CN114105891B - Fluorene derivative and organic electroluminescent device thereof - Google Patents
Fluorene derivative and organic electroluminescent device thereof Download PDFInfo
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- CN114105891B CN114105891B CN202111458913.4A CN202111458913A CN114105891B CN 114105891 B CN114105891 B CN 114105891B CN 202111458913 A CN202111458913 A CN 202111458913A CN 114105891 B CN114105891 B CN 114105891B
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- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 title claims abstract description 20
- 239000010410 layer Substances 0.000 claims description 125
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 33
- 229910052805 deuterium Inorganic materials 0.000 claims description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- 150000002431 hydrogen Chemical class 0.000 claims description 28
- 125000003118 aryl group Chemical group 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 19
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 17
- 239000012044 organic layer Substances 0.000 claims description 16
- 125000001624 naphthyl group Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 125000000732 arylene group Chemical group 0.000 claims description 12
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 12
- 125000004076 pyridyl group Chemical group 0.000 claims description 12
- 125000006732 (C1-C15) alkyl group Chemical group 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 125000005549 heteroarylene group Chemical group 0.000 claims description 7
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 7
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 6
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000004957 naphthylene 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
- 239000011247 coating layer Substances 0.000 claims description 3
- 125000005551 pyridylene group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 230000005540 biological transmission Effects 0.000 abstract description 9
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000000284 extract Substances 0.000 abstract description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 description 192
- 238000003786 synthesis reaction Methods 0.000 description 192
- 150000001875 compounds Chemical class 0.000 description 180
- 238000001819 mass spectrum Methods 0.000 description 58
- 238000004128 high performance liquid chromatography Methods 0.000 description 57
- 239000007787 solid Substances 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- 238000000034 method Methods 0.000 description 47
- 238000001704 evaporation Methods 0.000 description 39
- 238000002347 injection Methods 0.000 description 35
- 239000007924 injection Substances 0.000 description 35
- -1 benzofluorenyl Chemical group 0.000 description 32
- 150000002220 fluorenes Chemical class 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 24
- 230000000903 blocking effect Effects 0.000 description 23
- 238000001514 detection method Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010408 film Substances 0.000 description 17
- 238000010992 reflux Methods 0.000 description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 16
- 230000008020 evaporation Effects 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 15
- 230000005525 hole transport Effects 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000002346 layers by function Substances 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 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 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000002904 solvent Substances 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 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
- 235000010290 biphenyl Nutrition 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 7
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 7
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000010931 gold Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 125000000714 pyrimidinyl group Chemical group 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 125000004306 triazinyl group Chemical group 0.000 description 6
- 238000001771 vacuum deposition Methods 0.000 description 6
- 238000007738 vacuum evaporation Methods 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
- 125000006749 (C6-C60) aryl 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
- 125000005561 phenanthryl group Chemical group 0.000 description 5
- 125000003373 pyrazinyl group Chemical group 0.000 description 5
- 125000002098 pyridazinyl group Chemical group 0.000 description 5
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 5
- 239000000243 solution Substances 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
- 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 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 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
- CRPUJAZIXJMDBK-UHFFFAOYSA-N camphene Chemical compound C1CC2C(=C)C(C)(C)C1C2 CRPUJAZIXJMDBK-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229940126179 compound 72 Drugs 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000008204 material by function Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 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
- 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
- 125000005580 triphenylene group Chemical group 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
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-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
- 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
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 125000004122 cyclic group Chemical group 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
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 125000003367 polycyclic group Chemical group 0.000 description 3
- 235000011056 potassium acetate Nutrition 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
- 239000000376 reactant Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 3
- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- CINYXYWQPZSTOT-UHFFFAOYSA-N 3-[3-[3,5-bis(3-pyridin-3-ylphenyl)phenyl]phenyl]pyridine Chemical compound C1=CN=CC(C=2C=C(C=CC=2)C=2C=C(C=C(C=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)C=2C=C(C=CC=2)C=2C=NC=CC=2)=C1 CINYXYWQPZSTOT-UHFFFAOYSA-N 0.000 description 2
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 description 1
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000004949 mass spectrometry 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
- 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
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-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
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 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
- 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
- 229910000027 potassium carbonate Inorganic materials 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
- 125000005576 pyrimidinylene group Chemical group 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
- 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
- 238000000926 separation method Methods 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
- 229910000029 sodium carbonate 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
- 238000001228 spectrum Methods 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
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- KTQYWNARBMKMCX-UHFFFAOYSA-N tetraphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 KTQYWNARBMKMCX-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 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
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 238000004506 ultrasonic cleaning 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
- C07D401/14—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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- C07—ORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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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 electron withdrawing group is connected with the fluorenyl group through a distorted bridging group. The fluorene derivative has a better spatial three-dimensional configuration, and the material has better photoelectric performance, so that the organic electroluminescent device containing the fluorene derivative in the electron transmission area has better film stability and is not easy to crystallize, the device can enable holes to be blocked in the luminescent layer, can more effectively transmit electrons, enable the electrons and the holes in the device to be transmitted more in a balanced manner, and enable more electrons and holes to combine in the luminescent layer to generate excitons to emit light, thus lower driving voltage, higher luminous efficiency and longer service life are shown. In addition, the fluorene derivative has better 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 Diode (OLED) is rapidly developing as a new generation of flat panel display terminal technology. In general, OLEDs have advantages of approaching to natural light emission characteristics, wide viewing angle, light weight, high contrast ratio, low driving voltage, shock resistance, impact resistance, realization of flexibility and transparent display, etc., which make them have great growing and lifting spaces in various fields, and thus, they are paid great attention to both academia and industry. Currently, OLEDs have been gradually applied to high-end display fields such as cell phones, wearable devices, vehicles, and computers.
The organic electroluminescent device is typically a sandwich structure, i.e. the organic functional layer is sandwiched between an anode and a cathode on both sides 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, excitons are formed when the holes and the electrons meet at the light-emitting layer, the excitons transition 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.
The organic electroluminescent device may be classified into a single layer device, a double layer device, a multi-layer device, and the like 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 poorer performance because 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 carrier injection of the double-layer device is easier, the charge in the device is more balanced, and the quenching of excitons is reduced, so that better device performance is obtained. The organic functional layers of the multilayer device may contain, in addition to the hole transport layer, the light emitting layer, and the electron transport layer, organic functional layers such as a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, and a capping layer, and thus have excellent photoelectric properties due to different functions of the different functional layers.
At present, most of organic functional materials cannot meet the industrial requirements, especially the electronic transmission area materials or the cover layer materials, the performances of the organic functional materials still far do not reach the relevant standards, and the organic functional materials are used for devices which have the defects of high driving voltage, low luminous efficiency, short service life and the like, so that improvement of the relevant organic functional materials is urgently needed.
In addition, although the multilayer device has more excellent photoelectric properties than before due to the increase in the number of organic functional layers, most of the organic electroluminescent devices still cannot meet the industrial demands at present, and therefore, it is required to develop an organic electroluminescent device having a multilayer device structure with more excellent photoelectric properties, in particular, an organic electroluminescent device having a multilayer device structure with higher luminous efficiency.
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,
the Ar is as follows 1 Selected from the group represented by formula 1-a1, the Ar 2 Selected from the group represented by formula 1-a1 or formula 1-a2,
the Z's are identical or different and are selected from N or C (R z ) Wherein at least one Z is selected from N, said R z The 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, 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 ) The R is e 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, substituted or unsubstituted C2-C30 heteroaryl;
the L is selected from one of the following groups,
the L is 0 One 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; the n1 is the same or different and is selected from 0, 1, 2, 3 or 4; the n2 is the same or different and is selected from 0, 1, 2 or 3; the R is 1 The same or different alkyl groups are selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C10 alkyl groups and substituted or unsubstituted C3-C10 cycloalkyl groups;
The L is 1 、L 2 Independently selected from single bond or substituted or unsubstituted C6-C30 arylene;
the Ar is selected from the group shown below,
wherein the attachment site of the group of formula 1-a is any position;
the R is 0 The 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 R 0 Bonding to form a ring structure;
the R is the 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 is the same or different and is 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 fluorene derivatives 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 transport region, and the electron transport region contains fluorene derivatives shown in structural formula 1.
The beneficial effects are that:
the fluorene derivative has a better spatial three-dimensional configuration, and the material has better photoelectric performance, so that the organic electroluminescent device containing the fluorene derivative in the electron transmission area has better film stability and is not easy to crystallize, the device can enable holes to be blocked in the luminescent layer, can more effectively transmit electrons, enables the electrons and the holes in the device to be transmitted more in a balanced manner, enables more electrons and holes to combine in the luminescent layer to generate excitons to emit light, and has lower driving voltage, higher luminous efficiency and longer service life.
In addition, the fluorene derivative has better light extraction performance, can effectively extract light in the device, and effectively improves the luminous efficiency of the device.
In addition, the hole blocking layer and the cover layer respectively contain fluorene derivative of the structural formula 1 and heterocyclic compound of the structural formula 2, and the device has better luminous performance, higher luminous efficiency and longer service life due to the dual functions of the electron transmission area and the materials in the cover layer.
Detailed Description
The present invention is further illustrated below in conjunction with specific embodiments, it being understood that these embodiments are meant to be illustrative of the invention and not limiting the scope of the invention, and that modifications of the invention, which are all within the scope of the invention as claimed by those skilled in the art after reading the present invention.
In this 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, the number of the cells to be processed,can indicate->And so on.
In the present invention, "adjacent two groups are bonded to form a cyclic structure" means that a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring is formed by bonding adjacent groups to each other and optionally aromatizing. The hydrocarbon ring may be an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. The heterocycle may include aliphatic or aromatic heterocycles. 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 ring and the heterocyclic ring may be a single ring or a polycyclic group. In addition, a ring formed by bonding adjacent groups may be linked 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 substituents described herein represents the attachment site.
The term "unsubstituted" in the term "substituted or unsubstituted" as used herein means that a hydrogen atom on a group is not replaced by any substituent.
"substituted" in "substituted or unsubstituted" as used herein means that at least one hydrogen atom on the group is replaced with a substituent. When a plurality of hydrogens are replaced with a plurality of substituents, the plurality of substituents may be the same or different. The position of the hydrogen substituted with the substituent may be any position.
The substituent group represented by "substituent" in the above "substituted or unsubstituted" is selected from one of deuterium, cyano, nitro, halogen, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, for example, deuterium, cyano, nitro, halogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, camphene, norbornyl, phenyl, tolyl, pentadeuterated phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, anthryl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, benzofluorenyl, spirobifluorenyl, dibenzofuranyl, benzodibenzofuranyl, dibenzothienyl, benzodibenzothienyl, carbazolyl, 9-phenylcarbazolyl, benzocarbazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, benzoquinolinyl, quinazolinyl, quinoxalinyl, phenanthridinyl, phenanthroline, and the like, preferably deuterium, cyano, methyl, ethyl, isopropyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, alkyl, norbornyl, adamantyl, penta, pyridinyl, naphthyridinyl, and the like.
The alkanyl group having more than three carbon atoms of the present invention includes isomers thereof, for example, propyl group includes n-propyl group, isopropyl group, butyl group includes n-butyl group, sec-butyl group, isobutyl group, tert-butyl group. And so on.
The "C6-C60" in the "substituted or unsubstituted C6-C60 aryl" as used herein means the number of carbon atoms in the unsubstituted "aryl" and does not include the number of carbon atoms in the substituent. The "C2-C60" in the "substituted or unsubstituted C2-C60 heteroaryl" represents the number of carbon atoms in the unsubstituted "heteroaryl" and does not include the number of carbon atoms in the substituent. And so on.
The alkyl refers to a monovalent group formed by removing one hydrogen atom in an alkane molecule. The number of carbon atoms of the alkyl group is 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, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.
The cycloalkyl refers to a monovalent group formed by removing one hydrogen atom in a cycloparaffin molecule. The cycloalkyl group has a carbon number of 3 to 30, preferably 3 to 15, more preferably 3 to 10 or 3 to 7. Examples of cycloalkyl groups include, but are not limited to, cyclohexyl, adamantyl, camphene, norbornane, and the like.
The aryl refers to a monovalent group formed by removing one hydrogen atom from the aromatic nucleus carbon of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl groups, polycyclic aryl groups, and condensed ring aryl groups. The monocyclic aryl refers to a group with only one benzene ring in the structure, the polycyclic aryl refers to a group with two or more independent benzene rings in the structure, and the condensed ring aryl refers to a group with more than two benzene rings condensed by sharing two adjacent carbon atoms. The number of carbon atoms of the aryl group is from C6 to C60, preferably from C6 to C30, more preferably from C6 to C25, still more preferably from C6 to C18, still more preferably from C6 to C14, and still more preferably from C6 to C10. Examples of the aryl group include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, triphenylene, anthracenyl, fluorenyl, benzofluorenyl, spirobifluorenyl, benzospirobifluorenyl, and the like.
Heteroaryl as used herein refers to a monovalent group in which at least one of the aromatic nucleus carbon atoms in the aryl group is replaced with a heteroatom. Such heteroatoms include, but are not limited to, atoms as described below, O, S, N, si, B, P, and the like. The heteroaryl group includes monocyclic heteroaryl, fused ring heteroaryl. The monocyclic heteroaryl refers to a group with only one heteroaromatic ring in the structure, and the condensed ring heteroaryl refers to a group formed by fusing a benzene ring and a single heterocyclic ring or more than two single heterocyclic rings. The heteroaryl group has a carbon number of from C2 to C60, preferably from C2 to C30, more preferably from C2 to C25, still more preferably from C2 to C12, and still more preferably from C2 to C8. Examples of heteroaryl groups include, but are not limited to, quinazolinyl, quinoxalinyl, benzoquinazolinyl, quinolinyl, isoquinolinyl, benzoquinolinyl, benzoisoquinolinyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, naphthyridinyl, phenanthridinyl, phenanthroline, dibenzofuranyl, benzodibenzofuranyl, dibenzothiophenyl, benzodibenzothiophenyl, carbazolyl, and the like.
The arylene group refers to a divalent group formed by removing two hydrogen atoms from an aromatic nucleus carbon in an aromatic hydrocarbon molecule. The arylene group includes a monocyclic arylene group, a polycyclic arylene group, a fused ring arylene group, or a combination thereof. The arylene group has a carbon number of from C6 to C60, preferably from C6 to C30, more preferably from C6 to C25, still more preferably from C6 to C18, still more preferably from C6 to C14, and still more preferably from C6 to C10. Examples of the arylene group include, but are not limited to, phenylene, biphenylene, terphenylene, tetraphenylene, naphthylene, phenanthrylene, triphenylene, anthrylene, fluorenylene, benzofluorenylene, spirobifluorenylene, benzospirobifluorenylene, and the like.
Heteroaryl ene according to the present invention refers to a divalent group in which at least one carbon atom in the arylene group is replaced with a heteroatom. Such heteroatoms include, but are not limited to, the atoms shown below, O, S, N, si, B, P, and the like. The heteroarylene includes a monocyclic heteroarylene, a polycyclic heteroarylene, a fused ring heteroarylene, or a combination thereof. The polycyclic heteroarylene may have only one heteroatom-substituted benzene ring or may have a plurality of heteroatom-substituted benzene rings. The heteroarylene group has a carbon number of from 2 to 60, preferably from 2 to 30, more preferably from 2 to 25, still more preferably from 2 to 12, and still more preferably from 2 to 8. Examples of heteroarylene groups include, but are not limited to, a pyridyl, pyrimidinylene, pyridazinyl, pyrazinyl, triazinylene, dibenzofuranylene, benzodibenzofuranylene, dibenzothiophenylene, benzodibenzothiophenylene, carbazolylene, quinolinylene, isoquinolinyl, quinoxalinylene, quinazolinylene, and the like.
The invention provides a fluorene derivative, which has a general formula shown in a structural formula 1,
the Ar is as follows 1 Selected from the group represented by formula 1-a1, the Ar 2 Selected from the group represented by formula 1-a1 or formula 1-a2,
the Z is the same or differentFrom N or C (R) z ) Wherein at least one Z is selected from N, said R z The 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, 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 ) The R is e 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, substituted or unsubstituted C2-C30 heteroaryl;
the L is selected from one of the following groups,
the L is 0 One 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; the n1 is the same or different and is selected from 0, 1, 2, 3 or 4; the n2 is the same or different and is selected from 0, 1, 2 or 3; the R is 1 The same or different alkyl groups are selected from hydrogen, deuterium, cyano, substituted or unsubstituted C1-C10 alkyl groups and substituted or unsubstituted C3-C10 cycloalkyl groups;
the L is 1 、L 2 Independently selected from single bond or substituted or unsubstituted C6-C30 arylene;
the Ar is selected from the group shown below,
wherein the attachment site of the group of formula 1-a is any position;
the R is 0 The same or different alkyl groups selected from hydrogen, deuterium, substituted or unsubstituted C1-C30One of a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C2-C60 heteroaryl group, or two R' s 0 Bonding to form a ring structure;
the R is the 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 is the same or different and is 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 following groups,
The m1 is the same or different and is selected from 0, 1, 2, 3 or 4; the m2 is the same or different and is selected from 0, 1, 2 or 3;
the R is 01 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.
Preferably, R is as described in the present invention 0 The same or different one selected from hydrogen, deuterium, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, or two R 0 Bonding to form a ring structure;
preferably, R is the same or different 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 camphenethyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazinyl, quinolinyl, isoquinolinyl.
Preferably, the formula 1-a1 is selected from one of the groups shown below,
preferably, R is as described in the present invention z The same or different is selected from one of 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 benzodibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted benzodibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted quinoline, and substituted or unsubstituted isoquinoline.
Preferably, the formula 1-a2 is selected from one of the groups shown below,
preferably, ar is selected from one of the following groups,
preferably, R is the same or different 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 camphenethyl, substituted or unsubstituted norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted triazinyl, quinolinyl, isoquinolinyl.
Preferably, L is selected from one of the following groups,
preferably, the L 1 、L 2 Independently 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,
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the fluorene derivatives of the present invention of the formula 1 are exemplified above in specific chemical structures, but the present invention is not limited to these chemical structures, and substituents are included in any of the structures of the formula 1.
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 fluorene derivatives 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 transport region, and the electron transport region contains fluorene derivatives shown in structural formula 1.
Further, the organic electroluminescent device further comprises a cover layer containing a heterocyclic compound represented by formula 2,
Wherein the Ar is a Selected from the group represented by the formula 2-a,
the X is selected from O or S;
the ring A and the ring B are independently selected from any one of a benzene ring and a naphthalene ring, and at least one of the ring A or the ring B is selected from a benzene ring or a naphthalene ring;
the k are the same or different and are selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the R is 2 The same or different one selected from 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 R 2 Bonding to form a ring structure;
the Ar is as follows b 、Ar c Independently selected from one of the groups shown below,
the R is 3 The same or different one selected from hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said g 1 The same or different is selected from 0, 1, 2, 3, 4, 5, 6 or 7; said g 2 The same or different is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9;
the L is a 、L b 、L c Independently selected from single bond, substituted or unsubstituted Any one of C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene,
the L is b 、L c Carbazole rings can be formed by single bond connection with the aromatic amine N.
Preferably, the Ar a Selected from one of the groups shown below,
the R is 2 The same or different is selected from any one of hydrogen, deuterium, cyano, halogen, methyl, ethyl, isopropyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, 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 dibenzothiophenyl, and substituted or unsubstituted carbazolyl;
The k is 2 The same or different is selected from 0, 1, 2, 3 or 4; the k is 3 The same or different is selected from 0, 1, 2, 3, 4, 5 or 6; the k is 4 The same or different is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8.
Preferably, the Ar a Selected from one of the groups shown below,
preferably, the Ar b 、Ar c Independently selected from one of the groups shown below,
the R is 3 The same or different one selected from hydrogen, deuterium, cyano, methyl, ethyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted triazinyl;
the substituent in the substituted or unsubstituted is selected from any one of hydrogen, deuterium, cyano, methyl, ethyl, isopropyl, tertiary butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, phenyl, tolyl, pentadeuterated phenyl, biphenyl, naphthyl and pyridyl;
Said g 1 The same or different is selected from 0, 1, 2, 3, 4, 5, 6 or 7; said g 2 The same or different is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.
Preferably, the L a 、L b 、L c Independently selected from a single bond or one of the groups shown below,
wherein the R is 4 The same or different one is selected from any one of 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;
said f 1 The same or different are selected from 0, 1, 2, 3 or 4, f 2 The same or different is selected from 0, 1, 2, 3, 4, 5 or 6,f 3 The same or different is selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8, f 4 The same or different are selected from 0, 1, 2 or 3, f 5 The same or different are selected from 0, 1 or 2, f 6 The 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,
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the specific chemical structures of the heterocyclic compounds of the present invention represented by the structural formula 2 are listed above, but the present invention is not limited to the listed chemical structures, and substituents are included in the heterocyclic compounds as defined above, even when the heterocyclic compounds are based on the structures represented by 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 fluorene derivatives 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 not limited thereto, any functional layer having hole injection and/or transport properties or any functional layer having electron injection and/or transport properties should be included. Each functional layer may be formed of a single film or a plurality of films, and each film may contain one material or a plurality of materials.
The material of each layer of thin film in the organic electroluminescent device is not particularly limited, and materials known in the art can be used. The following describes each organic functional layer of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device, respectively:
The anode has the function of injecting holes into the hole injection/transport layer, and the film thickness of the anode is 50-500 nm. The material for the anode of the present invention may comprise: metal oxides, e.g. Indium Tin Oxide (ITO), indium oxide (In 2 O 3 ) Indium Zinc Oxide (IZO), zinc oxide (ZnO), and the like; laminated materials such as 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), and the like; 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/transport layer, and the film thickness of the cathode is 0.1-500 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), and the like; laminated 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 the hole injection barrier between the anode and the hole transport layer, and the film 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 organics, metal compounds, aromatic amine derivatives, and the like, for example (2E, 2'E,2 "E) -2,2' - (cyclopropane-1, 2, 3-triyl) tris (2- (perfluorophenyl) -acetonitrile), 1,4,5,8,9,11-hexaazabenzonitrile (HAT-CN), 2,3,5, 6-tetrafluoro-7, 7', 8' -tetracyanodimethyl-p-benzoquinone (F4-TCNQ), copper phthalocyanine (CuPc), molybdenum trioxide (MoO) 3 ) Vanadium pentoxide (V) 2 O 5 ) Tungsten trioxide (WO) 3 ) Ferric trichloride (FeCl) 3 ) 4,4 '-tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), 4' -tris [ 2-naphthylphenylamino)]Triphenylamine (2T-NATA), and the like. But is not limited thereto.
The hole transport layer has the effects of improving the balance of injection and transport of holes in the device and effectively blocking electrons in the light-emitting layer, and the film thickness of the hole transport layer is 5-1000 nm. The material for the hole transport layer of the present invention may comprise: amine compounds, fluorene compounds, carbazole compounds and the like, for example, such as N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB), N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) -2,2 '-dimethylbenzidine (NPD), N' -bis (naphthalen-1-yl) -N, N '-bis (phenyl) -2, 7-diamino-9, 9-spirobifluorene (spira-NPB), N4' -bis (biphenyl-4-yl) -N4, N4 '-diphenyl biphenyl-4, 4' -diamine (TPD 10) and the like. But is not limited thereto.
As the light emitting layer of the present invention, host materials include condensed aromatic ring derivatives, heterocyclic compounds, etc., such as 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 (pyren-1-yl) benzene (TPB 3), 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-2 CBP), 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, it is possible to include a styrylamine compound, an aromatic amine derivative, a metal complex, etc., for example, 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-tetraphenyltetracene (Rubrene), tris (2-phenylpyridine) iridium (III) (Ir (ppy) 3 ) Bis (2-phenylpyridine) (acetylacetonate) iridium (III) (Ir (ppy) 2 (acac)), bis (2- (naphthalen-2-yl) pyridine) (acetylacetonate) iridium (III) (Ir (npy) 2 acac), 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 not contain a host material.
The hole blocking layer of the present invention has the function of blocking holes injected from the anode from passing through the light emitting layer into the electron transport region, and the hole blocking layer has a film thickness of 0.1nm to 300nm. The material for the hole blocking layer of the present invention may comprise: phenanthroline derivatives, metal complexes, imidazole derivatives, and the like, such as 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. Fluorene derivatives represented by structural formula 1 of the present invention are preferable.
The electron transport layer has the function of improving the balance of electron injection and electron transport in the device, and the film thickness of the electron transport layer is 1 nm-1000 nm. The material for the electron transport layer of the present invention may comprise: metal complexes, imidazole derivatives, phenanthroline derivatives, triazines, pyridine derivatives, etc., e.g. tris (8-hydroxyquinoline) aluminum (III) (Alq) 3 ) The derivatives of 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi) and phenanthroline include 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)](TmPyPB), etc. But is not limited thereto. Fluorene derivatives represented by structural formula 1 of the present invention are 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 film 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 coating of the present invention has the effect of coupling out light trapped in the device, and the material for the coating of the present invention may comprise: metal compounds, aromatic amine derivatives, carbazole derivatives, and the like, but are not limited thereto. The film thickness of the cover layer is 1 nm-200 nm. The heterocyclic compound represented by formula 2 of the present invention is preferable.
The method for producing the thin films of each layer in the organic electroluminescent device of the present invention is not particularly limited, and vacuum deposition, sputtering, spin coating, spray coating, screen printing, laser transfer, etc. may be used, but are 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 a tablet personal computer, a flat television, a mobile phone, a smart watch, a digital camera, VR, a vehicle-mounted system, wearable equipment and the like.
Synthetic examples
(1) The method for producing the fluorene derivative of structural formula 1 of the present invention is not particularly limited, and conventional methods known to those skilled in the art can be employed. For example, the fluorene derivative of structural formula 1 of the present invention can be produced by the synthetic route shown below, for example, by carbon-carbon coupling reaction.
(2) The method for producing the heterocyclic compound of the structural formula 2 of the present invention is not particularly limited, and conventional methods known to those skilled in the art can be employed. For example, carbon-nitrogen coupling reactions, carbon-carbon coupling reactions, and the like.
When L b 、L c The heterocyclic compound of the structural formula 2 of the present invention can be prepared by using the synthetic route shown below when not connected by a single bond:
When L b 、L c When connected by single bond, the heterocyclic compound of the structural formula 2 can be prepared by adopting the synthetic route shown as follows:
the X is n Selected from halogen such as Cl, br, I; the B is n Selected from the group consisting of-B (OH) 2 Or alternativelyThe "- - - -" represents L b And L is equal to c It is assumed that the connection is by a single bond.
Raw materials and reagents: the starting materials or reagents used in the following synthetic examples are not particularly limited and may be commercially available products or prepared by methods well known to those skilled in the art. The raw materials and the reagents used in the invention are all reagent pure.
Instrument: g2—si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); vario EL cube organic element analyzer (Elementar, germany).
Synthesis example 1: synthesis of Compound 11
1L of tetrahydrofuran solvent, a-1 (37.85 g,140 mmol), b-1 (71.10 g,280 mmol), pd (dppf) Cl were sequentially added to a three-necked flask under nitrogen atmosphere 2 (0.51 g,0.70 mmol) and potassium acetate (39.26 g,400 mmol), and the mixture was stirred to give a mixed solution of the above-mentioned reactantsHeating and refluxing for 7 hours; after the reaction was completed, cooled and distilled water was added, and the mixture was filtered and dried in a vacuum oven. The obtained residue was purified by column chromatography on silica gel (petroleum ether: ethyl acetate=1:1) to give compound c-1 (42.35 g, yield 83%).
600mL of tetrahydrofuran solvent and compound c-1 (36.45 g,100 mmol) were added to a three-necked flask under nitrogen atmosphere and dissolved with stirring, and d-1 (41.81 g,200 mmol) and Pd (PPh) were added thereto 3 ) 4 (11.56 g,10 mmol) and continuously stirring the mixture, and then adding a saturated aqueous potassium carbonate solution (41.46 g,300 mmol) thereto, and heating and refluxing the mixed solution of the above-mentioned reactants for 12 hours; after the completion of the reaction, distilled water was added to the reaction solution, and extraction was performed with methylene chloride, and the obtained organic layer was dried over anhydrous MgSO 4 Removing water, filtering, concentrating the filtrate under reduced pressure, and removing solvent. The obtained residue was purified by silica gel column separation (cyclohexane: ethyl acetate=10:1) to give compound e-1 (27.29 g, yield 74%).
350mL of 1, 4-dioxane, e-1 (22.13 g,60 mmol), b-1 (18.28 g,72 mmol), pd (dppf) Cl were added to a three-necked flask under nitrogen 2 (2.19 g,3.00 mmol) and potassium acetate (17.66 g,180 mmol) were heated under reflux with stirring for 24h. After the completion of the reaction, the mixture was cooled naturally, distilled water was added thereto, the reaction mixture was extracted with ethyl acetate, and washed with saturated brine for 3 times to obtain an organic layer containing anhydrous MgSO 4 Drying, filtering, concentrating the filtrate under reduced pressure to remove the solvent. The obtained residue was purified by silica gel column chromatography (chloroform: ethyl acetate=2:1) to give compound f-1 (21.54 g, yield 78%).
Under nitrogen, 300mL of tetrahydrofuran, g-1 (23.85 g,80 mmol), h-1 (12.51 g,80 mmol), pd (PPh) were added to a three-necked flask 3 ) 4 (2.89 g,2.50 mmol), naOH (9.53 g,238.25 mmol), water (130 mL), and the mixture was stirred and heated at reflux for reaction for 5h; after the reaction is finished, CH is used for 2 Cl 2 And water extraction, the organic layer was collected using MgSO 4 Drying, filtering, concentrating the filtrate under reduced pressure to remove the solvent. The obtained residue was subjected to a silica gel column and then recrystallized in toluene to obtain compound i-1 (18.73 g, yield 71%).
A three-necked flask was charged with a mixed solvent of 216mL of toluene, 72mL of ethanol and 72mL of water under a nitrogen atmosphere, i-1 (15.83 g,48 mmol), f-1 (18.41 g,40 mmol), pd (dppf) Cl 2 (1.46 g,2 mmol), sodium carbonate (7.63 g,72 mmol), stirring the mixture, heating and refluxing the mixture for 24h, cooling to room temperature after the reaction, extracting with dichloromethane, combining the organic phases, and using anhydrous MgSO 4 Drying, filtering, concentrating the filtrate under reduced pressure to remove the solvent, and recrystallizing with toluene to obtain compound 11 (17.07 g, 68%); HPLC purity. Mass spectrum m/z:627.2447 (theory: 627.2423). Theoretical element content (%) C 44 H 29 N 5 : c,84.19; h,4.66; n,11.16. Measured element content (%): c,84.07; h,4.73; n,11.24.
Synthesis example 2: synthesis of Compound 13
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-13, and the other things were the same, synthesis of Compound 13 (25.04 g), and HPLC detection of solid purity ≡ 99.85%. Mass spectrum m/z:754.3080 (theory: 754.3096). Theoretical element content (%) C 55 H 38 N 4 : c,87.50; h,5.07; n,7.42. Measured element content (%): c,87.46; h,5.03; n,7.49.
Synthesis example 3: synthesis of Compound 49
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-49, h-1 was replaced with equimolar h-49, and the purity of the solid was ≡ 99.68% by HPLC using the same method as in Synthesis example 49 (25.70 g). Mass spectrum m/z:834.3683 (theory: 834.3661). Theoretical element content (%) C 61 H 38 D 4 N 4 ：C,87.74；H,5.55；N,6.71. Measured element content (%): c,87.82; h,5.49; n,6.66.
Synthesis example 4: synthesis of Compound 55
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-55, g-1 was replaced with equimolar g-55, h-1 was replaced with equimolar h-55, and the other was identical, compound 55 (23.87 g) was synthesized, and the purity of the solid was not less than 99.69% by HPLC. Mass spectrum m/z:854.3431 (theory: 854.3409). Theoretical element content (%) C 63 H 42 N 4 : c,88.50; h,4.95; n,6.55. Measured element content (%): c,88.59; h,4.89; n,6.49.
Synthesis example 5: synthesis of Compound 58
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-58, g-1 was replaced with equimolar g-13, h-1 was replaced with equimolar h-55, and the purity of the solid was. Mass spectrum m/z:906.3738 (theory: 906.3722). Theoretical element content (%) C 67 H 46 N 4 : c,88.71; h,5.11; n,6.18. Measured element content (%): c,88.75; h,5.17; n,6.09.
Synthesis example 6: synthesis of Compound 67
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-67, and the other things were the same, compound 67 (23.80 g) was synthesized, and the purity of the solid was not less than 99.86% by HPLC. Mass spectrum m/z:804.3277 (theory: 804.3253). Theoretical element content (%) C 59 H 40 N 4 : c,88.03; h,5.01; n,6.96. Measured element content (%): c,88.07; h,5.09; n,6.85.
Synthesis example 7: synthesis of Compound 69
Using the same method as in Synthesis example 1, a-1 was changed to equimolar a-69, d-1 was changed to equimolar d-13, g-1 was changed to equimolar g-69, h-1 was changed to equimolar h-69, and the same was repeated except that compound 69 (22.83 g) was synthesized, and the purity of the solid was ∈ 99.63% by HPLC detection. Mass spectrum m/z:829.3230 (theory: 829.3205). Theoretical element content (%) C 60 H 39 N 5 : c,86.83; h,4.74; n,8.44. Measured element content (%): c,86.92; h,4.70; n,8.37.
Synthesis example 8: synthesis of Compound 72
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-72, and the compound 72 (27.39 g) was synthesized in the same manner, and the purity of the solid was not less than 99.86% by HPLC. Mass spectrum m/z:878.3426 (theory: 878.3409). Theoretical element content (%) C 65 H 42 N 4 : c,88.81; h,4.82; n,6.37. Measured element content (%): c,88.73; h,4.86; n,6.44.
Synthesis example 9: synthesis of Compound 129
Using the same method as in Synthesis example 1, a-1 was changed to equimolar a-129, d-1 was changed to equimolar d-129, g-1 was changed to equimolar g-13, and the other was the same, synthesized compound 129 (18.07 g), and the purity of the solid was not less than 99.85% by HPLC. Mass Spectrometry m-And z:600.2582 (theory: 600.2565). Theoretical element content (%) C 45 H 32 N 2 : c,89.97; h,5.37; n,4.66. Measured element content (%): c,89.87; h,5.44; n,4.70.
Synthesis example 10: synthesis of Compound 233
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-233, g-1 was replaced with equimolar g-233, h-1 was replaced with equimolar h-55, and the purity of the solid was. Mass spectrum m/z:772.2886 (theory: 772.2878). Theoretical element content (%) C 59 H 36 N 2 : c,91.68; h,4.69; n,3.62. Measured element content (%): c,91.65; h,4.79; n,3.57.
Synthesis example 11: synthesis of Compound 252
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-252, g-1 was replaced with equimolar g-13, h-1 was replaced with equimolar h-252, and the other things were identical, synthesis of Compound 252 (25.54 g), and the purity of the solid was ≡ 99.65% by HPLC detection. Mass spectrum m/z:840.4063 (theory: 840.4037). Theoretical element content (%) C 61 H 32 D 10 N 4 : c,87.11; h,6.23; n,6.66. Measured element content (%): c,87.20; h,6.18; n,6.63.
Synthesis example 12: synthesis of Compound 253
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-13, and h-1 was replaced with equimolar g-13H-252, other times the same, synthetic compound 253 (25.89 g) with a purity of > 99.98% by HPLC. Mass spectrum m/z:830.3431 (theory: 830.3409). Theoretical element content (%) C 61 H 42 N 4 : c,88.16; h,5.09; n,6.74. Measured element content (%): c,88.19; h,5.01; n,6.80.
Synthesis example 13: synthesis of Compound 286
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-13, h-1 was replaced with equimolar h-286, and other things were identical, compound 286 (24.90 g) was synthesized, and the purity of the solid was not less than 99.86% as measured by HPLC. Mass spectrum m/z:830.3427 (theory: 830.3409). Theoretical element content (%) C 61 H 42 N 4 : c,88.16; h,5.09; n,6.74. Measured element 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 other things were identical, synthesis Compound 316 (27.42 g) was found to have a solid purity of ≡99.88% by HPLC. Mass spectrum m/z:952.3592 (theory: 952.3566). Theoretical element content (%) C 71 H 44 N 4 : c,89.47; h,4.65; n,5.88. Measured element content (%): c,89.55; h,4.62; n,5.84.
Synthesis example 15: synthesis of Compound 319
The same procedure as in Synthesis example 1 was usedIn the same manner as above, d-1 was replaced with equimolar d-319, g-1 was replaced with equimolar g-319, h-1 was replaced with equimolar h-252, and compound 319 (25.33 g) was synthesized, and the solid purity was ≡ 99.73% by HPLC. Mass spectrum m/z:892.3579 (theory: 892.3566). Theoretical element content (%) C 66 H 44 N 4 : c,88.76; h,4.97; n,6.27. Measured element content (%): c,88.82; h,4.87; n,6.34.
Synthesis example 16: synthesis of Compound 325
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-325, h-1 was replaced with equimolar h-252, and the purity of the solid was not less than 99.79% as measured by HPLC using Compound 325 (25.68 g). Mass spectrum m/z:856.3581 (theory: 856.3566). Theoretical element content (%) C 63 H 44 N 4 : c,88.29; h,5.17; n,6.54. Measured element content (%): c,88.35; h,5.22; n,6.42.
Synthesis example 17: synthesis of Compound 338
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-72, h-1 was replaced with equimolar h-286, and the other was identical, synthesis Compound 338 (27.09 g), and the purity of the solid was ≡ 99.75% by HPLC. Mass spectrum m/z:954.3734 (theory: 954.3722). Theoretical element content (%) C 71 H 46 N 4 : c,89.28; h,4.85; n,5.87. Measured element content (%): c,89.36; h,4.82; n,5.80.
Synthesis example 18: synthesis of Compound 357
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-129, g-1 was replaced with equimolar g-13, h-1 was replaced with equimolar h-252, and the other was identical, synthesis Compound 357 (21.63 g) was synthesized, and the purity of the solid was not less than 99.91% by HPLC. Mass spectrum m/z:676.2893 (theory: 676.2878). Theoretical element content (%) C 51 H 36 N 2 : c,90.50; h,5.36; n,4.14. Measured element content (%): c,90.46; h,5.30; n,4.25.
Synthesis example 19: synthesis of Compound 368
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-368, g-1 was replaced with equimolar g-368, h-1 was replaced with equimolar h-252, and other things were identical, compound 368 (20.78 g) was synthesized, and the solid purity was ≡ 99.64% by HPLC. Mass spectrum m/z:753.3164 (theory: 753.3144). Theoretical element content (%) C 56 H 39 N 3 : c,89.21; h,5.21; n,5.57. Measured element content (%): c,89.25; h,5.24; n,5.48.
Synthesis example 20: synthesis of Compound 394
Using the same method as in Synthesis example 1, a-1 was replaced with equimolar a-394, d-1 was replaced with equimolar d-,94, g-1 was replaced with equimolar g-394, h-1 was replaced with equimolar h-252, and the other was identical, synthesis Compound 394 (24.84 g) was synthesized, and the purity of the solid was ≡ 99.76% by HPLC. Mass spectrum m/z:828.3518 (theory: 828.3504). Theoretical element content (%) C 63 H 44 N 2 : c,91.27; h,5.35; n,3.38. Measured element content (%): c,91.30; h,5.26; n,3.43.
Synthesis example 21: synthesis of Compound 408
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-408, g-1 was replaced with equimolar g-13, h-1 was replaced with equimolar h-286, and the other was identical, compound 408 (26.35 g) was synthesized, and the purity of the solid was not less than 99.65% by HPLC. Mass spectrum m/z:928.3833 (theory: 928.3817). Theoretical element content (%) C 71 H 48 N 2 : c,91.78; h,5.21; n,3.01. Measured element content (%): c,91.73; h,5.19; n,3.14.
Synthesis example 22: synthesis of Compound 430
Using the same method as in Synthesis example 1, a-1 was replaced with equimolar a-394, d-1 was replaced with equimolar d-,94, g-1 was replaced with equimolar g-394, h-1 was replaced with equimolar h-252, and the same was repeated except that synthetic compound 394 (25.60 g) was replaced with equimolar h-252, and the purity of the solid was ≡ 99.87% by HPLC detection. Mass spectrum m/z:800.3173 (theory: 800.3191). Theoretical element content (%) C 61 H 40 N 2 : c,91.47; h,5.03; n,3.50. Measured element content (%): c,91.38; h,5.08; n,3.58.
Synthesis example 23: synthesis of Compound 432
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-408, g-1 was replaced with equimolar g-432, h-1 was replaced with equimolar h-252, and the purity of the solid was not less than 99.76% as measured by HPLC using Compound 432 (24.48 g). Mass spectrum m/z:850.3357 (theory: 850.3348). Theoretical element content (%) C 65 H 42 N 2 : c,91.73; h,4.97; n,3.29. Measured element content (%): c,91.78; h,4.86; n,3.33。
Synthesis example 24: synthesis of Compound 441
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-441, g-1 was replaced with equimolar g-441, h-1 was replaced with equimolar h-252, and the purity of the solid was ≡ 99.85% by HPLC detection of synthetic compound 441 (28.75 g). Mass spectrum m/z:910.4294 (theory: 910.4287). Theoretical element content (%) C 69 H 54 N 2 : c,90.95; h,5.97; n,3.07. Measured element content (%): c,90.88; h,5.93; n,3.17.
Synthesis example 25: synthesis of Compound 465
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-129, g-1 was replaced with equimolar g-464, h-1 was replaced with equimolar h-252, and the purity of the solid was ≡ 99.89% by HPLC using the same synthetic compound 464 (25.49 g). Mass spectrum m/z:768.3518 (theory: 768.3504). Theoretical element content (%) C 58 H 44 N 2 : c,90.59; h,5.77; n,3.64. Measured element content (%): c,90.65; h,5.68; n,3.68.
Synthesis example 26: synthesis of Compound 477
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-477, g-1 was replaced with equimolar g-319, h-1 was replaced with equimolar h-477, and the other was identical, synthesis Compound 477 (20.96 g) was found to have a solid purity of ≡ 99.74% by HPLC. Mass spectrum m/z:738.3057 (theory: 738.3035). Theoretical element content (%) C 56 H 38 N 2 : c,91.03; h,5.18; n,3.79. Measured element content (%): c,91.15; h,5.15; n,3.72.
Synthesis example 27: synthesis of Compound 483
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-129, g-1 was replaced with equimolar g-483, h-1 was replaced with equimolar h-286, and the purity of the solid was 99.86% as measured by HPLC using Compound 483 (24.91 g). Mass spectrum m/z:800.3211 (theory: 800.3191). Theoretical element content (%) C 61 H 40 N 2 : c,91.47; h,5.03; n,3.50. Measured element content (%): c,91.43; h,5.12; n,3.46.
Synthesis example 28: synthesis of Compound 506
A three-necked flask was charged with a mixed solvent of a-506 (46.65 g,147 mmol), j-506 (24.22 g,140 mmol), potassium carbonate (38.70 g,280 mmol), 300mL of toluene, 60mL of ethanol, and 60mL of water in this order under a nitrogen atmosphere. The mixture was stirred, warmed to 50℃and Pd (PPh 3 ) 4 (1.62 g,1.40 mmol) was further heated to reflux for 8 hours, distilled water was added to the reaction solution under stirring after the completion of the reaction, the mixture was separated at rest, the aqueous phase was collected, extracted with toluene, the organic phases were combined, and anhydrous MgSO was used 4 The water was removed, filtered, the filtrate was concentrated under reduced pressure to remove the solvent, and n-heptane was added to carry out recrystallization, followed by filtration and drying in a vacuum oven to give compound c-506 (37.47 g, yield 84%).
650mL of tetrahydrofuran solvent, c-506 (35.05 g,110 mmol), b-1 (27.93 g,110 mmol), pd (dppf) Cl were sequentially added to a three-necked flask under nitrogen atmosphere 2 (0.21 g,0.29 mmol) and potassium acetate (14.72 g,150 mmol), and the mixture was stirred, and the mixture of the above reactants was heated under reflux 9h, performing H; after the reaction was completed, cooled and distilled water was added, and the mixture was filtered and dried in a vacuum oven. The obtained residue was purified by column chromatography on silica gel (petroleum ether: acetone=1:1) to give compound k-506 (32.58 g, yield 81%).
Under nitrogen atmosphere, 500mL of tetrahydrofuran solvent and compound k-506 (29.25 g,80 mmol) were added to a three-necked flask and dissolved with stirring, and d-13 (22.81 g,80 mmol) and Pd (PPh) were added thereto 3 ) 4 (4.62 g,4 mmol) and continuously stirring the mixture, and then adding a saturated aqueous potassium carbonate solution (22.11 g,160 mmol) thereto, and refluxing the mixed solution of the above-mentioned reactants under heating for 10 hours; after the completion of the reaction, distilled water was added to the reaction solution, extraction was performed with tetrahydrofuran, and the obtained organic layer was dried over anhydrous MgSO 4 Removing water, filtering, concentrating the filtrate under reduced pressure, and removing solvent. The obtained residue was purified by silica gel column chromatography (cyclohexane: methanol=8:1) to give compound e-506 (24.50 g, yield 69%).
Using the same preparation as f-1, 11 in Synthesis example 1, substituting e-1 with equimolar e-506 gave 22.49g (70%) of Compound f-506; substitution of h-1 for equimolar h-252 and f-1 for equimolar f-506 gives 21.41g of compound 506; HPLC detection of solid purity ∈ 99.72%. Mass spectrum m/z:753.3151 (theory: 753.3144). Theoretical element content (%) C 56 H 39 N 3 : c,89.21; h,5.21; n,5.57. Measured element content (%): c,89.16; h,5.14; n,5.66.
Synthesis example 29: synthesis of Compound 512
Into a reaction flask were charged 3-bromo-3 '-chloro-1, 1' -biphenyl (36.12 g,135 mmol), THF (450 ml), 1, 3-phenyldiboronic acid (24.61 g,148.5 mmol), pd (PPh) under nitrogen atmosphere 3 ) 4 (2.37 g,2.05 mmol), naOH (16.2 g,405 mmol), water (220 ml) and reacted under reflux for 8 hours. After the reaction was completed, cooled to room temperature, and treated with CH 2 Cl 2 And water extraction, combining the organic phases,the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed from the filtrate under reduced pressure, and the obtained residue was purified by column chromatography on silica gel (dichloromethane: n-hexane=1:1) to give compound h-512 (25.83 g, yield 62%).
Using the same preparation as that of Compound 11 in Synthesis example 1, d-1 was changed to equimolar d-129, g-1 was changed to equimolar d-13, h-1 was changed to equimolar h-512, and Compound 512 (24.67 g) was synthesized in the same manner, and the purity of the solid was ≡ 99.88% by HPLC detection. Mass spectrum m/z:752.3215 (theory: 752.3191). Theoretical element content (%) C 57 H 40 N 2 : c,90.92; h,5.35; n,3.72. Measured element content (%): c,90.79; h,5.40; n,3.79.
Synthesis example 30: synthesis of Compound 520
The same procedure as in Synthesis example 29 was used to convert 1, 3-benzenediboronic acid to equimolar [1,1' -biphenyl ]]-3,3' -diyldiboronic acid, d-129 was replaced by equimolar d-408, g-1 was replaced by equimolar g-483, and the same was true for synthetic compound 520 (24.51 g), solid purity ≡ 99.87% by HPLC. Mass spectrum m/z:828.3522 (theory: 828.3504). Theoretical element content (%) C 63 H 44 N 2 : c,91.27; h,5.35; n,3.38. Measured element content (%): c,91.34; h,5.31; n,3.32.
Synthesis example 31: synthesis of Compound 534
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-534, g-1 was replaced with equimolar g-13, and the other things were the same, compound 534 (24.64 g) was synthesized, and the purity of the solid was not less than 99.74% by HPLC. Mass spectrum m/z:906.3741 (theory: 906.3722). Theoretical element content (%) C 67 H 46 N 4 : c,88.71; h,5.11; n,6.18. Actual measurementElemental content (%): c,88.64; h,5.21; n,6.13.
Synthesis example 32: synthesis of Compound 537
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-537, g-1 was replaced with equimolar g-537, h-1 was replaced with equimolar h-252, and the purity of the solid was 99.75% by HPLC as measured with respect to the synthesized compound 537 (19.53 g). Mass spectrum m/z:678.2797 (theory: 678.2783). Theoretical element content (%) C 49 H 34 N 4 : c,86.70; h,5.05; n,8.25. Measured element content (%): c,86.61; h,5.12; n,8.29.
Synthesis example 33: synthesis of Compound 540
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-540, g-1 was replaced with equimolar g-540, and the other things were the same, synthetic compound 540 (21.71 g), and the purity of the solid was not less than 99.68% by HPLC. Mass spectrum m/z:835.3149 (theory: 835.3172). Theoretical element content (%) C 56 H 37 N 9 : c,80.46; h,4.46; n,15.08. Measured element content (%): c,80.39; h,4.44; n,15.20.
Synthesis example 34: synthesis of Compound 550
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-550, g-1 was replaced with equimolar g-550, h-1 was replaced with equimolar h-252, and the other was identical, synthesis Compound 550 (22.41 g) was synthesized, and the purity of the solid was not less than 99.74% as measured by HPLC. Mass spectrum m/z:800.2957 (theory: 800.2940). Theoretical element content (%) C 59 H 36 N 4 : c,88.47; h,4.53; n,7.00. Measured element content (%): c,88.41; h,4.45; n,7.12.
Synthesis example 35: synthesis of Compound 565
Using the same method as in Synthesis example 28, j-506 was changed to equimolar j-565, g-13 was changed to equimolar g-394, h-252 was changed to equimolar h-286, and other things were equal, synthetic compound 565 (19.96 g), and the purity of the solid was ≡ 99.76% by HPLC detection. Mass spectrum m/z:703.2995 (theory: 703.2987). Theoretical element content (%) C 52 H 37 N 3 : c,88.73; h,5.30; n,5.97. Measured element content (%): c,88.76; h,5.35; n,5.89.
Synthesis example 36: synthesis of Compound 570
Using the same method as in Synthesis example 28, j-506 was changed to equimolar j-565, d-13 was changed to equimolar d-570, g-13 was changed to equimolar g-430, h-252 was changed to equimolar h-11, and the other things were the same, synthetic compound 570 (22.82 g) was changed to equimolar h-11, and the purity of the solid was ∈ 99.73% by HPLC detection. Mass spectrum m/z:827.3316 (theory: 827.3300). Theoretical element content (%) C 62 H 41 N 3 : c,89.93; h,4.99; n,5.07. Measured element content (%): c,89.88; h,4.93; n,5.16.
Synthesis example 37: synthesis of Compound 586
Using the same method as in Synthesis example 28, j-506 was changed to equimolar j-565, d-13 was changed to equimolar d-129, and other things were equal, synthesis Compound 586 (19.03 g), and HPLC detection of solid The bulk purity is not less than 99.86%. Mass spectrum m/z:626.2743 (theory: 626.2722). Theoretical element content (%) C 47 H 34 N 2 : c,90.06; h,5.47; n,4.47. Measured element content (%): c,90.14; h,5.44; n,4.39.
Synthesis example 38: synthesis of Compound 608
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-608, g-1 was replaced with equimolar g-13, h-1 was replaced with equimolar h-608, and the other things were identical, synthesis Compound 608 (19.18 g), and the purity of the solid was not less than 99.76% by HPLC. Mass spectrum m/z:676.2896 (theory: 676.2878). Theoretical element content (%) C 51 H 36 N 2 : c,90.50; h,5.36; n,4.14. Measured element content (%): c,90.44; h,5.41; n,4.17.
Synthesis example 39: synthesis of Compound 614
Using the same method as in Synthesis example 1, d-1 was replaced with equimolar d-13, g-1 was replaced with equimolar g-55, h-1 was replaced with equimolar h-614, and other things were equal, synthesis Compound 614 (19.93 g) was synthesized, and the purity of the solid was not less than 99.74% as measured by HPLC. Mass spectrum m/z:755.3058 (theory: 755.3049). Theoretical element content (%) C 54 H 37 N 5 : c,85.80; h,4.93; n,9.26. Measured element content (%): c,85.77; h,4.86; n,9.39.
Synthesis example 40: synthesis of Compounds 2-17
A reaction flask was charged with a1-1 (10.74 g,44.15 mmol), b1-1 (15.38 g,40.14 mmol), sodium t-butoxide (6.36 g,66.23 mmol), palladium acetate (180 mg,0.8 mmol), triphenylphosphine (210 mg,0.8 mmol) and 200ml toluene under nitrogen, and reacted under reflux for 4.5 hours. After the completion of the reaction, the reaction solution was cooled to room temperature, washed with distilled water, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure, and the obtained residue was purified by column chromatography on silica gel (n-hexane: dichloromethane=3:1) to obtain A1-1 (16.88 g, yield 77%).
A1-1 (15.44 g,28.30. Mmol), c1-1 (8.01 g,26.95 mmol), sodium t-butoxide (3.88 g,40.42 mmol), pd were added to the flask under nitrogen 2 (dba) 3 (494 mg,0.54 mmol), X-Phos (257 mg,0.54 mmol) and 150mL of toluene were reacted under reflux for 4 hours. After the reaction, the reaction mixture was poured into water, dichloromethane was added, the layers were separated, the aqueous layer was extracted with dichloromethane, the organic phases were combined, the solvent was removed under reduced pressure, toluene was recrystallized to give compound 2-17 (16.43 g, yield 80%), and the purity of the solid was not less than 99.75% by HPLC detection. Mass spectrum m/z:761.2731 (theory: 761.2719). Theoretical element content (%) C 58 H 35 NO: c,91.43; h,4.63; n,1.84. Measured element content (%): c,91.49; h,4.58; n,1.88.
Synthesis example 41: synthesis of Compounds 2-50
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-50, b1-1 was replaced with equimolar b1-50, c1-1 was replaced with equimolar c1-50, and the other was identical, synthesis of Compound 2-50 (15.01 g), and HPLC detection of solid purity ≡ 99.76%. Mass spectrum m/z:687.2579 (theory: 687.2562). Theoretical element content (%) C 52 H 33 NO: c,90.80; h,4.84; n,2.04. Measured element content (%): c,90.71; h,4.89; n,2.11.
Synthesis example 42: synthesis of Compounds 2-74
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-74, b1-1 was replaced with equimolar b1-74, and c1-1 was replaced with equimolar c1-74, and the other was identical, synthesis of Compound 2-74 (15.91 g), and HPLC detection of solid purity ≡ 99.74%. Mass spectrum m/z:787.2896 (theory: 787.2875). Theoretical element content (%) C 60 H 37 NO: c,91.46; h,4.73; n,1.78. Measured element content (%): c,91.51; h,4.79; n,1.71.
Synthesis example 43: synthesis of Compounds 2-126
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-126, b1-1 was replaced with equimolar b1-126, c1-1 was replaced with equimolar c1-126, and other things were equal, synthesis of Compound 2-126 (16.32 g), and HPLC detection of solid purity ≡ 99.87%. Mass spectrum m/z:713.2733 (theory: 713.2719). Theoretical element content (%) C 54 H 35 NO: c,90.85; h,4.94; n,1.96. Measured element content (%): c,90.93; h,4.88; n,1.89.
Synthesis example 44: synthesis of Compounds 2-152
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-152, b1-1 was replaced with equimolar b1-126, and c1-1 was replaced with equimolar c1-152, and other things were equal, synthesis of Compound 2-152 (17.44 g), and HPLC detection of solid purity ≡ 99.86%. Mass spectrum m/z:789.3047 (theory: 789.3032). Theoretical element content (%) C 60 H 39 NO: c,91.23; h,4.98; n,1.77. Measured element content (%): c,91.32; h,4.94; n,1.89.
Synthesis example 45: synthesis of Compound 2-181
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-181, b1-1 was replaced with equimolar b1-181, and c1-1 was replaced with equimolar c1-181, and the other things were identical, synthesis of Compound 2-181 (14.25 g), and HPLC detection of solid purity ≡ 99.85%. Mass spectrum m/z:637.2424 (theory: 637.2406). Theoretical element content (%) C 48 H 31 NO: c,90.40; h,4.90; n,2.20. Measured element content (%): c,90.35; h,4.83; n,2.27.
Synthesis example 46: synthesis of Compounds 2-190
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-50, b1-1 was replaced with equimolar b1-190, c1-1 was replaced with equimolar c1-190, and other things were equal, synthesis of Compound 2-190 (14.42 g), and HPLC detection of solid purity ≡ 99.98%. Mass spectrum m/z:637.2419 (theory: 637.2406). Theoretical element content (%) C 48 H 31 NO: c,90.40; h,4.90; n,2.20. Measured element content (%): c,90.46; h,4.81; n,2.26.
Synthesis example 47: synthesis of Compounds 2-211
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-211, b1-1 was replaced with equimolar b1-211, c1-1 was replaced with equimolar c1-211, and the other things were identical, synthesis of Compound 2-211 (16.04 g), and HPLC detection of solid purity ≡ 99.74%. Mass spectrum m/z:763.2892 (theory: 763.2875). Theoretical element content (%) C 58 H 37 NO: c,91.19; h,4.88; n,1.83. Measured element content (%): c,91.27; h,4.83; n,1.77.
Synthesis example 48: synthesis of Compounds 2-238
Using the same method as in Synthesis example 40, a1-1 was replaced with equimolar a1-50, b1-1 was replaced with equimolar b1-238, c1-1 was replaced with equimolar c1-238, and other things were equal, synthesis of Compound 2-238 (15.95 g), and HPLC detection of solid purity ≡ 99.73%. Mass spectrum m/z:805.2820 (theory: 805.2803). Theoretical element content (%) C 60 H 39 NS: c,89.41; h,4.88; n,1.74. Measured element content (%): c,89.48; h,4.82; n,1.66.
Synthesis example 49: synthesis of Compound 2-292
A2-1 (31.25 mmol,10.16 g), b2-1 (63.75 mmol,16.20 g), pd (PPh) were added to the flask under nitrogen 3 ) 4 (0.625mmol，700mg)、K 2 CO 3 (93.75 mmol,12.96 g), 200mL toluene and 80mL ethanol were stirred under reflux for 4 hours. After the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=5: 1 was recrystallized to give intermediate A2-1 (10.75 g, yield 82%).
A2-1 (25.00 mmol,10.49 g), c1-50 (25.5 mmol,7.58 g), 100mL of 1, 4-dioxane, cuI (0.375 mmol,71.4 mg), trans-1, 2-cyclohexanediamine (2.50 mmol, 284 mg), K were added to the flask under nitrogen 3 PO 4 (75.00 mmol,15.92 g) was stirred under reflux for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, water was then added thereto, the mixture was extracted with methylene chloride, and the organic phase was separated with anhydrous MgSO 4 Drying, removal of solvent under reduced pressure, and recrystallization from acetonitrile gave compound 2-292 (13.35 g, yield 84%); the purity of the solid detected by HPLC is not less than 99.89%. Mass spectrum m/z:635.2263 (theory: 635.2249). Theoretical element content (%) C 48 H 29 NO：C,90.68；H,4.60；N,2.20. Measured element content (%): c,90.65; h,4.56; n,2.24.
Synthesis example 50: synthesis of Compounds 2-331
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Substitution of b2-1 in Synthesis example 49 with equimolar b2-331 gave Compound 2-331 (15.13 g); the purity of the solid detected by HPLC is not less than 99.81%. Mass spectrum m/z:787.2887 (theory: 787.2875). Theoretical element content (%) C 60 H 37 NO: c,91.46; h,4.73; n,1.78. Measured element content (%): c,91.51; h,4.76; n,1.72.
Synthesis example 51: synthesis of Compound 2-363
Substitution of b2-1 in Synthesis example 49 with equimolar b2-363 and c1-50 with equimolar c2-363 gives Compound 2-363 (13.78 g); the purity of the solid detected by HPLC is not less than 99.71%. Mass spectrum m/z:735.2581 (theory: 735.2562). Theoretical element content (%) C 56 H 33 NO: c,91.40; h,4.52; n,1.90. Measured element 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 gives compound 2-377 (14.85 g); the purity of the solid detected by HPLC is not less than 99.75%. Mass spectrum m/z:835.2861 (theory: 835.2875). Theoretical element content (%) C 64 H 37 NO: c,91.95; h,4.46; n,1.68. Measured element content (%): c,91.92; h,4.51; n,1.64.
Synthesis example 53: synthesis of Compounds 2-388
A2-388 (37.5 mmol,10.52 g), b2-377 (38.25 mmol,13.55 g), KOAc (75 mmol,7.36 g), pd (OAc) were added to the flask under nitrogen 2 (0.75 mmol,168 mg), 200mL toluene, 80mL ethanol, and stirred under reflux for 2.5 hours. After the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/methanol=4: 1 was recrystallized to give intermediate A' -388 (12.68 g, yield 79%).
A' -388 (31.25 mmol,13.37 g), b2-388 (31.88 mmol,10.53 g), pd (PPh) were added to the flask under nitrogen 3 ) 4 (0.625mmol，722mg)、K 2 CO 3 (62.5 mmol,8.64 g), 120mL toluene, 42mL ethanol, and the mixture was stirred under reflux for 3 hours. After the reaction was completed, cooled to room temperature, suction filtered to obtain a filter cake, and the filter cake was rinsed with ethanol, and finally the filter cake was purified with toluene/ethanol=20: 3 to give intermediate A2-388 (14.66 g, 86% yield).
A2-388 (25.00 mmol,13.64 g), c1-50 (25.5 mmol,7.58 g), 100mL of 1, 4-dioxane, cuI (0.375 mmol,71 mg), trans-1, 2-cyclohexanediamine (2.5 mmol, 284 mg), K were added to the flask under nitrogen 3 PO 4 (75.00 mmol,15.92 g) was heated to reflux for 36 hours. After the reaction was completed, the mixture was cooled to room temperature, water was then added thereto, the mixture was extracted with methylene chloride, and the organic phase was separated with anhydrous MgSO 4 Drying, removal of solvent under reduced pressure, and recrystallization from acetonitrile gave compounds 2-388 (14.82 g, 73% yield); the purity of the solid detected by HPLC is not less than 99.78%. Mass spectrum m/z:811.2892 (theory: 811.2875). Theoretical element content (%) C 62 H 37 NO: c,91.71; h,4.59; n,1.73. Measured element content (%): c,91.75; h,4.56; n,1.69.
Synthesis example 54: synthesis of Compounds 2-406
Substitution of b2-1 in Synthesis example 49 with equimolar b2-406 and c1-50 with equimolar c2-406 gave Compound 2-406 (13.06 g); HPLC detection of solid purity ∈ 99.80%. Mass spectrum m/z:635.2271 (theory: 635.2249). Theoretical element content (%) C 48 H 29 NO: c,90.68; h,4.60; n,2.20. Measured element content (%): c,90.64; h,4.57; n,2.25.
Synthesis example 55: synthesis of Compounds 2-442
Replacement of a2-1 in Synthesis example 49 with equimolar a2-442, b2-1 with equimolar b2-406, and c1-50 with equimolar c2-442 gave Compound 2-442 (20.08 g); the purity of the solid detected by HPLC is not less than 99.71%. Mass spectrum m/z:635.2263 (theory: 635.2249). Theoretical element content (%) C 48 H 29 NO: c,90.68; h,4.60; n,2.20. Measured element content (%): c,90.64; h,4.63; n,2.23.
Synthesis example 56: synthesis of Compound 2-452
Under the protection of nitrogen, the raw materials e2-452 (11.83 g,34.38 mmol), f2-452 (6.75 g,35.06 mmol) and Na are mixed 2 CO 3 (7.29g，68.76mmol)、Pd(PPh 3 ) 4 (397 mg,0.34 mmol) and 150mL of toluene, 52.5mL of ethanol were added to the flask, and the mixture was heated under reflux for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, suction filtered to obtain a cake, and the cake was rinsed with ethanol, and finally the cake was purified with toluene/ethanol=4: 1 to give intermediate c2-452 (9.18 g, yield 81%).
Substitution of c2-50 in Synthesis example 49 with equimolar c2-452 gave Compound 2-452 (14.93 g); HPLC detection of solid purity ≡ 99.74Percent of the total weight of the composition. Mass spectrum m/z:712.2529 (theory: 712.2515). Theoretical element content (%) C 53 H 32 N 2 O: c,89.30; h,4.52; n,3.93. Measured element content (%): c,89.33; h,4.55; n,3.86.
Synthesis example 57: synthesis of Compound 2-478
Substitution of c1-50 in synthetic example 49 with equimolar c1-238 gave compound 2-478 (12.22 g); HPLC detection of solid purity ∈ 99.76%. Mass spectrum m/z:651.2042 (theory: 651.2021). Theoretical element content (%) C 48 H 29 NS: c,88.45; h,4.48; n,2.15. Measured element content (%): c,88.50; h,4.45; n,2.11.
Synthesis example 58: synthesis of Compounds 2-504
Substitution of b2-1 in Synthesis example 49 with equimolar b2-504 and c1-50 with equimolar c1-238 gives Compound 2-504 (14.49 g); the purity of the solid detected by HPLC is not less than 99.69%. Mass spectrum m/z:805.2568 (theory: 805.2552). Theoretical element content (%) C 58 H 35 N 3 S: c,86.43; h,4.38; n,5.21. Measured element content (%): c,86.39; h,4.34; n,5.26.
Synthesis example 59: synthesis of Compounds 2-553
Substitution of b2-1 in Synthesis example 49 with equimolar b2-553 and c1-50 with equimolar c2-553 gave Compound 2-553 (16.95 g); HPLC detection of solid purity ∈ 99.76%. Mass spectrum m/z:903.2978 (theory: 903.2960). Theoretical element content (%) C 68 H 41 NS：C,90.33; h,4.57; n,1.55. Measured element content (%): c,90.38; h,4.54; n,1.51.
Device embodiment
In the invention, the ITO/Ag/ITO or ITO glass substrate is ultrasonically cleaned by 5% glass cleaning solution for 2 times, 20 minutes each time, and then ultrasonically cleaned by deionized water for 2 times, 10 minutes each time. Sequentially ultrasonic cleaning with acetone and isopropanol for 20 min, and drying at 120deg.C. The organic materials are sublimated, and the purity is over 99.99 percent.
Test software, a computer, a K2400 digital source list manufactured by Keithley company in U.S. and a PR788 spectrum scanning luminance meter manufactured by Photo Research company in U.S. are combined into a combined IVL test system to test the driving voltage, luminous efficiency and CIE color coordinates of the organic electroluminescent device. Life testing an M6000 OLED life test system from McScience was used. The environment tested was atmospheric and the temperature was room temperature.
The preparation of the device is completed by adopting a vacuum evaporation system and continuously evaporating under the condition of continuous vacuum. The materials are respectively arranged in quartz crucibles of different evaporation sources, and the temperature of the evaporation sources can be controlled independently. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5×10 during the film manufacturing process -5 Under Pa, the organic layer and the metal electrode were vapor deposited by replacing the mask plate, the vapor deposition rate was detected by using an Infinion SQM160 quartz crystal film thickness detector, and the film thickness was detected by using a quartz crystal oscillator.
Example 1: preparation of organic electroluminescent device 1
ITO is used as an anode on the glass substrate; vacuum evaporating 2-TNATA on the anode as a hole injection layer, wherein the evaporating thickness is 60nm; vacuum evaporation of NPD in the hole injection layer is carried out to obtain a hole transport layer, wherein the evaporation thickness is 45nm; vacuum deposition of mCBP: ir (ppy) on hole transport layer 3 (5 wt%) as a light-emitting layer, the vapor deposition thickness was 30nm; vacuum evaporating the compound 13 as a hole blocking layer on the light-emitting layer, wherein the evaporation thickness is 10nm; vacuum evaporation TmPyPB is used as an electron transport layer on the hole blocking layer, and the evaporation thickness is 25nm; vacuum on electron transport layerEvaporating LiF as an electron injection layer, wherein the evaporating thickness is 0.2nm; al is vacuum evaporated on the electron injection layer to serve as a cathode, and the evaporation thickness is 150nm.
Examples 2 to 21: preparation of organic electroluminescent devices 2 to 21
The hole blocking layers of example 1 were each replaced with a compound 55, a compound 58, a compound 67, a compound 72, a compound 129, a compound 253, a compound 319, a compound 325, a compound 357, a compound 408, a compound 430, a compound 441, a compound 483, a compound 512, a compound 534, a compound 537, a compound 565, a compound 586, a compound 608, and a compound 614, respectively, to obtain organic electroluminescent devices 2 to 21 in the same manner.
Comparative examples 1 to 4: preparation of comparative organic electroluminescent devices 1 to 4
The compound 13 in the hole blocking layer of example 1 was changed to R-1, R-2, R-3, R-4, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 1 to 4.
The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 1 to 21 of the present invention and comparative examples 1 to 4 are shown in table 1.
Table 1 light emission characteristic test data of organic electroluminescent device
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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 fluorene derivative of structural formula 1 in the hole blocking layer is more stable, and holes can be effectively blocked in the light emitting layer, so that electrons and holes can effectively recombine and emit light in the light emitting layer. The fluorene derivative has a better space three-dimensional configuration, so that the material has better electron transmission/hole blocking capability, and has good film forming property, difficult deformation and better 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 as a hole injection layer, wherein the evaporating thickness is 60nm; vacuum evaporating TNB in the hole injection layer as a hole transport layer, wherein the evaporating thickness is 55nm; vacuum deposition of CBP: ir (npy) on hole transport 2 acac (10 wt%) as a light emitting layer, the vapor deposition thickness was 35nm; vacuum evaporating BCP on the light-emitting layer to serve as a hole blocking layer, wherein the evaporation thickness is 10nm; vacuum evaporating the compound 11 as an electron transport layer on the hole blocking layer, wherein the evaporation thickness is 30nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 0.5nm; al is vacuum evaporated on the electron injection layer as a cathode, and the evaporation thickness is 200nm.
Examples 23 to 39: preparation of organic electroluminescent devices 23 to 39
The electron transport layer of example 22 was changed to compound 49, compound 69, compound 233, compound 252, compound 286, compound 316, compound 338, compound 368, compound 394, compound 432, compound 464, compound 477, compound 506, compound 520, compound 540, compound 550, and compound 570, respectively, and the other steps were the same, to obtain 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 changed to R-1, R-2, R-3, R-4, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 5 to 8.
The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 22 to 39 and comparative examples 5 to 8 according to the present invention are shown in table 2.
Table 2 light emission 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 efficiency and longer service lives than the comparative organic electroluminescent devices 5 to 8. This indicates that the organic electroluminescent device having the fluorene derivative of formula 1 in the electron transport layer can efficiently transport electrons, and more electrons and holes are combined with each other to form excitons to emit light. This shows that the fluorene derivative of the present invention has good photoelectric properties, and is an organic photoelectric material with excellent properties.
Example 40: preparation of organic electroluminescent device 40
ITO/Ag/ITO is used as an anode on a glass substrate; vacuum evaporating 2-TNATA on the anode as a hole injection layer, wherein the evaporating thickness is 60nm; vacuum evaporation of TPD10 in the hole injection layer as a hole transport layer, wherein the evaporation thickness is 50nm; vacuum deposition of DMFL-CBP: ir (ppy) on hole transport 2 (acac) (5 wt%) as a light-emitting layer, the vapor deposition thickness was 35nm; vacuum evaporating the compound 13 as a hole blocking layer on the light-emitting layer, wherein the evaporation thickness is 10nm; vacuum evaporation of Alq on hole blocking layer 3 As an electron transport layer, the vapor deposition thickness is 40nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1.0nm; vacuum evaporating Mg of Ag=1:9 serving as a cathode on the electron injection layer, wherein the evaporation thickness is 20nm; at the cathodeThe compound 2-74 of the present invention was vacuum-deposited as a coating layer, and the thickness of the vapor deposition was 60nm.
Examples 41 to 59: preparation of organic electroluminescent devices 41 to 59
The organic devices 41 to 59 were obtained by replacing compound 13 in the hole blocking layer of example 40 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, replacing compound 2-74 in the cap layer with compound 2-553, compound 2-211, compound 2-452, compound 2-50, compound 2-152, compound 2-478, compound 2-17, compound 2-181, compound 2-292, compound 2-363, compound 2-190, compound 2-126, compound 2-406, compound 2-442, compound 2-377, compound 2-331, compound 2-504, compound 2-388, compound 2-238, and the like, respectively.
Comparative examples 9 to 10: preparation of contrast organic electroluminescent devices 9 to 10
The compound 13 in the hole blocking layer of example 40 was changed to compound 13 and compound 319, respectively, and the compounds 2 to 74 in the cap layer were changed to CP-1 and CP-2, respectively, in the same manner, to obtain comparative organic electroluminescent devices 9 to 10.
The results of the light emitting characteristics test of the organic electroluminescent devices prepared in examples 40 to 59 of the present invention and comparative examples 9 to 10 are shown in table 3.
Table 3 light emission characteristics test data 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 effective combined luminescence of electrons and holes in the luminescent layer, but also can couple out light trapped in the device to achieve an optimal luminescence state; in addition, each layer of the organic electroluminescent device, especially the hole blocking layer and the covering layer, have a relatively stable film form, are not easy to be influenced by factors such as photo-thermal water oxygen and the like, and effectively prolong the service life of the device.
Example 60: preparation of organic electroluminescent device 60
ITO/Ag/ITO is used as an anode on a glass substrate; vacuum evaporating HAT-CN on the anode as a hole injection layer, wherein the evaporation thickness is 10nm; vacuum evaporating Spiro-NPB in the hole injection layer as a hole transport layer, wherein the evaporation thickness is 70nm; vacuum deposition of CBP: ir (ppy) on hole transport 2 (acac) (4 wt%) as a light-emitting layer, the vapor deposition thickness was 42nm; vacuum evaporation of Alq on light-emitting layer 3 As an electron transport layer, the vapor deposition thickness was 33nm; vacuum evaporating LiF on the electron transport layer as an electron injection layer, wherein the evaporating thickness is 1.0nm; vacuum evaporating Mg of Ag=1:9 serving as a cathode on the electron injection layer, wherein the evaporation thickness is 15nm; the compound 13 of the present invention was vacuum-deposited as a coating layer on the cathode, with a deposition thickness of 53nm.
Examples 61 to 66: preparation of organic electroluminescent devices 61 to 66
The organic electroluminescent devices 61 to 66 were obtained by replacing compound 13 in the cap layer of example 60 with compound 253, compound 325, compound 357, compound 430, compound 441 and compound 512, respectively, and the other steps were the same.
Comparative examples 11 to 12: preparation of contrast organic electroluminescent devices 11 to 12
The compound 13 in the cover layer of example 60 was changed to 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 light emitting characteristics test 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 light emission characteristics test data 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 indicates that the fluorene derivatives of the present invention have better light extraction performance, and can effectively couple out light in the device, thereby improving luminous efficiency of the device.
It should be noted that while the invention has been particularly described with reference to individual embodiments, those skilled in the art may make various modifications in form or detail without departing from the principles of the invention, which modifications are also within the scope of the invention.
Claims (9)
1. Fluorene derivatives characterized by having one of the general formulas shown in structural formulas 1-1 to 1-2,
the Ar is as follows 1 Selected from the group represented by formula 1-a1, the Ar 2 Selected from the group represented by formula 1-a1 or formula 1-a2,
the formula 1-a1 is selected from one of the following groups,
the R is z The same or different radicals are selected from hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstitutedOne of the substituted naphthyl groups, and at most one R z Selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl;
the formula 1-a2 is selected from one of the following groups,
the L is selected from one of the following groups,
the L is 0a One selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted pyridylene group, and the L 0 Selected from single bonds; the n1 is the same or different and is selected from 0, 1, 2, 3 or 4; the n2 is the same or different and is selected from 0, 1, 2 or 3; the R is 1a The R is the same or different and is selected from one of hydrogen, deuterium and cyano 1 The same or different hydrogen and deuterium; when R is 1a When selected from cyano, n1 is selected from 1;
L 1 、L 2 independently selected from one of single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene;
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 phenyl and substituted or unsubstituted pyridyl;
the substituent group represented by "substitution" in the above "substituted or unsubstituted" is selected from deuterium.
2. Fluorene derivative according to claim 1, characterized in that said formula 1-a1 is selected from one of the groups shown below,
The R is z The same or different is selected from one of hydrogen, deuterium, substituted or unsubstituted phenyl, and at most one R z Selected from substituted or unsubstituted phenyl groups.
3. Fluorene derivative according to claim 1, characterized in that said formula 1-a2 is selected from the group represented by,
4. fluorene derivative according to claim 1, characterized in that Ar is selected from one of the groups shown below,
the R is the same or different and is selected from one of hydrogen, deuterium, cyano, substituted or unsubstituted phenyl and substituted or unsubstituted pyridyl.
5. Fluorene derivative according to claim 1, characterized in that L is selected from one of the groups shown below,
6. a fluorene derivative, characterized in that the fluorene derivative is selected from one of the following structures,
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7. an organic electroluminescent device comprising, in order, an anode, an organic layer, a cathode, and a coating layer containing the fluorene derivative as claimed in any one of claims 1 to 6.
8. An organic electroluminescent device comprising, in order, an anode, an organic layer comprising an electron transport region containing a fluorene derivative as claimed in any one of claims 1 to 6, and a cathode.
9. The organic electroluminescent device as claimed in claim 8, further comprising a capping layer comprising a heterocyclic compound represented by formula 2,
wherein the Ar is a Selected from the group represented by the formula 2-a,
the X is selected from O or S;
the ring A and the ring B are independently selected from any one of a benzene ring and a naphthalene ring, and at least one of the ring A or the ring B is selected from a benzene ring or a naphthalene ring;
the k are the same or different and are selected from 0, 1, 2, 3, 4, 5, 6, 7 or 8; the R is 2 The same or different one selected from 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 R 2 Bonding to form a ring structure;
the Ar is as follows b 、Ar c Independently selected from one of the groups shown below,
the R is 3 The same or different one selected from hydrogen, deuterium, cyano, halogen, nitro, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;
said g 1 The same or different is selected from 0, 1, 2, 3, 4, 5, 6 or 7; said g 2 The same or different is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9;
the L is a 、L b 、L c Independently selected from any one of single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene,
the L is b 、L c Carbazole rings can be formed by single bond connection with the aromatic amine N;
the substituent group represented by the substituent in the substituent or the unsubstituted substituent is selected from one of deuterium, cyano, nitro, halogen, C1-C15 alkyl, C3-C15 cycloalkyl, C6-C30 aryl and C2-C30 heteroaryl.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6171715B1 (en) * | 1997-08-07 | 2001-01-09 | Fuji Photo Film Co., Ltd. | Organic electroluminescent element |
| KR20190007789A (en) * | 2017-07-13 | 2019-01-23 | 에스에프씨 주식회사 | organic light-emitting diode with high efficiency and long lifetime |
| CN112028853A (en) * | 2020-09-09 | 2020-12-04 | 长春海谱润斯科技股份有限公司 | Arylamine derivative and organic electroluminescent device thereof |
| CN112442023A (en) * | 2020-11-30 | 2021-03-05 | 长春海谱润斯科技股份有限公司 | Heterocyclic derivative and organic electroluminescent device thereof |
| CN112864334A (en) * | 2019-11-12 | 2021-05-28 | 广州华睿光电材料有限公司 | Organic electroluminescent device containing light extraction layer material |
| CN113683630A (en) * | 2021-09-24 | 2021-11-23 | 长春海谱润斯科技股份有限公司 | Nitrogen-containing heterocyclic derivative and organic electroluminescent device thereof |
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| KR102255197B1 (en) * | 2014-05-02 | 2021-05-25 | 삼성디스플레이 주식회사 | Organic light emitting device |
| KR102244071B1 (en) * | 2014-05-02 | 2021-04-26 | 삼성디스플레이 주식회사 | Organic light emitting device |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6171715B1 (en) * | 1997-08-07 | 2001-01-09 | Fuji Photo Film Co., Ltd. | Organic electroluminescent element |
| KR20190007789A (en) * | 2017-07-13 | 2019-01-23 | 에스에프씨 주식회사 | organic light-emitting diode with high efficiency and long lifetime |
| CN112864334A (en) * | 2019-11-12 | 2021-05-28 | 广州华睿光电材料有限公司 | Organic electroluminescent device containing light extraction layer material |
| CN112028853A (en) * | 2020-09-09 | 2020-12-04 | 长春海谱润斯科技股份有限公司 | Arylamine derivative and organic electroluminescent device thereof |
| CN112442023A (en) * | 2020-11-30 | 2021-03-05 | 长春海谱润斯科技股份有限公司 | Heterocyclic derivative and organic electroluminescent device thereof |
| CN113683630A (en) * | 2021-09-24 | 2021-11-23 | 长春海谱润斯科技股份有限公司 | Nitrogen-containing heterocyclic derivative and organic electroluminescent device thereof |
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