CN113735878B - Organic compound and electroluminescent application thereof - Google Patents
Organic compound and electroluminescent application thereof Download PDFInfo
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- CN113735878B CN113735878B CN202111243728.3A CN202111243728A CN113735878B CN 113735878 B CN113735878 B CN 113735878B CN 202111243728 A CN202111243728 A CN 202111243728A CN 113735878 B CN113735878 B CN 113735878B
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 13
- -1 spirobifluorenyl group Chemical group 0.000 claims description 38
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 20
- 229910052805 deuterium Inorganic materials 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 claims description 5
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- 125000001041 indolyl group Chemical group 0.000 claims description 5
- 125000000168 pyrrolyl group Chemical group 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
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 4
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 125000002883 imidazolyl group Chemical group 0.000 claims description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000000842 isoxazolyl group Chemical group 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000001715 oxadiazolyl group Chemical group 0.000 claims description 4
- 125000002971 oxazolyl group Chemical group 0.000 claims description 4
- 125000005561 phenanthryl group Chemical group 0.000 claims description 4
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 4
- 125000001725 pyrenyl group Chemical group 0.000 claims description 4
- 125000004076 pyridyl group Chemical group 0.000 claims description 4
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 4
- 125000001113 thiadiazolyl group Chemical group 0.000 claims description 4
- 125000000335 thiazolyl group Chemical group 0.000 claims description 4
- 125000001544 thienyl group Chemical group 0.000 claims description 4
- 125000004306 triazinyl group Chemical group 0.000 claims description 4
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims description 3
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 3
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 3
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 3
- 125000001422 pyrrolinyl group Chemical group 0.000 claims description 3
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 125000005580 triphenylene group Chemical group 0.000 claims description 2
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000005509 dibenzothiophenyl group Chemical group 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 9
- 239000007924 injection Substances 0.000 abstract description 9
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 9
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 67
- 150000001875 compounds Chemical class 0.000 description 54
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 239000000203 mixture Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- 239000000543 intermediate Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 239000012043 crude product Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 230000005525 hole transport Effects 0.000 description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000010898 silica gel chromatography Methods 0.000 description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 238000004949 mass spectrometry Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 238000004440 column chromatography Methods 0.000 description 5
- 125000001072 heteroaryl group Chemical group 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 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
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 101710110702 Probable chorismate pyruvate-lyase 1 Proteins 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical class C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 2
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical group [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006757 (C2-C30) heterocyclic group Chemical group 0.000 description 1
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- HCCNHYWZYYIOFM-UHFFFAOYSA-N 3h-benzo[e]benzimidazole Chemical class C1=CC=C2C(N=CN3)=C3C=CC2=C1 HCCNHYWZYYIOFM-UHFFFAOYSA-N 0.000 description 1
- 229910016036 BaF 2 Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Chemical class C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 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
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 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
- 239000011787 zinc oxide Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/16—Electron transporting layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
- H10K85/6565—Oxadiazole compounds
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- 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
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
- H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention provides an organic compound, which has a structure shown as a formula (I). The invention provides an electron transport material with a S and O-like structure, which has proper HOMO and lower LUMO values and can improve the electron injection and transport capacity; meanwhile, the organic compound has higher triplet state energy level, high electron mobility, excellent thermal stability and film stability, and is used for an organic light-emitting device and beneficial to improving the light-emitting efficiency.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and relates to an organic compound and application thereof.
Background
The electron transport material used in the conventional electroluminescent device is 8-hydroxyquinoline aluminum (Alq 3), but Alq3 has relatively low electron mobility (about l 0-6 cm) 2 Vs) such that electron transport and hole transport of the device are unbalanced. With the commercialization and practicability of electroluminescent devices, ETL materials with higher transmission efficiency and better service performance are desired, and in this field, researchers have made a lot of research.
Patent number WO 2007/01170al and chinese patent publication number CN101003508A of LG chemistry disclose a series of derivatives of naphthoimidazole and pyrene, respectively, which are used as electron transport and injection materials in electroluminescent devices, improving the luminous efficiency of the devices.
In U.S. patent nos. US2006/0204784 and US2007/0048545 by kodak corporation, organic electroluminescent devices are disclosed that are mixed electron transport materials that are doped with: (a) A first compound having a lowest LUMO level in the layer, (b) a second compound having a LUMO level higher than the first compound and a low turn-on voltage; a metal material having a work function of less than 4.2 eV. However, the electron transport material has a planar molecular structure, and has large intermolecular attraction, which is unfavorable for evaporation and application; in addition, the electron transport material has the defects of low mobility, poor energy level matching, poor thermal stability, short service life, doping property and the like, and limits the further development of OLED display devices.
Therefore, the design and development are stable and efficient, the high electron mobility and the high glass transition temperature can be achieved, and the electron transport material and/or the electron injection material which are effectively doped with the metal Yb or Liq can reduce the threshold voltage, improve the device efficiency and prolong the service life of the device, so that the method has important practical application value.
The existing electron transport materials such as bathophenanthroline (BPhen), bathocuproine (BCP) and tmpyreb, which are commonly used in the market, generally meet the market demands of organic electroluminescent panels, but the glass transition temperature of the electron transport materials is lower, generally lower than 85 ℃, and the generated joule heat can cause molecular degradation and change of molecular structure when the device is operated, so that the panel has lower efficiency and poorer thermal stability. Meanwhile, the molecular structure is very regular in symmetry and can be easily crystallized after a long time. Once the electron transport material is crystallized, the charge transition mechanism between molecules is different from the amorphous film mechanism which normally operates, so that the electron transport performance is reduced, the mobility of electrons and holes of the whole device is unbalanced, the exciton formation efficiency is greatly reduced, and the exciton formation is concentrated at the interface of the electron transport layer and the light emitting layer, so that the device efficiency and the service life are seriously reduced.
Accordingly, there is a need in the art to develop a greater variety of higher performance electron transport materials to meet the application requirements of OLED display devices.
Disclosure of Invention
In view of the above, the present invention is to provide an organic compound and an electroluminescent application thereof, wherein the organic compound has a suitable HOMO and a low LUMO value as an electron transport material, and can improve the electron injection and transport capability.
The invention provides an organic compound, which has a structure shown in a formula (I),
wherein X is S or O; y is S or O; and X and Y are different;
the R is 1 And R is R 2 Each independently selected from hydrogen, deuterium, cyano, substituted amino, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl; and R is 1 And R is R 2 Not both hydrogen or deuterium;
the substituents in the substituted C1-C20 alkyl, substituted amino, substituted C6-C40 aryl and substituted C2-C40 heteroaryl are each independently selected from one or more of deuterium, cyano, carbonyl, substituted amino, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C40 aryl and substituted and unsubstituted C2-C40 heterocyclyl.
The invention provides a display panel, which comprises an organic light-emitting device; the organic light emitting device includes an anode, a cathode, and at least one organic compound layer between the anode and the cathode; the organic compound layer includes at least one organic compound represented by formula (1).
The invention provides a display device which comprises the display panel.
Compared with the prior art, the invention provides the electron transport material with the spiro-like structure, wherein the organic compound is shown in the formula (I) and contains S and O, has proper HOMO and lower LUMO values, and can improve the electron injection and transport capacity; meanwhile, the organic compound has higher triplet state energy level, high electron mobility, excellent thermal stability and film stability, and is used for an organic light-emitting device and beneficial to improving the light-emitting efficiency.
Drawings
Fig. 1 is a schematic structural view of an organic light emitting device according to the present invention;
fig. 2 is a schematic diagram of a display device provided by the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides an organic compound, which has a structure shown in a formula (I):
wherein X is S or O; y is S or O; and X and Y are different;
the R is 1 And R is R 2 Each independently is hydrogen, deuterium, cyano, substituted amino, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C2-C40 heteroaryl, and R 1 And R is R 2 Not both hydrogen or deuterium; preferably hydrogen, deuterium, cyano, substituted amino, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, and R 1 And R is R 2 Not both hydrogen or deuterium; more preferably hydrogen, deuterium, cyano, substituted amino, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetrabiphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or substituted
A group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted isoxazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted pyrrolinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted anthronyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted pyrrolyl group, and R is 1 And R is R 2 Not both hydrogen or deuterium; more preferably hydrogen, deuterium, phenylamino, diphenylamino, phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, anthracenyl, triphenylenyl, pyrenyl, and +, ->
A group, fluorenyl, spirobifluorenyl, pyrrolyl, furanyl, thienyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, indolyl, benzofuranyl, benzimidazolyl, benzothienyl, quinolinyl, isoquinolinyl, quinoxalinyl,quinazolinyl, pyrrolinyl, carbazolyl, dibenzofuranyl, dibenzothienyl, anthronyl, fluoranthenyl, indenocarbazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, indolocarbazolyl, indolofuranyl, indolobenzthienyl, benzofuranpyrimidinyl, benzothiophenyl, a group formed by a combination of the above groups or a group formed by a fusion of the above groups, and R 1 And R is R 2 Not both hydrogen and deuterium.
The substituents in the substituted C1-C20 alkyl group, the substituted amino group, the substituted C6-C40 aryl group and the substituted C2-C40 heteroaryl group are each independently deuterium, cyano, carbonyl, substituted amino group, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C6-C40 aryl group, one or more of substituted and unsubstituted C2-C40 heterocyclic groups, preferably deuterium, cyano, carbonyl, substituted amino group, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C6-C30 aryl group, one or more of substituted and unsubstituted C2-C30 heterocyclic groups, more preferably deuterium, cyano, carbonyl, substituted amino group, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C6-C20 aryl group, one or more of substituted and unsubstituted C2-C40 heterocyclic groups, more preferably deuterium, cyano, carbonyl, C1-C10 alkyl group, substituted or unsubstituted C2-C20 aryl group, one or more of substituted and unsubstituted C20 heterocyclic groups, preferably one or more of deuterium, cyano, carbonyl, C1-C10 alkyl group, substituted and unsubstituted C2-C20 heterocyclic group, most preferably one or more of substituted and unsubstituted phenyl group, more of cyano, phenyl group, and one or more of substituted and unsubstituted phenyl group. Wherein the heteroatom in the heterocyclic group is preferably one or more of O, S and N.
According to the present invention, more preferably, the R 1 Or R is 2 Is hydrogen.
Further preferably, in the present invention, X may be O or S, Y may be O or S, and X and Y may be different elements. When X is S and Y is O, the organic compound is selected from one or more of the structures shown in the formulas (1) to (36):
when X is O and Y is S, the organic compound is selected from one or more of structures shown in formulas (37) to (72):
the invention provides an electron transport material with S and O-like structure, which has proper HOMO and lower LUMO values, and hetero atoms in five-membered heterocycle can increase the overlap of molecular orbitals among molecules to a certain extent due to small atomic radius and large electronegativity, thereby being beneficial to improving the capability of electron injection and transport; meanwhile, the organic compound has higher triplet state energy level, high electron mobility, excellent thermal stability and film stability, and is used for an organic light-emitting device and beneficial to improving the light-emitting efficiency.
Still preferably, the organic compound provided by the invention comprises a rigid planar structure and an electron-deficient planar group, wherein the rigid planar structure is favorable for improving the glass transition temperature of the compound, the tendency of the rigid planar structure and the electron-deficient planar group is favorable for stacking and electron coupling of molecules, and the electron mobility of the compound is improved, so that the compound is further used as an electron transport material for an organic electroluminescent device to improve the efficiency.
The organic compound provided by the invention is obtained by Suzuki coupling reaction of a compound shown in the formula (II) and a compound shown in the formula (III) and/or a compound shown in the formula (IV).
Wherein X is 1 And X is 2 Each independently is halogen or hydrogen, and not both hydrogen; further, X 1 And X is 2 Each independently is chlorine or hydrogen.
The invention also provides application of the organic compound shown in the formula (I) as an electron transport material.
The invention also provides an organic light-emitting device, which comprises the organic compound shown in the formula (I).
The invention also provides a display panel, which comprises an organic light-emitting device; the organic light emitting device includes an anode, a cathode, and at least one organic compound layer between the anode and the cathode; the organic compound layer includes at least one organic compound represented by the above formula (I).
In the display panel provided by the present invention, the anode material of the organic light emitting device may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof. The anode material may also be selected from metal oxides such as indium oxide, zinc oxide, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), and the like; the anode material may also be selected from conductive polymers such as polyaniline, polypyrrole, poly (3-methylthiophene), and the like. In addition, the anode material may be selected from materials other than the anode materials listed above that facilitate hole injection, and combinations thereof, including materials known to be suitable as anodes.
In the display panel provided by the present invention, the cathode material of the organic light emitting device may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, etc., and alloys thereof. The cathode material may also be selected from multi-layered metallic materials such as LiF/Al, liO 2 /Al、BaF 2 Al, etc. In addition to the cathode materials listed above, the cathode materials may also be materials that facilitate electron injection and combinations thereof, including materials known to be suitable as cathodes.
At least one organic compound layer is arranged between the anode and the cathode; according to the present invention, the organic compound layer preferably includes an electron transport layer; the electron transport layer preferably includes at least one compound represented by the above formula (I).
According to an embodiment of the display panel of the present invention, the organic compound layer in the organic light emitting device includes at least a light emitting layer and an electron transporting layer, and preferably further includes one or more of a hole injecting layer, a hole transporting layer, an electron blocking layer, a hole blocking layer, and an electron injecting layer.
The organic electroluminescent device may be fabricated according to methods known in the art, and will not be described in detail herein. In the present invention, the organic electroluminescent device may be fabricated as follows: an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer. The organic thin layer may be formed by a known film forming method such as vapor deposition, sputtering, spin coating, dipping, ion plating, and the like.
Specifically, referring to fig. 1, fig. 1 is a schematic structural diagram of an organic light emitting device provided by the present invention, which includes a substrate 1, an anode 2, a first hole transport layer 3, a second hole transport layer 4, a light emitting layer 5, a first electron transport layer 6, a second electron transport layer 7, a cathode 8, and a cap layer 9 that are sequentially stacked.
The invention also provides a display device which comprises the display panel; referring to fig. 2, fig. 2 is a schematic structural diagram of a display device provided by the present invention, wherein 20 is a display panel, and 30 is a display device. In the invention, the display device can be a mobile phone display screen, a computer display screen, a television display screen, a smart watch display screen, a smart car display screen, a VR or AR helmet display screen, display screens of various intelligent devices, and the like.
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is shown, however, only some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Intermediate Synthesis example
Synthesis of intermediate 1-2
In a three-necked flask, compound 1-1 (80 mmol), compound a (90 mmol), potassium carbonate (0.3 mol), tetrahydrofuran (250 mL), water (120 mL) and tetraphenylphosphine palladium (0.6 g) were sequentially added, and under the protection of nitrogen, the mixture was heated and refluxed for 12 hours, cooled, extracted with dichloromethane, concentrated, and the crude product was purified by column chromatography to obtain intermediate 1-2.
Synthesis of intermediates 1-3
In a three-necked flask, intermediate 1-2 (50 mmol) and dry tetrahydrofuran (120 mL) were sequentially added, cooled to-70℃under nitrogen protection, 3.0M n-butyllithium (20 mL) was slowly added, the reaction was completed dropwise for 1 hour, and then 70mL of tetrahydrofuran solution in which compound b (53 mmol) was dissolved was added. After the addition, slowly heating to room temperature, reacting for 3 hours, adding dichloromethane for extraction, concentrating, adding acetic acid (120 mL) and concentrated hydrochloric acid (3 mL), heating and refluxing for 8 hours, cooling, removing the solvent, using dichloromethane solvent for the crude product, washing with water, drying and concentrating the organic layer, and purifying the crude product by column chromatography to obtain the intermediate 1-3.
Synthesis of intermediate 2-2
In a three-necked flask, compound 2-1 (75 mmol), compound c (85 mmol), potassium carbonate (0.3 mol), tetrahydrofuran (250 mL), water (120 mL) and tetraphenylphosphine palladium (0.6 g) were sequentially added, and under the protection of nitrogen, the mixture was heated and refluxed for 12 hours, cooled, extracted with dichloromethane, concentrated, and the crude product was purified by column chromatography to obtain intermediate 2-2.
Synthesis of intermediate 2-3
In a three-necked flask, intermediate 2-2 (50 mmol) and dry tetrahydrofuran (120 mL) were sequentially added, cooled to-70℃under nitrogen protection, 3.0M n-butyllithium (20 mL) was slowly added, the reaction was completed dropwise for 1 hour, and then 70mL of a tetrahydrofuran solution in which compound d (55 mmol) was dissolved was added. After the addition, slowly heating to room temperature, reacting for 3 hours, adding dichloromethane for extraction, concentrating, adding acetic acid (120 mL) and concentrated hydrochloric acid (3 mL), heating and refluxing for 8 hours, cooling, removing the solvent, using dichloromethane solvent for the crude product, washing with water, drying and concentrating the organic layer, and purifying the crude product by column chromatography to obtain the intermediate 2-3.
Example 1: synthesis of Compound represented by the formula (7)
In a round-bottomed flask, intermediate 1-3 (4 mmol), compound e (6 mmol) and Pd (PPh) were added 3 ) 4 (0.3 mmol) was added to a mixture of toluene (180 mL)/ethanol (150 mL) and an aqueous solution of potassium carbonate (15 mmol) (10 mL), and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate was extracted with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the desired product of formula (7).
Characterization of the compound of formula (7): molecular formula C 40 H 21 N 3 O 2 S 2 ；
ESI-MS (M/z) [ M+1] is obtained by liquid phase mass spectrometry] + : theoretical 640.11 and test 639.95;
elemental analysis results: theoretical value: C75.10,H 3.31,N 6.57,O 5.00,S 10.02; test value: and C75.10,H 3.35,N 6.52,O 5.03,S 10.00.
Example 2: synthesis of Compound represented by the formula (11)
In a round-bottomed flask, intermediate 1-3 (4 mmol), compound f (6 mmol) and Pd (PPh) were added 3 ) 4 (0.3 mmol) was added to an aqueous solution of toluene (200 mL)/ethanol (150 mL) and potassium carbonate (15 mmol)In the mixture of (10 mL), the reaction was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate was extracted with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the desired product of formula (11).
Characterization of the compound of formula (11): molecular formula C 46 H 25 N 3 O 2 S 2 ；
ESI-MS (M/z) [ M+1] is obtained by liquid phase mass spectrometry] + : theoretical 716.14 and test 716.19;
elemental analysis results: theoretical value: C77.18,H 3.52,N 5.87,O 4.47,S 8.96; test value: and C77.15,H 3.55,N 5.90,O 4.44,S 8.89.
Example 3: synthesis of Compound represented by the formula (19)
In a round-bottomed flask, intermediate 1-3 (4 mmol), compound g (6 mmol) and Pd (PPh) were added 3 ) 4 (0.4 mmol) was added to a mixture of toluene (180 mL)/ethanol (150 mL) and an aqueous solution of potassium carbonate (15 mmol) (12 mL), and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate was extracted with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the desired product of formula (19).
Characterization of the compound of formula (19): molecular formula C 45 H 24 N 2 O 2 S 2 ；
ESI-MS (M/z) [ M+1] is obtained by liquid phase mass spectrometry] + : theoretical 689.13 and test 689.10;
elemental analysis results: theoretical value: C78.47,H 3.51,N 4.07,O 4.65,S 9.31; test value: and C78.50,H 3.49,N 4.06,O 4.63,S 9.33.
Example 4: synthesis of Compound represented by the formula (27)
In a round-bottomed flask, intermediate 1-3 (5 mmol), compound h (8 mmol) and Pd (PPh) were added 3 ) 4 (0.4 mmol) was added to a mixture of toluene (200 mL)/ethanol (150 mL) and an aqueous solution of potassium carbonate (15 mmol) (12 mL), and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate was extracted with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the desired product of formula (27).
Characterization of the compound of formula (27): molecular formula C 51 H 28 O 3 S 2 ；
ESI-MS (M/z) [ M+1] +: theoretical 753.15 and test 753.10;
elemental analysis results: theoretical value: C81.36,H 3.75,O 6.38,S 8.52; test value: and C81.30,H 3.80,O 6.35,S 8.54.
Example 5: synthesis of Compound represented by the formula (43)
In a round-bottomed flask, intermediate 2-3 (4 mmol), compound e (6 mmol) and Pd (PPh) were added 3 ) 4 (0.3 mmol) was added to a mixture of toluene (180 mL)/ethanol (150 mL) and an aqueous solution of potassium carbonate (15 mmol) (10 mL), and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate extracted with dichloromethane, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by column chromatography on silica gel to give the title compoundThe target product is a compound represented by formula (43).
Characterization of the compound of formula (43): molecular formula C 40 H 21 N 3 O 2 S 2 ；
ESI-MS (M/z) [ M+1] is obtained by liquid phase mass spectrometry] + : theoretical 640.11 and test 639.95;
elemental analysis results: theoretical value: C75.10,H 3.31,N 6.57,O 5.00,S 10.02; test value: and C75.08,H 3.34,N 6.56,O 5.04,S 9.98.
Example 6: synthesis of Compound represented by the formula (47)
In a round-bottomed flask, intermediate 2-3 (4 mmol), compound f (6 mmol) and Pd (PPh) were added 3 ) 4 (0.3 mmol) was added to a mixture of toluene (200 mL)/ethanol (150 mL) and an aqueous solution of potassium carbonate (15 mmol) (10 mL), and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate was extracted with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the desired product of formula (47).
Characterization of the compound of formula (47): molecular formula C 46 H 25 N 3 O 2 S 2 ；
ESI-MS (M/z) [ M+1] +: theoretical 716.14 and test 716.20;
elemental analysis results: theoretical value: C77.18,H 3.52,N 5.87,O 4.47,S 8.96; test value: and C77.15,H 3.58,N 5.84,O 4.45,S 8.88.
Example 7: synthesis of Compound represented by the formula (55)
In a round-bottomed flask, intermediate 2-3 (4 mmol), compound g (6 mmol) and Pd (PPh) were added 3 ) 4 (0.4 mmol) was added to a mixture of toluene (180 mL)/ethanol (150 mL) and an aqueous solution of potassium carbonate (15 mmol) (12 mL), and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate was extracted with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the desired product of formula (55).
Characterization of the compound of formula (55): molecular formula C 45 H 24 N 2 O 2 S 2 ；
ESI-MS (M/z) [ M+1] is obtained by liquid phase mass spectrometry] + : theoretical 689.13 and test 689.10;
elemental analysis results: theoretical value: C78.47,H 3.51,N 4.07,O 4.65,S 9.31; test value: and C78.50,H 3.55,N 4.00,O 4.63,S 9.33.
Example 8: synthesis of Compound represented by the formula (63)
In a round-bottomed flask, intermediate 2-3 (5 mmol), compound h (9 mmol) and Pd (PPh) were added 3 ) 4 (0.4 mmol) was added to a mixture of toluene (200 mL)/ethanol (150 mL) and an aqueous solution of potassium carbonate (15 mmol) (12 mL), and the mixture was refluxed under nitrogen atmosphere for 12h. The resulting mixture was cooled to room temperature, added to water, then filtered through a pad of celite, the filtrate was extracted with methylene chloride, then washed with water, and dried over anhydrous magnesium sulfate, filtered and evaporated, and the crude product was purified by silica gel column chromatography to give the desired product of formula (63).
Characterization of the compound of formula (63): molecular formula C 51 H 28 O 3 S 2 ；
ESI-MS (M/z) [ M+1] is obtained by liquid phase mass spectrometry] + : theoretical 753.15 and test 753.69;
elemental analysis results: theoretical value: C81.36,H 3.75,O 6.38,S 8.52; test value: and C81.32,H 3.79,O 6.36,S 8.54.
By using Density Functional Theory (DFT), with respect to the organic compounds provided in examples 1 to 8 of the present invention, the distribution of the molecular front orbitals HOMO and LUMO was optimized and calculated at the calculated level of B3LYP/6-31G (d) by the Guassian 09 package (Guassian Inc.), and the band gap E was obtained from the HOMO and LUMO energy levels g At the same time, the triplet state energy level E of the compound molecules is calculated based on the simulation of the time-density functional theory (TD-DFT) T The calculation results are shown in table 1.
TABLE 1 Gaussian simulation calculation results of organic Compounds
As can be seen from Table 1, the compounds provided by the invention have deeper LUMO energy levels (-1.856 to-1.999 eV), can reduce potential barrier of electron transmission, improve electron injection capability, and effectively reduce device voltage of OLED; the compounds all have deep HOMO energy levels (-5.382 to-5.579 eV), which can effectively block holes, so that more holes-electrons are recombined in a light-emitting region, and higher light-emitting efficiency can be realized.
Device example 1 blue organic light-emitting device (use of the Compound of the present invention as an electron transport layer Material)
The present embodiment provides an organic light emitting device. As shown in fig. 1, the organic light emitting device includes: the substrate 1, the ITO anode 2, the first hole transport layer 3, the second hole transport layer 4, the electron blocking layer 5, the light emitting layer 6, the first electron transport layer 7, the second electron transport layer 8, the cathode 9 (magnesium silver electrode, magnesium silver mass ratio is 9:1) and the cap layer (CPL) 10, wherein the thickness of the ITO anode 2 is 15nm, the thickness of the first hole transport layer 3 is 10nm, the thickness of the second hole transport layer 4 is 95nm, the thickness of the electron blocking layer 5 is 30nm, the thickness of the light emitting layer 6 is 30nm, the thickness of the first electron transport layer 7 is 30nm, the thickness of the second electron transport layer 8 is 5nm, the thickness of the magnesium silver electrode 9 is 15nm and the thickness of the cap layer (CPL) 10 is 100nm.
The preparation steps of the organic light emitting device of the invention are as follows:
1) Cutting the glass substrate 1 into 50mm×50mm×0.7mm sizes, respectively sonicating in isopropyl alcohol and deionized water for 30 minutes, and then exposing to ozone for about 10 minutes for cleaning; mounting the glass substrate with the ITO anode 2 obtained by magnetron sputtering on a vacuum deposition apparatus;
2) Evaporating a hole buffer layer material compound HT-1:HAT-CN on an ITO anode 2 in a vacuum evaporation mode, wherein the mass ratio of the compound HT1 to the HAT-CN is 98:2 to obtain a layer with the thickness of 10nm, and the layer is used as a first hole transport layer 3;
3) Vacuum evaporating a material compound HT-1 of the second hole transport layer 4 on the first hole transport layer 3 to obtain a layer with the thickness of 95nm, wherein the layer is used as the second hole transport layer 4;
4) Evaporating a material Prime-1 on the second hole transport layer 4 to obtain a layer with the thickness of 30nm, wherein the layer is used as an electron blocking layer 5;
5) Co-depositing a light-emitting layer 6 on the electron blocking layer 5, wherein a compound BH is used as a main material, a compound BD is used as a doping material, the mass ratio of the compound BH to the compound BD is 97:3, and the thickness of the light-emitting layer 6 is 30nm;
6) Vacuum evaporating a first electron transport layer 7 on the light emitting layer 6, wherein the material is the compound shown in the formula (1) prepared in the embodiment 1, so as to obtain a first electron transport layer 7 with the thickness of 30nm;
7) Vacuum evaporating material LiF of the second electron transport layer 8 on the first electron transport layer 7 to obtain a second electron transport layer 8 with a thickness of 5 nm;
8) Vacuum evaporating magnesium and silver on the second electron transport layer 8 to obtain a cathode 9 with the thickness of 15nm, wherein the mass ratio of Mg to Ag is 9:1;
9) The high refractive index hole-type material CPL-1 was vacuum deposited on the cathode 9 to a thickness of 100nm, and used as a cathode coating layer (capping layer or CPL) 10.
The structural formulas of the materials HAT-CN, HT-1, prime-1 and BH, BD, CPL-1 mentioned in the steps are respectively shown as follows:
device example 2
The present device example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is replaced with an equivalent amount of the organic compound represented by the formula (11) provided by the present invention; the other preparation steps were identical.
Device example 3
The present device example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is replaced with an equivalent amount of the organic compound represented by the formula (9) provided by the present invention; the other preparation steps were identical.
Device example 4
The present device example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is replaced with an equivalent amount of the organic compound represented by the formula (27) provided by the present invention; the other preparation steps were identical.
Device example 5
The present device example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is replaced with an equivalent amount of the organic compound represented by the formula (43) provided by the present invention; the other preparation steps were identical.
Device example 6
The present device example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is replaced with an equivalent amount of the organic compound represented by the formula (47) provided by the present invention; the other preparation steps were identical.
Device example 7
The present device example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is replaced with an equivalent amount of the organic compound represented by the formula (55) provided by the present invention; the other preparation steps were identical.
Device example 8
The present device example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is replaced with an equivalent amount of the organic compound represented by the formula (63) provided by the present invention; the other preparation steps were identical.
Device comparative example 1
The device comparative example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is used with the comparative compound M1 in an equivalent amount
Replacement; the other preparation steps were identical.
Device comparative example 2
The device comparative example differs from the device example 1 only in that the organic compound represented by the formula (7) in the step (6) is used with the comparative compound M2 in an equivalent amount
Replacement; the other preparation steps were identical.
Performance evaluation of OLED device:
testing the currents of the OLED device under different voltages by using a Keithley 2365A digital nano-volt meter, and dividing the currents by the light emitting areas to obtain the current densities of the OLED device under different voltages; testing the brightness and radiant energy density of the OLED device under different voltages by using a Konicaminolta CS-2000 spectroradiometer; according to the current density and brightness of the OLED device under different voltages, the OLED device with the same current density (10 mA/cm 2 ) Is the luminance 1Cd/m 2 A lower turn-on voltage; lifetime LT95 (at 50 mA/cm) was obtained by measuring the time when the luminance of the OLED device reached 95% of the initial luminance 2 Under test conditions; the specific data are shown in table 2.
Table 2 OLED device performance test results
Note that: E/CIEy represents the ratio of efficiency (E) to CIEy
As can be seen from the data of table 2, the electroluminescent devices using the organic compounds according to the present invention have a turn-on voltage of not higher than 3.85V, have a lower turn-on voltage, and have a turn-on voltage decreased by about 9%, relative to the devices of comparative examples 1 and 2, so that the power consumption of the devices can be effectively reduced; the device using the organic compound has higher current efficiency, and E/CIEy of some examples reaches 151.6-152.4 Cd/A, which is improved by about 14% compared with comparative examples 1 and 2; the device using the organic compound of the present invention has a longer lifetime, and the LT95 lifetime of some examples reaches 64 hours or more, which is prolonged by about 19% compared to the device lifetime of comparative examples 1 and 2.
The above description of the embodiments is only for aiding in the understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (8)
1. An organic compound, characterized in that the organic compound is used as an electron transport material;
the organic compound has a structure shown in a formula (I),
wherein X is S or O; y is S or O; and X and Y are different;
the R is 1 And R is R 2 Each independently selected from hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted tetrabiphenyl, substituted or unsubstitutedSubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyrenyl, substituted or unsubstituted
A group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted isoxazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted quinoxalinyl group a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted anthronyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted indenocarbazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted indolocarbazolyl group, a substituted or unsubstituted indolobenzfuranyl group, a substituted or unsubstituted indolobenzothienyl group, a substituted or unsubstituted benzofuranpyrimidinyl group, a substituted or unsubstituted benzothiophenyl pyrimidinyl group; and R is 1 And R is R 2 Not both hydrogen or deuterium;
the substituents are each independently selected from one or more of deuterium, cyano, carbonyl, phenyl, pyridinyl, and triazinyl.
2. The organic compound according to claim 1, wherein R 1 And R is R 2 Each independently selected from hydrogen, deuterium, phenyl, biphenyl, terphenyl, tetrabiphenyl, naphthyl, phenanthryl, anthracenyl, triphenylenyl, pyrenyl, and,
A group, fluorenyl, spirobifluorenyl, pyrrolyl, furanyl, thienyl, imidazolyl, thiazolyl, oxazolyl, pyrazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl, indolyl, benzofuranyl, benzimidazolyl, benzothienyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, pyrrolinyl, carbazolyl, dibenzofuranyl, dibenzothienyl, anthracenyl, fluoranthenyl, indenocarbazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, indolocarbazolyl, indolobenzfuranyl, indolobenzothienyl, benzofuranpyrimidinyl, benzothiophenyl.
3. The organic compound according to claim 1, wherein R 1 Or R is 2 Is hydrogen.
4. An organic compound characterized by the following structural formula:
5. an organic compound characterized by the following structural formula:
6. a display panel comprising an organic light emitting device; the organic light emitting device includes an anode, a cathode, and at least one organic compound layer between the anode and the cathode; the organic compound layer comprising at least one organic compound according to any one of claims 1 to 5.
7. The display panel according to claim 6, wherein the organic compound layer comprises an electron transport layer comprising at least one organic compound according to any one of claims 1 to 5.
8. A display device comprising the display panel of claim 6 or claim 7.
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