CN114478637A - Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device - Google Patents
Compound containing 1, 3-diketone ligand, application thereof and organic electroluminescent device Download PDFInfo
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- CN114478637A CN114478637A CN202110522974.6A CN202110522974A CN114478637A CN 114478637 A CN114478637 A CN 114478637A CN 202110522974 A CN202110522974 A CN 202110522974A CN 114478637 A CN114478637 A CN 114478637A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 152
- 239000003446 ligand Substances 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 69
- 229910052757 nitrogen Inorganic materials 0.000 claims description 92
- 125000000217 alkyl group Chemical group 0.000 claims description 57
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 37
- 125000001624 naphthyl group Chemical group 0.000 claims description 29
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 25
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 24
- 229920006395 saturated elastomer Polymers 0.000 claims description 20
- 125000001424 substituent group Chemical group 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- YRTCKZIKGWZNCU-UHFFFAOYSA-N furo[3,2-b]pyridine Chemical group C1=CC=C2OC=CC2=N1 YRTCKZIKGWZNCU-UHFFFAOYSA-N 0.000 claims description 15
- 125000002883 imidazolyl group Chemical group 0.000 claims description 15
- 125000001041 indolyl group Chemical group 0.000 claims description 15
- DBDCNCCRPKTRSD-UHFFFAOYSA-N thieno[3,2-b]pyridine Chemical group C1=CC=C2SC=CC2=N1 DBDCNCCRPKTRSD-UHFFFAOYSA-N 0.000 claims description 15
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 14
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 claims description 13
- ORCVNQIKKDETER-UHFFFAOYSA-N 12,17-diazatetracyclo[8.7.0.02,7.011,16]heptadeca-1(10),2,4,6,8,11(16),12,14-octaene Chemical group N1C2=CC=CN=C2C2=C1C1=CC=CC=C1C=C2 ORCVNQIKKDETER-UHFFFAOYSA-N 0.000 claims description 13
- TZPAYMQNBLEXRF-UHFFFAOYSA-N C1=CC(NC2=C3C=CC4=C2C=CC=N4)=C3N=C1 Chemical group C1=CC(NC2=C3C=CC4=C2C=CC=N4)=C3N=C1 TZPAYMQNBLEXRF-UHFFFAOYSA-N 0.000 claims description 13
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 13
- FBVBNCGJVKIEHH-UHFFFAOYSA-N [1]benzofuro[3,2-b]pyridine Chemical group C1=CN=C2C3=CC=CC=C3OC2=C1 FBVBNCGJVKIEHH-UHFFFAOYSA-N 0.000 claims description 13
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical group C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 claims description 13
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 13
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 13
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 claims description 13
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 13
- 230000000903 blocking effect Effects 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 230000005525 hole transport Effects 0.000 claims description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 6
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- SURCGQGDUADKBL-UHFFFAOYSA-N 2-(2-hydroxyethylamino)-5-nitrobenzo[de]isoquinoline-1,3-dione Chemical compound [O-][N+](=O)C1=CC(C(N(NCCO)C2=O)=O)=C3C2=CC=CC3=C1 SURCGQGDUADKBL-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 40
- 230000015572 biosynthetic process Effects 0.000 abstract description 39
- 238000010791 quenching Methods 0.000 abstract description 6
- 230000000171 quenching effect Effects 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 78
- 239000010410 layer Substances 0.000 description 48
- 238000000921 elemental analysis Methods 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 125000004432 carbon atom Chemical group C* 0.000 description 26
- 238000002360 preparation method Methods 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 24
- 238000001704 evaporation Methods 0.000 description 22
- 238000003756 stirring Methods 0.000 description 21
- -1 PEDOT/PSS) Chemical class 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000007787 solid Substances 0.000 description 18
- 150000001555 benzenes Chemical group 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 15
- 238000001816 cooling Methods 0.000 description 14
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000012043 crude product Substances 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical compound [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 150000002537 isoquinolines Chemical group 0.000 description 8
- 150000003248 quinolines Chemical group 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 229940093475 2-ethoxyethanol Drugs 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 6
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000010549 co-Evaporation Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000005051 trimethylchlorosilane Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 238000005401 electroluminescence Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 125000001725 pyrenyl group Chemical group 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001454 anthracenes Chemical class 0.000 description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 125000004623 carbolinyl group Chemical group 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- DKHNGUNXLDCATP-UHFFFAOYSA-N dipyrazino[2,3-f:2',3'-h]quinoxaline-2,3,6,7,10,11-hexacarbonitrile Chemical compound C12=NC(C#N)=C(C#N)N=C2C2=NC(C#N)=C(C#N)N=C2C2=C1N=C(C#N)C(C#N)=N2 DKHNGUNXLDCATP-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000005956 isoquinolyl group Chemical group 0.000 description 2
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000005041 phenanthrolines Chemical class 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 125000003373 pyrazinyl group Chemical group 0.000 description 2
- 125000002098 pyridazinyl group Chemical group 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 description 2
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 2
- 125000005493 quinolyl group Chemical group 0.000 description 2
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000000335 thiazolyl group Chemical group 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000004306 triazinyl group Chemical group 0.000 description 2
- HKRVHTFXSUGWIV-UHFFFAOYSA-N 1,1'-spirobi[fluorene]-2'-amine Chemical class C12=CC3=CC=CC=C3C1=CC=CC12C2=CC3=CC=CC=C3C2=CC=C1N HKRVHTFXSUGWIV-UHFFFAOYSA-N 0.000 description 1
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- XYUORYRNDCCNPG-UHFFFAOYSA-N 1-(3,5-dimethylphenyl)-6-propan-2-ylisoquinoline Chemical compound CC=1C=C(C=C(C=1)C)C1=NC=CC2=CC(=CC=C12)C(C)C XYUORYRNDCCNPG-UHFFFAOYSA-N 0.000 description 1
- NRSBAUDUBWMTGL-UHFFFAOYSA-N 2-(1-benzothiophen-2-yl)pyridine Chemical compound S1C2=CC=CC=C2C=C1C1=CC=CC=N1 NRSBAUDUBWMTGL-UHFFFAOYSA-N 0.000 description 1
- XNAMZBCMLZQBIC-UHFFFAOYSA-N 2-[2-[4-[5-[(1-ethylpyrazol-3-yl)amino]triazolo[4,5-d]pyrimidin-1-yl]phenyl]propan-2-yloxy]ethanol Chemical compound CCN1C=CC(NC=2N=C3N=NN(C3=CN=2)C=2C=CC(=CC=2)C(C)(C)OCCO)=N1 XNAMZBCMLZQBIC-UHFFFAOYSA-N 0.000 description 1
- WXLFOFRDXHNZFG-UHFFFAOYSA-N 2-methyl-5-phenylquinoline Chemical compound C=1C=CC2=NC(C)=CC=C2C=1C1=CC=CC=C1 WXLFOFRDXHNZFG-UHFFFAOYSA-N 0.000 description 1
- FIISKTXZUZBTRC-UHFFFAOYSA-N 2-phenyl-1,3-benzoxazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2O1 FIISKTXZUZBTRC-UHFFFAOYSA-N 0.000 description 1
- DMEVMYSQZPJFOK-UHFFFAOYSA-N 3,4,5,6,9,10-hexazatetracyclo[12.4.0.02,7.08,13]octadeca-1(18),2(7),3,5,8(13),9,11,14,16-nonaene Chemical group N1=NN=C2C3=CC=CC=C3C3=CC=NN=C3C2=N1 DMEVMYSQZPJFOK-UHFFFAOYSA-N 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- ZISGLVMVAWKGRE-UHFFFAOYSA-N C1=CC=CC=2C3=CC=CC=C3NC12.N1=NN=CC=C1 Chemical class C1=CC=CC=2C3=CC=CC=C3NC12.N1=NN=CC=C1 ZISGLVMVAWKGRE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 229940058303 antinematodal benzimidazole derivative Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- RLZFVPPGVAHZPE-UHFFFAOYSA-N ethyl 4-iodobutanoate Chemical compound CCOC(=O)CCCI RLZFVPPGVAHZPE-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 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
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000009289 huang-lien-chieh-tu-tang Substances 0.000 description 1
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical class C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- 125000005580 triphenylene group Chemical group 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Electroluminescent Light Sources (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention relates to the field of organic electroluminescent devices, and discloses a compound containing a1, 3-diketone ligand, application thereof and an organic electroluminescent device. The compound has Ir (L)A)(LB)2Structure shown, LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown. The compound containing the 1, 3-diketone ligand provided by the invention has the advantages of small synthesis difficulty and easiness in purification, and has excellent performance when being used as an organic electrophosphorescent materialThe luminescent property of the material can improve the service life of the device, increase the solubility of the phosphorescent material and reduce the probability of quenching from a triplet state to a triplet state.
Description
Technical Field
The invention relates to the field of organic electroluminescent devices, in particular to a compound containing a1, 3-diketone ligand, application thereof and an organic electroluminescent device.
Background
Compared with the traditional liquid crystal technology, the organic electroluminescence technology does not need backlight source irradiation and a color filter, pixels can emit light and are displayed on a color display panel, and the organic electroluminescence technology has the characteristics of ultrahigh contrast, ultra-wide visual angle, curved surface, thinness and the like.
In 1987, Duncong cloud Bos et al of Kodak company reported two organic semiconductor materials based on 8-hydroxyquinoline aluminum with high fluorescence efficiency and good electron transport property and aromatic diamine with good hole transport property, and promoted the research of organic electroluminescent materials.
In 1997, professor Forrest of the university of prolington, usa, discovered the phenomenon of phosphorescence electroluminescence, and increased the internal quantum efficiency of organic electroluminescent devices from the limit of 25% of fluorescent materials to 100%, which led the research of organic electroluminescent materials to enter a new period. The phosphorescent material is a phosphorescent material which is formed by doping transition metal complexes with small molecules, and enables triplet excitons to obtain high emission energy by utilizing a spin-orbit coupling effect caused by heavy metal atoms, so that the quantum efficiency of the organic electroluminescent device is improved.
The fluorescent material has low excitation energy, and energy is easily lost in a non-radiative mode in the excitation process, so that the fluorescent material with high fluorescence efficiency and good chromaticity is rare, the better luminescent material is mainly phosphorescent material, the phosphorescent material applied to the organic electroluminescent device at present is easy to generate aggregation quenching phenomenon under high concentration, and the phenomenon that the device efficiency is reduced due to the fact that the triplet state-triplet state mound is obviously extinguished exists in the high-brightness device. In order to meet the increasing demand of device performance, it is very important to develop a phosphorescent material having a weak aggregation quenching effect.
Disclosure of Invention
The invention aims to solve the problems of large efficiency roll-off and low luminous efficiency of the existing organic electroluminescent device.
In order to achieve the above object, a first aspect of the present invention provides a1, 3-diketone ligand-containing compound having Ir (L)A)(LB)2The structure shown, wherein LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown;
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C20Alkyl of (C)6-C20Aryl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C20Alkyl of (C)6-C20Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C10At least one of alkyl and phenyl.
A second aspect of the present invention provides the use of a compound containing a1, 3-diketone ligand as described in the first aspect above as an organic electrophosphorescent material.
A third aspect of the present invention provides an organic electroluminescent device comprising at least one of the 1, 3-diketone ligand-containing compounds described in the first aspect above.
The invention has the following specific advantages:
(1) the compound containing the 1, 3-diketone ligand has the advantages of small synthesis difficulty and easiness in purification, and can improve the phosphorescence quantum efficiency of a phosphorescence material when being used as an organic electrophosphorescent material, so that the compound has excellent luminescence performance;
(2) when the compound containing the 1, 3-diketone ligand is used as an organic electrophosphorescent material, the specific concentration quenching phenomenon of the phosphorescent material can be reduced, the thermal stability of the phosphorescent material can be improved, and the service life of a device can be prolonged;
(3) when the compound containing the 1, 3-diketone ligand provided by the invention is used as an organic electrophosphorescent material, the probability of triplet state-triplet state quenching can be reduced, and the luminous efficiency of a device is further improved.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, the terms of the present invention are explained as follows without making a contrary explanation:
C1-C20the alkyl group of (2) represents an alkyl group having 1 to 20 carbon atoms in total, and includes a straight-chain alkyl group, a branched-chain alkyl group and a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group and a cyclic alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 and 20 carbon atoms in total, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, a cyclobutyl group, an n-butyl group, a CH group3CH(CH3)-CH2-、CH3CH2CH(CH3) -, tert-butyl, n-pentyl, CH3CH(CH3)-CH2CH2-, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, and the like. For "C1-C15Alkyl of (2), "" C1-C10Alkyl of (2), "" C1-C8Alkyl of (2), "" C1-C7Alkyl of (2), "" C1-C6The same applies to alkyl groups "and the like, except that the total number of carbon atoms is different.
C6-C20The aryl group in (b) represents an aryl group having 6 to 20 carbon atoms in total, and the aryl group is directly connected to C of the parent nucleus structure provided by the present invention, and includes, but is not limited to, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, and the like. For "C6-C15Aryl of (2), "" C6-C12Aryl of (2), "" C6-C10The same applies to aryl "and the like, except that the total number of carbon atoms is different.
R1And R2And R3And R4At least one of the combinations of (a) represents R1And R2And R3And R4At least one of the combinations of (a) forms a saturated ring containing 4, 5 or 6 atoms, e.g. is
Substituted or unsubstituted benzene ring means that the benzene ring is directly connected with the C atom on the parent nucleus structure provided by the invention, and any position on the benzene ring which can be substituted. For example,
x in (1)1、X2、X3、X4May be substituted, the wavy line indicates the position of attachment, i.e. the position at which the group is chemically bonded to the parent nucleus structure via the wavy line, ┄ is the dotted line on the Q ring of formula (IB). Hereinafter, quinoline rings, naphthalene rings, etc. have similar definitions, and the present invention is not described in detail.
Substituted or unsubstituted quinoline ring means that the quinoline ring is directly linked to the C atom on the parent structure provided by the present invention, and any substitutable position on the quinoline ring may be substituted.
The substituted or unsubstituted isoquinoline ring means that the isoquinoline ring is directly connected with a C atom on the parent nucleus structure provided by the invention, and any position on the isoquinoline ring which can be substituted.
And a substituted or unsubstituted naphthalene ring, which means that the naphthalene ring is directly connected to the C atom on the parent structure provided by the present invention, and any position on the naphthalene ring which can be substituted.
The substituted or unsubstituted phenanthrene ring means that the phenanthrene ring is directly bonded to a C atom in the parent structure provided by the present invention, and any substitutable position on the phenanthrene ring may be substituted.
Substituted or unsubstituted benzothiophene ring, means that the benzothiophene ring is directly attached to a C atom on the parent structure provided by the present invention, and any substitutable position on the benzothiophene ring may be substituted.
Substituted or unsubstituted benzofuran ring means that the benzofuran ring is directly attached to a C atom of the parent nucleus structure provided by the present invention, and any substitutable position on the benzofuran ring may be substituted.
Substituted or unsubstituted indole ring means that the indole ring is directly linked to the C atom of the parent nucleus structure provided herein, and any substitutable position on the indole ring may be substituted.
The substituted or unsubstituted benzothiazole ring means that the benzothiazole ring is directly bonded to the C atom of the parent structure provided in the present invention, and any position on the benzothiazole ring which may be substituted.
Substituted or unsubstituted benzoxazole ring, meaning that the benzoxazole ring is directly attached to the C atom on the parent structure provided herein, and any substitutable position on the benzoxazole ring may be substituted.
The substituted or unsubstituted benzimidazole ring means that the benzimidazole ring is directly connected to a C atom on the parent structure provided by the present invention, and any substitutable position on the benzimidazole ring may be substituted.
The substituted or unsubstituted dibenzothiophene ring means that the dibenzothiophene ring is directly connected with a C atom on the parent structure provided by the invention, and any position on the dibenzothiophene ring which can be substituted.
A substituted or unsubstituted dibenzofuran ring, which means that the dibenzofuran ring is directly attached to a C atom on the parent structure provided by the present invention, and any substitutable position on the dibenzofuran ring may be substituted.
Substituted or unsubstituted benzofuropyridine ring, means that the benzofuropyridine ring is directly connected with the C atom on the parent nucleus structure provided by the invention, and any position on the benzofuropyridine ring which can be substituted.
Substituted or unsubstituted benzothienopyridine ring, which means that the benzothienopyridine ring is directly linked to the C atom on the parent structure provided by the present invention, and any position on the benzothienopyridine ring which may be substituted.
Substituted or unsubstituted benzindolopyridine ring means that the benzindolopyridine ring is directly connected with the C atom on the parent nucleus structure provided by the invention, and any position on the benzindolopyridine ring which can be substituted.
Substituted or unsubstituted pyridoindolopyridine ring means that the pyridoindolopyridine is directly linked to the C atom of the parent nucleus structure provided by the present invention, and any position on the pyridoindolopyridine which may be substituted.
The substituted or unsubstituted imidazole ring means that the imidazole ring is directly bonded to a C atom on the parent structure provided by the present invention, and any substitutable position on the imidazole ring may be substituted.
The substituted or unsubstituted pyrrolidine ring means that the pyrrolidine ring is directly connected with a C atom on the parent nucleus structure provided by the present invention, and any position on the pyrrolidine ring which can be substituted.
Substituted or unsubstituted pyridofuran ring, meaning that the pyridofuran ring is directly attached to a C atom on the parent structure provided herein, and any substitutable position on the pyridofuran ring may be substituted.
The substituted or unsubstituted pyridothiophene ring means that the pyridothiophene ring is directly connected with the C atom on the parent nucleus structure provided by the invention, and any position on the pyridothiophene ring which can be substituted.
C3The straight chain alkyl of (A) is CH3CH2CH2-，C3Branched alkyl of is CH3CH(CH3)-，C3Cycloalkyl of
C4The straight chain alkyl of (A) is CH3CH2CH2CH2-，C4The branched alkyl group of (A) may be CH3CH(CH3)-CH2-、CH3CH2-CH(CH3) -or (CH)3)3C-，C4Cycloalkyl of
C5The straight chain alkyl of (A) is CH3CH2CH2CH2CH2-，C5The branched alkyl group of (A) may be CH3CH2CH(CH3)-CH2-、(CH3)2CH-CH2CH2-、(CH3)3C-CH2-、CH3CH(CH3)CH(CH3)-、(CH3)3C-CH2-，C5Cycloalkyl of
C6The straight chain alkyl of (A) is CH3CH2CH2CH2CH2CH2-，C6The branched alkyl group of (A) may be CH3CH2CH2CH(CH3)CH2-、(CH3)2C(CH2CH2CH3)-、(CH3)2CHCH(CH2CH3)-、(CH3)2CHCH2CH(CH3)-、(CH3)2CHCH2CH2CH2-、CH3CH2CH(CH3)CH2CH2-、CH3CH2CH(CH3)CH(CH3)-、(CH3CH2)2C(CH3)-、CH3CH(CH3)CH(CH3)CH2-、(CH3CH2)2CHCH2-、(CH3)2CHC(CH3)2-，C6Cycloalkyl of
C7The straight chain alkyl of (A) is CH3CH2CH2CH2CH2CH2CH2-，C7The branched alkyl group of (A) may be CH3CH2CH2CH2CH(CH3)CH2-、(CH3)2CHCH2CH2CH2CH2-、(CH3)2C(CH2CH2CH2CH3)-、(CH3)2CHCH(CH2CH2CH3)-、(CH3)2CHCH2CH(CH2CH3)-、(CH3)2CHCH2CH2CH(CH3)-、CH3CH2CH2CH(CH3)CH2CH2-、CH3CH2CH(CH3)CH2CH2CH2-、CH3CH2CH2CH(CH3)CH(CH3)-、CH3CH2CH2C(CH3)(CH2CH3)-、CH3CH2CH(CH3)CH(CH2CH3)-、CH3CH2CH(CH3)CH2CH(CH3)-、CH3CH2CH2CHCH2(CH2CH3)-、CH3CH2CH2C(CH3)2CH2-、(CH3)3CCH2CH2CH2-、(CH3)3CCH(CH2CH3)-、(CH3)3CCH2CH(CH3)-、CH3CH2CH(CH3)CH(CH3)CH2-、(CH3)2CHCH(CH3)CH2CH2-、CH3CH2CH(CH3)C(CH3)2-、(CH3)2CHC(CH3)(CH2CH3)-、(CH3)2CHCH(CH3)CH(CH3)-、(CH3)2CHCH(CH2CH3)CH2-、(CH3)2CHCH2CH(CH3)CH2-、(CH3)2CHCH2C(CH3)2-、(CH3)2CHCH(CH(CH3)2)-、CH3CH2C(CH3)2CH2CH2-、CH3CH2C(CH3)2CH(CH3)-、(CH3CH2)2C(CH3)CH2-、(CH3)3C-CH(CH3)CH2-、(CH3)2CHC(CH3)2CH2-，C7Cycloalkyl of
"or R1、R2、R3、R4Any two of which are adjacent to each other and taken together form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring, and represents R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure of a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted pyridothiophene ring, and by R1、R2、R3、R4Any two adjacent to each otherThe chemical bond shared with the parent nuclear structure forms a fused ring with the parent nuclear structure. For example, is
In order to achieve the above object, a first aspect of the present invention provides a1, 3-diketone ligand-containing compound having Ir (L)A)(LB)2The structure shown, wherein LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown;
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C20Alkyl of (C)6-C20Aryl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C20Alkyl of (C)6-C20Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C10At least one of alkyl and phenyl.
According to preferred embodiments 1-1In Ir (L)A)(LB)2In the structure shown, LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown;
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C15Alkyl of (C)6-C15Aryl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C15Alkyl of (C)6-C15Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C8At least one of alkyl and phenyl.
According to preferred embodiments 1-2In Ir (L)A)(LB)2In the structure shown, LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown;
in formula (IA), R1、R2、R3、R4Each independently of the otherIs selected from H, C1-C10Alkyl of (C)6-C12Aryl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C10Alkyl of (C)6-C12Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the ring Q, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C6At least one of alkyl and phenyl.
According to a preferred embodiment, Ir (L) is used in the present inventionA)(LB)2In the configuration shown in the figures, the,
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C7Alkyl of (C)6-C10Aryl of (a); or R1And R2And R3And R4At least one combination of (a) is cyclized to form a 4-6 membered saturated ring.
According to particularly preferred embodiments 1 to 3In Ir (L)A)(LB)2In the configuration shown in the figures, the,
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C7Alkyl of (C)6-C10Aryl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C10Alkyl of (C)6-C12Aryl of (a); or R1、R2、R3、R4Any two adjacent of them are together loopedSynthesizing to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C6At least one of alkyl and phenyl.
According to another preferred embodiment, Ir (L) in the context of the present inventionA)(LB)2In the construction shown in the above-mentioned figures,
in formula (IA), R1、R2、R3、R4Each independently selected from H, methyl, ethyl, C3Straight chain alkyl group of (1), C3Branched alkyl of C3Cycloalkyl of, C4Straight chain alkyl group of (1), C4Branched alkyl of C4Cycloalkyl of, C5Straight chain alkyl group of (1), C5Branched alkyl of C5Cycloalkyl of, C6Straight chain alkyl group of (1), C6Branched alkyl of C6Cycloalkyl of, C7Straight chain alkyl group of (1), C7Branched alkyl of C7Cycloalkyl, phenyl of (a); or R1And R2And R3And R4At least one combination of (a) is cyclized to form a 4-6 membered saturated ring.
According to particularly preferred embodiments 1 to 4In Ir (L)A)(LB)2In the configuration shown in the figures, the,
in formula (IA), R1、R2、R3、R4Each independently selected from H, methyl, ethyl, C3Straight chain alkyl group of (1), C3Branched alkyl of C3Cycloalkyl of, C4Straight chain alkyl group of (1), C4Branched alkyl of C4Cycloalkyl of, C5Straight chain alkyl group of (1), C5Branched alkyl of C5Cycloalkyl of, C6Straight chain alkyl group of (1), C6Branched alkyl of C6Cycloalkyl of, C7Straight chain alkyl group of (1), C7Branched alkyl of C7Cycloalkyl, phenyl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C10Alkyl of (C)6-C12Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C6At least one of alkyl and phenyl.
According to a preferredDetailed description of the invention Ir (L)A)(LB)2In the structure shown, LASelected from the structures set forth in claim 6.
According to particularly preferred embodiments 1 to 5In Ir (L)A)(LB)2In the structure shown, LASelected from the structures set forth in claim 6;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C10Alkyl of (C)6-C12Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, and a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C6At least one of alkyl and phenyl.
According to another preferred embodiment, Ir (L) in the context of the present inventionA)(LB)2In the structure shown, LBSelected from the structures set forth in claim 7.
According to a preferred embodiment, the compound containing a1, 3-diketone ligand is selected from any one of the compounds shown in claim 7.
According to particularly preferred embodiments 1 to 6, in Ir (L)A)(LB)2In the structure shown, LASelected from the structures set forth in claim 6; and is
LBSelected from the structures set forth in claim 7.
According to preferred embodiments 1-7, Ir (L)A)(LB)2The structure shown is selected from the structures shown in claim 8.
The present invention is not particularly limited to the method for preparing the 1, 3-diketone ligand-containing compound according to the first aspect, and a person skilled in the art can determine an appropriate reaction route according to the structural formula in combination with a method known in the art of organic synthesis. The present invention is hereinafter exemplified by several methods for preparing the 1, 3-diketone ligand-containing compound described in the foregoing first aspect, and those skilled in the art should not be construed as limiting the present invention.
As mentioned above, the second aspect of the present invention provides the use of the 1, 3-diketone ligand-containing compound according to the first aspect as an organic electrophosphorescent material.
As described above, the third aspect of the present invention provides an organic electroluminescent device comprising at least one of the 1, 3-diketone ligand-containing compounds described in the first aspect.
Preferably, the compound containing a1, 3-diketone ligand is present in the light-emitting layer of the organic electroluminescent device.
Further preferably, the compound containing a1, 3-diketone ligand is a guest material in a light-emitting layer of the organic electroluminescent device.
According to a preferred embodiment, the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode.
The material forming the anode in the present invention is not particularly required, and those skilled in the art can select it in combination with techniques known in the art. In a preferred embodiment of the present invention, the anode material is a material having a large work function.
Preferably, the anode material is at least one selected from vanadium, chromium, copper, gold, aluminum, zinc oxide, indium tin oxide, indium zinc oxide, and tin dioxide.
The material for forming the hole injection layer in the present invention is not particularly required, and those skilled in the art can select it in combination with techniques known in the art. In a preferred embodiment of the present invention, the hole injection layer material is a material having a work function between that of the anode material and that of the surrounding organic material.
The material for forming the hole transport layer in the present invention is not particularly required, and those skilled in the art can select it in combination with techniques known in the art. In a preferred embodiment of the present invention, the material of the hole transport layer is a material that can receive holes from the anode or the hole injection layer, move the holes to the light emitting layer, and have high mobility to the holes.
Illustratively, the hole injection material and the hole transport material include, but are not limited to, aromatic amine derivatives (e.g., NPB, SqMA1), hexaazatriphenylene derivatives (e.g., HACTN), indolocarbazole derivatives, conductive polymers (e.g., PEDOT/PSS), phthalocyanines, porphyrin derivatives, dibenzoindenofluorenamines, spirobifluorenylamines, and the like.
According to a particularly preferred embodiment of the present invention, the hole injecting material and the hole transporting material are selected from at least one of structures represented by formula-1, formula-2, formula-3 and formula-4;
wherein, the groups from R1 to R9 are independently selected from single bond, hydrogen, deuterium and C1-C20Alkyl, phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthryl, benzophenanthryl, pyrenyl, fluorenyl, dimethylfluorenyl, spirobifluorenyl, carbazolyl, thienyl, benzothienyl, dibenzothienyl, furyl, benzofuryl, dibenzofuryl, indolyl, indolocarbazolyl, indenocarbazolyl, pyridyl, pyrimidyl, imidazolyl, thiazolyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, porphinyl, carbolinyl, pyrazinyl, pyridazinyl, triazinyl.
The material forming the electron blocking layer in the present invention is not particularly required, and those skilled in the art can select it in combination with techniques known in the art. In a preferred embodiment of the present invention, the electron blocking layer material is selected from materials having a shallow LUMO energy level and/or a large triplet energy level.
Illustratively, the electron blocking layer material includes, but is not limited to, aromatic amine derivatives (e.g., NPB), spirobifluorene amines (e.g., SpMA2), and the like.
Optionally, the light emitting layer further contains a host material. Illustratively, the host material includes, but is not limited to, anthracene derivatives, carbazole derivatives, fluorene derivatives, arylamine derivatives, organosilicon derivatives, carbazole-triazine derivatives, phosphoxy derivatives, phenanthroline derivatives, and the like.
Preferably, the anthracene derivative has a structure shown as a formula-5, and the phosphorus oxy derivative has a structure shown as a formula-6;
wherein R is11、R12、R13、R14、R15And R16Each independently selected from the group consisting of a single bond, hydrogen, deuterium, substituted or unsubstituted C1-C20Substituted or unsubstituted phenyl, substituted or unsubstituted biphenylyl, substituted or unsubstituted terphenylyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted benzophenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted dimethylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted furyl, substituted or unsubstituted benzofuryl, substituted or unsubstituted dibenzofuryl, substituted or unsubstituted indolyl, substituted or unsubstituted indolocarbazolyl, substituted or unsubstituted indenocarbazolyl, substituted or unsubstituted pyridyl, A substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted porphyrin group, a substituted or unsubstituted carbolinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted triazinyl group.
Preferably, the guest material is the 1, 3-diketone ligand-containing compound that produces emission via at least one of phosphorescence, fluorescence, TADF (thermally activated delayed fluorescence), MLCT (metal to ligand charge transfer), HLCT (with hybrid CT states), and triplet-triplet annihilation methods.
The material for forming the hole blocking layer in the present invention is not particularly required, and those skilled in the art can select it in combination with techniques known in the art. In a preferred embodiment of the present invention, the hole blocking layer material is a material having a shallow LUMO energy level and/or a large triplet energy.
Illustratively, the hole blocking layer material includes, but is not limited to, phenanthroline derivatives (e.g., Bphen, BCP), triphenylene derivatives, benzimidazole derivatives, and the like.
The material for forming the electron injection layer in the present invention is not particularly required, and those skilled in the art can select it in combination with techniques known in the art. Illustratively, the electron injection layer material includes, but is not limited to, LiF, CsF, Cs2CO3。
The material forming the cathode in the present invention is not particularly required, and those skilled in the art can select it in combination with techniques known in the art. The invention provides a preferred embodiment, and the cathode material is a material with a small work function.
Preferably, the cathode material is selected from at least one of Al, Mg and Ag.
The present invention will be described in detail below by way of examples.
In the present invention, the room temperature is 25. + -. 2 ℃ unless otherwise specified.
Wherein, the following examples relate to the structural formula of partial compounds as follows:
evaluation: evaluation of characteristics of organic light-emitting device
The color coordinates of the material were tested by using a german edinburgh FLS980 fluorescence spectrometer.
Preparation example 1: preparation of a Compound of formula M1
Synthesis of intermediate M1-1: under the protection of nitrogen, dissolving activated zinc powder (0.4mol) in 30ml of anhydrous THF, then adding trimethylchlorosilane (25ml), stirring for 15min, then adding 4-iodobutanoic acid ethyl ester (0.4mol), stirring for 12h at 30 ℃, cooling to-10 ℃, then adding copper cyanide (0.2mol) and lithium chloride (0.4mol) in THF solvent (200ml), heating to 0 ℃, stirring for 10min, and cooling to-78 ℃ to obtain solution No. 1.
Dissolving 2-cyclohexene-1-ketone (0.28mol) and trimethylchlorosilane (0.66mol) in diethyl ether (250ml), slowly dripping into the solution No. 1, stirring at-78 ℃ for 3h, heating to room temperature, and reacting for 12 h. Adding saturated NH4Cl (450ml) and saturated NH4Quenching reaction with OH (50ml) was carried out, extraction was carried out three times with ethyl acetate, the organic phases were combined, the solvent was removed by rotary evaporation of the organic phase, and the residue was recrystallized from methanol to give intermediate M1-1 as a white solid (yield: 75%).
Synthesis of a compound of formula M1: intermediate M1-1(75mmol), potassium tert-butoxide (0.19mol) were dissolved in anhydrous THF (160ml) and stirred with heating under nitrogen, warmed to reflux, TLC monitored the reaction to near completion, cooled to room temperature, the reaction was spun down under reduced pressure and the residue recrystallized to give the compound of formula M1 as a white solid (yield: 72%).
Mass spectrum: c10H14O2The theoretical value is as follows: 166.10, found: 166.0.
elemental analysis: theoretical value: c: 72.26%, H: 8.49%, found: c: 72.29%, H: 8.52 percent.
Preparation example 2: preparation of a Compound of formula M2
Synthesis of intermediate M2-1: dissolving 3-methyl-2-butanone (100mmol) and potassium tert-butoxide (100mmol) in anhydrous THF (100ml) at room temperature, cooling to 0 deg.C, stirring for 30min, adding ethyl acrylate (100mmol), heating to room temperature, and stirring for 1.5 h. Adding saturated NH4The reaction mixture was quenched with a Cl solution (50ml), anhydrous magnesium sulfate was added, the mixture was filtered, and then, dried by rotary drying under reduced pressure, and the residue was subjected to column chromatography to obtain intermediate M2-1 (yield: 82%) as a white solid.
Synthesis of intermediate M2-2: dissolving intermediate M2-1(80mmol) and p-toluenesulfonic acid (2mmol) in absolute ethanol (240mmol) and benzene (120ml), heating and stirring under the protection of nitrogen, heating to reflux reaction, monitoring by TLC to ensure that the reaction is almost complete, cooling to room temperature, performing reduced pressure spin-drying on the reaction liquid, and performing column chromatography on intermediate M2-1 to obtain intermediate M2-2 as a white solid (yield: 35%).
Synthesis of intermediate M2-3: intermediate M2-2(28mmol) and LiAlH (10mmol) were dissolved in anhydrous ether (100ml), stirred at room temperature for 8h, TLC monitored that the reaction was substantially complete, to the reaction solution were added water (30ml) and 10 wt% aqueous sulfuric acid (30ml) in this order, the organic layer was separated, the organic layer was washed three times with saturated sodium carbonate solution, dried over anhydrous magnesium sulfate, filtered and spin-dried under reduced pressure, and the residue was subjected to column chromatography to give intermediate M2-3 as a white solid (yield: 93%).
Synthesis of intermediate M2-4: dissolving gamma-butyrolactone (0.1mol) in anhydrous THF (100ml), cooling the mixture to-30 ℃ after complete dissolution, then slowly adding 1M Lithium Diisopropylamide (LDA) (120ml), continuing to react at-20 ℃ for 4h, then adding methyl iodide (0.15mol), slowly heating to room temperature, continuing to react for 4h, quenching with saturated aqueous sodium bisulfite solution, extracting three times with dichloromethane, combining organic phases, drying after filtration, spin-drying, and performing column chromatography to obtain intermediate M2-4 (yield: 66%) as a white solid.
Synthesis of intermediate M2-5: the same procedure as that for the synthesis of intermediate M2-4 gave intermediate M2-5 as a white solid (yield: 60%).
Synthesis of intermediate M2-6: boron tribromide (60mmol) and sodium iodide (90mmol) were dissolved in acetonitrile (150ml) and stirred uniformly to give solution No. 2.
Intermediate M2-2(66mmol) was dissolved in acetonitrile (80ml), and slowly added dropwise to solution No. 2, stirred at room temperature for 24h, quenched with ice/water and dichloromethane (120ml), extracted with saturated aqueous sodium bicarbonate (150ml), saturated aqueous sodium thiosulfate (150ml) and water (150ml), dried over anhydrous magnesium sulfate and spin-dried under reduced pressure, and subjected to column chromatography to give intermediate M2-6 as a white solid (yield: 75%).
Synthesis of a compound of formula M2: under the protection of nitrogen, dissolving activated zinc powder (50mmol) in 30ml of anhydrous THF and dibromoethane (2ml), heating to 65 ℃, keeping for 5min, cooling to 25 ℃, stirring for 20min, then adding trimethylchlorosilane (2ml), and stirring for 30min to obtain No. 3 solution.
Dissolving the intermediate M2-6(45mmol) in anhydrous THF (120ml), heating and stirring, heating to 30 ℃, slowly adding the solution No. 3 dropwise, stirring for reacting for 20h, cooling to-10 ℃, adding copper cyanide (45mmol) and lithium chloride (90mmol), heating to 0 ℃, stirring for 20min, and cooling to-78 ℃ to obtain the solution No. 4.
Dissolving intermediate M2-3(45mmol) and trimethylchlorosilane (90mmol) in diethyl ether (80ml), stirring well, slowly dropping into No. 4 solution, stirring at-78 deg.C for 5h, heating to room temperature, reacting for 20h, adding saturated NH4The reaction was quenched with Cl (20ml), extracted with ether, and the organic phases were combined, washed with deionized water (200ml), dried over anhydrous magnesium sulfate, and then spin-dried under reduced pressure to conduct column chromatography to obtain a white solid I (yield: 50%).
White solid I and potassium tert-butoxide (66mmol) were dissolved in anhydrous THF (80ml), heated with stirring under nitrogen, warmed to reflux, monitored by TLC for substantial completion, cooled to room temperature, the reaction was spun off under reduced pressure and the residue recrystallized to give the compound of formula M2 as a white solid (yield: 75%).
Mass spectrum: c14H22O2The theoretical value is as follows: 222.16, found: 222.2.
elemental analysis: theoretical value: c: 75.63%, H: 9.97%, found: c: 75.60%, H: 9.95 percent.
Preparation example 3: preparation of a Compound of formula M3
The synthesis of the intermediate M3-1 to the compound of formula M3 is similar to the synthesis of the intermediate M2-1 to the compound of formula M2, except that the starting materials are different.
Mass spectrum: c18H30O2The theoretical value is as follows: 278.22, found: 278.2.
elemental analysis: theoretical value: c: 77.65%, H: 10.86%, found: c: 77.63%, H: 10.88 percent.
Preparation example 4: preparation of the Compound of formula M4
The synthesis of intermediate M4-1 through intermediate M4-4 was similar to the synthesis of intermediate M2-1 through intermediate M2-4, except that the starting materials were different.
The synthesis of the compounds of formula M4 from intermediate M4-5 was similar to the synthesis of the compounds of formula M2-6 from intermediate M2, except that the starting materials were different.
Mass spectrum: c20H30O2The theoretical value is as follows: 302.22, found: 302.2.
elemental analysis: theoretical value: c: 79.42%, H: 10.00%, found: c: 79.45%, H: 10.03 percent.
Preparation example 5: preparation of a Compound of formula M5
The synthesis of intermediate M5-1 to intermediate M5-4 was similar to the synthesis of intermediate M2-1 to intermediate M2-4, except that the starting materials were different.
The synthesis of the intermediate M5-5 to the compound of formula M5 is similar to the synthesis of the intermediate M2-6 to the compound of formula M2, except that the starting materials are different.
Mass spectrum: c20H34O2The theoretical value is as follows: 306.26, found: 306.3.
elemental analysis: theoretical value: c: 78.38%, H: 11.18%, found: c: 78.42%, H: 11.15 percent.
Preparation example 6: preparation of a Compound of formula M6
The synthesis of the compound of formula M6 is similar to the synthesis of the compound of formula M2, except that the starting materials are different.
Mass spectrum: c15H24O2The theoretical value is as follows: 236.18, found: 236.2.
elemental analysis: theoretical value: c: 76.23%, H: 10.24%, found: c: 76.26%, H: 10.27 percent.
Preparation example 7: preparation of Compound A-10
Synthesis of intermediate A-10-1: under the protection of nitrogen, dissolving 5-phenyl-2-methylquinoline (40mmol) and iridium trichloride (10mmol) in a mixed solution of 60ml of ethoxyethanol and 30ml of water, heating and stirring, heating to 100 ℃, reacting for 28h, cooling to room temperature, performing suction filtration, and washing with deionized water, ethanol and petroleum ether in sequence to obtain a crude product. The crude product was refluxed and pulped with 100ml of ethanol and petroleum ether in this order, and filtered to obtain intermediate A-10-1 (yield: 55%).
Synthesis of Compound A-10: under the protection of nitrogen, dissolving intermediate A-10-1(12mmol), a compound of formula M1 (96mmol) and sodium carbonate (96mmol) in 2-ethoxyethanol (170ml), heating and stirring, heating to reflux reaction, cooling to room temperature, filtering, and performing column chromatography to obtain compound A-10 (yield: 42%) as orange-red solid.
Elemental analysis: theoretical value: c: 63.53%, H: 4.70%, N: 3.53 percent; measured value: c: 63.55%, H: 4.75%, N: 3.46 percent.
Preparation example 8: preparation of Compound A-52
Synthesis of intermediate A-52-1: under the protection of nitrogen, dissolving 2- (2-pyridyl) benzothiophene (20mmol) and iridium trichloride (5mmol) in a mixed solution of 40ml of ethoxyethanol and 20ml of water, heating and stirring, heating to 100 ℃, reacting for 20 hours, cooling to room temperature, performing suction filtration, and washing with deionized water, ethanol and petroleum ether in sequence to obtain a crude product. The crude product was refluxed and pulped with 50ml of ethanol and petroleum ether in this order, and filtered to obtain intermediate A-52-1 (yield: 57%).
Synthesis of Compound A-52: under the protection of nitrogen, intermediate A-52-1(2.8mmol), compound of formula M1 (22.4mmol) and sodium carbonate (22.4mol) were dissolved in 2-ethoxyethanol (50ml), heated and stirred, heated to reflux for reaction, cooled to room temperature for filtration, and subjected to column chromatography to obtain compound A-52 as a yellow-green solid (yield: 40%).
Elemental analysis: theoretical value: c: 55.58%, H: 3.76%, N: 3.60 percent; measured value: c: 55.54%, H: 3.78%, N: 3.58 percent.
Preparation example 9: synthesis of Compound A-114
Synthesis of intermediate A-114-1: under the protection of nitrogen, dissolving 2-phenylbenzoxazole (25mmol) and iridium trichloride (6.25mmol) in a mixed solution of 40ml of ethoxyethanol and 20ml of water, heating and stirring, heating to 100 ℃, reacting for 18 hours, cooling to room temperature, performing suction filtration, and washing with deionized water, ethanol and petroleum ether in sequence to obtain a crude product. The crude product was refluxed and pulped with 50ml of ethanol and petroleum ether in this order, and filtered to give intermediate A-114-1 (yield: 52%).
Synthesis of Compound A-114: under the protection of nitrogen, intermediate A-114-1(3.25mmol), compound of formula M2 (26mmol) and sodium carbonate (26mmol) are dissolved in 2-ethoxyethanol (60ml), heated and stirred, heated to reflux for reaction, cooled to room temperature for filtration, and subjected to column chromatography to obtain compound A-114 as a yellow-green solid (yield: 38%).
Elemental analysis: theoretical value: c: 59.91%, H: 4.65%, N: 3.49 percent; measured value: c: 59.93%, H: 4.62%, N: 3.52 percent.
Preparation example 10: preparation of Compound A-141
Synthesis of intermediate A-141-1: under the protection of nitrogen, 1- (3, 5-dimethylphenyl) -6-isopropyl isoquinoline (20mmol) and iridium trichloride (5mmol) are dissolved in a mixed solution of 40ml of ethoxyethanol and 20ml of water, the mixture is heated and stirred, the temperature is raised to 100 ℃, the reaction lasts 18 hours, the temperature is reduced to room temperature, the filtration is carried out, and the washing is carried out by deionized water, ethanol and petroleum ether in sequence to obtain a crude product. The crude product was refluxed and pulped with 50ml of ethanol and petroleum ether in this order, and filtered to obtain intermediate A-141-1 (yield: 58%).
Synthesis of Compound A-141: under the protection of nitrogen, intermediate A-141-1(2.9mmol), compound of formula M3 (23.2mmol) and sodium carbonate (23.2mmol) were dissolved in 2-ethoxyethanol (60ml), heated and stirred, heated to reflux, cooled to room temperature and filtered, and column chromatography was performed to obtain compound A-141 as a dark red solid (yield: 39%).
Elemental analysis: theoretical value: c: 68.16%, H: 6.72%, N: 2.79 percent; measured value: c: 68.18%, H: 6.70%, N: 2.81 percent.
Preparation example 11: preparation of Compound A-185
Synthesis of intermediate A-185-1: under the protection of nitrogen, dissolving 2-phenylpyridine (10mmol) and iridium trichloride (2.5mmol) in a mixed solution of 20ml of ethoxyethanol and 10ml of water, heating and stirring, heating to 100 ℃, reacting for 10 hours, cooling to room temperature, performing suction filtration, and washing with deionized water, ethanol and petroleum ether in sequence to obtain a crude product. The crude product was then refluxed and pulped with 50ml of ethanol and petroleum ether in this order, and filtered to give intermediate A-185-1 (yield: 55%).
Synthesis of Compound A-185: under the protection of nitrogen, intermediate A-185-1(1.37mmol), compound of formula M5 (11mmol) and sodium carbonate (11mmol) were dissolved in 2-ethoxyethanol (30ml), heated and stirred, heated to reflux, cooled to room temperature, filtered and subjected to column chromatography to obtain compound A-185 as a yellow solid (yield: 41%).
Elemental analysis: theoretical value: c: 62.58%, H: 6.13%, N: 3.48 percent; measured value: c: 62.55%, H: 6.17%, N: 3.47 percent.
Preparation example 12: preparation of Compound A-187
Synthesis of intermediate A-187-1: under the protection of nitrogen, 2-phenylquinoline (15mmol) and iridium trichloride (3.75mmol) are dissolved in a mixed solution of 40ml of ethoxyethanol and 20ml of water, heated and stirred, heated to 100 ℃, reacted for 12 hours, cooled to room temperature, filtered, washed by deionized water, ethanol and petroleum ether in sequence, and a crude product is obtained. The crude product was then refluxed and pulped with 60ml of ethanol and petroleum ether in this order, and filtered to give intermediate A-185-1 (yield: 55%).
Synthesis of Compound A-187: under the protection of nitrogen, dissolving intermediate A-187-1(2mmol), compound of formula M4 (16mmol) and sodium carbonate (16mmol) in 2-ethoxyethanol (30ml), heating and stirring, heating to reflux reaction, cooling to room temperature, filtering, and performing column chromatography to obtain compound A-187 (yield: 43%) as an orange yellow solid.
Elemental analysis: theoretical value: c: 66.57%, H: 5.47%, N: 3.11 percent; measured value: c: 66.55%, H: 5.48%, N: 3.14 percent.
Preparation example 13: preparation of Compound A-210
Synthesis of Compound A-210: under the protection of nitrogen, the intermediate A-141-1(5mmol), the compound of formula M6 (40mmol) and sodium carbonate (40mmol) are dissolved in 2-ethoxyethanol (80ml), heated and stirred, heated to reflux for reaction, cooled to room temperature for filtration, and subjected to column chromatography to obtain the compound A-210 as a dark red solid (yield: 44%).
Elemental analysis: theoretical value: c: 67.45%, H: 6.79%, N: 2.86 percent; measured value: c: 67.49%, H: 6.77%, N: 2.88 percent.
The following compounds were prepared in a similar manner to the synthesis of compound a-10, except that the starting materials were replaced as appropriate.
Compound A-1: elemental analysis: theoretical value: c: 57.73%, H: 4.39%, N: 4.21 percent; measured value: c: 57.76%, H: 4.40%, N: 4.23 percent.
Compound A-6: elemental analysis: theoretical value: c: 64.99%, H: 5.34%, N: 3.30 percent; measured value: c: 64.97%, H: 5.38%, N: 3.33 percent.
Compound A-15: elemental analysis: theoretical value: c: 64.29%, H: 5.03%, N: 3.41 percent; measured value: c: 64.33%, H: 5.05%, N: 3.42 percent.
Compound A-17: elemental analysis: theoretical value: c: 64.99%, H: 5.34%, N: 3.30 percent; measured value: c: 64.95%, H: 5.32%, N: 3.30 percent.
Compound A-23: elemental analysis: theoretical value: c: 63.53%, H: 4.70%, N: 3.53 percent; measured value: c: 63.57%, H: 4.74%, N: 3.44 percent.
Compound A-32: elemental analysis: theoretical value: c: 66.27%, H: 5.90%, N: 3.09%; measured value: c: 66.29%, H: 5.93%, N: 3.04 percent.
Compound A-33: elemental analysis: theoretical value: c: 62.73%, H: 4.34%, N: 3.66 percent; measured value: c: 62.70%, H: 4.36%, N: 3.62 percent.
Compound A-46: elemental analysis: theoretical value: c: 64.29%, H: 5.03%, N: 3.41 percent; measured value: c: 64.32%, H: 5.06%, N: 3.44 percent.
Compound A-65: elemental analysis: theoretical value: c: 60.05%, H: 4.91%, N: 7.00 percent; measured value: c: 60.02%, H: 4.93%, N: 7.02 percent.
Compound A-69: elemental analysis: theoretical value: c: 59.89%, H: 5.17%, N: 3.88 percent; measured value: c: 59.93%, H: 5.15%, N: 3.89 percent.
Compound A-73: elemental analysis: theoretical value: c: 66.27%, H: 5.90%, N: 3.09%; measured value: c: 66.30%, H: 5.90%, N: 3.07 percent.
Compound A-76: elemental analysis: theoretical value: c: 66.27%, H: 5.90%, N: 3.09%; measured value: c: 66.32%, H: 5.88%, N: 3.02 percent.
Compound A-80: elemental analysis: theoretical value: c: 65.65%, H: 5.62%, N: 3.19 percent; measured value: c: 65.67%, H: 5.60%, N: 3.22 percent.
Compound A-119: elemental analysis: theoretical value: c: 62.49%, H: 5.81%, N: 6.34 percent; measured value: c: 62.52%, H: 5.83%, N: 6.31 percent.
Compound A-122: elemental analysis: theoretical value: c: 67.14%, H: 5.74%, N: 3.01 percent; measured value: c: 67.16%, H: 5.75%, N: 3.03 percent.
Compound A-127: elemental analysis: theoretical value: c: 67.40%, H: 6.39%, N: 2.91 percent; measured value: c: 67.42%, H: 6.37%, N: 2.92 percent.
Compound A-132: elemental analysis: theoretical value: c: 66.85%, H: 6.15%, N: 3.00 percent; measured value: c: 66.83%, H: 6.18%, N: 3.02 percent.
Compound A-139: elemental analysis: theoretical values are as follows: c: 68.68%, H: 6.46%, N: 2.76 percent; measured value: c: 68.67%, H: 6.45%, N: 2.73 percent.
Compound A-160: elemental analysis: theoretical value: c: 67.92%, H: 6.62%, N: 2.83 percent; measured value: c: 67.90%, H: 6.65%, N: 2.84 percent.
Compound A-165: elemental analysis: theoretical value: c: 59.37%, H: 5.10%, N: 3.15 percent; measured value: c: 59.39%, H: 5.13%, N: 3.16 percent.
Compound A-173: elemental analysis: theoretical value: c: 65.96%, H: 5.19%, N: 3.20 percent; measured value: c: 65.98%, H: 5.22%, N: 3.18 percent.
Compound A-177: elemental analysis: theoretical value: c: 64.99%, H: 5.34%, N: 3.30 percent; measured value: c: 64.97%, H: 5.36%, N: 3.33 percent.
Compound a-182: elemental analysis: theoretical value: c: 68.87%, H: 7.03%, N: 2.68 percent; measured value: c: 68.85%, H: 7.04%, N: 2.66 percent.
Compound A-82: elemental analysis: theoretical value: c: 67.40%, H: 6.39%, N: 2.91 percent; measured value: c: 67.36%, H: 6.41%, N: 2.93 percent.
Compound A-89: elemental analysis: theoretical value: c: 67.40%, H: 6.39%, N: 2.91 percent; measured value: c: 67.38%, H: 6.43%, N: 2.90 percent.
Example 1: preparation of organic electroluminescent device
Sequentially with deionized water, and acetone: after a glass substrate having an Indium Tin Oxide (ITO) electrode (anode) was ultrasonically treated with ethanol (v: v ═ 1: 1), the treated glass substrate was dried in a clean environment, washed with ultraviolet light and ozone, and the surface of the glass substrate was bombarded with a low-energy cation beam;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-4Pa, evaporating a compound HAT-CN on the anode layer film to form a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness is 5 nm;
evaporating a compound NPB on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the thickness is 60 nm;
evaporating a host material compound RH and a guest material compound A-10 on the hole transport layer film by adopting a multi-source co-evaporation method to form a light-emitting layer, and adjusting the evaporation rate of the host material to be 0.1nm/s, the evaporation rate of the guest material to be 10% of the evaporation rate of the host material and the thickness to be 30 nm;
evaporating a compound ET-1 and a compound ET-2 on the luminescent layer film by adopting a multi-source co-evaporation method to form an electron transport layer, wherein the evaporation rate is 0.1nm/s, and the thickness is 30 nm;
evaporating LiF on the electron transport layer film to form an electron injection layer; the thickness is 1 nm;
al is evaporated on the electron injection layer film to form a cathode with a thickness of 150 nm.
Examples 2 to 16
An organic electroluminescent device was produced in a similar manner to example 1, except that the compound A-10 in example 1 was replaced with the corresponding compound in Table 1, and the rest was the same as in example 1.
Example 17
Sequentially with deionized water, and acetone: after a glass substrate having an Indium Tin Oxide (ITO) electrode (anode) was ultrasonically treated with ethanol (v: v ═ 1: 1), the treated glass substrate was dried in a clean environment, washed with ultraviolet light and ozone, and the surface of the glass substrate was bombarded with a low-energy cation beam;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-4Pa, evaporating and plating a compound HAT-CN on the anode layer film to form a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness is 5 nm;
evaporating a compound NPB on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the thickness is 60 nm;
evaporating a host material compound GH and a guest material compound A-1 on the hole transport layer film by adopting a multi-source co-evaporation method to form a light-emitting layer, and adjusting the evaporation rate of the host material to be 0.1nm/s, the evaporation rate of the guest material to be 10% of the evaporation rate of the host material and the thickness of the guest material to be 30 nm;
evaporating a compound ET-1 and a compound ET-2 on the luminescent layer film by adopting a multi-source co-evaporation method to form an electron transport layer, wherein the evaporation rate is 0.1nm/s, and the thickness is 30 nm;
evaporating LiF on the electron transport layer film to form an electron injection layer with the thickness of 1 nm;
al is evaporated on the electron injection layer film to form a cathode with a thickness of 150 nm.
Examples 18 to 28
An organic electroluminescent device was produced in a similar manner to example 17, except that the compound A-1 in example 1 was replaced with the corresponding compound in Table 2, and the rest was the same as in example 17.
Comparative example 1
An organic electroluminescent device was produced in a similar manner to example 1, except that the compound A-10 in example 1 was replaced with a compound represented by the formula Ref-1, and the rest was the same as in example 1.
Comparative example 2
An organic electroluminescent device was produced in a similar manner to example 1, except that the compound A-10 in example 1 was replaced with a compound represented by the formula Ref-2, and the rest was the same as in example 1.
Comparative example 3
An organic electroluminescent device was produced in a similar manner to example 1, except that the compound A-10 in example 1 was replaced with a compound represented by the formula Ref-3, and the rest was the same as in example 1.
Comparative example 4
An organic electroluminescent device was produced in a similar manner to example 17, except that the compound A-1 in example 17 was replaced with a compound represented by the formula Ref-4, and the rest was the same as in example 17.
Test example 1
At a luminance of 2000cd/m2Next, the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples and comparative examples were measuredThe results are shown in Table 1.
Test example 2
At a luminance of 10000cd/m2Next, the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples and comparative examples were measured, and the results are shown in table 2.
TABLE 1
TABLE 2
| Guest material | Drive voltage (V) | Current efficiency (cd/A) | CIE | Colour(s) | |
| Example 17 | Compound A-1 | 4.23 | 63.1 | (0.31，0.64) | Green colour |
| Example 18 | Compound A-52 | 4.35 | 63.5 | (0.32，0.65) | Green colour |
| Example 19 | Compound A-69 | 4.27 | 65.4 | (0.31，0.65) | Green colour |
| Example 20 | Compound A-114 | 4.40 | 62.4 | (0.35，0.60) | Green colour |
| Example 21 | Compound A-122 | 4.42 | 66.7 | (0.31，0.64) | Green colour |
| Example 22 | Compound A-173 | 4.45 | 64.0 | (0.31，0.64) | Green colour |
| Example 23 | Compound A-185 | 4.46 | 64.2 | (0.32，0.65) | Green colour |
| Example 24 | Compound A-33 | 4.14 | 23.7 | (0.49，0.51) | Yellow colour |
| Example 25 | Compound A-46 | 4.32 | 23.9 | (0.49，0.53) | Yellow colour |
| Example 26 | Compound A-160 | 4.44 | 24.5 | (0.47，0.54) | Yellow colour |
| Example 27 | Compound A-165 | 4.43 | 23.4 | (0.47，0.52) | Yellow colour |
| Example 28 | Compound A-187 | 4.45 | 24.2 | (0.48，0.51) | Yellow colour |
| Comparative example 4 | The compound of formula Ref-4 | 4.64 | 52.3 | (0.32，0.62) | Green colour |
As can be seen from the results in table 1, when the compound of the present invention is used as a guest material in a light emitting layer of an organic electroluminescent device, the compound has a lower driving voltage and higher light emitting efficiency when applied to the organic electroluminescent device, compared to the prior art.
It can be seen from the results of table 2 that when the compound of the present invention is used as a guest material in a light emitting layer of an organic electroluminescent device, the compound has higher luminous efficiency when applied to the organic electroluminescent device compared to the prior art.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A compound comprising a1, 3-dione ligand, wherein the compound has Ir (L)A)(LB)2Shown inIn which LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown;
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C20Alkyl of (C)6-C20Aryl of (a); or R1And R2And R3And R4At least one combination of (a) cyclizes to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C20Alkyl of (C)6-C20Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form a ring selected from the group consisting of a substituted or unsubstituted benzene ring, a substituted or unsubstitutedAt least one ring structure of a naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted pyridothiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C10At least one of alkyl and phenyl.
2. The compound of claim 1, wherein Ir (L)A)(LB)2In the structure shown, LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown;
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C15Alkyl of (C)6-C15Aryl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C15Alkyl of (C)6-C15Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted thienopyridine ring, and a substituted or unsubstituted thiophene ring;
and optionally a substituent on the ring Q, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C8At least one of alkyl and phenyl.
3. The compound according to claim 1 or 2, wherein Ir (L)A)(LB)2In the structure shown, LAHas a structure represented by formula (IA), LBIs a structure represented by the formula (IB), LB310Shown structure, LB311Shown structure, LB312Shown structure, LB313Structure shown or LB314The structure shown;
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C10Alkyl of (C)6-C12Aryl of (a); or R1And R2And R3And R4At least one of the combinations of (a) is cyclized to form a 4-6 membered saturated ring;
in formula (IB), X is C or N,
the ring Q is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted indole ring, a substituted or unsubstituted benzothiazole ring, a substituted or unsubstituted benzoxazole ring, a substituted or unsubstituted benzimidazole ring, a substituted or unsubstituted dibenzothiophene ring, a substituted or unsubstituted dibenzofuran ring, a substituted or unsubstituted benzofuropyridine ring, a substituted or unsubstituted benzothienopyridine ring, a substituted or unsubstituted benzindolopyridine ring, a substituted or unsubstituted pyridoindolopyridine ring, a substituted or unsubstituted imidazole ring, a substituted or unsubstituted pyrrolidine ring;
R1、R2、R3、R4each independently selected from H, C1-C10Alkyl of (C)6-C12Aryl of (a); or R1、R2、R3、R4Any two of which are cyclized together to form at least one ring structure selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted benzofuran ring, a substituted or unsubstituted pyridofuran ring, a substituted or unsubstituted benzothiophene ring, a substituted or unsubstituted thienopyridine ring, and a substituted or unsubstituted thiophene ring;
and optionally a substituent on the Q ring, and R1、R2、R3、R4Each of the substituents optionally present on (A) is independently selected from C1-C6At least one of alkyl and phenyl.
4. The compound of claim 3, wherein Ir (L)A)(LB)2In the configuration shown in the figures, the,
in formula (IA), R1、R2、R3、R4Each independently selected from H, C1-C7Alkyl of (C)6-C10Aryl of (a); or R1And R2And R3And R4At least one combination of (a) is cyclized to form a 4-6 membered saturated ring.
5. The compound of claim 4, wherein Ir (L)A)(LB)2In the configuration shown in the figures, the,
in formula (IA), R1、R2、R3、R4Each independently selected from H, methyl, ethyl, C3Straight chain alkyl of (1), C3Branched alkyl of C3Cycloalkyl of, C4Straight chain alkyl group of (1), C4Branched alkyl of (2), C4Cycloalkyl of, C5Straight chain alkyl group of (1), C5Branched alkyl of C5Cycloalkyl of, C6Straight chain alkyl group of (1), C6Branched alkyl of C6Cycloalkyl of, C7Straight chain alkyl of (1), C7Branched alkyl of C7Cycloalkyl, phenyl of (a); or R1And R2And R3And R4At least one combination of (a) is cyclized to form a 4-6 membered saturated ring.
6. The compound of claim 5, wherein Ir (L)A)(LB)2In the structure shown, LASelected from the group consisting of:
7. the compound according to any one of claims 1-6, wherein Ir (L)A)(LB)2In the structure shown, LBSelected from the group consisting of:
preferably, the 1, 3-dione ligand-containing compound is selected from any one of the following compounds:
8. the compound of any one of claims 1-7, wherein Ir (L)A)(LB)2The structures shown are selected from the group consisting of:
9. use of a1, 3-dione ligand-containing compound according to any one of claims 1 to 8 as an organic electrophosphorescent material;
preferably, the organic electrophosphorescent material is an organic electrophosphorescent material in an organic electroluminescent device.
10. An organic electroluminescent element comprising at least one compound containing a1, 3-diketone ligand according to any one of claims 1 to 8;
preferably, the compound containing a1, 3-diketone ligand is present in the light-emitting layer of the organic electroluminescent device;
preferably, the compound containing the 1, 3-diketone ligand is a guest material in a light-emitting layer of the organic electroluminescent device;
preferably, the organic electroluminescent device comprises an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode.
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| CN114478642B (en) | 2023-08-18 |
| CN114478641A (en) | 2022-05-13 |
| CN114478638B (en) | 2024-03-15 |
| CN114478638A (en) | 2022-05-13 |
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