CN111592464A - Organic compound containing spirobifluorene structure and application thereof - Google Patents
Organic compound containing spirobifluorene structure and application thereof Download PDFInfo
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- CN111592464A CN111592464A CN201910125836.7A CN201910125836A CN111592464A CN 111592464 A CN111592464 A CN 111592464A CN 201910125836 A CN201910125836 A CN 201910125836A CN 111592464 A CN111592464 A CN 111592464A
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- 150000002894 organic compounds Chemical class 0.000 title claims description 45
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical group C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 37
- 238000002347 injection Methods 0.000 claims abstract description 36
- 239000007924 injection Substances 0.000 claims abstract description 36
- 230000005525 hole transport Effects 0.000 claims abstract description 29
- 125000005266 diarylamine group Chemical group 0.000 claims abstract description 19
- -1 spirobifluorene organic compound Chemical class 0.000 claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 5
- 239000011368 organic material Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 8
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 230000009471 action Effects 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 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 claims description 4
- 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 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005549 heteroarylene group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 4
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 2
- FIARMZDBEGVMLV-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanolate Chemical group [O-]C(F)(F)C(F)(F)F FIARMZDBEGVMLV-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 2
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 2
- VXFWYDCBQHYEOC-UHFFFAOYSA-N [bromo(phenyl)methyl]boronic acid Chemical compound OB(O)C(Br)C1=CC=CC=C1 VXFWYDCBQHYEOC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 229910052805 deuterium Inorganic materials 0.000 claims description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 claims description 2
- 125000005561 phenanthryl group Chemical group 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims 1
- ANYCDYKKVZQRMR-UHFFFAOYSA-N lithium;quinoline Chemical compound [Li].N1=CC=CC2=CC=CC=C21 ANYCDYKKVZQRMR-UHFFFAOYSA-N 0.000 claims 1
- 230000008520 organization Effects 0.000 claims 1
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 7
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 80
- 239000000543 intermediate Substances 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000012043 crude product Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000012265 solid product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- ZEEBGORNQSEQBE-UHFFFAOYSA-N [2-(3-phenylphenoxy)-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound C1(=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)C1=CC=CC=C1 ZEEBGORNQSEQBE-UHFFFAOYSA-N 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 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 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- XZTIQYJKLKQFIS-UHFFFAOYSA-N 2'-bromo-9-chlorospiro[benzo[c]fluorene-7,9'-fluorene] Chemical compound C1=CC=C2C(=C1)C=CC3=C2C4=C(C35C6=CC=CC=C6C7=C5C=C(C=C7)Br)C=C(C=C4)Cl XZTIQYJKLKQFIS-UHFFFAOYSA-N 0.000 description 1
- MQGZRENMFSBZEF-UHFFFAOYSA-N 2-bromobenzo[a]fluoren-1-one Chemical compound BrC=1C(C=2C(C=CC3=C4C=CC=CC4=CC=23)=CC=1)=O MQGZRENMFSBZEF-UHFFFAOYSA-N 0.000 description 1
- MTCARZDHUIEYMB-UHFFFAOYSA-N 2-bromofluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Br)=CC=C3C2=C1 MTCARZDHUIEYMB-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- QRMLAMCEPKEKHS-UHFFFAOYSA-N 9,9-dimethyl-n-(4-phenylphenyl)fluoren-2-amine Chemical compound C1=C2C(C)(C)C3=CC=CC=C3C2=CC=C1NC(C=C1)=CC=C1C1=CC=CC=C1 QRMLAMCEPKEKHS-UHFFFAOYSA-N 0.000 description 1
- KIWPRIROZPTWRK-UHFFFAOYSA-N 9-bromo-2'-chlorospiro[benzo[c]fluorene-7,9'-fluorene] Chemical compound C1=CC=C2C(=C1)C=CC3=C2C4=C(C35C6=CC=CC=C6C7=C5C=C(C=C7)Cl)C=C(C=C4)Br KIWPRIROZPTWRK-UHFFFAOYSA-N 0.000 description 1
- UTMSVDJHIFRVSW-UHFFFAOYSA-N 9-bromobenzo[c]fluoren-7-one Chemical compound BrC=1C=CC=2C=3C4=C(C=CC=3C(C=2C=1)=O)C=CC=C4 UTMSVDJHIFRVSW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- REAYFGLASQTHKB-UHFFFAOYSA-N [2-[3-(1H-pyrazol-4-yl)phenoxy]-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound N1N=CC(=C1)C=1C=C(OC2=NC(=CC(=C2)CN)C(F)(F)F)C=CC=1 REAYFGLASQTHKB-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 1
- IMKMFBIYHXBKRX-UHFFFAOYSA-M lithium;quinoline-2-carboxylate Chemical compound [Li+].C1=CC=CC2=NC(C(=O)[O-])=CC=C21 IMKMFBIYHXBKRX-UHFFFAOYSA-M 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- BZHGXQBPJUHVFW-UHFFFAOYSA-N toluene;tritert-butylphosphane Chemical compound CC1=CC=CC=C1.CC(C)(C)P(C(C)(C)C)C(C)(C)C BZHGXQBPJUHVFW-UHFFFAOYSA-N 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
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Abstract
The invention discloses a spirobifluorene organic compound containing diarylamine substituent groups, which has a structure shown as a formula (1). The compound has a non-planar spatial structure, a higher glass transition temperature, suitable HOMO and LUMO energy levels, and a higher Eg, energyThe compound can be sublimated under the condition of no decomposition or residue, can effectively improve the luminous performance of the OLED device and the service life of the OLED device, and is suitable for the OLED devices of phosphorescence and fluorescence, especially when the compound is used as a hole injection material and/or a hole transport material.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescence (organic EL, also called OLED), and particularly relates to an organic compound containing a spirobifluorene structure and an application thereof in an OLED device, and also relates to the OLED device containing the organic compound.
Background
The OLED device has the advantages of self-luminescence, high contrast ratio, good color saturation, wide viewing angle, high reaction speed, curling and the like, and is the currently recognized new generation display technology with the most prospect. The inorganic photoelectric material is a block material consisting of hard bound metal, metalloid and semiconductor elements, and the whole block cannot be bent; the OLED material is different from the prior OLED material, is a continuous film formed by stacking organic molecules, is soft and bendable, and can be freely applied to the Internet of things, wearable devices, military aircrafts and the like, and the thickness of each layer of the film is less than 0.0001 centimeter (namely, the submicron level). OLEDs also have the advantage of energy saving if applied to white light illumination and are therefore the red-falling member of photovoltaic materials.
The OLED photoelectric functional material film layer constituting the OLED device at least includes two or more layers, and the OLED device generally includes a plurality of film layers such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an emission layer (EML), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL), which means that the photoelectric functional material of the OLED device at least includes a hole injection material, a hole transport material, a light emitting material, and an electron transport material. The material types and the collocation forms of the photoelectric functional materials have the characteristics of richness and diversity, and the used photoelectric functional materials have stronger selectivity for OLED devices with different structures.
The spirobifluorene molecule has a non-planar spatial structure, and two fluorene monomers are represented by sp3The hybridized C atoms are bridged together as a center. The organic electroluminescent material is introduced into molecules with electroluminescent characteristics, and has potential high application value for improving the thermal stability, the spectral stability and the like of the molecules.
Disclosure of Invention
The invention aims to provide an organic compound of a spirobifluorene structure containing diarylamine substituent groups, which has a non-planar spatial structure, a higher glass transition temperature, appropriate HOMO and LUMO energy levels and a higher Eg, can be sublimated without decomposition or residues, can effectively improve the light-emitting performance of an OLED device and the service life of the OLED device, and is suitable for OLED devices of phosphorescence and fluorescence (including TADF), especially when the compound is used as a hole injection material and/or a hole transport material.
Specifically, the organic compound of the spirobifluorene structure containing diarylamine substituent groups has a structure shown in the following chemical formula (1):
wherein the content of the first and second substances,
ring A, B and C, independently or simultaneously, each independently represent a condensed aryl or heteroaryl group having 6 to 18 carbon atoms in the ring, substituted or unsubstituted;
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6each independently represents a substituted or unsubstituted aryl or heterocyclic aryl group, and Ar1And Ar2Can pass through E1Are linked to each other to form a ring, Ar3And Ar4Can pass through E2Are linked to each other to form a ring, Ar5And Ar6Can pass through E3Are connected with each other to form a ring;
E1、E2、E3each independentlyRepresents a direct bond, O, S, CRR 'or NR, wherein R and R' each independently represent C1-C8Straight or branched alkyl of (2), C1-C8Alkoxy group of (C)7-C14Aralkyl group of (1);
S1、S2、S3each independently represents a direct bond, a substituted or unsubstituted arylene, a substituted or unsubstituted heteroarylene;
m, n, t each independently represent an integer of 0 to 3;
R1、R2、R3、R4each independently represents hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, or a substituted or unsubstituted heterocyclic group;
x and y each independently represent 0 or 1, and both are not 0 at the same time.
As a preferred embodiment of the present invention, ring A, B and C are present alone, i.e., only A or B or C is present. Further preferably, rings A, B and C each independently represent a benzene ring.
Preferably, Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Each independently having 6 to 60 carbon atoms, and each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolyl group.
Preferably, S1、S2、S3Each independent earth surfaceDirect bond, C6-C20Arylene or heteroarylene of (a). More preferably, S1、S2、S3Denotes a direct bond, i.e. the spirobifluorene structure is directly attached to the N atom.
Preferably, R1、R2、R3、R4Each independently represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, phenyl, 1-naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutyloxy, n-pentoxy, sec-pentoxy, neopentoxy, cyclopentoxy, n-hexoxy, neohexoxy, cyclohexoxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, 2-methylbutyloxy, 2-methylo, Trifluoromethoxy and pentafluoroethoxy. More preferably, R1、R2、R3、R4Each independently represents hydrogen or phenyl.
In a preferred embodiment of the present invention, S in the structure of formula (1)1、S2And S3Both are direct bonds, and rings A, B and C exist independently in a benzene ring structure. That is, the organic compound of spirobifluorene structure of the present invention is selected from the compounds of the following formulae (2) to (4):
further preferably, R1、R2、R3、R4All represent hydrogen, that is, the organic compound of spirobifluorene structure of the present invention is selected from the compounds of the following formulae (2-1) to (4-1):
particularly preferably, the organic compound of spirobifluorene structure of the present invention is selected from compounds of formula (2-1) and the sum of x and y is equal to 1. That is, preferred are compounds such as the following formulas (2-2) and (2-3):
in the above general structures, Ar is preferably Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Each independently, is selected from the following structures:
wherein the dotted line represents a linking site bonded to nitrogen; r5Each independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, n-octyl, phenyl, 4-tert-butylphenyl, cycloalkyl.
Without limitation, the following are some preferred examples of compounds of the present invention:
after determining the above-described organic compounds of the present invention and their structural characteristics, it is easy for those skilled in the art of organic chemistry to determine how to prepare the compounds. Practice shows that the target product can be synthesized by adopting various paths.
Illustratively, the synthesis method shown below is preferable.
The method comprises the following steps:
(1) synthesis of Compound of formula (2-2)
The method comprises the steps of performing addition reaction on a raw material A and bromofluorenone under the action of an N-butyllithium reagent to obtain an intermediate alcohol B, performing cyclization after hydrolysis to generate dihalogenated benzospirobifluorene C, performing C-N coupling reaction with diarylamine step by step to obtain a compound D substituted by the monodiarylamine, and then obtaining the compound of formula (2-2).
(2) Synthesis of Compound of formula (2-3)
The raw material A 'is added with dihalofluorenone under the action of an N-butyllithium reagent to obtain an intermediate alcohol B', and the intermediate alcohol B 'is hydrolyzed and cyclized to generate dihalogenated benzospirobifluorene C', and then the dihalogenated benzospirobifluorene C 'and diarylamine are subjected to C-N coupling reaction step by step to obtain a compound D' substituted by the monodirectional diarylamine and then obtain a compound of a formula (2-3).
The second method comprises the following steps:
synthesis of Compound of formula (2-2)
Reacting 1-bromo-2-methyl naphthoate (E) with bromobenzylboronic acid to obtain an intermediate product F, hydrolyzing to generate an intermediate G, and cyclizing to obtain an intermediate H; under the action of an N-butyllithium reagent, reacting the intermediate H with dihalobiphenyl to obtain an intermediate alcohol B, performing cyclization after hydrolysis to generate dihalogenated benzospirobifluorene C ", and then performing C-N coupling reaction with diarylamine step by step to obtain the compound shown in the formula (2-2).
It will be readily appreciated that, in the above synthetic scheme, if the two diarylamine substituents in the final product are the same, the step of stepwise C-N coupling of the intermediate dihalobenzspirobifluorene with diarylamine can be simplified and the product can be obtained directly by C-N coupling of the dihalobenzspirobifluorene with the same diarylamine.
The invention also relates to application of the organic compound of the spirobifluorene structure containing the diarylamine substituent group in an OLED device and the OLED device containing the organic compound.
As an exemplary embodiment, the OLED device includes: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers comprise the above-described organic compound of the present invention.
The organic material layer may be formed of a single layer structure or a multi-layer structure in which two or more organic material layers are stacked. For example, the light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like as an organic material layer. The device structure is not limited thereto, and may include a smaller number of organic layers.
As another exemplary embodiment, the organic material layer includes a hole transport layer, and the hole transport layer includes the above-described organic compound of the present invention.
As an exemplary embodiment, the organic material layer includes a hole injection layer and a hole transport layer, wherein the hole transport layer includes the above-described organic compound of the present invention, and the hole injection layer uses a compound HAT-CN having the following structural formula:
as an exemplary embodiment, the organic material layer includes a hole injection layer including the above-described organic compound of the present invention.
Further, the hole injection layer contains a p-type dopant material doped at a doping concentration of 1 to 20 wt% in addition to the above-mentioned organic compound of the present invention, and the chemical structural formula of the p-type dopant material is as follows:
a p-type doped material.
As an exemplary embodiment, the organic material layer includes a hole injection layer and a hole transport layer, and both the hole injection layer and the hole transport layer include the above-described organic compound of the present invention.
As an exemplary embodiment, the organic material layer further includes an electron blocking layer using a compound HT2 of the following chemical structure:
as an exemplary embodiment, the organic material layer further includes a light emitting layer, and the light emitting layer uses a compound BH as a main light emitter and a compound BD as a guest light emitter, wherein the doping ratio of the guest light emitter is 1 to 10 wt%, and the chemical structural formulas of both are as follows:
as an exemplary embodiment, the organic material layer further includes an electron transport layer using a compound ET of the following chemical structure and containing Lithium quinolate (abbreviated as Liq) doped with 50 wt%:
as an exemplary embodiment, the organic material layer further includes an electron injection layer, and compounds that can be used for the electron injection layer are lithium fluoride (LiF), cesium fluoride (CsF), Liq, Yb, and the like.
The OLED device of the present invention may be a top emission type, a bottom emission type, or a bi-directional emission type, depending on the material used.
The organic compound is used for an organic material layer of an OLED device, and particularly when the organic compound is used for a hole injection material and/or a hole transport material, the efficiency, the driving voltage and/or the life characteristic of the device can be improved, the device has low driving voltage and long service life, and the device performance with high stability is shown.
Drawings
FIG. 1 is a schematic structural diagram of an OLED device in the characterization of device application performance; wherein the content of the first and second substances,
1. transparent base plate, 2, anode layer, 3, hole injection layer, 4, hole transport layer, 5, electron blocking layer, 6, luminescent layer, 7, electron transport layer, 8, electron injection layer, 9, cathode layer.
Detailed Description
The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. On the basis of this description, a person of ordinary skill in the art will be able to carry out the invention and prepare further compounds according to the invention within the full scope of the disclosure without inventive effort, and to use these compounds in electronic devices or to use the method according to the invention.
Preparation examples
Intermediates and target compounds were prepared according to the synthetic procedures described above.
1. Synthesis of intermediates
1.1 Synthesis of intermediate H (bromobenzofluorenone)
(1) Intermediate H1: 9-bromo-7H-benzo [ c ] fluoren-7-one
Fully drying the experimental device, adding 1-bromo-2-methyl naphthoate (E, 113mmo1, 30g), p-bromophenylboronic acid (114mmo1, 23g), toluene 450mL, ethanol 20mL, water 200mL, potassium carbonate (339mmo1, 47g) and tetrakis (triphenylphosphine) palladium (1mmo1, 1.2g) into a 1L four-neck flask under nitrogen, heating to 78 ℃ for refluxing, stirring for reaction for 5 hours, and tracking the progress of a raw material reaction by TLC; after the reaction is finished, stopping heating, cooling to 25 ℃, separating liquid, washing the organic phase once, removing the solvent by reduced pressure distillation, and purifying by column chromatography to obtain the off-white solid product F123 g with the yield of 60%.
Fully drying the experimental device, adding F1(67.4mmo1, 23g) and 200mL of hydrobromic acid and 50mL of dichloromethane into a clean 500mL four-neck flask, heating to 60 ℃, refluxing, stirring for reacting for 8h, and tracking the progress of the raw material reaction by HPLC; after the reaction is finished, stopping heating, cooling to 25 ℃, separating liquid, extracting the water phase once by using dichloromethane, combining organic phases, washing once by using water, separating liquid, removing the solvent under reduced pressure, and purifying by using column chromatography to obtain a yellow solid product G117.6g, wherein the yield is 80%.
Fully drying the experimental device, adding G1(53.8mmo1, 17.6G) and 250mL of 60% sulfuric acid solution into a clean 500mL four-neck flask, heating to 100 ℃, stirring for reacting for 12h, and tracking the reaction progress of raw materials by HPLC; stopping heating after the reaction is finished, cooling to 25 ℃, pouring the reaction liquid into a large amount of ice water, separating out a product, filtering, washing a filter cake once by using clear water, and filtering to obtain a crude product; heating and dissolving the mixture by using dichloromethane, and purifying the mixture by column chromatography to obtain a yellow solid product H18.3g with the yield of 50 percent.
The structure of product H1 was characterized and the results are shown below.
1H NMR(CDCl3,400MHz):8.41～8.37(d,J＝8.0Hz,1H),7.90～7.23(m,8H)；
IR(KBr)ν:3059,3018,1760cm-1；
MS[M+H]+＝308.99。
(2) Intermediate H2-H4
Referring to the preparation method of intermediate H1, intermediates H2-H4 were synthesized by using different starting materials. As shown in table 1 below.
TABLE 1
Note: 1. examples H2 and H3, which were made from the same starting material and were separated by column chromatography, gave two products depending on the ring closure position.
2. The yield in table 1 represents the actual yield of the last reaction.
1.2 Synthesis of intermediate C (dihalobenzspirobifluorene)
(1) Intermediate C1: 2 '-bromo-9-chloro spiro [ benzo [ c ] fluorene-7, 9' -fluorene ]
Fully drying the experimental device, adding raw material A1(126mmo1, 40g) and dried tetrahydrofuran (400mL) into a 1L four-neck flask under nitrogen, stirring to dissolve, cooling to below-78 ℃ by using liquid nitrogen, and slowly dropwise adding 50.6mL of 2.5M (126mmol) n-BuLi n-hexane solution; after the end of the dropwise addition, the mixture was stirred at-78 ℃ for 1 hour, then 2-bromo-9-fluorenone (126mmo1, 32.6g) was added in portions at this temperature, and after the end of the dropwise addition, the mixture was kept at-78 ℃ for 1 hour and then stirred at room temperature for 12 hours. After the reaction is finished, 4M hydrochloric acid solution is dripped to quench the reaction, ethyl acetate is used for extraction, the organic phase is washed by saturated saline solution, and the solvent is removed by spin drying to obtain intermediate alcohol B1. Without any purification, a 1L dry three-necked flask was charged with acetic acid 160mL and 36% hydrochloric acid 5g, and the reaction was terminated by heating and refluxing for 3 hours. After cooling to room temperature, filtering, washing twice with water, drying and purifying by column chromatography to obtain the off-white solid product C135 g with the total yield of 58%.
The structure of product C1 was characterized and the results are shown below.
1H NMR(CDCl3,400MHz):8.70(d,J＝8.0Hz,1H),8.23(d,J＝8.0Hz,1H),7.89～7.83(m,3H),7.73～7.49(m,4H),7.34(t,J＝8.0Hz,2H),7.05(t,J＝8.0Hz,2H),6.89(s,1H),6.78～6.66(m,2H)；
IR(KBr)ν:3060,3019cm-1；
MS[M+H]+＝479.02
(2) Intermediate C2: 2 '-chloro-9-bromospiro [ benzo [ c ] fluorene-7, 9' -fluorene ]
Fully drying the experimental device, adding 2-bromo-4 ' -chloro-1, 1' ' -biphenyl (126mmo1, 33.7g) and dried tetrahydrofuran (400mL) into a 1L four-neck flask under nitrogen, stirring to dissolve, cooling to below-78 ℃ by using liquid nitrogen, and slowly dropwise adding 50.6mL of 2.5M (126mmol) n-BuLi n-hexane solution; after the end of the dropwise addition, the mixture was stirred at-78 ℃ for 1H, then H1(126mmo1, 39g) was added portionwise at this temperature, and after the end of the dropwise addition, the mixture was kept at-78 ℃ for 1H and then stirred at room temperature for 12H. After the reaction is finished, 4M hydrochloric acid solution is dripped to quench the reaction, ethyl acetate is used for extraction, the organic phase is washed by saturated saline solution, and the solvent is removed by spin drying to obtain intermediate alcohol B2. Without any purification, a 1L dry three-necked flask was charged with acetic acid 160mL and 36% hydrochloric acid 5g, and the reaction was terminated by heating and refluxing for 3 hours. After cooling to room temperature, filtration, washing twice with water, drying, and purification by column chromatography gave the off-white solid product C238.7g, with a total yield of 64%.
The structure of product C2 was characterized and the results are shown below.
1H NMR(CDCl3,400MHz):8.70(d,J＝8.0Hz,1H),8.23(d,J＝8.0Hz,1H),7.89～7.83(m,3H),7.70～7.45(m,4H),7.34(t,J＝8.0Hz,2H),7.05(t,J＝8.0Hz,2H),6.84(s,1H),6.78～6.66(m,2H)；
IR(KBr)ν:3060,3019cm-1；
MS[M+H]+＝479.03。
(3) Intermediate C3-C18
Referring to the preparation method of intermediates C1 or C2, intermediates C3-C18 were synthesized by using different starting materials. As shown in table 2 below.
TABLE 2
1.3 Synthesis of intermediate D (Monodiarylamine-substituted halobenzospirobifluorenes)
And carrying out C-N coupling reaction on the intermediate C and diarylamine step by step to obtain the final target compound. In the process, the mono-diarylamine substituted halogenated benzospirobifluorene, namely the intermediate D, can be obtained through stepwise C-N coupling reaction by utilizing the reaction activity difference of different halogen substituted groups.
(1) Intermediate D1
The experimental set-up was thoroughly dried and C1, i.e., 2' -bromo-9-chlorospiro [ benzo [ C ], was added to a 500mL four-necked flask under nitrogen]Fluorene-7, 9' -fluorenes]21.6g (45mmol) and 17.9g (49.5mmol) of N- [1,1' -biphenyl-4-yl]-9, 9-dimethyl-9H-fluoren-2-amine, then dried and degassed toluene as solvent, 6.5g (67.5mmol) sodium tert-butoxide, 1.1g (1.13mmol) catalyst Pd2(dba)3And 1.2g (2.25mmol) of 1,1' -bis (diphenylphosphino) ferrocene, and the temperature is raised to 100 ℃ and 105 ℃ for reaction for 16 h. After the reaction is finished, cooling to room temperature, diluting with toluene, filtering with silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, and purifying the crude product by column chromatography to obtain 19.5g of a product D1 with the yield of 57%.
MS[M+H]+＝759.25。
(2) Intermediates D2-D10
Intermediates D2-D10 were synthesized by using different starting materials. As shown in table 3 below.
TABLE 3
2. Synthesis of target Compound
The mono-diaryl amine substituted halogenated benzospirobifluorene and diaryl amine are further subjected to C-N coupling reaction to obtain the target compound.
(1) Example 1: synthesis of Compounds 1 to 12
The experimental apparatus was thoroughly dried, and D1(34.2g, 45mmol) and 12.1g (49.5mmol) of N-phenyl-4-benzidine were added to a 500mL four-necked flask under nitrogen, dried and degassed toluene was added as a solvent, and 6.5g (67.5mmol) of sodium tert-butoxide and 0.88g (0.96mmol) of catalyst Pd were added2(dba)3Heating to 80 ℃, slowly dripping 4.5mL of tri-tert-butylphosphine toluene solution with the mass concentration of 10%, heating to 100-105 ℃ after dripping, and reacting for 6 h. After the reaction is finished, cooling to room temperature, diluting with toluene, filtering with silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, and purifying the crude product by column chromatography to obtain 26.6g of products 1-12 with the yield of 61%.
The structures of products 1-12 were characterized and the results are shown below.
1H NMR(CDCl3,400MHz):8.20～7.85(m,8H),7.76(d,J＝8.0Hz,4H),7.56(d,J＝8.0Hz,5H),7.50(t,J＝8.0Hz,4H),7.48～7.40(m,5H),7.38(d,J＝8.0Hz,4H),7.35～7.29(m,4H),7.27～7.19(m,6H),7.15～7.05(m,5H),6.98(t,J＝8.0Hz,1H),1.68(s,6H)；
MS[M+H]+＝968.42。
(2) Example 2: synthesis of Compounds 1-98
The experimental apparatus was thoroughly dried, C10(23.6g, 45mmol) and 22.3g (91mmol) of N-phenyl-4-benzidine were added to a four-necked flask under nitrogen, dried and degassed toluene was added as a solvent, 6.5g (67.5mmol) of sodium tert-butoxide and 0.88g (0.96mmol) of catalyst Pd were added2(dba)3Heating to 80 ℃, and slowly dripping 4.5mL of tri-tert-butylphosphine with the mass concentration of 10%And (3) after the dripping of the toluene solution is finished, heating to 100-105 ℃, and reacting for 6 h. After the reaction is finished, cooling to room temperature, diluting with toluene, filtering with silica gel, evaporating the solvent from the filtrate in vacuum to obtain a crude product, and purifying the crude product by column chromatography to obtain 25.7g of products 1-98 with the yield of 67%.
The structures of products 1-98 were characterized and the results are shown below.
1H NMR(CDCl3,400MHz):8.77～7.75(d,J＝8.2Hz,1H),8.22～8.20(d,J＝8.0Hz,1H),8.02～8.01(d,J＝8.0Hz,1H),7.88～7.74(m,4H),7.76(d,J＝8.0Hz,4H),7.57～7.54(m,5H),7.50(t,J＝8.0Hz,4H),7.45～7.36(m,9H),7.25～7.22(m,6H),7.10～7.00(m,9H)；
MS[M+H]+＝852.36。
(3) Examples 3 to 8
Referring to the preparation methods of the compounds 1-12 and 1-98, different intermediates C or D and diarylamine are used as raw materials to synthesize corresponding target compounds. Specifically, as shown in table 4 below.
TABLE 4
Performance characterization
3. Physical properties of the compound
The thermal properties, HOMO level and LUMO level of the organic compounds of the present invention were examined using some of the compounds as examples. The test subjects and the results thereof are shown in table 5 below.
TABLE 5
| Compound (I) | Tg | Td | HOMO | LUMO | Functional layer |
| 1-2 | 157 | 480 | 5.22 | 2.28 | HIL，HTL，EBL，EML |
| 1-36 | 160 | 488 | 5.29 | 2.26 | HIL，HTL，EBL，EML |
| 1-6 | 165 | 492 | 5.38 | 2.25 | HIL，HTL，EBL，EML |
| 1-43 | 172 | 497 | 5.43 | 2.27 | HIL，HTL，EBL，EML |
| 1-86 | 189 | 502 | 5.45 | 2.23 | HIL，HTL，EBL，EML |
Wherein the glass transition temperature Tg is determined by differential scanning calorimetry (DSC, DSC25 differential scanning calorimeter of TA company in USA), and the heating rate is 10 ℃/min; the thermal weight loss temperature Td is a temperature at which 5% of weight is lost in a nitrogen atmosphere, and is measured on a TGA55 thermogravimetric analyzer of the company TA of America, and the nitrogen flow is 20 mL/min; the highest occupied molecular orbital HOMO energy level and the lowest unoccupied molecular orbital LUMO energy level are measured by cyclic voltammetry.
As can be seen from the data in Table 5, the compound of the present invention has a higher glass transition temperature, and can ensure the thermal stability of the compound, thereby preventing the amorphous thin film of the compound from being transformed into a crystalline thin film, and improving the lifetime of the OLED device containing the organic compound of the present invention. Meanwhile, the compound has different HOMO and LOMO energy levels, and can be applied to different functional layers of OLED devices.
In particular, as shown in table 5, the organic compound of the present invention is particularly suitable for a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), and/or an emission layer (EML) in an OLED device. They may be provided as individual layers or as mixed components in the HIL, HTL, EBL or EML.
OLED device applications
The effect of the organic compounds of the present invention as materials for different functional layers in OLED devices is detailed in device examples 1-10 and comparative examples 1-2 below with reference to FIG. 1.
Other materials used in the device examples and comparative examples were known in the art and available on the market. The structural formula of the organic material used is as follows:
(1) device example 1
Referring to the structure shown in fig. 1, the OLED device is manufactured by the following specific steps: ultrasonically washing a glass substrate (Corning glass 50mm x 0.7mm) plated with ITO (indium tin oxide) with the thickness of 130nm with isopropanol and pure water for 5 minutes respectively, then cleaning with ultraviolet ozone, and then conveying the glass substrate into a vacuum deposition chamber; the hole injection material HAT-CN was evacuated to a thickness of 5nm (about 10nm)-7Torr) thermal deposition on a transparent ITO electrode, thereby forming a hole injection layer; depositing a compound 1-2 with the thickness of 140nm on the hole injection layer in vacuum to form a hole transport layer; depositing HT2 with the thickness of 10nm on the hole transport layer in vacuum to form an electron blocking layer; as a light emitting layer, a host BH and a 4% guest dopant BD are deposited in vacuum, and the thickness is 25 nm; forming an electron transport layer using an ET compound comprising 50% Liq (8-hydroxyquinoline lithium) doped to a thickness of 25 nm; finally, lithium fluoride (an electron injection layer) with the thickness of 1nm and aluminum with the thickness of 100nm are deposited in sequence to form a cathode; the device was transferred from the deposition chamber into a glove box and then encapsulated with a UV curable epoxy and a glass cover plate containing a moisture absorber.
The device structure is represented as: ITO (130nm)/HAT-CN (5 nm)/compound 1-2(140nm)/HT2(10nm)/BH: BD (25nm)/ET: Liq (25nm)/LiF (1nm)/Al (100 nm). The structure of the fabricated OLED light-emitting device is shown in table 6, and the test results are shown in table 7.
In the above manufacturing steps, the deposition rates of the organic material, lithium fluoride and aluminum were maintained at 0.1nm/s, 0.05nm/s and 0.2nm/s, respectively.
(2) Device example 2
An experiment was performed in the same manner as in device example 1 except that: as the hole transport layer, compounds 1 to 36 were used instead of compound 1 to 2 in example 1. The structure of the fabricated OLED light-emitting device is shown in table 6, and the test results are shown in table 7.
(3) Device example 3
An experiment was performed in the same manner as in device example 1 except that: as the hole transporting layer, compound 1-6 was used instead of compound 1-2 in example 1. The structure of the fabricated OLED light-emitting device is shown in table 6, and the test results are shown in table 7.
(4) Device example 4
An experiment was performed in the same manner as in device example 1 except that: as the hole transporting layer, compounds 1 to 43 were used instead of compound 1 to 2 in example 1. The structure of the fabricated OLED light-emitting device is shown in table 6, and the test results are shown in table 7.
(5) Device example 5
An experiment was performed in the same manner as in device example 1 except that: as the hole transporting layer, compounds 1 to 86 were used in place of compound 1 to 2 in example 1. The structure of the fabricated OLED light-emitting device is shown in table 6, and the test results are shown in table 7.
(6) Comparative example 1
An experiment was performed in the same manner as in device example 1 except that: as the hole transport layer, HT1 was used instead of compound 1-2 in example 1. The structure of the fabricated OLED light-emitting device is shown in table 6, and the test results are shown in table 7.
TABLE 6
Compared with comparative example 1, the device manufacturing processes in the device examples 1 to 5 are completely the same, and the same substrate and electrode material are adopted, and the film thickness of the electrode material is also kept consistent, except that the hole transport material HT1 in the device is replaced. The performance of the devices obtained in each example was 10mA/cm2The test results at current density are shown in table 7.
TABLE 7
Wherein the emission color is represented by CIEx,yJudging and defining chromaticity coordinates; the driving voltage is 1cd/m in luminance2Voltage of (d); the current efficiency refers to the luminous brightness under unit current density; luminous efficiency refers to the luminous flux produced by consuming a unit of electric power; external Quantum Efficiency (EQE) refers to the ratio of the number of photons exiting the surface of the component in the observation direction to the number of injected electrons; LT95@1000nits refers to the time for the device to decrease in brightness from the initial 100% to 95% under constant current conditions with 1000nits as the initial brightness.
As shown in the above table, the compounds used in device examples 1 to 5, which were used as hole transport layers in organic light emitting devices, had excellent hole transport ability and exhibited low voltage and high efficiency characteristics, as compared to the benzidine-type material HT 1. At the same time, the material shows better stability and service life based on high triplet energy (characteristics of spiro material). It can be seen that the organic light emitting device including the present invention has low driving voltage and long service life, and exhibits high-stability device performance.
To further verify the performance advantages of the present invention, OLED devices having the structure shown in table 8 were fabricated in the manner described above with reference to example 1.
TABLE 8
Compared with comparative example 2, the device manufacturing processes of device examples 6 to 10 of the present invention are completely the same, and the same substrate and electrode material are used, and the film thicknesses of the electrode materials are also kept the same, except that the hole injection material and the hole transport material in the device are replaced, and the hole injection layer is doped with 2 wt% of a p-type doping material.
The devices obtained in examples 6 to 10 and comparative example 2 were mixed at 10mA/cm2The results of the performance tests at current density are shown in table 9.
TABLE 9
The compounds used in device examples 6 to 10 were used as a host material for a hole injection layer and a hole transport layer in an organic light emitting device, and a p-type dopant compound was doped in the hole injection layer, and thus, compared to a benzidine-type material, the compounds had excellent hole injection and transport capabilities, exhibited low voltage and high efficiency characteristics, and also exhibited better stability and lifetime. It can be seen that the organic light emitting device including the present invention has low driving voltage and long service life, and exhibits high-stability device performance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (22)
1. An organic compound of a spirobifluorene structure containing diarylamine substituent groups has a structure represented by the following chemical formula (1):
wherein the content of the first and second substances,
ring A, B and C, independently or simultaneously, each independently represent a condensed aryl or heteroaryl group having 6 to 18 carbon atoms in the ring, substituted or unsubstituted;
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6each independently represents a substituted or unsubstituted aryl or heterocyclic aryl group, and Ar1And Ar2Can pass through E1Are linked to each other to form a ring, Ar3And Ar4Can pass through E2Are linked to each other to form a ring, Ar5And Ar6Can pass through E3Are connected with each other to form a ring;
E1、E2、E3each independently represents a direct bond, O, S, CRR 'or NR, wherein R and R' each independently represents C1-C8Straight or branched alkyl of (2), C1-C8Alkoxy group of (C)7-C14Aralkyl group of (1);
S1、S2、S3each independently represents a direct bond, a substituted or unsubstituted arylene, a substituted or unsubstituted heteroarylene;
m, n, t each independently represent an integer of 0 to 3;
R1、R2、R3、R4each independently represents hydrogen, deuterium, halogen, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted arylalkenyl group, or a substituted or unsubstituted heterocyclic group;
x and y each independently represent 0 or 1, and both are not 0 at the same time.
2. An organic compound according to claim 1, characterized in that: ring A, B and C exist separately.
3. An organic compound according to claim 1 or 2, characterized in that: ring A, B and C each independently represent a benzene ring.
4. An organic compound according to claim 1, characterized in that: ar (Ar)1、Ar2、Ar3、Ar4、Ar5、Ar6Each independently has 6-60Carbon atom, and each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted tetrabiphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted carbazolyl group.
5. An organic compound according to claim 1, characterized in that: s1、S2、S3Each independently represents a direct bond, C6-C20Arylene or heteroarylene of (a); more preferably, S1、S2、S3Representing a direct bond.
6. An organic compound according to claim 1, characterized in that: r1、R2、R3、R4Each independently represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, phenyl, 1-naphthyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, 2-methylbutyloxy, n-pentoxy, sec-pentoxy, neopentoxy, cyclopentoxy, n-hexoxy, neohexoxy, cyclohexoxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, 2-methylbutyloxy, 2-methylo, Trifluoromethoxy, pentafluoroethoxy; more preferably, R1、R2、R3、R4Each independently represents hydrogen or phenyl.
7. The organization of claim 1A compound characterized by: s1、S2And S3Both are direct bonds, ring A, B and C exist independently as a benzene ring structure;
namely, the organic compound is selected from the group consisting of compounds of the following formulae (2) to (4):
8. the organic compound of claim 7, wherein: r1、R2、R3、R4All represent hydrogen; namely, the organic compound is selected from the compounds of the following formulae (2-1) to (4-1):
9. the organic compound of claim 8, wherein: the organic compound is selected from compounds of formula (2-1) and the sum of x and y is equal to 1; namely, a compound selected from the following formulae (2-2) and (2-3):
10. the organic compound according to any one of claims 1 to 9, wherein: in each general structure, Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Each independently, is selected from the following structures:
wherein the dotted line represents a linking site bonded to nitrogen; r5Each independently represents methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, cycloheptyl, cyclopentyl,N-octyl, phenyl, 4-tert-butylphenyl, cycloalkyl.
11. The method for producing an organic compound according to claim 9, wherein the following method is employed:
the method comprises the following steps:
(1) synthesis of Compound of formula (2-2)
Performing addition reaction on a raw material A and bromofluorenone under the action of an N-butyllithium reagent to obtain an intermediate alcohol B, performing cyclization after hydrolysis to generate dihalogenated benzospirobifluorene C, and performing C-N coupling reaction with diarylamine step by step to obtain a compound D substituted by the monodiarylamine and then obtain a compound of a formula (2-2);
(2) synthesis of Compound of formula (2-3)
Adding a raw material A 'and dihalofluorenone under the action of an N-butyllithium reagent to obtain an intermediate alcohol B', hydrolyzing and cyclizing to generate dihalogenated benzospirobifluorene C ', and then carrying out C-N coupling reaction with diarylamine step by step to obtain a compound D' substituted by the monodiarylamine and then obtain a compound of a formula (2-3);
the second method comprises the following steps:
synthesis of Compound of formula (2-2)
Reacting 1-bromo-2-methyl naphthoate (E) with bromobenzylboronic acid to obtain an intermediate product F, hydrolyzing to generate an intermediate G, and cyclizing to obtain an intermediate H; under the action of an N-butyllithium reagent, reacting the intermediate H with dihalobiphenyl to obtain an intermediate alcohol B, performing cyclization after hydrolysis to generate dihalogenated benzospirobifluorene C ", and then performing C-N coupling reaction with diarylamine step by step to obtain the compound shown in the formula (2-2).
12. The method of claim 11, wherein: the two diarylamine substituents in the final product are the same, the step of stepwise C-N coupling reaction of the intermediate dihalogenated benzospirobifluorene and diarylamine is simplified, and the dihalogenated benzospirobifluorene and the same diarylamine are directly subjected to C-N coupling reaction to obtain the product.
13. Use of an organic compound according to any one of claims 1 to 10 in an OLED device.
An OLED device comprising the organic compound of any one of claims 1-10.
15. The OLED device of claim 14 including: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein one or more of the organic material layers contain the organic compound.
16. The OLED device of claim 15, wherein: the organic material layer includes a hole transport layer, and the hole transport layer contains the organic compound.
17. The OLED device of claim 15, wherein: the organic material layer includes a hole injection layer and a hole transport layer, wherein the hole transport layer contains the organic compound, and the hole injection layer uses a compound HAT-CN having the following structural formula:
18. the OLED device of claim 15, wherein: the organic material layer includes a hole injection layer containing the organic compound.
19. The OLED device of claim 18, wherein: the hole injection layer contains, in addition to the organic compound, a p-type doping material doped at a doping concentration of 1-20 wt%, the p-type doping material having the following chemical formula:
20. the OLED device of claim 15, wherein: the organic material layer includes a hole injection layer and a hole transport layer, and both the hole injection layer and the hole transport layer contain the organic compound.
21. The OLED device of claim 15, wherein: the organic material layer further comprises at least one of an electron blocking layer, a light emitting layer, an electron transport layer and an electron injection layer; wherein the content of the first and second substances,
the electron blocking layer uses compound HT2 of the following chemical structure:
the luminescent layer uses a compound BH as a main luminophor and a compound BD as a guest luminophor, wherein the doping proportion of the guest luminophor is 1-10 wt%, and the chemical structural formulas of the two are as follows:
the electron transport layer uses compound ET of the following chemical structure and comprises quinoline lithium doped with 50% by weight:
the electron injection layer uses a compound selected from lithium fluoride (LiF), cesium fluoride (CsF), Liq, Yb.
22. The OLED device of any one of claims 14-21, wherein: the OLED device is of a top emission type, a bottom emission type, or a bi-directional emission type.
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| CN113735694A (en) * | 2021-09-14 | 2021-12-03 | 西安瑞联新材料股份有限公司 | Method for synthesizing 9-halogen-7H-benzo [ c ] fluorene-7-ketone |
| WO2022067630A1 (en) * | 2020-09-30 | 2022-04-07 | 京东方科技集团股份有限公司 | Blue light oled device, display panel, and display apparatus |
| CN114507148A (en) * | 2022-02-17 | 2022-05-17 | 京东方科技集团股份有限公司 | Spirofluorene compound, light emitting device, and display device |
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| US20230413662A1 (en) * | 2020-11-03 | 2023-12-21 | Merck Patent Gmbh | Materials for electronic devices |
| CN114685284A (en) * | 2020-12-29 | 2022-07-01 | 江苏三月科技股份有限公司 | Triarylamine organic compound and application thereof |
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| WO2022067630A1 (en) * | 2020-09-30 | 2022-04-07 | 京东方科技集团股份有限公司 | Blue light oled device, display panel, and display apparatus |
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| CN114507148A (en) * | 2022-02-17 | 2022-05-17 | 京东方科技集团股份有限公司 | Spirofluorene compound, light emitting device, and display device |
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