CN111808142A - Organic phosphorus luminescent compound and preparation method and application thereof - Google Patents
Organic phosphorus luminescent compound and preparation method and application thereof Download PDFInfo
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- CN111808142A CN111808142A CN202010657498.4A CN202010657498A CN111808142A CN 111808142 A CN111808142 A CN 111808142A CN 202010657498 A CN202010657498 A CN 202010657498A CN 111808142 A CN111808142 A CN 111808142A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 22
- 239000011574 phosphorus Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 5
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 5
- 150000002367 halogens Chemical class 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 111
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 80
- 239000010410 layer Substances 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 239000003208 petroleum Substances 0.000 claims description 40
- 239000002904 solvent Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000003446 ligand Substances 0.000 claims description 24
- 238000004440 column chromatography Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 15
- 239000007924 injection Substances 0.000 claims description 15
- 238000010898 silica gel chromatography Methods 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002346 layers by function Substances 0.000 claims description 11
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 230000000903 blocking effect Effects 0.000 claims description 9
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229940126062 Compound A Drugs 0.000 claims description 6
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 6
- 230000005525 hole transport Effects 0.000 claims description 6
- -1 phenoxy benzothiazole compound Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- LNJXVUXPFZKMNF-UHFFFAOYSA-K iridium(3+);trichloride;trihydrate Chemical compound O.O.O.Cl[Ir](Cl)Cl LNJXVUXPFZKMNF-UHFFFAOYSA-K 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229920002098 polyfluorene Polymers 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000741 silica gel Substances 0.000 description 20
- 229910002027 silica gel Inorganic materials 0.000 description 20
- 239000003480 eluent Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000003463 adsorbent Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 5
- 238000000921 elemental analysis Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZTLUNQYQSIQSFK-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]naphthalen-1-amine Chemical compound C1=CC(N)=CC=C1C(C=C1)=CC=C1NC1=CC=CC2=CC=CC=C12 ZTLUNQYQSIQSFK-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KDOQMLIRFUVJNT-UHFFFAOYSA-N 4-n-naphthalen-2-yl-1-n,1-n-bis[4-(n-naphthalen-2-ylanilino)phenyl]-4-n-phenylbenzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(N(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C3C=CC=CC3=CC=2)C=C1 KDOQMLIRFUVJNT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229920001090 Polyaminopropyl biguanide Polymers 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008425 anthrones Chemical class 0.000 description 1
- 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 description 1
- 150000007980 azole derivatives Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- PJVZQNVOUCOJGE-CALCHBBNSA-N chembl289853 Chemical compound N1([C@H]2CC[C@H](O2)N2[C]3C=CC=CC3=C3C2=C11)C2=CC=C[CH]C2=C1C1=C3C(=O)N(C)C1=O PJVZQNVOUCOJGE-CALCHBBNSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- LBFXFIPIIMAZPK-UHFFFAOYSA-N n-[4-[4-(n-phenanthren-9-ylanilino)phenyl]phenyl]-n-phenylphenanthren-9-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C2=CC=CC=C2C=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C3=CC=CC=C3C=2)C=C1 LBFXFIPIIMAZPK-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 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
- 239000010409 thin film Substances 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [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 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- 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
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- 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
- H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
-
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Abstract
The invention discloses an organic phosphorus luminescent compound, which has a structural general formula shown in chemical formula 1:
in the formula R1a、R1b、R1c、R1d、R2a、R2b、R2c、R2d、R3a、R3b、R4a、R4b、R4c、R5a、R5b、R5c、R5dEach independently selected from the group consisting of: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, or a salt thereofSubstituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C6-C18 aryl; the preparation method provided by the invention is simple and feasible, the product purity is high, and the product purity can reach more than 99%; the organic phosphorus luminescent compound shown in chemical formula 1 prepared by the invention can reduce the driving voltage of an organic electroluminescent device to be below 4.0V, improve the luminous efficiency to be above 35cd/A, and prolong the service life T (95) to be above 670.
Description
Technical Field
The invention relates to the technical field of luminescent materials, in particular to an organic phosphorus luminescent compound and a preparation method and application thereof.
Background
2002- & 2005 was the growth stage of organic light emitting diodes, and people have been in wide contact with products with organic light emitting diodes, including vehicle-mounted displays, PDAs, mobile phones, DVDs, digital cameras, microdisplays for helmets, and household electrical appliances. Organic light emitting diode products are formally introduced into the market, and mainly enter the display fields of traditional LCD, VFD and the like. In this period, passive driving, single-color or multi-color display, and panels of 10 inches or less have been mainly used, but active driving, full-color, and panels of 10 inches or more have also come into use. In 2005, with the increasing maturity of the organic light emitting diode industrialization technology, the organic light emitting diode began to strike the display market and expand its application field, and the advantages of the organic light emitting diode in each technology were fully explored and exerted. The industrialization of organic light emitting diodes has begun, and it is now the stage where OLED technology is going to mature and market demand is growing at a high rate.
Although there are many new findings on high-efficiency heavy metal phosphors on the market, they all have high power, short lifetime, and low luminous efficiency;
therefore, it is an urgent technical problem to provide an organic phosphorus light-emitting compound and an organic electroluminescent device having lower power, longer lifetime and higher luminous efficiency.
Disclosure of Invention
In view of the above, the present invention provides an organic phosphorus light-emitting compound having high light-emitting efficiency, low driving voltage, and long lifetime;
in order to achieve the purpose, the invention adopts the following technical scheme: the organic phosphorus luminescent compound has a structural general formula shown in chemical formula 1:
wherein R is1a、R1b、R1c、R1d、R2a、R2b、R2c、R2d、R3a、R3b、R4a、R4b、R4c、R5a、R5b、R5c、R5dEach independently selected from: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, and substituted or unsubstituted C6-C18 aryl.
Further, the halogen is selected from one of fluorine, chlorine, bromine or iodine; preferably fluorine;
further, in the substituted or unsubstituted C1-C8 alkyl, any one or more C atoms may be substituted by N, O, S, Si, Se or Ge; preferably, the alkyl group is selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl;
further, the substituted or unsubstituted cycloalkyl group having C3 to C30 is preferably a cycloalkyl group having C3 to C15; the cycloalkyl is monocyclic alkyl, polycyclic alkyl or spiroalkyl; more preferably, the cycloalkyl group is selected from cyclopropyl, cyclopentyl, cyclohexyl or adamantyl; the cycloalkyl is optionally substituted, and the substituent is selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C8 alkyl;
further, in the substituted or unsubstituted aryl group having C6-C18, the aryl group includes a monocyclic group or a polycyclic group. Wherein the polycyclic group includes two or more rings having two carbon atoms in two adjoining common and at least one of the rings is an aromatic ring and the other ring is a cycloalkyl, cycloalkenyl, aryl or heteroaryl group; the aryl group is more preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group or a fluorenyl group; aryl is optionally substituted, the substituents being preferably selected from deuterium, methyl, ethyl, propyl, isopropyl, phenyl.
The above-mentioned "substitution" means that a hydrogen atom bonded to a carbon atom of a compound becomes an additional substituent, and the position of substitution is not limited as long as the position is a position at which the hydrogen atom is substituted, that is, a position at which the substituent can be substituted, and when two or more substituents are substituted, the two or more substituents may be the same as or different from each other.
Preferably, the organic phosphorus luminescent compound has a structural formula of any one of the following structural formulas:
the invention also provides a preparation method of the organic phosphorus luminescent compound, which comprises the following steps:
(1) under the protection of inert gas, mixing the compound A and iridium trichloride trihydrate, adding the mixture into a solvent I for heating reaction, performing suction filtration after the reaction is finished, and sequentially washing and drying to obtain a bridging ligand B;
(2) under the protection of inert gas, mixing the bridging ligand B and silver trifluoromethanesulfonate, adding the mixture into a solvent II for heating reaction, and performing column chromatography separation and rotary evaporation concentration after the reaction to obtain an intermediate C;
(3) under the protection of inert gas, mixing the intermediate C with the compound D, adding the mixture into a solvent III for heating reaction, and performing suction filtration, washing, drying, column chromatography, rotary evaporation and concentration after the reaction is finished to obtain an organophosphorus luminescent compound shown in a chemical formula 1;
the synthetic route of the organic phosphorus luminescent compound shown in chemical formula 1 is as follows:
in the compound C shown, "-OTf" means silver trifluoromethanesulfonate ion
Further, the inert gases in the steps (1) to (3) are all nitrogen or argon;
the molar ratio of the compound A to the iridium trichloride trihydrate in the step (1) is (2-3) to 1, and preferably 2.6: 1;
the heating reaction temperature is 130-140 ℃, and the reaction time is 20-30 h;
the solvent I is ethylene glycol ethyl ether and/or water; when the solvent I is a mixed solution of ethylene glycol ethyl ether and water, the volume ratio of the ethylene glycol ethyl ether to the water is 3: 1;
the ratio of the compound A to the solvent I is 64.4mmol: 350-400 mL;
the detergent is one or a mixture of water, absolute ethyl alcohol and petroleum ether; preferably, water, absolute ethyl alcohol and petroleum ether are adopted for washing in sequence;
the drying temperature is 70-80 ℃.
Further, the molar ratio of the bridging ligand B to the silver trifluoromethanesulfonate in the step (2) is 1: 2-3, preferably 1: 3;
the reaction temperature is 55-65 ℃, and the reaction time is 20-30 h;
the solvent II is dichloromethane and/or methanol; when the solvent II is a mixed solution of dichloromethane and methanol, the volume ratio of the dichloromethane to the methanol is 5: 2;
the ratio of the bridging ligand B to the solvent II is 6.4mmol: 105-140 mL.
The column chromatography separation adopts a short column for column chromatography.
Further, the inert gas in the step (3) is nitrogen or argon;
the molar ratio of the intermediate C to the compound D is 1 (2-3); preferably 1: 3.
The reaction temperature is 75-80 ℃, and the reaction time is 20-30 h;
the solvent III is ethanol;
the ratio of the intermediate C to the solvent III is 11.2mmol: 90-130 mL.
The washing is washing with ethanol; the drying temperature is 70-80 ℃;
the column chromatography is carried out by using dichloromethane and petroleum ether according to the weight ratio of 1: mixing the raw materials in a volume ratio of 1-15 to serve as a solvent, and performing silica gel column chromatography.
The invention has the beneficial effects that: the preparation method provided by the invention is simple and feasible, the product purity is high, and the product purity can reach more than 99%; the organic phosphorus luminescent compound shown in chemical formula 1 prepared by the invention can reduce the driving voltage of an organic electroluminescent device to be below 4.0V, improve the luminous efficiency to be above 35cd/A, and prolong the service life T (95) to be above 670.
The invention also provides an application of the organic phosphorus luminescent compound in preparing organic electroluminescent devices.
An organic electroluminescent device comprising an anode, a cathode and an intermediate layer disposed between the anode and cathode; wherein the intermediate layer includes a light emitting layer including the organic phosphorus light emitting compound of chemical formula 1.
Further, the anode is indium tin oxide, zinc oxide or indium oxide, and the thickness of the anode is 10-500 nm;
the cathode is Al, Li, Na, K, Mg, Ca, Au, Ag or Pb, and the thickness of the cathode is 100-1000 nm.
Further, the organic phosphorus luminescent compound accounts for 0.5-10% of the mass of the luminescent layer;
the luminescent layer also comprises a main material, and the main material is one or a mixture of more of 4, 4'-N, N' -biphenyl dicarbazole, octahydroxyquinoline, a metal phenoxy benzothiazole compound, polyfluorene, aromatic condensed rings and a zinc complex;
the thickness of the light emitting layer is 10-500 nm.
Further, the intermediate layer further comprises a functional layer; the functional layer is one or more of a hole injection layer, a hole transport layer, a hole injection-hole transport functional layer, an Electron Blocking Layer (EBL), a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport-electron injection functional layer.
Further, the hole injection layer is one of 2-TNATA (i.e., N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylphenyl-1, 4-diamine), phthalocyanine and porphyrin compounds, conductive polymers, N-type semiconducting organic complexes, metal organic complexes; the thickness of the hole injection layer is preferably 10-500 nm;
the hole transport layer is one of NPB (namely N, N '-diphenyl-N, N' - (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine), TPD (namely N, N '-diphenyl-N, N' - (3-methylphenyl) -1, 1 '-biphenyl-4, 4' -diamine), PAPB (namely N, N '-bis (phenanthrene-9-yl) -N, N' -diphenyl benzidine), arylamine carbazole compound and indolocarbazole compound; the thickness of the hole transport layer is preferably 10-500 nm;
the thickness of the electron blocking layer is preferably 10-500 nm;
the hole blocking layer is one of BAlq, BCP and BPhen; the thickness of the hole blocking layer is preferably 10-500 nm;
the electron transport layer is one of Alq3, coumarin No. 6, triazole derivatives, azole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives and anthrone derivatives; the thickness of the electron transmission layer is preferably 10-500 nm;
the electron injection layer is LiF, CsF or Li2O、Al2O3MgO; the thickness of the electron injection layer is preferably 0.1-10 nm.
The thickness of the electron transmission-electron injection functional layer is preferably 10-500 nm.
In the present invention, the light-emitting layer and various other functional layers may be formed by vapor deposition.
Compared with the prior art, the invention has the beneficial effects that: the organic electroluminescent device provided by the invention has high luminous efficiency, low driving voltage and longer service life. The organic electroluminescent device according to the present invention may be applied to an Organic Light Emitting Device (OLED), an Organic Solar Cell (OSC), electronic paper (e-paper), an Organic Photoreceptor (OPC), or an Organic Thin Film Transistor (OTFT) using the same principle.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
EXAMPLE 1 preparation of luminescent Compound J010
S1, weighing the compound A010 (64.02 mmol, 10.0g) and IrC1 of 2-phenyl-3-deuterated pyridine under the protection of nitrogen3·3H2O (24.62mmol, 8.68g) is put into the reaction system, and a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, and the mixture is heated and refluxed at 130 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was cooled to 25 ℃ to precipitate, and the precipitate was filtered, washed with water, absolute ethanol, and petroleum ether in this order, and then dried to obtain bridging ligand B010(7.7g, 58% yield) as a yellow powder.
S2, weighing bridging ligand B010(6.97mmol, 7.5g), adding silver trifluoromethanesulfonate (20.9mmol, 5.37g), adding 100mL of dichloromethane and 40mL of methanol into the system, and heating and refluxing at 55 ℃ for 24 hours under the protection of nitrogen. Thereafter, the mixture was cooled to 25 ℃ and the column chromatography (short column) filtrate was concentrated to precipitate a solid, to obtain intermediate C010(9.1g, yield 91%) as a yellow-green powder.
Wherein, the column chromatography conditions are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 455g of silica gel (200-300 meshes) as an adsorbent, adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: 1, purifying it using the eluent.
S3, weighing intermediate C010(12.61mmol, 9g), adding ligand D010(37.83mmol, 9.89g), adding 120mL absolute ethyl alcohol into the system, and heating and refluxing at 75 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was subjected to suction filtration, alcohol washing and drying, and then silica gel column chromatography using dichloromethane as a solvent was performed, and the filtrate was concentrated until a solid precipitated, to obtain a yellow compound J010(3.8g, yield 39%).
Wherein, the conditions of the silica gel column chromatography are as follows: dichloromethane and petroleum ether are selected as a solvent, 510g of silica gel (200-300 meshes) is used as an adsorbent, petroleum ether is added, the mixture is fully stirred until the mixture is uniform and poured into a column, after the silica gel is settled, the mixture is added, and the proportion of a developing agent is dichloromethane: the volume ratio of petroleum ether is 1: and 8, purifying the eluent.
The reaction route of the preparation process is as follows:
the detection analysis of the obtained compound J010 showed that:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 762.9; the test value was 763.1.
Elemental analysis:
the calculated values are: c: 61.40 percent; h: 3.70 percent; n: 5.51 percent; s: 4.20 percent; ir: 25.19 percent;
the test values are: c: 61.41 percent; h: 3.72 percent; n: 5.52 percent; s: 4.18 percent; ir: 25.17 percent.
As can be seen from the above test results, example 1 produces a compound of the J010 structure with high purity.
EXAMPLE 2 preparation of luminescent Compound J036
S1, weighing compound A036 (53.4 mmol, 10.0g) and IrC1 (2- (4-ethyl) phenyl-tetradeuterated pyridine) under the protection of nitrogen3·3H2O (20.54mmol, 7.24g) is put into the reaction system, and a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, and the mixture is heated and refluxed at 135 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was cooled to 25 ℃ to precipitate, and the precipitate was filtered, washed with water, absolute ethanol, and petroleum ether in this order, and then dried to obtain bridging ligand B036(6.2g, 50% yield) as a yellow powder.
S2, weighing bridging ligand B036(5mmol, 6g), adding silver trifluoromethanesulfonate (14.99mmol, 3.85g), adding dichloromethane 100mL and methanol 40mL, and heating under reflux at 60 ℃ for 24 hours under the protection of nitrogen. Thereafter, it was cooled to 25 ℃ and the column chromatography (short column) filtrate was concentrated to precipitate a solid, yielding intermediate C036(7.2g, 92% yield) as a yellow-green powder.
Wherein, the column chromatography conditions are as follows: the solvent is dichloromethane and petroleum ether, the adsorbent is silica gel (200-300 meshes), 360g is weighed, the petroleum ether is added, the mixture is poured into a column after the silica gel is settled, and the mixture is added, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: and 4, purifying the eluent.
S3, intermediate C036(9.02mmol, 7g) was weighed, ligand D036(27.07mmol, 7.07g) was added, 120mL of absolute ethanol was added to the system, and the mixture was heated under reflux at 75 ℃ for 24 hours under nitrogen protection. Then, the reaction mixture was subjected to suction filtration, alcohol washing and drying, and then silica gel column chromatography using dichloromethane as a solvent was performed, and the filtrate was concentrated until a solid precipitated, to obtain yellow compound J036(3.1g, yield 41%).
Wherein, the conditions of the silica gel column chromatography are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 520g of silica gel (200-300 meshes) as an adsorbent, adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: and 6, purifying the eluent.
The reaction route of the preparation process is as follows:
the detection analysis of the compound J036 was carried out, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 825.08; the test value was 825.26.
Elemental analysis:
the calculated values are: c: 62.6 percent; h: 5.13 percent; n: 5.09%; s: 3.89 percent; ir: 23.30 percent;
the test values are: c: 62.61 percent; h: 5.12 percent; n: 5.11 percent; s: 3.87 percent; ir: 23.31 percent.
As can be seen from the above test results, example 2 produces a compound of the structure J036 of high purity.
EXAMPLE 3 preparation of luminescent Compound J048
S1, weighing Compound A036(2- (deuterated methyl) phenyl-pyridine (58.06mmol, 10.0g) and IrC1 under nitrogen protection system3·3H2O (22.33mmol, 7.87g) is put into the reaction system, and a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water is added, and the mixture is heated and refluxed at 140 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was cooled to 25 ℃ to precipitate, and the precipitate was filtered, washed with water, absolute ethanol, and petroleum ether in this order, and then dried to obtain bridging ligand B048(7.1g, yield 55%) as a yellow powder.
S2, weighing bridging ligand B048(6.14mmol, 7g), adding silver trifluoromethanesulfonate (18.42mmol, 4.73g), adding 100mL of dichloromethane and 40mL of methanol into the system, and heating and refluxing at 55 ℃ for 24 hours under the protection of nitrogen. Thereafter, it was cooled to 25 ℃ and the column chromatography (short column) filtrate was concentrated to precipitate a solid, yielding intermediate C048(8.7g, 95% yield) as a yellow-green powder.
Wherein, the column chromatography conditions are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 435g of silica gel (200-300 meshes) as an adsorbent, adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: and 3, purifying the eluent by using the eluent.
S3, weighing intermediate C048(11.4mmol, 8.5g), adding ligand D048(34.19mmol, 8.94g), adding 120mL of absolute ethanol into the system, and heating and refluxing at 80 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was subjected to suction filtration, alcohol washing and drying, and then silica gel column chromatography using dichloromethane as a solvent was performed, and the filtrate was concentrated until a solid precipitated, to obtain a yellow compound J048(3.2g, yield 35%).
Wherein, the conditions of the silica gel column chromatography are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 500g of silica gel (200-300 meshes) as an adsorbent, adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: and 7, purifying the eluent.
The reaction route of the preparation process is as follows:
the compound J048 obtained was subjected to detection analysis, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 795.01; the test value was 795.21.
Elemental analysis:
the calculated values are: c: 61.94 percent; h: 4.56 percent; n: 5.29 percent; s: 4.03 percent; ir: 24.18 percent;
the test values are: c: 61.95 percent; h: 4.57 percent; n: 5.29 percent; s: 4.01 percent; ir: 24.17 percent.
As can be seen from the above test results, example 3 produces a compound of the structure J048 with high purity.
EXAMPLE 4 preparation of luminescent Compound J054
S1, weighing Compound A054(2- (deuterated methyl) phenyl-pyridine (55.49mmol, 10.0g) and IrC1 under nitrogen protection system3·3H2O (21.34mmol, 7.53g) was added to the reaction system, and a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water was added thereto, and the mixture was heated under reflux at 135 ℃ for 24 hours under nitrogen protection. Then, the reaction mixture was cooled to 25 ℃ to precipitate, and the precipitate was filtered, washed with water, absolute ethanol, and petroleum ether in this order, and then dried to obtain bridging ligand B054(6.8g, 54% yield) as a yellow powder.
S2, weighing bridging ligand B054(5.55mmol, 6.5g), adding silver trifluoromethanesulfonate (16.64mmol, 4.27g), adding dichloromethane 100mL and methanol 40mL into the system, and heating and refluxing at 55 ℃ for 24 hours under the protection of nitrogen. Thereafter, the mixture was cooled to 25 ℃ and the column chromatography (short column) filtrate was concentrated to precipitate a solid, to give intermediate C054(8g, yield 94%) as a yellow-green powder.
Wherein, the column chromatography conditions are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 400g of silica gel (200-300 meshes) as an adsorbent, adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: 2.5, purifying it using the eluent.
S3, weighing intermediate C054(10.5mmol, 8g), adding ligand D054(31.5mmol, 8.27g), adding 120mL absolute ethyl alcohol into the system, and heating and refluxing at 80 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was subjected to suction filtration, alcohol washing and drying, and then silica gel column chromatography using dichloromethane as a solvent was performed, and the filtrate was concentrated until a solid precipitated, to obtain a yellow compound J054(3.1g, yield 36%).
Wherein, the conditions of the silica gel column chromatography are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 490g of an adsorbent which is silica gel (200-300 meshes), adding the petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: and 6, purifying the eluent.
The reaction route of the preparation process is as follows:
the detection analysis of the obtained compound J054 showed the following results:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 811.95; the test value was 812.14.
Elemental analysis:
the calculated values are: c: 60.65 percent; h: 3.10 percent; n: 8.63 percent; s: 3.95 percent; ir: 23.67 percent;
the test values are: c: 60.67 percent; h: 3.12 percent; n: 8.65 percent; s: 3.97 percent; ir: 23.65 percent.
As can be seen from the above test results, example 4 was prepared to obtain a compound of J054 structure with high purity.
EXAMPLE 5 preparation of luminescent Compound J070
S1, weighing Compound A070 (2-phenyl-pyridine (128.87mmol, 20.0g) and IrC1 under nitrogen protection system3·3H2O (49.57mmol, 17.48g) was added to the reaction system, and a mixed solution of 300mL of ethylene glycol ethyl ether and 100mL of purified water was added thereto, and the mixture was heated under reflux at 140 ℃ for 24 hours under nitrogen protection. Then, the reaction mixture was cooled to 25 ℃ to precipitate, and the precipitate was filtered, washed with water, absolute ethanol, and petroleum ether in this order, and then dried to obtain bridging ligand B070(13.6g, yield 51%) in the form of a yellow powder.
S2, weighing bridging ligand B070(12.59mmol, 13.5g), adding silver trifluoromethanesulfonate (37.78mmol, 9.71g), adding 100mL of dichloromethane and 40mL of methanol into the system, and heating and refluxing at 60 ℃ for 24 hours under the protection of nitrogen. Thereafter, the mixture was cooled to 25 ℃ and the column chromatography (short column) filtrate was concentrated to precipitate a solid, yielding intermediate C070 as a yellow-green powder (15.8g, 88% yield).
Wherein, the column chromatography conditions are as follows: selecting dichloromethane and petroleum ether as a solvent, weighing 790g of an adsorbent which is silica gel (200-300 meshes), adding petroleum ether, fully stirring until the mixture is uniform, pouring the mixture into a column, and adding a mixture after the silica gel is settled, wherein the developing agent is dichloromethane: the volume ratio of petroleum ether is 1: 1, purifying it using the eluent.
S3, weighing intermediate C070(21.78mmol, 15.5g), adding ligand D070(65.33mmol, 22.11g), adding 120mL of absolute ethyl alcohol into the system, and heating and refluxing at 75 ℃ for 24 hours under the protection of nitrogen. Then, the reaction mixture was subjected to suction filtration, alcohol washing and drying, and then silica gel column chromatography using dichloromethane as a solvent was performed, and the filtrate was concentrated until a solid precipitated, to obtain yellow compound J070(6.7g, yield 36%).
Wherein, the conditions of the silica gel column chromatography are as follows: dichloromethane and petroleum ether are selected as a solvent, 970g of silica gel (200-300 meshes) is weighed as an adsorbent, the petroleum ether is added, the mixture is fully stirred until the mixture is uniform and poured into a column, after the silica gel is settled, the mixture is added, and the proportion of a developing agent is dichloromethane: the volume ratio of petroleum ether is 1: and 3, purifying the eluent by using the eluent.
The reaction route of the preparation process is as follows:
the compound J070 obtained was subjected to detection and analysis, and the results were as follows:
HPLC purity: is more than 99 percent.
Mass spectrometry test: a theoretical value of 838.02; the test value was 838.18.
Elemental analysis:
the calculated values are: c: 64.49 percent; h: 3.73 percent; n: 5.01 percent; s: 3.83 percent; ir: 22.94 percent;
the test values are: c: 64.51 percent; h: 3.71 percent; n: 5.02 percent; s: 3.83 percent; ir: 22.93 percent.
As can be seen from the above test results, example 5 produced a compound of structure J070 of high purity.
Examples 6 to 20
According to the preparation method of the above example, the compound a and the compound D are respectively replaced by the compounds corresponding to the corresponding ligand structures in the target product, and the material usage amounts are correspondingly adjusted according to the corresponding stoichiometric ratio, so as to obtain the following series of luminescent compounds, as shown in table 1 below. The detection analysis of each product was carried out according to the detection method in example 1, and the result was shown to be a luminescent compound of the corresponding structure.
TABLE 1 products of examples 6-28
| Compound (I) | Molecular formula | Theoretical value of mass spectrum | Mass spectrometric test values | Purity of | |
| Example 6 | J001 | C39H26IrN3S | 760.92 | 761.14 | ＞99％ |
| Example 7 | J004 | C45H34IrN3S | 841.21 | 841.05 | ＞99％ |
| Example 8 | J009 | C47H38IrN3S | 869.10 | 869.24 | ＞99％ |
| Example 9 | J016 | C47H36IrN5S | 895.12 | 895.23 | ＞99％ |
| Example 10 | J024 | C48H37IrN4S | 894.13 | 894.24 | ＞99％ |
| Example 11 | J029 | C48H44IrN3S | 887.18 | 887.29 | ＞99％ |
| Example 12 | J035 | C46H36D2IrN3S | 859.12 | 859.25 | ＞99％ |
| Example 13 | J044 | C57H54IrN3S | 1005.36 | 1005.37 | ＞99％ |
| Example 14 | J050 | C40H25IrN4S | 785.93 | 786.14 | ＞99％ |
| Example 15 | J051 | C42H23IrN6S | 835.97 | 836.13 | ＞99％ |
| Example 16 | J058 | C45H25D5IrN3S | 842.05 | 842.21 | ＞99％ |
| Example 17 | J061 | C43H32IrN3S | 815.03 | 815.19 | ＞99％ |
| Example 18 | J063 | C40H28IrN3S | 774.95 | 775.16 | ＞99％ |
| Example 19 | J066 | C40H28IrN3S | 774.95 | 775.16 | ＞99％ |
| Example 20 | J069 | C45H30IrN3S | 837.02 | 837.17 | ＞99％ |
| Example 21 | J071 | C45H26D4IrN3S | 841.04 | 841.20 | ＞99％ |
| Example 22 | J074 | C48H42IrN3S | 885.14 | 885.27 | ＞99％ |
| Example 23 | J075 | C42H22D8IrN3S | 809.03 | 809.22 | ＞99％ |
| Example 24 | J076 | C53H38IrN3S | 941.19 | 941.24 | ＞99％ |
| Example 25 | J087 | C39H25FIrN3S | 778.91 | 779.13 | ＞99％ |
| Example 26 | J090 | C63H42IrN3S | 1065.30 | 1065.27 | ＞99％ |
| Example 27 | J099 | C59H38IrN3S | 1013.23 | 1013.24 | ＞99％ |
| Example 28 | J107 | C56H60IrN3S | 999.37 | 999.41 | ＞99％ |
Example 29 preparation of organic electroluminescent device (OLED) Using light-emitting Compound
The structure of the prepared OLED device is as follows: ITO anode/HIL/HTL/EML/HBL/ETL/EIL/cathode a, ITO anode: coating with a thickness of
Cleaning the ITO (indium tin oxide) glass substrate in distilled water for 2 times, ultrasonically cleaning for 30min, repeatedly cleaning with distilled water for 2 times, ultrasonically cleaning for 10min, ultrasonically cleaning with methanol, acetone and isopropanol in sequence (each time for 5min), drying, transferring into a plasma cleaning machine for cleaning for 5min, and transferring into an evaporation machine to useThe substrate is an anode, and other functional layers are sequentially evaporated on the substrate.
b. HIL (hole injection layer): a hole injection layer was formed by evaporation of 2-TNATA (N1- (2-naphthyl) -N4, N4-bis (4- (2-naphthyl (phenyl) amino) phenyl) -N1-phenylbenzene-1, 4-diamine) at 60 nm.
c. HTL (hole transport layer): NPB (i.e., N '-diphenyl-N, N' - (1-naphthyl) -1, 1 '-biphenyl-4, 4' -diamine) was evaporated to 60nm to form a hole transport layer.
d. EML (light-emitting layer): a host material CBP (namely 4, 4'-N, N' -biphenyl dicarbazole) and a doping material J010 are mixed and evaporated at a weight ratio of 90:10 for 30nm to form a light-emitting layer.
e. HBL (hole blocking layer): a hole blocking layer was formed by evaporation of BALq 10 nm.
f. ETL (electron transport layer): alq 340 nm was evaporated to form an electron transport layer.
g. EIL (electron injection layer): and evaporating LiF by 0.2nm to form an electron injection layer.
h. Cathode: and evaporating Al for 150nm to form an anode, thereby obtaining the OLED device.
With reference to the above method, a series of OLED devices having different light-emitting compounds were prepared by replacing the light-emitting compound J010 with J036, J048, J054, J070, J001, J004, J009, J016, J024, J029, J035, J044, J050, J051, J058, J061, J063, J066, J069, J071, J074, J075, J076, J087, J090, J099, and J107, respectively.
Comparative example 1
An OLED device was fabricated as in example 21, except that the dopant material in the light-emitting layer was replaced with ir (ppy)3, having the following structure:
example 30
The OLED devices obtained in examples 1-20 and comparative example 1 were tested for emission performance using a KEITHLEY model 2400 measuring cell, a CS-2000 spectroradiometer, and for driving voltage, emission lifetime, and emission efficiency. The test results are shown in Table 2.
Table 2 luminescence property test results of examples 1 to 28 and comparative example 1
From the test results, the organic phosphorus luminescent compound shown in the chemical formula 1 provided by the invention can effectively reduce the driving voltage of an OLED device, and improve the luminous efficiency and the service life.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. An organic phosphorus luminescent compound, wherein the structural general formula of the organic phosphorus luminescent compound is shown in chemical formula 1:
wherein R is1a、R1b、R1c、R1d、R2a、R2b、R2c、R2d、R3a、R3b、R4a、R4b、R4c、R5a、R5b、R5c、R5dEach independently selected from: hydrogen, deuterium, halogen, cyanogenThe aryl group comprises a substituent or non-substituent C1-C8 alkyl group, a substituent or non-substituent C3-C30 cycloalkyl group and a substituent or non-substituent C6-C18 aryl group.
2. A preparation method of an organic phosphorus luminescent compound is characterized by comprising the following steps:
(1) under the protection of inert gas, mixing the compound A and iridium trichloride trihydrate, adding the mixture into a solvent I for heating reaction, wherein the solvent I is ethylene glycol ethyl ether and/or water, performing suction filtration after the reaction is finished, and sequentially washing and drying to obtain a bridging ligand B;
(2) under the protection of inert gas, mixing the bridging ligand B and silver trifluoromethanesulfonate, adding the mixture into a solvent II for heating reaction, wherein the solvent II is dichloromethane and/or methanol, and performing column chromatography separation and rotary evaporation concentration after the reaction to obtain an intermediate C;
(3) under the protection of inert gas, mixing the intermediate C with the compound D, adding the mixture into a solvent III, heating and reacting, wherein the solvent III is ethanol and/or tetrahydrofuran, and performing suction filtration, washing, drying, column chromatography and rotary evaporation concentration after the reaction is finished to obtain an organophosphorus luminescent compound shown in a chemical formula 1;
the synthetic route of the organic phosphorus luminescent compound shown in chemical formula 1 is as follows:
3. the method of claim 2, wherein the inert gas used in steps (1) to (3) is nitrogen or argon;
in the step (1):
the molar ratio of the compound A to the iridium trichloride trihydrate is (2-3) to 1;
the heating reaction temperature is 130-140 ℃, and the reaction time is 20-30 h;
the volume ratio of the ethylene glycol ethyl ether to the water in the solvent I is 3: 1;
the ratio of the compound A to the solvent I is 64.4mmol (350-400) mL;
the detergent is one or a mixture of water, absolute ethyl alcohol and petroleum ether;
the drying temperature is 70-80 ℃, and the drying time is 5 h.
4. The method for preparing an organophosphorus luminescent compound according to claim 2, wherein the molar ratio of the bridging ligand B to the silver trifluoromethanesulfonate in the step (2) is 1 (2-3);
the reaction temperature is 55-65 ℃, and the reaction time is 20-30 h;
the volume ratio of dichloromethane to methanol in the solvent II is 5: 2;
the ratio of the bridging ligand B to the solvent II is 6.4mmol: 105-140 mL.
The column chromatography separation adopts a short column for column chromatography.
5. The method for preparing an organophosphorus luminescent compound according to claim 2, wherein the molar ratio of the intermediate C to the compound D in the step (3) is 1 (2-3);
the reaction temperature is 75-80 ℃, and the reaction time is 20-30 h;
ethanol in the solvent III;
the ratio of the intermediate C to the solvent III is 11.2mmol: 90-130 mL.
The detergent is ethanol; the drying temperature is 70-80 ℃, and the drying time is 5 hours;
the column chromatography is carried out by using dichloromethane and petroleum ether according to the weight ratio of 1: mixing the raw materials in a volume ratio of 1-15 to serve as a solvent, and performing silica gel column chromatography.
6. Use of the organophosphorus light-emitting compound according to claim 1 for producing an organic electroluminescent device.
7. An organic electroluminescent device comprising an anode, a cathode and an intermediate layer disposed between the anode and the cathode;
wherein the intermediate layer comprises a light-emitting layer comprising the organic phosphorus light-emitting compound according to claim 1.
8. The organic electroluminescent device as claimed in claim 7, wherein the anode is selected from indium tin oxide, zinc oxide or indium oxide, and the thickness of the anode is 10 to 500 nm;
the cathode is selected from Al, Li, Na, K, Mg, Ca, Au, Ag or Pb, and the thickness of the cathode is 100-1000 nm.
9. The organic electroluminescent device as claimed in claim 7, wherein the organic phosphorus luminescent compound accounts for 0.5-10% of the luminescent layer;
the luminescent layer also comprises a main material, and the main material is one or a mixture of more of 4, 4'-N, N' -biphenyl dicarbazole, octahydroxyquinoline, a metal phenoxy benzothiazole compound, polyfluorene, aromatic condensed rings and a zinc complex;
the thickness of the light emitting layer is 10-500 nm.
10. The organic electroluminescent device according to claim 7, wherein the intermediate layer further comprises a functional layer;
the functional layer is one or more of a hole injection layer, a hole transport layer, a hole injection-hole transport functional layer, an Electron Blocking Layer (EBL), a hole blocking layer, an electron transport layer, an electron injection layer and an electron transport-electron injection functional layer.
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