WO2020056860A1 - 一种9,10-二氢吖啶衍生物及其制备方法和用途 - Google Patents
一种9,10-二氢吖啶衍生物及其制备方法和用途 Download PDFInfo
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- WO2020056860A1 WO2020056860A1 PCT/CN2018/113121 CN2018113121W WO2020056860A1 WO 2020056860 A1 WO2020056860 A1 WO 2020056860A1 CN 2018113121 W CN2018113121 W CN 2018113121W WO 2020056860 A1 WO2020056860 A1 WO 2020056860A1
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- Prior art keywords
- ring
- formula
- substituted
- dihydroacridine derivative
- unsubstituted
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- HJCUTNIGJHJGCF-UHFFFAOYSA-N 9,10-dihydroacridine Chemical class C1=CC=C2CC3=CC=CC=C3NC2=C1 HJCUTNIGJHJGCF-UHFFFAOYSA-N 0.000 title claims abstract description 289
- 238000002360 preparation method Methods 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 210
- 239000010410 layer Substances 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 48
- 230000005525 hole transport Effects 0.000 claims abstract description 33
- 239000002346 layers by function Substances 0.000 claims abstract description 11
- -1 pentenenyl Chemical group 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 40
- 238000005401 electroluminescence Methods 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 14
- 125000004076 pyridyl group Chemical group 0.000 claims description 14
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 12
- 239000004305 biphenyl Substances 0.000 claims description 11
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 11
- 125000005561 phenanthryl group Chemical group 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 10
- 235000010290 biphenyl Nutrition 0.000 claims description 10
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 10
- 125000002883 imidazolyl group Chemical group 0.000 claims description 10
- 125000001041 indolyl group Chemical group 0.000 claims description 10
- 125000001624 naphthyl group Chemical group 0.000 claims description 10
- 125000002971 oxazolyl group Chemical group 0.000 claims description 10
- 125000001791 phenazinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3N=C12)* 0.000 claims description 10
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 10
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 10
- 125000000168 pyrrolyl group Chemical group 0.000 claims description 10
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 10
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims description 8
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 claims description 8
- 125000004623 carbolinyl group Chemical group 0.000 claims description 8
- 125000002541 furyl group Chemical group 0.000 claims description 8
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 8
- 125000004592 phthalazinyl group Chemical group C1(=NN=CC2=CC=CC=C12)* 0.000 claims description 8
- 125000001042 pteridinyl group Chemical group N1=C(N=CC2=NC=CN=C12)* 0.000 claims description 8
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 8
- 125000000335 thiazolyl group Chemical group 0.000 claims description 8
- 125000001544 thienyl group Chemical group 0.000 claims description 8
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 7
- 125000004306 triazinyl group Chemical group 0.000 claims description 7
- 125000005580 triphenylene group Chemical group 0.000 claims description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 6
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 229910052805 deuterium Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 150000004756 silanes Chemical class 0.000 claims description 6
- 125000004426 substituted alkynyl group Chemical group 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical group 0.000 claims description 5
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 4
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 4
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 4
- KCMCIQNPQUSQKQ-UHFFFAOYSA-N 2-oxido-1,2,5-oxadiazol-2-ium Chemical group [O-][N+]1=CC=NO1 KCMCIQNPQUSQKQ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 4
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 4
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 4
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 4
- 125000002619 bicyclic group Chemical group 0.000 claims description 4
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 4
- XHQZXHMRBXBPEL-UHFFFAOYSA-N eaton reagent Chemical compound CS(O)(=O)=O.O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 XHQZXHMRBXBPEL-UHFFFAOYSA-N 0.000 claims description 4
- 125000005059 halophenyl group Chemical group 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000001977 isobenzofuranyl group Chemical group C=1(OC=C2C=CC=CC12)* 0.000 claims description 4
- 125000000904 isoindolyl group Chemical group C=1(NC=C2C=CC=CC12)* 0.000 claims description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000001786 isothiazolyl group Chemical group 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 125000004593 naphthyridinyl group Chemical group N1=C(C=CC2=CC=CN=C12)* 0.000 claims description 4
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 4
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 claims description 4
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 4
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 claims description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000004625 phenanthrolinyl group Chemical group N1=C(C=CC2=CC=C3C=CC=NC3=C12)* 0.000 claims description 4
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 claims description 4
- 125000000561 purinyl group Chemical group N1=C(N=C2N=CNC2=C1)* 0.000 claims description 4
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 claims description 4
- 125000003003 spiro group Chemical group 0.000 claims description 4
- KTQYWNARBMKMCX-UHFFFAOYSA-N tetraphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 KTQYWNARBMKMCX-UHFFFAOYSA-N 0.000 claims description 4
- 125000005458 thianyl group Chemical group 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- SVUOLADPCWQTTE-UHFFFAOYSA-N 1h-1,2-benzodiazepine Chemical compound N1N=CC=CC2=CC=CC=C12 SVUOLADPCWQTTE-UHFFFAOYSA-N 0.000 claims description 3
- 229940049706 benzodiazepine Drugs 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000005493 quinolyl group Chemical group 0.000 claims description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- JHYNEQNPKGIOQF-UHFFFAOYSA-N 3,4-dihydro-2h-phosphole Chemical group C1CC=PC1 JHYNEQNPKGIOQF-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical group FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005577 anthracene group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical group C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical group C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 claims description 2
- CPNGPNLZQNNVQM-UHFFFAOYSA-N pteridine Chemical group N1=CN=CC2=NC=CN=C21 CPNGPNLZQNNVQM-UHFFFAOYSA-N 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
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- 230000002194 synthesizing effect Effects 0.000 claims 1
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 12
- 230000009477 glass transition Effects 0.000 abstract description 10
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 9
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- 239000002904 solvent Substances 0.000 description 23
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- 238000012360 testing method Methods 0.000 description 7
- UXJHQQLYKUVLIE-UHFFFAOYSA-N 1,2-dihydroacridine Chemical group C1=CC=C2N=C(C=CCC3)C3=CC2=C1 UXJHQQLYKUVLIE-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- 239000007864 aqueous solution Substances 0.000 description 5
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 5
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- 229910052749 magnesium Inorganic materials 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
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- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 4
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- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
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- 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
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
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- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- 125000006617 triphenylamine group Chemical class 0.000 description 1
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- C07D219/02—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with only hydrogen, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- 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
- C07D401/04—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 directly linked by a ring-member-to-ring-member bond
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- 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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- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
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- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/10—Triplet emission
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- H10K2101/00—Properties of the organic materials covered by group H10K85/00
- H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
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- H10K50/00—Organic light-emitting devices
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- H10K50/18—Carrier blocking layers
Definitions
- the invention belongs to the field of display technology, and particularly relates to a 9,10-dihydroacridine derivative, a preparation method and an application thereof.
- OLEDs Organic light-emitting diodes
- OLED is a carrier double-injection light-emitting device.
- the light-emitting mechanism is: driven by an external electric field, electrons and holes are injected into the organic light-emitting layer from the cathode and the anode, respectively, and exciton and exciton are recombined in the organic light-emitting layer. Radiation transitions back to the ground state and emits light.
- Pope and others first discovered the electroluminescence phenomenon of organic anthracene crystals as a light-emitting material.
- the device used as a light-emitting layer has a high driving voltage (400V), low luminous brightness, and the efficiency and lifetime of the device are less than At that time, devices made of inorganic materials, so organic electroluminescence did not attract people's attention.
- Triarylamine materials are currently widely used as hole transport layer materials, of which triphenylamines and carbazoles are the most widely used.
- N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine (TPD), N, N'-diphenyl -N, N '-(1-naphthyl) -1,1'-biphenyl-4,4'-diamine (NPB) is two common triarylamine materials.
- the structure of triarylamine makes TPD and NPB have Good hole transport performance, but the glass transition temperature of TPD is about 60 °C, and the glass transition temperature of NPB is also less than 100 °C. TPD and NPB molecules are easily arranged closely and cause crystallization, which does not have good amorphous film formation.
- thermal stability on the other hand, an increase in the molecular weight of the hole-transporting material can improve the thermal stability of the material, but at the same time reduce the triplet energy level of the material, exacerbate the energy return from the light-emitting layer to the hole-transporting layer, and affect Luminous efficiency and lifetime of the device.
- the technical problem to be solved by the present invention is that the hole transport material in the prior art has the defects of low glass transition temperature and poor thermal stability, and cannot have both good thermal stability and high triplet energy level.
- the present invention provides a 9,10-dihydroacridine derivative having a structure represented by formula (I):
- T is selected from O, S, C (R 3 ) (R 4 ) or N (R 5 );
- R 1 -R 5 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted Substituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silane, C6-C60 substituted or unsubstituted Substituted aryl, or C3-C30 substituted or unsubstituted heteroaryl;
- R 6 -R 7 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted Substituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silane, C6-C60 substituted or unsubstituted A substituted aryl, a C3-C30 substituted or unsubstituted heteroaryl, or a ring A that shares a side with an adjacent phenyl to form a fused ring; the ring A is selected from a benzene ring, a 3- to 7-membered saturation Or a partially unsaturated carbocyclic ring, a 3- to 7-
- Ar 1 and Ar 2 are independently selected from hydrogen, deuterium, halogen, cyano, C1-C30 substituted or unsubstituted alkyl, C2-C30 substituted or unsubstituted alkenyl, C2-C30 substituted or unsubstituted Substituted alkynyl, C3-C30 substituted or unsubstituted cycloalkyl, C1-C30 substituted or unsubstituted alkoxy, C1-C30 substituted or unsubstituted silane, C6-C60 substituted or unsubstituted Substituted aryl, or C3-C30 substituted or unsubstituted heteroaryl;
- heteroaryl, heterocyclic and fused ring heteroaryl independently of each other have at least one heteroatom independently selected from nitrogen, sulfur, oxygen, phosphorus, boron, or silicon.
- the Ar 1 and Ar 2 are independently selected from the substituted or unsubstituted aryl group of C6-C60, or the substituted or unsubstituted C3-C30 group. Heteroaryl.
- the Ar 2 is selected from any one of the following groups:
- p is an integer of 0-5
- q 1 is an integer of 0-6
- q 2 is an integer of 0-4, and
- q 3 is an integer of 0-4.
- X is selected from O, S, C (R 3 ) (R 4 ) or N (R 5 ), and Y is independently selected from carbon or nitrogen;
- Ar 3 , Ar 4 are independently selected from hydrogen, unsubstituted or 1-4 R 1a substituted groups:
- R 1a is C 1 -C 6 alkyl.
- the Ar 1 is selected from hydrogen or any one of the following groups:
- the R 1 -R 5 are independently selected from hydrogen, C 1 -C 6 alkyl, phenyl, biphenyl, naphthyl, Anthracenyl, phenanthryl, fluorenyl, fluorenyl, fluorenyl, fluorenyl, trienyl, triphenylene, fluoranthenyl, pyridyl, pyrimidinyl, pyranyl, thianyl, pyrazinyl, pyridazinyl, triphenylene Azinyl, phthalazinyl, phenazinyl, thienyl, furanyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, carbazolyl, indolocarbazolyl, three Aromatic amine, diaromatic amine, phenanthryl, fluorenyl, fluorenyl, fluorenyl,
- the R 6 -R 7 are independently selected from hydrogen, C 1 -C 6 alkyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, fluorenyl, fluorenyl, and pentene Group, triphenylene, fluoranthenyl, pyridyl, pyrimidinyl, pyranyl, thianyl, pyrazinyl, pyridazinyl, triazinyl, phthalazinyl, phenazinyl, thienyl, furanyl, Pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, indolyl, carbazolyl, indolocarbazolyl, triaromatic amino, diaromatic amino, phenanthryl, acridinyl, Pyrimidinyl, pteridinyl, quinazolin
- the ring A is selected from The ring B is selected from the group consisting of a benzene ring, a biphenyl ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring, a fluorene ring, a fluorene ring, a bowlene ring, a triphenylene ring, a fluoranthene ring, a pyridine ring, a pyrimidine ring, and a pyridine Ran ring, thioan ring, pyrazine ring, pyridazine ring, triazine ring, phthalazine ring, phenazine ring, thiophene ring, furan ring, pyrrole ring, pyrazole ring, imidazole ring, oxazole ring, thiazole ring, Indole ring, carbazole
- the above 9,10-dihydroacridine derivative has a molecular structure shown in any of the following:
- the present invention provides a method for preparing the above-mentioned 9,10-dihydroacridine derivative.
- the synthetic steps of the compound represented by formula (I) are as follows:
- intermediate 1 is obtained through a nucleophilic addition reaction
- intermediate 1 and the compound represented by formula (D) exist in the Eaton reagent
- Intermediate 2 is obtained through dehydration condensation reaction
- Intermediate 2 and a compound represented by formula (E) are subjected to a coupling reaction in the presence of a catalyst to obtain a compound represented by formula (I);
- a compound represented by the formula (A) and a compound represented by the formula (E) are used as starting materials, and an intermediate 3 is obtained through a nucleophilic addition reaction; the intermediate 3 is formed into an intermediate 3 'through a nucleophilic substitution reaction, Intermediate 3 'reacts with a compound represented by formula (G) to form intermediate 4 through a Suzuki reaction.
- Intermediate 4 reacts with a compound represented by formula (E) by a coupling reaction in the presence of a catalyst to obtain a compound represented by formula (I) Compound
- W is selected from hydrogen, fluorine, chlorine, bromine or iodine, and -OTf is triflate.
- the invention provides an application of the above-mentioned 9,10-dihydroacridine derivative as a hole transporting material.
- the present invention provides an organic electroluminescence device. At least one functional layer of the organic electroluminescence device contains the above-mentioned 9,10-dihydroacridine derivative.
- the functional layer is a hole transport layer and / or an electron blocking layer.
- the functional layer is a light emitting layer.
- the 9,10-dihydroacridine derivative provided by the present invention has a structure as shown in formula (I).
- a dibenzoheterocyclic structure connected to a dihydroacridine group By designing a dibenzoheterocyclic structure connected to a dihydroacridine group, a strong supply is formed.
- An electronic property group, the nitrogen atom in the dihydroacridine group forms an ammonium ion radical under the action of an electric field, and has good hole mobility.
- the compound of the structure represented by formula (I) has a suitable HOMO energy level, and the HOMO energy level of the hole transport layer formed by the compound can match the anode and the light emitting layer on both sides to reduce the injection of holes from the anode into the light emitting layer.
- the potential barrier to be overcome increases the proportion of holes injected into the light-emitting layer and reduces the operating voltage of the OLED device.
- the HOMO energy level of the structural compound represented by formula (I) is optimized, which further matches the work function of the anode, and the potential barrier value of holes injected from the anode is further reduced. Increased effective hole injection.
- a dihydroacridine group having a high triplet energy level (T 1 ) and a dibenzoheterocyclic ring are connected by a ⁇ bond, wherein Dibenzoheterocycles further increase the triplet energy level of 9,10-dihydroacridine derivatives by selecting groups of dibenzofuran, carbazole, and fluorene having high triplet energy levels; at the same time, both
- the triplet energy level (T 1 ) of the compound can be further adjusted, so that the 9,10-dihydroacridine derivative has a high triplet energy level (T 1 ), which is beneficial to Electron and hole recombination excitons in OLED devices are confined in the light-emitting area of the light-emitting layer to avoid the energy return of the light-emitting layer to the adjacent hole-transporting layer; at the same time,
- the 9,10-dihydroacridine derivative represented by formula (I) has a high glass transition temperature, good film-forming properties, and good thermal and morphological stability after film formation, which can be avoided During film formation or after film formation, crystals are formed due to heat generation during the operation of the OLED device, which improves the device's performance and service life.
- the 9,10-dihydroacridine derivative provided by the present invention by adjusting the Ar 1 group and the Ar 2 group in the structure represented by formula (I), introduces a group of electron donating properties (for example, carbazole Groups, fluorenyl groups, and aromatic amine groups such as diphenylamine and triphenylamine), to further improve the hole transport properties of the material molecules, adjust the HOMO and LUMO energy levels of 9,10-dihydroacridine derivatives, and increase 9,
- the triplet energy level of the 10-dihydroacridine derivative can also improve the hole mobility of the material molecules; and by setting the Ar 1 group and the Ar 2 group, the molecular stacking can be reduced to increase the 9,10-bis Thermal stability of hydroacridine derivatives.
- the method for preparing the 9,10-dihydroacridine derivative provided by the present invention the starting materials are easy to obtain, the reaction conditions are mild, and the operation steps are simple, which is the large-scale production of the above 9,10-dihydroacridine derivative A simple and easy-to-implement preparation method is provided.
- the organic electroluminescence device provided by the present invention includes at least one functional layer containing the above-mentioned 9,10-dihydroacridine derivative.
- the functional layer is a hole transport layer, and a hole transport layer formed by using a 9,10-dihydroacridine derivative as a hole transport material. Since the 9,10-dihydroacridine derivative has a suitable HOMO energy level And LUMO energy level, matching the HOMO energy level of the hole transport layer with the light emitting layer and the anode on both sides, reducing the potential barrier to be overcome by the hole injection from the anode into the light emitting layer, and increasing the hole injection ratio; 9,10-dihydroacridine derivatives have good hole transport properties, which can increase the effective transport of holes in the transport layer; on the other hand, 9,10-dihydroacridine derivatives have relatively high LUMO energy Level, can prevent electrons from diffusing from the light-emitting layer, avoid the loss of electrons, and then increase the recombination probability of electrons and holes, so that the light-emitting efficiency of the OLED device is improved.
- the triplet (T 1 ) energy level of the 9,10-dihydroacridine derivative is high, which can prevent the energy of the light-emitting layer from transferring back to the hole-transport layer, thereby ensuring the effective light emission of the device and improving the light-emitting efficiency of the device.
- the 9,10-dihydroacridine derivative has a high glass transition temperature, has good film-forming properties and thermal stability, and can prevent the film caused by the temperature increase during the formation of the film layer of the OLED device and the working process of the device.
- the recrystallization in the layer enables the OLED device to maintain stable operating performance and prolong the service life of the device.
- the functional layer may also be a light-emitting layer.
- a 9,10-dihydroacridine derivative may be used alone as the host material of the light-emitting layer, or together with a material having an electron-transporting property, an exciplex may be used as the host material of the light-emitting layer.
- the 10-dihydroacridine derivative has a high triplet energy level, can promote the energy transfer from the host material to the guest material, avoid energy return, and improve the luminous efficiency of the OLED device.
- the high glass transition temperature of the 9,10-dihydroacridine derivative enables the light-emitting layer formed therewith to have good thermal stability, thereby improving the service life of the OLED device.
- FIG. 1 is a schematic structural diagram of an organic electroluminescent device in Examples 74 to 83 and Comparative Example 1 of the present invention
- FIG. 2 is a theoretical calculation of the compound shown by Formula C-2 provided in Example 2 of the present invention and the compound NPB provided by Comparative Example 1, the HOMO level, LUMO level, and single-triplet state energy difference ⁇ Est. Results comparison chart;
- 3 is a comparison chart of theoretical calculation results of HOMO energy levels, LUMO energy levels, and single-triplet energy range ⁇ Est of compounds C-61, C-109, and C-12 provided by the present invention
- 1-anode 2-hole injection layer, 3-hole transport layer, 4-light emitting layer, 5-electron transport layer, 6-electron injection layer, 7-cathode.
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-1:
- the method for preparing the 9,10-dihydroacridine derivative represented by Formula C-1 specifically includes the following steps:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-2:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-3:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-4:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-5:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-6:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-7:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-8:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-9:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-10:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-11:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-12:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-1:
- the method for preparing the 9,10-dihydroacridine derivative represented by Formula C-13 specifically includes the following steps:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-14:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-15:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-16:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-17:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-18:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-19:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-20:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-21:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-22:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-23:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-24:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-25:
- the method for preparing the 9,10-dihydroacridine derivative represented by Formula C-25 specifically includes the following steps:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-26:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-27:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-28:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-29:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-30:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-31:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-32:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-33:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-34:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-35:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-36:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-49:
- the method for preparing the 9,10-dihydroacridine derivative represented by Formula C-49 specifically includes the following steps:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-50:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-51:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-52:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-53:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-54:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-55:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-56:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-57:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-58:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-59:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-60:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-61:
- the method for preparing a 9,10-dihydroacridine derivative represented by Formula C-61 specifically includes the following steps:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-62:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-63:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-64:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-65:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-66:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-67:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-68:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-69:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-70:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-71:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-72:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-74:
- the method for preparing the 9,10-dihydroacridine derivative represented by Formula C-74 specifically includes the following steps:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-73:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-75:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-76:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-78:
- the procedure for preparing the 9,10-dihydroacridine derivative represented by Formula C-78 and the procedure for preparing the 9,10-dihydroacridine derivative represented by C-74 provided in Example 61 differ only in that: The compound represented by the formula F-2 replaced the compound F-1 in the step (1) of Example 61.
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-77:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-79:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-80:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-82:
- the procedure for preparing the 9,10-dihydroacridine derivative represented by Formula C-82 and the procedure for preparing the 9,10-dihydroacridine derivative represented by C-74 provided in Example 61 are different only in that:
- the compound represented by the formula F-3 replaced the compound F-1 in the step (1) of Example 61.
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-81:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-83:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-84:
- This embodiment provides a 9,10-dihydroacridine derivative having a structure represented by the following formula C-89:
- the method for preparing a 9,10-dihydroacridine derivative represented by Formula C-89 specifically includes the following steps:
- the organic electroluminescent device includes an anode 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, an electron transport layer 5, Electron injection layer 6 and cathode 7.
- the anode is made of ITO; the cathode 7 is made of metal Al;
- HAT (CN) 6 has the following chemical structure:
- the material of the hole injection layer 3 is a 9,10-dihydroacridine derivative having a structure shown in Formula C-2:
- the light-emitting layer 4 is formed by co-doping the host material RH and the guest material RD, and the mass ratio of the host material RH and the guest material RD is 100: 5:
- the material of the electron transport layer 5 is a compound having the following structure:
- the material of the electron injection layer 6 is formed by doping a compound of the structure shown below and an electron injection material LiF:
- the organic light-emitting device has the following specific structure: ITO / hole injection layer (HIL) / hole transport layer (HTL, compound represented by Formula C-2) / organic light emitting layer (mass ratio of RH: RD is 100: 5) / Electron transport layer (ETL) / electron injection layer (EIL / LiF) / cathode (Al).
- HIL hole injection layer
- HTL hole transport layer
- Al organic light emitting layer
- the 9,10-dihydroacridine derivative shown in Formula C-2 is selected because of the hole transport layer, and the 9,10-dihydroacridine derivative shown in C-2 is compared with NPB.
- the energy level diagram is shown in Figure 2: Among them, the It is a group with strong electron-donating properties.
- the nitrogen atom in the dihydroacridine group forms an ammonium ion radical under the action of an electric field. It has good hole mobility and can ensure the effective transport of holes in the transport layer.
- the compound represented by formula C-2 introduces a phenyl-substituted carbazolyl group at the Ar 2 group position, and uses the electron-donating properties of the carbazole group to further improve its hole transport performance.
- the dihydroacridine derivative has a suitable HOMO energy level, which can reduce the potential barrier to be overcome by the injection of holes from the anode to the light-emitting layer, increase the effective injection of holes, and help reduce the operating voltage of the device and increase the device's Luminous efficiency.
- a dihydroacridine group having a high triplet energy level and a dibenzofuran group are connected through a sigma bond, so that the triplet energy level of the structure shown in C-2 is increased.
- a modifying group with a ⁇ bond to adjust the triplet energy level (T 1 ) of the 9,10-dihydroacridine derivative shown in C-2, and 9,10-dihydro shown in C-2
- the acridine derivative has a high triplet energy level, which is conducive to exciton recombination of electrons and holes of the OLED device in the light-emitting region of the light-emitting layer, and avoids the energy return of the light-emitting layer to the adjacent hole-transporting layer;
- the 9,10-dihydroacridine derivative of the above-mentioned connection method has an increased LUMO energy level, which increases the blocking effect on electrons, effectively retaining the electrons in the light-emitting layer, thereby
- the 9,10-dihydroacridine derivative represented by the formula C-2 has high glass transition temperature, high thermal stability and morphological stability, and excellent film forming performance, and can avoid the film formation process or film formation. Later, during the operation of the OLED device, crystals are formed due to heat generation, which improves the performance and service life of the device.
- the guest light-emitting material of the light-emitting layer may also select any 9,10-dihydroacridine derivative represented by the formulae (C-1), (C-3) to (C-109) .
- the guest light-emitting material of the light-emitting layer may also be selected from any other compound having a chemical structure represented by the general formula (I).
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This embodiment provides an organic electroluminescence device.
- the only difference from the organic electroluminescence device provided in Example 74 is that the material of the hole transport layer is a 9,10-dihydroacridine derivative with the structure shown below. :
- This comparative example provides an organic electroluminescent device, which is different from the organic electroluminescent device provided in Example 74 only in that the hole transport layer is selected from the compound NPB:
- DSC differential scanning calorimeter
- the LUMO energy level of the material molecule is calculated using the material's band gap and HOMO:
- the band gap ⁇ onset is the initial spectral absorption value of the material.
- the organic electroluminescent devices provided in Comparative Examples 74-83 and Comparative Example 1 were tested. The results are shown in Table 2. Compared with the devices in Comparative Example 1, the OLEDs provided in Examples 74-83 The working voltage of the device is reduced, and the current efficiency is improved, which shows that the use of 9,10-dihydroacridine provided in the present invention as a hole transport material for an OLED device can significantly improve the light emitting efficiency of the device, reduce the working voltage of the device, and improve the OLED. Performance.
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Abstract
本发明公开了一种9,10-二氢吖啶衍生物，具有如式(I)所示的结构，化合物具有适宜的HOMO能级，作为空穴传输层材料时与阳极和发光层相匹配，减小空穴传输至发光层所需克服的势垒，使器件的工作电压降低；同时，上述的9,10-二氢吖啶衍生物具有高的三线态能级和LUMO能级，避免了发光层能量的回传，并能够将电子阻挡在发光层内，增加电子和空穴在发光层复合的几率，提高器件的发光效率。式(I)示化合物的玻璃态转化温度高，具有良好的成膜性能和热稳定性。本发明公开了一种有机电致发光器件，至少有一个功能层中含有上述的9,10-二氢吖啶衍生物，以上述化合物作为空穴传输材料，能够得到具有高发光效率、低电压的发光器件。
Description
交叉引用
本申请要求在2018年9月17日提交中国专利局、申请号为201811084418.X、发明名称为“一种9,10-二氢吖啶衍生物及其制备方法和用途”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
本发明属于显示技术领域，具体涉及一种9,10-二氢吖啶衍生物及其制备方法和用途。
有机电致发光二极管(organic light-emitting diodes，OLEDs)由于自发光、高对比度、超薄、重量轻、能耗低、视角宽、色域广、响应快等优点，在显示和照明领域有极大的应用前景，越来越受到人们的重视。
OLED属于载流子双注入型发光器件，发光机理为：在外界电场的驱动下，电子和空穴分别由阴极和阳极注入到有机发光层，并在有机发光层中复合生成激子，激子辐射跃迁回到基态并发光。在20世纪60年代，Pope等首次发现有机蒽晶体作为发光材料的电致发光现象，然而该材料作为发光层的器件驱动电压高(400V)，发光亮度低，器件的效率和器件的寿命都不及当时的无机材料制备的器件，因此有机电致发光并没有引起人们的重视。
直至1987年，美国柯达公司的C.W.Tang(邓青云)和S.A.VanSlyke首次选用了具有电子传输能力的8-羟基喹啉作为发光材料，并且优化了器件结构，用芳胺衍生物作为空穴传输层，从而大大提高了空穴的注入效率，实现了较高的发光亮度和发光效率，并使驱动电压降低到10V以下，突破了有机电致发光器件的研究瓶颈，成为其发展历史上的一个里程碑。
空穴传输层等功能层的引入使得OLED器件的结构得到优化，提高了载流子向发光层传输的效率，促使载流子在理想的复合区域进行复合形成激子，从而提高OLED器件的发光效率。三芳胺类材料是目前普遍使用的空穴传输层材料，其中以三苯胺类、咔唑类应用最为广泛。N,N’-二苯基-N,N’-(3-甲基苯基)-1,1’-联苯-4,4’-二胺(TPD)，N,N'-二苯基-N,N'-(1-萘基)-1,1'-联苯-4,4'-二胺(NPB)是两种常见的三芳胺类材料，三芳胺的结构使TPD和NPB具有良好的空穴传输性能，但TPD的玻璃态转化温度在60℃左右，NPB的玻璃态转化温度也小于100℃，TPD和NPB分子间容易紧密排列导致结晶，不具有良好的无定形成膜性和热稳定性；另一方面，空穴传输材料分子量的增加，可以提升材料的热稳定性，但同时会降低材料的三线态能级，加剧发光层向空穴传输层的能量回传，影响器件的发光效率和使用寿命。
发明内容
因此，本发明要解决的技术问题在于现有技术中的空穴传输材料存在玻璃态转化温度低、热稳定性差，无法兼具良好的热稳定性与高三线态能级的缺陷。
为此，本发明提供如下技术方案：
本发明提供了一种9,10-二氢吖啶衍生物，具有如式(I)所示的结构：
其中，T选自O、S、C(R
3)(R
4)或N(R
5)；
R
1-R
5彼此独立地选自氢、氘、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基；
R
6-R
7彼此独立地选自氢、氘、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基、C3-C30的取代或未取代的杂芳基，或是与相邻苯基共有一边形成稠环的环A；所述环A选自苯环、3元到7元的饱和或部分不饱和的碳环、3元到7元的饱和或部分不饱和的杂环、C6-C60的稠环芳基或C3-C30的稠环杂芳基；
Ar
1、Ar
2彼此独立地选自氢、氘、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基；
所述杂芳基、杂环和稠环杂芳基彼此独立地具有至少一个独立地选自氮、硫、氧、磷、硼或硅的杂原子。
可选地，上述的9,10-二氢吖啶衍生物，所述Ar
1、Ar
2彼此独立地选自C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基。
可选地，上述的9,10-二氢吖啶衍生物，所述Ar
2选自下述任一基团：
其中，p为0-5的整数，q
1为0-6的整数，q
2为0-4的整数，q
3为0-4的整数，
表示选自单键或双键；所述
中，所述p、q
2和q
3不同时为0；
X选自O、S、C(R
3)(R
4)或N(R
5)，Y彼此独立地选自碳或氮；
Ar
3、Ar
4彼此独立地选自氢、未取代的或1-4个R
1a取代的下述基团：
苯基、联苯基、三联苯基、茚基、芴基、萘基、薁基、戊搭烯基、庚搭烯基、辛搭烯基、苯并二茚基、苊烯基、非那烯基、菲基、蒽基、三茚基、荧蒽基、醋菲基、醋蒽烯基、9,10-苯并菲基、芘基、1,2-苯并菲基、丁苯基、丁省基、七曜烯基、苉基、苝基、五苯基、并五苯基、亚四苯基、胆蒽基、螺烯基、己芬基、玉红省基、晕苯基、联三萘基、庚芬基、皮蒽基、卵苯基、心环烯基、蒽嵌蒽基、三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、氧杂蒽基、噁唑啉基、二苯并呋喃基、迫呫吨并呫吨基、噻吩基、噻吨基、噻蒽基、吩噁噻基、硫茚基、异硫茚基、并噻吩基、萘并噻吩基、二苯并噻吩基、吡咯基、吡唑基、碲唑基、硒唑基、噻唑基、异噻唑基、噁唑基、呋咱基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、吲嗪基、吲哚基、异吲哚基、吲唑基、嘌呤基、喹嗪基、异喹啉基、咔唑基、吲哚并咔唑基、咪唑基、萘啶基、酞嗪基、喹唑啉基、苯二氮卓基、喹喔啉基、噌啉基、喹啉基、蝶啶基、菲啶基、吖啶基、呸啶基、菲咯啉基、吩嗪基、咔啉基、吩碲嗪基、吩硒嗪基、吩噻嗪基、吩噁嗪基、三苯二噻嗪基、三苯二噁嗪基、蒽吖嗪基、苯并噻唑基、苯并咪唑基、苯并噁唑基、苯并异噁唑基、苯并异噻唑基，或者由上述基团形成稠环基、螺环基或联环基；
R
1a为C
1-C
6的烷基。
可选地，上述的9,10-二氢吖啶衍生物，所述Ar
1选自氢或下述任一基团：
苯基、联苯基、三联苯基、茚基、芴基、萘基、薁基、戊搭烯基、庚搭烯基、辛搭烯基、苯并二茚基、苊烯基、非那烯基、菲基、蒽基、三茚基、荧蒽基、醋菲基、醋蒽烯基、9,10-苯并菲基、芘基、1,2-苯并菲基、丁苯基、丁省基、七曜烯基、苉基、苝基、五苯基、并五苯基、亚四苯基、胆蒽基、螺烯基、己芬基、玉红省基、晕苯基、联三萘基、庚芬基、皮蒽基、卵苯基、心环烯基、蒽嵌蒽基、三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、氧杂蒽基、噁唑啉基、二苯并呋喃基、迫呫吨并呫吨基、噻吩基、噻吨基、噻蒽基、吩噁噻基、硫茚基、异硫茚基、并噻吩基、萘并噻吩基、二苯并噻吩基、吡咯基、吡唑基、碲唑基、硒唑基、噻唑基、异噻唑基、噁唑基、呋咱基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、吲嗪基、吲哚基、异吲哚基、吲唑基、嘌呤基、喹嗪基、异喹啉基、咔唑基、吲哚并咔唑基、咪唑基、萘啶基、酞嗪基、喹唑啉基、苯二氮卓基、喹喔啉基、噌啉基、喹啉基、蝶啶基、菲啶基、吖啶基、呸啶基、菲咯啉基、吩嗪基、咔啉基、吩碲嗪基、吩硒嗪基、吩噻嗪基、吩噁嗪基、三苯二噻嗪基、三苯二噁嗪基、蒽吖嗪基、苯并噻唑基、苯并咪唑基、苯并噁唑基、苯并异噁唑基、苯并 异噻唑基，或者由上述基团形成稠环基、螺环基联环基。
可选地，上述的9,10-二氢吖啶衍生物，所述R
1-R
5彼此独立地选自氢、C
1-C
6的烷基、苯基、联苯基、萘基、蒽基、菲基、芴基、芘基、苝基、碗烯基、三亚苯基、荧蒽基、吡啶基、嘧啶基、吡喃基、噻喃基、吡嗪基、哒嗪基、三嗪基、酞嗪基、吩嗪基、噻吩基、呋喃基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、咔唑基、吲哚并咔唑基、三芳香胺基、二芳香胺基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、喹啉基、菲罗啉基或咔啉基；
所述R
6-R
7彼此独立地选自氢、C
1-C
6的烷基、苯基、联苯基、萘基、蒽基、菲基、芴基、芘基、苝基、碗烯基、三亚苯基、荧蒽基、吡啶基、嘧啶基、吡喃基、噻喃基、吡嗪基、哒嗪基、三嗪基、酞嗪基、吩嗪基、噻吩基、呋喃基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、咔唑基、吲哚并咔唑基、三芳香胺基、二芳香胺基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、喹啉基、菲罗啉基、咔啉基或是与相邻苯基共有一边形成稠环的环A；
所述环A选自
所述环B选自苯环、联苯环、萘环、蒽环、菲环、芴环、芘环、苝环、碗烯环、三亚苯环、荧蒽环、吡啶环、嘧啶环、吡喃环、噻喃环、吡嗪环、哒嗪环、三嗪环、酞嗪环、吩嗪环、噻吩环、呋喃环、吡咯环、吡唑环、咪唑环、噁唑环、噻唑环、吲哚环、咔唑环、吲哚并咔唑环、三芳香胺环、二芳香胺环、菲啶环、吖啶环、呸啶环、蝶啶环、喹唑啉环、喹喔啉环、噌啉环、喹啉环、菲罗啉环或咔啉环。
可选地，上述的9,10-二氢吖啶衍生物，具有下述任一所示的分子结构：
本发明提供了一种上述的9,10-二氢吖啶衍生物的制备方法，所述式(I)所示化合物的合成步骤如下所示：
以式(A)所示的化合物和式(B)所示的化合物为起始原料，经亲核加成反应得到中间体1；中间体1与式(D)所示的化合物在伊顿试剂存在下经脱水缩合反应得到中间体2；中间体2与式(E)所示的化合物在催化剂存在下经偶联反应得到式(I)所示的化合物；
所述式(I)所示化合物的合成路径如下所示：
或者，以式(A)所示的化合物和式(E)所示的化合物为起始原料，经亲核加成反应得到中间体3；中间体3经亲核取代反应生成中间体3’，中间体3’与式(G)所示的化合物经铃木反应生成中间体4，中间体4与式(E)所示的化合物在催化剂存在下经偶联反应反应得到式(I)所示的化合物；
所述式(I)所示化合物的合成路径如下所示：
其中，W选自氢、氟、氯、溴或碘，-OTf为三氟甲磺酸酯。
本发明提供了一种上述的9,10-二氢吖啶衍生物作为空穴传输材料的应用。
本发明提供了一种有机电致发光器件，所述有机电致发光器件的至少有一个功能层中含有上述的9,10-二氢吖啶衍生物。
可选地，上述的有机电致发光器件，所述功能层为空穴传输层和/或电子阻挡层。
可选地，上述的有机电致发光器件，所述功能层为发光层。
本发明技术方案，具有如下优点：
1、本发明提供的9,10-二氢吖啶衍生物，具有如式(I)所示的结构，通过设计二氢吖啶基团上连接二苯并杂环结构，形成具有较强供电子性能的基团，二氢吖啶基团中的氮原子在电场作用下形成铵离子自由基，有较好的空穴迁移性。同时，式(I)所示结构的化合物具有合适的HOMO能级，以其形成的空穴传输层的HOMO能级能够匹配两侧的阳极和发光层，减小空穴由阳极注入到发光层所需克服的势垒，增加了空穴向发光层注入的比例，降低了OLED器件的工作电压。与现有的三芳胺类空穴传输材料相比，式(I)所示结构化合物的HOMO能级得到优化，与阳极的功函数进一步匹配，空穴由阳极注入的势垒值进一步减小，增加了空穴的有效注入。
式(I)所示的9,10-二氢吖啶衍生物中，具有高三线态能级(T
1)的二氢吖啶基团与二苯并杂环通过σ键相连接，其中的二苯并杂环通过选择具有高三线态能级的二苯并呋喃、咔唑以及芴的基团，以进一步提高9,10-二氢吖啶衍生物的三线态能级；同时，两者通过以σ键引入修饰基团，能够对化合物的三线态能级(T
1)进行进一步调节，使9,10-二氢吖啶衍生物具有高的三线态能级(T
1)，有利于OLED器件的电子和空穴复合的激子限制在发光层的发光区域内，避免发光层向相邻空穴传输层的能量回传；同时，上述的分子连接方式使9,10-二氢吖啶衍生物的LUMO能级提高，增加对电子的阻挡效果，有效地使电子滞留在发光层内，从而提高电子和空穴的复合几率。
式(I)所示的9,10-二氢吖啶衍生物，其玻璃态转化温度高，具有良好的成膜性能，且成膜后具有良好的热稳定性和形态学稳定性，能够避免在成膜过程中或成膜后在OLED器件的工作过程中由于发热形成结晶，提升了器件的使用性能和使用寿命。
2、本发明提供的9,10-二氢吖啶衍生物，通过调节式(I)所示结构中的Ar
1基团和Ar
2基团，引入供电子性能的基团(例如：咔唑基、芴基、以及二苯胺、三苯胺等芳香胺基基团)，进一步提高材料分子的空穴传输性能，调节9,10-二氢吖啶衍生物的HOMO和LUMO能级，提高9,10-二氢吖啶衍生物的三线态能级，同时可以提高材料分子的空穴迁移率；并能通过设置Ar
1基团和Ar
2基团，减少分子堆积，以提高9,10-二氢吖啶衍生物的热稳定性。
3、本发明提供的9,10-二氢吖啶衍生物的制备方法，起始原料易于获得，反应条件温和，操作步骤简单，为上述9,10-二氢吖啶衍生物的大规模生产提供了一种简单、易于实现的制备方法。
4、本发明提供的有机电致发光器件，至少有一个功能层中含有上述的9,10-二氢吖啶衍生物。
所述功能层为空穴传输层，以9,10-二氢吖啶衍生物作为空穴传输材料形成的空穴传输层，由于9,10-二氢吖啶衍生物具有适宜的HOMO能级和LUMO能级，使空穴传输层的HOMO能级与两侧的发光层和阳极相匹配，减小空穴由阳极注入到发光层中所需克服的势垒，增加空穴的注入比例；9,10-二氢吖啶衍生物具有良好的空穴传输性能，能够增加空穴在传输层中的有效传输；另一方面，9,10-二氢吖啶衍生物具有相对高的LUMO能级，能够阻挡 电子从发光层中扩散出来，避免电子的流失，进而提高电子和空穴的复合几率，使OLED器件的发光效率提高。另外，9,10-二氢吖啶衍生物的三线态(T
1)能级高，能够避免发光层能量向空穴传输层的能量回传，从而保证器件的有效发光，提高器件的发光效率。
9,10-二氢吖啶衍生物的玻璃态转化温度高，具有良好的成膜性能和热稳定性，在形成OLED器件的膜层以及器件工作过程中，能够防止由于温度升高导致的膜层内的重结晶，使OLED器件维持稳定的工作性能，延长器件的使用寿命。
所述功能层还可以是发光层，9,10-二氢吖啶衍生物可以单独作为发光层主体材料，或者与具有电子传输性能的材料共同形成激基复合物作为发光层的主体材料，9,10-二氢吖啶衍生物的三线态能级高，能够促进主体材料向客体材料的能量传递，避免能量回传，提高OLED器件的发光效率。9,10-二氢吖啶衍生物的高玻璃态转化温度使以其形成的发光层具有良好的热稳定性，从而提高OLED器件的使用寿命。
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明实施例74-实施例83和对比例1中有机电致发光器件的结构示意图；
图2为本发明中实施例2提供的式C-2所示的化合物与对比例1提供的化合物NPB，其HOMO能级、LUMO能级，以及单-三线态能极差△Est的理论计算结果对比图；
图3为本发明提供的化合物C-61、C-109和C-12的HOMO能级、LUMO能级，以及单-三线态能极差△Est的理论计算结果对比图；
附图标记说明：
1-阳极，2-空穴注入层，3-空穴传输层，4-发光层，5-电子传输层，6-电子注入层，7-阴极。
下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本发明的描述中，需要说明的是，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
本发明可以以许多不同的形式实施，而不应该被理解为限于在此阐述的实施例。相反，提供这些实施例，使得本公开将是彻底和完整的，并且将把本发明的构思充分传达给本领域技术人员，本发明将仅由权利要求来限定。在附图中，为了清晰起见，会夸大层和区域的尺寸和相对尺寸。应当理解的是，当元件例如层被称作“形成在”或“设置在”另一元件“上”时，该元件可以直接设置在所述另一元件上，或者也可以存在中间元件。相反，当元件被称作 “直接形成在”或“直接设置在”另一元件上时，不存在中间元件。
实施例1
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-1所示的结构：
式C-1所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-1所示9,10-二氢吖啶衍生物的制备方法具体包括以下步骤：
(1)合成中间体1-1
氮气保护下，1L的三口烧瓶中，加入19.5g(100mmol)9(10H)-吖啶酮(式A-1所示化合物)，700mL的四氢呋喃，-20℃下加入110mL(1M)苯基溴化镁(式B-1所示化合物)溶液，室温反应8小时后，加氯化铵水溶液淬灭反应，用二氯甲烷萃取三次后，旋蒸除去溶剂，过硅胶柱得到24g固体中间体1-1(产率：88％)；
(2)合成中间体2-1
氮气保护下，1L的三口烧瓶中，加入22.0g(80mmol)中间体1-1，27g(160mmol)二苯并呋喃(式D-1所示化合物)，600mL的二氯甲烷，逐滴加入1.8mL(0.9M)伊顿试剂，室温反应30分钟后，加入碳酸氢钠溶液淬灭反应，用甲苯萃取三次后，旋蒸除去溶剂，过硅胶柱得到13.5g固体中间体2-1(产率：40％)；
(3)合成9,10-二氢吖啶衍生物C-1
氮气保护下，加入8g中间体2-1(20mmol)，0.13g醋酸钯(0.6mmol)，0.45g三叔丁基膦(2.2mmol)，6.0g式 E-1所示的化合物(22mmol)，5.7g叔丁醇钠，甲苯300mL，110℃反应12小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到10.0g固体化合物C-1(产率82％)。
元素分析：(C46H33NO)理论值：C,89.73；H,5.40；N,2.27；O,2.60；实测值：C,89.71；H,5.45；N,2.28；O,2.57，HRMS(ESI)m/z(M+)：理论值：615.2562；实测值：615.2571。
实施例2
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-2所示的结构：
式C-2所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-2所示的化合物代替实施例1步骤(3)中的化合物E-1，产率80％：
实施例3
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-3所示的结构：
式C-3所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-3所示的化合物代替实施例1步骤(3)中的化合物E-1，产率78％：
实施例4
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-4所示的结构：
式C-4所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例1步骤(3)中的化合物E-1，产率85％：
实施例5
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-5所示的结构：
式C-5所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-5所示的化合物代替实施例1步骤(3)中的化合物E-1，产率84％：
实施例6
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-6所示的结构：
式C-6所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-6所示的化合物代替实施例1步骤(3)中的化合物E-1，产率84％：
实施例7
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-7所示的结构：
式C-7所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-7所示的化合物代替实施例1步骤(3)中的化合物E-1。产率83％：
实施例8
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-8所示的结构：
式C-8所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-8所示的化合物代替实施例1步骤(3)中的化合物E-1。产率84％：
实施例9
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-9所示的结构：
式C-9所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-9所示的化合物代替实施例1步骤(3)中的化合物E-1。产率85％：
实施例10
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-10所示的结构：
式C-10所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-10所示的化合物代替实施例1步骤(3)中的化合物E-1。产率84％：
实施例11
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-11所示的结构：
式C-11所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-11所示的化合物代替实施例1步骤(3)中的化合物E-1。产率83％：
实施例12
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-12所示的结构：
式C-12所示9,10-二氢吖啶衍生物的制备步骤与实施例1中提供的C-1所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例1步骤(3)中的化合物E-1。产率85％：
实施例13
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-1所示的结构：
式C-13所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-13所示9,10-二氢吖啶衍生物的制备方法具体包括以下步骤：
(1)合成中间体1-1
氮气保护下，1L的三口烧瓶中，加入19.5g(100mmol)9(10H)-吖啶酮(式A-1所示化合物)，700mL的四氢呋喃，-20℃下加入110mL(1M)苯基溴化镁(式B-1所示化合物)溶液，室温反应8小时后，加氯化铵水溶液淬灭反应，用二氯甲烷萃取三次后，旋蒸除去溶剂，过硅胶柱得到24g固体中间体1-1(产率：88％)；
(2)合成中间体2-2
氮气保护下，1L的三口烧瓶中，加入22.0g(80mmol)中间体1-1，29g(160mmol)二苯并噻吩(式D-2所示化合物)，600mL的二氯甲烷，逐滴加入1.8mL(0.9M)伊顿试剂，室温反应30分钟后，加入碳酸氢钠溶液淬灭反应，用甲苯萃取三次后，旋蒸除去溶剂，过硅胶柱得到13.3g固体中间体2-2(产率：38％)；
(3)合成9,10-二氢吖啶衍生物C-13
氮气保护下，加入8.8g中间体2-2(20mmol)，0.13g醋酸钯(0.6mmol)，0.45g三叔丁基膦(2.2mmol)，6.0g式E-1所示的化合物(22mmol)，5.7g叔丁醇钠，甲苯300mL，110℃反应12小时，冷却至室温后，氯仿萃取， 旋蒸除去溶剂，过硅胶柱得到10.7g固体化合物C-13(产率85％)。
元素分析：(C46H33NS)理论值：C,87.44；H,5.26；N,2.22；S,5.07；实测值：C,87.41；H,5.29；N,2.20；S,5.03，HRMS(ESI)m/z(M+)：理论值：631.2334；实测值：631.2347。
实施例14
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-14所示的结构：
式C-14所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-2所示的化合物代替实施例13步骤(3)中的化合物E-1，产率82％：
实施例15
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-15所示的结构：
式C-15所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-3所示的化合物代替实施例13步骤(3)中的化合物E-1，产率83％：
实施例16
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-16所示的结构：
式C-16所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例13步骤(3)中的化合物E-1，产率85％：
实施例17
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-17所示的结构：
式C-17所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-5所示的化合物代替实施例13步骤(3)中的化合物E-1，产率87％：
实施例18
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-18所示的结构：
式C-18所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-6所示的化合物代替实施例13步骤(3)中的化合物E-1，产率83％：
实施例19
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-19所示的结构：
式C-19所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-7所示的化合物代替实施例13步骤(3)中的化合物E-1。产率83％：
实施例20
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-20所示的结构：
式C-20所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-8所示的化合物代替实施例13步骤(3)中的化合物E-1。产率85％：
实施例21
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-21所示的结构：
式C-21所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-9所示的化合物代替实施例13步骤(3)中的化合物E-1。产率81％：
实施例22
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-22所示的结构：
式C-22所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-10所示的化合物代替实施例13步骤(3)中的化合物E-1。产率82％：
实施例23
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-23所示的结构：
式C-23所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-11所示的化合物代替实施例13步骤(3)中的化合物E-1。产率85％：
实施例24
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-24所示的结构：
式C-24所示9,10-二氢吖啶衍生物的制备步骤与实施例13中提供的C-13所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例13步骤(3)中的化合物E-1。产率83％：
实施例25
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-25所示的结构：
式C-25所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-25所示9,10-二氢吖啶衍生物的制备方法具体包括以下步骤：
(1)合成中间体1-1
氮气保护下，1L的三口烧瓶中，加入19.5g(100mmol)9(10H)-吖啶酮(式A-1所示化合物)，700mL的四氢呋喃，-20℃下加入110mL(1M)苯基溴化镁(式B-1所示化合物)溶液，室温反应8小时后，加氯化铵水溶液淬灭反应，用二氯甲烷萃取三次后，旋蒸除去溶剂，过硅胶柱得到24g固体中间体1-1(产率：88％)；
(2)合成中间体2-3
氮气保护下，2L的三口烧瓶中，加入22.0g(80mmol)中间体1-1，35g(160mmol)式D-3所示化合物，1000mL的二氯甲烷，逐滴加入1.8mL(0.9M)伊顿试剂，室温反应30分钟后，加入碳酸氢钠溶液淬灭反应，用甲苯萃取三次后，旋蒸除去溶剂，过硅胶柱得到12.8g固体中间体2-3(产率：34％)；
(3)合成9,10-二氢吖啶衍生物C-13
氮气保护下，加入9.5g中间体2-3(20mmol)，0.13g醋酸钯(0.6mmol)，0.45g三叔丁基膦(2.2mmol)，6.0g式E-1所示的化合物(22mmol)，5.7g叔丁醇钠，甲苯300mL，110℃反应12小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到11.3g固体化合物C-25(产率85％)。
元素分析：(C50H35NO)理论值：C,90.19；H,5.30；N,2.10；O,2.40；实测值：C,90.13；H,5.33；N,2.15；O,2.43，HRMS(ESI)m/z(M+)：理论值：665.2719；实测值：665.2707。
实施例26
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-26所示的结构：
式C-26所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-2所示的化合物代替实施例25步骤(3)中的化合物E-1，产率81％：
实施例27
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-27所示的结构：
式C-27所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-3所示的化合物代替实施例25步骤(3)中的化合物E-1，产率84％：
实施例28
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-28所示的结构：
式C-28所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例25步骤(3)中的化合物E-1，产率85％：
实施例29
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-29所示的结构：
式C-29所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-5所示的化合物代替实施例25步骤(3)中的化合物E-1，产率86％：
实施例30
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-30所示的结构：
式C-30所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-6所示的化合物代替实施例25步骤(3)中的化合物E-1，产率82％：
实施例31
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-31所示的结构：
式C-31所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-7所示的化合物代替实施例25步骤(3)中的化合物E-1。产率85％：
实施例32
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-32所示的结构：
式C-32所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-8所示的化合物代替实施例25步骤(3)中的化合物E-1。产率84％：
实施例33
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-33所示的结构：
式C-33所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-9所示的化合物代替实施例25步骤(3)中的化合物E-1。产率84％：
实施例34
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-34所示的结构：
式C-34所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-10所示的化合物代替实施例25步骤(3)中的化合物E-1。产率82％：
实施例35
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-35所示的结构：
式C-35所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-11所示的化合物代替实施例25步骤(3)中的化合物E-1。产率83％：
实施例36
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-36所示的结构：
式C-36所示9,10-二氢吖啶衍生物的制备步骤与实施例25中提供的C-25所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例25步骤(3)中的化合物E-1。产率84％：
实施例37
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-49所示的结构：
式C-49所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-49所示9,10-二氢吖啶衍生物的制备方法具体包括以下步骤：
(1)合成中间体5-1
氮气保护下，加入19.5g(100mmol)9(10H)-吖啶酮(式A-1所示化合物)，0.65g醋酸钯(3mmol)，2.25g三叔丁基膦(11.0mmol)，30.0g式E-1所示化合物(110mmol)，28.5g叔丁醇钠，甲苯100mL，110℃反应12小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到33.7g固体中间体5-1(产率87％)；
(2)合成中间体6-1
氮气保护下，加入31g(80mmol)中间体5-1，800mL的四氢呋喃，-20℃下加入88mL(1M)苯基溴化镁(式B-1所示化合物)溶液，室温反应8小时后，加氯化铵水溶液淬灭反应，用二氯甲烷萃取三次后，旋蒸除去溶剂，过硅胶柱得到29.1g固体中间体6-1(产率：78％)；
(3)合成9,10-二氢吖啶衍生物C-49
氮气保护下，加入23.5g(50mmol)中间体6-1，1000mL的四氢呋喃，19g(150mmol)三苯基膦，10g(60mmol)咔唑(式D-4所示化合物)，10.5g(60mmol)DEAD(偶氮二甲酸二乙酯)，室温反应12小时后，用二氯甲烷萃取三次后，旋蒸除去溶剂，过硅胶柱得到20.1g固体化合物化合物C-49(产率：66％)。
元素分析：(C46H34N2)理论值：C,89.87；H,5.57；N,4.56；实测值：C,89.91；H,5.59；N,4.51；HRMS(ESI)m/z(M+)：理论值：614.2722；实测值：614.2731。
实施例38
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-50所示的结构：
式C-50所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-2所示的化合物代替实施例37步骤(3)中的化合物E-1，产率85％：
实施例39
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-51所示的结构：
式C-51所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-3所示的化合物代替实施例37步骤(3)中的化合物E-1，产率78％：
实施例40
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-52所示的结构：
式C-52所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例37步骤(3)中的化合物E-1，产率85％：
实施例41
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-53所示的结构：
式C-53所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-5所示的化合物代替实施例37步骤(3)中的化合物E-1，产率82％：
实施例42
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-54所示的结构：
式C-54所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-6所示的化合物代替实施例37步骤(3)中的化合物E-1，产率84％：
实施例43
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-55所示的结构：
式C-55所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-7所示的化合物代替实施例37步骤(3)中的化合物E-1。产率81％：
实施例44
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-56所示的结构：
式C-56所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-8所示的化合物代替实施例37步骤(3)中的化合物E-1。产率84％：
实施例45
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-57所示的结构：
式C-57所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-9所示的化合物代替实施例37步骤(3)中的化合物E-1。产率85％：
实施例46
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-58所示的结构：
式C-58所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-10所示的化合物代替实施例37步骤(3)中的化合物E-1。产率82％：
实施例47
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-59所示的结构：
式C-59所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-11所示的化合物代替实施例37步骤(3)中的化合物E-1。产率83％：
实施例48
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-60所示的结构：
式C-60所示9,10-二氢吖啶衍生物的制备步骤与实施例37中提供的C-49所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例37步骤(3)中的化合物E-1。产率85％：
实施例49
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-61所示的结构：
式C-61所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-61所示9,10-二氢吖啶衍生物的制备方法具体包括以下步骤：
(1)合成中间体1-1
氮气保护下，1L的三口烧瓶中，加入19.5g(100mmol)9(10H)-吖啶酮(式A-1所示化合物)，700mL的四氢呋喃，-20℃下加入110mL(1M)苯基溴化镁(式B-1所示化合物)溶液，室温反应8小时后，加氯化铵水溶液淬灭反应，用二氯甲烷萃取三次后，旋蒸除去溶剂，过硅胶柱得到24g固体中间体1-1(产率：88％)；
(2)合成中间体2-4
氮气保护下，加入22.0g(80mmol)中间体1-1，20g(80mmol)9-苯基咔唑(式D-5所示化合物)，800mL的二氯甲烷，逐滴加入11.5mL(80mmol)三氟化硼乙醚溶液，室温反应5小时后，加入水淬灭反应，用甲苯萃取三次后，旋蒸除去溶剂，过硅胶柱得到33.3g固体中间体2-4(产率：85％)；
(3)合成9,10-二氢吖啶衍生物C-61
氮气保护下，加入10.0g中间体2-4(20mmol)，0.13g醋酸钯(0.6mmol)，0.45g三叔丁基膦(2.2mmol)，6.0g式E-1所示化合物(22mmol)，5.7g叔丁醇钠，甲苯300mL，110℃反应12小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到11.5g固体化合物C-61(产率84％)。
元素分析：(C52H38N2)理论值：C,90.40；H,5.54；N,4.05；实测值：C,90.43；H,5.51；N,4.03；HRMS(ESI)m/z(M+)：理论值：690.3035；实测值：690.3017。
实施例50
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-62所示的结构：
式C-62所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-2所示的化合物代替实施例49步骤(3)中的化合物E-1，产率82％：
实施例51
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-63所示的结构：
式C-51所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-63所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-3所示的化合物代替实施例49步骤(3)中的化合物E-1，产率80％：
实施例52
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-64所示的结构：
式C-64所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例49步骤(3)中的化合物E-1，产率81％：
实施例53
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-65所示的结构：
式C-65所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-5所示的化合物代替实施例49步骤(3)中的化合物E-1，产率85％：
实施例54
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-66所示的结构：
式C-66所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-6所示的化合物代替实施例49步骤(3)中的化合物E-1，产率83％：
实施例55
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-67所示的结构：
式C-67所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-7所示的化合物代替实施例49步骤(3)中的化合物E-1。产率82％：
实施例56
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-68所示的结构：
式C-68所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-8所示的化合物代替实施例49步骤(3)中的化合物E-1。产率85％：
实施例57
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-69所示的结构：
式C-69所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-9所示的化合物代替实施例49步骤(3)中的化合物E-1。产率83％：
实施例58
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-70所示的结构：
式C-70所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-10所示的化合物代替实施例49步骤(3)中的化合物E-1。产率86％：
实施例59
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-71所示的结构：
式C-71所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-11所示的化合物代替实施例49步骤(3)中的化合物E-1。产率82％：
实施例60
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-72所示的结构：
式C-72所示9,10-二氢吖啶衍生物的制备步骤与实施例49中提供的C-61所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例49步骤(3)中的化合物E-1。产率81％：
实施例61
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-74所示的结构：
式C-74所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-74所示9,10-二氢吖啶衍生物的制备方法具体包括以下步骤：
(1)合成中间体3-1
氮气保护下，加入24.6g(100mmol)式F-1所示化合物，四氢呋喃500mL，-78℃情况下逐滴加入63mL正丁基锂(1.6M)，低温反应30分钟，升温至30℃反应3小时，再次降温至-78℃，加入500mL9(10H)-吖啶酮(式A-1所示化合物)溶液(0.2M，9.5g(100mmol))，缓慢升温至30℃，反应15小时后加入氯化铵水溶液淬灭反应，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到20.3g固体中间体3-1(产率56％)；
(2)合成中间体3-1’
氮气保护下，加入14.5g(40mmol)中间体3-1，5.0g(48mmol)三乙胺，400mL的二氯甲烷，-20℃下加入13.5g(48mmol)三氟甲磺酸酐，室温反应3小时后，用甲苯萃取三次后，旋蒸除去溶剂，甲醇洗涤三次，得17g中间体3-1’(产率：87％)；
(3)合成中间体4-1
氮气保护下，加入14.8g(30mmol)中间体3-1’，3.7g(30mmol)苯基硼酸(式G-1所示化合物)，70g(33mmol)磷酸钾，1.7g(1.5mmol)四三苯基膦钯，水50mL，1,4-二氧六环300mL，120℃反应8小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到10.3g固体中间体4-1(产率81％)
(4)合成9,10-二氢吖啶衍生物C-74
氮气保护下，加入8.5g中间体4-1(20mmol)，0.13g醋酸钯(0.6mmol)，0.45g三叔丁基膦(2.2mmol)，6.0g 式E-1所示化合物(22mmol)，5.7g叔丁醇钠，甲苯300mL，110℃反应12小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到10.3g固体化合物C-74(产率84％)。
元素分析：(C46H33NO)理论值：C,89.73；H,5.40；N,2.27；O,2.60；实测值：C,89.79；H,5.37；N,2.30；O,2.57；HRMS(ESI)m/z(M+)：理论值：615.2562；实测值：615.2577。
实施例62
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-73所示的结构：
式C-73所示9,10-二氢吖啶衍生物的制备步骤与实施例61中提供的C-74所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例61步骤(4)中的化合物E-1，产率81％：
实施例63
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-75所示的结构：
式C-75所示9,10-二氢吖啶衍生物的制备步骤与实施例61中提供的C-74所示9,10-二氢吖啶衍生物的制备 步骤的区别仅在于：
以式E-11所示的化合物代替实施例61步骤(4)中的化合物E-1。产率82％：
实施例64
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-76所示的结构：
式C-76所示9,10-二氢吖啶衍生物的制备步骤与实施例61中提供的C-74所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例61步骤(4)中的化合物E-1。产率84％：
实施例65
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-78所示的结构：
式C-78所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-78所示9,10-二氢吖啶衍生物的制备步骤与实施例61中提供的C-74所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：以式F-2所示的化合物代替实施例61步骤(1)中的化合物F-1。
元素分析：(C46H33NS)理论值：C,87.44；H,5.26；N,2.22；S,5.07；实测值：C,87.39；H,5.24；N,2.27；S,5.11； HRMS(ESI)m/z(M+)：理论值：631.2334；实测值：631.2316。
实施例66
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-77所示的结构：
式C-77所示9,10-二氢吖啶衍生物的制备步骤与实施例65中提供的C-78所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例65中的化合物E-1，产率85％：
实施例67
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-79所示的结构：
式C-79所示9,10-二氢吖啶衍生物的制备步骤与实施例65中提供的C-78所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-11所示的化合物代替实施例65中的化合物E-1。产率82％：
实施例68
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-80所示的结构：
式C-80所示9,10-二氢吖啶衍生物的制备步骤与实施例65中提供的C-78所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例65中的化合物E-1。产率83％：
实施例69
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-82所示的结构：
式C-82所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-82所示9,10-二氢吖啶衍生物的制备步骤与实施例61中提供的C-74所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：以式F-3所示的化合物代替实施例61步骤(1)中的化合物F-1。
元素分析：(C49H39N)理论值：C,91.69；H,6.12；N,2.18；实测值：C,91.63；H,6.15；N,2.17；HRMS(ESI) m/z(M+)：理论值：641.3083；实测值：641.3095。
实施例70
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-81所示的结构：
式C-81所示9,10-二氢吖啶衍生物的制备步骤与实施例69中提供的C-82所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-4所示的化合物代替实施例69中的化合物E-1，产率81％：
实施例71
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-83所示的结构：
式C-83所示9,10-二氢吖啶衍生物的制备步骤与实施例69中提供的C-82所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-11所示的化合物代替实施例69中的化合物E-1。产率82％：
实施例72
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-84所示的结构：
式C-84所示9,10-二氢吖啶衍生物的制备步骤与实施例69中提供的C-82所示9,10-二氢吖啶衍生物的制备步骤的区别仅在于：
以式E-12所示的化合物代替实施例69中的化合物E-1。产率78％：
实施例73
本实施例提供一种9,10-二氢吖啶衍生物，具有下述式C-89所示的结构：
式C-89所示9,10-二氢吖啶衍生物的合成路径如下所示：
式C-89所示9,10-二氢吖啶衍生物的制备方法具体包括以下步骤：
(1)合成中间体3-4
氮气保护下，加入16.8g(100mmol)式F-4所示的化合物，四氢呋喃500mL，-78℃情况下逐滴加入63mL正丁基锂(1.6M)，低温反应30分钟，升温至30℃反应3小时，再次降温至-78℃，加入500mL 9(10H)-吖啶酮(式A-1所示化合物)溶液(0.2M，9.5g(100mmol))，缓慢升温至30℃，反应15小时后加入氯化铵水溶液淬灭反应，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到17.3g固体中间体3-4(产率47％)；
(2)合成中间体3-4’
氮气保护下，加入14.5g(40mmol)中间体3-4，5.0g(48mmol)三乙胺，400mL的二氯甲烷，-20℃下加入13.5g(48mmol)三氟甲磺酸酐，室温反应3小时后，用甲苯萃取三次后，旋蒸除去溶剂，甲醇洗涤三次，得17g中间体3-4’(产率：87％)；
(3)合成中间体4-4
氮气保护下，加入14.8g(30mmol)中间体3-4’，5.2g(30mmol)化合物G-2，70g(33mmol)磷酸钾，1.7g(1.5mmol)四三苯基膦钯，水50mL，1,4-二氧六环300mL，120℃反应8小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到11.1g固体中间体4-4(产率77％)；
(4)合成9,10-二氢吖啶衍生物C-89
氮气保护下，加入9.5g中间体4-4(20mmol)，0.13g醋酸钯(0.6mmol)，0.45g三叔丁基膦(2.2mmol)，7.1g式E-13所示的化合物(22mmol)，5.7g叔丁醇钠，甲苯300mL，110℃反应12小时，冷却至室温后，氯仿萃取，旋蒸除去溶剂，过硅胶柱得到12.5g固体化合物C-89(产率87％)。
元素分析：(C53H36N2O)理论值：C,88.80；H,5.06；N,3.91；O,2.23；实测值：C,88.77；H,5.09；N,3.87；O,2.24；HRMS(ESI)m/z(M+)：理论值：716.2828；实测值：716.2831。
实施例74
本实施例提供一种有机电致发光器件，如图1所示，包括从下向上依次层叠设置的阳极1、空穴注入层2、空穴传输层3、发光层4、电子传输层5、电子注入层6和阴极7。
有机电致发光器件中阳极选用ITO材料；阴极7选用金属Al；
空穴注入层2材料选用HAT(CN)6，HAT(CN)6具有如下所示化学结构：
空穴注入层3材料选用式C-2所示结构的9,10-二氢吖啶衍生物：
发光层4以主体材料RH和客体材料RD共掺杂形成，主体材料RH和客体材料RD掺杂的质量比为100:5：
电子传输层5材料选用如下所述结构的化合物：
电子注入层6材料由下述所示结构的化合物与电子注入材料LiF掺杂形成：
有机致电发光器件形成如下具体结构：ITO/空穴注入层(HIL)/空穴传输层(HTL，式C-2所示化合物)/有机发光层(RH：RD的质量比为100:5)/电子传输层(ETL)/电子注入层(EIL/LiF)/阴极(Al)。
上述的有机电致发光器件，由于空穴传输层选择式C-2所示的9,10-二氢吖啶衍生物，C-2所示9,10-二氢吖啶衍生物与NPB比较的能级图如图2所示：其中，C-2所示化合物中的
是具有强供电子性质的基团，二氢吖啶基团中的氮原子在电场作用下形成铵离子自由基，有较好的空穴迁移性，能够保证空穴在传输层的有效传输；同时，式C-2所示化合物在Ar
2基团位置引入苯基取代的咔唑基，利用咔唑基的供电子性质进一步提高其空穴传输性能，式C-2所示的9,10-二氢吖啶衍生物具有适宜的HOMO能级，能够减小空穴由阳极向发光层注入所需克服的势垒，增加空穴的有效注入，有利于降低器件的工作电压，提高器件的发光效率。
式C-2所示的结构中，具有高三线态能级的二氢吖啶基团与二苯并呋喃基团通过σ键相连接，使C-2所示的结构的三线态能级提高，以σ键引入修饰基团，对C-2所示的9,10-二氢吖啶衍生物的三线态能级(T
1)进行调节，C-2所示的9,10-二氢吖啶衍生物具有高的三线态能级，有利于OLED器件的电子和空穴复合的激子限制在发光层的发光区域内，避免发光层向相邻空穴传输层的能量回传；同时，上述连接方式的9,10-二氢吖啶衍生物的LUMO能级提高，增加了对电子的阻挡效果，有效地使电子滞留在发光层内，从而提高电子和空穴的复合几率，使器件 的发光效率得到提高。
式C-2所示的9,10-二氢吖啶衍生物，其玻璃态转变温度高、热稳定性和形态学稳定性高，成膜性能优异，能够避免在成膜过程中或成膜后在OLED器件的工作过程中由于发热形成结晶，提升了器件的使用性能和使用寿命。
作为可替代的实施方式，发光层的客体发光材料还可以选择式(C-1)、(C-3)～式(C-109)所示的任一9,10-二氢吖啶衍生物。
作为可替代的实施方式，发光层的客体发光材料还可以选择具有通式(I)所示化学结构的任一其他化合物。
实施例75
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例76
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例77
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例78
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例79
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例80
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例81
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例82
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
实施例83
本实施例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层材料选用下述所示结构的9,10-二氢吖啶衍生物：
对比例1
本对比例提供一种有机电致发光器件，与实施例74中提供有机电致发光器件的区别仅在于：空穴传输层选用化合物NPB：
测试例1
1、测定玻璃态转变温度
使用差示扫描量热仪(DSC)对本专利材料进行玻璃态转变温度进行测试，测试范围室温至400℃，升温速率10℃/min，氮气氛围下。
2、分别在298K以及77K温度下测定9,10-二氢吖啶衍生物的甲苯溶液(物质的量浓度：10
-5mol/L)的荧光以及磷光光谱，并根据计算公式E＝1240/λ计算出相应的三线态(T
1)能级。
3、使用电化学工作站利用循环伏安法(CV)对本专利材料的HOMO能级进行测试，以铂丝(Pt)为对电极，银/氯化银(Ag/AgCl)为参比电极。在氮气氛围下，在含有0.1M四丁基六氟磷酸铵的二氯甲烷电解液中以100mV/s的扫描速率进行测试，以二茂铁进行电位标定，设定二茂铁的电位在真空状态下的绝对能级为-4.8eV：
4、材料分子的LUMO能级利用材料的带隙和HOMO进行计算：
表1
测试例2
器件的电流、电压、亮度、发光光谱等特性采用PR 650光谱扫描亮度计和Keithley K 2400数字源表系统同步测试。对实施例67-77和对比例中的所提供的有机电致发光器件进行测试，结果如表2所示：
表2
对比实施例74-83和对比例1中的所提供的有机电致发光器件进行测试，结果如表2所示，相比于对比例1中的器件，实施例74-83中所提供的OLED器件的工作电压降低、电流效率提高，说明以本发明中提供的9,10-二氢吖啶作为OLED器件的空穴传输材料，能够显著提高器件的发光效率、降低器件的工作电压，提升OLED的性能。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。
Claims (11)
- 一种9,10-二氢吖啶衍生物，其特征在于，具有如式(I)所示的结构：
其中，T选自O、S、C(R 3)(R 4)或N(R 5)；R 1-R 5彼此独立地选自氢、氘、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基；R 6-R 7彼此独立地选自氢、氘、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基、C3-C30的取代或未取代的杂芳基，或是与相邻苯基共有一边形成稠环的环A；所述环A选自苯环、3元到7元的饱和或部分不饱和的碳环、3元到7元的饱和或部分不饱和的杂环、C6-C60的稠环芳基或C3-C30的稠环杂芳基；Ar 1、Ar 2彼此独立地选自氢、氘、卤素、氰基、C1-C30的取代或未取代的烷基、C2-C30的取代或未取代的烯基、C2-C30的取代或未取代的炔基、C3-C30的取代或未取代的环烷基、C1-C30的取代或未取代的烷氧基、C1-C30的取代或未取代的硅烷基、C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基；所述杂芳基、杂环和稠环杂芳基彼此独立地具有至少一个独立地选自氮、硫、氧、磷、硼或硅的杂原子。 - 根据权利要求1所述的9,10-二氢吖啶衍生物，其特征在于，所述Ar 1、Ar 2彼此独立地选自C6-C60的取代或未取代的芳基，或者C3-C30的取代或未取代的杂芳基。
- 根据权利要求1或2所述的9,10-二氢吖啶衍生物，其特征在于，所述Ar 2选自下述任一基团：
其中，p为0-5的整数，q 1为0-6的整数，q 2为0-4的整数，q 3为0-4的整数，表示选自单键或双键；所述
中，所述p、q 2和q 3不同时为0；
X选自O、S、C(R 3)(R 4)或N(R 5)，Y彼此独立地选自碳或氮；Ar 3、Ar 4彼此独立地选自氢、未取代的或1-4个R 1a取代的下述基团：苯基、联苯基、三联苯基、茚基、芴基、萘基、薁基、戊搭烯基、庚搭烯基、辛搭烯基、苯并二茚基、苊烯基、非那烯基、菲基、蒽基、三茚基、荧蒽基、醋菲基、醋蒽烯基、9,10-苯并菲基、芘基、1,2-苯并菲基、丁苯基、丁省基、七曜烯基、苉基、苝基、五苯基、并五苯基、亚四苯基、胆蒽基、螺烯基、己芬基、玉红省基、晕苯基、联三萘基、庚芬基、皮蒽基、卵苯基、心环烯基、蒽嵌蒽基、三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、氧杂蒽基、噁唑啉基、二苯并呋喃基、迫呫吨并呫吨基、噻吩基、噻吨基、噻蒽基、吩噁噻基、硫茚基、异硫茚基、并噻吩基、萘并噻吩基、二苯并噻吩基、吡咯基、吡唑基、碲唑基、硒唑基、噻唑基、异噻唑基、噁唑基、呋咱基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、吲嗪基、吲哚基、异吲哚基、吲唑基、嘌呤基、喹嗪基、异喹啉基、咔唑基、吲哚并咔唑基、咪唑基、萘啶基、酞嗪基、喹唑啉基、苯二氮卓基、喹喔啉基、噌啉基、喹啉基、蝶啶基、菲啶基、吖啶基、呸啶基、菲咯啉基、吩嗪基、咔啉基、吩碲嗪基、吩硒嗪基、吩噻嗪基、吩噁嗪基、三苯二噻嗪基、三苯二噁嗪基、蒽吖嗪基、苯并噻唑基、苯并咪唑基、苯并噁唑基、苯并异噁唑基、苯并异噻唑基，或者由上述基团形成稠环基、螺环基或联环基；R 1a为C 1-C 6的烷基。 - 根据权利要求1或2所述的9,10-二氢吖啶衍生物，其特征在于，所述Ar 1选自氢或下述任一基团：苯基、联苯基、三联苯基、茚基、芴基、萘基、薁基、戊搭烯基、庚搭烯基、辛搭烯基、苯并二茚基、苊烯基、非那烯基、菲基、蒽基、三茚基、荧蒽基、醋菲基、醋蒽烯基、9,10-苯并菲基、 芘基、1,2-苯并菲基、丁苯基、丁省基、七曜烯基、苉基、苝基、五苯基、并五苯基、亚四苯基、胆蒽基、螺烯基、己芬基、玉红省基、晕苯基、联三萘基、庚芬基、皮蒽基、卵苯基、心环烯基、蒽嵌蒽基、三聚茚基、呋喃基、苯并呋喃基、异苯并呋喃基、氧杂蒽基、噁唑啉基、二苯并呋喃基、迫呫吨并呫吨基、噻吩基、噻吨基、噻蒽基、吩噁噻基、硫茚基、异硫茚基、并噻吩基、萘并噻吩基、二苯并噻吩基、吡咯基、吡唑基、碲唑基、硒唑基、噻唑基、异噻唑基、噁唑基、呋咱基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、吲嗪基、吲哚基、异吲哚基、吲唑基、嘌呤基、喹嗪基、异喹啉基、咔唑基、吲哚并咔唑基、咪唑基、萘啶基、酞嗪基、喹唑啉基、苯二氮卓基、喹喔啉基、噌啉基、喹啉基、蝶啶基、菲啶基、吖啶基、呸啶基、菲咯啉基、吩嗪基、咔啉基、吩碲嗪基、吩硒嗪基、吩噻嗪基、吩噁嗪基、三苯二噻嗪基、三苯二噁嗪基、蒽吖嗪基、苯并噻唑基、苯并咪唑基、苯并噁唑基、苯并异噁唑基、苯并异噻唑基，或者由上述基团形成稠环基、螺环基联环基。
- 根据权利要求1-4任一项所述的9,10-二氢吖啶衍生物，其特征在于，所述R 1-R 5彼此独立地选自氢、C 1-C 6的烷基、苯基、联苯基、萘基、蒽基、菲基、芴基、芘基、苝基、碗烯基、三亚苯基、荧蒽基、吡啶基、嘧啶基、吡喃基、噻喃基、吡嗪基、哒嗪基、三嗪基、酞嗪基、吩嗪基、噻吩基、呋喃基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、咔唑基、吲哚并咔唑基、三芳香胺基、二芳香胺基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、喹啉基、菲罗啉基或咔啉基；所述R 6-R 7彼此独立地选自氢、C 1-C 6的烷基、苯基、联苯基、萘基、蒽基、菲基、芴基、芘基、苝基、碗烯基、三亚苯基、荧蒽基、吡啶基、嘧啶基、吡喃基、噻喃基、吡嗪基、哒嗪基、三嗪基、酞嗪基、吩嗪基、噻吩基、呋喃基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、咔唑基、吲哚并咔唑基、三芳香胺基、二芳香胺基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、喹啉基、菲罗啉基、咔啉基或是与相邻苯基共有一边形成稠环的环A；所述环A选自所述环B选自苯环、联苯环、萘环、蒽环、菲环、芴环、芘环、苝环、碗烯环、三亚苯环、荧蒽环、吡啶环、嘧啶环、吡喃环、噻喃环、吡嗪环、哒嗪环、三嗪环、酞嗪环、吩嗪环、噻吩环、呋喃环、吡咯环、吡唑环、咪唑环、噁唑环、噻唑环、吲哚环、咔唑环、吲哚并咔唑环、三芳香胺环、二芳香胺环、菲啶环、吖啶环、呸啶环、蝶啶环、喹唑啉环、喹喔啉环、噌啉环、喹啉环、菲罗啉环或咔啉环。
- 根据权利要求1-5任一项所述的9,10-二氢吖啶衍生物，其特征在于，具有下述任一所示的分 子结构：
- 一种如权利要求1-6任一项所述9,10-二氢吖啶衍生物的制备方法，其特征在于，所述式(I)所示化合物的合成步骤如下所示：以式(A)所示的化合物和式(B)所示的化合物为起始原料，经亲核加成反应得到中间体1；中间体1与式(D)所示的化合物在伊顿试剂存在下经脱水缩合反应得到中间体2；中间体2与式(E)所示的化合物在催化剂存在下经偶联反应得到式(I)所示的化合物；所述式(I)所示化合物的合成路径如下所示：
或者，以式(A)所示的化合物和式(E)所示的化合物为起始原料，经亲核加成反应得到中间体3；中间体3经亲核取代反应生成中间体3’，中间体3’与式(G)所示的化合物经铃木反应生成中间体4，中间体4与式(E)所示的化合物在催化剂存在下经偶联反应得到式(I)所示的化合物；所述式(I)所示化合物的合成路径如下所示：
其中，W选自氢、氟、氯、溴或碘，-OTf为三氟甲磺酸酯。 - 一种权利要求1-6任一项所述的9,10-二氢吖啶衍生物作为空穴传输材料的应用。
- 一种有机电致发光器件，其特征在于，所述有机电致发光器件的至少有一个功能层中含有权利要求1-6任一项所述的9,10-二氢吖啶衍生物。
- 根据权利要求9所述的有机电致发光器件，其特征在于，所述功能层为空穴传输层和/或电子阻挡层。
- 根据权利要求9所述的有机电致发光器件，其特征在于，所述功能层为发光层。
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