも発光する。なお、印加する交流の波形は任意でよい。
以下に、本発明を実施例に基づいて更に詳しく説明する。
When a DC voltage is applied to the organic EL device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, a transparent or translucent electrode is applied. Luminescence can be observed from the side (anode or cathode, and both). The organic EL element also emits light when an alternating voltage is applied. The alternating current waveform to be applied may be arbitrary.
Hereinafter, the present invention will be described in more detail based on examples.
合成例１：式（２−１−２）の化合物の合成
＜５−ブロモ−３，４’−ビピリジンの合成＞
４−ピリジンボロン酸９．８ｇ、３，５−ジブロモピリジン２３．７ｇ、Ｐｄ（ＰＰｈ３）４４．６ｇ、２．１Ｍ炭酸ナトリウム水溶液７６ｍｌ、トルエン２５０ｍｌ及びエタノール７ｍｌをフラスコに入れ、アルゴン雰囲気下、還流温度で２４時間攪拌した。加熱終了後、反応液を室温まで冷却し純水で洗浄した。有機層を濃縮し、濃縮物をシリカゲルカラムクロマトグラフィー（移動相：トルエン／酢酸エチル）にて精製し、次いでトルエンから再結晶して、５−ブロモ−３，４’−ビピリジン８．３ｇを得た。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： 7.5(d, 1H), 7.5(d, 1H), 8.1 (t, 1H), 8.7(ｍ, 3H), 8.8 (d, 1H).
Synthesis Example 1: Synthesis of compound of formula (2-1-2) <Synthesis of 5-bromo-3,4'-bipyridine>
A flask was charged with 9.8 g of 4-pyridineboronic acid, 23.7 g of 3,5-dibromopyridine, 4.6 g of Pd (PPh 3 ) 4 , 76 ml of 2.1M aqueous sodium carbonate solution, 250 ml of toluene and 7 ml of ethanol. The mixture was stirred at reflux temperature for 24 hours. After heating, the reaction solution was cooled to room temperature and washed with pure water. The organic layer is concentrated, and the concentrate is purified by silica gel column chromatography (mobile phase: toluene / ethyl acetate) and then recrystallized from toluene to obtain 8.3 g of 5-bromo-3,4'-bipyridine. It was.
1H-NMR (CDCl 3): 7.5 (d, 1H), 7.5 (d, 1H), 8.1 (t, 1H), 8.7 (m, 3H), 8.8 (d, 1H).
＜２−フェニルアントラセンの合成＞
２−クロロアントラセン５．００ｇ、フェニルボロン酸４．３ｇ、トリス（ジベンジリデンアセトン）二パラジウム（０）５３８ｍｇ、トリシクロヘキシルホスフィン４９４ｍｇ、リン酸三カリウム９．９８ｇ、およびトルエン７５ｍｌをフラスコに入れ、アルゴン雰囲気下、還流温度で２時間攪拌した。加熱終了後反応液に１．５リットルのトルエンを加え、室温まで冷却後濾別し、濾液をシリカゲルカラムクロマトグラフィー（移動相：ヘプタン）により精製した。溶媒を減圧留去し、濃縮物をトルエンから再結晶して、２−フェニルアントラセン５．０ｇを得た。
<Synthesis of 2-phenylanthracene>
A flask was charged with 5.00 g of 2-chloroanthracene, 4.3 g of phenylboronic acid, 538 mg of tris (dibenzylideneacetone) dipalladium (0), 494 mg of tricyclohexylphosphine, 9.98 g of tripotassium phosphate, and 75 ml of toluene. The mixture was stirred at reflux temperature for 2 hours under an atmosphere. After completion of the heating, 1.5 liters of toluene was added to the reaction solution, cooled to room temperature and filtered, and the filtrate was purified by silica gel column chromatography (mobile phase: heptane). The solvent was distilled off under reduced pressure, and the concentrate was recrystallized from toluene to obtain 5.0 g of 2-phenylanthracene.
＜９，１０−ジブロモ−２−フェニルアントラセンの合成＞
窒素雰囲気下のフラスコ中に、２−フェニルアントラセン３．３２ｇを４００ｍｌのジクロロメタンに溶かした。そこに、５．００ｇの臭素を３０ｍｌの四塩化炭素に溶かした溶液を１５分掛けて滴下した。滴下終了後、２時間室温で攪拌し、チオ硫酸ナトリウム水溶液で反応を停止した。有機層を抽出し、溶媒を減圧留去して得た濃縮物をトルエン５０ｍｌから再結晶し、９，１０−ジブロモ−２−フェニルアントラセン４．４ｇを得た。
<Synthesis of 9,10-dibromo-2-phenylanthracene>
In a flask under a nitrogen atmosphere, 3.32 g of 2-phenylanthracene was dissolved in 400 ml of dichloromethane. A solution prepared by dissolving 5.00 g of bromine in 30 ml of carbon tetrachloride was added dropwise thereto over 15 minutes. After completion of the dropping, the mixture was stirred for 2 hours at room temperature, and the reaction was stopped with an aqueous sodium thiosulfate solution. The organic layer was extracted, the solvent was distilled off under reduced pressure, and the resulting concentrate was recrystallized from 50 ml of toluene to obtain 4.4 g of 9,10-dibromo-2-phenylanthracene.
＜９，１０−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−２−フェニルアントラセンの合成＞
９，１０−ジブロモ−２−フェニルアントラセン１０．０ｇ、ビス（ピナコラート）ジボロン１４．８ｇ、ビス（ジベンジリデンアセトン）パラジウム（０）８３８ｍｇ、トリシクロヘキシルホスフィン１．０２ｇ、酢酸カリウム７．１５ｇおよび１，４−ジオキサン５０ｍｌをフラスコに入れ、アルゴン雰囲気下、還流温度で８時間攪拌した。加熱終了後反応液にトルエンを加え、室温まで冷却後固形物を濾別し、濾液を濃縮した。濃縮物をシリカゲルカラムクロマトグラフィー（移動相：トルエン）により精製した後、テトラヒドロフラン／ヘプタン混合溶液から再結晶し、９，１０−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−２−フェニルアントラセン８．３ｇを得た。
<Synthesis of 9,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-phenylanthracene>
9,10-dibromo-2-phenylanthracene 10.0 g, bis (pinacolato) diboron 14.8 g, bis (dibenzylideneacetone) palladium (0) 838 mg, tricyclohexylphosphine 1.02 g, potassium acetate 7.15 g and 1, 4-Dioxane (50 ml) was placed in a flask and stirred at reflux temperature for 8 hours under an argon atmosphere. After the heating was completed, toluene was added to the reaction solution, and after cooling to room temperature, the solid was filtered off and the filtrate was concentrated. The concentrate was purified by silica gel column chromatography (mobile phase: toluene), recrystallized from a tetrahydrofuran / heptane mixed solution, and 9,10-bis (4,4,5,5-tetramethyl-1,3,2). 8.3 g of -dioxaborolanyl) -2-phenylanthracene was obtained.
＜９,１０−ビス（３，４'−ビピリジン−５−イル）−２−フェニルアントラセンの合成＞
９，１０−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−２−フェニルアントラセン５．０６ｇ、５−ブロモ−３，４’−ビピリジン５．６４ｇ、トリス（ジベンジリデンアセトン）二パラジウム（０）２２８ｍｇ、トリシクロヘキシルホスフィン２１０ｍｇ、リン酸三カリウム１７ｇ、トルエン５０ｍｌ、エタノール１０ｍｌおよび純水１０ｍｌをフラスコに入れて、アルゴン雰囲気下、還流温度で１０時間攪拌した。加熱終了後反応液を室温まで冷却し、純水で洗浄した。有機層を濃縮し、濃縮物を活性アルミナカラムクロマトグラフィー（移動相：トルエン／酢酸エチル）にて精製した。減圧下溶媒を留去し、濃縮物を酢酸エチルで洗浄後、トルエンで再結晶し、９，１０−ビス（３，４’−ビピリジン−５−イル）−２−フェニルアントラセン５２０ｍｇを得た。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）： 7.3-7.4 (ｍ, 5H), 7.4-7.5 (ｍ, 2H), 7.6-7.8 (ｍ, 9H), 8.0-8.2 (ｍ, 2H), 8.7-8.8 (ｍ, 4H), 8.9 (m, 2H),9.2 (s, 2H).
<Synthesis of 9,10-bis (3,4'-bipyridin-5-yl) -2-phenylanthracene>
5,10-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -2-phenylanthracene 5.06 g, 5-bromo-3,4'-bipyridine 64 g, 228 mg of tris (dibenzylideneacetone) dipalladium (0), 210 mg of tricyclohexylphosphine, 17 g of tripotassium phosphate, 50 ml of toluene, 10 ml of ethanol and 10 ml of pure water were placed in a flask and refluxed for 10 hours under an argon atmosphere. Stir. After completion of heating, the reaction solution was cooled to room temperature and washed with pure water. The organic layer was concentrated, and the concentrate was purified by activated alumina column chromatography (mobile phase: toluene / ethyl acetate). The solvent was distilled off under reduced pressure, and the concentrate was washed with ethyl acetate and recrystallized from toluene to obtain 520 mg of 9,10-bis (3,4'-bipyridin-5-yl) -2-phenylanthracene.
1H-NMR (CDCl 3 ): 7.3-7.4 (m, 5H), 7.4-7.5 (m, 2H), 7.6-7.8 (m, 9H), 8.0-8.2 (m, 2H), 8.7-8.8 (m, 4H), 8.9 (m, 2H), 9.2 (s, 2H).
合成例２：式（２−１−２１）の化合物の合成
＜２，７−ジヒドロキシトリフェニレンの合成＞
１，２−ビス（３−メトキシフェニル）ベンゼン２ｇをフラスコに入れ、窒素雰囲気下、１００ｍｌのジクロロメタンに溶解させた。この溶液に塩化鉄（III）３．２５ｇを加え、室温で５６時間半攪拌した。メタノールを加え反応を終了させた後、水で洗浄した。有機層をシリカゲルカラムクロマトグラフィー（移動相：トルエン／ヘプタン）により精製した後、トルエン／ヘプタン混合溶媒から再結晶し、２，７−ジメトキシトリフェニレン１．４ｇを得た。得られた２，７−ジメトキシトリフェニレンを含むジクロロメタン溶液に三臭化ホウ素を加える事で、２，７−ジヒドロキシトリフェニレンを得た。
Synthesis Example 2: Synthesis of compound of formula (2-1-21) <Synthesis of 2,7-dihydroxytriphenylene>
2 g of 1,2-bis (3-methoxyphenyl) benzene was placed in a flask and dissolved in 100 ml of dichloromethane under a nitrogen atmosphere. To this solution, 3.25 g of iron (III) chloride was added and stirred at room temperature for 56 hours and a half. Methanol was added to complete the reaction, followed by washing with water. The organic layer was purified by silica gel column chromatography (mobile phase: toluene / heptane) and then recrystallized from a toluene / heptane mixed solvent to obtain 1.4 g of 2,7-dimethoxytriphenylene. Boron tribromide was added to the resulting dichloromethane solution containing 2,7-dimethoxytriphenylene to obtain 2,7-dihydroxytriphenylene.
＜２，７−ビス（トリフルオロメタンスルホニルオキシ）トリフェニレンの合成＞
窒素雰囲気下、２，７−ジヒドロキシトリフェニレン８．７ｇの入ったフラスコに脱水ピリジン１００ｍｌを加えた。この溶液を氷水で冷却し、トリフルオロメタンスルホン酸無水物２５ｇを滴下した。滴下終了後、室温で１８時間攪拌した後、水を加え反応を終了した。反応液を分液ロートに移し、酢酸エチル５００ｍｌで抽出した。有機層を減圧下濃縮し、濃縮物を水１００ｍｌ、メタノール１００ｍｌで洗浄した後、酢酸エチルから再結晶し、２，７−ビス（トリフルオロメタンスルホニルオキシ）トリフェニレン６．９ｇを得た。
<Synthesis of 2,7-bis (trifluoromethanesulfonyloxy) triphenylene>
Under a nitrogen atmosphere, 100 ml of dehydrated pyridine was added to a flask containing 8.7 g of 2,7-dihydroxytriphenylene. This solution was cooled with ice water, and 25 g of trifluoromethanesulfonic anhydride was added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 18 hours, and water was added to complete the reaction. The reaction solution was transferred to a separatory funnel and extracted with 500 ml of ethyl acetate. The organic layer was concentrated under reduced pressure, and the concentrate was washed with 100 ml of water and 100 ml of methanol, and then recrystallized from ethyl acetate to obtain 6.9 g of 2,7-bis (trifluoromethanesulfonyloxy) triphenylene.
＜２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）トリフェニレンの合成＞
２，７−ビス（トリフルオロメタンスルホニルオキシ）トリフェニレン６．３ｇ、ビス（ピナコラート）ジボロン６．７ｇ、ビス（ジベンジリデンアセトン）パラジウム（０）４１４ｍｇ、トリシクロヘキシルホスフィン４８５ｍｇ、酢酸カリウム３．５ｇ、およびエチレングリコールジメチルエーテル５０ｍｌをフラスコに入れ、アルゴン雰囲気下、還流温度で２時間攪拌した。加熱終了後、反応液にトルエンを加え、室温まで冷却後濾別し、濾液を減圧下濃縮した。濃縮物をエタノールで洗浄し、２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）トリフェニレン３．１ｇを得た。
<Synthesis of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) triphenylene>
2,7-bis (trifluoromethanesulfonyloxy) triphenylene 6.3 g, bis (pinacolato) diboron 6.7 g, bis (dibenzylideneacetone) palladium (0) 414 mg, tricyclohexylphosphine 485 mg, potassium acetate 3.5 g, and ethylene 50 ml of glycol dimethyl ether was placed in a flask and stirred at reflux temperature for 2 hours under an argon atmosphere. After completion of heating, toluene was added to the reaction solution, cooled to room temperature and filtered, and the filtrate was concentrated under reduced pressure. The concentrate was washed with ethanol to obtain 3.1 g of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) triphenylene.
＜２，７−ビス（３，４'−ビピリジン−５−イル）トリフェニレンの合成＞
２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）トリフェニレン２．０ｇ、５−ブロモ−３，４'−ビピリジン２．２ｇ、Ｐｄ（ＰＰｈ３）４３１７ｍｇ、炭酸ナトリウム１．８ｇおよびトルエン２０ｍｌ、エタノール７ｍｌ、水７ｍｌをフラスコに入れて、アルゴン雰囲気下、還流温度で６時間半攪拌した。加熱終了後、反応液を室温まで冷却した後、純水を加え、固形物を吸引濾過にて濾別した。この固形物をメタノールで洗浄した後、Ｎ，Ｎ−ジメチルホルムアミドから再結晶し、２，７−ビス（３，４’−ビピリジン−５−イル）トリフェニレン１．４ｇを得た。
１Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ６）：δ＝ 7.8 (ｍ, 2H), 7.95(ｍ, 4H), 8.2 (ｄ, 2H), 8.7 (ｓ, 2H), 8.75(ｍ, 4H), 9.0 (d, 2H), 9.05-9.1(ｍ, 4H), 9.2 (s, 2H)，9.25(m, 2H)
<Synthesis of 2,7-bis (3,4'-bipyridin-5-yl) triphenylene>
2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) triphenylene 2.0 g, 5-bromo-3,4'-bipyridine 2.2 g, Pd ( PPh 3 ) 4 ( 317 mg), sodium carbonate (1.8 g), toluene (20 ml), ethanol (7 ml), and water (7 ml) were placed in a flask and stirred at reflux temperature for 6 and a half hours under an argon atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, pure water was added, and the solid matter was separated by suction filtration. The solid was washed with methanol and recrystallized from N, N-dimethylformamide to obtain 1.4 g of 2,7-bis (3,4'-bipyridin-5-yl) triphenylene.
1H-NMR (DMSO-d6): δ = 7.8 (m, 2H), 7.95 (m, 4H), 8.2 (d, 2H), 8.7 (s, 2H), 8.75 (m, 4H), 9.0 (d, 2H), 9.05-9.1 (m, 4H), 9.2 (s, 2H), 9.25 (m, 2H)
合成例３：式（２−１−２３）の化合物の合成
＜２，７−ビス（トリフルオロメタンスルホニルオキシ）−９−フェニルカルバゾールの合成＞
窒素雰囲気下、２，７−ジヒドロキシ−９−フェニルカルバゾール９．６ｇの入ったフラスコに脱水ピリジン１００ｍｌを加えた。この溶液を氷水で冷却し、トリフルオロメタンスルホン酸無水物２５ｇを滴下した。滴下終了後、室温で１８時間攪拌した後、水を加え反応を終了した。反応液を分液ロートに移し、酢酸エチルで抽出した。有機層を減圧下濃縮し、濃縮物を水、メタノールで洗浄した後、酢酸エチル／メタノール混合溶媒から再結晶し、２，７−ビス（トリフルオロメタンスルホニルオキシ）−９−フェニルカルバゾール１４．６ｇを得た。
Synthesis Example 3 Synthesis of Compound of Formula (2-1-23) <Synthesis of 2,7-bis (trifluoromethanesulfonyloxy) -9-phenylcarbazole>
Under a nitrogen atmosphere, 100 ml of dehydrated pyridine was added to a flask containing 9.6 g of 2,7-dihydroxy-9-phenylcarbazole. This solution was cooled with ice water, and 25 g of trifluoromethanesulfonic anhydride was added dropwise. After completion of the dropping, the mixture was stirred at room temperature for 18 hours, and water was added to complete the reaction. The reaction solution was transferred to a separatory funnel and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure, and the concentrate was washed with water and methanol, and then recrystallized from a mixed solvent of ethyl acetate / methanol to obtain 14.6 g of 2,7-bis (trifluoromethanesulfonyloxy) -9-phenylcarbazole. Obtained.
＜２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９−フェニルカルバゾールの合成＞
２，７−ビス（トリフルオロメタンスルホニルオキシ）−９−フェニルカルバゾール１２．０ｇ、ビス（ピナコラート）ジボロン１１．２ｇ、ビス（ジベンジリデンアセトン）パラジウム（０）７４８ｍｇ、トリシクロヘキシルホスフィン８９７ｍｇ、酢酸カリウム６．５ｇおよびエチレングリコールジメチルエーテル１００ｍｌをフラスコに入れ、アルゴン雰囲気下、還流温度で１時間攪拌した。加熱終了後、反応液をエバポレータにより濃縮し、濃縮物にトルエン１００ｍｌを加えた。この溶液を吸引濾過にて濾別し、濾液をシリカゲルカラムクロマトグラフィー（移動層：トルエン）により精製した。更にジクロロメタン／ヘプタン混合溶媒から再結晶し、２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９−フェニルカルバゾール６．１ｇを得た。
<Synthesis of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9-phenylcarbazole>
2,7-bis (trifluoromethanesulfonyloxy) -9-phenylcarbazole 12.0 g, bis (pinacolato) diboron 11.2 g, bis (dibenzylideneacetone) palladium (0) 748 mg, tricyclohexylphosphine 897 mg, potassium acetate 6. 5 g and 100 ml of ethylene glycol dimethyl ether were placed in a flask and stirred at reflux temperature for 1 hour under an argon atmosphere. After completion of the heating, the reaction solution was concentrated with an evaporator, and 100 ml of toluene was added to the concentrate. This solution was separated by suction filtration, and the filtrate was purified by silica gel column chromatography (mobile layer: toluene). Furthermore, recrystallization from a dichloromethane / heptane mixed solvent gave 6.1 g of 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9-phenylcarbazole. It was.
＜２，７−ビス（３，４’−ビピリジン−５−イル）−９−フェニルカルバゾールの合成＞
２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９−フェニルカルバゾール２．５ｇ、５−ブロモ−３，４’−ビピリジン２．６ｇ、Ｐｄ（ＰＰｈ３）４６９４ｍｇ、炭酸ナトリウム２．１ｇ、トルエン３０ｍｌ、エタノール１０ｍｌおよび水１０ｍｌをフラスコに入れて、アルゴン雰囲気下、還流温度で３２．５時間攪拌した。加熱終了後、反応液を室温まで冷却し、水とクロロベンゼンを加え、分液ロートで分液した。有機層を濃縮し、濃縮物を活性アルミナカラムクロマトグラフィー（移動相：トルエン／酢酸エチル⇒酢酸エチル／メタノール）にて精製した。更にクロロベンゼンから再結晶し、２，７−ビス（３，４’−ビピリジン−５−イル）−９−フェニルカルバゾール５８８ｍｇを得た。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ＝ 7.55-7.7 (m, 13H), 8.1(m, 2H), 8.3 (d, 2H), 8.75(d, 4H), 8.85 (m, 2H), 8.95 (m, 2H)
<Synthesis of 2,7-bis (3,4'-bipyridin-5-yl) -9-phenylcarbazole>
2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9-phenylcarbazole 2.5 g, 5-bromo-3,4'-bipyridine 6 g, Pd (PPh 3 ) 4 694 mg, sodium carbonate 2.1 g, toluene 30 ml, ethanol 10 ml and water 10 ml were placed in a flask and stirred at reflux temperature for 32.5 hours under an argon atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, water and chlorobenzene were added, and the mixture was separated using a separatory funnel. The organic layer was concentrated, and the concentrate was purified by activated alumina column chromatography (mobile phase: toluene / ethyl acetate => ethyl acetate / methanol). Further, recrystallization from chlorobenzene gave 588 mg of 2,7-bis (3,4'-bipyridin-5-yl) -9-phenylcarbazole.
1H-NMR (CDCl 3 ): δ = 7.55-7.7 (m, 13H), 8.1 (m, 2H), 8.3 (d, 2H), 8.75 (d, 4H), 8.85 (m, 2H), 8.95 (m , 2H)
合成例４：式（２−１−２９）の化合物の合成
＜２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９，９’−スピロビフルオレンの合成＞
２，７−ジブロモ−９，９’−スピロビフルオレン７．５ｇ、ビス（ピナコラート）ジボロン９．１ｇ、（１，１’−ビス（ジフェニルホスフィノ）フェロセン）ジクロロパラジウム（II）７３０ｍｇ、酢酸カリウム８．８ｇおよびジメチルスルホキシド１００ｍｌをフラスコに入れ、アルゴン雰囲気下、８０℃で３．５時間攪拌した。加熱終了後室温まで冷却し、水を加え分液ロートに移し、酢酸エチルで抽出した。有機層を減圧下濃縮し、濃縮物をシリカゲルカラムクロマトグラフィー（移動層：トルエン／酢酸エチル）により精製し、２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９，９’−スピロビフルオレン７．７ｇを得た。
Synthesis Example 4: Synthesis of compound of formula (2-1-29) <2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9,9 '-Synthesis of Spirobifluorene>
2,7-Dibromo-9,9'-spirobifluorene 7.5 g, bis (pinacolato) diboron 9.1 g, (1,1'-bis (diphenylphosphino) ferrocene) dichloropalladium (II) 730 mg, potassium acetate 8.8 g and 100 ml of dimethyl sulfoxide were placed in a flask and stirred at 80 ° C. for 3.5 hours under an argon atmosphere. After heating, the mixture was cooled to room temperature, water was added, and the mixture was transferred to a separatory funnel and extracted with ethyl acetate. The organic layer was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (mobile layer: toluene / ethyl acetate) and 2,7-bis (4,4,5,5-tetramethyl-1,3,2). -Dioxaborolanyl) -9,9'-spirobifluorene 7.7g was obtained.
＜２，７−ビス（３，４’−ビピリジン−５−イル）−９，９’−スピロビフルオレンの合成＞
２，７−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９，９’−スピロビフルオレン４．０ｇ、５−ブロモ−３，４’−ビピリジン３．６ｇ、Ｐｄ（ＰＰｈ３）４４８５ｍｇ、炭酸ナトリウム３．１ｇ、トルエン３０ｍｌ、エタノール１０ｍｌおよび水１０ｍｌをフラスコに入れて、アルゴン雰囲気下、還流温度で３２．５時間攪拌した。加熱終了後、反応液を室温まで冷却し、飽和食塩水とトルエンを加え分液ロートで分液した。有機層を濃縮し、濃縮物をシリカゲルカラムクロマトグラフィー（移動相：トルエン／酢酸エチル⇒酢酸エチル／メタノール）にて精製した。更にクロロベンゼンから再結晶し、２，７−ビス（３，４’−ビピリジン−５−イル）−９，９’−スピロビフルオレン１．４ｇを得た。
１Ｈ−ＮＭＲ（ＣＤＣｌ３）：δ＝ 6.85 (d, 2H), 7.0 (s, 2H), 7.15 (t, 2H), 7.4(t, 2H), 7.45 (m, 4H), 7.7 (d, 2H), 7.9 (m, 4H), 8.05(d, 2H), 8.65-8.8(m, 8H)
<Synthesis of 2,7-bis (3,4'-bipyridin-5-yl) -9,9'-spirobifluorene>
2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9,9'-spirobifluorene, 4.0 g, 5-bromo-3,4 ' - bipyridine 3.6g, Pd (PPh 3) 4 485mg, sodium carbonate 3.1 g, put toluene 30 ml, of ethanol 10ml and water 10ml flask, under argon, and stirred 32.5 hours at reflux temperature. After completion of the heating, the reaction solution was cooled to room temperature, saturated brine and toluene were added, and the mixture was separated with a separatory funnel. The organic layer was concentrated, and the concentrate was purified by silica gel column chromatography (mobile phase: toluene / ethyl acetate => ethyl acetate / methanol). Further, recrystallization from chlorobenzene gave 1.4 g of 2,7-bis (3,4'-bipyridin-5-yl) -9,9'-spirobifluorene.
1H-NMR (CDCl 3 ): δ = 6.85 (d, 2H), 7.0 (s, 2H), 7.15 (t, 2H), 7.4 (t, 2H), 7.45 (m, 4H), 7.7 (d, 2H ), 7.9 (m, 4H), 8.05 (d, 2H), 8.65-8.8 (m, 8H)
合成例５：式（２−１−２８）の化合物の合成
＜３，６−ジブロモ−９−ナフタレン−１−イル−カルバゾールの合成＞
３，６−ジブロモ−９Ｈ−カルバゾール１０．００ｇ、１−フルオロナフタレン４．１ｍｌ、炭酸セシウム１２．０６ｇおよびジメチルスルホキシド３００ｍｌをフラスコに入れ、窒素雰囲気下、１４５℃で３６時間攪拌した。加熱終了後、室温まで冷却後反応液を濾別し、濾液を濃縮した。濃縮物をシリカゲルカラムクロマトグラフィー（移動相：ヘプタン／トルエン）により精製した後、メタノールで洗浄することで、３，６−ジブロモ−９−ナフタレン−１−イル−カルバゾール５．５ｇを得た。
Synthesis Example 5 Synthesis of Compound of Formula (2-1-28) <Synthesis of 3,6-dibromo-9-naphthalen-1-yl-carbazole>
3,6-Dibromo-9H-carbazole (10.00 g), 1-fluoronaphthalene (4.1 ml), cesium carbonate (12.06 g) and dimethyl sulfoxide (300 ml) were placed in a flask and stirred at 145 ° C. for 36 hours in a nitrogen atmosphere. After completion of heating, the reaction solution was filtered after cooling to room temperature, and the filtrate was concentrated. The concentrate was purified by silica gel column chromatography (mobile phase: heptane / toluene) and then washed with methanol to obtain 5.5 g of 3,6-dibromo-9-naphthalen-1-yl-carbazole.
＜３，６−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９−ナフタレン−１−イル−カルバゾールの合成＞
３，６−ジブロモ−９−ナフタレン−１−イル−カルバゾール２．００ｇ、ビス（ピナコラート）ジボロン２．４６ｇ、ビス（ジベンジリデンアセトン）パラジウム（０）３０４ｍｇ、トリシクロヘキシルホスフィン３５８ｍｇ、酢酸カリウム１．３０ｇおよび１，４−ジオキサン３０ｍｌをフラスコに入れ、アルゴン雰囲気下還流温度で７時間攪拌した。加熱終了後反応液にトルエンを加え、室温まで冷却後濾別し、濾液を濃縮した。濃縮物をシリカゲルカラムクロマトグラフィー（移動相：トルエン）により精製し、３，６−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９−ナフタレン−１−イル−カルバゾール８２０ｍｇを得た。
<Synthesis of 3,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9-naphthalen-1-yl-carbazole>
3,6-dibromo-9-naphthalen-1-yl-carbazole 2.00 g, bis (pinacolato) diboron 2.46 g, bis (dibenzylideneacetone) palladium (0) 304 mg, tricyclohexylphosphine 358 mg, potassium acetate 1.30 g And 30 ml of 1,4-dioxane was put into the flask and stirred at reflux temperature for 7 hours under an argon atmosphere. After completion of heating, toluene was added to the reaction solution, cooled to room temperature and filtered, and the filtrate was concentrated. The concentrate was purified by silica gel column chromatography (mobile phase: toluene) and 3,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9-naphthalene. 820 mg of -1-yl-carbazole was obtained.
＜３，６−ビス（３，４’−ビピリジン−５−イル）−９−ナフタレン−１−イル−カルバゾールの合成＞
３，６−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−９−ナフタレン−１−イル−カルバゾール、５−ブロモ−３，４'−ビピリジン、Ｐｄ（ＰＰｈ３）４、リン酸三カリウム、１，４−ジオキサンおよび水をフラスコに入れて、アルゴン雰囲気下還流温度で攪拌する。加熱終了後反応液を室温まで冷却し、飽和塩化ナトリウム水溶液で洗浄する。有機層をエバポレータにより濃縮し、濃縮物を活性アルミナカラムクロマトグラフィーやシリカゲルクロマトグラフィーにて精製することで、３,６−ビス（３，４'−ビピリジン−５−イル）−９−ナフタレン−１−イル−カルバゾールを得ることが出来る。
<Synthesis of 3,6-bis (3,4'-bipyridin-5-yl) -9-naphthalen-1-yl-carbazole>
3,6-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -9-naphthalen-1-yl-carbazole, 5-bromo-3,4'-bipyridine , Pd (PPh 3 ) 4 , tripotassium phosphate, 1,4-dioxane and water are placed in a flask and stirred at reflux temperature under an argon atmosphere. After completion of heating, the reaction solution is cooled to room temperature and washed with a saturated aqueous sodium chloride solution. The organic layer is concentrated by an evaporator, and the concentrate is purified by activated alumina column chromatography or silica gel chromatography, whereby 3,6-bis (3,4'-bipyridin-5-yl) -9-naphthalene-1 -Yl-carbazole can be obtained.
合成例６：式（２−２−３３）の化合物の合成
＜５，９−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−７，７−ジフェニル−ベンゾ〔ｃ〕フルオレンの合成＞
５，９−ビス（トリフルオロメタンスホニルオキシ）−７，７−ジフェニル−ベンゾ〔ｃ〕フルオレン１３．１ｇ、ビス（ピナコラート）ジボロン１１．２ｇ、ビス（ジベンジリデンアセトン）パラジウム（０）１．２ｇ、トリシクロヘキシルホスフィン１．４ｇ、酢酸カリウム６．５ｇおよび１,４−ジオキサン３００ｍｌをフラスコに入れ、アルゴン雰囲気下８０℃で４時間半攪拌した。加熱終了後反応液を濃縮した。濃縮物をシリカゲルカラムクロマトグラフィー（移動相：トルエン）により精製した後、エタノールで洗浄し、５，９−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−７，７−ジフェニル−ベンゾ〔ｃ〕フルオレン９．８を得た。
Synthesis Example 6 Synthesis of Compound of Formula (2-233) <5,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -7,7 -Synthesis of diphenyl-benzo [c] fluorene>
5,9-bis (trifluoromethanesulfonyloxy) -7,7-diphenyl-benzo [c] fluorene 13.1 g, bis (pinacolato) diboron 11.2 g, bis (dibenzylideneacetone) palladium (0) 1.2 g , 1.4 g of tricyclohexylphosphine, 6.5 g of potassium acetate and 300 ml of 1,4-dioxane were placed in a flask and stirred at 80 ° C. for 4 hours and a half in an argon atmosphere. After completion of the heating, the reaction solution was concentrated. The concentrate was purified by silica gel column chromatography (mobile phase: toluene), washed with ethanol, and 5,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborola). Nyl) -7,7-diphenyl-benzo [c] fluorene 9.8.
＜５，９−ビス（３，４'−ビピリジン−５−イル）−７，７−ジフェニル−ベンゾ〔ｃ〕フルオレンの合成＞
５，９−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−７，７−ジフェニル−ベンゾ〔ｃ〕フルオレン、５−ブロモ−３，４'−ビピリジン、Ｐｄ（ＰＰｈ３）４、リン酸三カリウム、１，４−ジオキサンおよび水をフラスコに入れて、アルゴン雰囲気下還流温度で攪拌する。加熱終了後反応液を室温まで冷却し、飽和塩化ナトリウム水溶液で洗浄する。有機層をエバポレータにより濃縮し、濃縮物を活性アルミナカラムクロマトグラフィーやシリカゲルクロマトグラフィーにて精製することで、５，９−ビス（３，４'−ビピリジン−５−イル）−７，７−ジフェニル−ベンゾ〔ｃ〕フルオレンを得ることが出来る。
<Synthesis of 5,9-bis (3,4'-bipyridin-5-yl) -7,7-diphenyl-benzo [c] fluorene>
5,9-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -7,7-diphenyl-benzo [c] fluorene, 5-bromo-3,4 ' - bipyridine, Pd (PPh 3) 4, tripotassium phosphate, 1,4-dioxane and water placed in a flask and stirred under an argon atmosphere to reflux temperature. After completion of heating, the reaction solution is cooled to room temperature and washed with a saturated aqueous sodium chloride solution. The organic layer is concentrated by an evaporator, and the concentrate is purified by activated alumina column chromatography or silica gel chromatography, whereby 5,9-bis (3,4'-bipyridin-5-yl) -7,7-diphenyl is purified. -Benzo [c] fluorene can be obtained.
合成例７：式（２−１−１５）の化合物の合成
＜１，４−ビス（３，４’−ビピリジン−５−イル）−ナフタレンの合成＞
１，４−ビス（４，４，５，５−テトラメチル−１，３，２−ジオキサボロラニル）−ナフタレン、５−ブロモ−３，４’−ビピリジン、トリス（ジベンジリデンアセトン）二パラジウム（０）、トリシクロヘキシルホスフィン、リン酸三カリウムおよびトルエンをフラスコに入れて、アルゴン雰囲気下還流温度で攪拌する。加熱終了後反応液を室温まで冷却し、飽和塩化ナトリウム水溶液で洗浄する。有機層を濃縮し、濃縮物を活性アルミナカラムクロマトグラフィーやシリカゲルクロマトグラフィーにて精製することで、１，４−ビス（３，４’−ビピリジン−５−イル）−ナフタレンを得ることが出来る。
Synthesis Example 7 Synthesis of Compound of Formula (2-1-15) <Synthesis of 1,4-bis (3,4'-bipyridin-5-yl) -naphthalene>
1,4-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl) -naphthalene, 5-bromo-3,4'-bipyridine, tris (dibenzylideneacetone) Palladium (0), tricyclohexylphosphine, tripotassium phosphate and toluene are placed in a flask and stirred at reflux temperature under an argon atmosphere. After completion of heating, the reaction solution is cooled to room temperature and washed with a saturated aqueous sodium chloride solution. The organic layer is concentrated, and the concentrate is purified by activated alumina column chromatography or silica gel chromatography, whereby 1,4-bis (3,4'-bipyridin-5-yl) -naphthalene can be obtained.
原料の化合物を適宜選択することにより、上記の合成例に準じた方法で、本発明の他の発光材料を合成することができる。 By appropriately selecting a raw material compound, another light emitting material of the present invention can be synthesized by a method according to the above synthesis example.
ＩＴＯを１５０ｎｍの厚さに蒸着した２５ｍｍ×７５ｍｍ×１．１ｍｍのガラス基板（東京三容真空（株）製）を透明支持基板とした。この透明支持基板を市販の蒸着装置（真空機工（株）製）の基板ホルダーに固定し、銅フタロシアニンを入れたモリブデン製蒸着用ボート、Ｎ，Ｎ'−ジフェニル−Ｎ，Ｎ'−ジナフチル−４，４'−ジアミノビフェニル（以下、ＮＰＤと略記する。）を入れたモリブデン製蒸着用ボート、下記化合物（Ａ）：９−フェニル−１０−〔６−（１，１’；３，１’’）テルフェニル−５’−イル〕ナフタレン−２−イル〕アントラセンを入れたモリブデン製蒸着用ボート、下記スチリルアミン誘導体（Ｂ）：Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ（４−ビフェニリル）−４，４’−ジアミノスチルベンを入れたモリブデン製蒸着用ボート、化合物（２−１−２）を入れたモリブデン製蒸着用ボート、弗化リチウムを入れたモリブデン製蒸着用ボート、およびアルミニウムを入れたタングステン製蒸着用ボートを装着した。
真空槽を１×１０−３Ｐａまで減圧し、銅フタロシアニンが入った蒸着用ボートを加熱して、膜厚２０ｎｍになるように蒸着して正孔注入層を形成し、次いで、ＮＰＤ入りの蒸着用ボートを加熱して、膜厚３０ｎｍになるようにＮＰＤを蒸着して正孔輸送層を形成した。次に、化合物（Ａ）を入れた蒸着用ボートと化合物（Ｂ）を入れた蒸着用ボートを同時に加熱して、膜厚３０ｎｍになるように蒸着して発光層を形成した。化合物（Ａ）と化合物（Ｂ）の重量比がおよそ９５対５になるように蒸着速度を調節した。次に化合物（２−２−１）入りの蒸着用ボートを加熱して、膜厚２０ｎｍになるように蒸着して電子輸送層を形成した。以上の蒸着速度は０．００１〜３．０ｎｍ／秒であった。その後、弗化リチウム入りの蒸着用ボートを加熱して、膜厚０．５ｎｍになるように０．００３〜０．０１ｎｍ／秒の蒸着速度で蒸着し、次いで、アルミニウム入りの蒸着用ボートを加熱して、膜厚１００ｎｍになるように０．１〜１．０ｎｍ／秒の蒸着速度で蒸着することにより、有機ＥＬ素子を得た。ＩＴＯ電極を陽極、弗化リチウム／アルミニウム電極を陰極として、直流電圧を印加すると、約波長４５５ｎｍの青色発光を得た。輝度１０００ｃｄ／ｍ２を得るための駆動電圧は５．７３Ｖで、８０時間経過時の輝度は８９０ｃｄ／ｍ２だった。 Depressurize the vacuum chamber to 1 × 10 −3 Pa, heat the vapor deposition boat containing copper phthalocyanine, and form a hole injection layer by vapor deposition to a film thickness of 20 nm, and then vapor deposition with NPD The boat was heated and NPD was deposited to a film thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time and vapor-deposited to a film thickness of 30 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound (2-2-1) was heated and evaporated to a film thickness of 20 nm to form an electron transport layer. The above deposition rate was 0.001 to 3.0 nm / second. Thereafter, the vapor deposition boat containing lithium fluoride is heated to deposit at a deposition rate of 0.003 to 0.01 nm / second so that the film thickness is 0.5 nm, and then the vapor deposition boat containing aluminum is heated. Then, an organic EL device was obtained by vapor deposition at a vapor deposition rate of 0.1 to 1.0 nm / second so as to have a film thickness of 100 nm. When a direct current voltage was applied using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, blue light emission with a wavelength of about 455 nm was obtained. Driving voltage for obtaining a luminance 1000 cd / m 2 at 5.73V, brightness in course 80 hours was 890 cd / m 2.
スパッタリングにより１８０ｎｍの厚さに製膜したＩＴＯを１５０ｎｍまで研磨した、２６ｍｍ×２８ｍｍ×０．７ｍｍのガラス基板（（株）オプトサイエンス製）を透明支持基板とした。この透明支持基板を実施例８で使用した蒸着装置の基板ホルダーに固定し、ＣｕＰｃを入れたモリブデン製蒸着用ボート、ＮＰＤを入れたモリブデン製蒸着用ボート、化合物（Ａ）を入れたモリブデン製蒸着用ボート、化合物（Ｂ）を入れたモリブデン製蒸着用ボート、化合物（２−１−２１）を入れたモリブデン製蒸着用ボート、弗化リチウムを入れたモリブデン製蒸着用ボート、およびアルミニウムを入れたタングステン製蒸着用ボートを装着した。 A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate was fixed to the substrate holder of the vapor deposition apparatus used in Example 8, and a molybdenum vapor deposition boat containing CuPc, a molybdenum vapor deposition boat containing NPD, and a molybdenum vapor deposition containing compound (A). Boat, molybdenum vapor deposition boat containing compound (B), molybdenum vapor deposition boat containing compound (2-1-21), molybdenum vapor deposition boat containing lithium fluoride, and aluminum A tungsten evaporation boat was installed.
透明支持基板のＩＴＯ膜の上に順次、下記各層を形成した。真空槽を５×１０−４Ｐａまで減圧し、まず、ＣｕＰｃが入った蒸着用ボートを加熱して膜厚５０ｎｍになるように蒸着して正孔注入層を形成し、ついで、ＮＰＤが入った蒸着用ボートを加熱して膜厚３０ｎｍになるように蒸着して正孔輸送層を形成した。次に、化合物（Ａ）が入った蒸着用ボートと化合物（Ｂ）の入った蒸着用ボートを同時に加熱して膜厚３５ｎｍになるように蒸着して発光層を形成した。化合物（Ａ）と化合物（Ｂ）の重量比がおよそ９５対５になるように蒸着速度を調節した。次に、化合物（２−１−２１）の入った蒸着用ボートを加熱して膜厚１５ｎｍになるように蒸着して電子輸送層を形成した。各層の蒸着速度は０．０１〜１ｎｍ／秒であった。 The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 −4 Pa, and first, a vapor deposition boat containing CuPc was heated and vapor-deposited to a film thickness of 50 nm to form a hole injection layer, and then NPD was contained. A vapor deposition boat was heated to deposit a film with a thickness of 30 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 35 nm. The deposition rate was adjusted so that the weight ratio of compound (A) to compound (B) was approximately 95 to 5. Next, the evaporation boat containing the compound (2-1-21) was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / second.
その後、弗化リチウム入りの蒸着用ボートを加熱して膜厚０．５ｎｍになるように０．００３〜０．１ｎｍ／秒の蒸着速度で蒸着し、次いで、アルミニウム入りの蒸着用ボートを加熱して膜厚１００ｎｍになるように０．０１〜１０ｎｍ／秒の蒸着速度で蒸着することにより、陰極を形成し、有機電界発光素子を得た。 Thereafter, the vapor deposition boat containing lithium fluoride is heated to deposit at a deposition rate of 0.003 to 0.1 nm / second so that the film thickness becomes 0.5 nm, and then the vapor deposition boat containing aluminum is heated. The cathode was formed by vapor deposition at a deposition rate of 0.01 to 10 nm / second so that the film thickness was 100 nm, and an organic electroluminescent element was obtained.
ＩＴＯ電極を陽極、弗化リチウム／アルミニウム電極を陰極として、直流電圧を印加すると、約波長４５５ｎｍの青色発光を得た。また、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施した。駆動試験開始電圧は４．９６Ｖで、８０時間経過時の輝度は１６１８ｃｄ／ｍ２だった。 When a direct current voltage was applied using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, blue light emission with a wavelength of about 455 nm was obtained. In addition, a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m 2 . The drive test starting voltage was 4.96 V, and the luminance after 80 hours was 1618 cd / m 2 .
化合物（２−１−２１）を化合物（２−１−２３）に替えた以外は実施例９と同様にして有機ＥＬ素子を得た。ＩＴＯ電極を陽極、弗化リチウム／アルミニウム電極を陰極として、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施した。駆動試験開始電圧は６．１７Ｖで８０時間経過時の輝度は１６７８ｃｄ／ｍ２であった。 An organic EL device was obtained in the same manner as in Example 9 except that the compound (2-1-21) was changed to the compound (2-1-23). A constant current driving test was performed using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 . The drive test start voltage was 6.17 V, and the luminance after 80 hours was 1678 cd / m 2 .
（比較例１）
化合物（２−１−２）を化合物（Ｃ）（特許文献２に記載の化合物II−４）に替えた以外は実施例８と同様にして有機ＥＬ素子を得た。ＩＴＯ電極を陽極、弗化リチウム／アルミニウム電極を陰極として、初期輝度１０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施した。駆動試験開始電圧は３．７１Ｖで８０時間経過時の輝度は４９６ｃｄ／ｍ２であった。
An organic EL device was obtained in the same manner as in Example 8 except that the compound (2-1-2) was changed to the compound (C) (Compound II-4 described in Patent Document 2). A constant current driving test was performed using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 1000 cd / m 2 . The drive test starting voltage was 3.71 V, and the luminance after 80 hours was 496 cd / m 2 .
（比較例２）
化合物（２−１−２）をトリス（８−キノリノール）アルミニウム（Ａｌｑ３）に替えた以外は実施例８と同様にして有機ＥＬ素子を得た。ＩＴＯ電極を陽極、弗化リチウム／アルミニウム電極を陰極として、初期輝度１０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施した。駆動試験開始電圧は６．３６Ｖで８０時間経過時の輝度は８３０ｃｄ／ｍ２であった。
(Comparative Example 2)
An organic EL device was obtained in the same manner as in Example 8 except that the compound (2-1-2) was changed to tris (8-quinolinol) aluminum (Alq 3 ). A constant current driving test was performed using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 1000 cd / m 2 . The drive test start voltage was 6.36 V, and the luminance after 80 hours was 830 cd / m 2 .
（比較例３）
化合物（２−２−２１）を上記化合物（Ｃ）（特許文献２に記載の化合物II−４）に替えた以外は実施例９と同様にして有機ＥＬ素子を得た。ＩＴＯ電極を陽極、弗化リチウム／アルミニウム電極を陰極として、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施した。駆動試験開始電圧は４．１４Ｖで８０時間経過時の輝度は１３７５ｃｄ／ｍ２であった。
(Comparative Example 3)
An organic EL device was obtained in the same manner as in Example 9 except that the compound (2-2-21) was changed to the compound (C) (compound II-4 described in Patent Document 2). A constant current driving test was performed using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 . The drive test start voltage was 4.14 V, and the luminance after 80 hours was 1375 cd / m 2 .
（比較例４）
化合物（２−２−２１）をトリス（８−キノリノール）アルミニウム（Ａｌｑ３）に替えた以外は実施例９と同様にして有機ＥＬ素子を得た。ＩＴＯ電極を陽極、弗化リチウム／アルミニウム電極を陰極として、初期輝度２０００ｃｄ／ｍ２を得るための電流密度により、定電流駆動試験を実施した。駆動試験開始電圧は６．５８Ｖで８０時間経過時の輝度は１５６２ｃｄ／ｍ２であった。
(Comparative Example 4)
An organic EL device was obtained in the same manner as in Example 9 except that the compound (2-2-21) was changed to tris (8-quinolinol) aluminum (Alq 3 ). A constant current driving test was performed using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m 2 . The driving test start voltage was 6.58 V, and the luminance after 80 hours was 1562 cd / m 2 .
本発明の好ましい態様によれば、駆動電圧、素子寿命において更に性能のよい有機ＥＬ素子を提供することができる。殊に青色発光の素子の駆動電圧、素子寿命が改善され、より実用的になるので、それを備えた高性能なディスプレイ装置などを提供することができる。 According to a preferred aspect of the present invention, it is possible to provide an organic EL device having better performance in terms of driving voltage and device life. In particular, since the driving voltage and device life of the blue light emitting device are improved and become more practical, it is possible to provide a high-performance display device equipped with the device.
Claims (57)
Ｒ１〜Ｒ４は独立して水素、１価の基またはＧに結合する遊離原子価であり、Ｒ５〜Ｒ８は独立して水素または１価の基であるが、Ｒ１〜Ｒ４の１つはＧに結合する遊離原子価であり；そして、ｎ個の３，４’−ビピリジル基は同一でもよく、異なっていてもよい。 A compound represented by the following formula (1).
R 1 to R 4 are independently hydrogen, a monovalent group or a free valence bonded to G, and R 5 to R 8 are independently hydrogen or a monovalent group, but R 1 to R 4 Is the free valence attached to G; and the n 3,4′-bipyridyl groups may be the same or different.
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