CN110343048A - 一种含有螺二苯并环庚烯芴结构的有机化合物及其应用 - Google Patents
一种含有螺二苯并环庚烯芴结构的有机化合物及其应用 Download PDFInfo
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- CN110343048A CN110343048A CN201810301250.7A CN201810301250A CN110343048A CN 110343048 A CN110343048 A CN 110343048A CN 201810301250 A CN201810301250 A CN 201810301250A CN 110343048 A CN110343048 A CN 110343048A
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- dibenzocycloheptene
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- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- PJQCANLCUDUPRF-UHFFFAOYSA-N dibenzocycloheptene Chemical compound C1CC2=CC=CC=C2CC2=CC=CC=C12 PJQCANLCUDUPRF-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 89
- 239000010410 layer Substances 0.000 claims description 74
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 32
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 32
- 229910052799 carbon Inorganic materials 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 18
- 239000000741 silica gel Substances 0.000 claims description 18
- 229910002027 silica gel Inorganic materials 0.000 claims description 18
- 229960001866 silicon dioxide Drugs 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 14
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 230000000903 blocking effect Effects 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 11
- 238000010189 synthetic method Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000005401 electroluminescence Methods 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 8
- 230000004888 barrier function Effects 0.000 claims description 8
- -1 general formula (3) Chemical class 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 8
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
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- 235000011056 potassium acetate Nutrition 0.000 claims description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 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 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000002346 layers by function Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
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- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000009477 glass transition Effects 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
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- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical group C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
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- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
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- 230000005525 hole transport Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 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 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 1
- YJLIKUSWRSEPSM-WGQQHEPDSA-N (2r,3r,4s,5r)-2-[6-amino-8-[(4-phenylphenyl)methylamino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CNC1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O YJLIKUSWRSEPSM-WGQQHEPDSA-N 0.000 description 1
- MHSLDASSAFCCDO-UHFFFAOYSA-N 1-(5-tert-butyl-2-methylpyrazol-3-yl)-3-(4-pyridin-4-yloxyphenyl)urea Chemical compound CN1N=C(C(C)(C)C)C=C1NC(=O)NC(C=C1)=CC=C1OC1=CC=NC=C1 MHSLDASSAFCCDO-UHFFFAOYSA-N 0.000 description 1
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- ZOKIJILZFXPFTO-UHFFFAOYSA-N 4-methyl-n-[4-[1-[4-(4-methyl-n-(4-methylphenyl)anilino)phenyl]cyclohexyl]phenyl]-n-(4-methylphenyl)aniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C1(CCCCC1)C=1C=CC(=CC=1)N(C=1C=CC(C)=CC=1)C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 ZOKIJILZFXPFTO-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126657 Compound 17 Drugs 0.000 description 1
- LIMFPAAAIVQRRD-BCGVJQADSA-N N-[2-[(3S,4R)-3-fluoro-4-methoxypiperidin-1-yl]pyrimidin-4-yl]-8-[(2R,3S)-2-methyl-3-(methylsulfonylmethyl)azetidin-1-yl]-5-propan-2-ylisoquinolin-3-amine Chemical compound F[C@H]1CN(CC[C@H]1OC)C1=NC=CC(=N1)NC=1N=CC2=C(C=CC(=C2C=1)C(C)C)N1[C@@H]([C@H](C1)CS(=O)(=O)C)C LIMFPAAAIVQRRD-BCGVJQADSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000004776 molecular orbital Methods 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003513 tertiary aromatic amines Chemical group 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/57—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton
- C07C211/61—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings being part of condensed ring systems of the carbon skeleton with at least one of the condensed ring systems formed by three or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
- C07D219/14—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hydrocarbon radicals, substituted by nitrogen atoms, attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/46—Phenazines
- C07D241/48—Phenazines with hydrocarbon radicals, substituted by nitrogen atoms, directly attached to the ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
- C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
- C07D265/38—[b, e]-condensed with two six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
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Abstract
本发明公开了一种含有螺二苯并环庚烯芴结构的有机化合物及其应用,所述含有螺二苯并环庚烯芴结构的化合物通过单键、取代或未取代的:苯基、联苯基或萘基连接含氮的支链。本发明化合物不易结晶,具有良好的成膜性和热稳定性,具有较高的玻璃化温度,合适的HOMO和LUMO能级,通过器件结构优化,可有效提升OLED器件的光电性能以及OLED器件的寿命,从而更好的适应和满足面板制造企业的应用要求。
Description
技术领域
本发明涉及半导体技术领域,尤其是涉及一种含有螺二苯并环庚烯芴结构的化合物材料及其在OLED领域的应用。
背景技术
有机电致发光(OLED:Organic Light Emission Diodes)器件技术既可以用来制造新型显示产品,也可以用于制作新型照明产品,有望替代现有的液晶显示和荧光灯照明,应用前景十分广泛。OLED发光器件犹如三明治的结构,包括电极材料膜层,以及夹在不同电极膜层之间的有机功能材料,各种不同功能材料根据用途相互叠加在一起共同组成OLED发光器件。作为电流器件,当对OLED发光器件的两端电极施加电压,并通过电场作用有机层功能材料膜层中的正负电荷,正负电荷进一步在发光层中复合,即产生OLED电致发光。
当前,OLED显示技术已经在智能手机,平板电脑等领域获得应用,进一步还将向电视等大尺寸应用领域扩展,但是,和实际的产品应用要求相比,OLED器件的发光效率,使用寿命等性能还需要进一步提升。对于OLED发光器件提高性能的研究包括:降低器件的驱动电压,提高器件的发光效率,提高器件的使用寿命等。为了实现OLED器件的性能的不断提升,不但需要从OLED器件结构和制作工艺的创新,更需要OLED光电功能材料不断研究和创新,创制出更高性能OLED的功能材料。
应用于OLED器件的OLED光电功能材料从用途上可划分为两大类,即电荷注入传输材料和发光材料,进一步,还可将电荷注入传输材料分为电子注入传输材料、电子阻挡材料、空穴注入传输材料和空穴阻挡材料,还可以将发光材料分为主体发光材料和掺杂材料。
为了制作高性能的OLED发光器件,要求各种有机功能材料具备良好的光电特性,譬如,作为电荷传输材料,要求具有良好的载流子迁移率,高玻璃化转化温度等,作为发光层的主体材料要求材料具有良好双极性,适当的HOMO/LUMO能阶等。
构成OLED器件的OLED光电功能材料膜层至少包括两层以上结构,产业上应用的OLED器件结构,则包括空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层等多种膜层,也就是说应用于OLED器件的光电功能材料至少包含空穴注入材料,空穴传输材料,发光材料,电子传输材料等,材料类型和搭配形式具有丰富性和多样性的特点。另外,对于不同结构的OLED器件搭配而言,所使用的光电功能材料具有较强的选择性,相同的材料在不同结构器件中的性能表现,也可能完全迥异。
因此,针对当前OLED器件的产业应用要求,以及OLED器件的不同功能膜层,器件的光电特性需求,必须选择更适合,具有高性能的OLED功能材料或材料组合,才能实现器件的高效率、长寿命和低电压的综合特性。就当前OLED显示照明产业的实际需求而言,目前OLED材料的发展还远远不够,落后于面板制造企业的要求,作为材料企业开发更高性能的有机功能材料显得尤为重要。
发明内容
针对现有技术存在的上述问题,本发明提供了一种含有螺二苯并环庚烯芴结构的化合物及其在有机电致发光器件上应用。所述螺二苯并环庚烯芴结构通过苯基、联苯基或萘基连接含氮的支链。本发明化合物不易结晶,具有良好的成膜性和热稳定性,具有较高的玻璃化温度,合适的HOMO和LUMO能级,通过器件结构优化,可有效提升OLED器件的光电性能以及OLED器件的寿命,从而更好的适应和满足面板制造企业的应用要求。
本发明的技术方案如下:
一种含有螺二苯并环庚烯芴结构的有机化合物,所述化合物的结构如通式(1)所示:
其中,R1、R2、R3、R4分别独立地表示为氢原子、氟原子、CN、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有6-60个碳原子的芳基、含有一个或多个杂原子的5-60元杂芳基或通式(2)所示结构;R1、R2、R3与R4相同或者不同;R1、R2至少有一个表示为通式(2)所示结构;R1、R3、R4至少有一个表示为氟原子、CN、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有6-60个碳原子的芳基、含有一个或多个杂原子的5-60元杂芳基;
通式(2)中,R5、R6分别独立地表示为取代或未取代的:C6-60芳基、含有一个或多个杂原子的5-60元杂芳基;所述杂原子为氮、氧或硫;R5与R6相同或者不同;
Ar1表示为单键、取代或未取代的:C6-60亚芳基、含有一个或多个杂原子5~60元杂亚芳基;所述杂原子为氮、氧或硫。
优选方案之一,所述化合物的结构如通式(3)、通式(4)所示:
所述Ar1表示为单键、取代或未取代的:亚苯基、亚联苯基或亚萘基中的一种。
优选方案之二,所述化合物的结构如通式(5)所示:
其中,R7、R8表示为氢原子、氟原子、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有一个或多个杂原子的5-60元杂芳基。
优选方案之三,所述化合物的结构如通式(6)所示:
其中,R9表示为氢原子、氟原子、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有一个或多个杂原子的取代或未取代的5-30元杂芳基;X表示为氧原子、硫原子、烷基取代的亚甲基、芳基取代的亚甲基或芳基取代的亚胺基。
优选方案之四,所述化合物的结构如通式(7)所示:
其中,R9表示为氢原子、氟原子、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有一个或多个杂原子的取代或未取代的5-30元杂芳基;X表示为氧原子、硫原子、烷基取代的亚甲基、芳基取代的亚甲基或芳基取代的亚胺基。
所述通式(2)具体结构表示如下,但不限于此:
中的任意一种。
所述含有螺二苯并环庚烯芴结构的有机化合物的具体结构如下,但不限于此:
中的任意一种。
一种所述含有螺二苯并环庚烯芴结构的有机化合物的制备方法,所述制备方法包括如下两种情况:
(1)当螺二苯并环庚烯芴与R1、R2以C-C键相连时,以R2表示为通式(2)所示结构为例,反应方程式如反应式I-1所示:
反应式I-1
具体制备方法为:称取中间体A和用体积比为1.5~3:1的甲苯乙醇混合溶剂溶解;再加入Na2CO3水溶液、Pd(PPh3)4;在惰性气氛下,将上述反应物的混合溶液于反应温度90~110℃下反应10~24小时,冷却、过滤反应溶液,滤液旋蒸,过硅胶柱,得到产物;所述中间体A与的摩尔比为1:1.0~1.5;Pd(PPh3)4与中间体A的摩尔比为0.006~0.02:1,Na2CO3与中间体A的摩尔比为2.0~3.0:1。
(2)当螺二苯并环庚烯芴与R1、R2以C-N键相连时,Ar1表示为单键时,反应方程式如反应式II-1所示:
反应式II-1
具体制备方法为:称取中间体A和H-R2,用甲苯溶解;再加入Pd2(dba)3、P(t-Bu)3、叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于95~110℃下反应10~24小时,冷却并过滤反应溶液,滤液旋蒸,过硅胶柱,得到上述目标产物;所述中间体A与H-R2的摩尔比为1:1.2~3.0,Pd2(dba)3与中间体A的摩尔比为0.006~0.02:1,三叔丁基膦与中间体A的摩尔比为0.006~0.02:1,叔丁醇钠与中间体A的摩尔比为1.0~3.0:1。
所述H-R2与的合成方法分别如反应式2-1、反应式2-2所示:
反应式2-1
上述反应中的中间体BI代表H-R2;
上述反应的具体制备方法为:称取原料O和原料P用甲苯溶解,再加入Pd2(dba)3、P(Ph)3和叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于反应温度90~110℃下反应10~24小时,冷却、过滤反应溶液,滤液旋蒸,过硅胶柱,得到中间体BI;所述原料O与原料P的摩尔比为1:1.0~1.5;Pd2(dba)3与原料O的摩尔比为0.006~0.02:1,叔丁醇钠与原料O的摩尔比为2.0~3.0:1;P(Ph)3与原料O的摩尔比为2.0~3.0:1;
反应式2-2
上述反应中的中间体BII代表
上述反应的具体制备方法为:称取中间体BI和原料N,用甲苯溶解;再加入Pd2(dba)3、P(Ph)3、叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于95~110℃下反应10~24小时,冷却并过滤反应溶液,滤液旋蒸,过硅胶柱,得到中间体C;所述中间体BI与原料N的摩尔比为1:1.0~1.5,Pd2(dba)3与中间体BI的摩尔比为0.006~0.02:1,P(Ph)3与中间体BI的摩尔比为0.006~0.02:1,叔丁醇钠与中间体BI的摩尔比为1.0~3.0:1;
在氮气的气氛下,称取中间体C、双(频哪醇合)二硼、Pd(dppf)Cl2、醋酸钾溶于甲苯中,100~120℃下反应12~24小时,取样点板,反应完全,自然冷却,过滤,滤液旋蒸,得到粗产品,过中性硅胶柱得到中间体BII;中间体C与双(频哪醇合)二硼的摩尔比为2:1~1.5,中间体C与Pd(dppf)Cl2的摩尔比为1:0.01~0.05,中间体C与醋酸钾的摩尔比为1:2~2.5。
一种含有所述含有螺二苯并环庚烯芴结构的有机化合物的有机电致发光器件,所述有机电致发光器件包括至少一层功能层含有所述含有螺二苯并环庚烯芴结构的有机化合物。
一种含有所述含有螺二苯并环庚烯芴结构的有机化合物的有机电致发光器件,包括空穴传输层或电子阻挡层,所述空穴传输层或电子阻挡层材料为所述含有螺二苯并环庚烯芴结构的有机化合物。
一种含有所述含有螺二苯并环庚烯芴结构的有机化合物的有机电致发光器件,包括发光层,所述发光层含有所述含有螺二苯并环庚烯芴结构的有机化合物。
本发明有益的技术效果在于:
本发明化合物中的p-π共轭效应使得其有很强的空穴传输能力,高的空穴传输速率能够提高有机电致发光器件的效率;化合物中不对称的三芳胺结构能够降低分子的结晶性,降低分子的平面性,阻止分子在平面上移动从而提高了分子的热稳定性。相比较于申请号为2017109090670的专利,本发明的化合物母核中的苯被F、CN或烷基等修饰,整个分子的电子云密度更加平衡,螺环的键能更加稳定,在加热过程中不易断键,具有更高的耐热温度,使其耐热稳定性有显著的提高,进一步提高器件的使用寿命。
本发明的化合物的结构使得电子和空穴在发光层的分布更加平衡,在恰当的HOMO能级下,提升了空穴注入和传输性能;在合适的LUMO能级下,又起到了电子阻挡的作用,提升激子在发光层中的复合效率;作为OLED发光器件的发光功能层材料使用时,螺二苯并环庚烯芴搭配本发明范围内的支链可有效提高激子利用率和高荧光辐射效率,降低高电流密度下的效率滚降,降低器件电压,提高器件的电流效率和寿命。
本发明的化合物在OLED器件应用时,通过器件结构优化,可保持高的膜层稳定性,可有效提升OLED器件的光电性能以及OLED器件的寿命。本发明所述化合物在OLED发光器件中具有良好的应用效果和产业化前景。
附图说明
图1为本发明所列举的材料应用于OLED器件的结构示意图;
其中,1、透明基板层,2、ITO阳极层,3、空穴注入层,4、空穴传输层5、电子阻挡层,6、发光层,7、空穴阻挡层/电子传输层,8、电子注入层,9、阴极反射电极层。
图2为器件在不同温度下测量的效率曲线图。
图3为本发明器件实施例3与器件比较例1所制作的器件进行反向电压的漏电流测试曲线图。
具体实施方式
实施例1:中间体BI的合成:
称取原料O和原料P用甲苯溶解,再加入Pd2(dba)3、P(Ph)3和叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于反应温度90~110℃下反应10~24小时,冷却、过滤反应溶液,滤液旋蒸,过硅胶柱,得到中间体BI;所述原料O与原料P的摩尔比为1:1.0~1.5;Pd2(dba)3与原料O的摩尔比为0.006~0.02:1,叔丁醇钠与原料P的摩尔比为2.0~3.0:1;P(Ph)3与原料O的摩尔比为2.0~3.0:1;
以中间体B1的合成为例:
在250ml的三口瓶中,通氮气保护下,加入0.01mol原料O1,0.012mol原料P1,150ml甲苯搅拌混合,然后加入5×10-5molPd2(dba)3,5×10-5mol P(Ph)3,0.03mol叔丁醇钠,加热至105℃,回流反应24小时,取样点板,显示无溴代物剩余,反应完全;自然冷却至室温,过滤,滤液旋蒸至无馏分,过中性硅胶柱,得到目标产物中间体B1;HPLC纯度99.50%,收率75.9%;元素分析结构(分子式C27H23N):理论值:C,89.71;H,6.41;N,3.87;测试值:C,89.70;H,6.41;N,3.88。ESI-MS(m/z)(M+):理论值为361.49,实测值为361.52。
实施例2:中间体BII的合成:
上述反应的具体制备方法为:称取中间体BI和原料N,用甲苯溶解;再加入Pd2(dba)3、P(Ph)3、叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于95~110℃下反应10~24小时,冷却并过滤反应溶液,滤液旋蒸,过硅胶柱,得到中间体C;所述中间体BI与原料N的摩尔比为1:1.0~1.5,Pd2(dba)3与中间体BI的摩尔比为0.006~0.02:1,P(Ph)3与中间体BI的摩尔比为0.006~0.02:1,叔丁醇钠与中间体BI的摩尔比为1.0~3.0:1。
在氮气的气氛下,称取中间体C、双(频哪醇合)二硼、Pd(dppf)Cl2、醋酸钾溶于甲苯中,100~120℃下反应12~24小时,取样点板,反应完全,自然冷却,过滤,滤液旋蒸,得到粗产品,过中性硅胶柱得到中间体BII;中间体C与双(频哪醇合)二硼的摩尔比为2:1~1.5,中间体C与Pd(dppf)Cl2的摩尔比为1:0.01~0.05,中间体C与醋酸钾的摩尔比为1:2~2.5。
以中间体B3的合成为例:
在250ml的三口瓶中,通氮气保护下,加入0.01mol的中间体B7,0.012mol原料N1,150ml甲苯搅拌混合,然后加入5×10-5molPd2(dba)3,5×10-5mol P(Ph)3,0.03mol叔丁醇钠,加热至105℃,回流反应24小时,取样点板,显示无溴代物剩余,反应完全;自然冷却至室温,过滤,滤液旋蒸至无馏分,过中性硅胶柱,得到目标产物中间体C1;
在氮气的气氛下,称取0.02mol中间体C1、0.012mol双(频哪醇合)二硼、0.0002molPd(dppf)Cl2、0.05mol醋酸钾溶于甲苯中,120℃下反应24小时,取样点板,反应完全,自然冷却,过滤,滤液旋蒸,得到粗产品,过中性硅胶柱得到中间体B3;HPLC纯度99.40%,收率74.0%;元素分析结构(分子式C45H42BNO2):理论值C,84.50;H,6.62;B,1.69;N,2.19;O,5.00;测试值:C,84.51;H,6.62;B,1.68;N,2.19;O,5.00。ESI-MS(m/z)(M+):理论值为639.65,实测值为639.64。
实施例中所需的中间体B的合成原料如表1:
表1
实施例3:中间体A的合成:
以R1表示为Br为例:
在烘干的烧瓶中,将0.01mol原料N溶解在500mL的无水THF中,将反应混合物冷却至-78℃,随后,慢慢滴加34.3mL的n-BuLi(2.5mol/L,己烷溶液),搅拌1h,然后将0.01mol的原料M溶解在THF中,并在-70℃下滴加。在加入结束后,将反应混合物逐渐加热至室温,用氯化铵萃取并在旋转蒸发仪上进行浓缩,将500mL的乙酸小心加入浓缩溶液中,并接着加入100mL的发烟盐酸。将混合物加热至75℃,并保持5h,期间会有白色固体出来,然后将混合物冷却至室温,并用吸滤将沉淀的固体滤出,用甲醇洗涤,在减压下于40℃干燥残余物。
按实施例3中的中间体A的合成方法制备实施例中所需的中间体A。实施例中所需的中间体A的合成原料如表2所示:
表2
实施例4:化合物8的合成:
在250ml的三口瓶中,通氮气保护下,加入0.01mol中间体A1,0.012mol中间体B1,150ml甲苯搅拌混合,然后加入5×10-5molPd2(dba)3,5×10-5mol P(t-Bu)3,0.03mol叔丁醇钠,加热至105℃,回流反应24小时,取样点板,显示无溴代物剩余,反应完全;自然冷却至室温,过滤,滤液旋蒸至无馏分,过中性硅胶柱,得到目标产物,HPLC纯度99.77%,收率75.0%。元素分析结构(分子式C58H47N):理论值:C,91.90;H,6.25;N,1.85;测试值:C,91.91;H,6.25;N,1.84。HPLC-MS:材料分子量为758.02,实测分子量758.0。
实施例5:化合物17的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A2代替中间体A1,中间体B2代替中间体B1;元素分析结构(分子式C61H51N):理论值:C,91.80;H,6.44;N,1.76;测试值:C,91.81;H,6.43;N,1.76。HPLC-MS:材料分子量为798.09,实测分子量798.12。
实施例6:化合物30的合成:
在250ml的三口瓶中,加入中间体0.01mol中间体A3、0.015mol中间体B3,用体积比为2:1的甲苯与乙醇的混合溶剂溶解;在惰性气氛下,再加入0.02mol Na2CO3水溶液(2M)、0.0001molPd(PPh3)4;将上述反应物的混合溶液于反应温度95~110℃,反应15个小时,冷却并过滤反应溶液,滤液旋蒸,过硅胶柱,得到目标产物,HPLC纯度99.79%,收率73.5%。元素分析结构(分子式C74H63N):理论值:C,91.98;H,6.57;N,1.45;测试值:C,91.99;H,6.57;N,1.44。HPLC-MS:材料分子量为966.32,实测分子量966.30。
实施例7:化合物48的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A4代替中间体A1,中间体B4代替中间体B1;元素分析结构(分子式C61H46N2):理论值:C,90.78;H,5.75;N,3.47;测试值:C,90.78;H,5.76;N,3.46。HPLC-MS:材料分子量为807.05,实测分子量807.01。
实施例8:化合物61的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A5代替中间体A1,中间体B5代替中间体B1;元素分析结构(分子式C58H45NO):理论值:C,90.24;H,5.88;N,1.81;O,2.07;测试值:C,90.26;H,5.88;N,1.80;O,2.06。HPLC-MS:材料分子量为772.00,实测分子量771.92。
实施例9:化合物81的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A6代替中间体A1,中间体B6代替中间体B1;元素分析结构(分子式C69H51N):理论值:C,91.55;H,6.64;N,1.81;测试值:C,91.54;H,6.64;N,1.82。HPLC-MS:材料分子量为774.06,实测分子量774.09。
实施例10:化合物109的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A7代替中间体A1,中间体B7代替中间体B1;元素分析结构(分子式C62H55N):理论值:C,91.47;H,6.81;N,1.72;测试值:C,91.49;H,6.80;N,1.71。HPLC-MS:材料分子量为814.13,实测分子量814.10。
实施例11:化合物129的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A8代替中间体A1,中间体B8代替中间体B1;元素分析结构(分子式C53H33N3):理论值:C,89.42;H,4.67;N,5.90;测试值:C,89.43;H,4.66;N,5.90。HPLC-MS:材料分子量为711.87,实测分子量711.90。
实施例12:化合物138的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A9代替中间体A1,中间体B9代替中间体B1;元素分析结构(分子式C56H43N):理论值:C,92.14;H,5.94;N,1.92;测试值:C,92.15;H,5.94;N,1.91。HPLC-MS:材料分子量为729.97,实测分子量729.94。
实施例13:化合物150的合成:
按实施例4中化合物8的合成方法制备,不同点在于用中间体A10代替中间体A1,中间体B2代替中间体B1;元素分析结构(分子式C69H67N):理论值:C,91.04;H,7.42;N,1.54;测试值:C,91.05;H,7.42;N,1.53。HPLC-MS:材料分子量为910.30,实测分子量910.25。
本发明化合物在发光器件中使用,可以作为电子阻挡层材料,也可以作为发光层主客体材料使用。对本发明上述实施例制备的化合物分别进行热性能、T1能级、HOMO能级、蒸镀温度和耐热分解温度的测试,检测结果如表3所示。
表3
注:玻璃化温度Tg由示差扫描量热法(DSC,德国耐驰公司DSC204F1示差扫描量热仪)测定,升温速率10℃/min;热失重温度Td是在氮气气氛中失重1%的温度,在日本岛津公司的TGA-50H热重分析仪上进行测定,氮气流量为20mL/min;三线态能级T1是由日立的F4600荧光光谱仪测试,材料的测试条件为2*10-5的甲苯溶液;最高占据分子轨道HOMO能级及最低占据分子轨道LUMO能级是由光电子发射谱仪(IPS-3)测试,测试为大气环境;蒸镀温度是材料在蒸镀过程中达到的速率时的温度,蒸镀设备为200规格设备OLED镀膜机;耐热分解温度是材料在某一特定温度下保持48小时后,通过HPLC测试判断材料纯度的变化,导致材料纯度开始降低时的温度是耐热分解温度。
由上表数据可知,本发明的有机化合物具有高的玻璃转化温度,可提高材料膜相态稳定性,具有较高的耐热分解温度,保证材料在蒸镀的过程中不会发生分解,进一步提高器件使用寿命;具有高的T1能级,可以阻挡发光层能量损失,从而提升器件发光效率;合适的HOMO能级可以解决载流子的注入问题,可降低器件电压;较高的荧光量子效率和折射率,可提高OLED器件的发光效率。因此,本发明含有螺二苯并环庚烯芴结构的化合物在应用于OLED器件的不同功能层后,可有效提高器件的发光效率及使用寿命。
以下通过器件实施例1~10和比较例1详细说明本发明合成的OLED材料在器件中的应用效果。本发明所述器件实施例2~10与器件实施例1相比所述器件的制作工艺完全相同,并且所采用了相同的基板材料和电极材料,电极材料的膜厚也保持一致,所不同的是对器件中的空穴传输材料或电子阻挡层材料做了更换。各实施例所得器件的性能测试结果如表4所示。
器件实施例1
如图1所示,一种电致发光器件,其制备步骤包括:a)清洗透明基板层1上的ITO阳极层2,分别用去离子水、丙酮、乙醇超声清洗各15分钟,然后在等离子体清洗器中处理2分钟;b)在ITO阳极层2上,通过真空蒸镀方式蒸镀空穴注入层材料HAT-CN,厚度为10nm,这层作为空穴注入层3;c)在空穴注入层3上,通过真空蒸镀方式蒸镀空穴输层材料本发明化合物8,厚度为60nm,该层为空穴传输层4;d)在空穴传输层材料4之上,通过真空蒸镀的方式蒸镀TAPC,厚度为20nm,该层为电子阻挡层5;e)在电子阻挡层5之上蒸镀发光层6,使用CBP作为双主体材料,Ir(ppy)3作为掺杂材料,Ir(ppy)3和CBP的质量比为10:100,厚度为30nm;f)在发光层6之上,通过真空蒸镀方式蒸镀电子传输材料TPBI,厚度为40nm,这层有机材料作为空穴阻挡/电子传输层7使用;g)在空穴阻挡层/电子传输层7之上,真空蒸镀电子注入层LiF,厚度为1nm,该层为电子注入层8;h)在电子注入层8之上,真空蒸镀阴极Al(100nm),该层为阴极反射电极层9;按照上述步骤完成电致发光器件的制作后,测量器件的电流效率和寿命,其结果见表4所示。相关材料的分子结构式如下所示:
器件实施例2:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为本发明化合物17。器件实施例3:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为本发明化合物30。器件实施例4:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为本发明化合物48。器件实施例5:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为本发明化合物61。器件实施例6:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为本发明化合物81。器件实施例7:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为本发明化合物109。器件实施例8:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为NPB,电子阻挡层材料为本发明化合物129。器件实施例9:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为NPB,电子阻挡层材料为本发明化合物138。器件实施例10:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为本发明化合物150。器件比较例1:本实施例与器件实施例1的不同之处在于:电致发光器件的空穴传输材料为NPB,电子阻挡层材料为化合物EB-1,所得电致发光器件的检测数据见表4所示。
表4
编号 | 电流效率(cd/A) | 色彩 | LT95寿命(Hr)@5000nits |
器件实施例1 | 47.6 | 绿光 | 88.1 |
器件实施例2 | 47.9 | 绿光 | 91.3 |
器件实施例3 | 49.8 | 绿光 | 86.9 |
器件实施例4 | 46.4 | 绿光 | 89.7 |
器件实施例5 | 46.8 | 绿光 | 88.8 |
器件实施例6 | 49.5 | 绿光 | 93.2 |
器件实施例7 | 48.6 | 绿光 | 88.5 |
器件实施例8 | 53.7 | 绿光 | 98.7 |
器件实施例9 | 53.5 | 绿光 | 96.2 |
器件实施例10 | 48.0 | 绿光 | 89.5 |
器件比较例1 | 44.8 | 绿光 | 38.7 |
注:寿命测试系统为本发明所有权人与上海大学共同研究的OLED器件寿命测试仪。
由表4的结果可以看出,本发明制备的含有螺二苯并环庚烯芴结构的化合物可应用于OLED发光器件制作,并且与器件比较例相比,无论是效率还是寿命均比已知OLED材料获得较大改观,特别是器件的寿命衰减获得较大的提升。
进一步的本发明材料制备的OLED器件在低温下工作时效率也比较稳定,将器件实施例2、8、10和器件比较例1在-10~80℃区间进行效率测试,所得结果如表5和图2所示。
表5
从表5和图2的数据可知,器件实施例2、8、10为本发明材料和已知材料搭配的器件结构,和器件比较例1相比,不仅低温效率高,而且在温度升高过程中,效率平稳升高。
为进一步测试本发明化合物所产生的有益效果,将本发明器件实施例3和器件比较例1所制作器件进行反向电压的漏电流测试,测试数据图3所示,其从图3中可得知应用本发明化合物的器件实施例3和器件比较例1所制作器件相比,漏电流很小,且电流曲线稳定,因此,本发明材料应用于器件制作后,具有较长使用寿命。
综上,以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (13)
1.一种含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述化合物的结构如通式(1)所示:
其中,R1、R2、R3、R4分别独立地表示为氢原子、氟原子、CN、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有6-60个碳原子的芳基、含有一个或多个杂原子的5-60元杂芳基或通式(2)所示结构;R1、R2、R3与R4相同或者不同;R1、R2至少有一个表示为通式(2)所示结构;R1、R3、R4至少有一个表示为氟原子、CN、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有6-60个碳原子的芳基、含有一个或多个杂原子的5-60元杂芳基;
通式(2)中,R5、R6分别独立地表示为取代或未取代的:C6-60芳基、含有一个或多个杂原子的5-60元杂芳基;所述杂原子为氮、氧或硫;R5与R6相同或者不同;
Ar1表示为单键、取代或未取代的:C6-60亚芳基、含有一个或多个杂原子5~60元杂亚芳基;所述杂原子为氮、氧或硫。
2.根据权利要求1所述的含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述化合物的结构如通式(3)、通式(4)所示:
3.根据权利要求1或2所述的含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述Ar1表示为单键、取代或未取代的:亚苯基、亚联苯基或亚萘基中的一种。
4.根据权利要求1或2所述的含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述化合物的结构如通式(5)所示:
其中,R7、R8表示为氢原子、氟原子、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有一个或多个杂原子的5-60元杂芳基。
5.根据权利要求4所述的含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述化合物的结构如通式(6)所示:
其中,R9表示为氢原子、氟原子、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有一个或多个杂原子的取代或未取代的5-30元杂芳基;X表示为氧原子、硫原子、烷基取代的亚甲基、芳基取代的亚甲基或芳基取代的亚胺基。
6.根据权利要求1或2所述的含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述化合物的结构如通式(7)所示:
其中,R9表示为氢原子、氟原子、含有1-20碳原子的直链或支链烷基、取代或未取代的:含有3-20个碳原子的环状烷基、含有一个或多个杂原子的取代或未取代的5-30元杂芳基;X表示为氧原子、硫原子、烷基取代的亚甲基、芳基取代的亚甲基或芳基取代的亚胺基。
7.根据权利要求1所述的含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述通式(2)具体结构表示如下,但不限于此:
中的任意一种。
8.根据权利要求1所述的含有螺二苯并环庚烯芴结构的有机化合物,其特征在于,所述化合物具体结构如下,但不限于此:
中的任意一种。
9.一种权利要求1~8任一项所述的含有螺二苯并环庚烯芴结构的有机化合物的制备方法,其特征在于,所述制备方法包括如下两种情况:
(1)当螺二苯并环庚烯芴与R1、R2以C-C键相连时,以R2表示为通式(2)所示结构为例,反应方程式如反应式I-1所示:
具体制备方法为:称取中间体A和用体积比为1.5~3:1的甲苯乙醇混合溶剂溶解;再加入Na2CO3水溶液、Pd(PPh3)4;在惰性气氛下,将上述反应物的混合溶液于反应温度90~110℃下反应10~24小时,冷却、过滤反应溶液,滤液旋蒸,过硅胶柱,得到产物;所述中间体A与的摩尔比为1:1.0~1.5;Pd(PPh3)4与中间体A的摩尔比为0.006~0.02:1,Na2CO3与中间体A的摩尔比为2.0~3.0:1。
(2)当螺二苯并环庚烯芴与R1、R2以C-N键相连时,Ar1表示为单键时,反应方程式如反应式II-1所示:
具体制备方法为:称取中间体A和H-R2,用甲苯溶解;再加入Pd2(dba)3、P(t-Bu)3、叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于95~110℃下反应10~24小时,冷却并过滤反应溶液,滤液旋蒸,过硅胶柱,得到上述目标产物;所述中间体A与H-R2的摩尔比为1:1.2~3.0,Pd2(dba)3与中间体A的摩尔比为0.006~0.02:1,三叔丁基膦与中间体A的摩尔比为0.006~0.02:1,叔丁醇钠与中间体A的摩尔比为1.0~3.0:1。
10.根据权利要求9所述的制备方法,其特征在于,所述H-R2与的合成方法分别如反应式2-1、反应式2-2所示:
上述反应中的中间体BI代表H-R2;
上述反应的具体制备方法为:称取原料O和原料P用甲苯溶解,再加入Pd2(dba)3、P(Ph)3和叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于反应温度90~110℃下反应10~24小时,冷却、过滤反应溶液,滤液旋蒸,过硅胶柱,得到中间体BI;所述原料O与原料P的摩尔比为1:1.0~1.5;Pd2(dba)3与原料O的摩尔比为0.006~0.02:1,叔丁醇钠与原料O的摩尔比为2.0~3.0:1;P(Ph)3与原料O的摩尔比为2.0~3.0:1;
上述反应中的中间体BII代表
上述反应的具体制备方法为:称取中间体BI和原料N,用甲苯溶解;再加入Pd2(dba)3、P(Ph)3、叔丁醇钠;在惰性气氛下,将上述反应物的混合溶液于95~110℃下反应10~24小时,冷却并过滤反应溶液,滤液旋蒸,过硅胶柱,得到中间体C;所述中间体BI与原料N的摩尔比为1:1.0~1.5,Pd2(dba)3与中间体BI的摩尔比为0.006~0.02:1,P(Ph)3与中间体BI的摩尔比为0.006~0.02:1,叔丁醇钠与中间体BI的摩尔比为1.0~3.0:1;
在氮气的气氛下,称取中间体C、双(频哪醇合)二硼、Pd(dppf)Cl2、醋酸钾溶于甲苯中,100~120℃下反应12~24小时,取样点板,反应完全,自然冷却,过滤,滤液旋蒸,得到粗产品,过中性硅胶柱得到中间体BII;中间体C与双(频哪醇合)二硼的摩尔比为2:1~1.5,中间体C与Pd(dppf)Cl2的摩尔比为1:0.01~0.05,中间体C与醋酸钾的摩尔比为1:2~2.5。
11.一种含有权利要求1~8任一项所述含有螺二苯并环庚烯芴结构的有机化合物的有机电致发光器件,其特征在于所述有机电致发光器件包括至少一层功能层含有所述含有螺二苯并环庚烯芴结构的有机化合物。
12.一种含有权利要求1~8任一项所述含有螺二苯并环庚烯芴结构的有机化合物的有机电致发光器件,包括空穴传输层或电子阻挡层,其特征在于,所述空穴传输层或电子阻挡层材料为所述含有螺二苯并环庚烯芴结构的有机化合物。
13.一种含有权利要求1~8任一项所述含有螺二苯并环庚烯芴结构的有机化合物的有机电致发光器件,包括发光层,其特征在于,所述发光层含有所述含有螺二苯并环庚烯芴结构的有机化合物。
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