WO2011086935A1 - 含窒素複素環誘導体及びそれを含んでなる有機エレクトロルミネッセンス素子 - Google Patents
含窒素複素環誘導体及びそれを含んでなる有機エレクトロルミネッセンス素子 Download PDFInfo
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- WO2011086935A1 WO2011086935A1 PCT/JP2011/000156 JP2011000156W WO2011086935A1 WO 2011086935 A1 WO2011086935 A1 WO 2011086935A1 JP 2011000156 W JP2011000156 W JP 2011000156W WO 2011086935 A1 WO2011086935 A1 WO 2011086935A1
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- Prior art keywords
- substituted
- group
- unsubstituted
- carbon atoms
- nitrogen
- Prior art date
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- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 61
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 93
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 22
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 13
- 125000004429 atom Chemical group 0.000 claims abstract description 6
- 238000005401 electroluminescence Methods 0.000 claims description 41
- 230000004888 barrier function Effects 0.000 claims description 38
- 125000001424 substituent group Chemical group 0.000 claims description 24
- 125000006413 ring segment Chemical group 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 19
- 238000002347 injection Methods 0.000 claims description 16
- 239000007924 injection Substances 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000004104 aryloxy group Chemical group 0.000 claims description 13
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 12
- 125000005104 aryl silyl group Chemical group 0.000 claims description 11
- 150000002430 hydrocarbons Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001454 anthracenes Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001721 carbon Chemical class 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 4
- 125000001769 aryl amino group Chemical group 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 117
- 230000015572 biosynthetic process Effects 0.000 description 66
- 238000003786 synthesis reaction Methods 0.000 description 66
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 44
- 239000000243 solution Substances 0.000 description 43
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- 150000001875 compounds Chemical class 0.000 description 25
- 239000012044 organic layer Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 22
- 235000019341 magnesium sulphate Nutrition 0.000 description 22
- 230000006870 function Effects 0.000 description 21
- -1 aromatic ring compound Chemical class 0.000 description 20
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- 239000002019 doping agent Substances 0.000 description 17
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- PPYIZNYOMNYZCG-UHFFFAOYSA-N 1-(4-bromophenyl)-2-phenylbenzimidazole Chemical compound C1=CC(Br)=CC=C1N1C2=CC=CC=C2N=C1C1=CC=CC=C1 PPYIZNYOMNYZCG-UHFFFAOYSA-N 0.000 description 14
- 238000010898 silica gel chromatography Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
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- QIXXMBYCFDAKNW-UHFFFAOYSA-N benzo[c]phenanthren-5-ylboronic acid Chemical compound C1=CC=C2C(B(O)O)=CC3=CC=C(C=CC=C4)C4=C3C2=C1 QIXXMBYCFDAKNW-UHFFFAOYSA-N 0.000 description 11
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 11
- 238000001816 cooling Methods 0.000 description 10
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- JZOIZKBKSZMVRV-UHFFFAOYSA-N benzo(a)triphenylene Chemical compound C1=CC=CC2=C3C4=CC=CC=C4C=CC3=C(C=CC=C3)C3=C21 JZOIZKBKSZMVRV-UHFFFAOYSA-N 0.000 description 8
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- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 7
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 7
- LDPCTBXVSGTSNJ-UHFFFAOYSA-N fluoranthen-3-ylboronic acid Chemical compound C12=CC=CC=C2C2=CC=CC3=C2C1=CC=C3B(O)O LDPCTBXVSGTSNJ-UHFFFAOYSA-N 0.000 description 7
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- 238000000034 method Methods 0.000 description 7
- XFQUMMGPGWTPOT-UHFFFAOYSA-N 1-(3-bromophenyl)-2-phenylbenzimidazole Chemical compound BrC1=CC=CC(N2C3=CC=CC=C3N=C2C=2C=CC=CC=2)=C1 XFQUMMGPGWTPOT-UHFFFAOYSA-N 0.000 description 6
- 0 CC*CN(*)C(*)=C(*)C(*)=C(C)C Chemical compound CC*CN(*)C(*)=C(*)C(*)=C(C)C 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- OOJVFRCGOPTRRN-UHFFFAOYSA-N 2-(6-fluoranthen-3-ylnaphthalen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(C=C(C=C2)C=3C=4C=CC=C5C6=CC=CC=C6C(C=45)=CC=3)C2=C1 OOJVFRCGOPTRRN-UHFFFAOYSA-N 0.000 description 5
- AGXBDFLBYGQPOB-UHFFFAOYSA-N 5-bromo-1-methyl-2-phenylbenzimidazole Chemical compound N=1C2=CC(Br)=CC=C2N(C)C=1C1=CC=CC=C1 AGXBDFLBYGQPOB-UHFFFAOYSA-N 0.000 description 5
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- 150000001342 alkaline earth metals Chemical class 0.000 description 5
- 230000005283 ground state Effects 0.000 description 5
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 5
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- 238000005215 recombination Methods 0.000 description 5
- 230000006798 recombination Effects 0.000 description 5
- OLEZQMVRAQBUNV-UHFFFAOYSA-N (3-fluoranthen-3-ylphenyl)boronic acid Chemical compound OB(O)C1=CC=CC(C=2C=3C=CC=C4C5=CC=CC=C5C(C=34)=CC=2)=C1 OLEZQMVRAQBUNV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- GBROPGWFBFCKAG-UHFFFAOYSA-N benzochrysene Natural products C1=CC2=C3C=CC=CC3=CC=C2C2=C1C1=CC=CC=C1C=C2 GBROPGWFBFCKAG-UHFFFAOYSA-N 0.000 description 4
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- AKQIBJOTAFMVCY-UHFFFAOYSA-N 2-(3-bromophenyl)imidazo[1,2-a]pyridine Chemical compound BrC1=CC=CC(C=2N=C3C=CC=CN3C=2)=C1 AKQIBJOTAFMVCY-UHFFFAOYSA-N 0.000 description 3
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- WWCQJSKCEVYQID-UHFFFAOYSA-N 5-bromobenzo[c]phenanthrene Chemical compound C1=CC=C2C(Br)=CC3=CC=C(C=CC=C4)C4=C3C2=C1 WWCQJSKCEVYQID-UHFFFAOYSA-N 0.000 description 3
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- 150000004820 halides Chemical class 0.000 description 3
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- JTZWOVTYKFJSBI-UHFFFAOYSA-N n-(4-bromo-2-nitrophenyl)-n-methylbenzamide Chemical compound C=1C=C(Br)C=C([N+]([O-])=O)C=1N(C)C(=O)C1=CC=CC=C1 JTZWOVTYKFJSBI-UHFFFAOYSA-N 0.000 description 3
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- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 125000006836 terphenylene group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000005557 thiazolylene group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000005730 thiophenylene group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000005558 triazinylene group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000005559 triazolylene group Chemical group 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Definitions
- the present invention relates to a nitrogen-containing heterocyclic derivative and an organic electroluminescence device comprising the same.
- An organic electroluminescence (EL) element is a self-luminous element utilizing the principle that a fluorescent substance emits light by recombination energy of holes injected from an anode and electrons injected from a cathode by applying an electric field. .
- the organic EL element includes a pair of electrodes composed of an anode and a cathode, and an organic thin film layer between the electrodes.
- the organic thin film layer is composed of a laminate of layers having various functions. For example, an anode, a hole injection layer, a hole transport layer, a light emitting layer, a barrier layer, an electron transport layer, and an electron injection layer are stacked in this order. It is a laminated body.
- Organic EL elements can be classified into two types, fluorescent and phosphorescent, according to the light emission principle.
- the fluorescence type organic EL element uses light emission by singlet excitons
- the phosphorescence type organic EL element uses light emission by triplet excitons.
- triplet energy is applied to the layer adjacent to the cathode side interface of the light emitting layer for the purpose of preventing the diffusion of triplet excitons having a longer exciton lifetime than that of the singlet excitons. It is known to achieve high efficiency by using large materials.
- Patent Document 1 discloses a technique for improving efficiency by providing a barrier layer made of BCP (bathocuproin), which is a phenanthroline derivative, adjacent to a light emitting layer and confining triplet excitons.
- BCP bathoproin
- Patent Document 2 a specific aromatic ring compound is used for the hole blocking layer to achieve high efficiency and long life.
- light emission caused by triplet excitons has also been reported recently in fluorescent organic EL devices (for example, Non-Patent Documents 1 and 2, and Patent Document 3).
- An object of the present invention is to provide a novel nitrogen-containing heterocyclic derivative that prevents an increase in applied voltage and enables high-efficiency light emission of an organic EL element by utilizing a TTF (triplet-triplet fusion) phenomenon.
- Another object of the present invention is to provide an optimum barrier material for promoting the TTF phenomenon.
- a nitrogen-containing heterocyclic derivative represented by the following formula (1) (Wherein any one of R 1 to R 12 is a hydrogen atom, a fluorine atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring atom. It is a heterocyclic group of several 5 to 30, and any one of R 1 to R 12 is a single bond and is bonded to L 1 .
- L 1 is a single bond, a substituted or unsubstituted b + 1 valent hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted b + 1 valent heterocyclic group having 5 to 30 ring atoms.
- HAr is a substituted or unsubstituted nitrogen-containing heterocyclic group.
- a and b are each an integer of 1 to 4, and at least one of a and b is 1. ) 2.
- R 111 to R 130 are each a hydrogen atom or a substituent, or adjacent substituents of R 111 to R 130 are bonded together to form a saturated or unsaturated ring. However, any one of R 111 to R 115 , any one of R 116 to R 119 , any one of R 120 to R 122 , any one of R 123 to R 126 , and R 127 to Any one of R 130 is a single bond and is bonded to L 1 . ) 3. 3.
- any one of R substituted on the heterocyclic skeleton is a single bond and is bonded to L 1.
- the other R is a hydrogen atom or a substituent, or is bonded between adjacent Rs. To form a saturated or unsaturated ring.
- R 201 to R 214 is a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 3 to 8 carbon atoms, A cycloalkyl group, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 8 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms Any one of R 201 to R 214 is a single bond
- L 1 represents a single bond, a substituted or unsubstituted b + 1 valent hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted b + 1 valent heterocyclic group having 5 to 30 ring atoms.
- HAr is a substituted or unsubstituted nitrogen-containing heterocyclic group.
- a and b are each an integer of 1 to 4, and at least one of a and b is 1. ) 6). 6.
- R 111 to R 130 are each a hydrogen atom or a substituent, or adjacent substituents of R 111 to R 130 are bonded together to form a saturated or unsaturated ring. However, any one of R 111 to R 115 , any one of R 116 to R 119 , any one of R 120 to R 122 , any one of R 123 to R 126 , and R 127 to Any one of R 130 is a single bond and is bonded to L 1 . ) 7).
- any one of R substituted on the heterocyclic skeleton is a single bond and is bonded to L 1.
- the other R is a hydrogen atom or a substituent, or is bonded between adjacent Rs. To form a saturated or unsaturated ring.
- R 401 to R 416 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted.
- L 1 represents a single bond, a substituted or unsubstituted c + d valent hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted c + d valent heterocyclic group having 5 to 30 ring atoms.
- c and d each represent an integer of 1 to 3.
- L 1 and R 401 to R 416 are not anthracene-containing groups.
- the nitrogen-containing heterocyclic derivative according to 9 or 10 represented by the following formula (32). (Wherein R 402 to R 416 , L 1 , and d represent the same groups as 9). 12 12.
- the nitrogen-containing heterocyclic derivative according to 14, wherein the organic electroluminescence element material is a barrier layer material.
- An anode, a light emitting layer, a barrier layer, and a cathode are provided in this order, An organic electroluminescence device wherein the barrier layer contains the nitrogen-containing heterocyclic derivative according to any one of 1 to 13. 17.
- R 301 to R 308 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted carbon number.
- the nitrogen-containing heterocyclic derivative of the present invention is represented by the following formula (1).
- any one of R 1 to R 12 is a hydrogen atom, a fluorine atom, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring atom. It is a heterocyclic group of several 5 to 30, and any one of R 1 to R 12 is a single bond and is bonded to L 1 .
- L 1 is a single bond, a substituted or unsubstituted b + 1 valent hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted b + 1 valent heterocyclic group having 5 to 30 ring atoms.
- HAr is a substituted or unsubstituted nitrogen-containing heterocyclic group.
- a and b are each an integer of 1 to 4, and at least one of a and b is 1.
- the bonding position of L 1 with the benzophenanthrene moiety is preferably R 5 or R 8 . Since R 5 and R 8 are highly reactive bonding positions, the binding of L 1 and R 5 or L 1 and R 8 causes the nitrogen-containing heterocyclic derivative represented by the formula (1) to react with electrons. Can be more stable.
- the nitrogen-containing heterocyclic derivative of the present invention is represented by the following formula (21).
- any one of R 201 to R 214 is a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted carbon group having 3 to 8 carbon atoms, A cycloalkyl group, a substituted or unsubstituted alkylsilyl group having 3 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 8 to 30 ring carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 20 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having
- L 1 represents a single bond, a substituted or unsubstituted b + 1 valent hydrocarbon ring group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted b + 1 valent heterocyclic group having 5 to 30 ring atoms.
- HAr is a substituted or unsubstituted nitrogen-containing heterocyclic group.
- a and b are each an integer of 1 to 4, and at least one of a and b is 1.
- HAr when a is 2 or more, 2 or more HAr may be the same or different.
- b when b is 2 or more, the benzochrysene sites may be the same or different.
- the coupling position of the formula (21), and benzochrysene site of L 1 is preferably R 205. Since R 205 is a highly reactive bonding position, the nitrogen-containing heterocyclic derivative represented by the formula (21) can be more stable with respect to electrons by bonding L 1 and R 205 .
- the substituted or unsubstituted nitrogen-containing heterocyclic group of HAr in the formulas (1) and (21) is preferably any of nitrogen-containing heterocyclic groups represented by the following formulas (2) to (6), More preferably, it is any of nitrogen-containing heterocyclic groups represented by the following formulas (7) to (20).
- R 111 to R 130 are each a hydrogen atom or a substituent, or adjacent substituents of R 111 to R 130 are bonded together to form a saturated or unsaturated ring.
- any one of R 111 to R 115 , any one of R 116 to R 119 , any one of R 120 to R 122 , any one of R 123 to R 126 , and R 127 to Any one of R 130 is a single bond and is bonded to L 1 .
- any one of R substituted on the heterocyclic skeleton is a single bond and is bonded to L 1.
- the other R is a hydrogen atom or a substituent, or is bonded between adjacent Rs. To form a saturated or unsaturated ring.
- HAr include the following nitrogen-containing heterocyclic groups.
- the nitrogen-containing heterocyclic derivative of the present invention is represented by the following formula (31). (Wherein R 401 to R 416 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted.
- L 1 represents a single bond, a substituted or unsubstituted c + d valent hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted c + d valent heterocyclic group having 5 to 30 ring atoms.
- c and d each represent an integer of 1 to 3.
- L 1 and R 401 to R 416 are not anthracene-containing groups.
- c is preferably 1, and more preferably a nitrogen-containing heterocyclic derivative represented by the following formula (32).
- R 402 to R 416 , L 1 , and d represent the same groups as in formula (31).
- d is preferably 1, and more preferably a nitrogen-containing heterocyclic derivative represented by the following formula (33) or (34). (Wherein R 402 to R 414 , R 416 and L 1 represent the same group as in formula (31).)
- Examples of the aryl group having 6 to 30 ring carbon atoms of R 1 to R 12 , R 201 to R 214 and R 401 to R 416 include a phenyl group, a naphthyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a chrysenyl group, Examples thereof include a benzophenanthryl group, a benzanthryl group, a benzocrisenyl group, a fluorenyl group, and a fluoranthenyl group.
- R 401 to R 416 do not include an anthracene ring.
- Examples of the heterocyclic group having 5 to 30 ring atoms of R 1 to R 12 , R 201 to R 214 and R 401 to R 416 include pyridinyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, triazinyl group, indolinyl group, Quinolinyl, acridinyl, pyrrolidinyl, dioxanyl, piperidinyl, morpholyl, piperazinyl, carbazolyl, furanyl, thiophenyl, oxazolyl, oxadiazolyl, benzoxazolyl, thiazolyl, thiadiazolyl, benzothiazolyl , Triazolyl group, imidazolyl group, benzoimidazolyl group, benzofuranyl group, dibenzofuranyl group and the like.
- Examples of the alkyl group having 1 to 10 carbon atoms of R 201 to R 214 and R 401 to R 416 include an ethyl group, a methyl group, an i-propyl group, an n-propyl group, an s-butyl group, a t-butyl group, and pentyl. Group, hexyl group and the like.
- Examples of the cycloalkyl group having 3 to 8 carbon atoms of R 201 to R 214 and R 401 to R 416 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, and the like.
- Examples of the alkylsilyl group having 3 to 30 carbon atoms of R 201 to R 214 and R 401 to R 416 include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, and a propyldimethylsilyl group. It is done.
- Examples of the arylsilyl group having 8 to 30 ring carbon atoms of R 201 to R 214 and R 401 to R 416 include a triphenylsilyl group, a phenyldimethylsilyl group, a t-butyldiphenylsilyl group, a tolylsilylsilyl group, and a trixylyl group.
- a silyl group, a trinaphthyl silyl group, etc. are mentioned.
- the alkoxy group having 1 to 20 carbon atoms of R 201 to R 214 and R 401 to R 416 is a group represented by —OY, and examples of Y include the same examples as the above alkyl group.
- the aryloxy group having 6 to 20 ring carbon atoms of R 201 to R 214 and R 401 to R 416 is a group represented by —OAr, and examples of Ar are the same as the above aryl group.
- the alkylamino group and arylamino group of R 401 to R 416 are represented as —NY 1 Y 2, and examples of Y 1 and Y 2 include a hydrogen atom and the above examples of alkyl or aryl. Y 1 and Y 2 may be different from each other.
- Examples of the hydrocarbon ring group having 6 to 30 ring carbon atoms of L 1 include a divalent arylene group, such as a phenylene group, a naphthylene group, a biphenylene group, a terphenylene group, a picenylene group, a pyrenylene group, and a pentaphenylene group. Fluorenylene group, chrysenylene group and the like. When L 1 is trivalent or more, examples of L 1 include a residue corresponding to the divalent arylene group. However, L 1 in formula (31) does not include an anthracene ring.
- heterocyclic group having 5 to 30 ring atoms of L 1 for example, in the case of a divalent heterocyclic group, a pyridinylene group, a pyrazinylene group, a pyrimidinylene group, a pyridazinylene group, a triazinylene group, an indolenylene group, a quinolinylene group, an acridinylene group Group, pyrrolidinylene group, dioxanylene group, piperidinylene group, morpholinylene group, piperazinylene group, carbazolylene group, furanylene group, thiophenylene group, oxazolylene group, oxadiazolylene group, benzoxazolylene group, thiazolylene group, thiadiazolylene group, benzothiazolyl group
- Examples include a len group, a triazolylene group, an imidazolylene group, a benzimidazolylene group, a
- substituent for R examples include a halogen atom, a hydroxyl group, a cyano group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms.
- substituted or unsubstituted aryloxy group having 6 to 20 ring carbon atoms substituted or unsubstituted arylthio group having 6 to 20 ring carbon atoms, substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms Or a substituted or unsubstituted heterocyclic group having 5 to 50 ring-forming atoms.
- the substituent includes the above-described alkyl group, alkylsilyl group, halogen Alkyl group, aryl group, cycloalkyl group, alkoxy group, heterocyclic group, aralkyl group, aryloxy group, arylthio group, alkoxycarbonyl group, halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, dibenzofuranyl Group, fluorenyl group and the like.
- unsubstituted means that a hydrogen atom is substituted.
- the hydrogen atom of the nitrogen-containing heterocyclic derivative of the present invention includes light hydrogen and deuterium.
- the nitrogen-containing heterocyclic derivative of the present invention is preferably used as a material for an organic EL device, and more preferably used as a barrier material for an organic EL device.
- Benzophenanthrene, benzochrysene and fluoranthene which are the basic skeletons of the nitrogen-containing heterocyclic derivatives of the present invention, have high triplet energy and high triplet exciton confinement effect.
- the barrier layer in contact with the light emitting layer of the organic EL device By using it as a material, the TTF phenomenon can be promoted.
- benzophenanthrene, benzochrysene, and fluoranthene which are the basic skeletons of the nitrogen-containing heterocyclic derivatives of the present invention, have characteristics that molecular stacking in a thin film is improved due to high planarity, and electron mobility is increased. Therefore, it is possible to promote electron injection into the light emitting layer, increase the recombination efficiency in the light emitting layer, and efficiently cause the TTF phenomenon.
- the nitrogen-containing heterocyclic derivative of the present invention includes a nitrogen-containing heterocyclic ring having a high electron-injecting property from a metal-containing layer such as an electrode, an organic EL device with a low driving voltage can be formed without further stacking of an electron-injecting layer. Can be realized.
- the nitrogen-containing heterocyclic derivative of the present invention can be suitably used for the electron injection layer and / or the electron transport layer.
- the TTF phenomenon will be briefly described below.
- a voltage is applied to the organic EL element, electrons and holes are injected from the anode and the cathode, and the injected electrons and holes are recombined in the light emitting layer to generate excitons.
- the spin state is 25% for singlet excitons and 75% for triplet excitons.
- Conventionally known fluorescent elements emit light when singlet excitons relax to the ground state, but the remaining triplet excitons enter the ground state through a thermal deactivation process without emitting light.
- S.M. M.M. According to Bachilo et al. (J. Phys. Chem.
- the TTF phenomenon is a phenomenon in which singlet excitons are generated by collisional fusion of triplet excitons. If this TTF phenomenon is used, not only the 25% singlet excitons that are initially generated, but also triplet excitons Singlet excitons generated by collision fusion can also be used for light emission, and the light emission efficiency of the device can be increased.
- a barrier layer generally used for a phosphorescent element is adjacent to the light emitting layer of the fluorescent element, and the barrier layer contains the nitrogen-containing heterocyclic derivative of the present invention.
- a fluorescent element caused by singlet excitons having a short exciton lifetime it is common not to use a barrier layer that causes a process increase, but a barrier comprising the nitrogen-containing heterocyclic derivative of the present invention.
- the nitrogen-containing heterocyclic derivative of the present invention has a high triplet energy, the function of the barrier layer can be exhibited even in a conventional phosphorescent device, and diffusion of the triplet energy can be prevented.
- the term “barrier layer” means a layer having a barrier function against triplet energy, and its function is different from that of a hole barrier layer or a charge barrier layer.
- the barrier layer containing the nitrogen-containing heterocyclic derivative of the present invention preferably further contains a reducing dopant.
- the reducing dopant is preferably an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal It is one or more selected from the group consisting of oxides, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals.
- rubrene, anthracene, tetracene, pyrene, perylene and the like can be used, preferably an anthracene derivative, more preferably an anthracene derivative represented by the following formula (41).
- Ar 11 and Ar 12 are each a substituted or unsubstituted aryl group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms.
- R 301 to R 308 are each a hydrogen atom, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, or a substituted or unsubstituted carbon number.
- aryl group, heterocyclic group, alkyl group, cycloalkyl group, alkylsilyl group, arylsilyl group, alkoxy group, and aryloxy group include the above-described formulas (1), (21), and This is the same as the specific examples of R 1 to R 12 , R 201 to R 214 and R 401 to R 416 in the formula (31).
- the light emitting layer containing the anthracene derivative represented by the formula (41) is preferably in contact with the barrier layer containing the nitrogen-containing heterocyclic derivative of the present invention.
- the light emission efficiency can be increased by utilizing the TTF phenomenon.
- the triplet energy of the compound constituting the barrier layer comprising the nitrogen-containing heterocyclic derivative of the present invention must be higher than the triplet energy of the host mainly constituting the light emitting layer.
- the nitrogen-containing heterocyclic derivative of the present invention, the host and the dopant contained in the light emitting layer satisfy the following formulas (1) and (2).
- E T h, E T b, and E T d represent the triplet energy of the host material, the nitrogen-containing heterocyclic derivative of the barrier layer, and the dopant, respectively.
- FIG. 1 is a schematic configuration diagram of an organic EL element showing an example of the first embodiment of the present invention.
- FIG. 2A schematically shows the lowest excited singlet energy level and the lowest excited triplet energy level of each layer.
- the triplet energy means a difference between the energy in the lowest excited triplet state and the energy in the ground state
- the singlet energy (sometimes referred to as an energy gap) is the energy in the lowest excited singlet state and the ground state. This is the difference in energy.
- the organic EL element shown in FIG. 1 is laminated in order of the hole transport zone 50, the light emitting layer 20, the electron transport zone 30, and the cathode 40 in order from the anode 10.
- a hole transport zone 50 is preferably provided between the anode 10 and the light emitting layer 20.
- the electron transport zone has a configuration including only a barrier layer.
- the embodiment with only the barrier layer does not prevent the insertion of the electron injection layer having a higher injection property.
- the general compound conventionally used as an electron injection layer can be used, and a hetero ring-containing compound is preferable.
- FIG. 2A holes injected from the anode are injected into the light emitting layer through the hole transport band, and electrons injected from the cathode are injected into the light emitting layer through the electron transport band. Thereafter, holes and electrons are recombined in the light emitting layer, and singlet excitons and triplet excitons are generated.
- the triplet energies of the host and the dopant are E T h and E T d, respectively, it is preferable that the relationship E T h ⁇ E T d is satisfied.
- FIG. 2B triplet excitons generated by recombination on the host do not migrate to a dopant having a higher triplet energy.
- Triplet excitons generated by recombination on the dopant molecule rapidly transfer energy to the host molecule. That is, the triplet excitons collide with each other on the host efficiently by the TTF phenomenon without the host triplet excitons moving to the dopant, thereby generating singlet excitons. Furthermore, since the singlet energy E S d of the dopant is smaller than the singlet energy E S h of the host, singlet excitons generated by the TTF phenomenon transfer energy from the host to the dopant and contribute to the fluorescence emission of the dopant. To do. Originally, in a dopant used in a fluorescent element, a transition from an excited triplet state to a ground state is forbidden.
- the triplet exciton does not undergo optical energy deactivation and is thermally depleted. It was alive.
- the relationship between the triplet energy of the host and the dopant as described above singlet excitons are efficiently generated by collision with each other before the triplet excitons are thermally deactivated, and the luminous efficiency is increased. Will improve.
- a barrier layer is provided adjacent to the light emitting layer.
- the barrier layer prevents the triplet excitons generated in the light emitting layer from diffusing into the electron transport band, and increases the density of the triplet excitons by confining the triplet excitons in the light emitting layer, thereby improving the efficiency of the TTF phenomenon. Has the function to cause well.
- the triplet energy E T b of the compound constituting the barrier layer is preferably larger than E T h and more preferably larger than E T d.
- the barrier layer prevents triplet excitons generated in the light-emitting layer from diffusing into the electron transport band, so that the host triplet excitons efficiently become singlet excitons in the light-emitting layer.
- the exciton moves onto the dopant and is optically deactivated.
- the material forming the barrier layer is the nitrogen-containing heterocyclic derivative of the present invention.
- the barrier layer containing the nitrogen-containing heterocyclic derivative of the present invention can also serve as an electron injection / transport function.
- the unshared electron pair mediates transfer of electrons from the adjacent layer.
- the electrons injected into the barrier material are more likely to donate electrons through the electron transport structure site. That is, by moving to a structural portion having a low LUMO level, it contributes to electron injection into the light emitting layer.
- a low work function metal-containing layer may be provided between the electron transport zone and the cathode.
- the low work function metal-containing layer is a layer containing a low work function metal or a low work function metal compound. Even if it is formed of only a low work function metal or a low work metal compound, it is formed by adding a low work function metal, a low work function metal compound, or a low work function metal complex as a donor to the material used for the electron transport layer. May be.
- a low work function metal means a metal having a work function of 3.8 eV or less. Examples of the metal having a low work function of 3.8 eV or less include alkali metals and alkaline earth metals. Examples of the alkali metal include Li, Na, K, and Cs.
- alkaline earth metal examples include Mg, Ca, Sr, and Ba. Other examples include Yb, Eu and Ce.
- the oxide, halide, carbonate, borate of a low work metal function is preferable.
- Halides include fluoride, chloride and bromide, with fluoride being preferred.
- LiF is preferably used.
- the low work function metal complex is a low work function metal complex, and an alkali metal, alkaline earth metal, or rare earth metal organometallic complex is preferable.
- the triplet energy can be confined in the light emitting layer to improve the light emitting efficiency.
- the phosphorescent light emitting layer an effect of confining triplet energy in the light emitting layer can be obtained, diffusion of the triplet energy can be prevented, and the emission efficiency of the phosphorescent dopant can be improved.
- a substrate, an anode, a cathode, a hole injection layer, and a hole transport layer of the organic EL device of the present invention are PCT / JP2009 / 053247, PCT / JP2008 / 073180, US Patent Application No. 12 / 376,236, Known ones described in US Patent Application No. 11 / 766,281, US Patent Application No. 12 / 280,364, etc. can be appropriately selected and used.
- Synthesis example 1 (A) Synthesis of benzo [c] phenanthrene-5-boronic acid According to the following scheme, benzo [c] phenanthrene-5-boronic acid was synthesized.
- Synthesis example 7 (G) Synthesis of 2- (3-bromophenyl) -imidazo [1,2-a] pyridine As shown in the following synthesis scheme, 3-bromophenacyl bromide was used instead of 4-bromophenacyl bromide. Others were reacted in the same manner as in Synthesis Example 6 to synthesize 2- (3-bromophenyl) -imidazo [1,2-a] pyridine.
- reaction solution was stirred for 5 hours while warming to room temperature.
- the reaction solution was acidified with 2M hydrochloric acid, and the reaction solution was extracted with ethyl acetate. The aqueous layer was removed and the organic layer was washed with saturated brine and then dried over anhydrous sodium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was washed with a hexane-ethyl acetate mixed solution to obtain 7.9 g of the desired 4- (fluoranthen-3-yl) phenylboronic acid (yield 95%).
- Synthesis Example 9 (I) Synthesis of 3- (fluoranthen-3-yl) phenylboronic acid As shown in the following synthesis scheme, as in Synthesis Example 8, except that 3-iodobromobenzene was used instead of 4-bromoiodobenzene. Reaction was performed to synthesize 3- (fluoranthen-3-yl) phenylboronic acid.
- Example 11 Under an argon atmosphere, 2.7 g of fluoranthene-3-boronic acid, 3.5 g of 1- (4-bromophenyl) -2-phenyl-1H-benzimidazole synthesized in Synthesis Example 3, tetrakis (triphenylphosphine) palladium (0 ) 0.231 g, dimethoxyethane 40 mL, 2 M aqueous sodium carbonate solution 20 mL were charged into a flask, and the mixture was heated to reflux with stirring for 8 hours. After cooling to room temperature, the reaction solution was extracted with toluene. After removing the aqueous layer, the organic layer was washed with water and then dried over magnesium sulfate.
- Example 12 1- (3-bromophenyl) -2-phenyl-1H-benzimidazole synthesized in Synthesis Example 4 instead of 1- (4-bromophenyl) -2-phenyl-1H-benzimidazole in the synthesis of Compound 11 above
- the compound was synthesized in the same manner except that was used.
- Example 18 Benzo [g] chrysene-10-boronic acid is used in place of benzo [c] phenanthrene-5-boronic acid, and 6-bromo-in place of 1- (4-bromophenyl) -2-phenyl-1H-benzimidazole
- the reaction was conducted in the same manner as in Example 1 except that 2,2′-bipyridyl was used.
- Example 19 The materials used for the organic EL element are as follows.
- Emission ratio derived from TTF A voltage pulse waveform (pulse width: 500 microseconds, frequency: 20 Hz) output from a pulse generator (Agilent 8114A) is applied to the device, and EL emission is emitted from a photomultiplier tube (Hamamatsu Photonics). R928) manufactured by the company, and the pulse voltage waveform and the EL emission were synchronized with each other and taken in an oscilloscope (Tektronix 2440) to obtain a transient EL waveform. This was analyzed to determine the TTF-derived emission ratio (TTF ratio) (see Japanese Patent Application No. 2009-125883).
- TTF ratio TTF-derived emission ratio
- the transient EL waveform was obtained by obtaining the current density when the current efficiency (L / J) is maximum in the current density-current efficiency curve and applying a voltage pulse waveform corresponding to the current density. It should be noted that the improvement of internal quantum efficiency due to the TTF phenomenon is considered to be a theoretical limit of 62.5%, and in this case the emission ratio derived from TTF is 60%.
- Examples 20 to 27 and Comparative Examples 1 and 2 An organic EL device was prepared and evaluated in the same manner as in Example 19 except that the compounds shown in Table 1 were used as the host material, dopant material, and barrier layer material of the light emitting layer. The results are shown in Table 1.
- the organic EL device comprising the nitrogen-containing heterocyclic derivative of the present invention can be used for a display panel or a lighting panel for a large-sized television where low power consumption is desired.
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Abstract
Description
一方、蛍光型有機EL素子においても、三重項励起子に起因する発光が近年報告がされている(例えば、非特許文献1及び2、特許文献3)。
また、本発明の目的は、TTF現象を促進するために最適な障壁材料を提供することである。
1.下記式(1)で表される含窒素複素環誘導体。
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のb+1価の炭化水素環基、又は置換もしくは無置換の環形成原子数5~30のb+1価の複素環基である。
HArは、置換もしくは無置換の含窒素複素環基である。
a及びbは、それぞれ1~4の整数であり、a及びbの少なくとも一方は1である。)
2.HArが、下記式(2)~(6)で表される含窒素複素環基のいずれかである1に記載の含窒素複素環誘導体。
但し、R111~R115のいずれか1つ、R116~R119のいずれか1つ、R120~R122のいずれか1つ、R123~R126のいずれか1つ、及びR127~R130のいずれか1つは単結合であり、L1と結合する。)
3.HArが、下記式(7)~(20)で表される含窒素複素環基のいずれかである1又は2に記載の含窒素複素環誘導体。
4.aが1であり、bが1である1~3のいずれかに記載の含窒素複素環誘導体。
5.下記式(21)で表される含窒素複素環誘導体。
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のb+1価の炭化水素環基、又は置換もしくは無置換の環形成原子数5~30のb+1価の複素環基を示す。
HArは、置換もしくは無置換の含窒素複素環基である。
a及びbは、それぞれ1~4の整数であり、a及びbの少なくとも一方は1である。)
6.HArが、下記式(2)~(6)で表される含窒素複素環基のいずれかである5に記載の含窒素複素環誘導体。
但し、R111~R115のいずれか1つ、R116~R119のいずれか1つ、R120~R122のいずれか1つ、R123~R126のいずれか1つ、及びR127~R130のいずれか1つは単結合であり、L1と結合する。)
7.HArが、下記式(7)~(20)で表される含窒素複素環基のいずれかである5又は6に記載の含窒素複素環誘導体。
8.aが1であり、bが1である5~7のいずれかに記載の含窒素複素環誘導体。
9.下記式(31)で表される含窒素複素環誘導体。
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のc+d価の炭化水素基、又は置換もしくは無置換の環形成原子数5~30のc+d価の複素環基を示す。
c及びdはそれぞれ1~3の整数を示す。
但し、L1、R401~R416はアントラセン含有基ではない。)
10.cが1である9に記載の含窒素複素環誘導体。
11.下記式(32)で表される9又は10に記載の含窒素複素環誘導体。
12.dが1である11に記載の含窒素複素環誘導体。
13.下記式(33)又は(34)で表される12に記載の含窒素複素環誘導体。
14.有機エレクトロルミネッセンス素子用材料である1~13のいずれかに記載の含窒素複素環誘導体。
15.前記有機エレクトロルミネッセンス素子用材料が、障壁層材料である14に記載の含窒素複素環誘導体。
16.陽極、発光層、障壁層、及び陰極をこの順に備え、
前記障壁層が1~13のいずれかに記載の含窒素複素環誘導体を含有する有機エレクトロルミネッセンス素子。
17.発光層と陰極との間に、電子注入層及び/又は電子輸送層を有し、前記電子注入層及び電子輸送層の少なくとも1層が1~13のいずれかに記載の含窒素複素環誘導体を含有する有機エレクトロルミネッセンス素子。
18.前記発光層が、下記式(41)で表されるアントラセン誘導体を含む16又は17に記載の有機エレクトロルミネッセンス素子。
R301~R308は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基である。)
19.前記式(41)で表されるアントラセン誘導体を含有する発光層が、前記含窒素複素環誘導体を含有する障壁層と接している18に記載の有機エレクトロルミネッセンス素子。
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のb+1価の炭化水素環基、又は置換もしくは無置換の環形成原子数5~30のb+1価の複素環基である。
HArは、置換もしくは無置換の含窒素複素環基である。
a及びbは、それぞれ1~4の整数であり、a及びbの少なくとも一方は1である。)
また、式(1)において、L1のベンゾフェナントレン部位との結合位置は、好ましくはR5又はR8である。R5及びR8は反応性の高い結合位置であるため、L1とR5又はL1とR8が結合することにより、式(1)で表される含窒素複素環誘導体は電子に対してより安定となることができる。
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のb+1価の炭化水素環基、又は置換もしくは無置換の環形成原子数5~30のb+1価の複素環基を示す。
HArは、置換もしくは無置換の含窒素複素環基である。
a及びbは、それぞれ1~4の整数であり、a及びbの少なくとも一方は1である。)
また、式(21)において、L1のベンゾクリセン部位との結合位置は、好ましくはR205である。R205は反応性の高い結合位置であるため、L1とR205が結合することにより、式(21)で表される含窒素複素環誘導体は電子に対してより安定となることができる。
但し、R111~R115のいずれか1つ、R116~R119のいずれか1つ、R120~R122のいずれか1つ、R123~R126のいずれか1つ、及びR127~R130のいずれか1つは単結合であり、L1と結合する。)
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のc+d価の炭化水素基、又は置換もしくは無置換の環形成原子数5~30のc+d価の複素環基を示す。
c及びdはそれぞれ1~3の整数を示す。
但し、L1、R401~R416はアントラセン含有基ではない。)
R1~R12、R201~R214及びR401~R416の環形成炭素数6~30のアリール基としては、フェニル基、ナフチル基、フェナントリル基、ビフェニル基、ターフェニル基、クリセニル基、ベンゾフェナントリル基、ベンズアントリル基、ベンゾクリセニル基、フルオレニル基、フルオランテニル基等が挙げられる。
但し、R401~R416はアントラセン環は含まない。
L1が3価以上の場合、当該L1は、上記2価のアリーレン基に対応する残基が挙げられる。
但し、式(31)のL1は、アントラセン環を含まない。
L1が3価以上の場合、当該L1は、上記2価の複素環基に対応する残基が挙げられる。
本発明の含窒素複素環誘導体の基本骨格であるベンゾフェナントレン、ベンゾクリセン及びフルオランテンは三重項エネルギーが高く、三重項励起子の閉じ込め効果が高いため、例えば有機EL素子の発光層に接した障壁層の材料として利用することによって、TTF現象を促進させることができる。また、本発明の含窒素複素環誘導体の基本骨格であるベンゾフェナントレン、ベンゾクリセン及びフルオランテンは、その平面性の高さによって薄膜中での分子スタッキングが向上し、電子移動度が大きくなるという特徴を持つため、発光層への電子注入を促進し、発光層での再結合効率を高め、TTF現象を効率的に起こすことができる。さらに、本発明の含窒素複素環誘導体は、電極等の金属含有層からの電子注入性の高い含窒素複素環を含むため、電子注入層をさらに積層させることなく低駆動電圧の有機EL素子を実現させることができる。
尚、電子注入層及び/又は電子輸送層にも本発明の含窒素複素環誘導体は好適に使用できる。
有機EL素子に電圧を印加すると、陽極、陰極から電子と正孔が注入され、注入された電子と正孔は発光層内で再結合し励起子を生成する。そのスピン状態は、一重項励起子が25%、三重項励起子が75%である。従来知られている蛍光素子においては、一重項励起子が基底状態に緩和するときに光を発するが、残りの三重項励起子については光を発することなく熱的失活過程を経て基底状態に戻る。しかしながら、S.M.Bachiloらによれば(J.Phys.Cem.A,104,7711(2000))、当初生成した75%の三重項励起子のうち、1/5が一重項励起子に変化する。
TTF現象とは三重項励起子の衝突融合により一重項励起子が生成する現象であり、このTTF現象を利用すれば、当初生成する25%の一重項励起子だけでなく、三重項励起子の衝突融合により生じる一重項励起子も発光に利用でき、素子の発光効率を高めることができる。
本発明では、燐光素子に一般に用いる障壁層を蛍光素子の発光層にも隣接させ、当該障壁層が本発明の含窒素複素環誘導体を含有することが好ましい。励起子寿命が短い一重項励起子を起因とする蛍光素子においては、プロセスアップの原因となる障壁層を利用しないのが一般的であるが、本発明の含窒素複素環誘導体を含んでなる障壁層を蛍光素子に用いることによってTTF現象を引き起こし、高効率な有機EL素子を実現することができる。また、本発明の含窒素複素環誘導体は三重項エネルギーが高いため、従来の燐光素子においても障壁層の機能を発揮し、三重項エネルギーの拡散を防ぐことができる。
尚、本発明において単に障壁層といったときは三重項エネルギーに対する障壁機能を有する層をいうものとし、正孔障壁層や電荷障壁層とはその機能が異なる。
上記還元性ドーパントは、好ましくはアルカリ金属、アルカリ土類金属、希土類金属、アルカリ金属の酸化物、アルカリ金属のハロゲン化物、アルカリ土類金属の酸化物、アルカリ土類金属のハロゲン化物、希土類金属の酸化物、希土類金属のハロゲン化物、アルカリ金属の有機錯体、アルカリ土類金属の有機錯体及び希土類金属の有機錯体からなる群から選択される1種又は2種以上である。
R301~R308は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基である。)
尚、上記のアリール基、複素環基、アルキル基、シクロアルキル基、アルキルシリル基、アリールシリル基、アルコキシ基、及びアリールオキシ基の具体例は、上述した式(1)、式(21)及び式(31)のR1~R12、R201~R214及びR401~R416等の具体例と同様である。
ETb>ETh・・・(1)
ETd>ETh・・・(2)
(ETh、ETb及びETdは、それぞれホスト材料、障壁層の含窒素複素環誘導体及びドーパントの三重項エネルギーを示す。)
本発明の含窒素複素環誘導体を含む障壁層は、電子注入・輸送機能の役割も果たすことができる。これは、非共有電子対が隣接層からの電子の授受を媒介するためである。次に、障壁材料に注入された電子は、電子輸送構造部位を介してより電子を供与しやすい。即ちLUMO準位の低い構造部位へと移動することによって、発光層への電子注入に寄与することとなる。
燐光発光層においては、三重項エネルギーを発光層内に閉じ込める効果を得ることが可能であり、三重項エネルギーの拡散を防ぎ、燐光発光性ドーパントの発光効率の向上に寄与できる。
アルゴン雰囲気下、1,4-ジブロモナフタレン230g、2-ホルミルフェニルボロン酸121g、及びテトラキス(トリフェニルホスフィン)パラジウム(0)18.5gをフラスコに仕込み、ジメトキシエタン(DME)2.4L、2M炭酸ナトリウム水溶液1.2Lを加え、8時間加熱還流攪拌した。室温まで冷却後、水層を除去し、有機層を水、飽和食塩水で洗浄して、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。残渣をシリカゲルカラムクロマトグラフィで精製し、目的の1-ブロモ-4-(2-ホルミルフェニル)ナフタレン170g(収率67%)を得た。
アルゴン雰囲気下、1-ブロモ-4-(2-ホルミルフェニル)ナフタレン170g、メトキシメチルトリフェニルホスフォニウムクロリド207g、及びテトラヒドロフラン(THF)2.0Lを仕込み、室温にて攪拌中に、t-ブトキシカリウム73.6gを加えた。室温にて2時間攪拌した後、水1.5Lを加えた。反応溶液をジエチルエーテルで抽出し、水層を除去した。有機層を水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。残渣をシリカゲルカラムクロマトグラフィで精製し、目的の1-ブロモ-4-[2-(2-メトキシビニル)フェニル]ナフタレン180g(収率99%)を得た。
1-ブロモ-4-[2-(2-メトキシビニル)フェニル]ナフタレン180g、及びジクロロメタン1.0Lを仕込み、室温下攪拌中にメタンスルホン酸を25mL加えた。室温で8時間攪拌を続けた。反応終了後10%炭酸カリウム水溶液1Lを加えた。水層を除去し、有機層を水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。残渣をシリカゲルカラムクロマトグラフィで精製し、目的の5-ブロモベンゾ[c]フェナントレン24.4g(収率15%)を得た。
アルゴン雰囲気下、5-ブロモベンゾ[c]フェナントレン10.1gをフラスコに仕込み、脱水エーテル400mLを加えた。反応溶液を-40℃まで冷却し、1.6M n-ブチルリチウムのヘキサン溶液22mLを加え、0℃まで昇温し、1時間攪拌した。反応溶液を-60℃まで冷却し、ホウ酸トリイソプロピル14.4gの脱水エーテル10mL溶液を滴下した。反応溶液を室温まで昇温しながら5時間攪拌を続けた。10%塩酸水溶液100mLを加え、1時間攪拌した。水層を除去し、有機層を水、飽和食塩水で洗浄後、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。得られた固体をヘキサンで洗浄し、目的のベンゾ[c]フェナントレン-5-ボロン酸5.37g(収率60%)を得た。
アルゴン雰囲気下、9-ブロモフェナントレン25.7g、2-ホルミルフェニルボロン酸16.5g、及びテトラキス(トリフェニルホスフィン)パラジウム(0)2.31gをフラスコに仕込み、DME340mL、2M炭酸ナトリウム水溶液170mLを加え、8時間加熱還流攪拌した。室温まで冷却後、水層を除去した。有機層を水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。残渣をシリカゲルカラムクロマトグラフィで精製し、目的の9-(2-ホルミルフェニル)フェナントレン25.0g(収率89%)を得た。
アルゴン雰囲気下、9-(2-ホルミルフェニル)フェナントレン25.0g、メトキシメチルトリフェニルホスフォニウムクロリド33.4g、及びTHF300mLを仕込み、室温にて攪拌中に、t-ブトキシカリウム11.9gを加えた。室温にて2時間攪拌した後、水200mLを加えた。反応溶液をジエチルエーテルで抽出し、水層を除去した。有機層を水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。残渣をシリカゲルカラムクロマトグラフィで精製し、目的の9-[2-(2-メトキシビニル)フェニル]フェナントレン24.0g(収率87%)を得た。
9-[2-(2-メトキシビニル)フェニル]フェナントレン24.0g、及びジクロロメタン100mLを仕込み、室温下攪拌中にメタンスルホン酸をパスツールピペットで6滴加えた。室温で8時間攪拌を続けた。反応終了後10%炭酸カリウム水溶液100mLを加えた。水層を除去し、有機層を水、飽和食塩水で洗浄した後、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。残渣をシリカゲルカラムクロマトグラフィで精製し、目的のベンゾ[g]クリセン5.21g(収率25%)を得た。
ベンゾ[g]クリセン5.21g、及びN,N-ジメチルホルムアミド50mLをフラスコに仕込み、N-ブロモスクシンイミド4.00gのN,N-ジメチルホルムアミド10mL溶液を加えた。80℃で8時間加熱攪拌した。室温まで冷却後、反応溶液を水200mL中に注いだ。析出した固体を濾取し、水、メタノールで洗浄した。得られた個体をシリカゲルカラムクロマトグラフィで精製し、10-ブロモベンゾ[g]クリセン5.87g(収率88%)を得た。
アルゴン雰囲気下、10-ブロモベンゾ[g]クリセン5.87gをフラスコに仕込み、脱水エーテル100mLを加えた。反応溶液を-40℃まで冷却し、1.6M n-ブチルリチウムのヘキサン溶液11mLを加え、0℃まで昇温し、1時間攪拌した。反応溶液を-60℃まで冷却し、ホウ酸トリイソプロピル7.72gの脱水エーテル10mL溶液を滴下した。反応溶液を室温まで昇温しながら5時間攪拌を続けた。10%塩酸水溶液50mLを加え、1時間攪拌した。水層を除去し、有機層を水、飽和食塩水で洗浄後、硫酸マグネシウムで乾燥させた。硫酸マグネシウムを濾別後、有機層を濃縮した。得られた固体をヘキサンで洗浄し、目的のベンゾ[g]クリセン-10-ボロン酸3.18g(収率60%)を得た。
2-ブロモニトロベンゼン10g(49.5mmol)、酢酸ナトリウム13g(163mmol)、及び4-ブロモアニリン10g(59mmol)をアルゴン雰囲気下180℃で8時間加熱攪拌した。反応溶液を室温まで冷却し、酢酸エチルで薄め、ろ過した。ろ液を濃縮後、残査をメタノールで洗浄することで、(4-ブロモフェニル)-(2-ニトロフェニル)アミン3.8gをオレンジ色結晶として得た(収率22%)。
(4-ブロモフェニル)-(2-ニトロフェニル)アミン3.8g(13mmol)をテトラヒドロフラン30mLに溶解させ、アルゴン雰囲気下、室温で攪拌しているところに、ハイドロサルファイトナトリウム11g(64mmol)/水30mLの溶液を滴下した。5時間攪拌した後、酢酸エチル20mLを加えて、炭酸水素ナトリウム2.2g(26mmol)/水20mLの溶液を加えた。さらにベンゾイルクロリド2.5g(18mmol)/酢酸エチル10mLの溶液を滴下し、室温で1時間攪拌した。酢酸エチルで抽出し、10%炭酸カリウム水溶液、水、飽和食塩水で順次洗浄した後、無水硫酸ナトリウムで乾燥し、溶媒を減圧留去し、N-[2-(4-ブロモフェニルアミノ)フェニル]ベンズアミド2.1g(収率45%)を得た。
N-[2-(4-ブロモフェニルアミノ)フェニル]ベンズアミド2.1g(5.7mmol)をキシレン30mL中に懸濁させ、p-トルエンスルホン酸1水和物0.6g(2.9mmol)を加え、3時間加熱還流させながら共沸脱水を行った。放冷後、反応溶液に酢酸エチル、塩化メチレン、水を加え、不溶物をろ別した。母液から有機層を抽出し、水、飽和食塩水で洗浄後、無水硫酸ナトリウムで乾燥し、溶媒を減圧留去した。残査をシリカゲルカラムクロマトグラフィにて精製し、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾール1.0gをわずかにピンク色の白色結晶として得た(収率52%)
(D)1-(3-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの合成
下記合成スキームに示されるように、4-ブロモアニリンの代わりに3-ブロモアニリンを用いた他は合成例3と同様に反応を行なって、1-(3-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールを合成した。
N-メチル-2-ニトロアニリン5.0g(33mmol)、及びN-ブロモスクシンイミド5.9g(33mmol)に酢酸60mLを加え、7時間加熱還流を行った。反応終了後、反応溶液を水500mLに注ぎ、析出した固体をろ別した。ろ別した固体を酢酸エチルに溶解させ、硫酸マグネシウムで乾燥させた。ろ過後、溶媒を減圧留去し、室温で減圧乾燥後、4-ブロモ-N-メチル-2-ニトロアニリンの橙色固体7.1g(収率93%)を得た。
4-ブロモ-N-メチル-2-ニトロアニリン6.8g(29mmol)をピリジン20mLに溶解させ、さらにベンゾイルクロライド5.0g(35mmol)を加え、アルゴン雰囲気下、90℃で7時間加熱攪拌した。反応終了後、酢酸エチル200mLを加え、有機層を10%塩酸水溶液、10%炭酸カリウム水溶液、飽和食塩水で洗浄後、硫酸マグネシウムで乾燥させた。ろ過後、溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィで精製し、4’-ブロモ-N-メチル-2’-ニトロベンズアニリドの緑白色固体9.5g(収率96%)を得た。
4’-ブロモ-N-メチル-2’-ニトロベンズアニリド9.5g(28mmol)をテトラヒドロフラン100mLに溶解させ、アルゴン雰囲気下、室温で攪拌させながらハイドロサルファイトナトリウム25g(142mmol)/水90mLの溶液を加えた。さらにメタノール10mLを加えて3時間攪拌させた。次に酢酸エチル100mLを加え、炭酸水素ナトリウム12g(142mmol)/水125mLの溶液を加えた。1時間室温で攪拌後、酢酸エチルで抽出した。水層を除去し、有機層を10%炭酸カリウム水溶液、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥させた。ろ過後、溶媒を減圧留去させ、4’-ブロモ-N-メチル-2’-アミノベンズアニリドの白色固体7.8g(収率90%)を得た。
4’-ブロモ-N-メチル-2’-アミノベンズアニリド7.8g(26mmol)をキシレン50mL中に懸濁させ、p-トルエンスルホン酸1水和物1.5g(7.7mmol)を加え、7時間加熱還流させた。反応終了後ろ過した。得られた固体を塩化メチレンに溶解させ、10%炭酸カリウム水溶液、飽和食塩水で洗浄し、硫酸マグネシウムで乾燥後、溶媒を減圧留去した。ろ液からも同様の洗浄方法で有機物を回収し、合わせてシリカゲルカラムクロマトグラフィで精製し、5-ブロモ-1-メチル-2-フェニル-1H-ベンズイミダゾールの白色結晶6.5g(収率89%)を得た。
(F)2-(4-ブロモフェニル)-イミダゾ[1,2-a]ピリジンの合成
4-ブロモフェナシルブロミド15g(54mmol)、及び2-アミノピリジン5.2g(55mmol)をエタノール100mLに溶解し、炭酸水素ナトリウム7.0gを加え、6時間加熱還流した。反応終了後、生成した結晶をろ別し、水、エタノールで洗浄し、2-(4-ブロモ-フェニル)-イミダゾ[1,2-a]ピリジン12.5g(収率85%)を得た。
(G)2-(3-ブロモフェニル)-イミダゾ[1,2-a]ピリジンの合成
下記合成スキームに示されるように、4-ブロモフェナシルブロミドの代わりに3-ブロモフェナシルブロミドを用いた他は合成例6と同様に反応を行って、2-(3-ブロモフェニル)-イミダゾ[1,2-a]ピリジンを合成した。
アルゴン雰囲気下、フルオランテン-3-ボロン酸9.1g、4-ブロモヨードベンゼン10.5g、テトラキス(トリフェニルホスフィン)パラジウム(0)2.1g、トルエン186mL、2M炭酸ナトリウム水溶液74mLをフラスコに仕込み、100℃にて8時間攪拌を行った。室温まで冷却後、反応溶液をトルエンで抽出した。水層を除去し有機層を飽和食塩水で洗浄した後、無水硫酸ナトリウムで乾燥させた。ろ過後、溶媒を減圧留去し残渣をシリカゲルクロマトグラフィで精製し、目的の3-(4-ブロモフェニル)フルオランテン9.2g(収率70%)を得た。
アルゴン雰囲気下、3-(4-ブロモフェニル)フルオランテン9.2g、テトラヒドロフラン129mLをフラスコに仕込み、反応溶液を-70℃に冷却し、1.65M n-ブチルリチウムのヘキサン溶液を17.2mL滴下し、-70℃にて2時間攪拌を行った。反応溶液にホウ酸トリイソプロピル17.7mLを滴下し、-70℃にて1時間攪拌した後、反応溶液を室温まで昇温しながら5時間攪拌した。反応液に2M塩酸を加えて酸性にした後、反応溶液を酢酸エチルで抽出した。水層を除去し有機層を飽和食塩水で洗浄した後、無水硫酸ナトリウムで乾燥させた。ろ過後、溶媒を減圧留去し残渣をヘキサン-酢酸エチル混合溶液で洗浄し、目的の4-(フルオランテン-3-イル)フェニルボロン酸7.9g(収率95%)を得た。
(I)3-(フルオランテン-3-イル)フェニルボロン酸の合成
下記合成スキームに示されるように、4-ブロモヨードベンゼンの代わりに3-ヨードブロモベンゼンを用いたほかは合成例8と同様に反応を行って、3-(フルオランテン-3-イル)フェニルボロン酸を合成した。
(J)6-(フルオランテン-3-イル)ナフタレン-2-イルボロン酸ピナコールエステルの合成
下記合成スキームに従って、6-(フルオランテン-3-イル)ナフタレン-2-イルボロン酸ピナコールエステルを合成した。
アルゴン雰囲気下、フルオランテン-3-ボロン酸2.7g、6-ブロモ-2-ナフトール2.0g、テトラキス(トリフェニルホスフィン)パラジウム(0)0.31g、1,2-ジメトキシエタン27mL、2M炭酸ナトリウム水溶液13.5mLをフラスコに仕込み、4時間加熱還流攪拌を行った。室温まで冷却後、反応溶液に2M塩酸を加えて酸性にした後、ジクロロメタンで抽出した。水層を除去し有機層を飽和食塩水で洗浄した後、無水硫酸ナトリウムで乾燥させた。ろ過後、溶媒を減圧留去し、残渣をジクロロメタン中で分散洗浄し、目的の6-(フルオランテン-3-イル)-2-ナフトール2.75g(収率89%)を得た。
アルゴン雰囲気下、6-(フルオランテン-3-イル)-2-ナフトール2.75g、ピリジン2mL、ジクロロメタン80mLをフラスコに仕込んだ。反応液に氷冷下、トリフルオロメタンスルホン酸無水物2mLを滴下し、20分間攪拌した後、室温に昇温しながら3時間攪拌を行った。反応液にトリフルオロメタンスルホン酸0.5mL滴下し、30分間攪拌を行った。反応液に慎重に水を滴下して反応をクエンチした後、0.5M塩酸200mLを加え、ジクロロメタンで抽出を行った。水層を除去し有機層を無水硫酸ナトリウムで乾燥させた。ろ過後、溶媒を減圧留去し、残渣をトルエンにて再結晶を行い、目的の6-(フルオランテン-3-イル)-2-トリフルオロメタンスルホキシナフタレン3.11g(収率82%)を得た。
アルゴン雰囲気下、6-(フルオランテン-3-イル)-2-トリフルオロメタンスルホキシナフタレン3.11g、ビスピナコラートジボロン1.83g、[1,1’-ビス(ジフェニルホスフィノ)フェロセン]パラジウム(II)ジクロリドジクロロメタン付加物(0.27g)、1,1’-ビス(ジフェニルホスフィノ)フェロセン(0.18g)、酢酸カリウム(1.93g)、ジメチルホルムアミド65mLをフラスコに仕込み、80℃にて8時間攪拌を行った。室温まで冷却後、反応液に水を加えた後、混合物をトルエンで抽出した。得られたトルエン溶液をシリカゲルショートカラムに通し、溶出液の溶媒を減圧留去した。残渣をトルエンより再結晶し、目的の6-(フルオランテン-3-イル)ナフタレン-2-イルボロン酸ピナコールエステル1.53g(収率52%)を得た。
実施例1
アルゴン雰囲気下、ベンゾ[c]フェナントレン-5-ボロン酸3.0g、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾール3.5g、テトラキス(トリフェニルホスフィン)パラジウム(0)0.231g、ジメトキシエタン40mL、及び2M炭酸ナトリウム水溶液20mLをフラスコに仕込み、8時間加熱還流攪拌した。室温まで冷却後、反応溶液をトルエンで抽出した。水層を除去した後、有機層を水で洗浄した後、硫酸マグネシウムで乾燥させた。ろ過後、溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィで精製し、淡黄色固体3.8gを得た。得られた化合物は、マススペクトル分析の結果、下記化合物1であり、分子量496.19に対し、m/e=496であった。
1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに1-(3-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物2であり、分子量496.19に対し、m/e=496であった。
1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに5-ブロモ-1-メチル-2-フェニル-1H-ベンズイミダゾールを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物3であり、分子量434.18に対し、m/e=434であった。
1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに2-(4-ブロモフェニル)-イミダゾ[1,2-a]ピリジンを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物4であり、分子量420.16に対し、m/e=420であった。
1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに2-(3-ブロモフェニル)-イミダゾ[1,2-a]ピリジンを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物5であり、分子量420.16に対し、m/e=420であった。
ベンゾ[c]フェナントレン-5-ボロン酸の代わりにベンゾ[g]クリセン-10-ボロン酸を用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物6であり、分子量546.21に対し、m/e=546であった。
ベンゾ[c]フェナントレン-5-ボロン酸の代わりにベンゾ[g]クリセン-10-ボロン酸を用い、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに1-(3-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物7であり、分子量546.21に対し、m/e=546であった。
ベンゾ[c]フェナントレン-5-ボロン酸の代わりにベンゾ[g]クリセン-10-ボロン酸を用い、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに5-ブロモ-1-メチル-2-フェニル-1H-ベンズイミダゾールを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物8であり、分子量484.19に対し、m/e=484であった。
ベンゾ[c]フェナントレン-5-ボロン酸の代わりにベンゾ[g]クリセン-10-ボロン酸を用い、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに2-(4-ブロモフェニル)-イミダゾ[1,2-a]ピリジンを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物9であり、分子量470.18に対し、m/e=470であった。
ベンゾ[c]フェナントレン-5-ボロン酸の代わりにベンゾ[g]クリセン-10-ボロン酸を用い、1-(3-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに2-(4-ブロモフェニル)-イミダゾ[1,2-a]ピリジンを用いた他は実施例1と同様に反応を行なった。
得られた化合物は、マススペクトル分析の結果、下記化合物10であり、分子量470.18に対し、m/e=470であった。
アルゴン雰囲気下、フルオランテン-3-ボロン酸2.7g、合成例3で合成した1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾール3.5g、テトラキス(トリフェニルホスフィン)パラジウム(0)0.231g、ジメトキシエタン40mL、2M炭酸ナトリウム水溶液20mLをフラスコに仕込み、8時間加熱還流攪拌した。室温まで冷却後、反応溶液をトルエンで抽出した。水層を除去した後、有機層を水で洗浄した後、硫酸マグネシウムで乾燥させた。ろ過後、溶媒を減圧留去し、残渣をシリカゲルカラムクロマトグラフィで精製し、淡黄色固体3.4gを得た。このものは、マススペクトル分析の結果、下記化合物11であり、分子量470.18に対し、m/e=470であった。
上記化合物11の合成において、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに合成例4で合成した1-(3-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールを用いた他は、同様の方法で合成した。マススペクトル分析の結果、得られたものは下記化合物12であり、分子量470.18に対し、m/e=470であった。
化合物11の合成において、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに合成例5で合成した5-ブロモ-1-メチル-2-フェニル-1H-ベンズイミダゾールを用いた他は、同様の方法で合成した。マススペクトル分析の結果、得られたものは下記化合物13であり、分子量408.16に対し、m/e=408であった。
上記化合物11の合成において、フルオランテン-3-ボロン酸の代わりに合成例8で合成した4-(フルオランテン-3-イル)フェニルボロン酸を用いた他は、同様の方法で合成した。マススペクトル分析の結果、得られた物は下記化合物14であり、分子量546.21に対し、m/e=546であった。
上記化合物11の合成において、フルオランテン-3-ボロン酸の代わりに合成例9で合成した3-(フルオランテン-3-イル)フェニルボロン酸を用いた他は、同様の方法で合成した。マススペクトル分析の結果、得られた物は下記化合物15であり、分子量546.21に対し、m/e=546であった。
上記化合物11の合成において、フルオランテン-3-ボロン酸の代わりに合成例10で合成した6-(フルオランテン-3-イル)ナフタレン-2-イルボロン酸ピナコールエステルを用い、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに合成例4で合成した1-(3-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールを用いた他は、同様の方法で合成した。マススペクトル分析の結果、得られた物は下記化合物16であり、分子量596.23に対し、m/e=596であった。
上記化合物11の合成において、フルオランテン-3-ボロン酸の代わりに合成例9で合成した3-(フルオランテン-3-イル)フェニルボロン酸を用い、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに合成例5で合成した5-ブロモ-1-メチル-2-フェニル-1H-ベンズイミダゾールを用いた他は、同様の方法で合成した。マススペクトル分析の結果、得られた物は下記化合物17であり、分子量484.19に対し、m/e=484であった。
ベンゾ[c]フェナントレン-5-ボロン酸の代わりにベンゾ[g]クリセン-10-ボロン酸を用い、1-(4-ブロモフェニル)-2-フェニル-1H-ベンズイミダゾールの代わりに6-ブロモ-2,2’-ビピリジルを用いた他は実施例1と同様に反応を行った。
得られた化合物は、マススペクトル分析の結果、下記化合物18であり、分子量432.16に対し、m/e=432であった。
陽極:ITO(130)
正孔注入層:HT1(50)
正孔輸送層:HT2(45)
発光層:BH1とBD1(BD1は5%ドープ)(25)
障壁層:化合物6(25)
低仕事関数金属含有層:LiF(1)
陰極:Al(80)
(1)初期性能(電圧、色度、電流効率、外部量子効率、主ピーク波長)
電流値が10mA/cm2となるように素子に電圧を印加し、そのときの電圧値を測定した。またそのときのEL発光スペクトルを分光放射輝度計(CS-1000:コミカミノルタ社製)を用いて計測した。得られた分光放射輝度スペクトルから、色度、電流効率(cd/A)、外部量子効率(%)を算出した。
パルスジェネレータ(アジレント社製8114A)から出力した電圧パルス波形(パルス幅:500マイクロ秒、周波数:20Hz)を素子に印加し、EL発光を光電子増倍管(浜松ホトニクス社製R928)に入力し、パルス電圧波形とEL発光とを同期させてオシロスコープ(テクトロニクス社製2440)に取り込んで過渡EL波形を得た。これを解析してTTF由来の発光比率(TTF比率)を決定した(特願2009-125883参照)。
尚、TTF現象による内部量子効率の向上は62.5%が理論的限界と考えられ、この場合のTTF由来の発光比率は60%になる。
特開2006-278035に記載の方法にもとづき発光層内での発光分布と光取出し効率を決定した。その後、分光放射輝度計で測定したELスペクトルを、決定した光取り出し効率で割り、内部ELスペクトルを求め、そのスペクトルから求められる内部発生光子数と電子数の比を内部量子効率とした。
この明細書に記載の文献の内容を全てここに援用する。
Claims (19)
- aが1であり、bが1である請求項1~3のいずれかに記載の含窒素複素環誘導体。
- 下記式(21)で表される含窒素複素環誘導体。
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のb+1価の炭化水素環基、又は置換もしくは無置換の環形成原子数5~30のb+1価の複素環基を示す。
HArは、置換もしくは無置換の含窒素複素環基である。
a及びbは、それぞれ1~4の整数であり、a及びbの少なくとも一方は1である。) - aが1であり、bが1である請求項5~7のいずれかに記載の含窒素複素環誘導体。
- 下記式(31)で表される含窒素複素環誘導体。
L1は、単結合、置換もしくは無置換の環形成炭素数6~30のc+d価の炭化水素基、又は置換もしくは無置換の環形成原子数5~30のc+d価の複素環基を示す。
c及びdはそれぞれ1~3の整数を示す。
但し、L1、R401~R416はアントラセン含有基ではない。) - cが1である請求項9に記載の含窒素複素環誘導体。
- dが1である請求項11に記載の含窒素複素環誘導体。
- 有機エレクトロルミネッセンス素子用材料である請求項1~13のいずれかに記載の含窒素複素環誘導体。
- 前記有機エレクトロルミネッセンス素子用材料が、障壁層材料である請求項14に記載の含窒素複素環誘導体。
- 陽極、発光層、障壁層、及び陰極をこの順に備え、
前記障壁層が請求項1~13のいずれかに記載の含窒素複素環誘導体を含有する有機エレクトロルミネッセンス素子。 - 発光層と陰極との間に、電子注入層及び/又は電子輸送層を有し、前記電子注入層及び電子輸送層の少なくとも1層が請求項1~13のいずれかに記載の含窒素複素環誘導体を含有する有機エレクトロルミネッセンス素子。
- 前記発光層が、下記式(41)で表されるアントラセン誘導体を含む請求項16又は17に記載の有機エレクトロルミネッセンス素子。
R301~R308は、それぞれ水素原子、フッ素原子、置換もしくは無置換の炭素数1~10のアルキル基、置換もしくは無置換の炭素数3~10のシクロアルキル基、置換もしくは無置換の炭素数3~30のアルキルシリル基、置換もしくは無置換の環形成炭素数8~30のアリールシリル基、置換もしくは無置換の炭素数1~20のアルコキシ基、置換もしくは無置換の環形成炭素数6~20のアリールオキシ基、置換もしくは無置換の環形成炭素数6~30のアリール基、又は置換もしくは無置換の環形成原子数5~30の複素環基である。) - 前記式(41)で表されるアントラセン誘導体を含有する発光層が、前記含窒素複素環誘導体を含有する障壁層と接している請求項18に記載の有機エレクトロルミネッセンス素子。
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WO2014030666A1 (ja) | 2012-08-24 | 2014-02-27 | コニカミノルタ株式会社 | 透明電極、電子デバイス、および透明電極の製造方法 |
US20140284580A1 (en) * | 2013-03-22 | 2014-09-25 | E-Ray Optoelectronics Techonology Co., Ltd. | Electron transporting compounds and organic electroluminescent devices using the same |
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CN102471269A (zh) | 2012-05-23 |
EP2524913B1 (en) | 2017-07-26 |
KR101450959B1 (ko) | 2014-10-15 |
JPWO2011086935A1 (ja) | 2013-05-20 |
EP3192789A1 (en) | 2017-07-19 |
US9126943B2 (en) | 2015-09-08 |
KR20120115083A (ko) | 2012-10-17 |
JP5722238B2 (ja) | 2015-05-20 |
EP2524913A4 (en) | 2013-06-12 |
US20120132899A1 (en) | 2012-05-31 |
TW201137084A (en) | 2011-11-01 |
CN102471269B (zh) | 2016-02-03 |
EP2524913A1 (en) | 2012-11-21 |
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