CN101200634B - Soluble branch substituted anthracene molecule blue material as well as preparation method and uses thereof - Google Patents
Soluble branch substituted anthracene molecule blue material as well as preparation method and uses thereof Download PDFInfo
- Publication number
- CN101200634B CN101200634B CN2007100312713A CN200710031271A CN101200634B CN 101200634 B CN101200634 B CN 101200634B CN 2007100312713 A CN2007100312713 A CN 2007100312713A CN 200710031271 A CN200710031271 A CN 200710031271A CN 101200634 B CN101200634 B CN 101200634B
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- China
- Prior art keywords
- anthracene
- preparation
- soluble branch
- reaction
- bromide
- Prior art date
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 150000001454 anthracenes Chemical class 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 50
- -1 9-anthracene boric acid ester Chemical class 0.000 claims abstract description 28
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 18
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 14
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000004327 boric acid Substances 0.000 claims abstract description 10
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005577 anthracene group Chemical group 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 7
- 238000005401 electroluminescence Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract 2
- ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 9-bromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=CC2=C1 ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 0.000 abstract 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 28
- 239000000203 mixture Substances 0.000 description 28
- 239000003921 oil Substances 0.000 description 28
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- 238000004440 column chromatography Methods 0.000 description 23
- 238000005406 washing Methods 0.000 description 22
- 238000004821 distillation Methods 0.000 description 21
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 19
- 238000001816 cooling Methods 0.000 description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000010410 layer Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- OJAJSXUQPFAGQH-UHFFFAOYSA-N 2-bromo-1-phenyl-9h-carbazole Chemical compound BrC1=CC=C(C2=CC=CC=C2N2)C2=C1C1=CC=CC=C1 OJAJSXUQPFAGQH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000010338 boric acid Nutrition 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- GMVJKSNPLYBFSO-UHFFFAOYSA-N 1,2,3-tribromobenzene Chemical compound BrC1=CC=CC(Br)=C1Br GMVJKSNPLYBFSO-UHFFFAOYSA-N 0.000 description 4
- BRSRUYVJULRMRQ-UHFFFAOYSA-N 1-phenylanthracene Chemical compound C1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 BRSRUYVJULRMRQ-UHFFFAOYSA-N 0.000 description 4
- FIHILUSWISKVSR-UHFFFAOYSA-N 3,6-dibromo-9h-carbazole Chemical compound C1=C(Br)C=C2C3=CC(Br)=CC=C3NC2=C1 FIHILUSWISKVSR-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 239000012230 colorless oil Substances 0.000 description 4
- 239000000412 dendrimer Substances 0.000 description 4
- 229920000736 dendritic polymer Polymers 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KHUBQFGTXOUHKT-UHFFFAOYSA-N 1-naphthalen-1-yl-9h-carbazole Chemical compound C1=CC=C2C(C3=C4NC=5C(C4=CC=C3)=CC=CC=5)=CC=CC2=C1 KHUBQFGTXOUHKT-UHFFFAOYSA-N 0.000 description 3
- UBYXVKSUVOLUQB-UHFFFAOYSA-N CC(C)(C)C1=C(C(=CC=C1)Br)C2=CC=CC=C2 Chemical class CC(C)(C)C1=C(C(=CC=C1)Br)C2=CC=CC=C2 UBYXVKSUVOLUQB-UHFFFAOYSA-N 0.000 description 3
- 0 CC(C)O*1OC(C)(C)C(C)(C)O1 Chemical compound CC(C)O*1OC(C)(C)C(C)(C)O1 0.000 description 3
- 229920000144 PEDOT:PSS Polymers 0.000 description 3
- 229910000085 borane Inorganic materials 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- ANPSUGBBTPJBLQ-UHFFFAOYSA-N 1-(3-bromophenyl)naphthalene Chemical compound BrC1=CC=CC(C=2C3=CC=CC=C3C=CC=2)=C1 ANPSUGBBTPJBLQ-UHFFFAOYSA-N 0.000 description 2
- YZDVVYQMGKAORT-UHFFFAOYSA-N 1-bromo-2-(2-ethylhexoxy)benzene Chemical compound CCCCC(CC)COC1=CC=CC=C1Br YZDVVYQMGKAORT-UHFFFAOYSA-N 0.000 description 2
- UEVKWTASYVIROP-UHFFFAOYSA-N 1-bromo-2-butylbenzene Chemical group CCCCC1=CC=CC=C1Br UEVKWTASYVIROP-UHFFFAOYSA-N 0.000 description 2
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical class BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 2
- QPTWWBLGJZWRAV-UHFFFAOYSA-N 2,7-dibromo-9-H-carbazole Natural products BrC1=CC=C2C3=CC=C(Br)C=C3NC2=C1 QPTWWBLGJZWRAV-UHFFFAOYSA-N 0.000 description 2
- FWPXWVYUNHYGPE-UHFFFAOYSA-N 2-(3-bromophenyl)naphthalene Chemical compound BrC1=CC=CC(C=2C=C3C=CC=CC3=CC=2)=C1 FWPXWVYUNHYGPE-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGCASFLJQULJBN-UHFFFAOYSA-N CCCCC(CC)COC1=CC=CC(Br)=C1C1=CC=CC=C1 Chemical compound CCCCC(CC)COC1=CC=CC(Br)=C1C1=CC=CC=C1 HGCASFLJQULJBN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LZTBZQSQFMLGQH-UHFFFAOYSA-N naphthalen-1-yloxyboronic acid Chemical compound C1=CC=C2C(OB(O)O)=CC=CC2=C1 LZTBZQSQFMLGQH-UHFFFAOYSA-N 0.000 description 2
- DCMWJXWYTURQIM-UHFFFAOYSA-N naphthalen-2-yloxyboronic acid Chemical compound C1=CC=CC2=CC(OB(O)O)=CC=C21 DCMWJXWYTURQIM-UHFFFAOYSA-N 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- KTADSLDAUJLZGL-UHFFFAOYSA-N 1-bromo-2-phenylbenzene Chemical compound BrC1=CC=CC=C1C1=CC=CC=C1 KTADSLDAUJLZGL-UHFFFAOYSA-N 0.000 description 1
- MRWOLCXDZFDRIG-UHFFFAOYSA-N 1-naphthalen-2-yl-9h-carbazole Chemical compound C1=CC=CC2=CC(C3=C4NC=5C(C4=CC=C3)=CC=CC=5)=CC=C21 MRWOLCXDZFDRIG-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- NZWIYPLSXWYKLH-UHFFFAOYSA-N 3-(bromomethyl)heptane Chemical compound CCCCC(CC)CBr NZWIYPLSXWYKLH-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OWDFLNXJWZQZAT-UHFFFAOYSA-N Brc(cc1)ccc1-[n](c(c(c1c2)c3)ccc3-c3c(cccc4)c4ccc3)c1ccc2-c1cccc2c1cccc2 Chemical compound Brc(cc1)ccc1-[n](c(c(c1c2)c3)ccc3-c3c(cccc4)c4ccc3)c1ccc2-c1cccc2c1cccc2 OWDFLNXJWZQZAT-UHFFFAOYSA-N 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N Brc1cc(Br)cc(Br)c1 Chemical compound Brc1cc(Br)cc(Br)c1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- OINIUIKKLHQRFO-UHFFFAOYSA-N CC1(C)OB(c2c(cccc3)c3c(-c3cc(-c(c(F)c4)ccc4F)cc(-c(ccc(F)c4)c4F)c3)c3c2cccc3)OC1(C)C Chemical compound CC1(C)OB(c2c(cccc3)c3c(-c3cc(-c(c(F)c4)ccc4F)cc(-c(ccc(F)c4)c4F)c3)c3c2cccc3)OC1(C)C OINIUIKKLHQRFO-UHFFFAOYSA-N 0.000 description 1
- GBHRGHJTZFOAKE-UHFFFAOYSA-N CC1(C)OB(c2c(cccc3)c3cc3ccccc23)OC1(C)C Chemical compound CC1(C)OB(c2c(cccc3)c3cc3ccccc23)OC1(C)C GBHRGHJTZFOAKE-UHFFFAOYSA-N 0.000 description 1
- YILGGFDTMLLWTP-UHFFFAOYSA-N CCCCC(CC)COC1=C(C=C(C=C1)C2=CC3=CC=CC=C3C=C2)C4=CC=CC=C4 Chemical compound CCCCC(CC)COC1=C(C=C(C=C1)C2=CC3=CC=CC=C3C=C2)C4=CC=CC=C4 YILGGFDTMLLWTP-UHFFFAOYSA-N 0.000 description 1
- OVPRRDUNZQOJHI-UHFFFAOYSA-N CCCCC(CC)COC1=C(C=C(C=C1)C2=CC=CC3=CC=CC=C32)C4=CC=CC=C4 Chemical compound CCCCC(CC)COC1=C(C=C(C=C1)C2=CC=CC3=CC=CC=C32)C4=CC=CC=C4 OVPRRDUNZQOJHI-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- LKAXNQLBFBBFBR-UHFFFAOYSA-N Fc(cc1)cc(F)c1-c1cc(-c2c(cccc3)c3c(-c(cc3)ccc3N(c(ccc(-c3cccc4c3cccc4)c3)c3C3=C4)C3=CCC4c3cccc4c3cccc4)c3c2cccc3)cc(-c(c(F)c2)ccc2F)c1 Chemical compound Fc(cc1)cc(F)c1-c1cc(-c2c(cccc3)c3c(-c(cc3)ccc3N(c(ccc(-c3cccc4c3cccc4)c3)c3C3=C4)C3=CCC4c3cccc4c3cccc4)c3c2cccc3)cc(-c(c(F)c2)ccc2F)c1 LKAXNQLBFBBFBR-UHFFFAOYSA-N 0.000 description 1
- 235000001018 Hibiscus sabdariffa Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000005291 Rumex acetosa Nutrition 0.000 description 1
- 240000007001 Rumex acetosella Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001126918 Sycon Species 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- IRVOXGVXGLJEIX-UHFFFAOYSA-N anthracene bromobenzene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C12.BrC1=CC=CC=C1 IRVOXGVXGLJEIX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical class 0.000 description 1
- 229950001336 bromamide Drugs 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
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- 238000004020 luminiscence type Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 235000007715 potassium iodide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
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- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000003513 sheep sorrel Nutrition 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012546 transfer Methods 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
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Indole Compounds (AREA)
Abstract
The present invention discloses soluble branch substituted anthracene molecular blue light-emitting material and a preparation method and an application thereof. The anthracene molecular blue light-emitting material considers anthracene as a center, and soluble branch group Dendron and rigid group Ar1 are respectively accessed at the two ends of the anthracene to ensure that the prepared emittingmaterial with an asymmetrical structure has certain solubility and can be purified by solution method. When the anthracene molecular blue light-emitting material is prepared, 9-bromoanthracene or 9-anthracene boric acid ester is used as reaction raw material, the soluble branch group Dendron is introduced by the palladium catalysis Suzuki coupling reaction, then N-bromosuccinimide is used for bromizing at 10-position of the anthracene to obtain an anthracene molecular bromide; the Ar1 is introduced into the obtained bromide or boric acid prepared from the bromide by the palladium catalysis Suzuki coupling reaction to obtain a target product. The material has the advantages of synthesis and purification and has important application prospect at electroluminescence display, illumination andlaser.
Description
Technical field
The present invention relates to the anthracene molecular material that soluble branch replaces.Be specifically related to anthracene molecule blue material of soluble branch replacement and preparation method thereof, the invention still further relates to the application of this molecular material in luminescent material and photodiode and illuminating device preparation.
Background technology
1987, the Tang of Kodak and VanSlyke prepared with small molecules organometallic complex 8-hydroxyquinoline aluminum (Alq
3) as " sandwich type " (anode/luminescent layer/negative electrode) membrane electro luminescent device of luminescent layer, started electroluminescent basis of minimum molecule and applied research.In 20 years, organic electroluminescent LED (OLEDs) is owing to its potential application in indicating meter of new generation and lighting engineering causes extensive attention in the past.
In recent years, organic conjugate dendrimer (conjugated dendrimers), because have small molecules (structure is determined, controlledly synthesis, conventional organic chemistry method purifying) and both advantages of macromolecular material (film-formability) concurrently, the application in electroluminescent device comes into one's own just day by day.Dendrimer is made up of three parts usually, i.e. nuclear (core), branch (dendron) and surface group (surface/peripheral groups) is by to the change of above-mentioned three integral parts or modify the functionalization that can realize dendrimer easily.The branch group can also utilize its space structure characteristics to avoid piling up mutually between the molecule except increasing the film forming properties that has improved solubility of material, can also transfer energy to luminescence center as " branch sub antenna " simultaneously.Recently, a series of organic molecule luminescent materials that have branch are developed.Yet, make commercial luminescent device, now still there are some important challenges, comprise the external quantum efficiency (EQE) of material, operating voltage (power consumption), illuminant colour purity and permanent stability etc. be optimized choice again all.The researchist makes great efforts to improve the method for luminescent device performance, and wherein material is one of important factor.It is higher that many research groups are devoted to develop external quantum efficiency (EQE) always, and operating voltage (power consumption) is lower, better and the molecular luminescence material with permanent stability of illuminant colour purity.
Summary of the invention
The anthracene molecule blue material that provides soluble branch to replace is provided at existing technical disadvantages.This molecular material has the quantum yield height, high color purity, the advantage that permanent stability are good.Be applicable to panchromatic demonstration of high resolution and illumination.
Another object of the present invention is to provide the preparation method of the anthracene molecule blue light electroluminescence material that a kind of soluble branch replaces.
Of the present invention also have a purpose to be the application that the anthracene molecule blue material that soluble branch replaces is applied to prepare luminescent layer in photodiode and the illuminating device.
To achieve the above object of the invention, the present invention has adopted following technical scheme:
The anthracene molecule blue material that soluble branch replaces is characterized in that this material has a kind of in the following chemical structural formula:
Described Dendron is solvable type branch group, for containing the lyotropy alkyl, alkoxyl group, the perhaps phenyl of fluorine-based replacement; Described Ar
1Be rigid radical, be aromatic hydrocarbons, condensed-nuclei aromatics or derivatives thereof.
The described lyotropy alkyl that contains, alkoxyl group, perhaps fluorine-based phenyl branch Dendron have a kind of in following structural unit (1)～(4):
Wherein, R
1～R
5Be to contain alkyl, alkoxyl group or the fluorine atom that carbon number is 1-20.
Described Ar
1Have a kind of in (5) in the following structural unit～(18):
Wherein, R
1Be to contain alkyl or the alkoxyl group that carbon number is 1-20.
Described anthracene molecule blue material dissolves in organic solvent.
The preparation method of the anthracene molecule blue material that soluble branch replaces comprises the steps:
(1) with 9-bromine anthracene or 9-anthracene boric acid ester as reaction raw materials, introduce soluble branch group Dendron by palladium catalysis Suzuki linked reaction, use the N-bromo-succinimide in the 10-position of anthracene bromination then, obtain anthracene molecule bromide; The mol ratio of 9-bromine anthracene or 9-anthracene boric acid ester and Dendron is 1: 1;
(2), introduce Ar by palladium catalysis Suzuki linked reaction with step (1) gained bromide or the boric acid ester for preparing by bromide
1, obtain target product; Bromide or the boric acid ester and the Ar that prepare by bromide
1Mol ratio be 1: 1.
Described palladium catalysis Suzuki linked reaction is introduced soluble branch group Dendron and is meant that reactant is under protection of inert gas; range of reaction temperature is at 70～110 ℃; reaction time range is at 8～36h, and using mol ratio is that 1%～3% triphenyl is seen and four closed palladium as catalyzer.
Described palladium catalysis Suzuki linked reaction is introduced Ar
1Be meant reactant under protection of inert gas, range of reaction temperature is at 70～110 ℃, and reaction time range is at 8～36h, and using mol ratio is that 1%～3% triphenyl is seen and four closed palladium as catalyzer.
The application in the preparation luminescent material of the anthracene molecule blue material that described soluble branch replaces.
The application in preparing luminous and laser diode of the anthracene molecule blue material that described soluble branch replaces.
Than existing material and technology, the present invention has following advantage and beneficial effect:
(1) the anthracene molecule blue light electroluminescence material of soluble branch replacement is synthetic simple, and it is convenient to purify; The anthracene molecule blue material that soluble branch of the present invention replaces adopts the molecular designing of unsymmetric structure, can synthesize different modules, i.e. Dendron and Ar earlier
1, the two ends of receiving the anthracene molecule then respectively, so synthetic route is fairly simple, it is convenient to purify.
(2) anthracene molecule blue light electroluminescence material has solvability and film-forming properties preferably; Because the introducing of branch (Dendron) group and the sterie configuration of whole molecule make material can be dissolved in multiple organic solvent, as toluene, chloroform, chlorobenzene etc., and the film of method formation homogeneous that can be by vacuum evaporation or spin coating.
(3) anthracene molecule blue light electroluminescence material has higher film morphology stability (vacuum evaporation or spin-coating film); Because the rigid radical (Ar of anthracene molecule self rigidity and introducing
1) make material have preferably thermostability and have higher film morphology stability, avoided material crystallization and influence the performance and the life-span of device in the life-time service process.
(4) photoluminescence that anthracene molecule blue light electroluminescence material is high and electroluminescent efficiency.The molecular structure of branch group and bifurcated has been avoided intermolecular buildup effect, therefore has high photoluminescence and electroluminescent efficiency.
Embodiment
Come the preparation of anthracene molecule blue material that soluble branch is replaced to be further described below in conjunction with specific embodiment and legend, but the present invention's scope required for protection is not limited to the related scope of embodiment.
Embodiment 1,2,4, the preparation of 6-three bromo-iodobenzenes:
The mechanism of reaction is as follows:
With 2,4, (46.95g 142mmol) pours in the there-necked flask 6-bromamide, and (13.95g, 7.62mL 142mmol), are added drop-wise in the flask mechanical stirring rapidly then to measure the vitriol oil under cryosel bath condition.Take by weighing Sodium Nitrite (14.73g, 213mmol) be dissolved in the 100mL distilled water, pour in the dropping funnel, treat that temperature begins slow dropping when dropping to below-5 ℃, controlled temperature is no more than 5 ℃ and dropwises back stirring 1h, with potassiumiodide (47.25g, 282mmol) be dissolved in the 100ml distilled water, pour in the dropping funnel, temperature control slowly drips and adds strong mixing at 0～5 ℃, dropwises the back and stirs 30min.Mixing liquid is poured into the NaHSO of 300mL
3Use CH after stirring in the aqueous solution
2Cl
2Extraction, oil reservoir NaHCO
3After washing 2 times, solution uses anhydrous MgSO
4Dry.Rotary evaporation obtains red solid after removing and desolvating, and obtains white, needle-shaped crystals through recrystallization.
Embodiment 2,3, the preparation of two pairs of tert-butyl-phenyl bromobenzenes of 5-:
The there-necked flask of 500mL with Ar exhaust 30min after, (11.1g 468.45mmol), iodine crystalline substance (3～4), THF (200mL), stirs to add the magnesium powder.Will (89.73g 416.4mmol) injects constant pressure funnel with the THF of 50mL dilution back, logical Ar gas shiled to tertiary butyl bromobenzene.Slowly in flask, drip, and flask is heated, take off and seethe with excitement up to the brown of solution with hair dryer to tertiary butyl bromobenzene.Dropwise back oil bath backflow 2h and obtain Grignard reagent.Then Grignard reagent is transferred in the there-necked flask of 1L, with 2,4, (45.87g 104.1mmol) joins the THF dissolving of also using 150mL in the constant pressure funnel to 6-three bromo-iodobenzenes, slowly is added drop-wise in the flask then.Dropwise the back and continue to stir 1h, reflux 3h then.After mixing liquid is cooled to room temperature, slowly pours in the 300mL 2M dilute hydrochloric acid on the rocks and stir.Use CH then
2Cl
2Extraction, oil reservoir MgSO
4Dry.Underpressure distillation obtains yellow solid after removing and desolvating, and obtains white crystal behind recrystallization.
The proton nmr spectra analytical results:
1H NMR (300MHz, CDCl
3, ppm) δ 1.36 (s, 18H), 7.48 (td, 4H, J
1=8.7 Hz, J
2=2.2 Hz), 7.53 (td, 4H, J
1=8.7 Hz, J
2=2.2 Hz), 7.66 (d, 2H, J=1.6 Hz), 7.69 (t, 1H, J=1.6Hz).18 H in 18 H at chemical shift δ in the proton nmr spectra High-Field=1.36 places and the target molecule on the tertiary butyl are corresponding, in low the number of aryl moiety H also with target molecule meet fine.
The mechanism of reaction is as follows:
Embodiment 3,3, the preparation of two couples of tert-butyl-phenyl-1-of 5-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) benzene:
With 3, two pairs of tert-butyl-phenyls of 5--1-bromobenzene (4.21g 10mmol) is dissolved in the 80mL exsiccant tetrahydrofuran (THF),
Logical nitrogen protection is cooled to-78 ℃ with liquid nitrogen/Virahol.Slowly (5.6mL, 14mmol) in reaction flask, mixture is by the colourless yellow that becomes for the n-BuLi of dropping 2.5M.Dropwise the back and continue to stir 1h down, add 4,4,5 with syringe then at-78 ℃, 5-tetramethyl--1,3, (2.8mL, 14mmol), yellow disappears 2-Virahol ylboronic acid ester immediately, is warmed up to room temperature then naturally and stirs 24h.Mixture is used CH after washing with distillation
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.
Obtain white solid through column chromatography.
Embodiment 4
3, the preparation of 5-two (3, two pairs of tert-butyl-phenyl phenyl of 5-) bromobenzene
With 3, two couples of tert-butyl-phenyl-1-of 5-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) benzene (8.09g, 17.3mmol), 1-bromo-3, the 5-diiodo-benzene (3.53g, 8.64mmol) and toluene (60mL), ethanol (30mL), 2M aqueous sodium carbonate (30mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.2g 0.17mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 24h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain white solid through column chromatography.
Embodiment 4, to (2-ethyl hexyl oxy) bromobenzene:
(5g, 104.1mmol), (1.44g 8.7mmol) pours in the there-necked flask of 100mL KI, and adding 30mL ethanol is stirred to solid and all dissolves with KOH.(15g 86.7mmol) is dissolved in the 10mL ethanol, slowly is added drop-wise in the there-necked flask under protection of nitrogen gas, and solution gradually becomes reddish-brown, is heated to 80 ℃ of stirring reaction 3h with p bromophenol.(20.1g 104.1mmol) slowly is added drop-wise in the there-necked flask by constant pressure funnel, at 80 ℃ of following lucifuge backflow 48h with 1-bromo-2-ethyl hexane.The mixture cooled and filtered is with washing with alcohol filter cake twice, the anhydrous MgSO of sorrel oily liquids that obtains
4Dry.Through column chromatography, obtain colourless oil liquid.
Embodiment 5,2-(to (2-ethyl hexyl oxy) phenyl)-4,4,5,5-tetramethyl--1,3,2-two oxa-borines
Will (5.68g 20mmol) be dissolved in the 80mL exsiccant tetrahydrofuran (THF), and logical protection is cooled to-78 ℃ with liquid nitrogen/Virahol to (2-ethyl hexyl oxy) bromobenzene.Slowly (10mL, 25mmol) in reaction flask, mixture is by the colourless yellow that becomes for the n-BuLi of dropping 2.5M.Dropwise the back and continue to stir 1h down, add 4,4,5 with syringe then at-78 ℃, 5-tetramethyl--1,3, (4.65g, 25mmol), yellow disappears 2-Virahol ylboronic acid ester immediately, is warmed up to room temperature then naturally and stirs 24h.Mixture is used CH after washing with distillation
2Cl
2Extract oil reservoir MgSO 3 times
4Dried overnight.Underpressure distillation removes the back sherwood oil/CH that desolvates
2Cl
2Column chromatography obtains colourless oil liquid.
Embodiment 6,3, and 5-two is to the preparation of (2-ethyl hexyl oxy) phenyl bromobenzene:
With 2-(to (2-ethyl hexyl oxy) phenyl)-4,4,5,5-tetramethyl--1,3,2-two oxa-borine (6.64g, 20mmol), all tribromo-benzene (3.14g, 10mmol) and toluene (40mL), ethanol (20mL), 2M aqueous sodium carbonate (20mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.23g 0.2mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain colorless oil through column chromatography.
Embodiment 7,3, and 5-two is to the preparation of (2-ethyl hexyl oxy) phenyl-1-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) benzene
With 3, (1.27g 2.25mmol) is dissolved in the 25mL exsiccant tetrahydrofuran (THF) 5-two, and logical nitrogen protection is cooled to-78 ℃ with liquid nitrogen/Virahol to (2-ethyl hexyl oxy) phenyl bromobenzene.Slowly (1.2mL, 3mmol) in reaction flask, mixture is by the colourless yellow that becomes for the n-BuLi of dropping 2.5M.Dropwise the back and continue to stir 1h down, add 4,4,5 with syringe then at-78 ℃, 5-tetramethyl--1,3, (0.68mL, 3.4mmol), yellow disappears 2-Virahol ylboronic acid ester immediately, is warmed up to room temperature then naturally and stirs 24h.Mixture is used CH after washing with distillation
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain colorless oil through column chromatography.
Embodiment 8,3, the preparation of 5-two (3,5-two is to (2-ethyl hexyl oxy) phenyl) phenyl bromobenzene:
With 3,5-two is to (2-ethyl hexyl oxy) phenyl-1-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) benzene (1.23g, 2mmol), equal tribromo-benzene (0.29g, 0.92mmol) and toluene (20mL), ethanol (10mL), 2M aqueous sodium carbonate (10mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.046g 0.04mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain colorless oil through column chromatography.
Embodiment 9,1, the preparation of 3-two bromo-5-(1-naphthyl) benzene:
With 1-naphthyl boric acid (3.0g, 17.4mmol), all tribromo-benzene (8.24g, 26.2mmol) and toluene (50mL), ethanol (25mL), 2M aqueous sodium carbonate (25mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.
Pd (PPh with catalytic amount
3)
4(0.3g 0.26mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extraction, oil reservoir MgSO
4Dry.Obtain white solid through column chromatography.
Embodiment 10, and bromo-3-is to the preparation of (2-ethyl hexyl oxy) phenyl-5-(1-naphthyl) benzene:
With 2-(to (2-ethyl hexyl oxy) phenyl)-4,4,5,5-tetramethyl--1,3,2-two oxa-borine (3.684g, 11mmol), 1,3-two bromo-5-(1-naphthyl) benzene (4g, 11mmol) and toluene (50mL), ethanol (25mL), 2M aqueous sodium carbonate (25mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.127g 0.11mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain colorless oil through column chromatography.
Embodiment 11,1, the preparation of 3-two bromo-5-(2-naphthyl) benzene:
With 2-naphthyl boric acid (3.0g, 17.4mmol), all tribromo-benzene (8.24g, 26.2mmol) and toluene (50mL), ethanol (25mL), 2M aqueous sodium carbonate (25mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.3g 0.26mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extraction, oil reservoir MgSO
4Dry.Obtain white solid through column chromatography.
Embodiment 12, and bromo-3-is to the preparation of (2-ethyl hexyl oxy) phenyl-5-(2-naphthyl) benzene:
With 2-(to (2-ethyl hexyl oxy) phenyl)-4,4,5,5-tetramethyl--1,3,2-two oxa-borine (3.684g, 11mmol), 1,3-two bromo-5-(2-naphthyl) benzene (4g, 11mmol) and toluene (50mL), ethanol (25mL), 2M aqueous sodium carbonate (25mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.127g 0.11mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extraction, oil reservoir MgSO
4Dry.Obtain white solid through column chromatography.
Embodiment 13,3, the preparation of 5-two (2,4-two fluorine-based phenyl) bromobenzene
With 2,4-two fluorine-based phenylo boric acids (3.1g, 2mmol), 1-bromo-3, the 5-diiodo-benzene (4.1g, 1mmol) and toluene (30mL), ethanol (15mL), 2M aqueous sodium carbonate (15mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.07g 0.06mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain white solid through column chromatography.
The proton nmr spectra analytical results:
1H NMR (300MHz, CDCl
3, ppm) δ 6.9-7.01 (m, 4H), 7.38-7.46 (m, 2H), 7.54-7.56 (m, 1H), 7.65 (s, 2H).What the number of aryl moiety H and target molecule met in the low field of proton nmr spectra is fine.
Embodiment 14,3, the preparation of 6-two (1-naphthyl) carbazole:
With 1-naphthyl boric acid (4.87g, 28.3mmol), 3,6-dibromo carbazole (3.83g, 11.8mmol) and toluene (30mL), ethanol (15mL), 2M aqueous sodium carbonate (15mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.323g 0.28mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain white solid through column chromatography and recrystallization.
Embodiment 15,3, the preparation of 6-two (2-naphthyl) carbazole:
With 2-naphthyl boric acid (4.87g, 28.3mmol), 3,6-dibromo carbazole (3.83g, 11.8mmol) and toluene (30mL), ethanol (15mL), 2M aqueous sodium carbonate (15mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.
Pd (PPh with catalytic amount
3)
4(0.323g 0.28mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extraction, oil reservoir MgSO
4Dry.Obtain white solid through column chromatography and recrystallization.
Embodiment 16,3, and 6-two (1-naphthyl)-9-is to the preparation of bromophenyl carbazole:
With 3, and 6-two (1-naphthyl) carbazole (1.2g, 2.86mmol), 1, the 4-dibromobenzene (2.03g, 8.6mmol) and CuI (55mg), 1 8-crown-6 (38mg), K
2CO
3(1.2g), DMPU (1mL) joins in the two-mouth bottle, and logical nitrogen exhaust 30min is heated to 140 ℃ of reaction 12h then.Use CH after the mixture cooling
2Cl
2CH is used in dilution then
2Cl
2Oil is crossed a quick post and is removed inorganics.Obtain white solid through column chromatography and recrystallization again.
The proton nmr spectra analytical results:
1H NMR (300MHz, CDCl
3, ppm) δ 7.39-7.55 (m, 10H), 7.57-7.63 (m, 4H), 7.78-7.82 (m, 2H), 7.85-7.88 (m, 2H), 7.90-7.93 (m, 2H), 7.98-8.00 (m, 2H), 8.25 (d, 2H, J=0.9Hz)
What the number of aryl moiety H and target molecule met in the low field of proton nmr spectra is fine.
Embodiment 17,3, the preparation of 6-two (1-naphthyl)-9-(7-bromo-9,9 '-volution fluorenes-2-yl) carbazole:
With 3, and 6-two (1-naphthyl) carbazole (1.5g, 3.6mmol), 2,7-two bromo-9,9 '-volution fluorenes (2.55g, 5.5mmol) and CuI (68mg), 18-crown-6 (48mg), K
2CO
3(1.5g), DMPU (1mL) joins in the two-mouth bottle, and logical nitrogen exhaust 30min is heated to 140 ℃ of reaction 12h then.Use CH after the mixture cooling
2Cl
2CH is used in dilution then
2Cl
2Oil is crossed a quick post and is removed inorganics.Obtain white solid through column chromatography and recrystallization again.
Embodiment 18, the preparation of 9-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) anthracene:
(6.26g 24.4mmol) is dissolved in the 100mL exsiccant tetrahydrofuran (THF), and logical nitrogen protection is cooled to-78 ℃ with liquid nitrogen/Virahol with 9-bromine anthracene.Slowly (14.6ml, 36.5mmol) in reaction flask, mixture is by the colourless yellow that becomes for the n-BuLi of dropping 2.5M.Dropwise the back and continue to stir 1h down, add 4,4,5 with syringe then at-78 ℃, 5-tetramethyl--1,3, (10ml 48.7mmol), is warmed up to room temperature and stirs 24h 2-Virahol ylboronic acid ester then naturally.The mixture underpressure distillation is used CH after removing partial solvent after distilling washing
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain white solid through column chromatography and recrystallization again.
The proton nmr spectra analytical results:
1H NMR (300MHz, CDCl
3, ppm) δ 1.58 (s, 12H), 7.44-7.50 (m, 4H), 7.98-8.01 (m, 2H), 8.46 (d, 2H, J=9.3 Hz), 8.48 (s, 1H).12 H are corresponding with the H of four methyl in the proton nmr spectra High-Field, in low the number of aryl moiety H also with target molecule meet fine.
Embodiment 19, the preparation of 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-) anthracene:
Introducing soluble branch group Dendron (3, two pairs of tert-butyl-phenyl bromobenzenes of 5-) by palladium catalysis Suzuki linked reaction, specifically is with 9-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) anthracene (1.83g, 6mmol), 3, two pairs of tert-butyl-phenyl bromobenzenes of 5-(2.52g, 6mmol) and toluene (20mL), ethanol (10mL), 2M aqueous sodium carbonate (10mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.With Pd (PPh
3)
4(0.07g 0.06mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain white solid through column chromatography and recrystallization again.
The proton nmr spectra analytical results:
1H NMR (300 MHz, CDCl
3, ppm) δ 1.36 (s, 18H), 7.35-7.38 (m, 2H), 7.44-7.49 (m, 6H), 7.65-7.68 (m, 6H), 7.83 (d, 2H, J=9.0Hz), 8.01 (s, 1H), 8.06 (d, 2H, J=8.6Hz), 8.52 (s, 1H).18 H in 18 H at chemical shift δ in the proton nmr spectra High-Field=1.36 places and the target molecule on the tertiary butyl are corresponding, in low the number of aryl moiety H also with target molecule meet fine.
Embodiment 20,9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-bromine anthracene:
With 9-(3, two pairs of tertiary butyls of 5-) phenyl-bromide anthracene (2.1g, 4mmol), then with LiClO
4.3H
2O/SiO
2(5mg/200mg) join in the reaction flask, lucifuge stirs 10min.(0.8g 4.5mmol) joins in the reaction flask, stirs 1h with NBS then.Obtain yellow solid through column chromatography.
The proton nmr spectra analytical results:
1H NMR (300MHz, CDCl
3, ppm) δ 1.36 (s, 18H), 7.38 (ddd, 2H, J
1=8.8Hz, J
2=4.4Hz, J
3=1.2Hz), and 7.46-7.50 (m, 4H), 7.57-7.62 (m, 4H), 7.65 (dd, 4H, J
1=8.5 Hz, J
2=1.9 Hz), 7.81 (d, 2H, J=8.8Hz), 8.02 (t, 1H, J=1.8Hz), 8.63 (d, 2H, J=8.8Hz).18 H in 18 H at chemical shift δ in the proton nmr spectra High-Field=1.36 places and the target molecule on the tertiary butyl are corresponding, in low the number of aryl moiety H also with target molecule meet fine.
The preparation of embodiment 21:9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) anthracene
(4.45g 7.45mmol) is dissolved in the 70mL exsiccant tetrahydrofuran (THF), and logical nitrogen protection is cooled to-78 ℃ with liquid nitrogen/Virahol with 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-) anthracene.Slowly (4.5mL, 11.2mmol) in reaction flask, mixture is by the colourless yellow that becomes for the n-BuLi of dropping 2.5M.Dropwise the back and continue to stir 1h down, add 4,4,5 with syringe then at-78 ℃, 5-tetramethyl--1,3, (3mL 2.78mmol), is warmed up to room temperature and stirs 24h 2-Virahol ylboronic acid ester then naturally.The mixture underpressure distillation is used CH after removing partial solvent after distilling washing
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain light yellow solid through column chromatography.
The proton nmr spectra analytical results:
1H NMR (300MHz, CDCl
3, ppm) δ 1.36 (s, 18H), 1.61 (s, 12H), 7.32 (ddd, 2H, J
1=8.8Hz, J
2=4.4Hz, J
3=1.2Hz), and 7.45-7.50 (m, 6H), 7.59 (d, 2H, J=1.8 Hz), 7.66 (dd, 4H, J
1=8.6Hz, J
2=1.9Hz), 7.79 (d, 2H, J=8.6Hz), 7.99 (t, 1H, J=1.7Hz), 8.46 (d, 2H, J=8.6Hz).18 H in 18 H at chemical shift δ in the proton nmr spectra High-Field=1.36 places and the target molecule on the tertiary butyl are corresponding, 12 H in 12 H at δ=1.36 places and the target molecule on four methyl are corresponding, in low the number of aryl moiety H also with target molecule meet fine.
Embodiment 22, and 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-is to the preparation of (3,6-two (1-naphthyl) carbazole-9-yl) phenylanthracene:
Introduce Ar by palladium catalysis Suzuki linked reaction
1(3,6-two (1-naphthyl)-9-is to the bromophenyl carbazole) specifically is with 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) anthracene (0.31g, 0.5mmol), 3,6-two (1-naphthyl)-9-to the bromophenyl carbazole (0.29g, 0.5mmol) and toluene (16mL), ethanol (8mL), 2M aqueous sodium carbonate (8mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.057g 0.05mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain light yellow solid through column chromatography.
The proton nmr spectra analytical results:
1H NMR (300MHz, CDCl
3, ppm) δ 1.38 (s, 18H), 7.38-7.53 (m, 12H), 7.55-7.61 (m, 4H), 7.67-7.75 (m, 8H), 7.81-8.02 (m, 14H), 8.05-8.10 (m, 3H), 8.34 (d, 2H, J=1.1Hz).18 H in 18 H at chemical shift δ in the proton nmr spectra High-Field=1.38 places and the target molecule on the tertiary butyl are corresponding, in low the number of aryl moiety H also with target molecule meet fine.
Embodiment 23
9-(3,5-two (2,4-two fluorine-based phenyl) phenyl)-10-is to the preparation of (3,6-two (1-naphthyl) carbazole-9-yl) phenylanthracene
Introduce Ar by palladium catalysis Suzuki linked reaction
1(3,6-two (1-naphthyl)-9-is to the bromophenyl carbazole) specifically is with 9-(3,5-two (2,4-two fluorine-based phenyl) phenyl)-10-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) anthracene (0.3g, 0.5mmol), 3,6-two (1-naphthyl)-9-is to bromophenyl carbazole (0.29g, 0.5mmol) and toluene (16mL), ethanol (8mL), 2M aqueous sodium carbonate (8mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.057g 0.05mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain light yellow solid through column chromatography.
The proton nmr spectra analytical results:
1H NMR (300 MHz, CDCl
3, ppm) δ 6.94-7.03 (m, 4H), 7.43-7.63 (m, 14H), 7.69-7.71 (m, 4H), 7.82 (d, 2H, J=8.3 Hz), 7.84 (s, 1H), 7.87-7.96 (m, 10H), 8.00 (dd, 2H, J
1=8.3Hz, J
2=1.8Hz), 8.08 (J=8.4Hz), 8.34 (what J=1.5Hz) number of aryl moiety H and target molecule met in low of the proton nmr spectra is fine for d, 2H for d, 2H.
Embodiment 24, the preparation of 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-(7-(3,6-two (1-naphthyl) carbazole-9-yl)-9,9 '-volution fluorenes-2-yl) anthracene
Introduce Ar by palladium catalysis Suzuki linked reaction
1(3,6-two (1-naphthyl)-9-(7-bromo-9,9 '-volution fluorenes-2-yl) carbazole), specifically be with 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-(4,4,5,5-tetramethyl--1,3,2-two oxa-boryl) anthracene (0.32g, 0.5mmol), 3,6-two (1-naphthyl)-9-(7-bromo-9,9 '-volution fluorenes-2-yl) carbazole (0.42g, 0.5mmol) and toluene (16mL), ethanol (8mL), 2M aqueous sodium carbonate (8mL) join in the two-mouth bottle logical nitrogen bubble exhaust 30min.Pd (PPh with catalytic amount
3)
4(0.057g 0.05mmol) joins rapidly in the reaction flask, is heated to 90 ℃ of back flow reaction 12h then.CH is used after washing with distillation in mixture cooling back
2Cl
2Extract oil reservoir MgSO 3 times
4Dry.Obtain light yellow solid through column chromatography.
The proton nmr spectra analytical results:
1H NMR (300 MHz, CDCl
3, ppm) δ 1.35 (d, 18H, J=4.7Hz), 6.96 (s, 1H), 7.08-7.14 (m, 3H), 7.19-7.32 (m, 8H), 7.35-7.56 (m, 17H), 7.59-8.00 (m, 20H), 8.18-8.26 (m, 4H).18 H in 18 H at chemical shift δ in the proton nmr spectra High-Field=1.35 places and the target molecule on the tertiary butyl are corresponding, in low the number of aryl moiety H also with target molecule meet fine.
Embodiment 25, the preparation process of spin coating electroluminescent diode:
Resistance is that tin indium oxide (ITO) the conductive glass substrate of 10-20 Ω/mouth is successively through acetone, washing composition, deionized water and Virahol ultrasonic cleaning are after oven for drying, handled 4 minutes with PLASMA (oxygen plasma), further remove the organic impurity on the conductive glass.And then, be coated with one deck PEDOT:PSS (Baytron P4083 purchases in BayerAG) film in the spin coating mode on the ito glass sheet of handling, thickness is about 50nm.Afterwards, substrate 80 ℃ of dryings in vacuum drying oven were removed in 8 hours desolvate, then at glove box (Vacuum Atmosphere Co.) the lining spin coating luminescent layer of nitrogen atmosphere.Then be 3 * 10
-4Under the vacuum of Pa, evaporation metal Ba (4nm)/Al (120nm) negative electrode or CsF (2nm)/Al (120nm).The device efficient lighting area is 0.17cm
2Film thickness is measured with TencorAlfa Step-500 surface profiler.The sedimentation rate of metal electrode evaporation and thickness thereof are measured with thickness/speed instrument STM-100 of Sycon Instrument.Except the spin coating process of PEDOT:PSS film was finished in atmospheric environment, other all links were all finished in the glove box of nitrogen environment.As shown in table 1, the electroluminescent properties of spin coating device is with 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-is to (3,6-two (1-naphthyl) carbazole-9-yl) phenylanthracene (A), 9-(3,5-two (2,4-two fluorine-based phenyl) phenyl)-10-is that example describes to (3,6-two (1-naphthyl) carbazole-9-yl) phenylanthracene (B) as luminescent layer.Structure is: ITO/PEDOT:PSS (50nm)/A or B (55nm)/TPBI (30nm)/CsF (2nm)/Al (120nm).
As shown in table 1, when A, two kinds of materials of B were used for the electroluminescent diode of spin coating method making, it was very low to open bright voltage, and maximum current efficient is near 2cd/A, and high-high brightness is near 2000cd/m
2, chromaticity coordinates is positioned at ethereal blue light zone.Be that performance is higher in the film forming small molecules electroluminescent device of reporting at present of solution method.
Table 1
| Compound | Glow peak (nm) | Open bright voltage (V) | Maximum current efficient (cd/A) | High-high brightness (cd/m 2) | Chromaticity coordinates (x, y) |
| A B | 448 454 | 4.5 4.2 | 1.88@5.7V 1.81@5.4V | 1860 1266 | 0.158，0.104 0.162，0.122 |
Embodiment 26
The preparation process of evaporation electroluminescent diode:
Evaporation layer of metal oxide compound (MoO) on the ito glass substrate of handling at first, thickness is 6nm, then evaporation thickness be the NPB of 40nm as hole transmission layer, evaporation luminescent layer (30nm), electric transmission/hole blocking layer BCP (10nm) and electron transport material AlQ successively afterwards
3(20nm), at last again on organic layer evaporation interfacial layer LiF (1.5nm) and Al (200nm) metal level as negative electrode, all evaporations all in vacuum tightness less than 3 * 10
-4Carry out under the Pa, wherein the vaporator rate of organic materials is controlled at 2～5nm/s, and the vaporator rate of LiF is 0.02～0.04nm/s, and the vaporator rate of aluminium electrode is 8～10nm/s, and the light-emitting area of device is 9mm
2Organic light-emitting device thickness is monitored by the quartz oscillation film-thickness monitoring, electric current-the brightness of device-voltage characteristic is measured by Keithley 2400 that has corrected silicon photo-detector and Keithley 2000 measuring systems, electroluminescent spectrum is by JY SPEX CCD3000 spectrometer measurement, and all measurements are all carried out in air at room temperature.As shown in table 2, the electroluminescent properties of evaporation device is that example describes with 9-(3, two pairs of tert-butyl-phenyl phenyl of 5-)-10-(7-(3,6-two (1-naphthyl) carbazole-9-yl)-9,9 '-volution fluorenes-2-yl) anthracene (C) as luminescent layer.Structure is: ITO/MoO (6nm)/NPB (70nm)/sample (30nm)/BCP (10nm)/AlQ
3(20nm)/LiF (1.5nm)/Al.
As shown in table 2, when material C was used for electroluminescent diode that evaporation coating method makes, it was very low to open bright voltage, and maximum current efficient is near 3cd/A, the luminous blue region that also is positioned at.
Table 2
| Compound | Glow peak (nm) | Open bright voltage (V) | Maximum current efficient (cd/A) |
| C | 461 | 4.1 | 2.87@6.1V |
Claims (7)
1. the anthracene molecule blue material that replaces of soluble branch is characterized in that this material has a kind of in the following chemical structural formula:
Described Dendron is solvable type branch group, has following structural unit (1), wherein R
1～R
5Be to contain alkyl, alkoxyl group or the fluorine atom that carbon number is 1-20;
Described Ar
1Be rigid radical, have a kind of in the following structural unit:
2. the anthracene molecule blue material that soluble branch according to claim 1 replaces is characterized in that described anthracene molecule blue material is dissolved in organic solvent.
3. the preparation method of the anthracene molecule blue material of claim 1 or 2 described soluble branch replacements is characterized in that comprising the steps:
(1) with 9-bromine anthracene or 9-anthracene boric acid ester as reaction raw materials, introduce soluble branch group Dendron by palladium catalysis Suzuki linked reaction, use the N-bromo-succinimide in the 10-position of anthracene bromination then, obtain anthracene molecule bromide; The mol ratio of 9-bromine anthracene or 9-anthracene boric acid ester and Dendron is 1: 1;
(2), introduce Ar by palladium catalysis Suzuki linked reaction then with step (1) gained bromide or the boric acid ester for preparing by bromide
1, obtain target product; Bromide or the boric acid ester and the Ar that prepare by bromide
1Mol ratio be 1: 1.
4. the preparation method of the anthracene molecule blue material that soluble branch according to claim 3 replaces; it is characterized in that described palladium catalysis Suzuki linked reaction introducing soluble branch group Dendron is meant that reactant is under protection of inert gas; range of reaction temperature is at 70～110 ℃; reaction time range is at 8～36h, and using mol ratio is that 1%～3% triphenyl phosphorus four closes palladium as catalyzer.
5. the preparation method of the anthracene molecule blue material that soluble branch according to claim 3 replaces is characterized in that described palladium catalysis Suzuki linked reaction introducing Ar
1Be meant reactant under protection of inert gas, range of reaction temperature is at 70～110 ℃, and reaction time range is at 8～36h, and using mol ratio is that 1%～3% triphenyl phosphorus four closes palladium as catalyzer.
6. the application of anthracene molecule blue material in the preparation luminescent material of claim 1 or 2 described soluble branch replacements.
7. the application of anthracene molecule blue material in preparing luminous and laser diode of claim 1 or 2 described soluble branch replacements.
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