CN108864195A - A kind of metal iridium complex and its organic luminescent device - Google Patents
A kind of metal iridium complex and its organic luminescent device Download PDFInfo
- Publication number
- CN108864195A CN108864195A CN201810580259.6A CN201810580259A CN108864195A CN 108864195 A CN108864195 A CN 108864195A CN 201810580259 A CN201810580259 A CN 201810580259A CN 108864195 A CN108864195 A CN 108864195A
- Authority
- CN
- China
- Prior art keywords
- unsubstituted
- substituted
- metal iridium
- iridium complex
- independently selected
- 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.)
- Withdrawn
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 36
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 4
- -1 Boryl Chemical group 0.000 claims description 49
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 20
- 125000004076 pyridyl group Chemical group 0.000 claims description 13
- 125000001072 heteroaryl group Chemical group 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 150000004982 aromatic amines Chemical class 0.000 claims description 11
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 7
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 238000007363 ring formation reaction Methods 0.000 claims description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000006884 silylation reaction Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 4
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 11
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 150000004696 coordination complex Chemical class 0.000 abstract description 5
- 239000002019 doping agent Substances 0.000 abstract description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 5
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 abstract description 4
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005401 electroluminescence Methods 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 3
- 239000011365 complex material Substances 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 32
- 150000001875 compounds Chemical class 0.000 description 31
- 239000000047 product Substances 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 14
- 125000000217 alkyl group Chemical group 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000001819 mass spectrum Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- 239000000758 substrate Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- 150000002503 iridium Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000005561 phenanthryl group Chemical group 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 125000001725 pyrenyl group Chemical group 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 125000001544 thienyl group Chemical group 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000003107 substituted aryl group Chemical group 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- BZLZKLMROPIZSR-UHFFFAOYSA-N triphenylsilicon Chemical compound C1=CC=CC=C1[Si](C=1C=CC=CC=1)C1=CC=CC=C1 BZLZKLMROPIZSR-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- YSFLQVNTBBUKEA-UHFFFAOYSA-N 1-bromo-2,4-dimethylbenzene Chemical compound CC1=CC=C(Br)C(C)=C1 YSFLQVNTBBUKEA-UHFFFAOYSA-N 0.000 description 1
- QSSXJPIWXQTSIX-UHFFFAOYSA-N 1-bromo-2-methylbenzene Chemical compound CC1=CC=CC=C1Br QSSXJPIWXQTSIX-UHFFFAOYSA-N 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229940093475 2-ethoxyethanol Drugs 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- XYZWMVYYUIMRIZ-UHFFFAOYSA-N 4-bromo-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(Br)C=C1 XYZWMVYYUIMRIZ-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- UZTQYWLWRFMSSF-UHFFFAOYSA-N 6-bromo-1,2,3,4-tetrahydronaphthalene Chemical compound C1CCCC2=CC(Br)=CC=C21 UZTQYWLWRFMSSF-UHFFFAOYSA-N 0.000 description 1
- PVFOHMXILQEIHX-UHFFFAOYSA-N 8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]-9-[2-(2-bromophenyl)ethyl]purin-6-amine Chemical compound C=1C=2OCOC=2C=C(Br)C=1SC1=NC=2C(N)=NC=NC=2N1CCC1=CC=CC=C1Br PVFOHMXILQEIHX-UHFFFAOYSA-N 0.000 description 1
- VIJYEGDOKCKUOL-UHFFFAOYSA-N 9-phenylcarbazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2C2=CC=CC=C21 VIJYEGDOKCKUOL-UHFFFAOYSA-N 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- YFUOONKPDASRNO-UHFFFAOYSA-N [SiH4].CC1=C(OC=C1)C Chemical compound [SiH4].CC1=C(OC=C1)C YFUOONKPDASRNO-UHFFFAOYSA-N 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005110 aryl thio group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 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
- LGPQXCREBFMTOH-UHFFFAOYSA-N benzhydrylsilane Chemical compound C=1C=CC=CC=1C([SiH3])C1=CC=CC=C1 LGPQXCREBFMTOH-UHFFFAOYSA-N 0.000 description 1
- 125000000499 benzofuranyl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000707 boryl group Chemical group B* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- XAZXUBZWWHQQGF-UHFFFAOYSA-N cyclobutyl(methyl)silane Chemical compound C[SiH2]C1CCC1 XAZXUBZWWHQQGF-UHFFFAOYSA-N 0.000 description 1
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- MHDIVRGCDHHRIZ-UHFFFAOYSA-N dimethoxy(phenyl)silicon Chemical compound CO[Si](OC)C1=CC=CC=C1 MHDIVRGCDHHRIZ-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012065 filter cake Substances 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
- 230000003760 hair shine Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N methylethylethylene Natural products CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001484 phenothiazinyl group Chemical group C1(=CC=CC=2SC3=CC=CC=C3NC12)* 0.000 description 1
- 125000001644 phenoxazinyl group Chemical group C1(=CC=CC=2OC3=CC=CC=C3NC12)* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 125000005936 piperidyl group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- PIILXFBHQILWPS-UHFFFAOYSA-N tributyltin Chemical compound CCCC[Sn](CCCC)CCCC PIILXFBHQILWPS-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 238000006227 trimethylsilylation reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a kind of metal iridium complex and its organic luminescent devices, are related to technical field of organic electroluminescence.On the one hand, the guanidine group with class Cabbeen structure is introduced into metal complex molecule as assistant ligand, has constructed a kind of four-membered ring coordination structure, obtained a series of green phosphorescent complex material systems with completely new molecular structure and photoelectric properties.Due to its iridium atom with the more stable positive trivalent in center, make complex that there is better chemical stability and thermal stability, and unnecessary vibrational energy loss can be reduced, to drop low molecular nonradiative transition to improve the luminous efficiency of complex.On the other hand, the structures such as the pyridine, pyrimidine, pyrazine, the triazine that introduce in structure can effectively increase the transmission and distribution of electronics.It is prepared into device using metal iridium complex of the present invention as dopant material, device shows the advantages of driving voltage is low, luminous efficiency is high and high color purity, is better than existing common OLED device.
Description
Technical field
The present invention relates to technical field of organic electroluminescence more particularly to a kind of metal iridium complexes and its organic illuminator
Part.
Background technique
Organic electroluminescent LED (Organic Light Emitting Diode, OLED) is to utilize electrons and holes
The recombination luminescence in organic film and the luminescent device prepared, have the following advantages that：(1) from main light emission, backlight is not needed；
(2) brightness is high, there is high contrast, pure in colour, the problem of almost without visible angle；(3) ultra-thin, by very thin organic
Material coating and basis material are constituted, small in size to be suitable for portable product；(4) power consumption is very small, environmental protection and energy saving；(5) it rings
It answers speed fast, is the one thousandth of LCD；(6) use temperature range is wide, remains to normally show at -40 DEG C.
General organic luminescent device (OLED) is the organic matter layer structure by being inserted between cathode, anode and cathode and anode
At, the composition of device is transparent ITO anode, hole injection layer (HIL), hole transmission layer (HTL), luminescent layer (EL), hole
The cathodes such as barrier layer (HBL), electron transfer layer (ETL), electron injecting layer (EIL), LiAl are formed.
Emitting layer material is divided into fluorescent material and phosphor material, and the forming method of luminescent layer is adulterated in fluorescent host material
The method of method and fluorescent host material doping fluorescent (organic matter comprising nitrogen) dopant of phosphor material (organic metal).Its
In, heavy metal complex causes in the application study of organic electroluminescent LED greatly due to its efficient luminescent properties
Attention.And these metal complexs for being used as organic electroluminescent LED are mostly platinum (Pt), osmium (Os) and iridium (Ir)
Metal complex, wherein iridium metal complex is maximally efficient, usually contains the regular octahedron structure of positive trivalent oxidation state, efficiently
It is since the configuration of extra-nuclear electron of metal complex has caused by strong SO coupling that the phosphorescence of rate, which shines,.
Currently, the research of electroluminescent organic material is carried out in academia and industry extensively, a large amount of function admirables
Electroluminescent organic material be developed successively, but the technological industrialization process still faces many critical issues how
The luminescent material for designing the better metal iridium complex of new performance is adjusted, and is always that those skilled in the art are urgently to be resolved
The problem of.
Summary of the invention
The object of the present invention is to provide a kind of metal iridium complex and its organic luminescent devices.Metal iridium provided by the invention
Thermal analysis can be high, which is used to use and manufactured organic luminescent device in luminescent layer, table by good film-forming property
Reveal the advantage that driving voltage is low, luminous efficiency is high and excitation purity is preferable, is the luminous organic material of function admirable.
The present invention provides a kind of metal iridium complexes, and general formula of molecular structure is as shown in I：
Wherein, X1、X2Independently selected from nitrogen-atoms, oxygen atom, sulphur atom or phosphorus atoms；
R1Selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C2~C10Alkenyl, replace or not
Substituted C2~C10Alkynyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl,
Substituted or unsubstituted C1~C10Silylation, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50
Heteroaryl, substituted or unsubstituted C2~C30Alkylamino radical, substituted or unsubstituted C6~C50One of aryl amine；
R2、R3Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alcoxyl
Base, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50One of heteroaryl；
R4~R11Independently selected from hydrogen atom, D-atom, halogen atom, substituted or unsubstituted C1~C10Alkyl, take
Generation or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50's
Heteroaryl, substituted or unsubstituted C2~C30Alkylamino radical, substituted or unsubstituted C6~C50One of aryl amine or institute
State R4~R11The condensed cyclization of both middle arbitrary neighborhoods.
Preferably, the X1And X2For nitrogen-atoms.
Preferably, the R1Selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl,
Or substituted or unsubstituted following group：Trimethylsilyl, phenyl, xenyl, naphthalene, fluorenyl, dimethyl amido, diphenyl
Amido, carbazyl, acridinyl, pyridyl group, pyrazinyl or triazine radical.
Preferably, the R2、R3Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary fourth
Base, cyclohexyl or substituted or unsubstituted following group：Phenyl, xenyl, naphthalene, pyridyl group, pyrazinyl or triazine radical.
Preferably, the structure on the right side of the metal iridium is with one of flowering structure：
Preferably, the R4~R7Independently selected from hydrogen atom, D-atom, halogen atom, C1~C10Alkyl, replace or
Unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl
Base, substituted or unsubstituted C2~C10Alkylamino radical, substituted or unsubstituted C6~C30One of aryl amine or the R4
~R7The condensed cyclization of both middle arbitrary neighborhoods.
Preferably, the R8~R11Independently selected from H, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine
Base, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazine radical.
Preferably, the R8~R11Independently selected from H, substituted or unsubstituted triazine radical.
Preferably, the metal iridium complex, any one in chemical structure as follows：
The present invention also provides a kind of organic luminescent device, including cathode, anode and it is placed in the cathode and the anode
Between one or more organic compound layers, the organic compound layer contains the metal iridium complex.
Beneficial effects of the present invention：
The present invention provides a kind of metal iridium complexes, have the following effects that：
Firstly, the guanidine group with class Cabbeen structure is introduced into metal complex molecule by we as assistant ligand,
A kind of four-membered ring coordination structure, i.e. Ir-N-C-N ring have been constructed, has replaced and is spread out in traditional complex using pentanedione (acac)
The hexa-atomic ring configuration that the assistant ligands such as biology and central metal atom are formed, to obtain a series of with completely new molecular structure
And the green phosphorescent complex material system of photoelectric properties.The electron rich coordination structure of this dinitrogen being capable of better stable center
The iridium atom of positive trivalent, to obtain higher chemical stability and thermal stability.
Secondly as four-membered ring is more more rigid than six-membered ring structure and close, it is even closer with the connection of center iridium atom,
Unnecessary vibrational energy loss can be reduced, so that low molecular nonradiative transition is dropped, it in this way can be in synthesis green emitting
It reduces the negative effect of energy gap rule bring when material to the greatest extent, and the luminous efficiency of complex is greatly improved, effectively drop
Low burying in oblivion for triplet excitons.
In addition, pyridine has the diversity of stronger coordination ability and coordination configuration, it is further introduced into pyridine groups
The structures such as pyridine, pyrimidine, pyrazine, triazine can effectively increase the transmission and distribution of electronics, especially connect triazine and pyridine
Connect, can effective balance electronic and hole injection quantity, to reduce roll-offing for device efficiency.
It is prepared into organic luminescent device using metal iridium complex of the present invention as dopant material, device shows driving voltage
The advantages of low, luminous efficiency is high and high color purity, is better than existing common OLED device, shows in OLED luminescent device
Good application effect, this point show it with good industrialization prospect.
Specific embodiment：
It is clearly and completely described below in conjunction with the technical solution of the specific embodiment of the invention, it is clear that described
Embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Technical staff's every other embodiment obtained without making creative work, belongs to protection model of the invention
It encloses.
It should be noted that unless otherwise prescribed, the meaning of scientific and technical terminology used in the present invention and those skilled in the art
The meaning that member is generally understood is identical.
Alkyl of the present invention refers to alkyl made of minusing one or several hydrogen atoms in alkane molecule, can be straight
Alkyl group, branched alkyl, naphthenic base, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl,
Tert-butyl, amyl, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Alkenyl of the present invention refers to alkyl made of minusing one or several hydrogen atoms in olefin hydrocarbon molecules, can be straight
Alkenyl, branched-chain alkenyl, example may include vinyl, allyl, 1- acrylic, 1- cyclobutenyl, 2- cyclobutenyl, 3- cyclobutenyl,
2- methyl but-2-ene base, 3- methyl but-1-ene base, 1- pentenyl, 3- pentenyl and 4- hexenyl etc., but not limited to this.
Alkynyl of the present invention refers to alkyl made of minusing one or several hydrogen atoms in alkynes molecule, can be straight
Alkynyl group, branch alkynyl, example may include acetenyl, propinyl (such as l- propinyl, 2-propynyl), 3- butynyl, pentyne
Base, hexin base and the amyl- 2- alkynyl of 1- methyl etc., but not limited to this.
Alkoxy of the present invention refer to alkyl and oxygen atom connection after group, example may include methoxyl group, ethyoxyl,
2- propoxyl group, 2- cyclohexyloxy etc., but not limited to this.
Silylation of the present invention can enumerate trimethyl silane, triethylsilane, tri-phenyl-silane, trimethoxy silane,
Dimethoxy phenylsilane, benzhydryl silane, silane, hexichol alkene silane, methyl-cyclobutyl silane, dimethyl furan silane etc.,
But not limited to this.
Aryl of the present invention refers to remove a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule after, be left the total of univalent perssad
Claiming, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but
It is without being limited thereto.
Heteroaryl of the present invention refers to the group that one or more aromatic core carbon in aryl are substituted by hetero atom
General name, the hetero atom include but is not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl
Base, example may include pyridyl group, pyrrole radicals, pyridyl group, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene
Pheno base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
Alkylamino radical of the present invention refers to amino-NH2In the general name of group that is replaced by alkyl of hydrogen atom, example
It may include-N (CH3)2、-N(CH2CH3)2Deng, but not limited to this.
Aryl amine of the present invention refers to amino-NH2In the general name of group that is substituted with aryl of hydrogen atom, example
May include such as flowering structure, but not limited to this.
Substituted alkyl of the present invention, substituted alkenyl, substituted alkynyl, substituted alkoxy, substituted boryl,
Substituted silylation, substituted aryl, substituted heteroaryl, substituted alkylamino radical, in substituted aryl amine, the substituent group can
With the independent alkane for being selected from D-atom, cyano, nitro, halogen atom, the alkyl of C1-C10, the alkoxy of C1-C10, C1-C10
Sulfenyl, the aryl of C6-C30, the aryloxy group of C6-C30, the arylthio of C6-C30, C3-C30 heteroaryl, C1~C30Silane
Base, C2~C10Alkylamino radical, C6~C30Aryl amine etc., such as D-atom, cyano, nitro, halogen, methyl, ethyl, propyl,
Isopropyl, tert-butyl, methoxyl group, methyl mercapto, phenyl, xenyl, terphenyl, naphthalene, anthryl, phenanthryl, benzo phenanthryl,
Base, pyrenyl, fluorenyl, 9,9- dimethyl fluorenyl, benzyl, phenoxy group, thiophenyl, hexichol amido, dimethylamino, carbazyl, 9-
Phenyl carbazole base, furyl, thienyl, triphenyl silicon substrate, trimethyl silicon substrate, trifluoromethyl, phenothiazinyl, phenoxazine group, a word used for translation
Piperidinyl, piperidyl, pyridyl group, pyrazinyl, triazine radical, pyrimidine radicals etc., but not limited to this.
Condensed cyclization of the present invention refers to that two groups are connected to each other by chemical bond.As follows：
In the present invention, the ring that is fused into can be five-membered ring or hexatomic ring, for example, naphthalene, hexamethylene and phenyl, quinolyl,
Isoquinolyl, dibenzothiophene, phenanthryl or pyrenyl, but not limited to this.
The present invention provides a kind of metal iridium complexes, and general formula of molecular structure is as shown in I：
Wherein, X1、X2Independently selected from nitrogen-atoms, oxygen atom, sulphur atom or phosphorus atoms；
R1Selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C2~C10Alkenyl, replace or not
Substituted C2~C10Alkynyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl,
Substituted or unsubstituted C1~C10Silylation, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50
Heteroaryl, substituted or unsubstituted C2~C30Alkylamino radical, substituted or unsubstituted C6~C50One of aryl amine；
R2、R3Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alcoxyl
Base, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50One of heteroaryl；
R4~R11Independently selected from hydrogen atom, D-atom, halogen atom, substituted or unsubstituted C1~C10Alkyl, take
Generation or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50's
Heteroaryl, substituted or unsubstituted C2~C30Alkylamino radical, substituted or unsubstituted C6~C50One of aryl amine or institute
State R4~R11The condensed cyclization of both middle arbitrary neighborhoods.
Preferably, the X1And X2For nitrogen-atoms.
Preferably, the R1Selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Silicon
Alkyl, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl, substituted or unsubstituted C2
~C10Alkylamino radical, substituted or unsubstituted C6~C30One of aryl amine；It is furthermore preferred that the R1Selected from methyl, second
Base, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl or substituted or unsubstituted following group：Trimethyl
Silylation, phenyl, xenyl, naphthalene, fluorenyl, dimethyl amido, diphenyl amido, carbazyl, acridinyl, pyridyl group, pyrazine
Base or triazine radical.It is described it is " substituted " in substituent group it is as defined above, details are not described herein.
Preferably, the R2、R3Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1
~C10Alkoxy, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl in one
Kind；It is furthermore preferred that the R2、R3Independently selected from methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, ring
Hexyl or substituted or unsubstituted following group：Phenyl, xenyl, naphthalene, pyridyl group, pyrazinyl or triazine radical.It is described " to take
Generation " in substituent group it is as defined above, details are not described herein.
Preferably, the structure on the right side of the metal iridium is with one of flowering structure：
Preferably, the R4~R7Independently selected from hydrogen atom, D-atom, halogen atom, C1~C10Alkyl, replace or
Unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl
Base, substituted or unsubstituted C2~C10Alkylamino radical, substituted or unsubstituted C6~C30One of aryl amine or the R4
~R7The condensed cyclization of both middle arbitrary neighborhoods；It is furthermore preferred that the R4~R7Independently selected from hydrogen atom, D-atom, C1~C4's
Alkyl, C1~C4Alkoxy or substituted or unsubstituted following group：Dimethyl amido, hexichol amido, phenyl, xenyl,
Naphthalene, pyridyl group, pyrazinyl or triazine radical；Or R4~R7Both middle arbitrary neighborhoods are fused into five-membered ring or hexatomic ring.It is described
Substituent group in " substituted " is as defined above, and details are not described herein.
Preferably, the R8~R11Independently selected from H, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine
Base, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazine radical.It is described it is " substituted " in substituent group be as defined above
Described, details are not described herein.
Preferably, the R8~R11Independently selected from H, substituted or unsubstituted triazine radical.It is described it is " substituted " in take
Dai Ji is as defined above, and details are not described herein.
As an example, it is not particularly limited, the metal iridium complex is any in chemical structure as follows
It is a kind of：
Metal iridium complex of the invention, preparation route are as follows：
According to the present invention, intermediate A is prepared according to method as follows：
Under nitrogen protection, in the case that tetra-triphenylphosphine palladium is catalyst, compound d and tributyl tin is anti-for object b
It answers, obtains compound c, later under nitrogen protection, compound c and hydrated iridium trichloride are anti-in 2- ethoxy ethanol solvent
It should obtain target product intermediate A.
According to the present invention, compound I is prepared according to method as follows：
N-BuLi is added dropwise in the hexane solution containing R1 bromo-derivative, the diene containing R2, R3 is added dropwise again later
Compound is to obtain intermediate B.Intermediate A reacts to obtain target product compound I with intermediate B.
The present invention does not have special limitation to the above-mentioned reaction condition respectively reacted, and use is well-known to those skilled in the art
Reaction condition.The present invention is not particularly limited the source of raw material employed in above-mentioned each reaction, can be commercially available
Product is prepared using preparation method well-known to those skilled in the art.Aromatic amine compound synthesis step of the present invention
Suddenly less, processing it is simple, easy to industrialized production.
The present invention also provides a kind of organic luminescent device, including cathode, anode and it is placed in the cathode and the anode
Between one or more organic compound layers, the organic compound layer include hole injection layer, hole transmission layer, electronics resistance
At least one layer of barrier, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer；The organic compound layer includes this
The invention metal iridium complex.
Preferably, the metal iridium complex is as the dopant material in organic luminescent device.
However, the structure of organic luminescent device of the present invention is not limited to this, as an example, in reality of the invention
Applying the device architecture that uses in example can be for：NPB is used as hole mobile material, and CBP is used as material of main part, and the metal iridium is matched
It closes object and is used as dopant material, TPBi is used as electron transport material, to manufacture the organic luminescent device of construction same as below：
ITO/NPB/CBP：Metal iridium complex (the 5%)/TPBi/LiF/Al.The organic electroluminescence device can be used for putting down
The application fields such as plate display, lighting source, direction board, signal lamp.
The synthesis of [embodiment 1] compound TM1
Under nitrogen protection, into 2L reaction kettle be added the bromo- 2- tributyl tin-pyridine of compound 5- (80.0g,
179mmol), compound a 1 (28.0g, 183mmol), K2CO3(37.1g, 268.5mmol), toluene 500mL stirring.Temperature liter
When height is to 70 DEG C, four triphenyl phosphorus palladium (4.2g, 3.58mmol) of catalyst is added, distilled water 100mL is added and stirs 11h.Sufficiently
After reaction, adding 150mL water, reaction was completed.It is filtered under diminished pressure to obtain target compound crude product, is washed with distilled water three times, then uses
Acetone, toluene, THF is recrystallized to give solid, and sublimation purifying is handled again, and re crystallization from toluene obtains compound b1 (63.9g, yield
75%).
By bromobenzene (25.7g, 165mmol), compound b1 (71.4,150mmol) and four triphenyl phosphorus palladiums (3.52g,
It 3mmol) is put into the reaction flask equipped with 720mL meta-xylene.This mixture is deaerated, continues 35 after being then heated to 130 DEG C
Hour.Reaction mixture is cooled to room temperature, is then extracted with 15% hydrochloric acid solution.Water phase is washed with ether first, is then used
50% sodium hydrate aqueous solution neutralizes, then is extracted with chloroform, merges organic layer, and dry with anhydrous magnesium sulfate, is concentrated via column
Chromatography obtains compound c1 (33.0g, yield 84%).
In 1L there-necked flask, be added hydrated iridium trichloride (10.6g, 30mmol) and compound c1 (30.1g,
115mmol), 300mL2- ethoxy ethanol and 100mL water is then added, mixture is refluxed overnight in a nitrogen atmosphere.Reaction
After, it is cooled to room temperature, precipitating is filtered and is washed with methanol, intermediate A 1 (19.8g, yield 88%) is dried to obtain.
The hexane solution (100mL) of bromobenzene (3.1g, 20mmol) is added in 100mL four-hole boiling flask, is cooled to -80
DEG C, the hexane solution (8mL) of the n-BuLi of 2.5M is added dropwise under nitrogen atmosphere, after stirring 1.5 hours, into mixed liquor
N is added dropwise, N '-diisopropylcarbodiimide (2.5g, 20mmol) after being added dropwise, continues stirring 2 hours, obtains faint yellow molten
This solution is added dropwise in tetrahydrofuran (100mL) solution of intermediate A 1 (15.0g, 10mmol) by liquid, after being added dropwise, is risen
Temperature stirs 12 hours to 60 DEG C, and reaction solution is cooled to room temperature, and has a solid appearance, filter and with washed with ether filter cake three times, so
It is dissolved afterwards with methylene chloride, evaporating column chromatography obtains compound TM1 (6.1g, 33%).Mass spectrum m/z：919.23 (calculated values：
919.35).Theoretical elemental content (%) C45H46IrN10：C,58.80；H,5.04；Ir,20.91；N, 15.24 actual measurement elements contain
It measures (%)：C,58.69；H,5.05；Ir,20.98；N,15.20.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 2] compound TM3
Changing the bromobenzene in embodiment 1 into equimolar o-bromotoluene, other steps are identical as the synthesis of embodiment 1,
Obtain target product compound TM3.Mass spectrum m/z：947.25 (calculated values：947.38).Theoretical elemental content (%)
C47H50IrN10：C,59.60；H,5.32；Ir, 20.29N, 14.79 survey constituent content (%)：C,59.51；H,5.35；Ir,
20.24N,14.76.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 3] compound TM5
Change the bromobenzene in embodiment 1 into equimolar 1- bromo- 2,4 dimethylbenzene, conjunction of other steps with embodiment 1
At identical, target product compound TM5 is obtained.Mass spectrum m/z：975.56 (calculated values：975.42).Theoretical elemental content (%)
C49H54IrN10：C,60.35；H,5.58；Ir, 19.71N, 14.36 survey constituent content (%)：C,60.49；H,5.57；Ir,
19.72N,14.35.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 4] compound TM15
Change the bromobenzene in embodiment 1 into equimolar 4- bromo- N, N dimethyl aniline, other steps with embodiment 1
It synthesizes identical, obtains target product compound TM15.Mass spectrum m/z：1005.33 (calculated value： 1005.44).Theoretical elemental content
(%) C49H56IrN12：C,58.54；H,5.62；Ir, 19.12N, 16.72 survey constituent content (%)：C,58.49；H,5.67；
Ir,19.12N,16.75.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 5] compound TM18
Change the bromobenzene in embodiment 1 into equimolar 2- bromonaphthalene, other steps are identical as the synthesis of embodiment 1, obtain
To target product compound TM18.Mass spectrum m/z：1019.23 (calculated value：1019.38).Theoretical elemental content (%)
C53H50IrN10：C,62.45；H,4.94；Ir, 18.86N, 13.74 survey constituent content (%)：C,62.39；H,4.97；Ir,
18.82N,13.75.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 6] compound TM19
Change the bromobenzene in embodiment 1 into equimolar 6- bromo- 1,2,3,4-tetrahydro-naphthalene, other steps are and embodiment
1 synthesis is identical, obtains target product compound TM19.Mass spectrum m/z：1027.38 (calculated value： 1027.45).Theoretical elemental
Content (%) C53H58IrN10：C,61.96；H,5.69；Ir,18.71；N, 13.63 actual measurements constituent content (%)：C,61.88；H,
5.68；Ir,18.76；N,13.60.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 7] compound TM21
Change the a1 in embodiment 1 into equimolar a2, other steps are identical as the synthesis of embodiment 1, obtain target
Product Compound TM21.Mass spectrum m/z：1167.34 (calculated value：1167.42).Theoretical elemental content (%) C65H54IrN10：C,
66.87；H,4.66；Ir,16.46；N, 12.00 actual measurements constituent content (%)： C,66.81；H,4.44；Ir,16.43；N,
11.97.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 8] compound TM41
Change the bromo- 2- tributyl tin-pyridine of 5- in embodiment 1 into equimolar 4- bromo- 2- tributyl tin-pyridine,
His step is identical as the synthesis of embodiment 1, obtains target product compound TM41.Mass spectrum m/z：919.28 (calculated values：
919.35).Theoretical elemental content (%) C45H46IrN10：C,58.80；H,5.04；Ir,20.91；N, 15.24 actual measurement elements contain
It measures (%)：C,58.74；H,5.05；Ir,20.96；N,15.20.The above results confirm that obtaining product is target product.
The synthesis of [embodiment 9] compound TM61
Change the a1 in embodiment 1 into equimolar a2, that pyridine changes equimolar 4- into 5- bromo- 2- tributyl tin-is bromo-
2- tributyl tin-pyridine, other steps are identical as the synthesis of embodiment 1, obtain target product compound TM61.Mass spectrum m/
z：1167.36 (calculated value：1167.42).Theoretical elemental content (%) C65H54IrN10： C,66.87；H,4.66；Ir,16.46；
N, 12.00 actual measurements constituent content (%)：C,66.80；H,4.44；Ir,16.48； N,11.95.The above results confirm to obtain product
For target product.
[comparison Application Example]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and 30 points under ultraviolet light of exposure
Clock is then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 70nm is deposited first
NPB as hole transmission layer, evaporation rate 0.1nm/s, followed by the vapor deposition of luminescent layer, mixing vapor deposition CBP/Ir
(PPy)3, doping concentration 5wt%, evaporation rate 0.005nm/s, evaporation thickness 30nm, the subsequent TPBi that 50nm is deposited
As electron transfer layer, evaporation rate 0.01nm/s, on the electron transport layer successively vacuum evaporation LiF and Al as cathode,
With a thickness of 200nm.
[Application Example]
Transparent anode electrode ito substrate is cleaned by ultrasonic 15 minutes in isopropanol, and 30 points under ultraviolet light of exposure
Clock is then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 70nm is deposited first
NPB as hole transmission layer, evaporation rate 0.1nm/s, followed by the vapor deposition of luminescent layer, mixing vapor deposition CBP/ present invention gold
Belong to complex of iridium, the TPBi of 50nm is then deposited as electron-transport in doping concentration 5wt%, evaporation rate 0.005nm/s
Layer, evaporation rate 0.01nm/s, successively vacuum evaporation LiF and Al is as cathode on the electron transport layer, with a thickness of 200nm.
The electron luminescence characteristic of the organic luminescent device of above method manufacture indicates in the following table：
The above result shows that metal iridium complex of the invention is applied in organic luminescent device, especially as doping
Material shows the advantage that driving voltage is low, luminous efficiency is high, is luminous organic material of good performance.
Obviously, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should refer to
It out, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical field
Bright some improvement and modification can also be carried out, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of metal iridium complex, general formula of molecular structure is as shown in I：
Wherein, X1、X2Independently selected from nitrogen-atoms, oxygen atom, sulphur atom or phosphorus atoms；
R1Selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C2~C10Alkenyl, substituted or unsubstituted
C2~C10Alkynyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C1~C10Boryl, replace or
Unsubstituted C1~C10Silylation, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl
Base, substituted or unsubstituted C2~C30Alkylamino radical, substituted or unsubstituted C6~C50One of aryl amine；
R2、R3Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, take
Generation or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50One of heteroaryl；
R4~R11Independently selected from hydrogen atom, D-atom, halogen atom, substituted or unsubstituted C1~C10Alkyl, replace or
Unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl
Base, substituted or unsubstituted C2~C30Alkylamino radical, substituted or unsubstituted C6~C50One of aryl amine or the R4
~R11The condensed cyclization of both middle arbitrary neighborhoods.
2. a kind of metal iridium complex according to claim 1, which is characterized in that the X1And X2For nitrogen-atoms.
3. a kind of metal iridium complex according to claim 1, which is characterized in that the R1Selected from methyl, ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl or substituted or unsubstituted following group：Trimethylsilyl,
Phenyl, xenyl, naphthalene, fluorenyl, dimethyl amido, diphenyl amido, carbazyl, acridinyl, pyridyl group, pyrazinyl or triazine
Base.
4. a kind of metal iridium complex according to claim 1, which is characterized in that the R2、R3Independently selected from methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, cyclohexyl or substituted or unsubstituted following group：Phenyl,
Xenyl, naphthalene, pyridyl group, pyrazinyl or triazine radical.
5. a kind of metal iridium complex according to claim 1, which is characterized in that structure on the right side of the metal iridium be with
One of flowering structure：
6. a kind of metal iridium complex according to claim 1, which is characterized in that the R4~R7Independently selected from hydrogen original
Son, D-atom, halogen atom, C1~C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, substituted or unsubstituted C6
~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl, substituted or unsubstituted C2~C10Alkylamino radical, replace or not
Substituted C6~C30One of aryl amine or the R4~R7The condensed cyclization of both middle arbitrary neighborhoods.
7. a kind of metal iridium complex according to claim 1, which is characterized in that the R8~R11Independently selected from H, take
Generation or unsubstituted pyridyl group, substituted or unsubstituted pyrimidine radicals, substituted or unsubstituted pyrazinyl, substituted or unsubstituted three
Piperazine base.
8. a kind of metal iridium complex according to claim 1, which is characterized in that the R8~R11Independently selected from H, take
Generation or unsubstituted triazine radical.
9. a kind of metal iridium complex according to claim 1, which is characterized in that in chemical structure as follows
Any one：
10. a kind of organic luminescent device, which is characterized in that the organic luminescent device includes cathode, anode and is placed in the yin
One or more organic compound layers between pole and the anode, the organic compound layer, which contains claim 1-9, appoints
Metal iridium complex described in one.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810580259.6A CN108864195A (en) | 2018-06-07 | 2018-06-07 | A kind of metal iridium complex and its organic luminescent device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810580259.6A CN108864195A (en) | 2018-06-07 | 2018-06-07 | A kind of metal iridium complex and its organic luminescent device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108864195A true CN108864195A (en) | 2018-11-23 |
Family
ID=64337159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810580259.6A Withdrawn CN108864195A (en) | 2018-06-07 | 2018-06-07 | A kind of metal iridium complex and its organic luminescent device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108864195A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438521A (en) * | 2018-12-04 | 2019-03-08 | 吉林大学 | A kind of complex of iridium and its application |
| CN114605478A (en) * | 2022-03-25 | 2022-06-10 | 中国科学院长春应用化学研究所 | Iridium complex containing fused indole and phenylpyridine structures and electroluminescent device |
| JP2023009002A (en) * | 2021-07-02 | 2023-01-19 | 北京夏禾科技有限公司 | Organic electroluminescent material and device thereof |
| US11952390B2 (en) | 2020-06-20 | 2024-04-09 | Beijing Summer Sprout Technology Co., Ltd. | Phosphorescent organic metal complex and use thereof |
-
2018
- 2018-06-07 CN CN201810580259.6A patent/CN108864195A/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438521A (en) * | 2018-12-04 | 2019-03-08 | 吉林大学 | A kind of complex of iridium and its application |
| CN109438521B (en) * | 2018-12-04 | 2021-04-16 | 吉林大学 | Iridium complex and application thereof |
| US11952390B2 (en) | 2020-06-20 | 2024-04-09 | Beijing Summer Sprout Technology Co., Ltd. | Phosphorescent organic metal complex and use thereof |
| JP2023009002A (en) * | 2021-07-02 | 2023-01-19 | 北京夏禾科技有限公司 | Organic electroluminescent material and device thereof |
| CN114605478A (en) * | 2022-03-25 | 2022-06-10 | 中国科学院长春应用化学研究所 | Iridium complex containing fused indole and phenylpyridine structures and electroluminescent device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Novel bipolar host materials based on 1, 3, 5-triazine derivatives for highly efficient phosphorescent OLEDs with extremely low efficiency roll-off | |
| CN108864195A (en) | A kind of metal iridium complex and its organic luminescent device | |
| CN108912175A (en) | A kind of metal iridium complex and its organic luminescent device | |
| CN107353298A (en) | The aromatic amine derivant and its organic luminescent device of a kind of class formation containing carbazole | |
| CN107057681A (en) | A kind of photoelectric material containing xanthene structure and its application in OLED fields | |
| CN107382824A (en) | A kind of aromatic amine derivant and its organic luminescent device based on carbazoles condensed cyclic structure | |
| CN109134348A (en) | A kind of carbazole compound and its organic luminescent device | |
| CN109020971A (en) | A kind of azepine carbazole compound and its organic luminescent device | |
| CN109293516A (en) | A kind of tri-arylamine group compound and its organic luminescent device | |
| CN109096268A (en) | A kind of organic electroluminescent compounds and its organic electroluminescence device | |
| CN108558768A (en) | A kind of class compound in the wrong and its organic luminescent device containing glyoxaline structure | |
| CN108822155A (en) | It is a kind of miscellaneous with iridium complex and its organic luminescent device | |
| CN108084195A (en) | A kind of bis-carbazole fused ring compound and its organic luminescent device | |
| CN108774266A (en) | A kind of complex of iridium and its organic luminescent device | |
| CN108047233A (en) | A kind of carbazole analog derivative and its organic luminescent device | |
| CN108822154A (en) | A kind of complex of iridium and its organic luminescent device | |
| CN108610383A (en) | A kind of complex compound and its organic luminescent device | |
| CN108084197A (en) | A kind of bis-carbazole derivative and its organic luminescent device | |
| CN108516960A (en) | A kind of glyoxaline compound and its organic luminescent device | |
| WO2016102413A1 (en) | Process for the manufacture of spirodibenzosuberane compounds | |
| CN108586533A (en) | A kind of nitrogenous heterocyclic luminous organic material and its application | |
| CN108218787A (en) | A kind of pyrene compound and its organic luminescent device | |
| WO2016102414A1 (en) | Novel spirobenzosuberane compounds for use in organic electronic devices | |
| CN107827808A (en) | A kind of derivative and its organic luminescent device containing carbazole class formation | |
| CN109020970A (en) | A kind of electron transport material and its organic luminescent device |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20181123 |
|
| WW01 | Invention patent application withdrawn after publication |