CN116535443A - Organic electroluminescent material and device thereof - Google Patents
Organic electroluminescent material and device thereof Download PDFInfo
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- CN116535443A CN116535443A CN202211472133.XA CN202211472133A CN116535443A CN 116535443 A CN116535443 A CN 116535443A CN 202211472133 A CN202211472133 A CN 202211472133A CN 116535443 A CN116535443 A CN 116535443A
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- 239000000463 material Substances 0.000 title abstract description 48
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 91
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 239000003446 ligand Substances 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 416
- 125000001424 substituent group Chemical group 0.000 claims description 182
- -1 phosphino groups Chemical group 0.000 claims description 139
- 239000010410 layer Substances 0.000 claims description 80
- 125000000217 alkyl group Chemical group 0.000 claims description 66
- 125000003118 aryl group Chemical group 0.000 claims description 60
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 55
- 229910052805 deuterium Inorganic materials 0.000 claims description 55
- 125000001072 heteroaryl group Chemical group 0.000 claims description 54
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims description 44
- 239000001257 hydrogen Substances 0.000 claims description 44
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 42
- 125000006413 ring segment Chemical group 0.000 claims description 39
- 150000002431 hydrogen Chemical class 0.000 claims description 31
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- 125000000623 heterocyclic group Chemical group 0.000 claims description 25
- 229910052736 halogen Inorganic materials 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 24
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 22
- 239000011737 fluorine Substances 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 19
- 125000004104 aryloxy group Chemical group 0.000 claims description 19
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 19
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 16
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 16
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 16
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 16
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 16
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 16
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- 125000000304 alkynyl group Chemical group 0.000 claims description 15
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 15
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 15
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 125000000732 arylene group Chemical group 0.000 claims description 11
- 125000005549 heteroarylene group Chemical group 0.000 claims description 11
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 10
- 125000002252 acyl group Chemical group 0.000 claims description 10
- 125000005104 aryl silyl group Chemical group 0.000 claims description 10
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 9
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 9
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 9
- 229910005965 SO 2 Inorganic materials 0.000 claims description 8
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 7
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 7
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 7
- WLKSSWJSFRCZKL-UHFFFAOYSA-N trimethylgermanium Chemical compound C[Ge](C)C WLKSSWJSFRCZKL-UHFFFAOYSA-N 0.000 claims description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 150000002739 metals Chemical group 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 4
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- DHFABSXGNHDNCO-UHFFFAOYSA-N dibenzoselenophene Chemical compound C1=CC=C2C3=CC=CC=C3[se]C2=C1 DHFABSXGNHDNCO-UHFFFAOYSA-N 0.000 claims description 4
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical compound C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 claims description 4
- 229960005544 indolocarbazole Drugs 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 125000005580 triphenylene group Chemical group 0.000 claims description 4
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000004474 heteroalkylene group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 3
- BPMFPOGUJAAYHL-UHFFFAOYSA-N 9H-Pyrido[2,3-b]indole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=N1 BPMFPOGUJAAYHL-UHFFFAOYSA-N 0.000 claims description 2
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-UHFFFAOYSA-N 0.000 claims description 2
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003636 chemical group Chemical group 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- UTUZBCDXWYMYGA-UHFFFAOYSA-N silafluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=[Si]2 UTUZBCDXWYMYGA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000006467 substitution reaction Methods 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000003111 delayed effect Effects 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 150000003384 small molecules Chemical class 0.000 description 7
- 229910052732 germanium Inorganic materials 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 5
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 5
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 238000005538 encapsulation Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 4
- 229940093475 2-ethoxyethanol Drugs 0.000 description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N benzopyrrole Natural products C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000005525 hole transport Effects 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- SKEDXQSRJSUMRP-UHFFFAOYSA-N lithium;quinolin-8-ol Chemical compound [Li].C1=CN=C2C(O)=CC=CC2=C1 SKEDXQSRJSUMRP-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Chemical group C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- BNRDGHFESOHOBF-UHFFFAOYSA-N 1-benzoselenophene Chemical compound C1=CC=C2[se]C=CC2=C1 BNRDGHFESOHOBF-UHFFFAOYSA-N 0.000 description 2
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 2
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical group OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 2
- 125000006282 2-chlorobenzyl group Chemical group [H]C1=C([H])C(Cl)=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 2
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 2
- 229920001621 AMOLED Polymers 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229920000547 conjugated polymer Polymers 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 125000003564 m-cyanobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(C#N)=C1[H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 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 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000013086 organic photovoltaic Methods 0.000 description 2
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- 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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Abstract
An organic electroluminescent material and a device thereof are disclosed. The organic electroluminescent material is a material comprising L having the structure of formula 1 a The metal complexes of the ligand can be applied to organic electroluminescent devices to obtain very excellent device performance, in particular to improve the service life and the efficiency of the devices. Has great application prospect in the aspects of white light and low blue light sources. Also disclosed are an organic electroluminescent device comprising the metal complex and a compound composition comprising the metal complex.
Description
Technical Field
The present invention relates to compounds for use in organic electronic devices, such as organic electroluminescent devices. More particularly, it relates to a composition comprising L having the structure of formula 1 a Metal complexes of ligands, organic electroluminescent devices and compound compositions comprising the same.
Background
Organic electronic devices include, but are not limited to, the following: organic Light Emitting Diodes (OLEDs), organic field effect transistors (O-FETs), organic light emitting transistors (OLEDs), organic photovoltaic devices (OPVs), dye-sensitized solar cells (DSSCs), organic optical detectors, organic photoreceptors, organic field effect devices (OFQDs), light emitting electrochemical cells (LECs), organic laser diodes and organic electroluminescent devices.
In 1987, tang and Van Slyke of Isomandah reported a double-layered organic electroluminescent device comprising an arylamine hole transport layer and a tris-8-hydroxyquinoline-aluminum layer as an electron transport layer and a light emitting layer (Applied Physics Letters,1987,51 (12): 913-915). Once biased into the device, green light is emitted from the device. The invention lays a foundation for the development of modern Organic Light Emitting Diodes (OLEDs). Most advanced OLEDs may include multiple layers, such as charge injection and transport layers, charge and exciton blocking layers, and one or more light emitting layers between the cathode and anode. Because OLEDs are self-emitting solid state devices, they offer great potential for display and lighting applications. Furthermore, the inherent properties of organic materials, such as their flexibility, may make them well suited for particular applications, such as in flexible substrate fabrication.
OLEDs can be divided into three different types according to their light emission mechanism. The OLED of the Tang and van Slyke invention is a fluorescent OLED. It uses only singlet light emission. The triplet states generated in the device are wasted through non-radiative decay channels. Thus, the Internal Quantum Efficiency (IQE) of fluorescent OLEDs is only 25%. This limitation prevents commercialization of OLEDs. In 1997, forrest and Thompson reported phosphorescent OLEDs using triplet emission from heavy metals containing complexes as emitters. Thus, both singlet and triplet states can be harvested, achieving a 100% IQE. Because of its high efficiency, the discovery and development of phosphorescent OLEDs has contributed directly to the commercialization of Active Matrix OLEDs (AMOLEDs). Recently, adachi achieved high efficiency by Thermally Activated Delayed Fluorescence (TADF) of organic compounds. These emitters have a small singlet-triplet gap, making it possible for excitons to return from the triplet state to the singlet state. In TADF devices, triplet excitons can generate singlet excitons by reverse intersystem crossing, resulting in high IQE.
OLEDs can also be classified into small molecule and polymeric OLEDs depending on the form of the materials used. Small molecule refers to any organic or organometallic material that is not a polymer. The molecular weight of the small molecules can be large as long as they have a precise structure. Dendrimers with a defined structure are considered small molecules. Polymeric OLEDs include conjugated polymers and non-conjugated polymers having pendant luminescent groups. Small molecule OLEDs can become polymeric OLEDs if post-polymerization occurs during fabrication.
Various methods of OLED fabrication exist. Small molecule OLEDs are typically fabricated by vacuum thermal evaporation. Polymeric OLEDs are manufactured by solution processes such as spin coating, inkjet printing and nozzle printing. Small molecule OLEDs can also be fabricated by solution processes if the material can be dissolved or dispersed in a solvent.
The emission color of an OLED can be achieved by the structural design of the luminescent material. The OLED may include a light emitting layer or layers to achieve a desired spectrum. Green, yellow and red OLEDs, phosphorescent materials have been successfully commercialized. Blue phosphorescent devices still have problems of blue unsaturation, short device lifetime, high operating voltage, and the like. Commercial full color OLED displays typically employ a mixing strategy using blue fluorescent and phosphorescent yellow, or red and green. Currently, a rapid decrease in efficiency of phosphorescent OLEDs at high brightness remains a problem. In addition, it is desirable to have a more saturated emission spectrum, higher efficiency and longer device lifetime.
In US2014021447A1, a metal complex structure having the following formula is disclosedWherein Z is a single bond or is absent, further disclosed are iridium complexes of:this application discloses metal complexes having carbazole groups attached to the 5-position of pyridine in phenyl-pyridine ligands, but does not disclose and teach metal complexes having specific substituents attached to the 4-position of pyridine in hexapenta-hexa-fused ring-pyridine ligands and their impact on device performance.
US7816016B1 discloses a metal complex structure having the followingWherein R1 is selected from indole, indoline, carbazole, tetrahydrocarbazole, phenanthroline, phenazine, phenanthridine, quinoxaline, pyrrole or CHAR 2 The isostructure further discloses that 4-position of pyridine in fluorine-containing substituted phenylpyridine is provided with carbazole substituted ligand +.>Metal complexes of (a) are provided. This application discloses metal complexes with some heteroaryl groups such as carbazole attached at the 4-position of pyridine and fluorine substitution on the phenyl group in phenyl-pyridine ligands, but does not disclose organic electroluminescent device data, nor disclose and teach metal complexes with specific substituents attached at the 4-position of pyridine and their impact on device performance in ligands of other structures, such as hexapenta-hexa-fused ring-pyridine ligands.
Disclosure of Invention
The present invention is directed to a series of compounds comprising L having the structure of formula 1 a Metal complexes of ligands to solve at least part of the above problems. The metal complexes are useful as luminescent materials in electroluminescent devices. The novel compounds can provide better device performance, such as the improvement of device efficiency and device service life, when applied to electroluminescent devices, and the comprehensive performance of the devices is remarkably improved.
According to one embodiment of the invention, a gold is disclosedA metal complex comprising a metal M and a ligand L coordinated to the metal M a ，L a Has a structure represented by formula 1:
wherein,,
the metal M is selected from metals with relative atomic mass of more than 40;
z is selected from the group consisting of O, S, se, NR ', CR ' R ' and SiR ' R '; when two R's are present at the same time, the two R's are the same or different;
substituent R y Represents monosubstituted, polysubstituted or unsubstituted;
X 1 -X 8 is selected identically or differently on each occurrence from C, CR x Or N; and X is 1 -X 4 One of which is selected from C and is linked to pyridine of formula 1;
substituent R n Has a structure represented by formula 2:
wherein, in the formula 2,
substituent R A And R is B Each occurrence, identically or differently, represents mono-, poly-or unsubstituted;
ring a and ring B are identically or differently selected from carbocycles having 3 to 30 ring atoms, or heterocycles having 3 to 30 ring atoms;
A 1 ，A 2 ，B 1 ，B 2 E is selected identically or differently on each occurrence from C, N, B, P, CR ' ", siR '" or GeR ' ";
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR ", P (O) R", R "c=cr", a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted heteroalkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted alkylene group having 3 to 20 carbon atomsCycloalkyl having from 3 to 20 ring atoms, substituted or unsubstituted heterocyclylene having from 6 to 30 carbon atoms, substituted or unsubstituted arylene having from 3 to 30 carbon atoms, substituted or unsubstituted heteroarylene, or a combination thereof;
substituents R ', R ", R'", R x ，R y ，R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;
"onium" represents the attachment position of formula 2;
adjacent substituents R', R x ，R”，R”’，R A ，R B ，R y Can optionally be linked to form a ring.
According to another embodiment of the present invention, there is also disclosed an electroluminescent device including: an anode, a cathode, and an organic layer disposed between the anode and the cathode, at least one of the organic layers comprising the metal complex described in the above embodiments.
According to another embodiment of the present invention, there is also disclosed a compound composition comprising the metal complex described in the above embodiment.
The invention discloses a series of L containing a structure with a formula 1 a The novel metal complexes of the ligand can be used as luminescent materials in electroluminescent devices, and can obtain very excellent device performances, such as the improvement of device efficiency and device service life, and the comprehensive performance of the device is remarkably improved. Has great application prospect in the aspects of white light and low blue light sources.
Drawings
Fig. 1 is a schematic view of an organic light emitting device that may contain the metal complex and compound compositions disclosed herein.
Fig. 2 is a schematic view of another organic light emitting device that may contain the metal complex and compound compositions disclosed herein.
Detailed Description
OLEDs can be fabricated on a variety of substrates, such as glass, plastic, and metal. Fig. 1 schematically illustrates, without limitation, an organic light-emitting device 100. The drawings are not necessarily to scale, and some of the layer structures in the drawings may be omitted as desired. The device 100 may include a substrate 101, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light emitting layer 150, a hole blocking layer 160, an electron transport layer 170, an electron injection layer 180, and a cathode 190. The device 100 may be fabricated by sequentially depositing the layers described. The nature and function of the layers and exemplary materials are described in more detail in U.S. patent US7,279,704B2, columns 6-10, the entire contents of which are incorporated herein by reference.
There are more instances of each of these layers. For example, a flexible and transparent substrate-anode combination is disclosed in U.S. patent No. 5,844,363, which is incorporated by reference in its entirety. An example of a p-doped hole transport layer is doped with F in a 50:1 molar ratio 4 m-MTDATA of TCNQ as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Issuance incorporated by reference in its entirety Examples of host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al. An example of an n-doped electron transport layer is BPhen doped with Li in a molar ratio of 1:1 as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of cathodes are disclosed in U.S. Pat. nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, including composite cathodes having a thin layer of metal, such as Mg: ag, with an overlying transparent, electrically conductive, sputter deposited ITO layer. The principles and use of barrier layers are described in more detail in U.S. patent No. 6,097,147 and U.S. patent application publication No. 2003/0230980, which are incorporated by reference in their entirety. Examples of implant layers are provided in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety. A description of protective layers can be found in U.S. patent application publication No. 2004/0174116, which is incorporated by reference in its entirety.
The above-described hierarchical structure is provided by way of non-limiting example. The function of the OLED may be achieved by combining the various layers described above, or some of the layers may be omitted entirely. It may also include other layers not explicitly described. Within each layer, a single material or a mixture of materials may be used to achieve optimal performance. Any functional layer may comprise several sublayers. For example, the light emitting layer may have two layers of different light emitting materials to achieve a desired light emission spectrum.
In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. The organic layer may include one or more layers.
The OLED also requires an encapsulation layer, such as the organic light emitting device 200 shown schematically and without limitation in fig. 2, which differs from fig. 1 in that an encapsulation layer 102 may also be included over the cathode 190 to prevent harmful substances from the environment, such as moisture and oxygen. Any material capable of providing an encapsulation function may be used as the encapsulation layer, such as glass or an organic-inorganic hybrid layer. The encapsulation layer should be placed directly or indirectly outside the OLED device. Multilayer film packages are described in U.S. patent US7,968,146B2, the entire contents of which are incorporated herein by reference.
Devices manufactured according to embodiments of the present invention may be incorporated into a variety of consumer products having one or more electronic component modules (or units) of the device. Some examples of such consumer products include flat panel displays, monitors, medical monitors, televisions, billboards, lights for indoor or outdoor lighting and/or signaling, heads-up displays, displays that are fully or partially transparent, flexible displays, smart phones, tablet computers, tablet phones, wearable devices, smart watches, laptops, digital cameras, camcorders, viewfinders, micro-displays, 3-D displays, vehicle displays, and taillights.
The materials and structures described herein may also be used in other organic electronic devices as listed above.
As used herein, "top" means furthest from the substrate and "bottom" means closest to the substrate. In the case where the first layer is described as being "disposed" on "the second layer, the first layer is disposed farther from the substrate. Unless a first layer is "in contact with" a second layer, other layers may be present between the first and second layers. For example, a cathode may be described as "disposed on" an anode even though various organic layers are present between the cathode and the anode.
As used herein, "solution processable" means capable of being dissolved, dispersed, or transported in and/or deposited from a liquid medium in the form of a solution or suspension.
A ligand may be referred to as "photosensitive" when it is believed that the ligand directly contributes to the photosensitive properties of the emissive material. When it is believed that the ligand does not contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary," but ancillary ligands may alter the properties of the photosensitive ligand.
It is believed that the Internal Quantum Efficiency (IQE) of fluorescent OLEDs can be limited by spin statistics that delay fluorescence by more than 25%. Delayed fluorescence can be generally classified into two types, i.e., P-type delayed fluorescence and E-type delayed fluorescence. The P-type delayed fluorescence is generated by triplet-triplet annihilation (TTA).
On the other hand, the E-type delayed fluorescence does not depend on the collision of two triplet states, but on the transition between the triplet states and the singlet excited state. Compounds capable of generating E-type delayed fluorescence need to have very small mono-triplet gaps in order for the conversion between the energy states. The thermal energy may activate a transition from the triplet state back to the singlet state. This type of delayed fluorescence is also known as Thermally Activated Delayed Fluorescence (TADF). A significant feature of TADF is that the delay component increases with increasing temperature. The fraction of backfill singlet excited states may reach 75% if the reverse intersystem crossing (RISC) rate is fast enough to minimize non-radiative decay from the triplet states. The total singlet fraction may be 100%, well in excess of 25% of the spin statistics of the electrically generated excitons.
Type E delayed fluorescence features can be found in excitation complex systems or in single compounds. Without being bound by theory, it is believed that E-delayed fluorescence requires a luminescent material with a small mono-triplet energy gap (Δe S-T ). Organic non-metal containing donor-acceptor luminescent materials may be able to achieve this. The emission of these materials is typically characterized as donor-acceptor Charge Transfer (CT) type emission. The spatial separation of HOMO from LUMO in these donor-acceptor compounds generally results in a small Δe S-T . These states may include CT states. Typically, donor-acceptor luminescent materials are constructed by linking an electron donor moiety (e.g., an amino or carbazole derivative) to an electron acceptor moiety (e.g., an N-containing six-membered aromatic ring).
Definition of terms for substituents
Halogen or halide-as used herein, includes fluorine, chlorine, bromine and iodine.
Alkyl-as used herein, includes straight and branched chain alkyl groups. The alkyl group may be an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, neopentyl, 1-methylpentyl, 2-methylpentyl, 1-pentylhexyl, 1-butylpentyl, 1-heptyloctyl, 3-methylpentyl. Among the above, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl and n-hexyl are preferred. In addition, the alkyl group may be optionally substituted.
Cycloalkyl-as used herein, includes cyclic alkyl. Cycloalkyl groups may be cycloalkyl groups having 3 to 20 ring carbon atoms, preferably 4 to 10 carbon atoms. Examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like. Among the above, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-dimethylcyclohexyl are preferred. In addition, cycloalkyl groups may be optionally substituted.
Heteroalkyl-as used herein, a heteroalkyl comprises an alkyl chain in which one or more carbons is replaced by a heteroatom selected from the group consisting of nitrogen, oxygen, sulfur, selenium, phosphorus, silicon, germanium, and boron. The heteroalkyl group may be a heteroalkyl group having 1 to 20 carbon atoms, preferably a heteroalkyl group having 1 to 10 carbon atoms, more preferably a heteroalkyl group having 1 to 6 carbon atoms. Examples of heteroalkyl groups include methoxymethyl, ethoxymethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, ethylthioethyl, methoxymethoxymethyl, ethoxymethoxymethyl, ethoxyethoxyethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, mercaptomethyl, mercaptoethyl, mercaptopropyl, aminomethyl, aminoethyl, aminopropyl, dimethylaminomethyl, trimethylgermylmethyl, trimethylgermylethyl, dimethylethylgermylmethyl, dimethylisopropylgermylmethyl, t-butyldimethylgermylmethyl, triethylgermylmethyl, triethylgermylethyl, triisopropylgermylmethyl, triisopropylgermylethyl, trimethylsilylmethyl, trimethylsilylethyl, trimethylsilylisopropyl, triisopropylsilylmethyl. In addition, heteroalkyl groups may be optionally substituted.
Alkenyl-as used herein, covers straight chain, branched chain, and cyclic alkylene groups. Alkenyl groups may be alkenyl groups containing 2 to 20 carbon atoms, preferably alkenyl groups having 2 to 10 carbon atoms. Examples of alkenyl groups include ethenyl, propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, 1-methylvinyl, styryl, 2-diphenylvinyl, 1-methallyl, 1-dimethylallyl, 2-methallyl, 1-phenylallyl, 2-phenylallyl, 3-diphenylallyl, 1, 2-dimethylallyl, 1-phenyl-1-butenyl, 3-phenyl-1-butenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cycloheptenyl, cycloheptatrienyl, cyclooctenyl, cyclooctatetraenyl and norbornenyl. In addition, alkenyl groups may be optionally substituted.
Alkynyl-as used herein, straight chain alkynyl is contemplated. The alkynyl group may be an alkynyl group containing 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 10 carbon atoms. Examples of alkynyl groups include ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-dimethyl-1-butynyl, 3-ethyl-3-methyl-1-pentynyl, 3-diisopropyl-1-pentynyl, phenylethynyl, phenylpropynyl and the like. Among the above, preferred are ethynyl, propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl and phenylethynyl. In addition, alkynyl groups may be optionally substituted.
Aryl or aromatic-as used herein, non-fused and fused systems are contemplated. The aryl group may be an aryl group having 6 to 30 carbon atoms, preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Examples of the aryl group include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene,perylene and azulene, preferably phenyl, biphenyl, terphenyl, triphenylene, fluorene and naphthalene. Examples of non-condensed aryl groups include phenyl, biphenyl-2-yl, biphenyl-3-yl, biphenyl-4-yl, p-terphenyl-3-ylP-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl, m-terphenyl-2-yl, o-tolyl, m-tolyl, p- (2-phenylpropyl) phenyl, 4 '-methylbiphenyl-yl, 4' -tert-butyl-p-terphenyl-4-yl, o-cumyl, m-cumyl, p-cumyl, 2, 3-xylyl, 3, 4-xylyl, 2, 5-xylyl, mesityl and m-tetrabiphenyl. In addition, aryl groups may be optionally substituted.
Heterocyclyl or heterocycle-as used herein, non-aromatic cyclic groups are contemplated. The non-aromatic heterocyclic group includes a saturated heterocyclic group having 3 to 20 ring atoms and an unsaturated non-aromatic heterocyclic group having 3 to 20 ring atoms, at least one of which is selected from the group consisting of nitrogen atom, oxygen atom, sulfur atom, selenium atom, silicon atom, phosphorus atom, germanium atom and boron atom, and preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms including at least one hetero atom such as nitrogen, oxygen, silicon or sulfur. Examples of non-aromatic heterocyclic groups include oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxacycloheptatrienyl, thietaneyl, azepanyl and tetrahydrosilol. In addition, the heterocyclic group may be optionally substituted.
Heteroaryl-as used herein, non-fused and fused heteroaromatic groups that may contain 1 to 5 heteroatoms, at least one of which is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms. Heteroaryl also refers to heteroaryl. The heteroaryl group may be a heteroaryl group having 3 to 30 carbon atoms, preferably a heteroaryl group having 3 to 20 carbon atoms, more preferably a heteroaryl group having 3 to 12 carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrolopyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indenoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, benzofuranopyridine, furodipyridine, benzothiophene, thienodipyridine, benzoselenophene, selenodipyridine, preferably dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, triazine, benzimidazole, 1, 2-aza-boron, 1, 3-aza-boron, 1-aza-boron-4-aza, boron-doped compounds, and the like. In addition, heteroaryl groups may be optionally substituted.
Alkoxy-as used herein, is represented by-O-alkyl, -O-cycloalkyl, -O-heteroalkyl, or-O-heterocyclyl. Examples and preferred examples of the alkyl group, cycloalkyl group, heteroalkyl group and heterocyclic group are the same as described above. The alkoxy group may be an alkoxy group having 1 to 20 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, tetrahydrofuranyloxy, tetrahydropyranyloxy, methoxypropyloxy, ethoxyethyloxy, methoxymethyloxy and ethoxymethyloxy. In addition, the alkoxy group may be optionally substituted.
Aryloxy-as used herein, is represented by-O-aryl or-O-heteroaryl. Examples and preferred examples of aryl and heteroaryl groups are the same as described above. The aryloxy group may be an aryloxy group having 6 to 30 carbon atoms, preferably an aryloxy group having 6 to 20 carbon atoms. Examples of aryloxy groups include phenoxy and biphenoxy. In addition, the aryloxy group may be optionally substituted.
Aralkyl-as used herein, encompasses aryl-substituted alkyl. The aralkyl group may be an aralkyl group having 7 to 30 carbon atoms, preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 13 carbon atoms. Examples of aralkyl groups include benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl tert-butyl, α -naphthylmethyl, 1- α -naphthyl-ethyl, 2- α -naphthylethyl, 1- α -naphthylisopropyl, 2- α -naphthylisopropyl, β -naphthylmethyl, 1- β -naphthyl-ethyl, 2- β -naphthyl-ethyl, 1- β -naphthylisopropyl, 2- β -naphthylisopropyl, p-methylbenzyl, m-methylbenzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-chlorobenzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, o-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl, o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, cyano, o-cyanobenzyl, o-chlorobenzyl, 1-chlorophenyl and 1-isopropyl. Among the above, preferred are benzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylisopropyl and 2-phenylisopropyl. In addition, aralkyl groups may be optionally substituted.
Alkyl-as used herein, alkyl-substituted silicon groups are contemplated. The silyl group may be a silyl group having 3 to 20 carbon atoms, preferably a silyl group having 3 to 10 carbon atoms. Examples of the alkyl silicon group include trimethyl silicon group, triethyl silicon group, methyldiethyl silicon group, ethyldimethyl silicon group, tripropyl silicon group, tributyl silicon group, triisopropyl silicon group, methyldiisopropyl silicon group, dimethylisopropyl silicon group, tri-t-butyl silicon group, triisobutyl silicon group, dimethyl-t-butyl silicon group, and methyldi-t-butyl silicon group. In addition, the alkyl silicon group may be optionally substituted.
Arylsilane-as used herein, encompasses at least one aryl-substituted silicon group. The arylsilane group may be an arylsilane group having 6 to 30 carbon atoms, preferably an arylsilane group having 8 to 20 carbon atoms. Examples of arylsilyl groups include triphenylsilyl, phenyldiphenylsilyl, diphenylbiphenyl silyl, phenyldiethylsilyl, diphenylethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, phenyldiisopropylsilyl, diphenylisopropylsilyl, diphenylbutylsilyl, diphenylisobutylsilyl, diphenyltert-butylsilyl. In addition, arylsilane groups may be optionally substituted.
Alkyl germanium group-as used herein, alkyl substituted germanium groups are contemplated. The alkylgermanium group may be an alkylgermanium group having 3 to 20 carbon atoms, preferably an alkylgermanium group having 3 to 10 carbon atoms. Examples of alkyl germanium groups include trimethyl germanium group, triethyl germanium group, methyl diethyl germanium group, ethyl dimethyl germanium group, tripropyl germanium group, tributyl germanium group, triisopropyl germanium group, methyl diisopropyl germanium group, dimethyl isopropyl germanium group, tri-t-butyl germanium group, triisobutyl germanium group, dimethyl-t-butyl germanium group, methyl-di-t-butyl germanium group. In addition, alkyl germanium groups may be optionally substituted.
Arylgermanium group-as used herein, encompasses at least one aryl or heteroaryl substituted germanium group. The arylgermanium group may be an arylgermanium group having 6-30 carbon atoms, preferably an arylgermanium group having 8 to 20 carbon atoms. Examples of aryl germanium groups include triphenylgermanium group, phenylbiphenyl germanium group, diphenylbiphenyl germanium group, phenyldiethyl germanium group, diphenylethyl germanium group, phenyldimethyl germanium group, diphenylmethyl germanium group, phenyldiisopropylgermanium group, diphenylisopropylgermanium group, diphenylbutylgermanium group, diphenylisobutylglycol group, and diphenyltert-butylgermanium group. In addition, the arylgermanium group may be optionally substituted.
The term "aza" in azadibenzofurans, azadibenzothiophenes and the like means that one or at least two C-H groups in the corresponding aromatic fragment are replaced by nitrogen atoms. For example, azatriphenylenes include dibenzo [ f, h ] quinoxalines, dibenzo [ f, h ] quinolines, and other analogs having two or more nitrogens in the ring system. Other nitrogen analogs of the above-described aza derivatives will be readily apparent to those of ordinary skill in the art, and all such analogs are intended to be included in the terms described herein.
In the present disclosure, when any one of the terms from the group consisting of: substituted alkyl, substituted cycloalkyl, substituted heteroalkyl, substituted heterocyclyl, substituted aralkyl, substituted alkoxy, substituted aryloxy, substituted alkenyl, substituted alkynyl, substituted aryl, substituted heteroaryl, substituted alkylsilyl, substituted arylsilyl, substituted alkylgermanium, substituted arylgermanium, substituted amino, substituted acyl, substituted carbonyl, substituted carboxylic acid, substituted ester, substituted sulfinyl, alkyl, cycloalkyl, heteroalkyl, heterocyclyl, aralkyl, alkoxy, aryloxy, alkenyl, alkynyl, aryl, heteroaryl, alkylsilyl, arylsilyl, alkylgermanium, arylgermanium, amino, acyl, carbonyl, carboxylic acid, ester, sulfinyl, sulfonyl and phosphino groups, any one or more of which may be substituted with one or at least two groups selected from deuterium, halogen, unsubstituted alkyl having 1 to 20 carbon atoms, unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, unsubstituted cycloalkyl having 1 to 20 carbon atoms, unsubstituted heteroaryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkoxy having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkenyl having 3 to 30 carbon atoms, aryl having 3 to 20 carbon atoms, unsubstituted aryl having 3 to 30 carbon atoms, unsubstituted aryl having 3 to 20 carbon atoms, unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, unsubstituted arylgermanium groups having 6 to 20 carbon atoms, unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphine groups, and combinations thereof.
It will be appreciated that when a fragment of a molecule is described as a substituent or otherwise attached to another moiety, its name may be written according to whether it is a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or according to whether it is an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of specifying substituents or linking fragments are considered equivalent.
In the compounds mentioned in this disclosure, the hydrogen atoms may be partially or completely replaced by deuterium. Other atoms such as carbon and nitrogen may also be replaced by their other stable isotopes. Substitution of other stable isotopes in the compounds may be preferred because of their enhanced efficiency and stability of the device.
In the compounds mentioned in this disclosure, multiple substitution is meant to encompass double substitution up to the maximum available substitution range. When a substituent in a compound mentioned in this disclosure means multiple substitution (including di-substitution, tri-substitution, tetra-substitution, etc.), it means that the substituent may be present at a plurality of available substitution positions on its linking structure, and the substituent present at each of the plurality of available substitution positions may be of the same structure or of different structures.
In the compounds mentioned in this disclosure, adjacent substituents in the compounds cannot be linked to form a ring unless explicitly defined, for example, adjacent substituents can optionally be linked to form a ring. In the compounds mentioned in this disclosure, adjacent substituents can optionally be linked to form a ring, both in the case where adjacent substituents can be linked to form a ring and in the case where adjacent substituents are not linked to form a ring. Where adjacent substituents can optionally be joined to form a ring, the ring formed can be monocyclic or polycyclic (including spiro, bridged, fused, etc.), as well as alicyclic, heteroalicyclic, aromatic or heteroaromatic. In this expression, adjacent substituents may refer to substituents bonded to the same atom, substituents bonded to carbon atoms directly bonded to each other, or substituents bonded to further distant carbon atoms. Preferably, adjacent substituents refer to substituents bonded to the same carbon atom and substituents bonded to carbon atoms directly bonded to each other.
The expression that adjacent substituents can optionally be linked to form a ring is also intended to mean that two substituents bonded to the same carbon atom are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
The expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that two substituents bonded to carbon atoms directly bonded to each other are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that the two substituents bound to further distant carbon atoms are linked to each other by a chemical bond to form a ring, which can be exemplified by the following formula:
furthermore, the expression that adjacent substituents can optionally be linked to form a ring is also intended to be taken to mean that, in the case where one of the adjacent two substituents represents hydrogen, the second substituent is bonded at the position to which the hydrogen atom is bonded, thereby forming a ring. This is exemplified by the following formula:
according to one embodiment of the present invention, a metal complex is disclosed comprising a metal M, and a ligand L coordinated to the metal M a ，L a Has a structure represented by formula 1:
wherein,,
the metal M is selected from metals with relative atomic mass of more than 40;
z is selected from the group consisting of O, S, se, NR ', CR ' R ' and SiR ' R '; when two R's are present at the same time, the two R's are the same or different;
substituent R y Represents monosubstituted, polysubstituted or unsubstituted;
X 1 -X 8 Each time it occurs, the sameOr is variously selected from C, CR x Or N; and X is 1 -X 4 Wherein two of the two are selected from C, wherein one C is connected with pyridine in formula 1, and the other C is coordinated with metal to form a metal-carbon bond;
substituent R n Has a structure represented by formula 2:
wherein, in the formula 2,
substituent R A And R is B Each occurrence, identically or differently, represents mono-, poly-or unsubstituted;
ring a and ring B are identically or differently selected from carbocycles having 3 to 30 ring atoms, or heterocycles having 3 to 30 ring atoms;
A 1 ，A 2 ，B 1 ，B 2 e is selected identically or differently on each occurrence from C, N, B, P, CR ' ", siR '" or GeR ' ";
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR ", P (O) R", R "c=cr", a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclylene group having 3 to 20 ring atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
substituents R ', R ", R'", R x ，R y ，R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, takenSubstituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"onium" represents the attachment position of formula 2;
adjacent substituents R', R x ，R”，R”’，R A ，R B ，R y Can optionally be linked to form a ring.
Herein, "L is selected from a single bond" is intended to mean that expression 2 has the following structure:wherein A is 1 ，A 2 ，B 1 ，B 2 E, ring A, ring B, R A And R is B Is as defined herein.
Herein, "adjacent substituents R', R x ，R”，R”’，R A ，R B ，R y Can optionally be linked to form a ring ", is intended to mean groups of substituents adjacent thereto, for example, between two substituents R', two substituents R x Between two substituents R A Between two substituents R B Between two substituents R y Between, substituents R' and R x Between, substituents R' and R y Between, substituent R A And R is B Between, substituent R A And R 'between, substituents R' and R B Between, substituent R A And R is y Between, substituent R y And R is B In between, any one or more of these substituent groups may be linked to form a ring. Obviously, these substituents may not all be linked to form a ring.
According to one embodiment of the invention, wherein the ligand L a Any one of the structures selected identically or differently on each occurrence from the group consisting of:
z is selected from the group consisting of O, S, se, NR ', CR ' R ' and SiR ' R '; when two R's are present at the same time, the two R's are the same or different;
Substituent R y Represents monosubstituted, polysubstituted or unsubstituted;
in formula 1a and formula 1c, X 3 -X 8 Is selected from CR, identically or differently at each occurrence x Or N;
in formula 1b, X 1 And X 4 -X 8 Is selected from CR, identically or differently at each occurrence x Or N;
in formula 1d and formula 1e, X 1 -X 2 And X 5 -X 8 Is selected from CR, identically or differently at each occurrence x Or N;
substituent R n Has a structure represented by formula 2:
wherein, in the formula 2,
substituent R A And R is B Each occurrence, identically or differently, represents mono-, poly-or unsubstituted;
ring a and ring B are identically or differently selected from carbocycles having 3 to 30 ring atoms, or heterocycles having 3 to 30 ring atoms;
A 1 ，A 2 ，B 1 ，B 2 e is the same for each occurrenceOr are selected differently from C, N, B, P, CR ' ", siR '" or GeR ' ";
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR ", P (O) R", R "c=cr", a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclylene group having 3 to 20 ring atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Substituents R ', R ", R'", R x ，R y ，R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;
"onium" represents the attachment position of formula 2;
adjacent substituents R', R x ，R”，R”’，R A ，R B ，R y Can optionally be linked to form a ring.
According to one embodiment of the invention, wherein the metal complex has M (L a ) m (L b ) n (L c ) q Is of the general formula (I);
wherein,,
the metal M is selected from metals with relative atomic mass of more than 40; preferably, M is selected identically or differently on each occurrence from the group consisting of Cu, ag, au, ru, rh, pd, os, ir and Pt; more preferably, M is selected, identically or differently, for each occurrence, from Pt or Ir;
L a 、L b and L c A first ligand, a second ligand and a third ligand, respectively, which are coordinated to the metal M, and L c And said L a Or L b Is the same or different; wherein L is a 、L b And L c Can optionally be linked to form a multidentate ligand; for example ligand L a 、L b And L c Any two of which are linked to form a tetradentate ligand, or ligand L a 、L b And L c Ligating to form a hexadentate ligand, or ligand L a 、L b And L c Or may not be linked to form a multidentate ligand;
m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, m+n+q is equal to the oxidation state of the metal M; when m is greater than or equal to 2, a plurality of L a The same or different; when n is equal to 2, two L b The same or different; when q is equal to 2, two L c The same or different;
L b and L c A structure shown at each occurrence as being the same or different selected from any one of the group consisting of:
Wherein,,
substituent R a And R is b Each occurrence, identically or differently, represents mono-substituted, poly-substituted, or unsubstituted;
X b and is selected identically or differently on each occurrence from the group consisting of: o, S, se, NR N1 ，CR C1 R C2 ；
Substituent R a ，R b ，R c ，R N1 ，R C1 And R is C2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkyl germanium having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, carbonyl having 0 to 20 carbon atoms, cyano, sulfonyl, cyano, carbonyl, cyano, sulfonyl, cyano, or the like;
Adjacent substituents R a ，R b ，R c ，R N1 ，R C1 And R is C2 Can optionally be linked to form a ring.
Herein, "adjacent substituent R a ，R b ，R c ，R N1 ，R C1 And R is C2 Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent theretoFor example, two substituents R a Between two substituents R b Between, substituent R a And R is b Between, substituent R a And R is c Between, substituent R b And R is c Between, substituent R a And R is N1 Between, substituent R b And R is N1 Between, substituent R a And R is C1 Between, substituent R a And R is C2 Between, substituent R b And R is C1 Between, substituent R b And R is C2 Between, and R C1 And R is C2 In between, any one or more of these substituent groups may be linked to form a ring. Obviously, these substituents may not all be linked to form a ring.
According to one embodiment of the invention, the metal complex has Ir (L a ) m( L b ) 3-m And is represented by formula 3:
wherein,,
m is selected from 1,2 or 3; when m is selected from 1, two L b The same or different; when m is selected from 2 or 3, a plurality of L a The same or different;
z is selected from the group consisting of O, S, se, NR ', CR ' R ' and SiR ' R '; when two R's are present at the same time, the two R's are the same or different;
substituent R y Represents monosubstituted, polysubstituted or unsubstituted;
X 3 -X 8 Is selected from CR, identically or differently at each occurrence x Or N;
substituent R n Has a structure represented by formula 2:
wherein, in the formula 2,
substituent R A And R is B Each occurrence, identically or differently, represents mono-, poly-or unsubstituted;
ring a and ring B are identically or differently selected from carbocycles having 3 to 30 ring atoms, or heterocycles having 3 to 30 ring atoms;
A 1 ，A 2 ，B 1 ，B 2 e is selected identically or differently on each occurrence from C, N, B, P, CR ' ", siR '" or GeR ' ";
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR ", P (O) R", R "c=cr", a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclylene group having 3 to 20 ring atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
substituents R ', R ", R'", R x ，R y ，R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted alkylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium having 3 to 20 carbon atoms Aryl germanium groups having 6-20 carbon atoms, substituted or unsubstituted amino groups having 0-20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"onium" represents the attachment position of formula 2;
adjacent substituents R', R x ，R”，R”’，R A ，R B ，R y Can optionally be linked to form a ring;
adjacent substituents R 1 -R 8 Can optionally be linked to form a ring.
In this embodiment, "adjacent substituent R 1 -R 8 Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent thereto, e.g., R 1 -R 8 Any one or more of which may be linked to form a ring. Obviously, these substituents may not all be linked to form a ring.
According to one embodiment of the invention, wherein Z is selected from O or S.
According to one embodiment of the invention, wherein Z is selected from O.
According to one embodiment of the invention, wherein X 1 -X 8 Is selected from CR, identically or differently at each occurrence x 。
According to one embodiment of the invention, wherein X 3 -X 8 Is selected from CR, identically or differently at each occurrence x 。
According to one embodiment of the invention, wherein X 1 -X 8 At least one of which is selected from N. For example X 1 -X 8 One of which is selected from N or two of which are selected from N.
According to one embodiment of the invention, wherein X 3 -X 8 At least one of which is selected from N. For example X 3 -X 8 One of which is selected from N or two of which are selected from N.
According to one embodiment of the invention, wherein the substituents R x Is selected identically or differently on each occurrence from the group consisting ofThe group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 6 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, biphenyl, pyridinyl, trimethylsilyl, trimethylgermanium, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully deuterated.
According to one embodiment of the invention, wherein the substituents R n Has a structure represented by formula 4:
A 3 -A 6 is selected from CR, identically or differently at each occurrence A Or N;
B 3 -B 6 is selected from CR, identically or differently at each occurrence B Or N;
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR, P (O) R ", R" c=cr ", alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclylene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms, heteroarylene having 3 to 30 carbon atoms, or a combination thereof;
Substituent R A 、R B And R "is, identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
Adjacent substituents R ", R A ，R B Can optionally be linked to form a ring;
"onium" means the position of the linkage of formula 4.
Herein, "adjacent substituents R", R A ，R B Can optionally be linked to form a ring ", intended to mean groups of substituents adjacent thereto, e.gBetween the two substituents R ', the two substituents R' A Between two substituents R B Between, substituents R' and R A Between, substituents R' and R B In between, any one or more of these substituent groups may be linked to form a ring. Obviously, these substituents may not all be linked to form a ring.
According to one embodiment of the invention, wherein ring a and ring B are identically or differently selected from carbocycles having 6 ring atoms, or heterocycles having 5-6 ring atoms.
According to one embodiment of the invention, wherein ring a and ring B are identically or differently selected from benzene rings, or heteroaromatic rings having 5 to 6 ring atoms.
According to one embodiment of the invention, wherein A 3 -A 6 Is selected from CR, identically or differently at each occurrence A Substituent R A And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein B 3 -B 6 Is selected from CR, identically or differently at each occurrence B The method comprises the steps of carrying out a first treatment on the surface of the Substituent R B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 6 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 6 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, neopentyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridyl, trimethylsilyl, trimethylgermanium, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully deuterated.
According to one embodiment of the present invention, wherein L is selected from a single bond, O, S, se, NR, siR "R", geR "R", BR ", PR", P (O) R ", R" c=cr ", a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, a substituted or unsubstituted heterocyclylene group having 3 to 10 ring atoms, a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 10 carbon atoms, or a combination thereof.
According to one embodiment of the invention, wherein L is selected from a single bond, O, S, se, NR ", siR" R ", geR" R ", BR", PR ", P (O) R", a substituted or unsubstituted alkylene group having 1-10 carbon atoms, a substituted or unsubstituted arylene group having 6-10 carbon atoms, a substituted or unsubstituted heteroarylene group having 3-10 carbon atoms, or a combination thereof;
according to one embodiment of the invention, wherein L is selected from a single bond, O, S, NR', a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted phenylene group.
According to one embodiment of the invention, wherein L is selected from a single bond, O, S, NR', or phenylene.
According to one embodiment of the invention, wherein the substituents R ', R "and R'" are, for each occurrence, identical or different, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 6 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R ', R "and R'" are, for each occurrence, identical or different, selected from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 6 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R ', R "and R'" are, for each occurrence, identical or different, selected from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridinyl, trimethylsilyl, trimethylgermanium, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully deuterated.
According to one embodiment of the invention, wherein X 3 -X 8 At least one of them is CR x The substituent R x Selected from cyano or fluoro.
According to one embodiment of the invention, wherein X 5 -X 8 At least one of them is CR x The substituent R x Selected from cyano or fluoro.
According to one embodiment of the invention, wherein X 7 Or X 8 Is CR (CR) x The R is x Selected from cyano groups.
According to one embodiment of the invention, wherein X 7 Is CR (CR) x The R is x Selected from fluorine.
According to one embodiment of the invention, wherein X 3 -X 8 At least two of them are selected from CR x And one of the substituents R x Selected from cyano or fluoro, another of said substituents R x Selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted Or an unsubstituted aryl silyl group having 6 to 20 carbon atoms, a substituted or unsubstituted alkyl germanium group having 3 to 20 carbon atoms, a substituted or unsubstituted aryl germanium group having 6 to 20 carbon atoms, a cyano group, an isocyano group, and combinations thereof.
According to one embodiment of the invention, wherein X 5 -X 8 At least two of them are selected from CR x And one of the substituents R x Selected from cyano or fluoro, another of said substituents R x Selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having 6 to 20 carbon atoms, cyano groups, isocyano groups, and combinations thereof.
According to one embodiment of the invention, wherein X 7 And X 8 Selected from CR x And one of the substituents R x Is cyano or fluoro, the other of said substituents R x Selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having from 3 to 20 carbon atoms, cyano groups, isocyano groups, and combinations thereof.
According to one embodiment of the invention, wherein X 7 And X 8 Selected from CR x And one of the substituents R x Is cyano or fluoro, the other of said substituents R x Selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, cyano, isocyano, and combinations thereof.
According to one embodiment of the invention, wherein R n Is selected identically or differently on each occurrence from the group consisting of An 1 To An 96 A group consisting of An 1 To An 96 Is specified in claim 11.
According to one embodiment of the present invention, wherein An 1 To An 52 、An 54 To An 58 And An 61 To An 96 The hydrogen in (a) can be partially or completely replaced by deuterium.
According to one embodiment of the invention, wherein the substituents R y And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aralkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups having 6 to 20 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R y And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted silyl groups having 3 to 12 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R y At least one selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R y At least one selected from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated t-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, pyridinyl, trimethylsilyl, trimethylgermanium, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully deuterated.
According to one embodiment of the invention, wherein the substituents R 1 -R 8 At least one or at least two selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, or combinations thereof, and all of said R groups 1 -R 4 And/or R 5 -R 8 The sum of the number of carbon atoms of (2) is at least 4.
According to one embodiment of the invention, wherein the substituents R 1 -R 4 At least one or at least two selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, or combinations thereof, and all of said substituents R 1 -R 4 The sum of the number of carbon atoms of (2) is at least 4.
According to one embodiment of the invention, wherein the substituents R 5 -R 8 At least one or at least two selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, or combinations thereof, and all of said substituents R 5 -R 8 The sum of the number of carbon atoms of (2) is at least 4.
According to one embodiment of the invention, wherein the substituents R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all of which are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstitutedAryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all of which are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, and combinations thereof.
According to one embodiment of the invention, wherein the substituents R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all of which are selected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, neopentyl, t-pentyl, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully deuterated.
According to one embodiment of the invention, wherein the ligand L a Is selected identically or differently on each occurrence from the group consisting of L a1 To L a821 A group consisting of L a1 To L a821 Is specified in claim 15.
According to one embodiment of the invention, wherein the ligand L a1 To L a821 The hydrogen in (a) can be partially or completely replaced by deuterium.
According to one embodiment of the invention, wherein the ligand L b Is selected identically or differently on each occurrence from the group consisting of L b1 To L b334 A group consisting of L b1 To L b334 Is specified in claim 16.
According to one embodiment of the invention, wherein the ligand L b1 To L b334 The hydrogen in (a) can be partially or completely replaced by deuterium.
According to one embodiment of the invention, wherein the ligand L c Is selected identically or differently on each occurrence from the group consisting of L c1 To L c360 A group consisting of L c1 To L c360 Is shown in the right of the specific structureClaim 17.
According to one embodiment of the invention, wherein the metal complex has Ir (L a ) 3 、Ir(L a )(L b ) 2 、Ir(L a ) 2 (L b )、Ir(L a )(L c ) 2 、Ir(L a ) 2 (L c ) Or Ir (L) a )(L b )(L c ) Wherein said L is a The same or different at each occurrence is selected from the group consisting of L a1 To L a821 Group of L b Is selected identically or differently on each occurrence from the group consisting of L b1 To L b334 Group of ligands L c Is selected identically or differently on each occurrence from the group consisting of L c1 To L c360 A group of groups.
According to an embodiment of the invention, wherein the metal complex is selected from the group consisting of metal complex 1 to metal complex 432, wherein the specific structure of metal complex 1 to metal complex 432 is as described in claim 18.
According to one embodiment of the present invention, hydrogen in metal complexes 1 to 432 can be partially or completely replaced with deuterium.
According to an embodiment of the invention, wherein the metal complex is selected from the group consisting of metal complex 1 to metal complex 435, wherein the specific structure of metal complex 1 to metal complex 435 is as described in claim 18.
According to one embodiment of the present invention, wherein the hydrogen in metal complexes 1 to 435 can be partially or completely replaced by deuterium.
According to one embodiment of the present invention, an electroluminescent device is disclosed, comprising: an anode, a cathode, and an organic layer disposed between the anode and the cathode, at least one of the organic layers comprising the metal complex of any of the foregoing embodiments.
According to one embodiment of the invention, wherein the organic layer comprising the metal complex is a light emitting layer.
According to one embodiment of the invention, the organic electroluminescent device emits green light.
According to one embodiment of the invention, the organic electroluminescent device emits yellow light.
According to one embodiment of the present invention, the light-emitting layer further includes a first host compound.
According to one embodiment of the present invention, the light-emitting layer further comprises a second host compound
According to one embodiment of the invention, wherein at least one of the host compounds comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
According to one embodiment of the present invention, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 1% -30% of the total weight of the light emitting layer.
According to one embodiment of the invention, the metal complex is doped in the first host compound and the second host compound, and the weight of the metal complex accounts for 3% -13% of the total weight of the light-emitting layer.
According to one embodiment of the present invention, a compound composition is disclosed comprising the metal complex of any of the previous embodiments.
Combined with other materials
The materials described herein for specific layers in an organic light emitting device may be used in combination with various other materials present in the device. Combinations of these materials are described in detail in U.S. patent application 2016/0359122A1, paragraphs 0132-0161, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
Materials described herein as useful for specific layers in an organic light emitting device may be used in combination with a variety of other materials present in the device. For example, the metal complexes disclosed herein can be used in combination with a variety of hosts, transport layers, barrier layers, injection layers, electrodes, and other layers that may be present. Combinations of these materials are described in detail in U.S. patent application Ser. No. 2015/0349273A1, paragraphs 0080-0101, the entire contents of which are incorporated herein by reference. The materials described or mentioned therein are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one skilled in the art can readily review the literature to identify other materials that may be used in combination.
In the examples of material synthesis, all reactions were carried out under nitrogen protection, unless otherwise indicated. All reaction solvents were anhydrous and used as received from commercial sources. The synthetic products were subjected to structural confirmation and characterization testing using one or more equipment conventional in the art (including, but not limited to, bruker's nuclear magnetic resonance apparatus, shimadzu's liquid chromatograph, liquid chromatograph-mass spectrometer, gas chromatograph-mass spectrometer, differential scanning calorimeter, shanghai's optical technique fluorescence spectrophotometer, wuhan Koste's electrochemical workstation, anhui Bei Yi g sublimator, etc.), in a manner well known to those skilled in the art. In an embodiment of the device, the device characteristics are also tested using equipment conventional in the art (including, but not limited to, a vapor deposition machine manufactured by Angstrom Engineering, an optical test system manufactured by Frieda, st. John's, an ellipsometer manufactured by Beijing, etc.), in a manner well known to those skilled in the art. Since those skilled in the art are aware of the relevant contents of the device usage and the testing method, and can obtain the intrinsic data of the sample certainly and uninfluenced, the relevant contents are not further described in this patent.
Material synthesis examples:
the preparation method of the compound of the present invention is not limited, and is typically, but not limited to, exemplified by the following compounds, the synthetic routes and preparation methods thereof are as follows:
synthesis example 1: synthesis of metal complex 159
Step 1:
6-chloro-dibenzofuran-3-carbonitrile (3.4 g,13.9 mmol), B, was added sequentially to a dry 250mL round bottom flask 2 pin 2 (4.1g，16.0mmol)，Pd(OAc) 2 (0.09 g,0.4 mmol), xphos (0.4 g,0.8 mmol), KOAc (2.0 g,21.0 mmol), dioxane (90 mL), N 2 Under protection, heating to reflux reaction for 12h.
The reaction solution obtained above was cooled, and 2-bromo-4-fluoro-pyridine (2.9 g,16.7 mmol), pd (dppf) Cl was added 2 (0.5g,0.7mmol),K 2 CO 3 (2.9 g,16.7 mmol) and water (30 mL). N (N) 2 Under protection, heating to reflux reaction for 12h. After cooling, DCM was extracted and column chromatographed to give intermediate 1 (3.3 g, 82.5%).
Step 2:
a dry 250mL round bottom flask was charged with intermediate 1 (2.0 g,6.9 mmol), carbazole (1.7 g,10.4 mmol), potassium tert-butoxide (1.4 g,12.6 mmol) and DMF (50 mL), N 2 Under the protection, the reaction is heated at 100 ℃ for 12 hours. After the reaction was cooled, water was added, extraction was performed with methylene chloride, the organic layer was washed twice with saturated sodium chloride, the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography to give intermediate 2 (2.3 g,76.6% yield) as a white solid.
Step 3:
a dry 250mL round bottom flask was charged with intermediate 2 (1.6 g,3.6 mmol) and intermediate 3 (2.0 g,2.4 mm)ol), 2-ethoxyethanol (30 mL) and DMF (30 mL), N 2 Under the protection, the reaction is heated at 95 ℃ for 144h. After the reaction cooled, the celite was filtered. Methanol, n-hexane were washed 2 times respectively, and the yellow solid above celite was dissolved with methylene chloride, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 159 (0.84 g,33.5% yield) as a yellow solid. The product structure was determined to be the target product and the molecular weight was 1047.3.
Synthesis example 2: synthesis of Metal Complex 169
Step 1:
a dry 250mL round bottom flask was charged with intermediate 4 (1.0 g,3.3 mmol), 3, 6-di-tert-butylcarbazole (1.1 g,3.9 mmol), potassium tert-butoxide (0.5 g,4.9 mmol) and DMF (50 mL), N 2 Under the protection, the reaction is heated at 100 ℃ for 12 hours. After the reaction was cooled, water was added, extraction was performed with methylene chloride, the organic layer was washed twice with saturated sodium chloride, and the organic phase was collected, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by column chromatography to give intermediate 5 (1.1 g,61.1% yield) as a white solid.
Step 2:
a250 mL round bottom flask was dried and intermediate 5 (1.1 g,1.9 mmol), intermediate 3 (1.3 g,1.6 mmol), 2-ethoxyethanol (30 mL) and DMF (30 mL), N were added sequentially 2 Under the protection, the reaction is heated at 95 ℃ for 144h. After the reaction cooled, the celite was filtered. Methanol, n-hexane were washed 2 times respectively, and the yellow solid above celite was dissolved with dichloromethane, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give yellow metal complex 169 (0.45 g,23.9% yield). The product structure was determined to be the target product and the molecular weight was 1176.5.
Synthesis example 3: synthesis of Metal Complex 411
Step 1:
a250 mL round bottom flask was dried and charged with intermediate 2 (2.7 g,6.2 mmol), intermediate 6 (5.3 g,5.7 mmol), 2-ethoxyethanol (50 mL) and DMF (50 mL), N 2 Under the protection, the reaction is heated at 100 ℃ for 144h. After the reaction cooled, the celite was filtered. Methanol, n-hexane were washed 2 times respectively, and the yellow solid above celite was dissolved with methylene chloride, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give yellow solid metal complex 411 (2.4 g,36.4% yield). The product structure was determined to be the target product and the molecular weight was 1159.5.
Synthesis example 4: synthesis of Metal Complex 427
Step 1:
a dry 250mL round bottom flask was charged with intermediate 7 (2.1 g,4.9 mmol), intermediate 6 (3.8 g,4.1 mmol), 2-ethoxyethanol (50 mL) and DMF (50 mL), N 2 Under the protection, the reaction is heated at 100 ℃ for 144h. After the reaction cooled, the celite was filtered. Methanol, n-hexane were washed 2 times respectively, and the yellow solid above celite was dissolved with methylene chloride, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 427 as a yellow solid (2.8 g,59.0% yield). The product structure was determined to be the target product and the molecular weight was 1152.5.
Synthesis example 5: synthesis of Metal Complex 433
Step 1:
a dry 250mL round bottom flask was charged with intermediate 8 (1.6 g,3.6 mmol), intermediate 3 (2.0 g,2.4 mmol), and 2-ethoxyethylAlcohol (30 mL) and DMF (30 mL), N 2 Under the protection, the reaction is heated at 95 ℃ for 144h. After the reaction cooled, the celite was filtered. Methanol, n-hexane were washed 2 times respectively, and the yellow solid above celite was dissolved with methylene chloride, and the organic phase was collected, concentrated under reduced pressure, and purified by column chromatography to give metal complex 433 (0.84 g,33.5% yield) as a yellow solid. The product structure was determined to be the target product and the molecular weight was 1048.3.
Those skilled in the art will recognize that the above preparation method is only an illustrative example, and that those skilled in the art can modify it to obtain other compound structures of the present invention.
Device example 1
First, a glass substrate having an 80nm thick Indium Tin Oxide (ITO) anode was cleaned, and then treated with oxygen plasma and UV ozone. After the treatment, the substrate was baked in a glove box to remove moisture. The substrate is then mounted on a substrate support and loaded into a vacuum chamber. The organic layer specified below was at a vacuum level of about 10 -8 In the case of the support, vapor deposition was sequentially performed on the ITO anode by thermal vacuum vapor deposition at a rate of 0.2 to 2 Angstrom/sec. The compound HI is used as a Hole Injection Layer (HIL). The compound HT serves as a Hole Transport Layer (HTL). Compound H1 acts as an Electron Blocking Layer (EBL). The metal complex 159 of the present invention is then used as a dopant, and is co-deposited with the compound H1 and the compound H2 to serve as an emission layer (EML). On the EML, compound H3 acts as a Hole Blocking Layer (HBL). The compound ET and 8-hydroxyquinoline-lithium (Liq) were co-deposited as an Electron Transport Layer (ETL). Finally, 8-hydroxyquinoline-lithium (Liq) with a thickness of 1nm was evaporated as an electron injection layer, and 120nm of aluminum was evaporated as a cathode. The device was then transferred back to the glove box and packaged with a glass lid to complete the device.
Device example 2
The embodiment of device example 2 is the same as device example 1 except that the metal complex 159 of the present invention is replaced with the metal complex 411 in the light emitting layer (EML), and the weight ratio of the compound H1, the compound H2, and the metal complex 159 is 56:38:6.
Device comparative example 1
The embodiment of device comparative example 1 is the same as device example 1 except that the metal complex 159 of the present invention is replaced with the compound GD1 in the light-emitting layer (EML).
Device comparative example 2
The embodiment of device comparative example 2 is the same as device example 1 except that the metal complex 159 of the present invention is replaced with the compound GD2 in the light-emitting layer (EML).
Device comparative example 3
The embodiment of device comparative example 3 is the same as device example 1 except that the metal complex 159 of the present invention is replaced with a compound GD3 in the light-emitting layer (EML).
The detailed device layer structure and thickness are shown in the following table. Wherein more than one layer of the material used is doped with different compounds in the weight proportions described.
TABLE 1 partial device structures for device examples 1-2 and comparative examples 1-3
The material structure used in the device is as follows:
the IVL characteristics of the device were measured. At 1000cd/m 2 The CIE data of the device, the maximum emission wavelength lambda, are measured max Full width at half maximum (FWHM), driving voltage (V), current Efficiency (CE), and External Quantum Efficiency (EQE). Lifetime (LT 97) data was at 80mA/cm 2 The test was performed at constant current. These data are recorded and shown in table 2.
TABLE 2 device data for device examples 1-2 and comparative examples 1-3
Discussion:
table 2 shows the device properties of the inventive metal complexes and the comparative compounds. Example 1 compared with comparative example 1, the metal complex 159 of the present invention differs from comparative compound GD1 only in L a The carbazole substituent groups in the ligand are at different substitution positions of pyridine, the driving voltage is equivalent, the CE is improved by 14.4%, the EQE is improved by 11.4%, and the service life is improved by 5.9%. Indicating that the present application includes a specific bit R n Ligand L of substituent a The metal complex of the (E) can improve the efficiency (CE and EQE) and the service life of the device, and the comprehensive performance of the device is obviously improved.
In comparison with example 1 and comparative example 2, the metal complex 159 of the present invention differs from the comparative compound GD2 only in L a If carbazole is substituted at 4-position of pyridine in the ligand, driving voltage is slightly reduced, CE is increased by 8.4%, EQE is increased by 11.7%, and service life is prolonged by 19.5%. Indicating that the present application includes a specific bit R n Ligand L of substituent a The metal complex of the (E) can improve the efficiency (CE and EQE) and the service life of the device, and the comprehensive performance of the device is obviously improved.
Compared with comparative example 3, the difference between the metal complex 159 of the present invention and the comparative compound GD3 is that the 4-carbazole substituent of pyridine is replaced by phenyl in La ligand, the driving voltage is equivalent, CE is improved by 17.0%, EQE is improved by 8.3%, and the lifetime is improved by 21.8%. Indicating that the present application includes a specific bit R n Substituent L a The metal complex of the ligand can improve the efficiency (CE and EQE) and the service life of the device, and the comprehensive performance of the device is obviously improved.
In addition, the device of example 1 has a maximum emission wavelength in the region near yellow light, and achieves long lifetime and high efficiency device performance, which has a great application prospect in white light and low blue light sources.
Example 2 using the metal complex 411 of the present invention as a light emitting material in a light emitting layer, the voltage, CE, and EQE of example 2 all maintained excellent levels comparable to those of example 1, while the lifetime of example 2 was further improved. Meanwhile, the EQE and life of example 2 are greatly improved over those of comparative examples 1 to 3. Therefore, example 2 has excellent light emitting performance and device lifetime.
The above results all show that the invention provides a light-emitting diode comprising a light-emitting diode with a specific bit R n L of substituents a The metal complex of the ligand can be applied to the organic electroluminescent device to improve the device efficiency (CE and EQE) and prolong the service life, thereby achieving the beneficial effect of obviously improving the comprehensive performance of the device.
Device example 3
The embodiment of device example 3 is the same as device example 2 except that the metal complex 159 of the present invention is replaced with a metal complex 427 in the light emitting layer (EML).
Device example 4
The embodiment of device example 4 is the same as device example 2 except that the metal complex 159 of the present invention is replaced with a metal complex 433 in the light emitting layer (EML).
The detailed device layer structure and thickness are shown in table 3 below. Wherein more than one layer of the material used is doped with different compounds in the weight proportions described.
Table 3 device example 3 and example 4 device structures
The structure of the materials newly used in the device is as follows:
the IVL characteristics of the device were measured. At 1000cd/m 2 The CIE data of the device, the maximum emission wavelength lambda, are measured max Full width at half maximum (FWHM), driving voltage (V), current Efficiency (CE), and External Quantum Efficiency (EQE). These data are recorded and shown in table 4.
Table 4 device data for device example 3 and example 4
Discussion:
table 4 further shows the device properties of the metal complexes of the invention. Example 3 and example 4 use of the invention in the light-emitting layer respectively comprises having a specific bit R n L of substituents a The voltage, CE and EQE of the ligand metal complex 427 and metal complex 433 as light emitting materials were all kept comparable to those of example 1 in examples 3 and 4. Meanwhile, the EQEs of both example 3 and example 4 are greatly improved over those of comparative examples 1 to 3.
The results show that the invention provides a composition comprising R having specific bits different from each other n L of substituents a Ligands and different L b The metal complex of the ligand can be applied to the organic electroluminescent device to improve the device efficiency (CE and EQE) and/or the service life, thereby achieving the beneficial effect of obviously improving the comprehensive performance of the device.
It should be understood that the various embodiments described herein are by way of example only and are not intended to limit the scope of the invention. Thus, as will be apparent to those skilled in the art, the claimed invention may include variations of the specific and preferred embodiments described herein. Many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. It is to be understood that the various theories as to why the present invention works are not intended to be limiting.
Claims (23)
1. A metal complex comprising a metal M, and a ligand L coordinated to the metal M a ，L a Has a structure represented by formula 1:
wherein,,
the metal M is selected from metals with relative atomic mass of more than 40;
z is selected from the group consisting of O, S, se, NR ', CR ' R ' and SiR ' R '; when two R's are present at the same time, the two R's are the same or different;
substituent R y Represents monosubstituted, polysubstituted or unsubstituted;
X 1 -X 8 is selected identically or differently on each occurrence from C, CR x Or N; and X is 1 -X 4 One of which is selected from C and is linked to pyridine of formula 1;
substituent R n Has a structure represented by formula 2:
wherein, in the formula 2,
substituent R A And R is B Each occurrence, identically or differently, represents mono-, poly-or unsubstituted;
ring a and ring B are identically or differently selected from carbocycles having 3 to 30 ring atoms, or heterocycles having 3 to 30 ring atoms;
A 1 ，A 2 ，B 1 ，B 2 e is selected identically or differently on each occurrence from C, N, B, P, CR ' ", siR '" or GeR ' ";
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR ", P (O) R", R "c=cr", a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclylene group having 3 to 20 ring atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
substituents R ', R ", R'", R x ，R y ，R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstitutedSubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, substituted or unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"onium" represents the attachment position of formula 2;
adjacent substituents R', R x ，R”，R”’，R A ，R B ，R y Can optionally be linked to form a ring.
2. The metal complex as claimed in claim 1, wherein the metal complex has M (L a ) m (L b ) n (L c ) q Is of the general formula (I);
wherein,,
the metal M is selected from metals with relative atomic mass of more than 40; preferably, M is selected identically or differently on each occurrence from the group consisting of Cu, ag, au, ru, rh, pd, os, ir and Pt; more preferably, M is selected, identically or differently, for each occurrence, from Pt or Ir;
L a 、L b and L c A first ligand, a second ligand and a third ligand, respectively, which are coordinated to the metal M, and L c And said L a Or L b Is the same or different; wherein L is a 、L b And L c Can optionally be linked to form a multidentate ligand;
m is selected from 1, 2 or 3, n is selected from 0, 1 or 2, q is selected from 0, 1 or 2, m+n+q is equal to the oxidation state of the metal M; when m is greater than or equal to 2, a plurality of L a The same or different; when n is equal to 2, two L b The same or different; when q is equal to 2, two L c The same or different;
L b and L c A structure shown at each occurrence as being the same or different selected from any one of the group consisting of:
wherein,,
substituent R a And R is b Each occurrence, identically or differently, represents mono-substituted, poly-substituted, or unsubstituted;
X b And is selected identically or differently on each occurrence from the group consisting of: o, S, se, NR N1 ，CR C1 R C2 ；
Substituent R a ，R b ，R c ，R N1 ，R C1 And R is C2 And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atomsA group, a substituted or unsubstituted arylsilane group having 6 to 20 carbon atoms, a substituted or unsubstituted alkylgermanium group having 3 to 20 carbon atoms, a substituted or unsubstituted arylgermanium group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group having 0 to 20 carbon atoms, an acyl group, a carbonyl group, a carboxylic acid group, an ester group, a cyano group, an isocyano group, a hydroxyl group, a mercapto group, a sulfinyl group, a sulfonyl group, a phosphino group, and combinations thereof;
Adjacent substituents R a ，R b ，R c ，R N1 ，R C1 And R is C2 Can optionally be linked to form a ring.
3. The metal complex according to claim 1 or 2, wherein the metal complex has Ir (L a ) m( L b ) 3-m And is represented by formula 3:
wherein,,
m is selected from 1,2 or 3; when m is selected from 1, two L b The same or different; when m is selected from 2 or 3, a plurality of L a The same or different;
z is selected from the group consisting of O, S, se, NR ', CR ' R ' and SiR ' R '; when two R's are present at the same time, the two R's are the same or different;
substituent R y Represents monosubstituted, polysubstituted or unsubstituted;
X 3 -X 8 is selected from CR, identically or differently at each occurrence x Or N;
substituent R n Has a structure represented by formula 2:
wherein, in the formula 2,
substituent R A And R is B Each time it occurs, the sameOr differently represents mono-, poly-or unsubstituted;
ring a and ring B are identically or differently selected from carbocycles having 3 to 30 ring atoms, or heterocycles having 3 to 30 ring atoms;
A 1 ，A 2 ，B 1 ，B 2 e is selected identically or differently on each occurrence from C, N, B, P, CR ' ", siR '" or GeR ' ";
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR ", P (O) R", R "c=cr", a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heterocyclylene group having 3 to 20 ring atoms, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, or a combination thereof;
Substituent R 1 -R 8 ，R’，R”，R”’，R x ，R y ，R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted alkynyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atomsOr unsubstituted amino groups having from 0 to 20 carbon atoms, acyl groups, carbonyl groups, carboxylic acid groups, ester groups, cyano groups, isocyano groups, hydroxyl groups, mercapto groups, sulfinyl groups, sulfonyl groups, phosphino groups, and combinations thereof;
"onium" represents the attachment position of formula 2;
adjacent substituents R', R x ，R”，R”’，R A ，R B ，R y Can optionally be linked to form a ring;
adjacent substituents R 1 -R 8 Can optionally be linked to form a ring.
4. A metal complex as claimed in any one of claims 1 to 3 wherein Z is selected from O or S; preferably, Z is selected from O.
5. The metal complex as defined in any one of claims 1 to 4, wherein X 1 -X 8 Is selected from CR, identically or differently at each occurrence x Substituent R x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkyl germanium groups having 3 to 20 carbon atoms, cyano groups, and combinations thereof;
preferably, the substituent R x And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated cyclopentyl, deuterated cyclohexyl, phenyl, biphenyl, pyridinyl, trimethylsilyl, trimethylgermanium, and combinations thereof.
6. A metal according to any one of claims 1 to 3Complexes in which the substituents R n Has a structure represented by formula 4:
A 3 -A 6 is selected from CR, identically or differently at each occurrence A Or N;
B 3 -B 6 is selected from CR, identically or differently at each occurrence B Or N;
l is selected from single bond, O, S, SO 2 Se, NR ", CR" R ", siR" R ", ger" R ", BR", PR, P (O) R ", R" c=cr ", alkylene having 1 to 20 carbon atoms, heteroalkylene having 1 to 20 carbon atoms, cycloalkylene having 3 to 20 carbon atoms, heterocyclylene having 3 to 20 ring atoms, arylene having 6 to 30 carbon atoms, heteroarylene having 3 to 30 carbon atoms, or a combination thereof;
substituent R A 、R B And R "is, identically or differently, selected from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy having 6 to 30 carbon atoms, substituted or unsubstituted alkenyl having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium having 6 to 20 carbon atoms, substituted or unsubstituted amino having 0 to 20 carbon atoms, acyl, carbonyl, carboxylic acid, ester, cyano, isocyano, hydroxyl, mercapto Sulfinyl, sulfonyl, phosphino, and combinations thereof;
adjacent substituents R ", R A ，R B Can optionally be linked to form a ring;
"onium" means the position of the linkage of formula 4.
7. The metal complex according to claim 6, wherein A 3 -A 6 Is selected from CR, identically or differently at each occurrence A And/or B 3 -B 6 Is selected from CR, identically or differently at each occurrence B The method comprises the steps of carrying out a first treatment on the surface of the Substituent R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkyl germanium groups having 3 to 20 carbon atoms, cyano groups, and combinations thereof;
preferably, the substituent R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 6 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 12 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 12 carbon atoms, substituted or unsubstituted silyl groups having 3 to 6 carbon atoms, substituted or unsubstituted alkyl germanium groups having 3 to 6 carbon atoms, cyano groups, and combinations thereof;
More preferably, the substituent R A And R is B And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, fluorine, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, cyclopentyl, cyclohexyl, deuterated methyl, deuterated ethyl, deuterated propyl, deuterated isopropyl, deuterated n-butyl, deuterated isobutyl, deuterated tert-butyl, deuterated neopentyl, deuterated cyclopentyl, deuterated cyclohexyl,phenyl, pyridyl, trimethylsilyl, trimethylgermanium, and combinations thereof.
8. The metal complex of any one of claims 1-7, wherein L is selected from a single bond, O, S, se, NR, siR "R", geR "R", BR ", PR", P (O) R ", a substituted or unsubstituted alkylene group having 1-10 carbon atoms, a substituted or unsubstituted arylene group having 6-10 carbon atoms, a substituted or unsubstituted heteroarylene group having 3-10 carbon atoms, or a combination thereof;
preferably, L is selected from a single bond, O, S, NR', a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or phenylene;
more preferably, L is selected from single bonds.
9. A metal complex as claimed in any one of claims 1 to 3, wherein X 3 -X 8 At least one of them is CR x The substituent R x Selected from cyano or fluoro;
preferably X 5 -X 8 At least one of them is CR x The substituent R x Selected from cyano or fluoro;
more preferably X 7 Or X 8 Is CR (CR) x The R is x Selected from cyano; or X 7 Is CR (CR) x The substituent R x Selected from fluorine.
10. A metal complex as claimed in any one of claims 1 to 3, wherein X 3 -X 8 At least two of them are selected from CR x And one of the substituents R x Selected from cyano or fluoro, another of said substituents R x Selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted heterocyclyl having 3 to 20 ring atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aralkyl having 1 to 20 carbon atomsSubstituted or unsubstituted aryloxy groups having from 6 to 30 carbon atoms, substituted or unsubstituted alkenyl groups having from 2 to 20 carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having from 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having from 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having from 6 to 20 carbon atoms, cyano groups, isocyano groups, and combinations thereof;
Preferably X 5 -X 8 At least two of them are selected from CR x And one of the substituents R x Selected from cyano or fluoro, another of said substituents R x Selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, substituted or unsubstituted alkylsilyl groups having 3 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylgermanium groups having 3 to 20 carbon atoms, substituted or unsubstituted arylgermanium groups having 6 to 20 carbon atoms, cyano groups, isocyano groups, and combinations thereof;
more preferably X 7 And X 8 Selected from CR x And one of the substituents R x Is cyano or fluoro, the other of said substituents R x Selected from the group consisting of: deuterium, fluorine, substituted or unsubstituted alkyl groups having from 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having from 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having from 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having from 3 to 30 carbon atoms, substituted or unsubstituted silyl groups having from 3 to 20 carbon atoms, cyano groups, isocyano groups, and combinations thereof.
11. The metal complex as claimed in claim 1 or 2, wherein R n Each occurrence of which is identically or differently selected from the followingAnd (3) a group consisting of:
optionally, an as described above 1 To An 52 、An 54 To An 58 And An 61 To An 96 The hydrogen in (a) can be partially or completely replaced by deuterium.
12. A metal complex as claimed in any one of claims 1 to 3, wherein the substituents R y And is selected identically or differently on each occurrence from the group consisting of: hydrogen, deuterium, halogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted aralkyl having 7 to 30 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, substituted or unsubstituted silyl having 3 to 20 carbon atoms, substituted or unsubstituted arylsilane having 6 to 20 carbon atoms, substituted or unsubstituted amino having 6 to 20 carbon atoms, and combinations thereof;
preferably, the substituent R y At least one selected from the group consisting of: deuterium, halogen, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof.
13. As claimed in3, wherein the substituent R 1 -R 8 At least one or at least two selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, or combinations thereof, and all of said substituents R 1 -R 4 And/or substituents R 5 -R 8 Is at least 4;
substituent R 1 -R 4 At least one or at least two selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, or combinations thereof, and all of said substituents R 1 -R 4 Is at least 4; and/or substituents R 5 -R 8 At least one or at least two selected from the group consisting of substituted or unsubstituted alkyl groups of 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, or combinations thereof, and all of said substituents R 5 -R 8 The sum of the number of carbon atoms of (2) is at least 4.
14. A metal complex as claimed in claim 3, wherein the substituents R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all of which are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, substituted or unsubstituted aryl groups having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms, and combinations thereof;
Preferably, the substituent R 2 ，R 3 ，R 6 ，R 7 At least one or at least two or at least three or all of which are selected from the group consisting of: deuterium, substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 3 to 20 ring carbon atoms, and combinations thereof;
more preferably, the substituent R 2 ，R 3 ，R 6 ，R 7 At least one, or at least two, or at least three, or all ofSelected from the group consisting of: deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, neopentyl, t-pentyl, and combinations thereof; optionally, hydrogen in the above groups can be partially or fully deuterated.
15. The metal complex of claim 11, wherein L a Is selected identically or differently on each occurrence from the group consisting of L a1 To L a821 A group consisting of L a1 To L a821 The specific structure of (2) is as follows:
L a1 to L a773 Has the general structure shown as follows:wherein R is n 、R Y1 -R Y3 、R X4 -R X8 And Z is selected from the atoms or groups in the following table:
L a774 to L a789 Has the following general structure:wherein R is n 、R Y1 -R Y3 、R X4 -R X8 And Z is selected from the atoms or groups in the following table:
L a790 To L a805 Has the following general structure:wherein R is n 、R Y1 -R Y3 、R X4 -R X8 And Z is selected from the atoms or groups in the following table:
L a806 To L a821 Has the following general structure:wherein R is n 、R Y1 -R Y3 、R X4 -R X7 And Z is selected from the atoms or groups in the following table: />
Wherein R is s1 :R s2 :R s3 :R s4 :R s5 :R s6 :R s7 :R s8 :R s9 :R s10 :R s11 :R s12 :R s13 :R s14 :R s15 :R s16 :R s17 :Wherein ":" represents R s1 To R s17 Is connected with the connecting position of the connecting rod;
optionally, L is as described above a1 To L a821 The hydrogen in (a) can be partially or completely replaced by deuterium.
16. The metal complex as defined in claim 2, 3 or 15, wherein L b And is selected identically or differently on each occurrence from the group consisting of:
optionally, L is as described above b1 To L b334 The hydrogen atoms of (a) can be partially or completely substituted by deuterium.
17. The metal complex of claim 2, 15 or 16, wherein L c And is selected identically or differently on each occurrence from the group consisting of:
18. the metal complex as set forth in claim 16, wherein the metal complex is selected from the group consisting of metal complex 1 to metal complex 435, wherein the metal complex 1 to metal complex 435 has IrL a (L b ) 2 Two L' s b Identical, L a And L b Respectively corresponding to the structures indicated in the following table:
19. an organic electroluminescent device, comprising:
an anode is provided with a cathode,
a cathode electrode, which is arranged on the surface of the cathode,
and an organic layer disposed between the anode and the cathode, at least one of the organic layers comprising the metal complex of any one of claims 1-18.
20. The organic electroluminescent device of claim 19, wherein the organic layer comprising the metal complex is a light emitting layer.
21. The organic electroluminescent device of claim 20, wherein the light-emitting layer further comprises a first host compound;
preferably, the light emitting layer further comprises a second host compound;
more preferably, at least one of the host compounds comprises at least one chemical group selected from the group consisting of: benzene, pyridine, pyrimidine, triazine, carbazole, azacarbazole, indolocarbazole, dibenzothiophene, azadibenzothiophene, dibenzofuran, azadibenzofuran, dibenzoselenophene, triphenylene, azatriphenylene, fluorene, silafluorene, naphthalene, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene, azaphenanthrene, and combinations thereof.
22. The organic electroluminescent device of claim 21, wherein the metal complex is doped in the first and second host compounds, the metal complex accounting for 1% -30% of the total weight of the light emitting layer;
preferably, the metal complex accounts for 3% -13% of the total weight of the luminescent layer.
23. A compound composition comprising the metal complex of any one of claims 1-18.
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| KR1020230007912A KR20230114720A (en) | 2022-01-25 | 2023-01-19 | Organic electroluminescent material and device thereof |
| US18/157,225 US20230240129A1 (en) | 2022-01-25 | 2023-01-20 | Organic electroluminescent material and device thereof |
| JP2023009315A JP7522487B2 (en) | 2022-01-25 | 2023-01-25 | Organic electroluminescent material and device thereof |
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