CN114105891A - Fluorene derivative and organic electroluminescent device thereof - Google Patents
Fluorene derivative and organic electroluminescent device thereof Download PDFInfo
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- CN114105891A CN114105891A CN202111458913.4A CN202111458913A CN114105891A CN 114105891 A CN114105891 A CN 114105891A CN 202111458913 A CN202111458913 A CN 202111458913A CN 114105891 A CN114105891 A CN 114105891A
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- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 22
- 230000005540 biological transmission Effects 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 136
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 34
- -1 benzofluorenyl Chemical group 0.000 claims description 34
- 229910052805 deuterium Inorganic materials 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 31
- 150000002431 hydrogen Chemical class 0.000 claims description 31
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 27
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 27
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 23
- 125000001072 heteroaryl group Chemical group 0.000 claims description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 18
- 125000001624 naphthyl group Chemical group 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 13
- 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 12
- 125000004076 pyridyl group Chemical group 0.000 claims description 12
- 125000000732 arylene group Chemical group 0.000 claims description 11
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 11
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 10
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 10
- 125000005549 heteroarylene group Chemical group 0.000 claims description 10
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 9
- 239000004305 biphenyl Substances 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 8
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 8
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 8
- 125000004306 triazinyl group Chemical group 0.000 claims description 8
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 7
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 7
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 7
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 7
- 125000005493 quinolyl group Chemical group 0.000 claims description 7
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 6
- 125000006749 (C6-C60) aryl group Chemical group 0.000 claims description 6
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 125000005593 norbornanyl group Chemical group 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 125000005561 phenanthryl group Chemical group 0.000 claims description 4
- 125000005551 pyridylene group Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000006836 terphenylene group Chemical group 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical class C1(=NC=CC2=CC=CC=C12)* 0.000 claims 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 238000000605 extraction Methods 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 239000000284 extract Substances 0.000 abstract description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 169
- 230000015572 biosynthetic process Effects 0.000 description 125
- 238000003786 synthesis reaction Methods 0.000 description 125
- 238000004128 high performance liquid chromatography Methods 0.000 description 61
- 238000001819 mass spectrum Methods 0.000 description 58
- 239000007787 solid Substances 0.000 description 54
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 238000001704 evaporation Methods 0.000 description 34
- 238000002347 injection Methods 0.000 description 34
- 239000007924 injection Substances 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 28
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 150000002220 fluorenes Chemical class 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 230000000903 blocking effect Effects 0.000 description 20
- 230000008020 evaporation Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 238000010992 reflux Methods 0.000 description 17
- 229940125782 compound 2 Drugs 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 125000001424 substituent group Chemical group 0.000 description 13
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001514 detection method Methods 0.000 description 12
- 239000002346 layers by function Substances 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 230000005525 hole transport Effects 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 238000007738 vacuum evaporation Methods 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 125000005842 heteroatom Chemical group 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- BFXLJWUGRPGMFU-UHFFFAOYSA-N dipropoxyphosphinothioyl n,n-diethylcarbamodithioate;sulfane Chemical compound S.CCCOP(=S)(OCCC)SC(=S)N(CC)CC BFXLJWUGRPGMFU-UHFFFAOYSA-N 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 5
- 125000003367 polycyclic group Chemical group 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 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 4
- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- PKMUHQIDVVOXHQ-HXUWFJFHSA-N C[C@H](C1=CC(C2=CC=C(CNC3CCCC3)S2)=CC=C1)NC(C1=C(C)C=CC(NC2CNC2)=C1)=O Chemical compound C[C@H](C1=CC(C2=CC=C(CNC3CCCC3)S2)=CC=C1)NC(C1=C(C)C=CC(NC2CNC2)=C1)=O PKMUHQIDVVOXHQ-HXUWFJFHSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229940126179 compound 72 Drugs 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- OOKAZRDERJMRCJ-KOUAFAAESA-N (3r)-7-[(1s,2s,4ar,6s,8s)-2,6-dimethyl-8-[(2s)-2-methylbutanoyl]oxy-1,2,4a,5,6,7,8,8a-octahydronaphthalen-1-yl]-3-hydroxy-5-oxoheptanoic acid Chemical compound C1=C[C@H](C)[C@H](CCC(=O)C[C@@H](O)CC(O)=O)C2[C@@H](OC(=O)[C@@H](C)CC)C[C@@H](C)C[C@@H]21 OOKAZRDERJMRCJ-KOUAFAAESA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- WYFCZWSWFGJODV-MIANJLSGSA-N 4-[[(1s)-2-[(e)-3-[3-chloro-2-fluoro-6-(tetrazol-1-yl)phenyl]prop-2-enoyl]-5-(4-methyl-2-oxopiperazin-1-yl)-3,4-dihydro-1h-isoquinoline-1-carbonyl]amino]benzoic acid Chemical compound O=C1CN(C)CCN1C1=CC=CC2=C1CCN(C(=O)\C=C\C=1C(=CC=C(Cl)C=1F)N1N=NN=C1)[C@@H]2C(=O)NC1=CC=C(C(O)=O)C=C1 WYFCZWSWFGJODV-MIANJLSGSA-N 0.000 description 3
- XFJBGINZIMNZBW-CRAIPNDOSA-N 5-chloro-2-[4-[(1r,2s)-2-[2-(5-methylsulfonylpyridin-2-yl)oxyethyl]cyclopropyl]piperidin-1-yl]pyrimidine Chemical compound N1=CC(S(=O)(=O)C)=CC=C1OCC[C@H]1[C@@H](C2CCN(CC2)C=2N=CC(Cl)=CN=2)C1 XFJBGINZIMNZBW-CRAIPNDOSA-N 0.000 description 3
- IEQGNDONCZPWMW-UHFFFAOYSA-N 9-(7-carbazol-9-yl-9,9-dimethylfluoren-2-yl)carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C(C3(C)C)=CC(=CC=2)N2C4=CC=CC=C4C4=CC=CC=C42)C3=C1 IEQGNDONCZPWMW-UHFFFAOYSA-N 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- RAPBNVDSDCTNRC-UHFFFAOYSA-N Chlorobenzilate Chemical compound C=1C=C(Cl)C=CC=1C(O)(C(=O)OCC)C1=CC=C(Cl)C=C1 RAPBNVDSDCTNRC-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 3
- SPXSEZMVRJLHQG-XMMPIXPASA-N [(2R)-1-[[4-[(3-phenylmethoxyphenoxy)methyl]phenyl]methyl]pyrrolidin-2-yl]methanol Chemical compound C(C1=CC=CC=C1)OC=1C=C(OCC2=CC=C(CN3[C@H](CCC3)CO)C=C2)C=CC=1 SPXSEZMVRJLHQG-XMMPIXPASA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229940127271 compound 49 Drugs 0.000 description 3
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 3
- 150000005041 phenanthrolines Chemical class 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 235000011056 potassium acetate Nutrition 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 125000005580 triphenylene group Chemical group 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
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- BFBVQPCWYPBWEY-UHFFFAOYSA-N iridium(3+);pentane-2,4-dione;2-phenylpyridine Chemical compound [Ir+3].CC(=O)CC(C)=O.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 BFBVQPCWYPBWEY-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ONFSYSWBTGIEQE-UHFFFAOYSA-N n,n-diphenyl-4-[2-[4-[2-[4-(n-phenylanilino)phenyl]ethenyl]phenyl]ethenyl]aniline Chemical compound C=1C=C(C=CC=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=CC=1C=CC(C=C1)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ONFSYSWBTGIEQE-UHFFFAOYSA-N 0.000 description 1
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000005562 phenanthrylene group Chemical group 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- TUNODRIFNXIVIK-UHFFFAOYSA-N silver ytterbium Chemical compound [Ag].[Yb] TUNODRIFNXIVIK-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 125000005558 triazinylene group Chemical group 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
- C07D239/72—Quinazolines; Hydrogenated quinazolines
- C07D239/74—Quinazolines; Hydrogenated quinazolines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms of the hetero ring
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
- C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
- C07D217/04—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines with hydrocarbon or substituted hydrocarbon radicals attached to the ring nitrogen atom
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- C07D—HETEROCYCLIC COMPOUNDS
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- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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Abstract
The invention provides a fluorene derivative and an organic electroluminescent device thereof, and relates to the technical field of organic electroluminescent materials. One end of the fluorene derivative is an electron-withdrawing group, and the group is connected with a fluorene group through a twisted bridging group. The fluorene derivative has a better spatial configuration, and the material has better photoelectric property, so that the organic electroluminescent device containing the fluorene derivative in an electron transmission region has better film stability and is not easy to crystallize, holes can be blocked in a luminescent layer by the organic electroluminescent device, electrons can be transmitted more effectively, the transmission of the electrons and the holes in the organic electroluminescent device is more balanced, more electrons and holes are combined in the luminescent layer to generate excitons for luminescence, and the organic electroluminescent device shows lower driving voltage, higher luminous efficiency and longer service life. In addition, the fluorene derivative also has good light extraction performance, can effectively extract light in the device, and effectively improves the luminous efficiency of the device.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a fluorene derivative and an organic electroluminescent device thereof.
Background
In recent years, Organic Light-Emitting diodes (OLEDs) are rapidly developing as a new generation of flat display terminal technology. Generally, the OLED has the advantages of being close to natural light emission characteristics, wide in viewing angle, light in weight, high in contrast, low in driving voltage, shock-resistant, impact-resistant, capable of achieving flexible and transparent display and the like, so that the OLED has great growth and promotion space in multiple fields, and therefore great attention is paid to the academic world and the industrial world. At present, the OLED has been gradually applied to high-end display fields such as mobile phones, wearable devices, vehicles, and computers.
Organic electroluminescent devices are typically of a sandwich construction, i.e. the organic functional layer is sandwiched between an anode and a cathode on either side of the device. After a certain voltage is applied to two ends of the device, holes injected by the anode and electrons injected by the cathode migrate in the hole transmission area and the electron transmission area, when the holes and the electrons meet at the light emitting layer, excitons are formed and jump to a low energy level, in the process, part of energy is changed into heat energy to be dissipated, and the other part of energy is dissipated in the form of light energy, so that the purpose of light emission is achieved.
Organic electroluminescent devices may be classified into single-layer devices, double-layer devices, multi-layer devices, etc. according to the number of organic functional layers. The single-layer device is composed of two electrodes and an organic functional layer, and the single-layer device has poor performance due to the fact that the organic functional layer is single. The double-layer device is composed of a cathode, an anode, a hole transmission layer and an electron transmission layer, the injection of current carriers of the double-layer device is easier, the charge in the device is more balanced, the quenching of excitons is reduced, and therefore better device performance is obtained. The organic functional layers of the multilayer device can also comprise organic functional layers such as a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, a covering layer and the like besides a hole transport layer, a light emitting layer and an electron transport layer, and the different functional layers have different functions, so that the multilayer device has excellent photoelectric performance.
At present, most organic functional materials cannot meet industrial requirements, especially, the performance of the materials in an electron transport region or a covering layer is far from reaching relevant standards, and the materials used in devices show the defects of high driving voltage, low luminous efficiency, short service life and the like, so that the improvement of the relevant organic functional materials is urgently needed.
In addition, although the number of organic functional layers of the multi-layer device is increased, the photoelectric performance of the multi-layer device is more excellent than that of the conventional multi-layer device, but most of the organic electroluminescent devices still cannot meet the industrial demand, so that the development of the multi-layer device structure organic electroluminescent device having more excellent photoelectric performance, especially the multi-layer device structure organic electroluminescent device having higher luminous efficiency, is required.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a fluorene derivative and an organic electroluminescent device thereof.
The fluorene derivative provided by the invention has a general formula shown in a structural formula 1,
ar is1Selected from the group consisting of groups represented by formula 1-a1, Ar2Selected from the group consisting of those represented by the formula 1-a1 or formula 1-a2,
the Z is the same or different and is selected from N or C (R)z) Wherein at least one Z is selected from N, said RzThe same or different one selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the E is the same or different and is selected from N or C (R)e) Wherein one E is selected from N, whichThe remainder being selected from C (R)e) Said R iseOne selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the L is selected from one of the groups shown as follows,
said L0One selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, and a substituted or unsubstituted pyridylene group; n1 are the same or different and are selected from 0, 1,2,3 or 4; n2 are the same or different and are selected from 0, 1,2 or 3; the R is1The same or different one selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C3-C10 cycloalkyl;
said L1、L2Independently selected from single bond or substituted or unsubstituted arylene of C6-C30;
ar is selected from the group shown as follows,
the R is0The same or different one selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, or two R0Bonding to form a ring structure;
the R is same or different and is selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C2-C60 heteroaryl, or two adjacent R are bonded to form a cyclic structure;
the m1 are the same or different and are selected from 0, 1,2,3 or 4.
In addition, the invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer, a cathode and a covering layer, wherein the covering layer contains the fluorene derivative shown in the structural formula 1.
In addition, the invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer and a cathode, wherein the organic layer comprises an electron transmission region, and the electron transmission region contains the fluorene derivative shown in the structural formula 1.
Has the advantages that:
the fluorene derivative has better spatial configuration and better photoelectric property, so that the organic electroluminescent device containing the fluorene derivative in an electron transmission region has better film stability and is not easy to crystallize, holes can be blocked in a luminescent layer by the organic electroluminescent device, electrons can be transmitted more effectively, the electrons and the holes in the organic electroluminescent device are transmitted more evenly, more electrons and holes are combined in the luminescent layer to generate excitons for luminescence, and the organic electroluminescent device shows lower driving voltage, higher luminous efficiency and longer service life.
In addition, the fluorene derivative also has good light extraction performance, can effectively extract light in the device, and effectively improves the luminous efficiency of the device.
In addition, the device of the hole blocking layer and the covering layer respectively containing the fluorene derivative shown in the structural formula 1 and the heterocyclic compound shown in the structural formula 2 has better luminous performance, higher luminous efficiency and longer service life due to the dual functions of the materials in the electron transporting region and the covering layer.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will fall within the scope of the claims of this application after reading the present invention.
In the present specification, when the position of a substituent on an aromatic ring is not fixed, it means that it can be attached to any of the corresponding optional positions of the aromatic ring. For example,
can represent
And so on.
In the present invention, "adjacent two groups are bonded to form a cyclic structure" means that adjacent groups are bonded to each other and optionally aromatized to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring. The hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. The heterocyclic ring may include an aliphatic heterocyclic ring or an aromatic heterocyclic ring. The aliphatic cyclic hydrocarbon may be a saturated aliphatic hydrocarbon ring or an unsaturated aliphatic hydrocarbon ring, and the aliphatic heterocyclic ring may be a saturated aliphatic heterocyclic ring or an unsaturated aliphatic heterocyclic ring. The hydrocarbon rings and heterocycles may be monocyclic or polycyclic groups. In addition, a ring formed by the combination of adjacent groups may be connected to another ring to form a spiro structure. As exemplified below:
in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a condensed ring, such as benzene, naphthalene, fluorene, pyridine, pyrimidine, dibenzofuran, dibenzothiophene, phenanthrene or pyrene, but is not limited thereto.
The "-" on the substituent groups described herein represents the attachment site.
The term "unsubstituted" in "substituted or unsubstituted" as used herein means that a hydrogen atom on the group is not replaced with any substituent.
The term "substituted" in the "substituted or unsubstituted" as used herein means that at least one hydrogen atom on the group is replaced by a substituent. When a plurality of hydrogens is replaced with a plurality of substituents, the plurality of substituents may be the same or different. The position of the hydrogen substituted by the substituent may be any position.
The substituent represented by the "substituted" in the above "substituted or unsubstituted" is selected from one of deuterium, cyano, nitro, halogen, a substituted or unsubstituted alkyl group having C1 to C15, a substituted or unsubstituted cycloalkyl group having C3 to C15, a substituted or unsubstituted aryl group having C6 to C30, and a substituted or unsubstituted heteroaryl group having C2 to C30, for example, deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, bornanyl, norbornyl, phenyl, tolyl, pentadeuterphenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, anthryl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, dibenzofuranyl, and benzofluorenyl, The functional group is preferably selected from the group consisting of a benzodibenzofuranyl group, a dibenzothienyl group, a benzodibenzothienyl group, a carbazolyl group, a 9-phenylcarbazolyl group, a benzocarbazolyl group, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a benzoquinolyl group, a benzisoquinolyl group, a quinazolinyl group, a quinoxalinyl group, a phenanthridinyl group, a phenanthrolinyl group and the like, and preferably from the group consisting of deuterium, a cyano group, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a phenyl group, a tolyl group, a pentadeuterated phenyl group, a biphenyl group, a naphthyl group and a pyridyl group, but is not limited thereto.
The alkyl group having more than three carbon atoms in the present invention includes isomers thereof, for example, propyl group includes n-propyl group and isopropyl group, and butyl group includes n-butyl group, sec-butyl group, isobutyl group and tert-butyl group. And so on.
"C6 to C60" in the "substituted or unsubstituted aryl group having C6 to C60" in the present invention represent the number of carbon atoms in the unsubstituted "aryl group" and do not include the number of carbon atoms in the substituent. "C2 to C60" in the "substituted or unsubstituted heteroaryl group having C2 to C60" represents the number of carbon atoms in the unsubstituted "heteroaryl group" and does not include the number of carbon atoms in the substituent. And so on.
The alkyl refers to a univalent group formed by subtracting one hydrogen atom from alkane molecules. The alkyl group has a carbon number of from C1 to C30, preferably from C1 to C15, more preferably from C1 to C10, and still more preferably from C1 to C6. Examples of the alkyl group include, but are not limited to, the groups described below, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.
The cycloalkyl refers to a monovalent group formed by omitting one hydrogen atom from a cycloalkane molecule. The cycloalkyl group has a carbon number of C3 to C30, preferably C3 to C15, more preferably C3 to C10 or C3 to C7. Examples of the cycloalkyl group include, but are not limited to, the groups described below, cyclohexyl, adamantyl, bornyl, norbornyl and the like.
The aryl refers to a univalent group formed by subtracting one hydrogen atom from an aromatic nucleus carbon of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl group, polycyclic aryl group, and condensed ring aryl group. The monocyclic aryl group refers to a group having only one benzene ring in the structure, the polycyclic aryl group refers to a group having two or more independent benzene rings in the structure, and the fused ring aryl group refers to a group in the structure in which two or more benzene rings are fused together by sharing two adjacent carbon atoms. The aryl group has carbon atoms of C6 to C60, preferably C6 to C30, more preferably C6 to C25, even more preferably C6 to C18, still more preferably C6 to C14, and even more preferably C6 to C10. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, anthracenyl, fluorenyl, benzofluorenyl, spirobifluorenyl, benzospirobifluorenyl, and the like, as described below.
The heteroaryl group in the present invention refers to a monovalent group in which at least one of the aromatic nuclear carbon atoms in the aryl group is substituted with a heteroatom. Such heteroatoms include, but are not limited to, the atoms depicted below, O, S, N, Si, B, P, and the like. The heteroaryl includes monocyclic heteroaryl and fused ring heteroaryl. The monocyclic heteroaryl refers to a group having only one heteroaromatic ring in the structure, and the fused-ring heteroaryl refers to a group formed by fusing a benzene ring and a monocyclic heterocycle or by fusing two or more monocyclic heterocycles. The heteroaryl group has a carbon number of from C2 to C60, preferably from C2 to C30, more preferably from C2 to C25, even more preferably from C2 to C12, and even more preferably from C2 to C8. Examples of the heteroaryl group include, but are not limited to, groups such as a quinazolinyl group, a quinoxalinyl group, a benzoquinazolinyl group, a quinolyl group, an isoquinolyl group, a benzoquinolyl group, a benzoisoquinolyl group, a pyridyl group, a pyrimidinyl group, a pyridazinyl group, a pyrazinyl group, a triazinyl group, a naphthyridinyl group, a phenanthridinyl group, a phenanthrolinyl group, a dibenzofuranyl group, a dibenzothienyl group, a carbazolyl group and the like.
The arylene group in the invention is a divalent group formed by omitting two hydrogen atoms from an aromatic nucleus carbon in an aromatic hydrocarbon molecule. The arylene group includes monocyclic arylene, polycyclic arylene, fused ring arylene, or combinations thereof. The arylene group has carbon atoms of C6 to C60, preferably C6 to C30, more preferably C6 to C25, still more preferably C6 to C18, yet more preferably C6 to C14, and preferably C6 to C10. Examples of the arylene group include, but are not limited to, phenylene, biphenylene, terphenylene, quaterphenylene, naphthylene, phenanthrylene, triphenylene, anthracenylene, fluorenylene, benzofluorenylene, spirobifluorenylene, benzospirobifluorenylene, and the like.
The heteroarylene group according to the present invention means a divalent group in which at least one carbon atom in the arylene group is substituted with a heteroatom. The heteroatoms include, but are not limited to, the atoms shown below, O, S, N, Si, B, P, and the like. The heteroarylene group includes a monocyclic heteroarylene group, a polycyclic heteroarylene group, a fused ring heteroarylene group, or a combination thereof. The polycyclic heteroarylene group may have only one benzene ring substituted with a heteroatom or may have a plurality of benzene rings substituted with a heteroatom. The heteroarylene group has carbon atoms of C2 to C60, preferably C2 to C30, more preferably C2 to C25, even more preferably C2 to C12, and even more preferably C2 to C8. Examples of the heteroarylene group include, but are not limited to, a pyridylene group, a pyrimidylene group, a pyridazinyl group, a pyrazinyl group, a triazinylene group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a quinolylene group, an isoquinolylene group, a quinoxalylene group, a quinazolinylene group and the like.
The invention provides a fluorene derivative which has a general formula shown in a structural formula 1,
ar is1Selected from the group consisting of groups represented by formula 1-a1, Ar2Selected from the group consisting of those represented by the formula 1-a1 or formula 1-a2,
the Z is the same or different and is selected from N or C (R)z) Wherein at least one Z is selected from N, said RzThe same or different one selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the E is the same or different and is selected from N or C (R)e) Wherein one E is selected from N and the others are selected from C (R)e) Said R iseOne selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the L is selected from one of the groups shown as follows,
said L0One selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, and a substituted or unsubstituted pyridylene group; n1 are the same or different and are selected from 0, 1,2,3 or 4; n2 are the same or different and are selected from 0, 1,2 or 3; the R is1The same or different one selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C3-C10 cycloalkyl;
said L1、L2Independently selected from single bond or substituted or unsubstituted arylene of C6-C30;
ar is selected from the group shown as follows,
the R is0The same or different one selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, or two R0Bonding to form a ring structure;
the R is same or different and is selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C2-C60 heteroaryl, or two adjacent R are bonded to form a cyclic structure;
the m1 are the same or different and are selected from 0, 1,2,3 or 4.
Preferably, the fluorene derivative is selected from one of the structures shown below,
preferably, Ar is selected from one of the groups shown as follows,
m1 are the same or different and are selected from 0, 1,2,3 or 4; m2 are the same or different and are selected from 0, 1,2 or 3;
the R is01Selected from substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, phenyleneOne of substituted or unsubstituted naphthylene groups.
Preferably, R is as defined in the invention0The same or different one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or two R' s0Bonding to form a ring structure;
preferably, the R groups according to the present invention are the same or different and are selected from one of hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted bornyl, substituted or unsubstituted norbornanyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazinyl, quinolyl, and isoquinolyl.
Preferably, the formula 1-a1 is selected from one of the following groups,
preferably, R is as defined in the inventionzThe same or different is selected from hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted benzofluoreneThe compound is one of a phenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted quinoline, and a substituted or unsubstituted isoquinoline.
Preferably, the formula 1-a2 is selected from one of the following groups,
preferably, Ar is selected from one of the groups shown as follows,
preferably, the R groups according to the present invention are the same or different and are selected from one of hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted bornyl, substituted or unsubstituted norbornanyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazinyl, quinolyl, and isoquinolyl.
Preferably, the L is selected from one of the groups shown as follows,
preferably, said L1、L2Independently selected from one of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted tetrahydronaphthyl, and substituted or unsubstituted indanyl.
Preferably, the fluorene derivative of structural formula 1 is selected from any one of the following structures,
some specific chemical structures of the fluorene derivative shown in formula 1 of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all the structures based on the structure shown in formula 1 should include the substituents as defined above.
In addition, the invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer, a cathode and a covering layer, wherein the covering layer contains the fluorene derivative shown in the structural formula 1.
In addition, the invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer and a cathode, wherein the organic layer comprises an electron transmission region, and the electron transmission region contains the fluorene derivative shown in the structural formula 1.
Further, the organic electroluminescent device further comprises a cover layer containing a heterocyclic compound represented by formula 2,
wherein, Ar isaSelected from the group represented by formula 2-a,
x is selected from O or S;
the ring A and the ring B are independently selected from any one of no, a benzene ring and a naphthalene ring, and at least one of the ring A or the ring B is selected from the benzene ring or the naphthalene ring;
k is the same or different and is selected from 0, 1,2,3, 4,5, 6, 7 or 8; the R is2Any one of the same or different hydrogen, deuterium, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or two R2Bonding to form a ring structure;
ar isb、ArcIndependently selected from one of the groups shown in the following,
the R is3Any one of the same or different hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said g is1The same or different is selected from 0, 1,2,3, 4,5, 6 or 7; said g is2The same or different is selected from 0, 1,2,3, 4,5, 6, 7, 8 or 9;
said La、Lb、LcIndependently selected from any one of single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C2-C30,
said Lb、LcMay form a carbazole ring with the aromatic amine N by a single bond linkage.
Preferably, Ar isaIs selected from one of the groups shown below,
the R is2The same or different groups are selected from hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornanyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted pyridooxazolyl, substituted or unsubstituted pyridothiazolyl, substituted or unsubstituted fluorenyl, Substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dibenzofuranyl, or substituted or unsubstituted dibenzothiophenylAny one of unsubstituted carbazolyl groups;
k is2The same or different is selected from 0, 1,2,3 or 4; k is3The same or different is selected from 0, 1,2,3, 4,5 or 6; k is4The same or different is selected from 0, 1,2,3, 4,5, 6, 7 or 8.
Preferably, Ar isaIs selected from one of the groups shown below,
preferably, Ar isb、ArcIndependently selected from one of the groups shown in the following,
the R is3Any one of the same or different groups selected from hydrogen, deuterium, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, and substituted or unsubstituted triazinyl;
the substituent in the substituted or unsubstituted is selected from any one of hydrogen, deuterium, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, tolyl, pentadeuterated phenyl, biphenyl, naphthyl and pyridyl;
said g is1The same or different is selected from 0, 1,2,3, 4,5, 6 or 7; said g is2The same or different is selected from 0, 1,2,3, 4,5, 6, 7, 8 or 9.
Preferably, said La、Lb、LcIndependently selected from a single bond or one of the groups shown below,
wherein, R is4Any one of the same or different hydrogen, deuterium, cyano, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C6-C18 aryl and substituted or unsubstituted C2-C12 heteroaryl;
f is1Identical or different from 0, 1,2,3 or 4, f2Identical or different from 0, 1,2,3, 4,5 or 6, f3Identical or different from 0, 1,2,3, 4,5, 6, 7 or 8, f4Identical or different from 0, 1,2 or 3, f5Identical or different from 0, 1 or 2, f6The same or different is selected from 0, 1,2,3, 4 or 5.
Preferably, the heterocyclic compound represented by formula 2 is selected from any one of the structures shown below,
some specific chemical structures of the heterocyclic compound shown in the structural formula 2 of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all the substituents are the groups as defined above based on the structure shown in the structural formula 2.
In addition, the invention also provides an organic electroluminescent device which sequentially comprises an anode, an organic layer, a cathode and a covering layer, wherein the covering layer contains the fluorene derivative shown in the structural formula 1.
The electron transport region of the organic electroluminescent device of the present invention includes at least one of a hole blocking layer and an electron transport layer, and the organic layer of the organic electroluminescent device of the present invention may include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, and an electron injection layer, but is not limited thereto, and any functional layer having a hole injection and/or transport property or a functional layer having an electron injection and/or transport property should be included. Each functional layer may be formed of a single layer film or a multilayer film, and each layer film may contain one material or a plurality of materials.
The material of each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and those known in the art can be used. The organic functional layers of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device are described below:
the anode of the present invention has a function of injecting holes into the hole injection/transport layer, and the thickness of the anode is 50nm to 500 nm. The material for the anode of the present invention may comprise: metal oxides, e.g. Indium Tin Oxide (ITO), indium oxide (In)2O3) Indium Zinc Oxide (IZO), zinc oxide (ZnO), and the like; laminated materials, e.g. indium tin oxide/silver/indium tin oxide (ITO/Ag)ITO), aluminum/gold (Al/Au), aluminum/silver (Al/Ag), silver/indium tin oxide/silver (Ag/ITO/Ag), etc.; metals or alloys thereof, such as silver (Ag), aluminum (Al), platinum (Pt), gold (Au), zinc (Zn), and the like. But is not limited thereto.
The cathode has the function of injecting electrons into the electron injection/transmission layer, and the film thickness of the cathode is 0.1 nm-500 nm. The material for the cathode of the present invention may comprise: metal alloys such as magnesium-silver alloy (Mg: Ag), magnesium-silver alloy (Mg: Al), ytterbium-silver alloy (Yb: Ag), etc.; laminate materials such as calcium/magnesium (Ca/Mg), magnesium/aluminum (Mg/Al), aluminum/silver (Al/Ag), aluminum/gold (Al/Au), calcium/silver (Ca/Ag), and the like; metals such as aluminum (Al), indium (In), lead (Pb), silver (Ag), magnesium (Mg), calcium (Ca), lithium (Li), titanium (Ti), and the like. But is not limited thereto.
The hole injection layer of the device has the function of adjusting a hole injection barrier between the anode and the hole transport layer, and the thickness of the hole injection layer is 1 nm-1000 nm. The material for the hole injection layer of the present invention may comprise: polycyano conjugated organic compounds, metal compounds, aromatic amine derivatives, etc., such as (2E,2 'E) -2,2' - (cyclopropane-1, 2, 3-triylidene) tris (2- (perfluorophenyl) -acetonitrile), 1,4,5,8,9, 11-hexaazabenzonitrile (HAT-CN), 2,3,5, 6-tetrafluoro-7, 7',8,8' -tetracyanodimethyl-p-benzoquinone (F4-TCNQ), copper phthalocyanine (CuPc), molybdenum trioxide (MoO)3) Vanadium pentoxide (V)2O5) Tungsten trioxide (WO)3) Ferric chloride (FeCl)3) 4,4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), 4,4' -tris [ 2-naphthylphenylamino ] amino]Triphenylamine (2T-NATA), and the like. But is not limited thereto.
The hole transport layer has the functions of improving the balance of injection and transport of holes in the device and effectively blocking electrons in the light-emitting layer, and the thickness of the hole transport layer is 5 nm-1000 nm. The material for the hole transport layer of the present invention may comprise: examples of the amine compound, the fluorene compound, and the carbazole compound include N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-bis (naphthalene-1-yl) -N, N' -bis (phenyl) -2,2 '-dimethylbenzidine (NPD), N' -bis (naphthalene-1-yl) -N, N '-bis (phenyl) -2, 7-diamino-9, 9-spirobifluorene (Spiro-NPB), N4, N4' -bis (biphenyl-4-yl) -N4, N4 '-diphenylbiphenyl-4, 4' -diamine (TPD 10). But is not limited thereto.
As the light-emitting layer of the present invention, the host material includes a condensed aromatic ring derivative, a heterocyclic compound, and the like, for example, tris [4- (pyrenyl) -phenyl ] amine (TPyPA), 2, 7-bis (carbazol-9-yl) -9, 9-dimethylfluorene (DMFL-CBP), 3-bis (carbazolyl) biphenyl (MCBP), 1,3, 5-tris (pyrene-1-yl) benzene (TPB3), 1,3, 5-tris (carbazol-9-yl) benzene (TCP), 1, 3-bis (carbazol-9-yl) benzene (MCP), 4' -bis (carbazol-9-yl) biphenyl (CBP), 9-bis [4- (carbazol-9-yl) -phenyl ] fluorene (FL-2CBP), 2, 8-bis (9H-carbazol-9-yl) dibenzo [ b, d ] thiophene (DCzDBT). But is not limited thereto.
As the dopant material for the light-emitting layer of the present invention, there can be included a styrylamine compound, an aromatic amine derivative, a metal complex, etc., such as 1-4-bis- [4- (N, N-diphenyl) amino group]Styryl-benzene (DSA-Ph), 2, 7-bis [4- (diphenylamine) styryl]-9, 9-spirobifluorene (Spiro-BDAVBi), pyrene, anthracene, 5,6,11, 12-tetraphenylbenzo-ene (Rubene), tris (2-phenylpyridine) iridium (III) (Ir (ppy)3) Bis (2-phenylpyridine) (acetylacetone) iridium (III) (Ir (ppy)2(acac)), bis (2- (naphthalen-2-yl) pyridine) (acetylacetone) iridium (III) (Ir (npy)2acac), platinum complexes, and the like. But is not limited thereto.
The light-emitting layer of the present invention may contain both a host material and a dopant material, or may contain no host material.
The hole blocking layer has the function of blocking holes injected from the anode from passing through the luminescent layer and entering the electron transmission region, and the thickness of the hole blocking layer is 0.1 nm-300 nm. The material for a hole blocking layer of the present invention may comprise: phenanthroline derivatives, metal complexes, imidazole derivatives, and the like, for example, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), bis (2-methyl-8-hydroxyquinoline-N1, O8) - (1,1' -biphenyl-4-hydroxy) aluminum (BAlq), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), and the like. But is not limited thereto. The fluorene derivative represented by structural formula 1 of the present invention is preferable.
The electron transport layer of the present invention has an effect of improving the balance of injection and transport of electrons in a device, and the electron transport layerThe film thickness is 1nm to 1000 nm. The material for the electron transport layer of the present invention may comprise: metal complexes, imidazole derivatives, phenanthroline derivatives, triazine compounds, pyridine derivatives and the like, for example, tris (8-hydroxyquinoline) aluminum (III) (Alq)3) 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), phenanthroline derivatives including 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 4' -bis (4, 6-diphenyl-1, 3, 5-triazinyl) biphenyl (BTB), 3' - [5' - [3- (3-pyridyl) phenyl ] biphenyl (BTB), and pharmaceutically acceptable salts thereof](TmPyPB) and the like. But is not limited thereto. The fluorene derivative represented by structural formula 1 of the present invention is preferable.
The electron injection layer of the device has the function of adjusting the electron injection barrier between the cathode and the electron transport layer, and the thickness of the electron injection layer is 0.01 nm-100 nm. The material for the electron injection layer of the present invention may comprise: metals, metal fluorides, and the like, for example, lithium (Li), ytterbium (Yb), sodium (Na), magnesium (Mg), rubidium (Rb), lithium fluoride (LiF), cesium fluoride (CsF), sodium fluoride (NaF), and the like. But is not limited thereto.
The cladding layer of the present invention has an effect of coupling out light trapped in the device, and the material for the cladding layer of the present invention may include: metal compounds, aromatic amine derivatives, carbazole derivatives, and the like, but are not limited thereto. The thickness of the coating layer is 1nm to 200 nm. The heterocyclic compound represented by formula 2 of the present invention is preferable.
The method for preparing each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and vacuum evaporation, sputtering, spin coating, spray coating, screen printing, laser transfer printing, and the like can be used, but is not limited thereto.
The organic electroluminescent device is mainly applied to the technical field of information display, and is widely applied to various information displays in the aspect of information display, such as tablet computers, flat televisions, mobile phones, smart watches, digital cameras, VR, vehicle-mounted systems, wearable equipment and the like.
Synthetic examples
(1) The preparation method of the fluorene derivative of structural formula 1 of the present invention is not particularly limited, and conventional methods well known to those skilled in the art may be employed. For example, carbon-carbon coupling reaction, etc., the fluorene derivative of structural formula 1 of the present invention can be prepared by the following synthetic route.
(2) The preparation method of the heterocyclic compound of formula 2 of the present invention is not particularly limited, and conventional methods well known to those skilled in the art can be employed. For example, carbon-nitrogen coupling reaction, carbon-carbon coupling reaction, and the like.
When L isb、LcWhen not linked by a single bond, the heterocyclic compounds of formula 2 of the present invention can be prepared using the synthetic route shown below:
when L isb、LcWhen connected by a single bond, the heterocyclic compounds of formula 2 of the present invention can be prepared using the synthetic route shown below:
said XnSelected from halogens such as Cl, Br, I; b isnSelected from the group consisting of-B (OH)2Or
The "- - -" represents LbAnd LcAssuming a connection by a single bond.
Raw materials and reagents: the starting materials and reagents used in the following synthetic examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art. The raw materials and reagents used in the invention are all pure reagents.
The instrument comprises the following steps: G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); a Vario EL cube type organic element analyzer (Elementar Co., Germany).
Synthesis example 1: synthesis of Compound 11
To a three-necked flask, 1L of tetrahydrofuran solvent, a-1(37.85g, 140mmol), b-1(71.10g, 280mmol), Pd (dppf) Cl, were added in this order under a nitrogen atmosphere2(0.51g, 0.70mmol) and potassium acetate (39.26g, 400mmol), stirring the mixture, and heating and refluxing the mixed solution of the above reactants for 7 h; after the reaction was completed, it was cooled and distilled water was added, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified by silica gel column (petroleum ether: ethyl acetate: 1) to obtain compound c-1(42.35g, yield 83%).
600mL of tetrahydrofuran solvent and the compound c-1(36.45g, 100mmol) were added to a three-necked flask under nitrogen atmosphere and dissolved with stirring, and d-1(41.81g, 200mmol) and Pd (PPh) were added thereto3)4(11.56g, 10mmol), stirring the mixture continuously, adding saturated aqueous potassium carbonate solution (41.46g, 300mmol) thereto, and heating the above reaction mixture under reflux for 12 h; after completion of the reaction, distilled water was added to the reaction solution, extraction was performed with dichloromethane, and the obtained organic layer was extracted with anhydrous MgSO4Removing water, filtering, and concentrating the filtrate under reduced pressure to remove solvent. The obtained residue was separated and purified by silica gel column (cyclohexane: ethyl acetate: 10:1) to obtain compound e-1(27.29g, yield 74%).
To a three-necked flask, 350mL of 1, 4-dioxane, e-1(22.13g, 60mmol), b-1(18.28g, 72mmol), pd (dppf) Cl, under nitrogen, were added2(2.19g, 3.00mmol) and potassium acetate (17.66g, 180mmol) were heated under stirring at reflux for 24 h. After the reaction, the reaction mixture was cooled naturally, distilled water was added thereto, and the reaction mixture was extracted with ethyl acetate and washed with saturated brine 3 times to obtain an organic layer, which was then washed with anhydrous MgSO4Drying, filtering, and concentrating the filtrate under reduced pressure to remove the solvent. The residue obtained was subjected to silica gel column separation and purification (chloroform: B)Ethyl acid ester ═ 2: 1) compound f-1(21.54g, yield 78%) was obtained.
300mL of tetrahydrofuran, g-1(23.85g, 80mmol), h-1(12.51g, 80mmol), Pd (PPh) were added to a three-necked flask under nitrogen atmosphere3)4(2.89g, 2.50mmol), NaOH (9.53g, 238.25mmol), and water (130mL), stirring the mixture, and heating under reflux for 5 h; after the reaction is finished, using CH2Cl2And water extraction, collecting the organic layer using MgSO4Drying, filtering, and concentrating the filtrate under reduced pressure to remove the solvent. The obtained residue was subjected to silica gel column and then recrystallized in toluene to obtain compound i-1(18.73g, yield 71%).
A three-necked flask was charged with a mixed solvent of 216mL of toluene, 72mL of ethanol and 72mL of water, i-1(15.83g, 48mmol), f-1(18.41g, 40mmol), pd (dppf) Cl, under a nitrogen atmosphere2(1.46g, 2mmol) and sodium carbonate (7.63g, 72mmol), stirring the mixture, heating and refluxing for 24h, cooling to room temperature after the reaction is finished, extracting with dichloromethane, combining the organic phases, and using anhydrous MgSO4Drying, filtering, concentrating the filtrate under reduced pressure to remove the solvent, and recrystallizing with toluene to obtain compound 11(17.07g, 68%); HPLC purity ≧ 99.77%. Mass spectrum m/z: 627.2447 (theoretical value: 627.2423). Theoretical element content (%) C44H29N5: c, 84.19; h, 4.66; n, 11.16. Measured elemental content (%): c, 84.07; h, 4.73; n, 11.24.
Synthesis example 2: synthesis of Compound 13
Compound 13(25.04g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 in an equimolar amount and g-1 was replaced with g-13 in an equimolar amount, and the purity of the solid was not less than 99.85% by HPLC. Mass spectrum m/z: 754.3080 (theoretical value: 754.3096). Theoretical element content (%) C55H38N4: c, 87.50; h, 5.07; and N, 7.42. Measured elemental content (%): c, 87.46; h, 5.03; and N, 7.49.
Synthetic example 3: synthesis of Compound 49
Compound 49(25.70g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 in an equimolar amount, g-1 was replaced with g-49 in an equimolar amount, and h-1 was replaced with h-49 in an equimolar amount, and the purity of the solid was 99.68% by HPLC. Mass spectrum m/z: 834.3683 (theoretical value: 834.3661). Theoretical element content (%) C61H38D4N4: c, 87.74; h, 5.55; and N, 6.71. Measured elemental content (%): c, 87.82; h, 5.49; and N, 6.66.
Synthetic example 4: synthesis of Compound 55
Compound 55(23.87g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-55 in an equimolar amount, g-1 was replaced with g-55 in an equimolar amount, and h-1 was replaced with h-55 in an equimolar amount, and the purity of the solid was 99.69% by HPLC. Mass spectrum m/z: 854.3431 (theoretical value: 854.3409). Theoretical element content (%) C63H42N4: c, 88.50; h, 4.95; and N, 6.55. Measured elemental content (%): c, 88.59; h, 4.89; and N, 6.49.
Synthesis example 5: synthesis of Compound 58
Compound 58(27.54g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-58 in an equimolar amount, g-1 was replaced with g-13 in an equimolar amount, and h-1 was replaced with h-55 in an equimolar amount, and the purity of the solid was 99.75% by HPLC. Mass spectrum m/z: 906.3738 (theoretical value: 906.3722). Theoretical element content (%) C67H46N4: c, 88.71; h, 5.11; and N, 6.18. Measured elemental content (%)：C,88.75；H,5.17；N,6.09。
Synthetic example 6: synthesis of Compound 67
Compound 67(23.80g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 (equimolar amount) and g-1 was replaced with g-67 (equimolar amount), and the purity of the solid was 99.86% or more by HPLC. Mass spectrum m/z: 804.3277 (theoretical value: 804.3253). Theoretical element content (%) C59H40N4: c, 88.03; h, 5.01; and N, 6.96. Measured elemental content (%): c, 88.07; h, 5.09; and N, 6.85.
Synthetic example 7: synthesis of Compound 69
Compound 69(22.83g) was synthesized in the same manner as in Synthesis example 1 except that a-1 was replaced with equimolar a-69, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-69, and h-1 was replaced with equimolar h-69, and the purity by HPLC was ≧ 99.63%. Mass spectrum m/z: 829.3230 (theoretical value: 829.3205). Theoretical element content (%) C60H39N5: c, 86.83; h, 4.74; n, 8.44. Measured elemental content (%): c, 86.92; h, 4.70; n, 8.37.
Synthesis example 8: synthesis of Compound 72
Compound 72(27.39g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 (equimolar amount) and g-1 was replaced with g-72 (equimolar amount), and the solid purity was not less than 99.86% by HPLC. Mass spectrum m/z: 878.3426 (theoretical value: 878.3409). Theoretical element content (%) C65H42N4：C,88.81; h, 4.82; n, 6.37. Measured elemental content (%): c, 88.73; h, 4.86; n, 6.44.
Synthetic example 9: synthesis of Compound 129
Compound 129(18.07g) was synthesized in the same manner as in Synthesis example 1 except that a-1 was replaced with equimolar a-129 and d-1 was replaced with equimolar d-129 and g-1 was replaced with equimolar g-13, and the purity of the solid was not less than 99.85% by HPLC. Mass spectrum m/z: 600.2582 (theoretical value: 600.2565). Theoretical element content (%) C45H32N2: c, 89.97; h, 5.37; and N, 4.66. Measured elemental content (%): c, 89.87; h, 5.44; and N, 4.70.
Synthetic example 10: synthesis of Compound 233
Compound 233(22.24g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-233 (equimolar), g-1 was replaced with g-233 (equimolar), and h-1 was replaced with h-55 (equimolar), and the purity of the solid was 99.67% by HPLC. Mass spectrum m/z: 772.2886 (theoretical value: 772.2878). Theoretical element content (%) C59H36N2: c, 91.68; h, 4.69; and N, 3.62. Measured elemental content (%): c, 91.65; h, 4.79; and N, 3.57.
Synthetic example 11: synthesis of Compound 252
Compound 252(25.54g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-252, g-1 was replaced with g-13 and h-1 was replaced with h-252, and the purity of the solid was 99.65% by HPLC. Mass spectrum m/z: 840.4063 (theory)The value: 840.4037). Theoretical element content (%) C61H32D10N4: c, 87.11; h, 6.23; and N, 6.66. Measured elemental content (%): c, 87.20; h, 6.18; and N, 6.63.
Synthetic example 12: synthesis of Compound 253
Compound 253(25.89g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 in an equimolar amount, g-1 was replaced with g-13 in an equimolar amount, and h-1 was replaced with h-252 in an equimolar amount, and the purity of the solid was 99.98% by HPLC. Mass spectrum m/z: 830.3431 (theoretical value: 830.3409). Theoretical element content (%) C61H42N4: c, 88.16; h, 5.09; n, 6.74. Measured elemental content (%): c, 88.19; h, 5.01; and N, 6.80.
Synthetic example 13: synthesis of Compound 286
Compound 286(24.90g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 in an equimolar amount, g-1 was replaced with g-13 in an equimolar amount, and h-1 was replaced with h-286 in an equimolar amount, and the purity of the solid was 99.86% by HPLC. Mass spectrum m/z: 830.3427 (theoretical value: 830.3409). Theoretical element content (%) C61H42N4: c, 88.16; h, 5.09; n, 6.74. Measured elemental content (%): c, 88.28; h, 5.03; n, 6.67.
Synthesis example 14: synthesis of Compound 316
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-316, h-1 was replaced with equimolar h-252, and the othersIn the same manner, compound 316(27.42g) was synthesized with a solid purity of 99.88% by HPLC. Mass spectrum m/z: 952.3592 (theoretical value: 952.3566). Theoretical element content (%) C71H44N4: c, 89.47; h, 4.65; and N, 5.88. Measured elemental content (%): c, 89.55; h, 4.62; n, 5.84.
Synthetic example 15: synthesis of Compound 319
Compound 319(25.33g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-319 in an equimolar amount, g-1 was replaced with g-319 in an equimolar amount, and h-1 was replaced with h-252 in an equimolar amount, and the purity of the solid was 99.73% by HPLC. Mass spectrum m/z: 892.3579 (theoretical value: 892.3566). Theoretical element content (%) C66H44N4: c, 88.76; h, 4.97; and N, 6.27. Measured elemental content (%): c, 88.82; h, 4.87; and N, 6.34.
Synthetic example 16: synthesis of Compound 325
Compound 325(25.68g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 (equimolar), g-1 was replaced with g-325 (equimolar), and h-1 was replaced with h-252 (equimolar), and the purity of the solid was 99.79% by HPLC. Mass spectrum m/z: 856.3581 (theoretical value: 856.3566). Theoretical element content (%) C63H44N4: c, 88.29; h, 5.17; n, 6.54. Measured elemental content (%): c, 88.35; h, 5.22; and N, 6.42.
Synthetic example 17: synthesis of Compound 338
Using the same method as in Synthesis example 1, d-1Compound 338(27.09g) was synthesized by substituting d-13 in equimolar amount, g-1 in equimolar amount, and h-286 in equimolar amount for h-1, and the solid purity was 99.75% by HPLC. Mass spectrum m/z: 954.3734 (theoretical value: 954.3722). Theoretical element content (%) C71H46N4: c, 89.28; h, 4.85; and N, 5.87. Measured elemental content (%): c, 89.36; h, 4.82; and N, 5.80.
Synthetic example 18: synthesis of Compound 357
Compound 357(21.63g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-129 in an equimolar amount, g-1 was replaced with g-13 in an equimolar amount, and h-1 was replaced with h-252 in an equimolar amount, and the purity of the solid was 99.91% by HPLC. Mass spectrum m/z: 676.2893 (theoretical value: 676.2878). Theoretical element content (%) C51H36N2: c, 90.50; h, 5.36; n, 4.14. Measured elemental content (%): c, 90.46; h, 5.30; and N, 4.25.
Synthetic example 19: synthesis of Compound 368
Compound 368(20.78g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-368 in an equimolar amount, g-1 was replaced with g-368 in an equimolar amount, and h-1 was replaced with h-252 in an equimolar amount, and the purity of the solid was 99.64% by HPLC. Mass spectrum m/z: 753.3164 (theoretical value: 753.3144). Theoretical element content (%) C56H39N3: c, 89.21; h, 5.21; n, 5.57. Measured elemental content (%): c, 89.25; h, 5.24; and N, 5.48.
Synthesis example 20: synthesis of Compound 394
Compound 394(24.84g) was synthesized by the same method as in Synthesis example 1, except that a-1 was replaced with equimolar a-394, d-1 was replaced with equimolar d-,94, g-1 was replaced with equimolar g-394, and h-1 was replaced with equimolar h-252, and the purity by HPLC was ≧ 99.76%. Mass spectrum m/z: 828.3518 (theoretical value: 828.3504). Theoretical element content (%) C63H44N2: c, 91.27; h, 5.35; and N, 3.38. Measured elemental content (%): c, 91.30; h, 5.26; n, 3.43.
Synthetic example 21: synthesis of Compound 408
Compound 408(26.35g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-408 in an equimolar amount, g-1 was replaced with g-13 in an equimolar amount, and h-1 was replaced with h-286 in an equimolar amount, and the purity of the solid was 99.65% by HPLC. Mass spectrum m/z: 928.3833 (theoretical value: 928.3817). Theoretical element content (%) C71H48N2: c, 91.78; h, 5.21; and N, 3.01. Measured elemental content (%): c, 91.73; h, 5.19; and N, 3.14.
Synthetic example 22: synthesis of Compound 430
Compound 394(25.60g) was synthesized in the same manner as in Synthesis example 1 except that a-1 was replaced with equimolar a-394, d-1 was replaced with equimolar d-,94, g-1 was replaced with equimolar g-394, and h-1 was replaced with equimolar h-252, and the purity by HPLC was ≧ 99.87%. Mass spectrum m/z: 800.3173 (theoretical value: 800.3191). Theoretical element content (%) C61H40N2: c, 91.47; h, 5.03; and N, 3.50. Measured elemental content (%): c, 91.38; h, 5.08; and N, 3.58.
Synthetic example 23: synthesis of Compound 432
Compound 432(24.48g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-408 in an equimolar amount, g-1 was replaced with g-432 in an equimolar amount, and h-1 was replaced with h-252 in an equimolar amount, and the purity of the solid was 99.76% by HPLC. Mass spectrum m/z: 850.3357 (theoretical value: 850.3348). Theoretical element content (%) C65H42N2: c, 91.73; h, 4.97; and N, 3.29. Measured elemental content (%): c, 91.78; h, 4.86; n, 3.33.
Synthetic example 24: synthesis of Compound 441
Compound 441(28.75g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-441 (equimolar), g-1 was replaced with g-441 (equimolar), and h-1 was replaced with h-252 (equimolar), and the purity of the solid was 99.85% by HPLC. Mass spectrum m/z: 910.4294 (theoretical value: 910.4287). Theoretical element content (%) C69H54N2: c, 90.95; h, 5.97; and N, 3.07. Measured elemental content (%): c, 90.88; h, 5.93; and N, 3.17.
Synthetic example 25: synthesis of Compound 465
Compound 464(25.49g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-129 in an equimolar amount, g-1 was replaced with g-464 in an equimolar amount, and h-1 was replaced with h-252 in an equimolar amount, and the purity of the solid was 99.89% by HPLC. Mass spectrum m/z: 768.3518 (theoretical value: 768.3504). Theoretical element content (%) C58H44N2: c, 90.59; h, 5.77; and N, 3.64. Measured elemental content (%): c, 90.65; h, 5.68; and N, 3.68.
Synthetic example 26: synthesis of Compound 477
Compound 477(20.96g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-477, g-1 was replaced with g-319, and h-1 was replaced with h-477, and the purity of the solid was 99.74% by HPLC. Mass spectrum m/z: 738.3057 (theoretical value: 738.3035). Theoretical element content (%) C56H38N2: c, 91.03; h, 5.18; n, 3.79. Measured elemental content (%): c, 91.15; h, 5.15; and N, 3.72.
Synthetic example 27: synthesis of compound 483
Compound 483(24.91g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-129 in an equimolar amount, g-1 was replaced with g-483 in an equimolar amount, and h-1 was replaced with h-286 in an equimolar amount, and the purity of the solid was not less than 99.86% by HPLC. Mass spectrum m/z: 800.3211 (theoretical value: 800.3191). Theoretical element content (%) C61H40N2: c, 91.47; h, 5.03; and N, 3.50. Measured elemental content (%): c, 91.43; h, 5.12; and N, 3.46.
Synthetic example 28: synthesis of Compound 506
A three-necked flask was charged with a mixed solvent of a-506(46.65g, 147mmol), j-506(24.22g, 140mmol), potassium carbonate (38.70g, 280mmol), 300mL of toluene, 60mL of ethanol, and 60mL of water, in that order, under a nitrogen atmosphere. The mixture was stirred, warmed to 50 ℃ and Pd (PPh) was added rapidly3)4(1.62g, 1.40mmol), heating to reflux state, reacting for 8h, stirring after the reaction is finishedAdding distilled water into the reaction solution under stirring, standing for liquid separation, collecting water phase, extracting with toluene, mixing organic phases, and collecting filtrate with anhydrous MgSO4The water was removed, filtration was carried out, the filtrate was concentrated under reduced pressure to remove the solvent, n-heptane was added for recrystallization, filtration was carried out, and drying in a vacuum oven was carried out to obtain compound c-506(37.47g, yield 84%).
To a three-necked flask, 650mL of tetrahydrofuran solvent, c-506(35.05g, 110mmol), b-1(27.93g, 110mmol), Pd (dppf) and Cl were added in this order under a nitrogen atmosphere2(0.21g, 0.29mmol) and potassium acetate (14.72g, 150mmol), stirring the mixture, and heating and refluxing the mixed solution of the above reactants for 9 h; after the reaction was completed, it was cooled and distilled water was added, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified by a silica gel column (petroleum ether: acetone ═ 1:1) to obtain compound k-506(32.58g, yield 81%).
To a three-necked flask, 500mL of tetrahydrofuran solvent and compound k-506(29.25g, 80mmol) were added under nitrogen atmosphere, and dissolved with stirring, and d-13(22.81g, 80mmol) and Pd (PPh) were added3)4(4.62g, 4mmol), stirring the mixture continuously, adding saturated aqueous potassium carbonate solution (22.11g, 160mmol) thereto, and heating the above reaction mixture under reflux for 10 h; after the reaction, distilled water was added to the reaction solution, followed by extraction with tetrahydrofuran, and the obtained organic layer was anhydrous MgSO4Removing water, filtering, and concentrating the filtrate under reduced pressure to remove solvent. The obtained residue was subjected to silica gel column separation and purification (cyclohexane: methanol ═ 8:1) to obtain compound e-506(24.50g, yield 69%).
Using the same preparation method as that for f-1, 11 in Synthesis example 1, replacing e-1 with equimolar e-506 gave 22.49g (70%) of compound f-506; replacement of h-1 with equimolar h-252 and f-1 with equimolar f-506 gave 21.41g of compound 506; the purity of the solid is not less than 99.72 percent by HPLC detection. Mass spectrum m/z: 753.3151 (theoretical value: 753.3144). Theoretical element content (%) C56H39N3: c, 89.21; h, 5.21; n, 5.57. Measured elemental content (%): c, 89.16; h, 5.14; and N, 5.66.
Synthetic example 29: synthesis of Compound 512
To a reaction flask, under nitrogen, was added 3-bromo-3 '-chloro-1, 1' -biphenyl (36.12g, 135mmol), THF (450ml), 1, 3-benzenediboronic acid (24.61g, 148.5mmol), Pd (PPh)3)4(2.37g, 2.05mmol), NaOH (16.2g, 405mmol), and water (220ml) were reacted under reflux for 8 hours. After the reaction was complete, cool to room temperature and use CH2Cl2And water extraction, organic phases were combined, the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed from the filtrate under reduced pressure, and the obtained residue was subjected to silica gel column separation and purification (dichloromethane: n-hexane ═ 1:1) to obtain compound h-512(25.83g, yield 62%).
Compound 512(24.67g) was synthesized in the same manner as in Synthesis example 1, except that d-1 was replaced with d-129 in an equimolar amount, g-1 was replaced with d-13 in an equimolar amount, and h-1 was replaced with h-512 in an equimolar amount, and the purity by HPLC was ≧ 99.88%. Mass spectrum m/z: 752.3215 (theoretical value: 752.3191). Theoretical element content (%) C57H40N2: c, 90.92; h, 5.35; and N, 3.72. Measured elemental content (%): c, 90.79; h, 5.40; n, 3.79.
Synthetic example 30: synthesis of Compound 520
Using the same method as in Synthesis example 29, 1, 3-phenylboronic acid was changed to equimolar of [1,1' -biphenyl]3,3' -diyl diboronic acid, d-129 replaced by an equal mole of d-408, g-1 replaced by an equal mole of g-483, and the same applies to synthesize a compound 520(24.51g), wherein the solid purity is not less than 99.87% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 828.3522 (theoretical value: 828.3504). Theoretical element content (%) C63H44N2: c, 91.27; h, 5.35; and N, 3.38. Measured elemental content (%): c, 91.34; h, 5.31; and N, 3.32.
Synthetic example 31: synthesis of Compound 534
Compound 534(24.64g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-534 (equimolar), and g-1 was replaced with g-13 (equimolar), and the purity of solid was ≧ 99.74% by HPLC. Mass spectrum m/z: 906.3741 (theoretical value: 906.3722). Theoretical element content (%) C67H46N4: c, 88.71; h, 5.11; and N, 6.18. Measured elemental content (%): c, 88.64; h, 5.21; and N, 6.13.
Synthetic example 32: synthesis of compound 537
Compound 537(19.53g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-537 in an equimolar amount, g-1 was replaced with g-537 in an equimolar amount, and h-1 was replaced with h-252 in an equimolar amount, and the purity of the solid was 99.75% by HPLC. Mass spectrum m/z: 678.2797 (theoretical value: 678.2783). Theoretical element content (%) C49H34N4: c, 86.70; h, 5.05; and N, 8.25. Measured elemental content (%): c, 86.61; h, 5.12; and N, 8.29.
Synthetic example 33: synthesis of Compound 540
Compound 540(21.71g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-540 in an equimolar amount and g-1 was replaced with g-540 in an equimolar amount, and the solid purity was ≧ 99.68% by HPLC. Mass spectrum m/z: 835.3149 (theoretical value: 835.3172). Theoretical element content (%) C56H37N9: c, 80.46; h, 4.46; and N, 15.08. Measured elemental content (%): c, 80.39; h, 4.44; and N, 15.20.
Synthesis example 34: synthesis of Compound 550
Compound 550(22.41g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-550 (equimolar), g-1 was replaced with g-550 (equimolar), and h-1 was replaced with h-252 (equimolar), and the purity of the solid was 99.74% by HPLC. Mass spectrum m/z: 800.2957 (theoretical value: 800.2940). Theoretical element content (%) C59H36N4: c, 88.47; h, 4.53; and N, 7.00. Measured elemental content (%): c, 88.41; h, 4.45; and N, 7.12.
Synthetic example 35: synthesis of Compound 565
Compound 565(19.96g) was synthesized in the same manner as in Synthesis example 28 except that j-506 was replaced with equimolar j-565, g-13 was replaced with equimolar g-394 and h-252 was replaced with equimolar h-286, and the purity of the solid was 99.76% by HPLC. Mass spectrum m/z: 703.2995 (theoretical value: 703.2987). Theoretical element content (%) C52H37N3: c, 88.73; h, 5.30; and N, 5.97. Measured elemental content (%): c, 88.76; h, 5.35; and N, 5.89.
Synthetic example 36: synthesis of Compound 570
Compound 570(22.82g) was synthesized in the same manner as in Synthesis example 28 except that j-506 was replaced with equimolar j-565, d-13 was replaced with equimolar d-570, g-13 was replaced with equimolar g-430, and h-252 was replaced with equimolar h-11, and the purity of the solid was 99.73% by HPLC. Mass spectrum m/z: 827.3316 (theoretical value: 827.3300). Theoretical element content (%)C62H41N3: c, 89.93; h, 4.99; and N, 5.07. Measured elemental content (%): c, 89.88; h, 4.93; and N, 5.16.
Synthetic example 37: synthesis of Compound 586
Compound 586(19.03g) was synthesized in the same manner as in Synthesis example 28 except that j-506 was replaced with equal mol of j-565 and d-13 was replaced with equal mol of d-129, and the purity of the solid was not less than 99.86% by HPLC. Mass spectrum m/z: 626.2743 (theoretical value: 626.2722). Theoretical element content (%) C47H34N2: c, 90.06; h, 5.47; and N, 4.47. Measured elemental content (%): c, 90.14; h, 5.44; n, 4.39.
Synthetic example 38: synthesis of Compound 608
Compound 608(19.18g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-608 in an equimolar amount, g-1 was replaced with g-13 in an equimolar amount, and h-1 was replaced with h-608 in an equimolar amount, and the purity of the solid was 99.76% by HPLC. Mass spectrum m/z: 676.2896 (theoretical value: 676.2878). Theoretical element content (%) C51H36N2: c, 90.50; h, 5.36; n, 4.14. Measured elemental content (%): c, 90.44; h, 5.41; and N, 4.17.
Synthetic example 39: synthesis of Compound 614
Compound 614(19.93g) was synthesized in the same manner as in Synthesis example 1 except that d-1 was replaced with d-13 (equimolar), g-1 was replaced with g-55 (equimolar), and h-1 was replaced with h-614 (equimolar), and the purity of the solid was 99.74% by HPLC. Mass spectrometrym/z: 755.3058 (theoretical value: 755.3049). Theoretical element content (%) C54H37N5: c, 85.80; h, 4.93; and N, 9.26. Measured elemental content (%): c, 85.77; h, 4.86; and N, 9.39.
Synthetic example 40: synthesis of Compounds 2-17
A reaction flask was charged with a1-1(10.74g,44.15mmol), b1-1(15.38g,40.14mmol), sodium t-butoxide (6.36g,66.23mmol), palladium acetate (180mg,0.8mmol), triphenylphosphine (210mg,0.8mmol) and 200ml toluene under nitrogen atmosphere and reacted for 4.5 hours under reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with distilled water, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure from the organic phase, and the obtained residue was purified by silica gel column separation (n-hexane: dichloromethane ═ 3:1) to obtain a1-1(16.88g, yield 77%).
A1-1(15.44g,28.30 mmol), c1-1(8.01g,26.95mmol), sodium tert-butoxide (3.88g,40.42mmol), Pd were added to the flask under nitrogen2(dba)3(494mg,0.54mmol), X-Phos (257mg,0.54mmol) and 150mL of toluene were reacted under reflux for 4 hours. After the reaction is finished, pouring the reaction liquid into water, adding dichloromethane, layering, extracting a water layer with dichloromethane, combining organic phases, removing the solvent under reduced pressure, and recrystallizing with toluene to obtain the compound 2-17(16.43g, yield 80%), wherein the purity of solid is not less than 99.75% by HPLC (high performance liquid chromatography). Mass spectrum m/z: 761.2731 (theoretical value: 761.2719). Theoretical element content (%) C58H35NO: c, 91.43; h, 4.63; n, 1.84. Measured elemental content (%): c, 91.49; h, 4.58; n, 1.88.
Synthesis example 41: synthesis of Compounds 2-50
Using the same method as that for Synthesis example 40, a1-1 was replaced with equimolar a1-50The compound 2-50(15.01g) was synthesized by replacing b1-1 with b1-50 in equimolar amount and replacing c1-1 with c1-50 in equimolar amount, and the solid purity was not less than 99.76% by HPLC. Mass spectrum m/z: 687.2579 (theoretical value: 687.2562). Theoretical element content (%) C52H33NO: c, 90.80; h, 4.84; and N, 2.04. Measured elemental content (%): c, 90.71; h, 4.89; n, 2.11.
Synthesis example 42: synthesis of Compounds 2-74
Compound 2-74(15.91g) was synthesized in the same manner as in Synthesis example 40 except that a was used instead of a1-1 in an equimolar amount of a1-74, b1-1 in an equimolar amount of b1-74 and c1-1 in an equimolar amount of c1-74, and the purity of the solid was 99.74% by HPLC. Mass spectrum m/z: 787.2896 (theoretical value: 787.2875). Theoretical element content (%) C60H37NO: c, 91.46; h, 4.73; n, 1.78. Measured elemental content (%): c, 91.51; h, 4.79; n, 1.71.
Synthetic example 43: synthesis of Compounds 2-126
Compound 2-126(16.32g) was synthesized in the same manner as in Synthesis example 40 except that a was used instead of a1-1 in an equimolar amount of a1-126, b1-1 in an equimolar amount of b1-126 and c1-1 in an equimolar amount of c1-126, and the purity of the solid was 99.87% by HPLC. Mass spectrum m/z: 713.2733 (theoretical value: 713.2719). Theoretical element content (%) C54H35NO: c, 90.85; h, 4.94; and N, 1.96. Measured elemental content (%): c, 90.93; h, 4.88; n, 1.89.
Synthetic example 44: synthesis of Compounds 2-152
Compound 2-152(17.44g) was synthesized in the same manner as in Synthesis example 40 except that a was used instead of a1-1 in an equimolar amount of a1-152, b1-1 in an equimolar amount of b1-126 and c1-1 in an equimolar amount of c1-152, and the purity of the solid was 99.86% by HPLC. Mass spectrum m/z: 789.3047 (theoretical value: 789.3032). Theoretical element content (%) C60H39NO: c, 91.23; h, 4.98; n, 1.77. Measured elemental content (%): c, 91.32; h, 4.94; n, 1.89.
Synthetic example 45: synthesis of Compounds 2-181
Compound 2-181(14.25g) was synthesized in the same manner as in Synthesis example 40 except that a was used as a substitute for a1-1 in equimolar amounts of a1-181, b1-1 in equimolar amounts of b1-181 and c1-1 in equimolar amounts of c1-181, and the purity of the solid was 99.85% by HPLC. Mass spectrum m/z: 637.2424 (theoretical value: 637.2406). Theoretical element content (%) C48H31NO: c, 90.40; h, 4.90; and N, 2.20. Measured elemental content (%): c, 90.35; h, 4.83; and N, 2.27.
Synthesis example 46: synthesis of Compounds 2-190
Compound 2-190(14.42g) was synthesized in the same manner as in Synthesis example 40 except that a was used instead of a1-1 in an equimolar amount, b1-1 was used instead of a1-50 in an equimolar amount, c was used instead of b1-190 in an equimolar amount, and c1-1 was used instead of c1-190 in an equimolar amount, and the purity of the solid was 99.98% or more by HPLC. Mass spectrum m/z: 637.2419 (theoretical value: 637.2406). Theoretical element content (%) C48H31NO: c, 90.40; h, 4.90; and N, 2.20. Measured elemental content (%): c, 90.46; h, 4.81; and N, 2.26.
Synthetic example 47: synthesis of Compounds 2-211
Compound 2-211(16.04g) was synthesized in the same manner as in Synthesis example 40 except that a was used instead of a1-1 in an equimolar amount of a1-211, b1-1 in an equimolar amount of b1-211 and c1-1 in an equimolar amount of c1-211, and the purity of the solid was 99.74% by HPLC. Mass spectrum m/z: 763.2892 (theoretical value: 763.2875). Theoretical element content (%) C58H37NO: c, 91.19; h, 4.88; n, 1.83. Measured elemental content (%): c, 91.27; h, 4.83; n, 1.77.
Synthetic example 48: synthesis of Compounds 2-238
Compound 2-238(15.95g) was synthesized in the same manner as in Synthesis example 40 except that a1-1 was replaced with an equimolar a1-50, b1-1 was replaced with an equimolar b1-238, and c1-1 was replaced with an equimolar c1-238, and the purity of the solid was 99.73% or more by HPLC. Mass spectrum m/z: 805.2820 (theoretical value: 805.2803). Theoretical element content (%) C60H39And NS: c, 89.41; h, 4.88; n, 1.74. Measured elemental content (%): c, 89.48; h, 4.82; n, 1.66.
Synthetic example 49: synthesis of Compounds 2-292
A reaction flask was charged with a2-1(31.25mmol, 10.16g), b2-1(63.75mmol, 16.20g), Pd (PPh) under nitrogen atmosphere3)4(0.625mmol，700mg)、K2CO3(93.75mmol, 12.96g), 200mL of toluene, and 80mL of ethanol were stirred under reflux for 4 hours. After the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (5: 1 to yield intermediate A2-1(10.75g, 82% yield).
A2-1 (25.00) was added to the flask under nitrogen atmospheremmol, 10.49g), c1-50(25.5mmol, 7.58g), 100mL of 1, 4-dioxane, CuI (0.375mmol, 71.4mg), trans-1, 2-cyclohexanediamine (2.50mmol, 285mg), K3PO4(75.00mmol, 15.92g) and stirred at reflux for 36 h. After the reaction was completed, the reaction mixture was cooled to room temperature, water was added to the mixture, the mixture was extracted with dichloromethane, and the organic phase was extracted with anhydrous MgSO4Drying, removing the solvent under reduced pressure, and recrystallizing with acetonitrile to obtain compound 2-292(13.35g, yield 84%); the purity of the solid is not less than 99.89% by HPLC detection. Mass spectrum m/z: 635.2263 (theoretical value: 635.2249). Theoretical element content (%) C48H29NO: c, 90.68; h, 4.60; and N, 2.20. Measured elemental content (%): c, 90.65; h, 4.56; and N, 2.24.
Synthetic example 50: synthesis of Compound 2-331
Substitution of b2-1 for equimolar b2-331 in Synthesis example 49 gave compound 2-331(15.13 g); the purity of the solid is not less than 99.81 percent through HPLC detection. Mass spectrum m/z: 787.2887 (theoretical value: 787.2875). Theoretical element content (%) C60H37NO: c, 91.46; h, 4.73; n, 1.78. Measured elemental content (%): c, 91.51; h, 4.76; n, 1.72.
Synthetic example 51: synthesis of Compounds 2-363
Substitution of b2-1 for equimolar b2-363 and c1-50 for equimolar c2-363 in Synthesis example 49 gave compounds 2-363(13.78 g); the purity of the solid is not less than 99.71 percent by HPLC detection. Mass spectrum m/z: 735.2581 (theoretical value: 735.2562). Theoretical element content (%) C56H33NO: c, 91.40; h, 4.52; and N, 1.90. Measured elemental content (%): c, 91.44; h, 4.48; n, 1.88.
Synthesis example 52: synthesis of Compounds 2-377
Substitution of b2-1 in Synthesis example 49 with equimolar b2-377 gave compounds 2-377(14.85 g); the purity of the solid is not less than 99.75 percent by HPLC detection. Mass spectrum m/z: 835.2861 (theoretical value: 835.2875). Theoretical element content (%) C64H37NO: c, 91.95; h, 4.46; n, 1.68. Measured elemental content (%): c, 91.92; h, 4.51; n, 1.64.
Synthetic example 53: synthesis of Compounds 2-388
Under nitrogen atmosphere, a2-388(37.5mmol, 10.52g), b2-377(38.25mmol, 13.55g), KOAc (75mmol, 7.36g), Pd (OAc)2(0.75mmol, 168mg), 200mL of toluene, and 80mL of ethanol, and the mixture was stirred under reflux for 2.5 hours. After the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/methanol (4: 1 to yield intermediate A' -388(12.68g, 79% yield).
A' -388(31.25mmol, 13.37g), b2-388(31.88mmol, 10.53g), Pd (PPh) were added to the reaction flask under nitrogen atmosphere3)4(0.625mmol，722mg)、K2CO3(62.5mmol, 8.64g), 120mL of toluene, and 42mL of ethanol, and the mixture was stirred under reflux for 3 hours. After the reaction is finished, cooling to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (20: 3 to yield intermediate A2-388(14.66g, 86% yield).
To a reaction flask, A2-388(25.00mmol, 13.64g), c1-50(25.5mmol, 7.58g), 100mL of 1, 4-dioxane, CuI (0.375mmol, 71mg), trans-1, 2-cyclohexanediamine (2.5mmol, 285mg), K, under nitrogen, were added3PO4(75.00mmol, 15.92g), heated to reflux for 36 h. After the reaction is finished, cooling to room temperature, and mixingAdding water, extracting with dichloromethane, and collecting organic phase with anhydrous MgSO4Drying, removal of the solvent under reduced pressure and recrystallization from acetonitrile gave compound 2-388(14.82g, 73% yield); the purity of the solid is not less than 99.78 percent by HPLC detection. Mass spectrum m/z: 811.2892 (theoretical value: 811.2875). Theoretical element content (%) C62H37NO: c, 91.71; h, 4.59; n, 1.73. Measured elemental content (%): c, 91.75; h, 4.56; n, 1.69.
Synthetic example 54: synthesis of Compounds 2-406
Substitution of b2-1 for equimolar b2-406 and c1-50 for equimolar c2-406 in Synthesis example 49 gave compounds 2-406(13.06 g); the purity of the solid is not less than 99.80 percent by HPLC detection. Mass spectrum m/z: 635.2271 (theoretical value: 635.2249). Theoretical element content (%) C48H29NO: c, 90.68; h, 4.60; and N, 2.20. Measured elemental content (%): c, 90.64; h, 4.57; and N, 2.25.
Synthetic example 55: synthesis of Compounds 2-442
Substitution of a2-1 for equimolar a2-442, b2-1 for equimolar b2-406, and c1-50 for equimolar c2-442 in Synthesis example 49 gave Compound 2-442(20.08 g); the purity of the solid is not less than 99.71 percent by HPLC detection. Mass spectrum m/z: 635.2263 (theoretical value: 635.2249). Theoretical element content (%) C48H29NO: c, 90.68; h, 4.60; and N, 2.20. Measured elemental content (%): c, 90.64; h, 4.63; and N, 2.23.
Synthetic example 56: synthesis of Compounds 2-452
Under the protection of nitrogen, the nitrogen gas is used for protecting the reaction vessel,mixing raw materials e2-452(11.83g, 34.38mmol), f2-452(6.75g, 35.06mmol) and Na2CO3(7.29g，68.76mmol)、Pd(PPh3)4(397mg, 0.344mmol) and 150mL of toluene, 52.5mL of ethanol were added to the reaction flask, and the reaction was heated under reflux for 2 hours. After the reaction is finished, cooling the mixture to room temperature, performing suction filtration to obtain a filter cake, washing the filter cake with ethanol, and finally, adding toluene/ethanol (4: 1 to yield intermediate c2-452(9.18g, 81% yield).
Substitution of c2-50 in Synthesis example 49 with equimolar c2-452 gave compounds 2-452(14.93 g); the purity of the solid is not less than 99.74 percent by HPLC detection. Mass spectrum m/z: 712.2529 (theoretical value: 712.2515). Theoretical element content (%) C53H32N2O: c, 89.30; h, 4.52; and N, 3.93. Measured elemental content (%): c, 89.33; h, 4.55; and N, 3.86.
Synthetic example 57: synthesis of Compounds 2-478
Substitution of c1-50 in Synthesis example 49 with equimolar c1-238 gave compounds 2-478(12.22 g); the purity of the solid is not less than 99.76 percent by HPLC detection. Mass spectrum m/z: 651.2042 (theoretical value: 651.2021). Theoretical element content (%) C48H29And NS: c, 88.45; h, 4.48; and N, 2.15. Measured elemental content (%): c, 88.50; h, 4.45; n, 2.11.
Synthetic example 58: synthesis of Compounds 2-504
Substitution of b2-1 for equimolar b2-504 and c1-50 for equimolar c1-238 in Synthesis example 49 gave compounds 2-504(14.49 g); the purity of the solid is not less than 99.69 percent by HPLC detection. Mass spectrum m/z: 805.2568 (theoretical value: 805.2552). Theoretical element content (%) C58H35N3S: c, 86.43; h, 4.38; n, 5.21. Measured elemental content (%): c,86.39；H,4.34；N,5.26。
Synthetic example 59: synthesis of Compounds 2-553
Substitution of b2-1 for equimolar b2-553 and c1-50 for equimolar c2-553 in Synthesis example 49 gave compounds 2-553(16.95 g); the purity of the solid is not less than 99.76 percent by HPLC detection. Mass spectrum m/z: 903.2978 (theoretical value: 903.2960). Theoretical element content (%) C68H41And NS: c, 90.33; h, 4.57; n, 1.55. Measured elemental content (%): c, 90.38; h, 4.54; n, 1.51.
Device embodiments
In the invention, the ITO/Ag/ITO or ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning liquid, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. The organic materials are sublimated, and the purity of the organic materials is over 99.99 percent.
The driving voltage, the luminous efficiency and the CIE color coordinate of the organic electroluminescent device are tested by combining test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by Photo Research of the United states into a combined IVL test system. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature.
The device is prepared by adopting a vacuum evaporation system and continuously evaporating under a vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process-5And (3) evaporating an organic layer and a metal electrode respectively by replacing a mask plate under Pa, detecting the evaporation speed by using an SQM160 quartz crystal film thickness detector of Inficon, and detecting the film thickness by using a quartz crystal oscillator.
Example 1: preparation of organic electroluminescent device 1
ITO is used as an anode on a glass substrate; vacuum evaporating 2-TNATA on the anode to form a hole injection layer with the thickness of 60 nm; carrying out vacuum evaporation on NPD in the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 45 nm; depositing mCBP Ir (ppy) on the hole transport layer in vacuum3(5 wt%), as a light emitting layer, 30nm in thickness by vapor deposition; the compound 13 of the invention is vacuum evaporated on the luminescent layer to be used as a hole blocking layer, and the evaporation thickness is 10 nm; evaporating TmPyPB on the hole blocking layer in vacuum to be used as an electron transport layer, wherein the evaporation thickness is 25 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 0.2 nm; al was vacuum-deposited on the electron injection layer as a cathode, and the deposition thickness was 150 nm.
Examples 2 to 21: preparation of organic electroluminescent devices 2-21
By replacing the compound 13 in the hole-blocking layer in example 1 with the compound 55, the compound 58, the compound 67, the compound 72, the compound 129, the compound 253, the compound 319, the compound 325, the compound 357, the compound 408, the compound 430, the compound 441, the compound 483, the compound 512, the compound 534, the compound 537, the compound 565, the compound 586, the compound 608, and the compound 614, respectively, the same procedure was repeated, whereby organic electroluminescent devices 2 to 21 were obtained.
Comparative examples 1 to 4: preparation of comparative organic electroluminescent devices 1 to 4
The compound 13 in the hole blocking layer in example 1 was replaced with R-1, R-2, R-3, and R-4, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 4.
The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 1 to 21 and comparative examples 1 to 4 of the present invention are shown in table 1.
Table 1 test data of light emitting characteristics of organic electroluminescent device
As can be seen from Table 1, compared with the comparative organic electroluminescent devices 1 to 4, the organic electroluminescent devices 1 to 21 of the present invention have lower driving voltage, higher luminous efficiency and longer service life, which indicates that the organic electroluminescent device containing the fluorene derivative of formula 1 in the hole blocking layer is not only more stable, but also can effectively block holes in the light emitting layer, so that electrons and holes can effectively emit light compositely in the light emitting layer. The fluorene derivative has good spatial configuration, so that the material has good electron transport/hole blocking capability, good film forming property, difficult deformation and good stability.
Example 22: preparation of organic electroluminescent device 22
ITO is used as an anode on a glass substrate; vacuum evaporating 2-TNATA on the anode to form a hole injection layer with the thickness of 60 nm; TNB is evaporated in a vacuum mode in the hole injection layer to serve as a hole transport layer, and the evaporation thickness is 55 nm; vacuum evaporation of CBP Ir (npy) on hole transport2acac (10 wt%) as a light-emitting layer, evaporated to a thickness of 35 nm; BCP is evaporated on the luminous layer in vacuum to be used as a hole blocking layer, and the evaporation thickness is 10 nm; the compound 11 of the invention is vacuum evaporated on the hole barrier layer to be used as an electron transport layer, and the evaporation thickness is 30 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 0.5 nm; al is vacuum-evaporated on the electron injection layer to form a cathode, and the thickness of the vapor-deposited layer is 200 nm.
Examples 23 to 39: preparation of organic electroluminescent devices 23-39
The compound 11 in the electron transport layer in example 22 was replaced with a compound 49, a compound 69, a compound 233, a compound 252, a compound 286, a compound 316, a compound 338, a compound 368, a compound 394, a compound 432, a compound 464, a compound 477, a compound 506, a compound 520, a compound 540, a compound 550, and a compound 570, and other steps were performed in the same manner, thereby obtaining organic electroluminescent devices 23 to 39.
Comparative examples 5 to 8: preparation of comparative organic electroluminescent devices 5 to 8
The compound 11 in the electron transport layer of example 22 was replaced with R-1, R-2, R-3, and R-4, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 5 to 8.
The results of the tests on the light emitting characteristics of the organic electroluminescent devices prepared in examples 22 to 39 of the present invention and comparative examples 5 to 8 are shown in table 2.
Table 2 light emitting characteristic test data of organic electroluminescent device
As can be seen from Table 2, the organic electroluminescent devices 22 to 39 have lower driving voltages, higher luminous efficiencies and longer lifetimes than the comparative organic electroluminescent devices 5 to 8. This shows that the organic electroluminescent device containing the fluorene derivative of structural formula 1 in the electron transport layer can effectively transport electrons, so that more electrons and holes are combined with each other to form excitons to emit light. The fluorene derivative has better photoelectric property and is an organic photoelectric material with excellent performance.
Example 40: preparation of organic electroluminescent device 40
ITO/Ag/ITO is used as an anode on the glass substrate; vacuum evaporating 2-TNATA on the anode as hole injectionEntering a layer, and evaporating to form the layer with the thickness of 60 nm; vacuum evaporating TPD10 in the hole injection layer to form a hole transport layer with the thickness of 50 nm; vacuum evaporation of DMFL-CBP Ir (ppy) on hole transport2(acac) (5 wt%) as a light-emitting layer, evaporated to a thickness of 35 nm; the compound 13 of the invention is vacuum evaporated on the luminescent layer to be used as a hole blocking layer, and the evaporation thickness is 10 nm; vacuum evaporation of Alq on hole blocking layer3As an electron transport layer, the evaporation thickness is 40 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1.0 nm; vacuum evaporating Mg, Ag being 1:9, on the electron injection layer to form a cathode, wherein the evaporation thickness is 20 nm; the compounds 2 to 74 according to the invention were deposited as a cover layer on the cathode in vacuum with a thickness of 60 nm.
Examples 41 to 59: preparation of organic electroluminescent devices 41-59
Compound 13 in the hole-blocking layer in example 40 was replaced with Compound 67, Compound 72, Compound 129, Compound 253, Compound 316, Compound 319, Compound 325, Compound 338, Compound 357, Compound 430, Compound 432, Compound 441, Compound 464, Compound 483, Compound 512, Compound 520, Compound 534, Compound 537, Compound 586, respectively, Compound 2 to 74 in the overcoat layer was replaced with Compound 2 to 553, Compound 2 to 211, Compound 2 to 452, Compound 2 to 50, Compound 2 to 152, Compound 2 to 478, Compound 2 to 17, Compound 2 to 181, Compound 2 to 292, Compound 2 to 363, Compound 2 to 190, Compound 2 to 126, Compound 2 to 406, Compound 2 to 442, Compound 586, respectively, And obtaining the organic electroluminescent devices 41-59 by using the compounds 2-377, the compounds 2-331, the compounds 2-504, the compounds 2-388 and the compounds 2-238 in the same steps.
Comparative examples 9 to 10: preparation of comparative organic electroluminescent devices 9 to 10
The compound 13 in the hole blocking layer in example 40 was replaced with the compound 13 and the compound 319, the compounds 2 to 74 in the capping layer were replaced with the compounds CP-1 and CP-2, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 9 to 10.
The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 40 to 59 and comparative examples 9 to 10 of the present invention are shown in table 3.
Table 3 test data of light emitting characteristics of organic electroluminescent device
As can be seen from Table 3, the organic electroluminescent devices 40 to 59 of the present invention have a lower driving voltage, a higher luminous efficiency and a longer service life, which indicates that the organic electroluminescent devices of the present invention can emit light efficiently and are stable enough. The organic electroluminescent device not only can realize the effective combination luminescence of electrons and holes in the luminescent layer, but also can couple out the light trapped in the device to achieve the optimal luminescent state; in addition, each layer of the organic electroluminescent device, especially the hole blocking layer and the covering layer, has a stable film form, is not easily influenced by factors such as light, hot water and the like, and effectively prolongs the service life of the device.
Example 60: preparation of organic electroluminescent device 60
ITO/Ag/ITO is used as an anode on the glass substrate; HAT-CN is evaporated on the anode in vacuum to be used as a hole injection layer, and the evaporation thickness is 10 nm; performing vacuum evaporation on Spiro-NPB in the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 70 nm; vacuum evaporation of CBP Ir (ppy) on hole transport2(acac) (4 wt%) as a light-emitting layer, evaporated to a thickness of 42 nm; vacuum evaporation of Alq on the luminescent layer3As an electron transport layer, the evaporation thickness is 33 nm; evaporating LiF on the electron transport layer in vacuum to form an electron injection layer, wherein the evaporation thickness is 1.0 nm; vacuum evaporating Mg, Ag being 1:9, on the electron injection layer to form a cathode, wherein the evaporation thickness is 15 nm; the compound 13 of the present invention was vacuum-deposited on the cathode as a coating layer to a thickness of 53 nm.
Examples 61 to 66: preparation of organic electroluminescent devices 61-66
The compound 13 in the capping layer of example 60 was replaced with the compound 253, the compound 325, the compound 357, the compound 430, the compound 441, and the compound 512, respectively, and the same procedure was followed to obtain organic electroluminescent devices 61 to 66.
Comparative examples 11 to 12: preparation of comparative organic electroluminescent devices 11 to 12
The compound 13 in the capping layer of example 60 was replaced with R-5 and R-6, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 11 to 12.
The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 60 to 66 of the present invention and comparative examples 11 to 12 are shown in table 4.
Table 4 test data of light emitting characteristics of organic electroluminescent device
As can be seen from Table 4, examples 60 to 66 have higher luminous efficiency than comparative examples 11 to 12, which shows that the fluorene derivative of the present invention has better light extraction performance, can effectively couple out light in a device, and improves the luminous efficiency of the device.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.
Claims (10)
1. A fluorene derivative is characterized by having a general formula shown in a structural formula 1,
ar is1Selected from the group consisting of groups represented by formula 1-a1, Ar2Selected from the group consisting of those represented by the formula 1-a1 or formula 1-a2,
the Z is the same or different and is selected from N or C (R)z) Wherein at least one Z is selected from N, said RzThe same or different one selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the E is the same or different and is selected from N or C (R)e) Wherein one E is selected from N and the others are selected from C (R)e) Said R iseOne selected from hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
the L is selected from one of the groups shown as follows,
said L0One selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, and a substituted or unsubstituted pyridylene group; n1 are the same or different and are selected from 0, 1,2,3 or 4; n2 are the same or different and are selected from 0, 1,2 or 3; the R is1The same or different one selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C3-C10 cycloalkyl;
said L1、L2Independently selected from single bond or substituted or unsubstituted arylene of C6-C30;
ar is selected from the group shown as follows,
the R is0The same or different one selected from hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, or two R0Bonding to form a ring structure;
the R is same or different and is selected from one of hydrogen, deuterium, cyano, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C2-C60 heteroaryl, or two adjacent R are bonded to form a cyclic structure;
the m1 are the same or different and are selected from 0, 1,2,3 or 4.
2. The fluorene derivative according to claim 1, wherein Ar is selected from one of the following groups,
m1 are the same or different and are selected from 0, 1,2,3 or 4; m2 are the same or different and are selected from 0, 1,2 or 3;
the R is0The same or different one selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted cyclopentyl group, a substituted or unsubstituted cyclohexyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, or two R' s0Bonding to form a ring structure;
the R is the same or different and is selected from one of hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted bornyl, substituted or unsubstituted norbornanyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazinyl, quinolyl and isoquinolyl;
the R is01And one selected from the group consisting of a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, and a substituted or unsubstituted naphthylene group.
3. The fluorene derivative according to claim 1, wherein the formula 1-a1 is selected from one of the following groups,
the R iszThe same or different one selected from hydrogen, deuterium, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted benzofluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinoline, and substituted or unsubstituted isoquinoline.
4. The fluorene derivative according to claim 1, wherein the formula 1-a2 is selected from one of the following groups,
5. the fluorene derivative according to claim 1, wherein Ar is selected from one of the following groups,
the R is the same or different and is selected from one of hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopropyl, substituted or unsubstituted cyclobutyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted bornyl, substituted or unsubstituted norbornanyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazinyl, quinolyl and isoquinolyl.
6. The fluorene derivative according to claim 1, wherein L is selected from one of the following groups,
7. the fluorene derivative according to claim 1, wherein the fluorene derivative of formula 1 is selected from one of the following structures,
8. an organic electroluminescent device is characterized by sequentially comprising an anode, an organic layer, a cathode and a covering layer, wherein the covering layer contains a fluorene derivative shown in a structural formula 1.
9. An organic electroluminescent device is characterized by sequentially comprising an anode, an organic layer and a cathode, wherein the organic layer comprises an electron transmission region, and the electron transmission region contains a fluorene derivative shown in a structural formula 1.
10. The organic electroluminescent device according to claim 9, further comprising a cap layer containing a heterocyclic compound represented by formula 2,
wherein, Ar isaSelected from the group represented by formula 2-a,
x is selected from O or S;
the ring A and the ring B are independently selected from any one of no, a benzene ring and a naphthalene ring, and at least one of the ring A or the ring B is selected from the benzene ring or the naphthalene ring;
k is the same or different and is selected from 0, 1,2,3, 4,5, 6, 7 or 8; the R is2Any one of the same or different hydrogen, deuterium, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl; or two R2Bonding to form a ring structure;
ar isb、ArcIndependently selected from one of the groups shown in the following,
the R is3Any one of the same or different hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C2-C30 heteroaryl;
said g is1The same or different is selected from 0, 1,2,3, 4,5, 6 or 7; said g is2The same or different is selected from 0, 1,2,3, 4,5, 6, 7, 8 or 9;
said La、Lb、LcIndependently selected from any one of single bond, substituted or unsubstituted arylene of C6-C30 and substituted or unsubstituted heteroarylene of C2-C30,
said Lb、LcMay form a carbazole ring with the aromatic amine N by a single bond linkage.
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