CN116789625A - Main body material and preparation method thereof, luminescent layer material and organic electroluminescent device - Google Patents
Main body material and preparation method thereof, luminescent layer material and organic electroluminescent device Download PDFInfo
- Publication number
- CN116789625A CN116789625A CN202310759950.1A CN202310759950A CN116789625A CN 116789625 A CN116789625 A CN 116789625A CN 202310759950 A CN202310759950 A CN 202310759950A CN 116789625 A CN116789625 A CN 116789625A
- Authority
- CN
- China
- Prior art keywords
- formula
- layer
- organic
- substituted
- compound
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 77
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 5
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 80
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000012044 organic layer Substances 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 230000005525 hole transport Effects 0.000 claims description 8
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 96
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 60
- 238000006243 chemical reaction Methods 0.000 description 60
- 239000012074 organic phase Substances 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000011259 mixed solution Substances 0.000 description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- 238000005406 washing Methods 0.000 description 18
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 16
- 238000004440 column chromatography Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000003208 petroleum Substances 0.000 description 16
- 238000004809 thin layer chromatography Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000008346 aqueous phase Substances 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 125000005577 anthracene group Chemical group 0.000 description 12
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 12
- 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 12
- 230000032258 transport Effects 0.000 description 12
- -1 tetramethyl tetrahydronaphthyl Chemical group 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000009423 ventilation Methods 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 8
- 239000011368 organic material Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 238000005481 NMR spectroscopy Methods 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
- 239000002019 doping agent Substances 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
- 230000002035 prolonged effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 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 6
- 238000009825 accumulation Methods 0.000 description 5
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000004949 mass spectrometry Methods 0.000 description 5
- OPDGWSYNXPRREB-UHFFFAOYSA-N 5,6,7,8-tetramethyl-1,2,3,4-tetrahydronaphthalene Chemical group C1CCCC2=C(C)C(C)=C(C)C(C)=C21 OPDGWSYNXPRREB-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- FTMRMQALUDDFQO-UHFFFAOYSA-N naphtho[2,3-b][1]benzofuran Chemical compound C1=CC=C2C=C3C4=CC=CC=C4OC3=CC2=C1 FTMRMQALUDDFQO-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 238000004770 highest occupied molecular orbital Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- QENGPZGAWFQWCZ-UHFFFAOYSA-N 3-Methylthiophene Chemical compound CC=1C=CSC=1 QENGPZGAWFQWCZ-UHFFFAOYSA-N 0.000 description 2
- FKIFDWYMWOJKTQ-UHFFFAOYSA-N 9-bromo-10-naphthalen-2-ylanthracene Chemical compound C12=CC=CC=C2C(Br)=C(C=CC=C2)C2=C1C1=CC=C(C=CC=C2)C2=C1 FKIFDWYMWOJKTQ-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000002219 fluoranthenes Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 150000003220 pyrenes Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical compound C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical compound N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101100391182 Dictyostelium discoideum forI gene Proteins 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 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 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001082241 Lythrum hyssopifolia Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004235 Orange GGN Substances 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JUTIJVADGQDBGY-UHFFFAOYSA-N anthracene photodimer Chemical compound C12=CC=CC=C2C2C(C3=CC=CC=C33)C4=CC=CC=C4C3C1C1=CC=CC=C12 JUTIJVADGQDBGY-UHFFFAOYSA-N 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical compound B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000000609 carbazolyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004827 dibenzo-1,4-dioxins Chemical group 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002964 pentacenes Chemical class 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
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 150000002987 phenanthrenes Chemical class 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 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
- 229940083082 pyrimidine derivative acting on arteriolar smooth muscle Drugs 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to the technical field of organic electroluminescent materials, in particular to a main material and a preparation method thereof, a luminescent layer material and an organic electroluminescent device. The host material is selected from compounds shown in the following structural formula I:wherein m and n are independently selected from integers of 0 or 1, and m and n are not both 0 at the same time; when m is not 0, L represents a bond or a substituted or unsubstituted C6-C24 arylene group; when m is 0, L represents a substituted or unsubstitutedC6-C24 aryl; ar, when present, represents a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C6-C30 heteroaryl group fused to a benzene ring, the heteroatoms of which contain at least one of O, S, N, si and Se. The main material solves the problems of poor solubility and no film forming property of the existing luminescent material, and improves the problem that the luminescent material is not ideal in terms of device life and luminous efficiency.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to a main material and a preparation method thereof, a luminescent layer material and an organic electroluminescent device.
Background
The organic light emitting device converts electric energy into light by applying electric power to an organic electroluminescent material, and generally includes an anode, a cathode, and an organic layer formed between or outside of both electrodes. The organic layer may include a hole injection layer, a hole transport layer, a hole assist layer, a light emitting assist layer, an electron blocking layer, a light emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, a capping layer, and the like.
In order to manufacture an organic light emitting device in the related art, a deposition method is generally used. However, the deposition method for manufacturing an organic light emitting device generally has a problem of material loss, in order to solve the problem, a technology of a solution method capable of improving production efficiency by reducing the material loss to manufacture the device has been developed, and a material that can be used during the solution method has been developed.
The materials used in the solution process for the organic light emitting device are required to have the characteristics described below. First, materials used in organic light emitting devices need to be capable of forming a storable homogeneous solution. Since commercial materials used for the deposition method have good crystallinity, the materials are not well dissolved in the solution, or crystals thereof are easily formed even if the materials are formed into a solution, the concentration gradient of the solution is likely to change over the storage time, or defective devices are likely to be formed. Second, a material for the solution method needs to be excellent in coatability so that a thin film having a uniform thickness can be formed without occurrence of a hole or aggregation phenomenon during formation of the thin film, and when an organic light emitting device is manufactured, the material needs to have excellent current efficiency and excellent service life characteristics.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a main body material, a preparation method thereof, a luminescent layer material and an organic electroluminescent device. The main material solves the problems of poor solubility and no film forming property of the existing luminescent material, and improves the problem that the luminescent material is not ideal in terms of device life and luminous efficiency.
The invention is realized in the following way:
in a first aspect, the present invention provides a host material selected from the group consisting of compounds represented by the following structural formula I:
wherein m and n are independently selected from integers of 0 or 1, and m and n cannot be 0 at the same time;
when m is not 0, L represents a bond or a substituted or unsubstituted C6-C24 arylene group;
when m is 0, L represents a substituted or unsubstituted C6-C24 aryl group;
ar in the presence or absence thereof represents a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C6-C30 heteroaryl group condensed on a benzene ring, and the heteroatom thereof contains at least any one of O, S, N, si and Se.
In a second aspect, the present invention provides a method for preparing a host material according to the foregoing embodiment, including: the synthesis was performed with reference to the following synthesis route:
in a third aspect, the present invention provides a light emitting layer material comprising a dopant material and a host material according to the previous embodiments.
In a fourth aspect, the present invention provides an organic electroluminescent device, which includes an organic layer prepared from the light-emitting layer material according to the foregoing embodiment.
In an alternative embodiment, the organic layer includes at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and the light emitting layer is prepared from the above light emitting layer material.
The invention has the following beneficial effects: (1) According to the main material provided by the embodiment of the invention, the electron-withdrawing group (such as dibenzofuran or benzonaphthofuran) is introduced on the basis of the parent nucleus anthracene group, so that the electron transmission property of the material can be improved, the improvement of the device efficiency is promoted, meanwhile, the main material presents a rigid plane configuration, the accumulation and orientation of the material are facilitated in the process of forming a film, the high-efficiency energy transfer is realized, the stability of a compound can be improved, and the service life of the device is further prolonged. The tetramethyl tetralin group introduced at the other side of the anthryl group provides a conjugated electron distribution system of the compound, so that molecules are effectively and orderly stacked, and optimal carrier transmission and migration are exerted under a certain electric field; and meanwhile, the position of the substituent is adjusted, the molecular volume is increased, and the solubility of the material is effectively improved. Aryl (for example, phenyl or naphthyl) is introduced between the anthracene group and the tetramethyl tetrahydronaphthyl, and the non-para-position connection mode (for example, meta-position or ortho-position) enables the system to be prolonged through buffering of arylene on one hand, molecular mobility is high, so that luminous efficiency of the device is improved, on the other hand, the non-para-position connection mode can increase dihedral angles of the anthracene group and the tetramethyl tetrahydronaphthyl, molecular aggregation accumulation is reduced, solubility of a compound is improved, and operation of a device manufactured in a later stage is facilitated.
(2) The compound of the invention has excellent solubility, can be used for preparing the blue luminescent main material layer by a solution method, reduces the frequency of using a vacuum evaporation device, can form a film under the atmospheric pressure, and can be produced in a large area or continuously, thereby reducing the manufacturing cost.
(3) The main material and the blue light doped material can better transfer energy, reduce energy loss, realize the light emission of the doped material at about 460nm, effectively present the characteristics of the main material of the blue light emitting layer, and obviously improve the service life and the efficiency of the organic electroluminescent device prepared by the main material.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a compound 6 provided in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of compound 111 provided in example 2 of the present invention;
fig. 3 is a nuclear magnetic resonance hydrogen spectrum of a compound 191 provided in example 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The embodiment of the invention provides a main material which is selected from compounds shown in the following structural formula I:
wherein m andn is independently selected from integers of 0 or 1, and m and n cannot be 0 at the same time; when m is not 0, L represents a bond or a substituted or unsubstituted C6-C24 arylene group; when m is 0, L represents a substituted or unsubstituted C6-C24 aryl group; ar may be present or absent, where Ar is absent, the groups corresponding to n areDirectly attached to dibenzofuran, i.e.)>And may be attached to any position on the dibenzofuran. Ar, when present, represents a substituted or unsubstituted C6-C30 aryl or substituted or unsubstituted C6-C30 heteroaryl group fused to a benzene ring, the heteroatoms of which contain at least one of O, S, N, si, se.
According to the main material provided by the embodiment of the invention, the electron-withdrawing group (such as dibenzofuran or benzonaphthofuran) is introduced on the basis of the parent nucleus anthracene group, so that the electron transmission property of the material can be improved, the improvement of the device efficiency is promoted, meanwhile, the main material presents a rigid plane configuration, the accumulation and orientation of the material are facilitated in the process of forming a film, the high-efficiency energy transfer is realized, the stability of a compound can be improved, and the service life of the device is further prolonged. The tetramethyl tetralin group introduced at the other side of the anthryl group provides a conjugated electron distribution system of the compound, so that molecules are effectively and orderly stacked, and optimal carrier transmission and migration are exerted under a certain electric field; and meanwhile, the position of the substituent is adjusted, the molecular volume is increased, and the solubility of the material is effectively improved. Aryl (for example, phenyl or naphthyl) is introduced between the anthracene group and the tetramethyl tetrahydronaphthyl, and the non-para-position connection mode (for example, meta-position or ortho-position) enables the system to be prolonged through buffering of arylene on one hand, molecular mobility is high, so that luminous efficiency of the device is improved, on the other hand, the non-para-position connection mode can increase dihedral angles of the anthracene group and the tetramethyl tetrahydronaphthyl, molecular aggregation accumulation is reduced, solubility of a compound is improved, and operation of a device manufactured in a later stage is facilitated.
Further, when Ar is presentAr and dibenzofuran whenAny one of the three positions 1,2, 3 and 3,4 on the benzene ring is condensed.
Ar, when present, may be selected from a substituted or unsubstituted C6-C30 aryl (e.g., phenyl, naphthyl) or a substituted or unsubstituted C6-C30 heteroaryl having at least one of the heteroatoms O, S, N, si, se.
Further, when m is not 0, L represents any one of a bond, a phenylene group and a naphthylene group. When m is 0, L is selected from phenyl or naphthyl.
Further, the host material is selected from any one of the compounds represented by the following general formula I-1 or general formula I-2;
more preferably, the host material is selected from any one of the compounds of the following formulas I-a, I-b, I-c, I-d, I-e, I-f, I-g, I-h, I-I, I-j, I-k and I-l:
the definitions of m, n and Ar in the above general formulae I-1, I-2, I-a, I-b, I-c, I-d, I-e, I-f, I-g, I-h, I-I, I-j, I-k and I-l are consistent with those in the above general formula I.
More specifically, the host material is selected from any one of the compounds represented by the following structural formulas:
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
the compound provided by the embodiment of the invention has excellent solubility, can be used for preparing the blue light-emitting main body material layer by a solution method, reduces the frequency of using a vacuum evaporation device, can be used for forming films under the atmospheric pressure, and can be produced in a large area or continuously, thereby reducing the manufacturing cost.
The host materials provided by embodiments of the present invention may be prepared by synthetic methods known to those skilled in the art. Alternatively, the following reaction scheme is preferred for the preparation.
In a second aspect, the present invention provides a method for preparing a host material according to the foregoing embodiment, including: the synthesis was performed with reference to the following synthesis route:
in particular, for complex raw materials not disclosed, classical Suzuki coupling reactions are used for synthesis and are applied in the present invention. The preparation process comprises the following steps:
the step 1 specifically comprises the following steps:
adding a raw material A (1.0 eq), a raw material B (1.1 eq) and potassium carbonate (3.0 eq) into a reaction bottle, then adding a mixed solution of toluene, ethanol and water (V: V=3:1:1), ventilating three times, adding tetrakis (triphenylphosphine) palladium (0.01 eq) under the protection of nitrogen, heating to 80-120 ℃, and carrying out reflux reaction for 4-12h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:5) to give intermediate 1.
The step 2 specifically comprises the following steps:
adding the intermediate 1 (1.0 eq), the raw material C (1.1 eq) and cesium carbonate (2.0 eq) into a reaction bottle, then adding a mixed solution of toluene, ethanol and water (V: V=3:1:1), ventilating three times, adding palladium acetate (0.05 eq) and X-Phos (0.1 eq) under the protection of nitrogen, heating to 80-120 ℃, and refluxing for 4-12h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:6) to give intermediate 2.
The step 3 specifically comprises the following steps:
intermediate 2 (1.0 eq) and raw material D (1.1 eq) were added to a reaction flask, followed by dichloromethane, and reacted for 2-8h with stirring at room temperature; the reaction was detected by thin layer chromatography, after the reaction was completed, water was added to extract three times, the organic phase was retained, the organic phase was combined and concentrated, and intermediate 3 was obtained by purification by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:8).
The method comprises the steps of brominating an anthracene-containing intermediate product with N-bromosuccinimide, wherein active hydrogen is arranged at the para position of L-linked anthracene, and the substitution degree of bromination at the para position is highest.
Reference is made to:
1. basic organic chemistry (third edition, upper book), chen her own, pei Weiwei, xu Ruiqiu, pei Jian, press: higher education Press, publication time: 2005.06, ISBN:978-7-04-016637-8, pages 472-473.
2. Peng Ling the design, synthesis and application of phenyl bridged dianthracene-based organic deep blue luminescent material in organic electroluminescent device [ D ]. University of North America, 2019,36-38.
The step 4 specifically comprises the following steps:
adding the intermediate 3 (1.0 eq), the raw material E (1.1 eq) and the potassium carbonate (3.0 eq) into a reaction bottle, then adding a mixed solution of toluene, ethanol and water (V: V=3:1:1), ventilating for three times, adding tetra (triphenylphosphine) palladium (0.01 eq) under the protection of nitrogen, heating to 80-120 ℃, and refluxing for 4-12h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:5) to give intermediate 4.
The step 5 specifically comprises the following steps:
intermediate 4 (1.0 eq), raw material F (1.1 eq) and cesium carbonate (3.0 eq) are added into a reaction bottle, then a mixed solution of toluene, ethanol and water (V: V=3:1:1) is added, the mixture is ventilated three times, palladium acetate (0.05 eq) and X-Phos (0.1 eq) are added under the protection of nitrogen, the temperature is raised to 80-120 ℃, and reflux reaction is carried out for 4-12h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases are combined and concentrated and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:6) to give the general formula i.
In a third aspect, the present invention provides a light emitting layer material comprising a dopant material and a host material according to the previous embodiments.
In a fourth aspect, the present invention provides an organic electroluminescent device, which includes an organic layer prepared from the light-emitting layer material according to the foregoing embodiment. The organic layer may include a structure of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or the like as an organic layer. However, the structure of the organic light emitting element is not limited thereto, and may include a smaller or larger number of organic layers. Wherein the luminescent layer is prepared from the luminescent layer material.
In the case of producing an organic light-emitting device, the compound represented by the general formula I is applied by a solution coating method to form an organic layer. The solution coating method is, but not limited to, spin coating, dip coating, knife coating, ink jet printing, screen printing, spray coating, roll coating, and the like.
The organic light emitting element of the present invention may be of a top emission type, a bottom emission type or a bi-directional emission type, depending on the materials used.
As the anode material, a material having a large work function is generally preferable so that holes are smoothly injected into the organic material layer. Specific examples of anode materials that can be used in the present disclosure include: metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides such as zinc oxide, indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combination of metal and oxideFor example ZnO, al or SnO 2 Sb; conductive polymers, e.g. poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxythiophene)](PEDOT), polypyrrole, polyaniline, and the like, but is not limited thereto.
The hole injection material is a material that receives holes from the anode at a low voltage, and the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metalloporphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazabenzophenanthrene-based organic material, quinacridone-based organic material, perylene-based organic material, anthraquinone, and polyaniline-based and polythiophene-based conductive polymer, etc., but are not limited thereto, and may further contain additional compounds capable of p-doping.
The hole transporting material is a material capable of receiving holes from the anode or the hole injecting layer and transporting the holes to the light emitting layer, and a material having high hole mobility is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, a block copolymer having both a conjugated portion and a non-conjugated portion, and the like, but are not limited thereto.
The light emitting layer may include a host material and a dopant material. Examples of host materials include fused aromatic ring derivatives, heterocyclic ring-containing compounds, and the like. Specifically, examples of the condensed aromatic ring derivative include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and examples of the heterocycle-containing compound include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but examples thereof are not limited thereto.
Examples of dopant materials include aromatic amine derivatives, styrylamine compounds, borazine-based complexes, fluoranthene compounds, pyrene derivatives, metal complexes, and the like.
The hole blocking layer may be disposed between the electron transport layer and the light emitting layer, and materials known in the art, such as triazine-based compounds, may be used.
The electron transport layer may function to facilitate electron transport. The electron transporting material is a material that advantageously receives electrons from the cathode and transports the electrons to the light emitting layer, and a material having high electron mobility is suitable. The electron transport layer may include an electron buffer layer, a hole blocking layer, an electron transport layer.
As the cathode material, a material having a small work function is generally preferable so that electrons are smoothly injected into the organic material layer. Specific examples of the cathode material include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structural materials, e.g. LiF/Al or LiO 2 Al; etc., but is not limited thereto.
In addition to the inclusion of formula i in the host materials of the light-emitting layers disclosed herein, existing hole injection materials, hole transport materials, doping materials, hole blocking layers, electron transport layer materials may be used for other layer materials in OLED devices.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment of the invention provides a preparation method of a main material (compound 6), which is prepared by referring to the following synthetic route:
wherein, the raw material A-6 is the prior art (CAS number: 474688-73-8). The method comprises the following steps:
raw material A-6 (1.0 eq) (CAS number: 474688-73-8), raw material B-6 (1.1 eq) (CAS number: 2410249-54-4) and potassium carbonate (3.0 eq) were added to a reaction flask, followed by addition of a mixed solution of toluene, ethanol and water (V: V: 3:1:1), ventilation was performed three times, tetra (triphenylphosphine) palladium (0.01 eq) was added under nitrogen protection, the temperature was raised to 95℃and the reaction was refluxed for 6 hours; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:5) to give intermediate 1 (yield: 75.5%).
Intermediate 1 (1.0 eq), raw material C-6 (1.1 eq) (CAS number: 169126-63-0) and cesium carbonate (3.0 eq) were added to a reaction flask, followed by addition of a mixed solution of toluene, ethanol, water (V: V=3:1:1), ventilation three times, addition of palladium acetate (0.05 eq) and X-Phos (0.1 eq) under nitrogen protection, heating to 95 ℃, and reflux reaction for 8h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined, concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:6) to give compound-6 (yield: 77.6%).
The resulting compound-6 was subjected to detection analysis, and the results were as follows: HPLC purity: > 99.8%.
Mass spectrometry test: a mass spectrometer model Waters XEVO TQD, using an ESI source. Test value ((ESI, M/Z): [ M+H ]] + )：657.11。
Elemental analysis: the calculated values are: c,91.43; h,6.14; o,2.44; the test values are: c,91.12; h,6.36; o,2.68.
Nuclear magnetic resonance hydrogen spectrum: as shown in fig. 1 (compound 6).
Example 2
The embodiment of the invention provides a preparation method of a main material (compound 111), which is prepared by referring to the following synthetic route:
the method comprises the following steps: raw material A-111 (1.0 eq) (CAS number: 6134-55-0), raw material B-111 (1.1 eq) (CAS number: 2575133-50-3) and potassium carbonate (3.0 eq) were added into a reaction bottle, followed by adding a mixed solution of toluene, ethanol and water (V: V: V=3:1:1), ventilation was performed three times, tetrakis (triphenylphosphine) palladium (0.01 eq) was added under nitrogen protection, the temperature was raised to 95 ℃, and the reaction was refluxed for 6 hours; detecting the reaction by thin layer chromatography, and slightly after the reaction is finishedReducing the temperature, filtering with diatomite, removing salt and catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting the aqueous phase with dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:5) to give intermediate 1 (yield: 75.6%).
Intermediate 1 (1.0 eq), raw material C-111 (1.1 eq) (CAS number: 100622-34-2) and cesium carbonate (2.0 eq) were added to a reaction flask, followed by addition of a mixed solution of toluene, ethanol, water (V: V=3:1:1), three times of ventilation, addition of palladium acetate (0.05 eq) and X-Phos (0.1 eq) under nitrogen protection, heating to 95℃and reflux reaction for 7h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:6) to give intermediate 2 (yield: 71.4%).
Intermediate 2 (1.0 eq) and starting material D-111 (1.1 eq) (CAS number: 38144-44-4) were added to the reaction flask, followed by dichloromethane and reacted for 6h with stirring at room temperature; the reaction was detected by thin layer chromatography, after the completion of the reaction, water was added for extraction three times, the organic phases were retained, the organic phases were combined and concentrated, and intermediate 3 (yield: 80.2%) was obtained by purification by column chromatography using a mixed solution of methylene chloride and petroleum ether (V: v=1:8).
Intermediate 3 (1.0 eq), raw material E-111 (1.1 eq) (CAS number: 2639694-25-8) and potassium carbonate (3.0 eq) were added to a reaction flask, followed by addition of a mixed solution of toluene, ethanol, water (V: V=3:1:1), ventilation three times, addition of tetrakis (triphenylphosphine) palladium (0.01 eq) under nitrogen protection, heating to 95 ℃, and reflux reaction for 6h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:5) to give intermediate 4 (yield: 68.7%).
Intermediate 4 (1.0 eq), raw material F-111 (1.1 eq) (CAS number: 169126-63-0) and cesium carbonate (3.0 eq) were added to a reaction flask, followed by addition of a mixed solution of toluene, ethanol, water (V: V=3:1:1), ventilation three times, addition of palladium acetate (0.05 eq) and X-Phos (0.1 eq) under nitrogen protection, heating to 95 ℃, and reflux reaction for 8h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:6) to give compound-111 (yield: 80.1%).
The resulting compound-111 was subjected to detection analysis, and the results were as follows: HPLC purity: > 99.7%.
Mass spectrometry test: test value ((ESI, M/Z): [ M+H ] +): 843.35.
elemental analysis: the calculated values are: c,91.17; h,6.93; o,1.90; the test values are: c,90.89; h,7.17; o,2.15.
Nuclear magnetic resonance hydrogen spectrum: as shown in fig. 2 (compound 111).
Example 3
The embodiment of the invention provides a preparation method of a main material (compound 191), which is prepared by referring to the following synthetic route:
the method comprises the following steps: raw material A-191 (1.0 eq) (CAS number: 27452-17-1), raw material B-191 (1.1 eq) (CAS number: 63503-60-6) and potassium carbonate (3.0 eq) were added to a reaction flask, followed by adding a mixed solution of toluene, ethanol and water (V: V: 3:1:1), ventilation was performed three times, tetrakis (triphenylphosphine) palladium (0.01 eq) was added under nitrogen protection, the temperature was raised to 95 ℃, and the reaction was refluxed for 6 hours; detecting reaction by thin layer chromatography, slightly cooling after the reaction, filtering with diatomite, removing salt and catalyst, cooling filtrate to room temperature, washing with water for three times, retaining organic phase,then extracting the aqueous phase with dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:5) to give intermediate 1 (yield: 78.7%).
Intermediate 1 (1.0 eq), starting material C-191 (1.1 eq) (CAS No. 100622-34-2) and cesium carbonate (2.0 eq) were added to a reaction flask, followed by addition of a mixed solution of toluene, ethanol, water (V: v=3:1:1), three times of ventilation, addition of palladium acetate (0.05 eq) and X-Phos (0.1 eq) under nitrogen protection, heating to 95 ℃, and reflux reaction for 7h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:6) to give intermediate 2 (yield: 80.5%).
Intermediate 2 (1.0 eq) and starting material D-191 (1.1 eq) (CAS number 38144-44-4) were added to the reaction flask, followed by dichloromethane and reacted for 6h with stirring at room temperature; the reaction was detected by thin layer chromatography, after the completion of the reaction, water was added for extraction three times, the organic phases were retained, the organic phases were combined and concentrated, and intermediate 3 (yield: 79.8%) was obtained by purification by column chromatography using a mixed solution of methylene chloride and petroleum ether (V: v=1:8).
Intermediate 3 (1.0 eq), raw material E-191 (1.1 eq) (CAS number: 1627917-17-2) and potassium carbonate (3.0 eq) were added to a reaction flask, followed by addition of a mixed solution of toluene, ethanol, water (V: V=3:1:1), ventilation three times, addition of tetrakis (triphenylphosphine) palladium (0.01 eq) under nitrogen protection, heating to 95 ℃, and reflux reaction for 6h; detecting the reaction by using a thin layer chromatography, slightly reducing the temperature after the reaction is finished, filtering by using diatomite, removing salt and a catalyst, cooling the filtrate to room temperature, washing with water for three times, retaining an organic phase, and extracting an aqueous phase by using dichloromethane; the organic phases were combined and concentrated, and purified by column chromatography using a mixed solution of dichloromethane and petroleum ether (V: v=1:5) to give compound-191 (yield: 79.5%).
The resulting compound-191 was subjected to detection analysis, and the results were as follows: HPLC purity: > 99.8%.
Mass spectrometry test: test value ((ESI, M/Z): [ M+H ]] + )：657.05。
Elemental analysis: the calculated values are: c,91.43; h,6.14; o,2.44; the test values are: c,91.19; h,6.31; o,2.62.
Nuclear magnetic resonance hydrogen spectrum: as shown in fig. 3 (compound 191).
Examples 4 to 52
The synthesis of the following compounds was accomplished with reference to the synthesis methods of examples 1 to 3, using a mass spectrometer model Waters XEVO TQD, with low accuracy, using ESI source, and with mass spectrometry values as shown in table 1 below.
Table 1 mass spectrometry tests for examples 4-52
/>
Further, since other compounds of the present invention can be obtained by referring to the synthetic methods of the above-described examples, they are not exemplified herein.
Solubility test:
the host materials of examples 1 to 52 and the compounds represented by the following structural formulas (which were prepared by referring to the methods of examples 1 to 3 described above) were placed in chlorobenzene, toluene and methyl benzoate, respectively, and then the solubility of the compounds was recorded, and the results are shown in table 2.
Table 2 solubility test
/>
As is clear from the above table, the solubility of the compound of the present invention is far higher than that of the comparative compound in methyl benzoate, toluene and chlorobenzene, and particularly, the solubility in toluene is most excellent, so toluene is preferable as a solvent to dissolve the compound of the present invention in the production device.
Device example 1
The embodiment of the invention provides a preparation method of an organic electroluminescent device, which comprises the following steps:
a. ITO anode: washing ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, washing with ultrasonic waves for 30min, washing with distilled water for 2 times repeatedly, washing with ultrasonic waves for 10min, baking with a vacuum oven at 220 ℃ for 2 hours after washing, and cooling after baking is finished, so that the glass substrate can be used. And taking the substrate as an anode, and sequentially preparing other functional layers on the substrate.
b. HIL (hole injection layer): the hole injection layer materials HT (compound A) and P-dopant (compound B) were spin-coated on the prepared transparent ITO electrode with a coating composition mixed with cyclohexanone in a weight ratio of 8:2 to form a hole injection layer having a thickness of 30nm, and then the coating composition was cured on a hot plate at 220℃and 30 minutes under a nitrogen atmosphere.
c. HTL (hole transport layer): the hole injection layer was spin-coated with a composition of compound a dissolved in an organic solvent (toluene) at a weight ratio of 1%, thereby forming a hole transport layer having a thickness of 40nm, and then the coating composition was cured on a hot plate at 230 ℃ and 30 minutes under a nitrogen atmosphere.
d. EML (light emitting layer): a hole transport layer was spin-coated with a composition in which compound 1 provided in the above example was used as a host material and compound C (concentration: 3%) as a Dopant material was dissolved in an organic solvent (toluene) at a weight ratio of 0.1% to form a light emitting layer having a thickness of 20nm, and the coating composition was cured on a hot plate under a nitrogen atmosphere at 120 ℃ and 10 minutes.
And then the substrate is further transferred to an evaporator for evaporating other functional layers.
e. HBL (hole blocking layer): to be used forIs used as a hole blocking layer, and HB (compound D) of 5nm is vacuum deposited on the upper surface of the light-emitting layer.
f. ETL (electron transport layer): to be used forAn ET (compound E) of 20nm was vacuum-deposited as an electron transport layer on top of the hole blocking layer.
g. And (3) cathode: vapor deposition Al, thickness 100nm, vapor deposition rate
h. Packaging the substrate subjected to evaporation: firstly, a gluing device is adopted to carry out a coating process on a cleaned cover plate by UV glue, then the coated cover plate is moved to a lamination working section, a substrate subjected to vapor deposition is placed at the upper end of the cover plate, and finally the substrate and the cover plate are bonded under the action of a bonding device, and meanwhile, the UV glue is cured by illumination.
The above-mentioned required material structure is as follows:
device examples 2-52 and device comparative examples 1-6
Device examples 2-52 organic electroluminescent devices were manufactured with reference to the manufacturing method provided in device example 1, except that the compound 1 used in device example 1 was replaced with the compound 2,3, 4, 6, 7, 22, 28, 34, 43, 45, 47, 50, 51, 52, 63, 72, 81, 89, 95, 100, 111, 112, 113, 124, 148, 149, 160, 164, 169, 184, 185, 191, 193, 205, 213, 214, 223, 232, 235, 240, 244, 266, 274, 289, 290, 302, 307, 312, 316, 328, respectively, as a host material of the light emitting layer, and the corresponding organic electroluminescent devices were manufactured.
Device comparative examples 1-6 organic electronic devices were manufactured with reference to the manufacturing method provided in device example 1, except that compound 1 used in device example 1 was replaced with compounds a, b, c, d, e and f, respectively, described above.
The organic electroluminescent devices obtained in the above device examples 1 to 52 and device comparative examples 1 to 6 were characterized in terms of driving voltage, luminous efficiency, lifetime, etc. at a luminance of 1000 (nits), and the test results are shown in table 3 below:
TABLE 3 organic electroluminescent device test results
/>
Wherein, the luminous efficiency is current efficiency, and refers to the ratio of luminous brightness and current density of the device, and the unit is candela per ampere (cd/A); lifetime is defined as the time required for the brightness of the device to drop to 95% of the initial brightness under constant voltage or constant current conditions (T95).
As is clear from Table 3, the light emission wavelength of the device made of the compound of the present invention was about 460 nm. And compared with the organic electroluminescent devices prepared by using the comparative compounds a-f (device comparative examples 1-6) as the main materials, the organic electroluminescent devices prepared by using the compounds provided by the invention as the main materials in the luminescent layer have better solubility, are more favorable for preparing devices by a solvent method, and greatly improve the efficiency and the service life of the devices.
Comparative compound a and compound 191 are parallel comparative examples, which differ in that: the comparative compound a is connected with the position of the anthracene group and is a tetramethyl-tetrahydronaphthalene benzofuran group, the comparative compound has two groups (benzo-naphthofuran and tetramethyl-tetrahydronaphthalene benzofuran) with high rigidity and high steric hindrance, so that the configuration is twisted too much to easily form a carrier trap, and in the compound 191, the tetramethyl tetrahydronaphthalene and the anthracene group are bridged through the meta-position of the phenylene, so that the system is prolonged on one hand, the conjugation length of a main material is improved through the buffering of the phenylene, the long-range structure is formed, the injection and the transmission of carriers are facilitated, the luminous efficiency of the device is improved, the dihedral angles of the anthracene group and the tetramethyl tetrahydronaphthalene group are increased by a meta-position connection mode, the molecular volume is increased, the molecular aggregation accumulation is reduced, the solubility of the compound is improved, and the operation of the device manufactured in the later stage is facilitated.
Comparative compound b and compounds 4, 6 are parallel comparative examples, differing in that: in the invention, the compound 4 is connected with phenyl on one side of the anthracene group, the compound 6 is connected with naphthyl on one side of the anthracene group, and the comparative compound b is connected with dibenzo-p-dioxin group on one side of the anthracene group, and the group increases the molecular weight of the compound, so that the torsion angle of the configuration is larger, the inter-molecular distance is reduced, the operation of a device manufactured by the material in the later stage is not facilitated, the electrical stability of the group is poor, and the testing effect of the material in the later stage is influenced.
Comparative compounds c, d and compounds 184, 185 are parallel comparative examples, respectively, with the difference that: the comparative compounds c and d are previous researches of the inventor, which are recorded in CN113149943A, wherein a single phenyl group is connected at a corresponding position, and because the compounds c and d have low solubility in toluene, the materials are agglomerated, the doped materials cannot be doped into a main material well, the energy transfer efficiency is reduced, the efficiency and the service life are reduced, and the benzonaphthacene furan in the compounds 184 and 185 is connected with a tetramethyl tetrahydronaphthacene substituent, so that the rigidity structure of the compound is increased, the stability is enhanced, the molecular volume is increased, the solubility of the materials is effectively improved, and a device prepared by using the compound as a blue fluorescent main material has better luminous efficiency and longer service life.
Comparative compounds e, f and compounds 95, 266 and compounds 7, 164 are parallel comparative examples, respectively, which differ in that: the tetramethyl tetrahydronaphthyl and the anthryl in the comparative compound e are directly connected, the tetramethyl tetrahydronaphthyl in the comparative compound f is firstly connected with the phenyl, then the anthryl connected at the para position of the compound, the para position connection can reduce the solubility of the compound, and the tetramethyl tetrahydronaphthyl on one side of the compounds 95 and 266 and the compounds 7 and 164 are respectively connected with the dibenzofuran and the benzonaphthofuran and then are connected with the anthryl. In addition, the compound has a rigid plane configuration, so that the stability of the compound is improved, and the service life of a device is further prolonged.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A host material selected from the group consisting of compounds of the following structural formula I:
wherein m and n are independently selected from integers of 0 or 1, and m and n cannot be 0 at the same time;
when m is not 0, L represents a bond or a substituted or unsubstituted C6-C24 arylene group;
when m is 0, L represents a substituted or unsubstituted C6-C24 aryl group;
ar in the presence or absence thereof represents a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C6-C30 heteroaryl group condensed on a benzene ring, and the heteroatom thereof contains at least any one of O, S, N, si and Se.
2. The host material of claim 1, wherein the position at which Ar is fused to the benzene ring is any one of 3 positions of the benzene ring, 1,2, 3 and 3,4 positions;
preferably, ar is selected from phenyl.
3. The host material of claim 1, wherein when m is 0, L is selected from phenyl or naphthyl;
preferably, when m is not 0, L is selected from any one of a linkage, phenylene, and naphthylene.
4. A host material according to any one of claims 1 to 3, selected from any one of the compounds of the following general formula I-1 or general formula I-2;
5. a host material according to any one of claims 1-3, characterized in that it is selected from any one of the following compounds of formula I-a, formula I-b, formula I-c, formula I-d, formula I-e, formula I-f, formula I-g, formula I-h, formula I-I, formula I-j, formula I-k and formula I-l:
6. the host material of claim 1, selected from any one of the compounds of the following structural formulas:
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
/>
7. a method of preparing the host material of claim 1, comprising: the synthesis was performed with reference to the following synthesis route:
8. a light-emitting layer material, characterized in that it comprises a doping material and the host material of claim 1.
9. An organic electroluminescent device comprising an organic layer prepared from the luminescent layer material according to claim 8.
10. The organic electroluminescent device according to claim 9, wherein the organic layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, the light emitting layer being prepared from the light emitting layer material of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310759950.1A CN116789625A (en) | 2023-06-26 | 2023-06-26 | Main body material and preparation method thereof, luminescent layer material and organic electroluminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310759950.1A CN116789625A (en) | 2023-06-26 | 2023-06-26 | Main body material and preparation method thereof, luminescent layer material and organic electroluminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116789625A true CN116789625A (en) | 2023-09-22 |
Family
ID=88049246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310759950.1A Pending CN116789625A (en) | 2023-06-26 | 2023-06-26 | Main body material and preparation method thereof, luminescent layer material and organic electroluminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116789625A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117209461A (en) * | 2023-11-09 | 2023-12-12 | 浙江华显光电科技有限公司 | Organic photoelectric compound, composition with same and organic light-emitting device |
-
2023
- 2023-06-26 CN CN202310759950.1A patent/CN116789625A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117209461A (en) * | 2023-11-09 | 2023-12-12 | 浙江华显光电科技有限公司 | Organic photoelectric compound, composition with same and organic light-emitting device |
| CN117209461B (en) * | 2023-11-09 | 2024-03-22 | 浙江华显光电科技有限公司 | Organic photoelectric compound, composition with same and organic light-emitting device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1794259B1 (en) | New compound and organic light emitting device using the same(9) | |
| EP2660300B1 (en) | Novel compound, and organic light-emitting device using same | |
| CN112047873B (en) | Compound with triarylamine structure as core and preparation method thereof | |
| KR101567112B1 (en) | Compound having substituted pyridyl group and pyridoindole ring structure linked through phenylene group, and organic electroluminescent device | |
| CN109293516B (en) | Triarylamine compound and organic light-emitting device thereof | |
| CN115991689B (en) | Light-emitting auxiliary material, preparation method thereof and organic electroluminescent device | |
| WO2021136197A1 (en) | Nitrogen-containing compound, electronic element, and electronic device | |
| CN110903295A (en) | Organic compound with benzofuran derivative as core and application thereof | |
| CN111233867A (en) | Organic compound with carbazole derivative as core and application thereof in organic electroluminescent device | |
| CN112174835B (en) | Organic electroluminescent material and preparation method and application thereof | |
| CN117178652A (en) | Composition for organic optoelectronic device, and display device | |
| CN111662190A (en) | Organic compound containing pyrene or aza-pyrene and application thereof | |
| CN110776513B (en) | Organic compound and application thereof | |
| CN116789625A (en) | Main body material and preparation method thereof, luminescent layer material and organic electroluminescent device | |
| CN109574908B (en) | Compound containing spirodimethyl anthracene fluorene and application thereof in organic electroluminescent device | |
| CN115947706B (en) | Luminescent auxiliary material, preparation method and application | |
| KR20150082156A (en) | New compounds and organic light emitting device comprising the same | |
| CN112480114A (en) | Organic electroluminescent compound, preparation method and application thereof | |
| CN117164570A (en) | Electron transport material, preparation method thereof and organic electroluminescent device | |
| CN110003019B (en) | High-mobility organic compound with mesitylene as core and application thereof | |
| CN110734381B (en) | Compound with triarylamine as core and preparation method and application thereof | |
| CN114751888B (en) | Electron transport material, preparation method thereof, light-emitting device and light-emitting device | |
| CN115583887A (en) | Organic electroluminescent compound and preparation method and application thereof | |
| TW201127782A (en) | Triphenylene based aromatic compounds and OLEDs utilizing the same | |
| CN113004298B (en) | Anthracene ketone five-membered ring organic compound and application thereof |
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 |