CN111560011B - 一种有机化合物及其制备方法和应用 - Google Patents
一种有机化合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN111560011B CN111560011B CN202010671992.6A CN202010671992A CN111560011B CN 111560011 B CN111560011 B CN 111560011B CN 202010671992 A CN202010671992 A CN 202010671992A CN 111560011 B CN111560011 B CN 111560011B
- Authority
- CN
- China
- Prior art keywords
- substituted
- unsubstituted
- organic compound
- organic
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 83
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000010410 layer Substances 0.000 claims description 71
- 125000001424 substituent group Chemical group 0.000 claims description 32
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 150000002367 halogens Chemical class 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims description 23
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 22
- 229910052805 deuterium Inorganic materials 0.000 claims description 22
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 21
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 230000005525 hole transport Effects 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 150000004982 aromatic amines Chemical class 0.000 claims description 9
- 230000000903 blocking effect Effects 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 4
- 229910052722 tritium Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000005649 substituted arylene group Chemical group 0.000 claims description 2
- 125000005264 aryl amine group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 238000010791 quenching Methods 0.000 abstract description 8
- 230000000171 quenching effect Effects 0.000 abstract description 8
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 58
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 46
- 230000015572 biosynthetic process Effects 0.000 description 44
- 238000003786 synthesis reaction Methods 0.000 description 43
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000000543 intermediate Substances 0.000 description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 34
- 238000001035 drying Methods 0.000 description 29
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000012043 crude product Substances 0.000 description 25
- 238000004587 chromatography analysis Methods 0.000 description 20
- 235000019439 ethyl acetate Nutrition 0.000 description 20
- 238000001704 evaporation Methods 0.000 description 19
- 238000010992 reflux Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 230000008020 evaporation Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 11
- 235000019341 magnesium sulphate Nutrition 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000000921 elemental analysis Methods 0.000 description 9
- 239000000284 extract Substances 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- -1 phenylnaphthyl Chemical group 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 description 6
- 238000007792 addition Methods 0.000 description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 3
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 2
- JNETYVLEGPSOFY-UHFFFAOYSA-N 3-bromopyrrolidine-2,5-dione Chemical compound BrC1CC(=O)NC1=O JNETYVLEGPSOFY-UHFFFAOYSA-N 0.000 description 2
- HHVGZHHLRBNWAD-UHFFFAOYSA-N 4,6-diphenyltriazine Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=NN=N1 HHVGZHHLRBNWAD-UHFFFAOYSA-N 0.000 description 2
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical group C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KCBAMQOKOLXLOX-BSZYMOERSA-N CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O Chemical compound CC1=C(SC=N1)C2=CC=C(C=C2)[C@H](C)NC(=O)[C@@H]3C[C@H](CN3C(=O)[C@H](C(C)(C)C)NC(=O)CCCCCCCCCCNCCCONC(=O)C4=C(C(=C(C=C4)F)F)NC5=C(C=C(C=C5)I)F)O KCBAMQOKOLXLOX-BSZYMOERSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940125833 compound 23 Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- VUYVXCJTTQJVKJ-UHFFFAOYSA-L palladium(2+);tricyclohexylphosphane;dichloride Chemical compound Cl[Pd]Cl.C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 VUYVXCJTTQJVKJ-UHFFFAOYSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 description 1
- ZSYMVHGRKPBJCQ-UHFFFAOYSA-N 1,1'-biphenyl;9h-carbazole Chemical group C1=CC=CC=C1C1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3NC2=C1 ZSYMVHGRKPBJCQ-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- ZSBCVAQRAXTKGV-UHFFFAOYSA-N 2,7-ditert-butylfluoren-9-one Chemical compound C1=C(C(C)(C)C)C=C2C(=O)C3=CC(C(C)(C)C)=CC=C3C2=C1 ZSBCVAQRAXTKGV-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 125000000259 cinnolinyl group Chemical group N1=NC(=CC2=CC=CC=C12)* 0.000 description 1
- 238000010549 co-Evaporation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 1
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- PJULCNAVAGQLAT-UHFFFAOYSA-N indeno[2,1-a]fluorene Chemical group C1=CC=C2C=C3C4=CC5=CC=CC=C5C4=CC=C3C2=C1 PJULCNAVAGQLAT-UHFFFAOYSA-N 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical group COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/96—Spiro-condensed ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—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
- C07D405/14—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 three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/10—Spiro-condensed systems
- C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
-
- 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
- C07D495/02—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 two hetero rings
- C07D495/04—Ortho-condensed systems
-
- 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
- C07D495/02—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 two hetero rings
- C07D495/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
-
- 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
- H10K50/15—Hole transporting layers
-
- 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
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
-
- 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]
- H10K50/17—Carrier injection layers
- H10K50/171—Electron injection layers
-
- 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]
- H10K50/18—Carrier blocking 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
- H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
-
- 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
- H10K85/657—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
- C09K2211/1051—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with sulfur
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
本发明提供一种有机化合物及其制备方法和应用,所述有机化合物具有如式I所示结构,通过分子结构的特殊设计,使所述有机化合物具有分子结构的扭曲性,避免分子之间相互堆叠而导致的猝熄,有效提高了发光效率;同时,所述有机化合物具有适宜的刚性结构,分子稳定性高,成膜性好,热分解温度高,具有较高的热稳定性,能够避免在成膜和使用过程材料受热分解,提高器件的发光效率和发光性能。所述有机电致发光化合物尤其适于作为有机电致发光器件的发光层主体材料,可以显著改善器件效率和工作寿命,尤其适用于OLED器件的红光发光主体材料。
Description
技术领域
本发明属于有机电致发光材料技术领域,具体涉及一种有机化合物及其制备方法和应用。
背景技术
上世纪末,LED技术进入汽车行业,为汽车照明设计带来了更多的可行性,也使汽车照明在安全性和稳定性方面得到了提升。然而,LED作为点光源依然有它的局限性,比如它的灯光虽然有更好的穿透力,但对于行人和其他车辆乘员来说,也会存在晃眼或刺眼的情况。为了在灯光亮度、照明效果和安全性上找到更好的平衡点,OLED技术成为了关键的突破口。
OLED是一种有机半导体照明技术,作为一种平面光源,OLED可以做到发光更为均匀和柔和,更为重要的是,由于这种灯光元件更加轻薄,具有可挠性和不发热的特性,因此又决定了其不需要散热和导光结构,从而可以进一步缩小体积和厚度,在设计上的可塑性更强。
随着OLED技术的不断发展,OLED器件的结构被不断更新和优化,目前的OLED器件包含空穴注入层、空穴传输层、发光层、空穴阻挡层、电子传输层、及电子注入层中之复数层,并搭配合适之电极,该等层分别由以下材料所构成:空穴注入材料、空穴传输材料、发光材料、空穴阻挡材料、电子传输材料、及电子注入材料。其中,采用掺杂方式制作的OLED发光层在器件的发光效率上具有优势,发光层常利用主体材料掺杂客体材料形成,因此主体材料是影响OLED器件的发光效率和性能的重要因素。
4,4'-二(N-咔唑)联苯(CBP)是一种比较常用的主体材料,其具有良好的空穴传输性能,尤其适用于绿光主体材料。但是,CBP的玻璃化转变温度比较低,仅为60℃左右,影响器件的寿命;同时CBP的电子和空穴的传输不平衡,激子的复合效率低,发光区域不理想,器件在工作中滚降现象严重,导致了从主体材料向客体材料能量转移的效率低,降低了器件效率。
CN104073246A公开了一种有机电致磷光主体材料及其制备方法和有机电致发光器件,所述有机电致磷光主体材料包括茚并芴基团和5H-吡啶并[4,3-b]吲哚基团,具有较好的溶解性能、成膜性能和稳定性,并具有较高的电子传输性能,有利于载流子在复合区域的电荷平衡,能提高器件的发光效率。但是,包含该材料有机电致发光器件的发光效率和寿命还有很大的提升空间。
CN103232843A公开了一种电致发光材料及其应用,所述电致发光材料为二苯基三嗪类材料,以二苯基三嗪为配体与芳香类杂环发生取代反应,形成含两个杂环的化合物,所述芳香类杂环为咔唑、苯并咔唑、二苯并噻吩或二苯并呋喃,且两个杂环化合物直接连接或者通过芳香类基团连接。所述电致发光材料具有高的三重态能级和很好的热稳定性,可以作为蓝色磷光主体材料。但是该材料的使用寿命和发光效率还有待优化。
CN105733562A公开了一系列芴衍生物发光材料。所述材料具有在有机溶剂中易溶、热稳定性好,可用于打印、滴注、涂布、印刷等流体制程的方式制备发光设备。利用该材料用涂布的方式制备的有机电致发光器件功率效率好,材料利用率高,大大降低了OLED器件的制造成本,并且材料合成以及提纯的方法简单适于大规模生产等特点,是作为有机电致发光器件发光材料的理想选择。但是其开启电压较高,电流效率也有待进一步提升。
因此,提高发光层主体材料的玻璃化转变温度和载流子传输效率,从而使有机电致发光器件的发光效率和使用寿命进一步优化,是本领域的研究重点。
发明内容
针对现有技术的不足,本发明的目的在于提供一种有机化合物及其制备方法和应用,所述有机化合物具有较高的玻璃化转变温度、良好的分子稳定性和高的能量转移效率,尤其适于作为发光层主体材料,提升器件的发光效率和工作寿命。
为达到此发明目的,本发明采用以下技术方案:
第一方面,本发明提供一种有机化合物,所述有机化合物具有如式I所示结构:
式I中,R1、R2、R3、R4、R5各自独立地选自氘、氚、氰基、硝基、卤素、取代或未取代的C1
~C10直链或支链烷基、取代或未取代的C2~C10烯烃基、取代或未取代的C1~C10烷氧基、取代
或未取代的C6~C30芳氧基、取代或未取代的C6~C30芳基、取代或未取代C3~C30杂芳基、或,虚线代表基团的连接位点。
式I中,m、l各自独立地选自0~3的整数,例如0、1、2或3;o、p、q各自独立地选自0~4的整数,例如0、1、2、3或4;当m≥2时,R1相同或不同;当l≥2时,R2相同或不同;当o≥2时,R3相同或不同;当q≥2时,R4相同或不同;当p≥2时,R5相同或不同。
取代基R1、R2、R3、R4、R5彼此不连接,或相邻或间隔1~3(例如1、2或3)个碳原子的2个取代基通过化学键连接成环A;所述环A选自取代或未取代的C5~C30不饱和碳环、取代或未取代的C3~C30不饱和杂芳环。
Ar选自取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基、NAr1Ar2。
L、L1、L2、L3、L4各自独立地选自单键、取代或未取代的C6~C30亚芳基;当L为单键时,Ar直接与N相连;当L1为单键时,其所在基团中的N与式I中的六元环相连;当L2为单键时,其所在基团中的Si与式I中的六元环相连;当L3、L4为单键时,Ar3、Ar4直接与C相连。
Ar1、Ar2、Ar3、Ar4、R8、R9、R10、R11各自独立地选自取代或未取代的C6~C30芳基、取代或未取代的C3~C30杂芳基。
n选自1~3的整数,例如1、2或3;当n≥2时,Ar相同或不同。
所述C1~C10可以为C1、C2、C3、C4、C5、C6、C7、C8、C9或C10。
所述C2~C10可以为C2、C3、C4、C5、C6、C7、C8、C9或C10。
所述C6~C30可以为C6、C8、C10、C12、C13、C14、C15、C16、C18、C20、C22、C24、C26或C28等。
所述C3~C30可以为C4、C5、C6、C8、C10、C12、C13、C14、C15、C16、C18、C20、C22、C24、C26或C28等。
所述C5~C30可以为C5、C6、C8、C10、C12、C13、C14、C15、C16、C18、C20、C22、C24、C26或C28等。
本发明中,所述C1~C10直链或支链烷基示例性地包括但不限于:甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基或正己基等。
所述C6~C30芳基示例性地包括但不限于:苯基、联苯基、联三苯基、萘基、联萘基、苯基萘基、萘基苯基、芴基、苯基芴基、苯并芴基、菲基、蒽基、茚基、芘基、苝基、䓛基、荧蒽基或螺芴基等。
所述C3~C30杂芳基中的杂原子包括N、O、S、P、Si或B,示例性地包括但不限于:呋喃基、噻吩基、吡咯基、咪唑基、吡唑基、噻唑基、噁唑基、三嗪基、四嗪基、吡啶基、吡嗪基、嘧啶基、哒嗪基、喹啉基、异喹啉基、喹喔啉基、喹唑啉基、噌啉基、咔唑基、吲哚基、吖啶基、苯并咪唑基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、吡啶并吡嗪基或吡啶并嘧啶基等。
本发明中,所述氢为1H。
本发明中,所述“相邻的2个取代基通过化学键连接成环A”意指,当取代基R1、R2、R3、R4、R5的个数各自独立地≥2时,位于同一六元环中相邻位置的2个取代基之间可以通过化学键连接成环A,本发明对具体的成环方式不做限定。
所述“间隔1~3个碳原子的2个取代基通过化学键连接成环A”意指,位于不同六元环上、连接位点间隔1~3(例如1、2或3)个碳原子的2个取代基(例如R1与R2、R2与R3、R3与R4)之间可以通过化学键连接成环A,本发明对具体的成环方式不做限定。
本发明提供的有机化合物的特殊结构赋予了所述有机化合物分子结构的扭曲性,避免分子之间相互堆叠而导致的猝熄,有效提高了发光效率;同时,所述有机化合物具有适宜的刚性结构,分子稳定性高,成膜性好,热分解温度高,具有较高的热稳定性,能够避免在成膜和使用过程材料受热分解,避免材料层功能的丧失,提高器件的发光效率和发光性能。
优选地,所述取代的直链或支链烷基、取代的烯烃基、取代的烷氧基、取代的芳氧基、取代的芳基、取代的杂芳基、取代的亚芳基、取代的不饱和碳环、取代的不饱和杂芳环中的取代基各自独立地选自氘、卤素、氰基、硝基、未取代或R'取代的C1~C4(例如C1、C2、C3或C4)直链或直链烷基、未取代或R'取代的C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳基、未取代或R'取代的C3~C18(例如C3、C4、C5、C6、C8、C10、C12、C14、C16或C18等)杂芳基、C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳胺基。
R'选自氘、卤素、氰基或硝基。
本发明中,所述卤素包括氟、氯、溴或碘。
本发明中涉及到“取代或未取代”且没有指明具体取代基时,取代基均具有与上述相同的选择范围。
优选地,所述有机化合物具有如式II所示结构:
式II中,R1、R2、R3、R4、R5、L、Ar、n、m、l、o、p、q各自独立地具有与式I中相同的限定范围。
优选地,所述环A选自如下结构中的任意一种,或被取代基取代的如下结构中的任意一种:
其中,*代表环A的连接位点,即环A与母核结构的稠合位点。
n1选自1~3的整数,例如1、2或3;当n1≥2时,Ara相同或不同。
La、L3a、L4a各自独立地选自单键、取代或未取代的C6~C30(例如C6、C8、C10、C12、C13、C14、C15、C16、C18、C20、C22、C24、C26或C28等)亚芳基。
Ara、Ar3a、Ar4a各自独立地选自取代或未取代的C6~C30(例如C6、C8、C10、C12、C13、C14、C15、C16、C18、C20、C22、C24、C26或C28等)芳基、取代或未取代的C3~C30(例如C4、C5、C6、C8、C10、C12、C13、C14、C15、C16、C18、C20、C22、C24、C26或C28等)杂芳基。
所述取代基各自独立地选自氘、卤素、氰基、硝基、未取代或R'取代的C1~C4(例如C1、C2、C3或C4)直链或直链烷基、未取代或R'取代的C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳基、未取代或R'取代的C3~C18(例如C3、C4、C5、C6、C8、C10、C12、C14、C16或C18等)杂芳基、C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳胺基。
R'选自氘、卤素、氰基或硝基。
优选地,所述有机化合物具有如式III-1或式III-2所示结构:
式III-1、式III-2中,R51选自氘、卤素、氰基、硝基、未取代或R'取代的C1~C4(例如C1、C2、C3或C4)直链或直链烷基、未取代或R'取代的C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳基、未取代或R'取代的C3~C18(例如C3、C4、C5、C6、C8、C10、C12、C14、C16或C18等)杂芳基、C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳胺基。
R'选自氘、卤素、氰基或硝基。
式III-1、式III-2中,p1选自0~4的整数,例如0、1、2、3或4;当p1≥2时,R51相同或不同。
式III-1、式III-2中,R1、R2、R3、R4、Y、m、l、o、q各自独立地具有与式I中相同的限定范围。
优选地,所述Ar选自如下基团中的任意一种:
其中,虚线代表基团的连接位点。
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8各自独立地选自N或C-RY。
T1选自O、S、N-RT1或CRT2RT3。
RY、RT1、RT2、RT3、R6、R7各自独立地选自氢、氘、氚、氰基、硝基、卤素、取代或未取代的C1~C4(例如C1、C2、C3或C4)直链或支链烷基、取代或未取代的C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳基、取代或未取代C3~C18(例如C3、C4、C5、C6、C8、C10、C12、C14、C16或C18等)杂芳基、C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳胺基。
取代基RY彼此不连接或相邻的至少2个取代基通过化学键连接成环。
所述“相邻的至少2个取代基通过化学键连接成环”意指,位于同一六元环上相邻位置的2个或3个取代基RY之间可以通过化学键相互连接成环,本发明对具体的连接成环方式不做限定。
优选地,所述Ar选自如下基团中的任意一种,或被取代基取代的如下基团中的任意一种:
其中,虚线代表基团的连接位点。
所述取代基选自氘、卤素、氰基、硝基、未取代或R'取代的C1~C4(例如C1、C2、C3或C4)直链或直链烷基、未取代或R'取代的C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳基、未取代或R'取代的C3~C18(例如C3、C4、C5、C6、C8、C10、C12、C14、C16或C18等)杂芳基、C6~C18(例如C6、C8、C10、C12、C14、C16或C18等)芳胺基。
R'选自氘、卤素、氰基或硝基。
优选地,所述L、L1、L2、La各自独立地选自单键、取代或未取代的亚苯基、取代或未取代的亚联苯基、取代或未取代的亚萘基;所述取代的取代基选自氘、卤素、氰基、硝基、C1~C4(例如C1、C2、C3或C4)直链或支链烷基。
优选地,所述有机化合物包括如下化合物1~200中的任意一种:
另一方面,本发明提供一种如上所述的有机化合物的制备方法,所述制备方法包括如下步骤:
(3)步骤(2)得到的中间体2进行关环反应,得到具有如式I所示结构的所述有机化合物;
其中,X1、X2各自独立地选自卤素;
R1、R2、R3、R4、R5、Y、m、l、o、p、q各自独立地具有与式I相同的限定范围。
具体地,本发明所述有机化合物的制备方法如下所示:
上述合成路线中,X1、X2、X3各自独立地选自卤素,优选为溴或氯;Boc为N保护基。
合成路线II、当2个相邻的取代基R5相互连接形成的环A时,所述有机化合物可以通过如下方法制备得到:
上述合成路线中,X1、X2、X4、X5各自独立地选自卤素,优选为溴或氯;n-BuLi为正丁基锂。
合成路线III、当2个相邻的取代基R5相互连接形成的环A时,所述有机化合物还可以通过如下方法制备得到:
上述合成路线中,X5选自卤素,优选为溴或氯;中间体Z的制备方法与合成路线II中相同。
另一方面,本发明提供一种有机电致发光器件,所述有机电致发光器件包括第一电极和第二电极,以及位于所述第一电极和第二电极之间的至少一层有机层,所述有机层的材料包括如上所述的有机化合物中的任意一种或至少两种的组合。
优选地,所述有机层包括发光层,所述发光层的材料包括如上所述的有机化合物中的任意一种或至少两种的组合。
优选地,所述发光层包括主体材料和客体材料,所述有机化合物用作发光层主体材料。
优选地,所述客体材料包括磷光掺杂剂。
优选地,所述磷光掺杂剂在580~630 nm波长处发光。
优选地,所述有机层还包括空穴注入层、空穴传输层、电子阻挡层、空穴阻挡层、电子传输层或电子注入层中的任意一种或至少两种的组合。
优选地,所述空穴传输层的材料包括如上所述的有机化合物。
优选地,所述电子阻挡层的材料包括如上所述的有机化合物。
本发明提供的有机化合物尤其适用于发光层主体材料,还可用作空穴传输材料或电子阻挡材料。
另一方面,本发明提供一种如上所述的有机电致发光器件在显示装置或照明装置中的应用。
相对于现有技术,本发明具有以下有益效果:
本发明提供的有机化合物通过分子结构的特殊设计,使所述有机化合物具有分子结构的扭曲性,避免分子之间相互堆叠而导致的猝熄,有效提高了发光效率;同时,所述有机化合物具有适宜的刚性结构,分子稳定性高,成膜性好,热分解温度高,具有较高的热稳定性,其热分解温度可以达到350~441℃,能够避免在成膜和使用过程材料受热分解,提高器件的发光效率和发光性能。所述有机电致发光化合物尤其适于作为有机电致发光器件的发光层主体材料,可以显著改善器件效率和工作寿命,尤其适用于OLED器件的红光发光主体材料,使器件的驱动电压降低至4.4 V以下,电流效率提升至21~28 cd/A,寿命达到114~124 h。
附图说明
图1为本发明应用例1提供的有机电致发光器件的结构示意图,其中1基板,2为阳极,3为空穴注入层,4为空穴传输层,5为发光层,6为电子传输层,7为电子注入层,8为阴极。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
示例性地,以下实施例给出几种典型化合物的具体制备方法:
实施例1
本实施例提供一种有机化合物(化合物1),结构如下:
合成路线如下:
制备方法包括如下步骤:
(1)S3的合成:取100 mL三颈瓶,并放入搅拌子与上接回流管,充入氮气,加入原料S1(2.75 g,0.01 mol),原料S2(1.72 g,0.01 mol),碳酸钾(0.012 mol),四(三苯基膦)钯(0.5 mmol),甲苯(30 mL),水(5 mL),氮气保护下,60℃反应8 h,反应完成后冷却至室温,加入3 mL冰水淬灭,二氯甲烷(3×15 mL)萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得S3(1.32 g,产率41%)。
(2)S4的合成:在50 mL三颈瓶中,加入中间体S3(3.21 g,0.01 mol),Boc酸酐(0.012 mol),四氢呋喃(25 mL),通入氮气,搅拌均匀后,加入4-二甲氨基吡啶(0.002mol),后升温至70℃,反应2 h,冷却至室温后,减压蒸馏除去溶剂,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得中间体S4(3.87 g,产率92%)。
(3)S5的合成:在100 mL三颈瓶中,氮气保护下加入S4(4.21 g,0.01 mol),无水四氢呋喃(THF,30 mL),将反应液冷却至-78℃。在搅拌条件下,加入正丁基锂(4.4 mL,0.025mol),在此温度下反应1 h。将9-芴酮(1.8 g,0.01 mol)溶于10 mL无水四氢呋喃中,滴加至反应瓶中。室温条件下反应1 h后,向反应体系加入水,经二氯甲烷萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干;粗产物以层析纯化(乙酸乙酯/正己烷,1/10),得S5(4.50g,产率86%)。
(4)S6的合成:在50 mL三颈瓶中,加入中间体S5(5.23 g,0.01 mol),加入醋酸中,回流4 h,用饱和碳酸氢纳洗涤,有机层用无水硫酸镁干燥,除去有机溶剂,粗产物用四氢呋喃:乙醇=1:4重结晶,得到中间体S6(3.16 g,产率78%)。
(5)化合物1的合成:在100 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,分别加入中间体S6(4.05 g,0.01 mol)、L-Ar-1(2.84 g,0.01 mol)、碳酸铯(0.012 mol)、三(二亚苄基丙酮)二钯Pd2(dba)3(0.5 mmol)和2-二环己基磷-2',4',6'-三异丙基联苯(xphos,0.55 mmol),然后加入甲苯,混合物回流24 h,反应后冷却至室温,反应体系过滤后浓缩,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得目标产物化合物1(5.12 g,产率84%)。
元素分析:C45H27N3,理论值:C 88.64,H 4.46,N 6.89,实测值:C 88.60,H 4.48,N6.92;
HRMS(ESI)m/z(M+):理论值:609.2205,实测值:609.2212。
实施例2
本实施例提供一种有机化合物(化合物23),结构如下:
合成路线如下:
其制备方法与实施例1的区别仅在于,将实施例1步骤(5)中的L-Ar-1用L-Ar-23(3.6 g,0.01 mol)替换,得目标产物化合物23(5.34 g,产率78%)。
元素分析:C51H31N3,理论值:C 89.32,H 4.56,N 6.13,实测值:C 89.27,H 4.58,N6.15;
HRMS(ESI)m/z(M+):理论值:685.2518,实测值:685.2524。
实施例3
本实施例提供一种有机化合物(化合物56),结构如下:
合成路线如下:
其制备方法与实施例1的区别仅在于,将实施例1步骤(5)中的L-Ar-1用L-Ar-56(3.87 g,0.01 mol)替换,得目标产物化合物56(6.27 g,产率88%)。
元素分析:C52H32N4,理论值:C 87.62,H 4.52,N 7.86,实测值:C 87.68,H 4.51,N7.83;
HRMS(ESI)m/z(M+):理论值:712.2627,实测值:712.2635。
实施例4
本实施例提供一种有机化合物(化合物102),结构如下:
合成路线如下:
制备方法包括如下步骤:
(1)S3-102的合成:取50 mL三颈瓶,并放入搅拌子与上接回流管,充入氮气,加入原料S1(2.75 g,0.01 mol),原料S2-102(2.22 g,0.01 mol),碳酸钾(0.012 mol),四(三苯基膦)钯(0.5 mmol),甲苯(25 mL),水(5 mL),氮气保护下,60℃反应8 h,反应完成后冷却至室温,加入3 mL冰水淬灭,二氯甲烷(3×15 mL)萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得S3-102(1.60 g,产率43%)。
(2)S4-102的合成:在50 mL三颈瓶中,加入中间体S3-102(3.71 g,0.01 mol),BOC酸酐(0.012 mol),四氢呋喃(25 mL),通入氮气,搅拌均匀后,加入4-二甲氨基吡啶(0.002mol),后升温至70℃,反应2 h,冷却至室温后,减压蒸馏除去溶剂,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得中间体S4-102(4.29 g,产率91%)。
(3)S5-102的合成:在100 mL三颈瓶中,氮气保护下加入S4-102(4.71 g,0.01mol),无水THF(30 mL),将反应液冷却至-78℃。在搅拌条件下,加入正丁基锂(4.4 mL,0.025 mol),在此温度下反应1 h。将9-芴酮(1.8 g,0.01 mol)溶于10 mL无水四氢呋喃中,滴加至反应瓶中。室温条件下反应1 h后,向反应体系加入水,经二氯甲烷萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干;粗产物以层析纯化(乙酸乙酯/正己烷,1/10),得S5-102(4.93 g,产率86%)。
(4)S6-102的合成:在50 mL三颈瓶中,加入中间体S5-102(5.73 g,0.01 mol),加入醋酸中,回流4 h,用饱和碳酸氢纳洗涤,有机层用无水硫酸镁干燥,除去有机溶剂,粗产物用四氢呋喃:乙醇=1:4重结晶,得到中间体S6-102(3.41 g,产率75%)。
(5)化合物102的合成:取100 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,分别加入中间体S6-102(4.55 g,0.01 mol)、L-Ar-102(3.40 g,0.01 mol)、碳酸铯(0.012 mol)、三(二亚苄基丙酮)二钯(0.5 mmol)和2-二环己基磷-2',4',6'-三异丙基联苯(xphos,0.55 mmol),然后加入甲苯,混合物回流24 h,反应后冷却至室温,反应体系过滤后浓缩,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得目标产物化合物102(6.01 g,产率84%)。
元素分析:C51H29N3S,理论值:C 85.57,H 4.08,N 5.87,S 4.48,实测值:C 85.61,H4.07,N 5.85,S 4.47;
HRMS(ESI)m/z(M+):理论值:715.2082,实测值:715.2088。
实施例5
本实施例提供一种有机化合物(化合物105),结构如下:
合成路线如下:
制备方法包括如下步骤:
(1)S4的合成方法与实施例1中相同;
(2)S5-105的合成:在100 mL三颈瓶中,氮气保护下加入S4(4.21 g,0.01 mol),无水THF(30 mL),将反应液冷却至-78℃。在搅拌条件下,加入正丁基锂(4.4 mL,0.025 mol),在此温度下反应1 h。将2,7-二叔丁基-9-芴酮(2.9 g,0.01 mol)溶于10 mL无水四氢呋喃中,滴加至反应瓶中。室温条件下反应1 h后,向反应体系加入水,经二氯甲烷萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干;粗产物以层析纯化(乙酸乙酯/正己烷,1/10),得S5-105(4.95 g,产率78%)。
(3)S6-105的合成:在50 mL三颈瓶中,加入中间体S5-105(6.35 g,0.01 mol),加入醋酸中,回流4 h,用饱和碳酸氢纳洗涤,有机层用无水硫酸镁干燥,除去有机溶剂,粗产物用四氢呋喃:乙醇=1:4重结晶,得到中间体S6-105(3.83 g,产率74%)。
(4)化合物105的合成:取100 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,分别加入中间体S6-105(5.17 g,0.01 mol)、L-Ar-105(3.11 g,0.01 mol)、碳酸铯(0.012 mol)、三(二亚苄基丙酮)二钯(0.5 mmol)和2-二环己基磷-2',4',6'-三异丙基联苯(xphos,0.55 mmol),然后加入甲苯,混合物回流24 h,反应后冷却至室温,反应体系过滤后浓缩,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得目标产物化合物105(6.06 g,产率81%)。
元素分析:C54H44N4,理论值:C 86.60,H 5.92,N 7.48,实测值:C 86.55,H 5.94,N7.51;
HRMS(ESI)m/z(M+):理论值:748.3566,实测值:748.3572。
实施例6
本实施例提供一种有机化合物(化合物126),结构如下:
合成路线如下:
制备方法包括如下步骤:
(1)S3-126的合成:取50 mL三颈瓶,并放入搅拌子与上接回流管,充入氮气,加入原料S1-126(2.92 g,0.01 mol),原料S2-126(1.72 g,0.01 mol),碳酸钾(0.012 mol),四(三苯基膦)钯(0.5 mmol),甲苯(8 mL),水(2 mL),氮气保护下,60℃反应8 h,反应完成后冷却至室温,加入3 mL冰水淬灭,二氯甲烷(3×15 mL)萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得S3-126(1.35 g,产率40%)。
(2)S4-126的合成:在50 mL三颈瓶中,加入中间体S3-126(3.38 g,0.01 mol),四氢呋喃(2 mL),甲苯(8 mL),通入氮气,加入镁(0.015 mol),溴化铜(1.5 mmol),三氯化铋(0.5 mmol),溴化银(1 mmol),将体系升温至90℃,反应12 h,反应完成后将至室温,加入氯化铵水溶液,用乙酸乙酯萃取,有机相用无水硫酸镁干燥,减压蒸馏除去溶剂,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得中间体S4-126(3.43 g,产率78%)。
(3)S5-126的合成:在50 mL三颈瓶中,加入中间体S4-126(4.40 g,0.01 mol),加入醋酸中,回流4 h,用饱和碳酸氢纳洗涤,有机层用无水硫酸镁干燥,除去有机溶剂,粗产物用四氢呋喃:乙醇=1:4重结晶,得到中间体S5-126(3.33 g,产率79%)。
(4)S6-126的合成:取50 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,先分别加入中间体S5-126(4.22 g,0.01 mol),N-溴代琥珀酰亚胺(0.015 mol),10mL四氢呋喃,室温下搅拌10 h。反应完成后加入5 mL水。反应体系经二氯甲烷萃取三次,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干;粗产物以层析纯化(乙酸乙酯/己烷,1/10),得到中间体S6-126(3.55 g,产率71%)。
(5)中间体S8-126的合成:在50 mL三颈瓶中,氮气保护下加入中间体S6-126(5.00g,0.01 mol),邻氯苯胺(1.27 g,0.012 mol),叔丁醇钾(0.012 mol),三(二亚苄基丙酮)二钯(0.5 mmol),2-二环己基膦基-2',6'-二甲氧基联苯基(0.55 mmol),二甲苯(10 mL),升温至60℃反应8 h,反应体系加入水,经二氯甲烷萃取,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干;粗产物以层析纯化(乙酸乙酯/正己烷,1/10),得中间体S8-126(1.75 g,产率32%)。
(6)S9-126的合成:取50 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,分别加入S8-126(5.47 g,0.01 mol),二氯二(三环己基膦)钯(0.5 mmol),叔戊酸(0.2 mmol),碳酸铯(0.01 mol),二甲基乙酰胺(10 mL),150℃反应8 h,反应后冷却至室温,反应体系过滤后浓缩,粗产物以层析纯化(二氯甲烷/己烷,1/15),得S9-126(3.22 g,产率63%)。
(7)化合物126的合成:取50 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,分别加入中间体S9-126(5.11 g,0.01 mol)、S10-126(2.40 g,0.01 mol)、碳酸铯(0.012 mol)、三(二亚苄基丙酮)二钯(0.5 mmol)和2-二环己基磷-2',4',6'-三异丙基联苯(xphos,0.55 mmol),然后加入甲苯,混合物回流24 h,反应后冷却至室温,反应体系过滤后浓缩,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得目标产物化合物126(5.51 g,产率77%)。
元素分析:C51H29N3S,理论值:C 85.57,H 4.08,N 5.87,S 4.48,实测值:C 85.62,H4.07,N 5.85,S 4.46;
HRMS(ESI)m/z(M+):理论值:715.2082,实测值:715.2076。
实施例7
本实施例提供一种有机化合物(化合物159),结构如下:
合成路线如下:
制备方法包括如下步骤:
(1)S8-159的合成:将实施例6步骤(5)中的邻氯苯胺替换为原料S7-159(1.67 g,0.01 mol),得到S8-159(4.45 g,产率82%)。
(2)S9-159的合成:取50 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,分别加入中间体S8-159(5.43 g,0.01 mol)、三苯基膦(0.02 mol)和1,2-二氯苯(10 mL),180℃加热反应12 h,反应完成后冷却至室温,反应体系经浓缩,粗产物以层析纯化(乙酸乙酯/正己烷,1/10(体积比)),得中间体S9-159(3.78 g,产率74%)。
(3)化合物159的合成:同实施例6步骤(7)中的合成方法,区别在于用S9-159(5.11g,0.01 mol)替换S9-126,用S10-159(3.16 g,0.01 mol)替换S10-126,得目标产物化合物159(6.49 g,产率82%)。
元素分析:C57H33N3S,理论值:C 86.45,H 4.20,N 5.31,S 4.05,实测值:C 86.39,H4.21,N 5.33,S 4.07;
HRMS(ESI)m/z(M+):理论值:791.2395,实测值:791.2404。
实施例8
本实施例提供一种有机化合物(化合物180),结构如下:
合成路线如下:
制备方法包括如下步骤:
(1)S9-180的合成:同实施例6步骤(7)中化合物126的合成方法,区别在于用S7(4.05 g,0.01 mol)替换S9-126,S8-180(1.12 g,0.01 mol)替换S10-126,得S9-180(4.38g,产率91%)。
(2)S10-180的合成:同实施例6步骤(4)中S6-126的合成方法,区别在于用S9-180(4.81 g,0.01 mol)替代S5-126,得S10-180(4.14 g,产率74%)。
(3)S11-180的合成:同实施例6步骤(1)中S3-126的合成方法,区别在于用原料S10-180(5.59 g,0.01 mol)替换S1-126,用原料S12-180(0.01 mol)替换S2-126,得S11-180(5.0 g,产率83%)。
(4)S13-180的合成:同实施例7步骤(2)中S9-159的合成,区别在于用S11-180(6.02 g,0.01 mol)替代S8-159,得S13-180(4.39 g,产率77%)。
(5)化合物180的合成:同实施例6步骤(7)中化合物126的合成方法,区别在于用S13-180(5.70 g,0.01 mol)替换S9-126,用S14-180(2.40 g,0.01 mol)替换S10-126,得目标产物化合物180(6.73 g,产率87%)。
元素分析:C57H34N4,理论值:C 88.35,H 4.42,N 7.23,实测值:C 88.30,H 4.44,N7.26;
HRMS(ESI)m/z(M+):理论值:774.2783,实测值:774.2776。
实施例9
本实施例提供一种有机化合物(化合物196),结构如下:
合成路线如下:
制备方法包括如下步骤:
(1)S7-196的合成:取50 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,先分别加入中间体S6-196(5.05 g,0.01 mol,通过中间体S6与Boc酸酐反应而成,制备方法与实施例1中步骤(2)相同),N-溴代琥珀酰亚胺(0.015 mol),10 mL四氢呋喃,室温下搅拌10 h。反应完成后加入5 mL水。反应体系经二氯甲烷萃取三次,所得到的萃取液依序加入硫酸镁干燥、过滤及旋干;粗产物以层析纯化(乙酸乙酯/己烷,1/10),得到中间体S7-196(3.91 g,产率67%)。
(2)S9-196的合成:取50 mL三颈瓶中,加入S7-196(5.83 g,0.01 mol),S8-196(1.2 g,0.011 mol),N,N-二甲基甲酰胺(10 mL),碳酸钾(0.013 mol),70℃下搅拌,反应结束后加水猝灭,用二氯甲烷萃取,有机相用无水硫酸镁干燥,过滤除去无机物,旋转蒸发除去有机溶剂,粗产物以层析纯化(乙酸乙酯/己烷,1/10),得到中间体S9-196(5.61,产率90%)。
(3)S10-196的合成:取50 mL三颈瓶中,通入氮气保护,加入S9-196(6.23 g,0.01mol),四氢呋喃(10 mL),在-78℃条件下,加入叔丁醇钾(0.011 mol),加完后,搅拌2 h,升至室温,搅拌2 h,反应结束后,旋转蒸发除去溶剂,得到S10-196。
(4)S12-196的合成:取50 mL三颈瓶,通入氮气保护,加入S11-196(0.01 mol),N, N-二甲基甲酰胺(10 mL),上一步所得S10-196,碳酸钾(0.012 mol),碘化亚铜(1 mmol),体系加热至120℃,搅拌过夜,反应完成后,降至室温,加入水,体系用二氯甲烷萃取,水洗,无水硫酸镁干燥有机相,除去有机溶剂,粗产物以层析纯化(乙酸乙酯/己烷,1/10),得到中间体S12-196(1.36 g,产率21%)
(5)S13-196的合成:取50 mL双颈圆底烧瓶中放入搅拌子并上接回流管,干燥后充入氮气,分别加入S12-196(6.47 g,0.01 mol),二氯二(三环己基膦)钯(0.5 mmol),叔戊酸(0.2 mmol),碳酸铯(0.01 mol),二甲基乙酰胺(10 mL),150℃反应8 h,反应后冷却至室温,反应体系过滤后浓缩,粗产物以层析纯化(二氯甲烷/己烷,1/15),得S13-196(3.73 g,产率61%)。
(6)S14-196的合成:同实施例5步骤(3)中S6-105的方法,区别在于用S13-196(6.11 g,0.01 mol)替代S5-105,得S14-196(4.80 g,产率94%)。
(7)化合物196的合成:同实施例6步骤(7)中化合物126的合成方法,区别在于用S14-196(5.11 g,0.01 mol)替换S9-126,用S15-196(3.16 g,0.01 mol)替换S10-126,得目标产物化合物196(6.30 g,产率85%)。
元素分析:C53H31N3S,理论值:C 85.80,H 4.21,N 5.66,S 4.32,实测值:C 85.86,H4.20,N 5.64,S 4.30;
HRMS(ESI)m/z(M+):理论值:741.2239,实测值:741.2245。
应用例1
一种有机电致发光器件,结构示意图如图1所示,包括依次层叠设置于基板1上的阳极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和阴极8。具体包括:
阳极选用氧化铟锡(ITO)材料;
空穴注入层的材料为HAT(CN)6和NPB,且HAT(CN)6与NPB的质量比为3:97;
空穴传输层的材料为NPB。
发光层由主体材料和客体材料组成,主体材料选用实施例1合成的化合物1,客体材料选用Ir(DBQ)2(acac),主体材料和客体材料的质量比为95:5;
电子传输层选用BPhen和LiQ,且BPhen与LiQ的质量比为1:1;
电子注入层的材料为LiQ。
阴极为Mg/Ag电极,且Mg:Ag的质量比为9:1。
有机电致发光器件的具体制备方法如下:
(1)基板清理:将涂布了ITO透明电机基板在水性清洗剂(所述水性清洗剂的成分及浓度:乙二醇类溶剂≤10wt%,三乙醇胺≤1wt%)中超声处理,在去离子水中冲洗,在丙酮与乙醇的混合溶剂(体积比1:1)中超声除油,在洁净环境下烘烤至完全除去水分,然后用紫外光和臭氧清洗;
(2)蒸镀:把上述带有阳极层的玻璃基片置于真空腔内,抽真空至1×10-6至2×10-4 Pa,在上述阳极层膜上以共蒸的方式真空蒸镀空穴注入材料,HAT(CN)6与NPB按质量比调整速率,蒸镀速率为0.1 nm/s,蒸镀厚度为10 nm;
(3)在空穴注入层之上蒸镀空穴传输层,蒸镀速率为0.1 nm/s,蒸镀膜厚为80 nm;
(4)在空穴传输层之上蒸镀发光层,以共蒸的方式真空蒸镀发光主体材料和客体材料,主体材料与客体材料按质量比调整蒸镀速率,蒸镀总速率为0.01 nm/s,蒸镀总膜厚为40 nm;
(5)在发光层之上真空蒸镀一层电子传输层,其蒸镀速率为0.1 nm/s,蒸镀总膜厚为30 nm;
(6)在电子传输层上真空蒸镀一层电子注入层,其蒸镀速率为0.05 nm/s,蒸镀总膜厚为1 nm;
(7)Mg/Ag作为器件的阴极层,按质量比调整蒸镀速率,蒸镀总速率为0.1 nm/s,蒸镀总膜厚为80 nm。
应用例2~9相较于应用例1仅替换发光层的主体材料,具体详见表1和表2。
对比例1
对比例2
测试例1
针对本发明提供的有机化合物进行如下测试:
(1)热分解温度测试:
使用热重分析仪(TGA,美国TA TGA55)对实施例1~9提供的有机化合物进行热分解温度测试,测试范围室温至600℃,升温速率10℃/min,氮气氛围下,重量损失5%的温度定义为分解温度,用Td(℃)表示。
(2)HOMO能级和LUMO能级测试:
使用电化学工作站利用循环伏安法(CV,上海辰华CHI-600E)对实施例1~9提供的有机化合物的HOMO和LUMO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0.1 M四丁基六氟磷酸铵的二氯甲烷电解液中以100 mV/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-4.8 eV:
HOMO = -e(E ox - E 1/2,ferrocene)+(-4.8)eV
LUMO= -e(E re - E 1/2,ferrocene)+(-4.8)eV;
其中,E ox为氧化电位,E re为还原电位,E 1/2,ferrocene为二茂铁电位。
(3)三线态能级ET1测试:
使用荧光分光光度计(日立F-4600)在溶液状态(溶剂为甲苯,浓度2×10-5 mol/L)、-78℃条件下测试实施例1~9提供的有机化合物的三线态能级ET1,计算方式为:ET1=1240/ 最短紫外光。
上述测试的具体结果如表1所示:
表1
有机化合物 | Td(℃) | HOMO(eV) | LUMO(eV) | E<sub>T1</sub>(eV) |
1 | 350 | -5.43 | -2.78 | 2.17 |
23 | 394 | -5.42 | -2.79 | 2.14 |
56 | 400 | -5.44 | -2.78 | 2.23 |
102 | 402 | -5.35 | -2.77 | 2.18 |
105 | 414 | -5.39 | -2.76 | 2.13 |
126 | 409 | -5.36 | -2.72 | 2.19 |
159 | 468 | -5.34 | -2.73 | 2.17 |
180 | 441 | -5.35 | -2.74 | 2.23 |
196 | 420 | -5.33 | -2.75 | 2.21 |
从表1的数据可知,本发明提供的有机化合物具有高的热分解温度,其热分解温度可以达到350~441℃,使所述有机化合物作为发光材料在器件中保持优异的热稳定性,能够避免在成膜和使用过程材料受热分解,提高器件的发光效率和发光性能。所述有机化合物的三线态能级ET1较高,可以达到2.14~2.23 eV,有机化合物的HOMO能级和LUMO能级与相邻的传输层相匹配,使OLED器件具有小的驱动电压。
测试例2
针对应用例1~9和对比例1~2的有机电致发光器件进行如下测试: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;测试条件:电流密度为20 mA/cm2,25℃;
寿命测试:器件亮度下降至原始亮度的95%时记录时间(以小时计)。
测试结果如表2所示:
表2
器件编号 | 主体材料 | 电压(V) | 色度CIE(X, Y) | 电流效率(cd/A) | 寿命(h) |
应用例1 | 1 | 4.3 | (0.66, 0.33) | 23 | 117 |
应用例2 | 23 | 4.3 | (0.66, 0.34) | 24 | 115 |
应用例3 | 56 | 4.2 | (0.66, 0.33) | 25 | 118 |
应用例4 | 102 | 4.4 | (0.66, 0.32) | 23 | 114 |
应用例5 | 105 | 4.3 | (0.66, 0.33) | 21 | 116 |
应用例6 | 126 | 4.3 | (0.66, 0.32) | 26 | 124 |
应用例7 | 159 | 4.2 | (0.66, 0.34) | 28 | 122 |
应用例8 | 180 | 4.3 | (0.66, 0.34) | 27 | 123 |
应用例9 | 196 | 4.2 | (0.66, 0.33) | 28 | 121 |
对比例1 | D-1 | 4.5 | (0.66, 0.33) | 20 | 101 |
对比例2 | D-2 | 4.4 | (0.66, 0.33) | 18 | 109 |
根据表2的数据可知,以本发明提供的有机化合物作为发光层主体材料制备的有机电致发光器件具有较低的驱动电压,其驱动低压为4.2~4.4 V,电流效率较高,可以达到21~28 cd/A,寿命得以显著改善,工作寿命提升至114~124 h,可见本发明所述有机化合物作为发光层主体材料可以有效降低器件的工作电压,同时提升器件的发光效率和工作寿命,尤其适用于红光发光的主体材料。
表2中的器件测试数据也进一步验证,本发明提供的有机化合物主环结构扭曲,避免分子间相互堆叠,避免猝熄,提高发光效率;而且,母核的刚性结构使分子稳定性显著提升,对于器件寿命的延长具有很大贡献。如果发光层主体材料不具有本发明所限定的特殊化合物结构(对比例1~2),则会导致器件的发光效率较低,工作寿命明显缩短。
申请人声明,本发明通过上述实施例来说明本发明的一种有机化合物及其制备方法和应用,但本发明并不局限于上述工艺步骤,即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明所选用原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (17)
1.一种有机化合物,其特征在于,所述有机化合物具有如式I所示结构:
式I;
其中,R1、R2、R3、R4、R5各自独立地选自氘、氚、取代或未取代的C1~C10直链或支链烷基、取代或未取代的C6~C30芳基、取代或未取代C3~C30杂芳基;
m、l各自独立地选自0~3的整数;o、p、q各自独立地选自0~4的整数;
取代基R1、R2、R3、R4、R5彼此不连接,或相邻或间隔1~3个碳原子的2个取代基通过化学键连接成环A;所述环A选自取代或未取代的C5~C30不饱和碳环、取代或未取代的C3~C30不饱和杂芳环;
Ar选自如下基团中的任意一种:
其中,虚线代表基团的连接位点;
Y1、Y2、Y3、Y4、Y5、Y6、Y7、Y8各自独立地选自N或C-RY;
T1选自O、S、N-RT1或CRT2RT3;
RY、RT1、RT2、RT3、R6、R7各自独立地选自氢、氘、氚、氰基、硝基、卤素、取代或未取代的C1~C4直链或支链烷基、取代或未取代的C6~C18芳基、取代或未取代C3~C18杂芳基、C6~C18芳胺基;
取代基RY彼此不连接或相邻的至少2个取代基通过化学键连接成环;
L选自单键、取代或未取代的C6~C30亚芳基;
n选自1~3的整数;
所述取代的直链或支链烷基、取代的芳基、取代的杂芳基、取代的亚芳基、取代的不饱和碳环、取代的不饱和杂芳环中的取代基各自独立地选自氘、卤素、氰基、硝基、未取代或R'取代的C1~C4直链或支链烷基、未取代或R'取代的C6~C18芳基、未取代或R'取代的C3~C18杂芳基、C6~C18芳胺基;
R'选自氘、卤素、氰基或硝基。
6.根据权利要求3所述的有机化合物,其特征在于,所述L、La各自独立地选自单键、取代或未取代的亚苯基、取代或未取代的亚联苯基、取代或未取代的亚萘基;所述取代的取代基选自氘、卤素、氰基、硝基、C1~C4直链或支链烷基。
9.一种有机电致发光器件,其特征在于,所述有机电致发光器件包括第一电极和第二电极,以及位于所述第一电极和第二电极之间的至少一层有机层,所述有机层的材料包括如权利要求1~7任一项所述的有机化合物中的任意一种或至少两种的组合。
10.根据权利要求9所述的有机电致发光器件,其特征在于,所述有机层包括发光层,所述发光层的材料包括如权利要求1~7任一项所述的有机化合物中的任意一种或至少两种的组合。
11.根据权利要求10所述的有机电致发光器件,其特征在于,所述发光层包括主体材料和客体材料,所述有机化合物用作发光层主体材料。
12.根据权利要求11所述的有机电致发光器件,其特征在于,所述客体材料包括磷光掺杂剂。
13.根据权利要求12所述的有机电致发光器件,其特征在于,所述磷光掺杂剂在580~630 nm波长处发光。
14.根据权利要求9所述的有机电致发光器件,其特征在于,所述有机层还包括空穴注入层、空穴传输层、电子阻挡层、空穴阻挡层、电子传输层或电子注入层中的任意一种或至少两种的组合。
15.根据权利要求14所述的有机电致发光器件,其特征在于,所述空穴传输层的材料包括如权利要求1~7任一项所述的有机化合物。
16.根据权利要求14所述的有机电致发光器件,其特征在于,所述电子阻挡层的材料包括如权利要求1~7任一项所述的有机化合物。
17.一种如权利要求9~16任一项所述的有机电致发光器件在显示装置或照明装置中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010671992.6A CN111560011B (zh) | 2020-07-14 | 2020-07-14 | 一种有机化合物及其制备方法和应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010671992.6A CN111560011B (zh) | 2020-07-14 | 2020-07-14 | 一种有机化合物及其制备方法和应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111560011A CN111560011A (zh) | 2020-08-21 |
CN111560011B true CN111560011B (zh) | 2020-12-29 |
Family
ID=72068889
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010671992.6A Active CN111560011B (zh) | 2020-07-14 | 2020-07-14 | 一种有机化合物及其制备方法和应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111560011B (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103232843A (zh) * | 2013-04-18 | 2013-08-07 | 烟台万润精细化工股份有限公司 | 一种电致发光材料及其应用 |
CN104073246A (zh) * | 2013-03-29 | 2014-10-01 | 海洋王照明科技股份有限公司 | 一种有机电致磷光主体材料及其制备方法和有机电致发光器件 |
CN105733562A (zh) * | 2016-03-25 | 2016-07-06 | 石家庄诚志永华显示材料有限公司 | 一系列芴衍生物发光材料 |
WO2020037246A1 (en) * | 2018-08-17 | 2020-02-20 | The Regents Of The University Of California | Diversity-oriented polymers of intrinsic microporosity and uses thereof |
-
2020
- 2020-07-14 CN CN202010671992.6A patent/CN111560011B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104073246A (zh) * | 2013-03-29 | 2014-10-01 | 海洋王照明科技股份有限公司 | 一种有机电致磷光主体材料及其制备方法和有机电致发光器件 |
CN103232843A (zh) * | 2013-04-18 | 2013-08-07 | 烟台万润精细化工股份有限公司 | 一种电致发光材料及其应用 |
CN105733562A (zh) * | 2016-03-25 | 2016-07-06 | 石家庄诚志永华显示材料有限公司 | 一系列芴衍生物发光材料 |
WO2020037246A1 (en) * | 2018-08-17 | 2020-02-20 | The Regents Of The University Of California | Diversity-oriented polymers of intrinsic microporosity and uses thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111560011A (zh) | 2020-08-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100940938B1 (ko) | 신규한 유기 발광 화합물 및 이를 발광재료로서 채용하고있는 유기 전기 발광 소자 | |
CN110862381B (zh) | 一种有机电致发光化合物及其制备方法和应用 | |
CN101490207B (zh) | 用于有机电致发光器件的新材料 | |
KR100974562B1 (ko) | 신규한 유기 발광 화합물 및 이를 발광재료로서 채용하고있는 유기 발광 소자 | |
JP6238178B2 (ja) | 有機エレクトロルミネセント装置用の化合物及びこの化合物を用いる有機エレクトロルミネッセント装置 | |
TW201638079A (zh) | 用於電子裝置之材料 | |
KR20110049217A (ko) | 신규한 유기 발광 화합물 및 이를 채용하고 있는 유기 전계 발광 소자 | |
CN110041366B (zh) | 一种茚并蒽衍生物化合物及其应用 | |
JP2016147846A5 (zh) | ||
CN114853769B (zh) | 一种咔唑衍生物、有机电致发光元件、显示装置和照明装置 | |
CN115124433A (zh) | 一种螺二芴衍生物及其应用 | |
CN107759559A (zh) | 化合物及其有机电子装置 | |
CN112979616B (zh) | 一种苯并咪唑类化合物及其制备方法和应用 | |
CN111777614B (zh) | 一种有机电致发光化合物及其应用 | |
CN114685484B (zh) | 一种有机电致发光化合物及包含其的有机电致发光器件 | |
CN112759524A (zh) | 一种芳香胺衍生物及其有机电致发光器件 | |
CN112442037B (zh) | 一种发光材料及其应用 | |
CN117736218A (zh) | 一种螺环羰基氮化合物、聚合物、混合物及其应用 | |
CN110003019B (zh) | 一种以均苯为核心的高迁移率有机化合物及其应用 | |
CN114891000B (zh) | 一种吲哚衍生物、有机电致发光元件、显示装置和照明装置 | |
CN111560011B (zh) | 一种有机化合物及其制备方法和应用 | |
KR20190129509A (ko) | 다환 화합물 및 이를 포함하는 유기 발광 소자 | |
CN113444093B (zh) | 一种化合物及其应用 | |
CN111212829B (zh) | 螺环化合物及包含其的有机发光装置 | |
CN110894203A (zh) | 有机发光化合物及其应用和有机电致发光器件 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20210108 Address after: Room A2, building 6, No.2, Lane 189, Canghai Road, Ningbo hi tech Zone, Ningbo City, Zhejiang Province Patentee after: NINGBO LUMILAN NEW MATERIAL Co.,Ltd. Patentee after: Ningbo Institute of Northwest University of Technology Address before: Room A2, building 6, No.2, Lane 189, Canghai Road, Ningbo hi tech Zone, Ningbo City, Zhejiang Province Patentee before: NINGBO LUMILAN NEW MATERIAL Co.,Ltd. |
|
TR01 | Transfer of patent right |