CN116903663A - Organic electroluminescent material and device - Google Patents
Organic electroluminescent material and device Download PDFInfo
- Publication number
- CN116903663A CN116903663A CN202310416987.4A CN202310416987A CN116903663A CN 116903663 A CN116903663 A CN 116903663A CN 202310416987 A CN202310416987 A CN 202310416987A CN 116903663 A CN116903663 A CN 116903663A
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- substituted
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- cyano
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- 239000000463 material Substances 0.000 title abstract description 122
- 150000001875 compounds Chemical class 0.000 claims abstract description 150
- 239000003446 ligand Substances 0.000 claims abstract description 107
- 125000001424 substituent group Chemical group 0.000 claims description 119
- -1 amino, silyl Chemical group 0.000 claims description 105
- 125000003118 aryl group Chemical group 0.000 claims description 79
- 238000006467 substitution reaction Methods 0.000 claims description 70
- 229910052799 carbon Inorganic materials 0.000 claims description 69
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 69
- 125000000217 alkyl group Chemical group 0.000 claims description 68
- 125000001072 heteroaryl group Chemical group 0.000 claims description 65
- 229910052717 sulfur Inorganic materials 0.000 claims description 62
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 57
- 239000002184 metal Substances 0.000 claims description 57
- 229910052757 nitrogen Inorganic materials 0.000 claims description 56
- 229910052760 oxygen Inorganic materials 0.000 claims description 54
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims description 48
- 239000001257 hydrogen Substances 0.000 claims description 48
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 45
- 125000003342 alkenyl group Chemical group 0.000 claims description 43
- 125000000623 heterocyclic group Chemical group 0.000 claims description 42
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 40
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 40
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 36
- 239000012044 organic layer Substances 0.000 claims description 33
- 125000004122 cyclic group Chemical group 0.000 claims description 32
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 30
- 229910052805 deuterium Inorganic materials 0.000 claims description 30
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 30
- 150000002825 nitriles Chemical class 0.000 claims description 30
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 30
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 29
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 28
- 150000002148 esters Chemical class 0.000 claims description 28
- 150000002527 isonitriles Chemical class 0.000 claims description 28
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 28
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 28
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 25
- 125000003367 polycyclic group Chemical group 0.000 claims description 25
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 24
- 125000000304 alkynyl group Chemical group 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 22
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 21
- 229910052796 boron Inorganic materials 0.000 claims description 21
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 20
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 20
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 20
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 19
- 125000004104 aryloxy group Chemical group 0.000 claims description 19
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 19
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 18
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 18
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 17
- 125000002252 acyl group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 16
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 15
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 15
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 14
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 125000002950 monocyclic group Chemical group 0.000 claims description 14
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical compound C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052711 selenium Inorganic materials 0.000 claims description 14
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 13
- 150000002460 imidazoles Chemical class 0.000 claims description 13
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 12
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 12
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 12
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 11
- 150000002576 ketones Chemical class 0.000 claims description 11
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 claims description 11
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 10
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 10
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 claims description 10
- 150000001556 benzimidazoles Chemical class 0.000 claims description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 10
- 239000001752 chlorophylls and chlorophyllins Substances 0.000 claims description 10
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 10
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 10
- 150000002916 oxazoles Chemical class 0.000 claims description 10
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 claims description 10
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 claims description 10
- 150000003557 thiazoles Chemical class 0.000 claims description 10
- BNRDGHFESOHOBF-UHFFFAOYSA-N 1-benzoselenophene Chemical compound C1=CC=C2[se]C=CC2=C1 BNRDGHFESOHOBF-UHFFFAOYSA-N 0.000 claims description 9
- 150000001716 carbazoles Chemical class 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229930192474 thiophene Natural products 0.000 claims description 9
- 125000001054 5 membered carbocyclic group Chemical group 0.000 claims description 8
- 125000004008 6 membered carbocyclic group Chemical group 0.000 claims description 8
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims description 8
- 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 7
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 claims description 6
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 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 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical compound C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 claims description 2
- PFWJFKBTIBAASX-UHFFFAOYSA-N 9h-indeno[2,1-b]pyridine Chemical compound C1=CN=C2CC3=CC=CC=C3C2=C1 PFWJFKBTIBAASX-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 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
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 125000005549 heteroarylene group Chemical group 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 125000001475 halogen functional group Chemical group 0.000 claims 8
- 150000001735 carboxylic acids Chemical class 0.000 claims 5
- 150000000183 1,3-benzoxazoles Chemical class 0.000 claims 4
- 229940125904 compound 1 Drugs 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 28
- 238000000295 emission spectrum Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 136
- 125000004429 atom Chemical group 0.000 description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 35
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 28
- 239000002019 doping agent Substances 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 125000006575 electron-withdrawing group Chemical group 0.000 description 24
- 125000005842 heteroatom Chemical group 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 21
- 239000000047 product Substances 0.000 description 20
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- 230000007704 transition Effects 0.000 description 17
- 230000004888 barrier function Effects 0.000 description 16
- 230000032258 transport Effects 0.000 description 16
- 238000004770 highest occupied molecular orbital Methods 0.000 description 15
- 239000011541 reaction mixture Substances 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 235000019439 ethyl acetate Nutrition 0.000 description 13
- 229910052741 iridium Inorganic materials 0.000 description 13
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 11
- 150000003384 small molecules Chemical class 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000903 blocking effect Effects 0.000 description 10
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 235000010290 biphenyl Nutrition 0.000 description 9
- 150000004696 coordination complex Chemical class 0.000 description 9
- 230000005525 hole transport Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 8
- 238000003775 Density Functional Theory Methods 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 8
- 230000002950 deficient Effects 0.000 description 8
- 230000005281 excited state Effects 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 description 8
- 125000005580 triphenylene group Chemical group 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- DHFABSXGNHDNCO-UHFFFAOYSA-N dibenzoselenophene Chemical compound C1=CC=C2C3=CC=CC=C3[se]C2=C1 DHFABSXGNHDNCO-UHFFFAOYSA-N 0.000 description 7
- 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 description 7
- 229960005544 indolocarbazole Drugs 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 6
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 6
- UZVGSSNIUNSOFA-UHFFFAOYSA-N dibenzofuran-1-carboxylic acid Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2C(=O)O UZVGSSNIUNSOFA-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000011368 organic material Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 5
- 239000000412 dendrimer Substances 0.000 description 5
- 229920000736 dendritic polymer Polymers 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 125000006413 ring segment Chemical group 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 4
- 125000000477 aza group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000012634 fragment Substances 0.000 description 4
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 4
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000005693 optoelectronics Effects 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000003826 tablet Substances 0.000 description 4
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical compound C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 3
- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 3
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- 238000000302 molecular modelling Methods 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical class 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- KBBSSGXNXGXONI-UHFFFAOYSA-N phenanthro[9,10-b]pyrazine Chemical compound C1=CN=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 KBBSSGXNXGXONI-UHFFFAOYSA-N 0.000 description 1
- RIYPENPUNLHEBK-UHFFFAOYSA-N phenanthro[9,10-b]pyridine Chemical compound C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=N1 RIYPENPUNLHEBK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000005359 phenylpyridines Chemical class 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 125000004585 polycyclic heterocycle group Chemical group 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- WFMNHCSATCWAAQ-UHFFFAOYSA-M potassium;2,2-dimethylpropanoate Chemical compound [K+].CC(C)(C)C([O-])=O WFMNHCSATCWAAQ-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- 150000004892 pyridazines Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 150000003230 pyrimidines Chemical class 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005226 self-consistent reaction field Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Substances C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- KTQYWNARBMKMCX-UHFFFAOYSA-N tetraphenylene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C3=CC=CC=C3C2=C1 KTQYWNARBMKMCX-UHFFFAOYSA-N 0.000 description 1
- DBDCNCCRPKTRSD-UHFFFAOYSA-N thieno[3,2-b]pyridine Chemical compound C1=CC=C2SC=CC2=N1 DBDCNCCRPKTRSD-UHFFFAOYSA-N 0.000 description 1
- IZAJCEGIQMYVFM-UHFFFAOYSA-N thieno[3,2-c]pyridazine Chemical compound N1=CC=C2SC=CC2=N1 IZAJCEGIQMYVFM-UHFFFAOYSA-N 0.000 description 1
- RBNBDIMXFJYDLQ-UHFFFAOYSA-N thieno[3,2-d]pyrimidine Chemical compound C1=NC=C2SC=CC2=N1 RBNBDIMXFJYDLQ-UHFFFAOYSA-N 0.000 description 1
- 229940125670 thienopyridine Drugs 0.000 description 1
- 239000002175 thienopyridine Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- MJRFDVWKTFJAPF-UHFFFAOYSA-K trichloroiridium;hydrate Chemical compound O.Cl[Ir](Cl)Cl MJRFDVWKTFJAPF-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/40—Organosilicon compounds, e.g. TIPS pentacene
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present application relates to organic electroluminescent materials and devices. Provides a light-emitting device having the formula Ir (L) A* ) m (L B* ) n (L C* ) p A compound of (a); wherein each L A* 、L B* And L C* Are independently monoanionic bidentate ligands and are different from each other; n and p are each independently 0,1 or 2; m is 1 or 2; and m+n+p is 3; l (L) A* Has E at 77K A Is of the first triplet energy T 1 ；L B* Has E at 77K B Is of the first triplet energy T 1 ；L C* Has E at 77K C Is of the first triplet energy T 1 ；E A Less than E B And E is C Whether E B And E is C Which one exists; l (L) A Comprises at least one pi-electron withdrawing group; and the compound has an emission spectrum with a FWHM value of not more than 45 nm. Also provided is a composition comprising a first ligand L A The compound of (C), the L A Has the structure of formula I:
Description
cross reference to related applications
The present application is a partially continued application of co-pending U.S. patent application Ser. No. 18/058,461, U.S. patent application Ser. No. 17/844,331, and U.S. patent application Ser. No. 18/177,178, filed on Ser. No. 2023, month 3, and month 2, filed on day 23, each of which is incorporated herein by reference. The present application claims 35 U.S. C. ≡119 (e) U.S. provisional application No. 63/481,143, U.S. provisional application No. 63/476,204, U.S. provisional application No. 63/385,994, U.S. provisional application No. 63/385,730, U.S. provisional application No. 63/382,134, U.S. provisional application No. 63/417,746, U.S. provisional application No. 63/408,746, U.S. provisional application No. 63/408,686, U.S. provisional application No. 63/408,357, U.S. provisional application No. 63/407,981, U.S. provisional application No. 63/406, 019, U.S. provisional application No. 63/392,731 filed on 7 month 27 of 2022, U.S. provisional application No. 63/356,191 filed on 6 month 28 of 2022, U.S. provisional application No. 63/354,721 filed on 23 of 2022, U.S. provisional application No. 63/353,920 filed on 21 of 2022, U.S. provisional application No. 63/351,049 filed on 10 of 2022, U.S. provisional application No. 63/350,150 filed on 8 of 2022, U.S. provisional application No. 63/332,165 filed on 18 of 2022, all of which are incorporated herein by reference in their entirety.
Technical Field
The present disclosure relates generally to novel organometallic compounds and formulations and various uses thereof, including as emitters in devices such as organic light emitting diodes and related electronic devices.
Background
Optoelectronic devices utilizing organic materials are becoming increasingly popular for a variety of reasons. Many of the materials used to fabricate the devices are relatively inexpensive, so organic photovoltaic devices have the potential for cost advantages over inorganic devices. In addition, the inherent properties of organic materials (e.g., their flexibility) may make them more suitable for specific applications, such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting diodes/devices (OLEDs), organic phototransistors, organic photovoltaic cells, and organic photodetectors. For OLEDs, organic materials can have performance advantages over conventional materials.
OLEDs utilize organic thin films that emit light when a voltage is applied across the device. OLEDs are becoming an increasingly interesting technology for use in applications such as flat panel displays, lighting and backlighting.
One application of phosphorescent emissive molecules is in full color displays. Industry standards for such displays require pixels adapted to emit a particular color (referred to as a "saturated" color). In particular, these standards require saturated red, green and blue pixels. Alternatively, the OLED may be designed to emit white light. In conventional liquid crystal displays, the emission from a white backlight is filtered using an absorbing filter to produce red, green and blue emissions. The same technique can also be used for OLEDs. The white OLED may be a single emissive layer (EML) device or a stacked structure. The colors may be measured using CIE coordinates well known in the art.
Disclosure of Invention
The present disclosure provides novel metal complexes that emit the green spectrum that contain electron withdrawing groups on the bottom fused ring of the emissive ligand. This type of complex exhibits a narrower EL spectral emission line shape than currently available green-emitting metal complexes. The narrower line shape of the emitter dopant is advantageous for achieving higher efficiency in the OLED.
In one aspect, the present disclosure provides a composition having the formula Ir (L A* ) m (L B* ) n (L C* ) p A compound of (a); wherein:
L A* 、L B* and L C* Each independently a monoanionic bidentate ligand and different from each other;
each n and p is independently 0, 1 or 2; m is 1 or 2; and m+n+p is 3;
L A* has E at 77K A Is the first triplet energy T of 1 ；
L B* Has E at 77K B Is the first triplet energy T of 1 ；
L C* Has E at 77K C Is the first triplet energy T of 1 ；
E A Less than E B And E is C In E B And E is C The existence of the above is the right;
L A* comprises at least one pi-electron withdrawing group; and is also provided with
The compounds have an emission spectrum with a full width at half maximum (FWHM) value of no more than 45 nm.
In another aspect, the present disclosure provides a formulation comprising a compound having the formula Ir (L A* ) m (L B* ) n (L C* ) p Is a compound of (a).
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising an organic light emitting diode having the formula Ir (L A* ) m (L B* ) n (L C* ) p Is a compound of (a).
In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising an organic compound having the formula Ir (L A* ) m (L B* ) n (L C* ) p Is a compound of (a).
In another aspect, a kit is provided comprising a first ligand L A The compound of (C), the L A Has the structure of formula I:
in formula I: part a is a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic and polycyclic fused ring systems is independently a 5-or 6-membered carbocyclic or heterocyclic ring; k is selected from the group consisting of: direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) And Si (R) α )(R β )；Z 1 And Z 2 Each independently is C or N; x is X 1 To X 8 Each independently is C or N; y is selected from the group consisting of: BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr ', c=cr ' R ", s= O, SO 2 CR, CRR ', siRR ', and GeRR '; r is R 1 、R 2 And R is 3 Each independently represents a single substitution to a maximum allowable number of substitutions, or no substitution; at least one R 2 Or R is 3 Is a substituted 5-membered heterocycle, an unsubstituted 5-membered heterocycle, a substituted 6-membered heterocycle, an unsubstituted 6-membered heterocycle, or a moiety comprising a substituent selected from the group consisting of structures in the following electron withdrawing group list (EWG list): COR (continuous operation reactor) R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、S0 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R′ Substituted or unsubstituted dibenzoboroles, substituted or unsubstituted carbazole, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially or fully fluorinated alkyl, partially or fully fluorinated alkenyl, partially or fully fluorinated cycloalkyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, and combinations thereof;
each R is α 、R β 、R R 、R R′ 、R、R′、R″、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; l (L) A Coordinated to a metal M selected from the group consisting of: ir, rh, re, ru, os, pt, pd, ag, au and Cu; the metal M can be coordinated with other ligands; l (L) A Can be conjugated with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands; wherein any two substituents may join or fuse to form a ring.
In another aspect, the present disclosure provides a formulation comprising a first ligand L having formula I as described herein A Is a compound of (a).
In yet another aspect, the present disclosure provides an OLED having an organic layer comprising a first ligand L as described herein having formula I A Is a compound of (a).
In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising a first ligand L having formula I as described herein A Is a compound of (a).
Drawings
Fig. 1 shows an organic light emitting device.
Fig. 2 shows an inverted organic light emitting device without a separate electron transport layer.
Detailed Description
A. Terminology
Unless otherwise specified, the following terms used herein are defined as follows:
as used herein, the term "organic" includes polymeric materials and small molecule organic materials that can be used to fabricate organic optoelectronic devices. "Small molecule" refers to any organic material that is not a polymer, and may be substantial in nature. In some cases, the small molecule may include a repeating unit. For example, the use of long chain alkyl groups as substituents does not remove a molecule from the "small molecule" class. Small molecules may also be incorporated into the polymer, for example as pendant groups on the polymer backbone or as part of the backbone. Small molecules can also act as the core of a dendrimer, which consists of a series of chemical shells built on the core. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers may be "small molecules" and all dendrimers currently used in the OLED field are considered small molecules.
As used herein, "top" means furthest from the substrate, and "bottom" means closest to the substrate. Where a first layer is described as being "disposed" over "a 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 over" 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 contributes directly to the photosensitive properties of the emissive material. When the ligand is considered not to contribute to the photosensitive properties of the emissive material, the ligand may be referred to as "ancillary", but the ancillary ligand may alter the properties of the photosensitive ligand.
As used herein, and as will be generally understood by those of skill in the art, if the first energy level is closer to the vacuum energy level, then the first "highest occupied molecular orbital" (Highest Occupied Molecular Orbital, HOMO) or "lowest unoccupied molecular orbital" (Lowest Unoccupied Molecular Orbital, LUMO) energy level is "greater than" or "higher than" the second HOMO or LUMO energy level. Since Ionization Potential (IP) is measured as a negative energy relative to the vacuum level, a higher HOMO level corresponds to an IP with a smaller absolute value (less negative). Similarly, a higher LUMO energy level corresponds to an Electron Affinity (EA) with a smaller absolute value (less negative EA). On a conventional energy level diagram with vacuum energy level on top, the LUMO energy level of a material is higher than the HOMO energy level of the same material. The "higher" HOMO or LUMO energy level appears closer to the top of this figure than the "lower" HOMO or LUMO energy level.
As used herein, and as will be generally understood by those of skill in the art, a first work function is "greater than" or "higher than" a second work function if the first work function has a higher absolute value. Since work function is typically measured as a negative number relative to the vacuum level, this means that the "higher" work function is more negative (more negative). On a conventional energy level diagram with the vacuum energy level on top, a "higher" work function is illustrated as being farther from the vacuum energy level in a downward direction. Thus, the definition of HOMO and LUMO energy levels follows a different rule than work function.
The terms "halo", "halogen" and "halo" are used interchangeably and refer to fluoro, chloro, bromo and iodo.
The term "acyl" refers to a substituted carbonyl (C (O) -R s )。
The term "ester" refers to a substituted oxycarbonyl (-O-C (O) -R) s or-C (O) -O-R s ) A group.
The term "ether" means-OR s A group.
The terms "thio" or "thioether" are used interchangeably and refer to-SR s A group.
The term "selenoalkyl" refers to-SeR s A group.
The term "sulfinyl" refers to-S (O) -R s A group.
The term "sulfonyl" refers to-SO 2 -R s A group.
The term "phosphino" refers to-P (R s ) 3 A group wherein each R s May be the same or different.
The term "silane group" means-Si (R s ) 3 A group wherein each R s May be the same or different.
The term "germyl" refers to-Ge (R s ) 3 A group wherein each R s May be the same or different.
The term "boron group" means-B (R s ) 2 A group or Lewis addition product-B (R) s ) 3 A group, wherein R is s May be the same or different.
In each of the above, R s May be hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, and combinations thereof. Preferred R s Selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The term "alkyl" refers to and includes straight and branched chain alkyl groups. Preferred alkyl groups are those containing from one to fifteen carbon atoms and include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 2-dimethylpropyl, and the like. In addition, alkyl groups may be optionally substituted.
The term "cycloalkyl" refers to and includes monocyclic, polycyclic, and spiroalkyl groups. Preferred cycloalkyl groups are those containing 3 to 12 ring carbon atoms and include cyclopropyl, cyclopentyl, cyclohexyl, bicyclo [3.1.1] heptyl, spiro [4.5] decyl, spiro [5.5] undecyl, adamantyl, and the like. In addition, cycloalkyl groups may be optionally substituted.
The term "heteroalkyl" or "heterocycloalkyl" refers to an alkyl or cycloalkyl group, respectively, having at least one carbon atom replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. In addition, heteroalkyl or heterocycloalkyl groups may be optionally substituted.
The term "alkenyl" refers to and includes both straight and branched alkenyl groups. Alkenyl is essentially an alkyl group comprising at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl is essentially cycloalkyl including at least one carbon-carbon double bond in the cycloalkyl ring. The term "heteroalkenyl" as used herein refers to an alkenyl group having at least one carbon atom replaced with a heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. Preferred alkenyl, cycloalkenyl or heteroalkenyl groups are those containing from two to fifteen carbon atoms. In addition, alkenyl, cycloalkenyl, or heteroalkenyl groups may be optionally substituted.
The term "alkynyl" refers to and includes both straight and branched chain alkynyl groups. Alkynyl is essentially an alkyl group that includes at least one carbon-carbon triple bond in the alkyl chain. Preferred alkynyl groups are those containing from two to fifteen carbon atoms. In addition, alkynyl groups may be optionally substituted.
The term "aralkyl" or "arylalkyl" is used interchangeably and refers to an alkyl group substituted with an aryl group. In addition, aralkyl groups may be optionally substituted.
The term "heterocyclyl" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, si and Se, preferably O, S or N. Aromatic heterocyclic groups may be used interchangeably with heteroaryl. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl, and the like, and cyclic ethers/sulfides such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and the like. In addition, the heterocyclic group may be optionally substituted.
The term "aryl" refers to and includes monocyclic aromatic hydrocarbon groups and polycyclic aromatic ring systems. The polycyclic ring may have two or more rings in common in which two carbons are two adjoining rings (the rings being "fused"), wherein at least one of the rings is an aromatic hydrocarbon group, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. Preferred aryl groups are those containing from six to thirty carbon atoms, preferably from six to twenty carbon atoms, more preferably from six to twelve carbon atoms. Particularly preferred are aryl groups having six carbons, ten carbons or twelve carbons. Suitable aryl groups include phenyl, biphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, pa, phenanthrene, fluorene, pyrene, Perylene and azulene, preferably phenyl, biphenyl, triphenylene, fluorene and naphthalene. In addition, aryl groups may be optionally substituted.
The term "heteroaryl" refers to and includes monocyclic aromatic groups and polycyclic aromatic ring systems that include at least one heteroatom. Heteroatoms include, but are not limited to O, S, N, P, B, si and Se. In many cases O, S or N are preferred heteroatoms. The monocyclic heteroaromatic system is preferably a monocyclic ring having 5 or 6 ring atoms, and the ring may have one to six heteroatoms. The heteropolycyclic ring system may have two or more rings in which two atoms are common to two adjoining rings (the rings being "fused"), wherein at least one of the rings is heteroaryl, e.g., the other rings may be cycloalkyl, cycloalkenyl, aryl, heterocyclic, and/or heteroaryl. The heteropolycyclic aromatic ring system may have one to six heteroatoms in each ring of the polycyclic aromatic ring system. Preferred heteroaryl groups are those containing from three to thirty carbon atoms, preferably from three to twenty carbon atoms, more preferably from three to twelve carbon atoms. Suitable heteroaryl groups include dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, diazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene (xanthene), acridine, phenazine, phenothiazine, phenoxazine, benzofurandipyridine, benzothiophene pyridine, thienodipyridine, benzoselenophene dipyridine, dibenzofuran, dibenzoselenium, carbazole, indolocarbazole, benzimidazole, triazine, 1, 2-borazine, 1-boron-nitrogen, 1-nitrogen, 4-boron-nitrogen, boron-nitrogen-like compounds, and the like. In addition, heteroaryl groups may be optionally substituted.
Of the aryl and heteroaryl groups listed above, triphenylene, naphthalene, anthracene, dibenzothiophene, dibenzofuran, dibenzoselenophene, carbazole, indolocarbazole, imidazole, pyridine, pyrazine, pyrimidine, triazine, and benzimidazole, and their respective corresponding aza analogues, are of particular interest.
The terms alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aralkyl, heterocyclyl, aryl, and heteroaryl as used herein are independently unsubstituted or independently substituted with one or more common substituents.
In many cases, the typical substituents are selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, selenkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In some cases, preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, germyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.
In some cases, more preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, alkoxy, aryloxy, amino, silyl, aryl, heteroaryl, thio, and combinations thereof.
In other cases, the most preferred general substituents are selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
The terms "substituted" and "substituted" refer to substituents other than H bonded to the relevant position, such as carbon or nitrogen. For example, when R 1 When single substitution is represented, then one R 1 It must not be H (i.e., substitution). Similarly, when R 1 When two are substituted, two R 1 It must not be H. Similarly, when R 1 R represents zero or no substitution 1 For example, it may be hydrogen of available valence of the ring atoms, such as carbon atoms of benzene and nitrogen atoms in pyrrole, or for ring atoms having a fully saturated valence, it may simply represent none, such as nitrogen atoms in pyridine. The maximum number of substitutions possible in the ring structure will depend on the total number of available valences in the ring atom.
As used herein, "combination thereof" means that one or more members of the applicable list are combined to form a known or chemically stable arrangement that one of ordinary skill in the art can contemplate from the applicable list. For example, alkyl and deuterium can combine to form a partially or fully deuterated alkyl group; halogen and alkyl may combine to form a haloalkyl substituent; and halogen, alkyl and aryl may combine to form a haloaralkyl. In one example, the term substitution includes a combination of two to four of the listed groups. In another example, the term substitution includes a combination of two to three groups. In yet another example, the term substitution includes a combination of two groups. Preferred combinations of substituents are combinations containing up to fifty atoms other than hydrogen or deuterium, or combinations comprising up to forty atoms other than hydrogen or deuterium, or combinations comprising up to thirty atoms other than hydrogen or deuterium. In many cases, a preferred combination of substituents will include up to twenty atoms that are not hydrogen or deuterium.
The term "aza" in the fragments described herein, i.e., aza-dibenzofuran, aza-dibenzothiophene, etc., means that one or more of the C-H groups in the corresponding aromatic ring may be replaced with a nitrogen atom, for example and without limitation, aza-triphenylene encompasses dibenzo [ f, H ] quinoxaline and dibenzo [ f, H ] quinoline. Other nitrogen analogs of the aza-derivatives described above can be readily envisioned by those of ordinary skill in the art, and all such analogs are intended to be encompassed by the terms as set forth herein.
As used herein, "deuterium" refers to an isotope of hydrogen. Deuterated compounds can be readily prepared using methods known in the art. For example, U.S. patent No. 8,557,400, patent publication No. WO 2006/095951, and U.S. patent application publication No. US 2011/0037057 (which are incorporated herein by reference in their entirety) describe the preparation of deuterium-substituted organometallic complexes. Further reference is made to Yan Ming (Ming Yan) et al, tetrahedron (Tetrahedron) 2015, 71, 1425-30 and Azrote (Atzrodt) et al, germany application chemistry (Angew. Chem. Iht. Ed.) (review) 2007, 46, 7744-65, which is incorporated by reference in its entirety, describe the deuteration of methylene hydrogen in benzylamine and the efficient pathway of replacing aromatic ring hydrogen with deuterium, respectively.
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 as if it were a fragment (e.g., phenyl, phenylene, naphthyl, dibenzofuranyl) or as if it were an entire molecule (e.g., benzene, naphthalene, dibenzofuran). As used herein, these different ways of naming substituents or linking fragments are considered equivalent.
In some cases, a pair of adjacent substituents may optionally be joined or fused into a ring. Preferred rings are five-, six-, or seven-membered carbocycles or heterocycles, including both cases where a portion of the ring formed by the pair of substituents is saturated and a portion of the ring formed by the pair of substituents is unsaturated. As used herein, "adjacent" means that the two substituents involved can be next to each other on the same ring, or on two adjacent rings having two nearest available substitutable positions (e.g., the 2, 2' positions in biphenyl or the 1, 8 positions in naphthalene) so long as they can form a stable fused ring system.
B. Compounds of the present disclosure
Novel metal complexes are disclosed that emit the green spectrum comprising ligands having pyrimidine coordinates to metals. Complexes of this type exhibit a deeper HOMO level than the current commercial products. The deeper HOMO level of the green dopant is advantageous for achieving shorter EL transients in the OLED device. The novel metal complexes disclosed contain an electron withdrawing group on the bottom DBX ring of the emissive ligand. This type of complex exhibits a narrower EL spectral line shape than the currently commercially available green-emitting metal complexes. A green-emitting dopant having a narrower emission line shape is advantageous for achieving higher efficiency in an OLED device.
In one aspect, the present disclosure provides a composition having the formula Ir (L A* ) m (L B* ) n (L C* ) p A compound of (a);
wherein the method comprises the steps of
Each L A* 、L B* And L C* Are independently monoanionic bidentate ligands and are different from each other;
n and p are each independently 0, 1 or 2; m is 1 or 2; and m+n+p is 3;
L A* has E at 77K A Is the first triplet energy T of 1 ；
L B* Has E at 77K B Is the first triplet energy T of 1 ；
L C* Has E at 77K C Is the first triplet energy T of 1 ；
E A Less than E B And E is C In E B And E is C The existence of the above is the right;
L A comprises at least one pi-electron withdrawing group; and is also provided with
The compounds have an emission spectrum with a FWHM value of not more than 45 nm.
It is understood that as used herein, the free state of a ligand refers to a ligand of a compound in which the bond between the metal and the ligand is replaced with H. As used herein, FWHM refers to the full width half maximum of the electroluminescent spectrum. The free energy of the ligand and the FWHM of the spectrum can be measured/calculated by known methods, such as those disclosed in col.11, ll.1-66 and col.14, ll.23-67 of us patent No. 10,727,423B2, the entire contents of which are incorporated herein by reference.
In some embodiments, the compound has an emission spectrum with a FWHM value of no more than 40 nm. In some embodiments, the compound may have an emission spectrum with a FWHM value of no more than 37.5nm, or no more than 35.0nm, or no more than 32.5nm, or no more than 30.0nm, or no more than 27.5nm, or no more than 25.0nm, or no more than 22.5nm, or no more than 20.0nm, or no more than 17.5nm, or no more than 15.0nm, or no more than 12.5nm, or no more than 10.0 nm.
In some embodiments, E A Ratio E B And E is C As low as 0.25eV, as E B And E is C The presence of (3) is determined. In some embodiments, E A Ratio E B And E is C At most 0.24eV, or at most 0.23eV, or at most 0.22eV, or at most 0.21eV, or at most 0.20eV, or at most 0.19eV, or at most 0.18eV, or at most 0.17eV, or at most 0.16eV, or at most 0.15eV, or at most 0.14eV, or at most 0.13eV, or at most 0.12eV, or at most 0.11eV, or at most 0.10eV, or at most 0.09eV, or at most 0.08eV, or at most 0.07eV, or at most 0.06eV, or at most 0.05eV, or at most 0.04eV, or at most 0.03eV, in E B And E is C The presence of (3) is determined.
In some embodiments, the at least one pi-electron withdrawing group is selected from the group consisting of: CN, COCH 3 、CHO、COCF 3 、COOMe、COOCF 3 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、(R) 2 CCN、(R) 2 CCF 3 、CNC(CF 3 ) 2 、C(O)R、RC(CN) 2 、C(CN) 3 Pyridine, pyrimidine, pyrazine, pyridazine, triazine, oxazole, benzoxazole, thiazole, benzothiazole, imidazole, benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing cycloalkyl, cyano-containing aryl, and cyano-containing heteroaryl. In some embodiments, the at least one pi-electron withdrawing group is selected from the group of members identified above.
In some embodiments, the at least one pi electron withdrawing group is selected from CN, pyridine, pyrimidine, pyrazine, pyridazine, triazine, cyano-containing aryl, and cyano-containing heteroaryl.
In some embodiments, the electron withdrawing groups used herein may have a Hammett constant (Hammett constant) greater than 0. In some embodiments, the electron withdrawing group has a Hammett constant equal to or greater than 0.1, or greater than 0.2, or greater than 0.3, or greater than 0.4, or greater than 0.5, or greater than 0.6, or greater than 0.7, or greater than 0.8, or greater than 0.9, or greater than 1.0, or greater than 1.1.
In some embodiments, the pi electron deficient electron withdrawing group is selected from the group consisting of: CN, COCH 3 、CHO、COCF 3 、COOMe、COOCF 3 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R) 3 BRR', substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted or unsubstituted carbazoleSubstituted or unsubstituted pyridine, substituted or unsubstituted pyrimidine, substituted or unsubstituted pyrazine, substituted or unsubstituted pyridazine, substituted or unsubstituted triazine, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate group, Each of R, R e And R is f Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; wherein Y' is selected from the group consisting of: BR (BR) e 、NR e 、PR e 、O、S、Se、C＝O、S＝O、SO 2 、CR e R f 、SiR e R f And GeR e R f′ 。
In some embodiments, L A* A structure having the formula:wherein part a and part B are each independently a monocyclic or polycyclic fused ring structure comprising 5-membered and/or 6-membered carbocycles and/or heterocycles; r is R A And R is B Each independently represents a single substitution to a maximum allowable number of substitutions, or no substitution; each R is A And R is B Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, arylalkyl, alkoxy, aryloxy, aminoSilane, germane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; at least one R A Or R is B Comprises electron withdrawing groups or pi-electron deficient electron withdrawing groups; and any two substituents may join or condense to form a ring.
In some embodiments, part A or R A Comprising electron withdrawing groups or pi-electron deficient electron withdrawing groups. In some embodiments, part B or R B Comprising electron withdrawing groups or pi-electron deficient electron withdrawing groups. In some embodiments, part A or R A And part B or R B Comprising an electron withdrawing group. In some embodiments, part A or R A And part B or R B Comprising a pi electron-deficient electron withdrawing group.
In some embodiments, moiety a may be selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole-derived carbene, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthridine, fluorene, and aza variants thereof. In some embodiments, moiety B may be selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthridine, and fluorene. In some embodiments, moiety a may be selected from benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole-derived carbenes, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole, while moiety B may be selected from naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthridine, fluorene, and aza variants thereof. In some embodiments, moiety a and moiety B may each be independently selected from naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, dibenzofuran, dibenzothiophene, quinoxaline, phthalazine, phenanthridine, fluorene, and aza variants thereof.
In some embodiments, moiety a is an imidazole-derived carbene, imidazole, benzimidazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, pyrazole, pyrrole, oxazole, thiazole, selenazole, quinoline, isoquinoline, quinazoline, furopyridine, furopyrimidine, furopyridazine, thienopyridine, thienopyrimidine, thienopyridazine, benzoxazole, benzothiazole, benzoselenazole, aza-dibenzofuran, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, phenanthridine, fluorene, or an aza variant thereof.
In some embodiments, moiety a is an N-heterocyclic carbene, imidazole, benzimidazole, pyridine, pyrimidine, pyridazine, or pyrazine.
In some embodiments, part B is selected from the group consisting of the structures of the following list A1:
one of the dashed lines is attached to moiety a and the other is coordinated to Ir;
wherein X is 1 To X 12 Each independently is C or N;
wherein each Y B And Y B′ Independently selected from the group consisting of: BR (BR) e 、NR e 、PR e 、O、S、Se、C＝O、S＝O、SO 2 、CR e R f 、SiR e R f And GeR e R f ；
Each R is BB Independent and independentRepresents a single substitution to a maximum allowable number of substitutions, or no substitution;
R BB 、R e and R is f Each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, boron, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof;
At least one R BB Comprises electron withdrawing groups or pi-electron deficient electron withdrawing groups; and any two substituents may join or condense to form a ring.
In some embodiments, two R of each of the above structures BB Comprising electron withdrawing groups or pi-electron deficient electron withdrawing groups.
In some embodiments, L A* Selected from the group consisting of the following list A2:
wherein L is B* And L C* Each independently selected from the group consisting ofAnd the structure of list A2;
wherein T is selected from the group consisting of: B. al, ga and In;
wherein K is 1′ Is a direct bond or is selected from the group consisting of: NR (NR) e 、PR e O, S and Se;
wherein each Y 1 To Y 13 Independently selected from the group consisting of carbon and nitrogen;
wherein Y' is selected from the group consisting of: BR (BR) e 、NR e 、PR e 、O、S、Se、C＝O、S＝O、SO 2 、CR e R f 、SiR e R f And GeR e R f ；
Wherein R is e And R is f Can be fused or joined to form a ring;
wherein each R is a 、R b 、R c And R is d Can independently represent a single substitution to a maximum allowable number of substitutions, or no substitution;
wherein each R is a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e And R is f Independently hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; and is also provided with
Wherein R is a1 、R b1 、R c1 、R d1 、R a 、R b 、R c And R is d Any two of which may be fused or joined to form a ring or to form a multidentate ligand.
In some embodiments, L A* 、L B* And L C* Each independently selected from the group consisting of the structures of the following list A3:
Wherein R is a ′、R b ′、R c ′、R d ' and R e ' each independently represents zero substitution, a single substitution, or up to the maximum allowable number of substitutions to its associated ring;
wherein R is a ′、R b ′、R c ′、R d ' and R e ' each independently is hydrogen or a substituent selected from the group consisting of the general substituents as defined herein; and is also provided with
Wherein R is a ′、R b ′、R c ′、R d ' and R e Any two of the' may be fused or joined to form a ring or to form a multidentate ligand.
In some embodiments, the compound has a formula selected from the group consisting of: ir (L) A* )(L B* ) 2 、Ir(L A* ) 2 (L B* )、Ir(L A* ) 2 (L C* ) And Ir (L) A* )(L B* )(L C* )。
In some embodiments, the compound is selected from the group consisting of the structures of the following list A4:
wherein the method comprises the steps of
X 96 To X 99 Each independently is C or N;
each Y 100 Independently selected from the group consisting of: NR, O, S and Se;
R 10a 、R 20a 、R 30a 、R 40a and R is 50a Each independently represents a single substitution up to the maximum allowable number of substitutions, or no substitution;
R、R 10a 、R 11a 、R 12a 、R 13a 、R 20a 、R 30a 、R 40a 、R 50a 、R 60 、R 70 、R 97 、R 98 and R is 99 Each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boron, seleno, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and R, R 10a 、R 11a 、R 12a 、R 13a 、R 20a 、R 30a 、R 40a 、R 50a 、R 60 、R 70 、R 97 、R 98 And R is 99 At least one of which comprises an electron withdrawing group or a pi electron deficient electron withdrawing group; and is also provided with
Any two substituents may join or fuse to form a ring.
In some embodiments, the compound is selected from the group consisting of the structures of the following list A5:
in another aspect, the novel metal complexes comprise a multidentate (bidentate or higher) ligand that includes a DBX (dibenzofuran, dibenzothiophene, dibenzoselenophene, fluorene, etc.) structure substituted with an electron withdrawing group. Such complexes exhibit a narrower Electroluminescent (EL) spectral line shape than conventional products. The narrower linear shape of the dopant (e.g., green dopant) is critical to achieving the benefits of higher efficiency and greater color saturation in an OLED device.
In some embodiments, a composition comprising a first ligand L is provided A The compound of (C), the L A Has the structure of formula I:
in formula I:
part a is a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic and polycyclic fused ring systems is independently a 5-or 6-membered carbocyclic or heterocyclic ring;
k is selected from the group consisting of: direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) And Si (R) α )(R β )；
Z 1 And Z 2 Each independently is C or N;
X 1 to X 8 Each independently is C or N;
Y is selected from the group consisting of: BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr'C＝CR′R″、S＝O、SO 2 CR, CRR ', siRR ', and GeRR ';
R 1 、R 2 and R is 3 Each independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
at least one R 2 Or R is 3 Is a 5-or 6-membered heterocycle, substituted or unsubstituted, or is a moiety comprising a substituent selected from the group consisting of the following list of Electron Withdrawing Groups (EWGs): COR (continuous operation reactor) R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R′ Substituted or unsubstituted dibenzoboroles, substituted or unsubstituted carbazole, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially and fully fluorinated alkenyl, partially and fully fluorinated cycloalkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, and combinations thereof;
Each R is α 、R β 、R R 、R R′ 、R、R′、R″、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;
L A coordinated to a metal M selected fromA group consisting of: ir, rh, re, ru, os, pt, pd, ag, au and Cu;
the metal M can be coordinated with other ligands;
L A can be conjugated with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;
wherein any two substituents may join or fuse to form a ring.
In some embodiments, the formula Ir (L A* ) m (L B* ) n (L C* ) p The compound of (a) may be a first ligand L of formula I as described above A Is a compound of (a).
In some embodiments, if R 3 The substituents being heterocyclic, other R 3 The substituent is not F or CN.
In some embodiments, R 2 The substituent is not carbazole. In some embodiments, if moiety a is imidazole or pyridine, then R 2 The substituent is not carbazole.
In some embodiments, L A Does not compriseWherein X is O or S.
In some embodiments, the compound is not
In some embodiments, the compound does not include
In some embodimentsWherein each R is α 、R β 、R R 、R R′ 、R、R′、R″、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein. In some embodiments, each R α 、R β 、R R 、R R′ 、R、R′、R″、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of the more preferred general substituents defined herein. In some embodiments, each R α 、R β 、R R 、R R′ 、R、R′、R″、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of the most preferred general substituents defined herein.
In some embodiments, Z 1 Is N, and Z 2 Is C. In some embodiments, Z 1 Is C and Z 2 Is N. In some embodiments, Z 1 Is C and Z 2 Is C. At Z 1 In some embodiments of C, Z 1 Is a carbon olefinic carbon.
In some embodiments, K is a direct bond. In some embodiments, K is O. In some embodiments, K is S.
In some embodiments, K is N (R α )、P(R α ) Or B (R) α ). In some embodiments, K is C (R α )(R β ) Or Si (R) α )(R β )。
In some embodiments, part a is a single ring. In some embodiments, part a is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, and thiazole.
In some embodiments, moiety a is a polycyclic fused ring system. In some embodiments, part a is selected from the group consisting of: naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, aza-benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.
In some embodiments, moiety a is an aza-polycyclic fused ring system comprising one benzo ring with C replaced by N. In some such embodiments, N replacing C of the benzo ring is bonded to metal M.
In some embodiments, moiety a is selected from the group consisting of pyridine and benzimidazole.
In some embodiments, ring B is bonded to moiety a through a C atom.
In some embodiments, ring B is bonded to metal M through a C atom. In some embodiments, ring B is bonded to metal M through an N atom.
In some embodiments, X 1 To X 4 Each is C.
In some embodiments, moiety a is a polycyclic fused ring structure. In some embodiments, moiety a is independently a polycyclic fused ring structure comprising at least three fused rings. In some embodiments, the polycyclic fused ring structure has two 6 membered rings and one 5 membered ring. In some such embodiments, a 5-membered ring is fused to the ring coordinated to metal M, and a second 6-membered ring is fused to the 5-membered ring. In some embodiments, part a is selected from the group consisting of: dibenzofuran, dibenzothiophene, dibenzoselenophene, and aza variants thereof. In some such embodiments, moiety a may be independently further substituted at the ortho or meta position of the O, S or Se atom with a substituent selected from the group consisting of: deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some such embodiments, the aza variant contains only one N atom at position 6 (O, S or ortho to Se) and has a substituent at position 7 (O, S or meta to Se).
In some embodiments, moiety a is a polycyclic fused ring structure comprising at least four fused rings. In some embodiments, the polycyclic fused ring structure comprises three 6 membered rings and one 5 membered ring. In some such embodiments, a 5-membered ring is fused to a ring coordinated to metal M, a second 6-membered ring is fused to the 5-membered ring, and a third 6-membered ring is fused to the second 6-membered ring. In some such embodiments, the third 6-membered ring is further substituted with a substituent selected from the group consisting of: deuterium, fluorine, nitrile, alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, moiety a is a polycyclic fused ring structure comprising at least five fused rings. In some embodiments, the polycyclic fused ring structure comprises four 6 membered rings and one 5 membered ring or three 6 membered rings and two 5 membered rings. In some embodiments comprising two 5-membered rings, the 5-membered rings are fused together. In some embodiments comprising two 5-membered rings, the 5-membered rings are separated by at least one 6-membered ring. In some embodiments having one 5-membered ring, the 5-membered ring is fused to a ring coordinated to metal M, a second 6-membered ring is fused to the 5-membered ring, a third 6-membered ring is fused to the second 6-membered ring, and a fourth 6-membered ring is fused to the third 6-membered ring.
In some embodiments, moiety a is an aza form of the polycyclic fused ring described above. In some such embodiments, moiety a contains only one aza N atom. In some such embodiments, moiety a contains only two aza N atoms, which may be in one ring or in two different rings. In some such embodiments, the ring with the aza N atom is separated from the metal M atom by at least two other rings. In some such embodiments, the ring with the aza N atom is separated from the metal M atom by at least three other rings. In some such embodiments, each ortho to the aza N atom is substituted.
In some embodiments, X 1 To X 4 At least one of which is N. In some embodiments, X 1 To X 4 Only one of which is N.
In some embodiments, X 5 To X 8 Each is C. In some embodiments, X 5 To X 8 At least one of which is N. In some embodiments, X 5 To X 8 Only one of which is N.
In some embodiments, X 5 Is N. In some embodiments, X 6 Is N. In some embodiments, X 7 Is N. In some embodiments, X 8 Is N.
In some embodiments, Y is selected from the group consisting of: o, S and Se. In some embodiments, Y is O. In some embodiments, Y is S. In some embodiments, Y is Se.
In some embodiments, Y is selected from the group consisting of: BR, NR, PR and CR.
In some embodiments, Y is selected from the group consisting of: BRR ', CRR', siRR ', and GeRR'.
In some embodiments, Y is selected from the group consisting of: p (O) R, C = O, C = S, C =se, c=nr ', c=cr' R ", s=o and SO 2 。
In some embodiments, at least one R 1 Not hydrogen.
In some embodiments, at least one R 1 A cyclic moiety A1 selected from the group consisting of: cycloalkyl, aryl or heteroaryl, which may be further substituted. In some embodiments, at least one atom of cyclic moiety A1 adjacent to the bond to moiety a is substituted with a non-hydrogen moiety. In some embodiments, at least one atom of cyclic moiety A1 adjacent to the bond to moiety a is substituted with a moiety selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, at least one atom of cyclic moiety A1 adjacent to the bond to moiety a is substituted with an alkyl group comprising at least 3C atoms.
In some embodiments, each atom of cyclic moiety A1 adjacent to the bond to moiety a is substituted with a non-hydrogen moiety. In some embodiments, each atom of cyclic moiety A1 adjacent to the bond to moiety a is substituted with a moiety independently selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof. In some embodiments, each atom of cyclic moiety A1 adjacent to the bond to moiety a is substituted with a moiety that is independently an alkyl group comprising at least 3C atoms.
In some embodiments, at least one atom of cyclic moiety A1 that is not adjacent to the bond with moiety a is substituted with a non-hydrogen moiety. In some embodiments, at least one atom of cyclic moiety A1 that is not adjacent to a bond to moiety a is substituted with a moiety selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, and combinations thereof.
In some embodiments, at least one atom of cyclic moiety A1 that is not adjacent to the bond with moiety a is substituted with an alkyl group comprising at least 3C atoms. In some embodiments, at least one atom of cyclic moiety A1 that is not adjacent to the bond to moiety a is substituted with benzene or substituted benzene.
In some embodiments, cyclic moiety A1 is aryl or heteroaryl.
In some embodiments, the cyclic moiety A1 is a 6-membered ring. In some such embodiments, the atom para to the bond to moiety a is substituted with a moiety selected from the group consisting of: alkyl, cycloalkyl, aryl, heteroaryl, or combinations thereof. In some embodiments, cyclic moiety A1 is benzene.
In some embodiments, at least one R 2 Not hydrogen.
In some embodiments, at least one R 2 Is a substituent selected from the group consisting of: 5-or 6-membered heterocycles and structures in the EWG list as defined herein.
In some embodiments, at least one R 2 Substituents are 5-or 6-membered heterocycles containing at least two heteroatoms. In some such embodiments, each of the at least two heteroatoms is independently selected from N and O.
In some embodiments, at least one R 2 Substituents are 5-or 6-membered heterocycles containing at least three heteroatoms. In some such embodiments, the at least three heteroatoms are each independently selected from N, S and O.
In one embodiment, at least one R 2 The substituents are selected from the structures in the EWG list as defined herein.
In some embodiments, twoR 2 Joined or fused to form a ring.
In some embodiments, each R 2 Is hydrogen.
In some embodiments, at least one R 3 Not hydrogen. In some embodiments, at X 5 R at 3 Is not H. In some embodiments, at X 6 R at 3 Not hydrogen. In some embodiments, at X 7 R at 3 Not hydrogen. In some embodiments, at X 8 R at 3 Not hydrogen.
In some embodiments, at least one R 3 Is a substituent selected from the group consisting of: 5-membered heterocycles, 6-membered heterocycles, and structures in the EWG list as defined herein.
In some embodiments, at least one R 3 Substituents are 5-or 6-membered heterocycles containing at least two heteroatoms. In some such embodiments, the at least two heteroatoms are each independently selected from N and O.
In some embodiments, at least one R 3 Substituents are 5-or 6-membered heterocycles containing at least three heteroatoms. In some such embodiments, the at least three heteroatoms are each independently selected from N, S and O.
In some embodiments, at least one R 3 Substituents are 5-or 6-membered heterocycles containing at least three heteroatoms.
In some embodiments, at least one R 3 The substituents are selected from the structures in the EWG list as defined herein.
In some embodiments, two R 3 Joined or fused to form a ring.
In some embodiments, each R 3 Is hydrogen.
In some embodiments, ligand L A Selected from the group consisting of the structures of the following list 1:
wherein:
X 9 to X 17 Each independently is C or N;
when present, X 9 To X 13 At least one of which is N;
Y A selected from the group consisting of: BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr ', c=cr ' R ", s= O, SO 2 CR, CRR ', siRR ', and GeRR ';
R 4 represents a single substitution to a maximum allowable number of substitutions, or no substitution;
R W represents a single substitution to a maximum allowable number of substitutions;
each R is 4 Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;
Each R is W Independently selected from the group consisting of: substituted 5-membered heterocycles, unsubstituted 5-membered heterocycles, substituted 6-membered heterocycles, unsubstituted 6-membered heterocycles, and structures in the EWG list as defined herein.
In some embodiments, ligand L A Selected from the group consisting of the structures of the following list 2:
wherein: />
Y A Selected from the group consisting of: BR, BRR', N, NR, PR, P (O) R, O, S, se, S = O, SO 2 SiRR 'and GeRR';
R AA 、R BB and R is CC Each represents a single substitution to a maximum allowable number of substitutions, or no substitution;
each R is AA 、R BB 、R CC And R is NN Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein;
R BB and R is CC At least one of which is selected from the group consisting of the structures of the following list 3: r is R WW 、
Wherein the method comprises the steps of
X AA And X BB Each independently is C or N;
Y B selected from the group consisting of: BR, NR, O, S, se, CRR ', siRR ' and GeRR ';
R S is monosubstituted to the maximum allowable number of substitutions, or unsubstituted;
each R is N 、R S And R is O Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with
R WW Selected from the group consisting of structures in the EWG list as defined herein.
In the inclusion list 3In some embodiments of the structure, X AA Is that only X exists in the structure AA C, and X of those structures of List 3 of (C) AA And X BB Are all X in the structure AA And X BB C of those structures of (C).
In some embodiments of structures containing manifest 3, X AA Is N, and X BB Is the presence of X in the structure AA And X BB C of those structures of (C). In some embodiments of structures containing manifest 3, X AA Is C and X BB Is the presence of X in the structure AA And X BB N of those structures of (a).
In some embodiments including the structure of manifest 3, Y B Is O. In some embodiments including the structure of manifest 3, Y B Is S. In some embodiments including the structure of manifest 3, Y B Is NR.
In some embodiments including the structure of List 3, two R' s S The engagement forms a loop. In some embodiments including the structure of List 3, two R' s S Joining to form a ring system selected from the group consisting of: benzene, pyridine, pyrimidine, pyrazine, benzofuran, benzothiophene, indole, azabenzofuran, azabenzothiophene, and azaindole. In some embodiments including the structure of List 3, two R' s S Bonding to form a benzene ring, pyridine ring or benzofuran moiety.
In some embodiments, ligand L A Selected from the group consisting of L Ai (E A )(R K )(R L )(R M ) A group consisting of, wherein i is an integer from 1 to 86, E A Is a moiety selected from E1 to E140, and R K 、R L And R is M Each independently selected from R1 to R50; wherein L is A1 (E 1 )(R 1 )(R 1 )(R 1 ) To L A86 (E 140 )(R 50 )(R 50 )(R 50 ) Having the structure defined in the following list 4:
wherein R1 to R50 have the structure defined in the following list 5:
wherein E1 to E140 each have a structure defined in the following Table 6:
in some embodiments, the compound has the formula M (L A ) p (L B ) q (L C ) r Wherein L is B And L C Each being a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2; and p+q+r is the oxidation state of the metal M.
In some embodiments, the compound has a molecular structure selected from Ir (LA) 3 ，Ir(L A )(L B ) 2 ，Ir(L A ) 2 (L B )、Ir(L A ) 2 (L C ) And Ir (L) A )(L B )(L C ) A formula of the group consisting of; and wherein L is A 、L B And L C Different from each other.
In some embodiments, L B Is a substituted or unsubstituted phenylpyridine, and L C Is a substituted or unsubstituted acetylacetonate.
In some embodiments, the compound has the formula Pt (L A )(L B ) The method comprises the steps of carrying out a first treatment on the surface of the And wherein L is A And L B May be the same or different. In some such embodiments, L A And L B Ligation forms a tetradentate ligand.
In some embodiments, L B And L C Each independently selected from the group consisting of the structures of the following list 7:
Wherein:
t is selected from the group consisting of: B. al, ga and In;
K 1′ selected from the group consisting of: single bond, O, S, NR e 、PR e 、BR e 、CR e R f And SiR e R f ；
Y 1 To Y 13 Each independently selected from the group consisting of C and N;
y' is selected from the group consisting of: BR (BR) e 、BR e R f 、NR e 、PR e 、P(O)R e 、O、S、Se、C＝O、C＝S、C＝Se、C＝NR e 、C＝CR e R f 、S＝O、SO 2 、CR e R f 、SiR e R f And GeR e R f ；
R e And R is f Can be fused or joined to form a ring;
each R is a 、R b 、R c And R is d Independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R is f Each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with
R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c And R is d Any two substituents of (a) may be fused or joined to form a ring or to form a multidentate ligand.
In some embodiments, L B And L C Each independently selected from the group consisting of the structures of the following list 8:
wherein:
R a ′、R b ′、R c ′、R d ' and R e ' each independently represents zero substitution, a single substitution, or up to the maximum allowable number of substitutions to its associated ring;
R a ′、R b ′、R c ′、R d ', and R e ' each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with
R a ′、R b ′、R c ′、R d ' and R e The two substituents in' may be fused or joined to form a ring or to form a multidentate ligand.
In some embodiments, the compound has the formula Ir (L A ) 3 Ir (L) A )(L Bk ) 2 Ir (L) A ) 2 (L Bk ) Ir (L) A ) 2 (L Cj-I ) Or Ir (L) A ) 2 (L Cj-II ) Is characterized in that the structure of the (c) is that,
wherein L is A Is according to L described herein A The ligand of any one of the structures of (a) including list 1, list 2 and list 4, and L A1 (E 1 )(R 1 )(R 1 )(R 1 ) To L A86 (E 140 )(R 50 )(R 50 )(R 50 ) Is of a structure of (2);
wherein k is an integer from 1 to 474;
wherein j is an integer from 1 to 1416;
wherein each L Bk Having the structure defined in the following list 9:
wherein each L Cj-I With the basisIs of a structure of (2); and is also provided with
Each L Cj-II With basisWherein for L Cj-I And L Cj-II Each L of (3) Cj ，R 201 And R is 202 Each independently as defined in the following list 10:
wherein R is D1 To R D246 Has the structure shown in the following list 11:
in some embodiments, the compound is selected from only L Bk A group consisting of compounds corresponding to one of: l (L) B1 、L B2 、L B18 、L B28 、L B38 、L B108 、L B118 、L B122 、L B124 、L B126 、L B128 、L B130 、L B132 、L B134 、L B136 、L B138 、L B140 、L B142 、L B144 、L B156 、L B158 、L B160 、L B162 、L B164 、L B168 、L B172 、L B175 、L B204 、L B206 、L B214 、L B216 、L B218 、L B220 、L B222 、L B231 、L B233 、L B235 、L B237 、L B240 、L B242 、L B244 、L B246 、L B248 、L B250 、L B252 、L B254 、L B256 、L B258 、L B260 、L B262 、L B264 、L B265 、L B266 、L B267 、L B268 、L B269 And L B270 。
In some embodiments, the compound is selected from only L Bk A group consisting of compounds corresponding to one of: l (L) B1 、L B2 、L B18 、L B28 、L B38 、L B108 、L B118 、L B122 、L B126 、L B128 、L B132 、L B136 、L B138 、L B142 、L B156 、L B162 、L B204 、L B206 、L B214 、L B216 、L B218 、L B220 、L B231 、L B233 、L B237 、L B264 、L B265 、L B266 、L B267 、L B268 、L B269 And L B270 。
In some embodiments, the compound is selected from the group consisting of having L Cj-I Or L Cj-II A group consisting of compounds of ligands whose corresponding R 201 And R is 202 Defined as one of the following structures: r is R D1 、R D3 、R D4 、R D5 、R D9 、R D10 、R D17 、R D18 、R D20 、R D22 、R D37 、R D40 、R D41 、R D42 、R D43 、R D48 、R D49 、R D50 、R D54 、R D55 、R D58 、R D59 、R D78 、R D79 、R D81 、R D87 、R D88 、R D89 、R D93 、R D116 、R D117 、R D118 、R D119 、R D120 、R D133 、R D134 、R D135 、R D136 、R D143 、R D144 、R D145 、R D146 、R D147 、R D149 、R D151 、R D154 、R D155 、R D161 、R D175 R D190 、R D193 、R D200 、R D201 、R D206 、R D210 、R D214 、R D215 、R D21６ 、R D218 、R D219 、R D220 、R D227 、R D237 、R D241 、R D242 、R D245 And R is D246 。
In some embodiments, the compound is selected from the group consisting of having L Cj-I Or L Cj-II A group consisting of compounds of ligands whose corresponding R 201 And R is 202 Defined as one selected from the following structures: r is R D1 、R D3 、R D4 、R D5 、R D9 、R D10 、R D17 、R D22 、R D43 、R D50 、R D78 、R D116 、R D118 、R D133 、R D134 、R D135 、R D136 、R D143 、R D144 、R D145 、R D146 、R D149 、R D151 、R D154 、R D155 R D190 、R D193 、R D200 、R D201 、R D206 、R D210 、R D214 、R D215 、R D21６ 、R D218 、R D219 、R D220 、R D227 、R D237 、R D241 、R D242 、R D245 And R is D246 。
In some embodiments, the compound is selected from only those having the following relation to L Cj-I Those compounds of one of the structures in list 12 of ligands:
in some embodiments, L A Selected from the group consisting of structures of List 1, list 2, and List 4, and L B Selected from the group consisting of structures of list 7, list 8 and list 9. In some embodiments, L A Selected from the group consisting of structures of List 1, and L B Selected from the group consisting of the structures of manifest 9. In some embodiments, L A Selected from the group consisting of structures of List 2, and L B Selected from the group consisting of the structures of manifest 9. In some embodiments, L A Selected from list 4, and L B Selected from the group consisting of L Bk Is set forth in list 9, wherein n is an integer from 1 to 474.
In some embodiments, the compound may be Ir (L A ) 2 (L B ) Or Ir (L) A )(L B ) 2 . In some of these embodiments, L A May have formula I as defined herein. In some of these embodiments, L A May be selected from the group consisting of structures of manifest 1, manifest 2, and manifest 4 as defined herein. In some of these embodiments, L B May be selected from the group consisting of structures of manifest 7, manifest 8, and manifest 9 as defined herein.
In some of these embodiments, the compound can be Ir (L A ) 2 (L Bk )、Ir(L A )(L Bk ) 2 、Ir(L A )(L Bk )(L CJ-I ) Or Ir (L) A )(L Bk )(L CJ-II ). In some of these embodiments, the compound can be Ir (L Ai (E A )(R K )(R L )(R M )) 2 (L B )、Ir(L Ai (E A )(R K )(R L )(R M ))(L B ) 2 、Ir(L Ai (E A )(R K )(R L )(R M ))(L B )(L CJ-I ) Or Ir (L) Ai (E A )(R K )(R L )(R M ))(L B )(L CJ-II ). In some of these embodiments, the compound can be Ir (L Ai (E A )(R K )(R L )(R M )) 2 (L Bk )、Ir(L Ai (E A )(R K )(R L )(R M ))(L Bk ) 2 、Ir(L Ai (E A )(R K )(R L )(R M ))(L Bk )(L CJ-I ) Or Ir (L) Ai (E A )(R K )(R L )(R M ))(L Bk )(L CJ-II )。
In some embodiments, the compound is selected from the group consisting of the structures of list 13 below:
in some embodiments, a compound having the formula Ir (L A* ) m (L B* ) n (L C* ) p Or Ir (L) A ) p (L B ) q (L C ) r May be at least 30% deuterated, at least 40% deuterated, at least 50% deuterated, at least 60% deuterated, at least 70% deuterated, at least 80% deuterated, at least 90% deuterated, at least 95% deuterated, at least 99% deuterated, or 100% deuterated. As used herein, deuteration percentage has its ordinary meaning and includes the percentage of possible hydrogen atoms (e.g., hydrogen or deuterium sites) replaced by deuterium atoms.
In a compound having the formula Ir (L A* ) m (L B* ) n (L C* ) p Or M (L) A ) p (L B ) q (L C ) r In some embodiments of the heteroleptic compounds of (2), ligand L A* Or L A Having a first substituent R respectively I Wherein the first substituent R I Having a first atom a-I, said atoms being ligands L, respectively A* Or L A Is furthest from metal M among all atoms of (a). In addition, ligand L B* Or L B If present, has a second substituent R II Wherein the second substituent R Ⅱ Has a firstAtoms a-II, respectively, being ligands L B* Or L B Is furthest from metal M among all atoms of (a). In addition, ligand L C* Or L C If present, has a third substituent R III Wherein the third substituent R III Having first atoms a-III, said atoms being ligands L, respectively C* Or L C Is furthest from metal M among all atoms of (a).
In such heteroleptic compounds, the vector V can be defined D1 、V D2 And V D3 It is defined as follows. V (V) D1 Represents the direction from the metal M to the first atom a-I, and the vector V D1 Having a value D 1 Which represents a metal M and a first substituent R I a-I, the first atom a-I of the group. V (V) D2 Represents the direction from the metal M to the first atom a-II and the vector V D2 Having a value D 2 Which represents a metal M and a second substituent R Ⅱ a-II, the first atom a-II. V (V) D3 Represents the direction from the metal M to the first atom a-III, and the vector V D3 Having a value D 3 Which represents a metal M and a third substituent R III a-III, and a linear distance between the first atoms a-III.
In such heteroleptic compounds, a sphere is defined having a radius R, the center of which is the metal M, and the radius R is that which allows the sphere to enclose a group R other than a substituent R in the compound I 、R Ⅱ And R is III A minimum radius of all atoms of a portion of (a); and wherein D 1 、D 2 And D 3 At least one of which is larger than the radius r by at leastIn some embodiments, D 1 、D 2 And D 3 At least 2.9, 3.0, 4.3, 4.4, 5.2, 5.9, 7.3, 8.8, 10.3, 13.1, 17.6 or +.>
In some embodiments of such heteroleptic compounds, anThe compound has a transition dipole moment axis, and the transition dipole moment axis is aligned with a vector V D1 、V D2 And V D3 The angle between the transition dipole moment axis and the vector V is defined D1 、V D2 And V D3 At least one of the angles therebetween is less than 40 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 At least one of the angles therebetween is less than 30 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 At least one of the angles therebetween is less than 20 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 At least one of the angles therebetween is less than 15 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 At least one of the angles therebetween is less than 10 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 At least two of the angles therebetween are less than 20 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 At least two of the angles therebetween are less than 15 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 At least two of the angles therebetween are less than 10 °.
In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 All three angles therebetween are less than 20 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 All three angles therebetween are less than 15 °. In some embodiments, the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 All three angles therebetween are less than 10 °.
In some embodiments of such heteroleptic compounds, the compounds have a Vertical Dipole Ratio (VDR) of 0.33 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.30 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.25 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.20 or less. In some embodiments of such heteroleptic compounds, the compounds have a VDR of 0.15 or less.
Those of ordinary skill in the art will readily understand the meaning of the term transition dipole moment axis of a compound and the perpendicular dipole ratio of the compound. However, the meaning of these terms can also be found in U.S. patent No. 10,672,997, the disclosure of which is incorporated herein by reference in its entirety. In U.S. patent No. 10,672,997, the Horizontal Dipole Ratio (HDR) of a compound is discussed, rather than VDR. However, one skilled in the art will readily appreciate that vdr=1-HDR.
In some embodiments, the compound has formula II:
wherein:
M 1 is Pd or P t ；
Moieties E and F are each independently a single or multiple ring structure comprising 5-and/or 6-membered carbocycles or heterocycles;
Z 1′ and Z 2′ Each independently is C or N;
K 1 and K 2 Each independently selected from the group consisting of: direct bond, O and S, K, K 1 And K 2 At least one of which is a direct bond;
L 1 、L 2 and L 3 Each independently selected from the group consisting of: direct bond, BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr, c=crr', s= O, SO 2 CR, CRR ', siRR ', geRR ', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof, wherein L 1 And L 2 At least one of which is present;
R E and R is F Each independently represents zero substitution, mono substitution or to its associated ringUp to the maximum allowable number of substitutions;
R、R′、R E and R is F Each independently is hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with
Where chemically feasible, any two R, R', R 1 、R 2 、R 3 、R E And R is F May be joined or fused together to form a ring.
In some embodiments, R, R', R E And R is F Each independently is hydrogen or a substituent selected from the group consisting of the preferred general substituents defined herein.
In some embodiments of formula II, both moieties E and F are 6 membered aromatic rings.
In some embodiments of formula II, moiety F is a 5-or 6-membered heteroaromatic ring.
In some embodiments of formula II, L1 is O or CRR'.
In some embodiments of formula II, Z 2′ Is N, and Z 1′ Is C. In some embodiments of formula II, Z 2′ Is C and Z 1′ Is N.
In some embodiments of formula II, L 2 Is a direct bond. In some embodiments of formula II, L 2 Is NR.
In some embodiments of formula II, K 1 And K 2 Are direct keys. In some embodiments of formula II, K 1 Or K 2 One of them is O.
In some embodiments of formula II, the compound is selected from the group consisting of compounds having formula Pt (L A′ ) A group consisting of compounds of (Ly):
wherein ligand L A′ Selected from the group consisting of L A′i′ (E A )(R K )(R L )(R M ) A group consisting of, wherein i' is an integer from 1 to 69, E A Is selected from E1 to E140, and R K 、R L And R is M Each independently selected from R1 to R50; wherein L is A′1 (E 1 )(R 1 )(R 1 )(R 1 ) To L A′69 (E 140 )(R 50 )(R 50 )(R 50 ) Having the structure defined in the following list 14:
wherein L is y Selected from the group consisting of L y j- (Rs) (Rt) (Ru) wherein j is an integer from 1 to 42, s, t and u are each independently an integer from 1 'to 128', and wherein L,1- (R1 ') (R1 ') (R1 ') to L y 42- (R128 ') (R128 ') (R128 ') are each defined by the structure of the following list 15:
wherein R1 to R50 have the structure defined in list 5 as defined herein; wherein E1 to E140 have the structure defined in list 6 as defined herein; wherein R1 'to R128' have the structure in the following list 16:
in some embodiments, the compound is selected from the group consisting of the structures of list 17 below:
in some embodiments, the compounds described herein have the lowest triplet (T1) excited state, metal-ligand charge transfer 3 Ligand-centered involved in MLCT percentages (P1) and T1 states 3 Percentage of LC (P2); wherein P2 is equal to or greater than 55%. In some embodiments, P2 is equal to or greater than 57%. In some embodiments, P2 is equal to or greater than 59%. In some embodiments, P2 is equal to or greater than 61%. The parameter T is defined as the product of P1 and P2 (t=p1×p2). In some embodiments, T is equal to or greater than 0.095. In some embodiments, T is equal to or greater than 0.100. In some embodiments, T is equal to or greater than 0.105. In some embodiments, T is equal to or greater than 0.110.
DFT calculation was performed to determine the energy of the lowest triplet (T1) excitation state of the compound and the metal-ligand charge transfer [ ] 3 MLCT) percentages P1 and T1 involving ligand-centered 3 LC) percent P2. Data was collected using the program Gaussian 16. The geometry was optimized using the B3LYP functional set and the CEP-31G set. The excited state energy is calculated by TDDFT with optimized ground state geometry. The THF solvent was simulated using a self-consistent reaction field to further improve consistency with the experiment. Determination of metal-ligand charge transfer by transition density matrix analysis of excited states 3 MLCT) composition and ligand-centered 3 LC).
The calculated values obtained using the DFT functional groups and the base groups identified above are theoretical values. Computing a combined protocol, such as Gaussian16 using the B3LYP and CEP-31G protocols as used herein, relies on the following assumptions: the electronic effects are additive and thus can be extrapolated to Complete Basis Set (CBS) limits using larger basis sets. However, when the aim of the study is to understand the changes in HOMO, LUMO, S1, T1, bond dissociation energy etc. of a range of structurally related compounds, the additive effect is expected to be similar. Thus, while the absolute error using B3LYP may be significant compared to other calculation methods, the relative differences between HOMO, LUMO, S1, T1 and bond dissociation energy values calculated using the B3LYP protocol are expected to reproduce the experiment well. See, for example, flood (Hong) et al, "chemistry of materials (chem. Mater.)", 2016, 28, 5791-98, 5792-93 and supplemental information (discussing reliability of DFT calculations in the case of OLED materials). Furthermore, with respect to iridium or platinum complexes that can be used in the OLED field, the data obtained from DFT calculations are closely related to the actual experimental data. See Tagasli et al, J.Material chemistry journal (J.Mater. Chem.) "2012, 22, 6419-29, 6422 (Table 3) (DFT calculations showing close correlation with actual data for various emissive complexes); mo Leiluo, g.r. (Morello, g.r.), "journal of molecular modeling (j.mol.model.))," 2017, 23:174 (various DFT functional and basis sets were studied and it was inferred that the combination of B3LYP with CEP-31G was particularly accurate for the emission complex). The determination of the excited state transition properties is performed as a post-processing step of the DFT and TDDFT calculations mentioned above. This analysis allows the breakdown of the excited state into holes (i.e., where the excitation originated) and electrons (i.e., the final position of the excited state); see Martin (Martin), "journal of chemical physics (J.chem. Phys.)" 2003, 118, 4775 (discussing the theoretical background and implementation of the natural transition trajectories). Furthermore, since this analysis is performed on the computed characteristics, it is objective and repeatable; see wheat (Mai) et al, review of coordination chemistry (Coord. Chem. Rev.) 2018, 361, 74-97 (discussing the theoretical basis for decomposition of excited states in transition metal complexes).
C. OLED and device of the present disclosure
In another aspect, the present disclosure also provides an OLED device comprising a first organic layer containing a compound disclosed in the compound section of the present disclosure above.
In some embodiments, an OLED comprises: an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer comprises a material having the formula Ir (L A* ) m (L B* ) n (L C* ) p Or a compound comprising a first ligand L A The first ligand L A Having the structure of formula I as described herein.
In some embodiments, the organic layer may be an emissive layer and the compound as described herein may be an emissive dopant or a non-emissive dopant.
In some embodiments, the emissive layer includes one or more quantum dots.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a triphenylene comprising a benzofused thiophene or benzofused furan, wherein any substituent in the host is a non-fused substituent independently selected from the group consisting of: c (C) n H 2n+1 、OC n H 2n+1 、OAr 1 、N(C n H 2n+1 ) 2 、N(Ar 1 )(Ar 2 )、CH＝CH-C n H 2n+1 、C≡CC n H 2n+1 、Ar 1 、Ar 1 -Ar 2 、C n H 2n -Ar 1 Or unsubstituted, wherein n is an integer from 1 to 10; and wherein Ar is 1 With Ar 2 Independently selected from the group consisting of: benzene, biphenyl, naphthalene, triphenylene, carbazole, and heteroaromatic analogs thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises at least one chemical group selected from the group consisting of: triphenylene, carbazole, indolocarbazole, dibenzothiophene, dibenzofuran, dibenzoselenophene, 5λ2-benzo [ d ] benzo [4,5] imidazo [3,2-a ] imidazole, 5, 9-dioxa-13 b-boronaphtho [3,2,1-de ] anthracene, triazine, boron group, silane group, azatriphenylene, azacarbazole, aza-indolocarbazole, aza-dibenzothiophene, aza-dibenzofuran, aza-dibenzoselenophene, aza-5λ2-benzo [ d ] benzo [4,5] imidazo [3,2-a ] imidazole and aza- (5, 9-dioxa-13 b-boronaphtho [3,2,1-de ] anthracene.
In some embodiments, the subject may be selected from the group of subjects consisting of:
and combinations thereof.
In some embodiments, the organic layer may further comprise a host, wherein the host comprises a metal complex.
In some embodiments, the emissive layer may include two bodies, a first body and a second body. In some embodiments, the first host is a hole transport layer and the second host is an electron transport layer. In some embodiments, the first host and the second host may form an exciplex.
In some embodiments, a compound as described herein may be a sensitizer; wherein the device may further comprise a recipient; and wherein the receptor may be selected from the group consisting of: fluorescent emitters, delayed fluorescent emitters, and combinations thereof.
In yet another aspect, the OLED of the present disclosure may further comprise an emissive region containing a compound as disclosed in the above compound portion of the present disclosure.
In some embodiments, the emissive region may comprise a light emitting device having the formula Ir (L A* ) m (L B* ) n (L C* ) p Or a compound comprising a first ligand L A The first ligand LA has the structure of formula I as described herein.
In some embodiments, at least one of the anode, cathode, or new layer disposed over the organic emissive layer serves as the enhancement layer. The enhancement layer includes a plasmonic material exhibiting surface plasmon resonance, the plasmonic material non-radiatively coupled to the emitter material and transferring excited state energy from the emitter material to a non-radiative mode of surface plasmon polaritons. The enhancement layer is disposed no further than a threshold distance from the organic emissive layer, wherein the emitter material has a total non-radiative decay rate constant and a total radiative decay rate constant due to the presence of the enhancement layer, and the threshold distance is where the total non-radiative decay rate constant is equal to the total radiative decay rate constant. In some embodiments, the OLED further comprises an outcoupling layer. In some embodiments, the outcoupling layer is disposed on the enhancement layer on an opposite side of the organic emissive layer. In some embodiments, the outcoupling layer is disposed on the opposite side of the emission layer from the enhancement layer, but is still able to outcouple energy from the surface plasmon mode of the enhancement layer. The outcoupling layer scatters energy from the surface plasmon polaritons. In some embodiments, this energy is scattered into free space as photons. In other embodiments, energy is scattered from surface plasmon modes of the device into other modes, such as, but not limited to, an organic waveguide mode, a substrate mode, or another waveguide mode. If the energy is scattered to the non-free space mode of the OLED, other outcoupling schemes may be incorporated to extract the energy into free space. In some embodiments, one or more intervening layers may be disposed between the enhancement layer and the outcoupling layer. Examples of intervening layers may be dielectric materials, including organic, inorganic, perovskite, oxides, and may include stacks and/or mixtures of these materials.
The enhancement layer alters the effective properties of the medium in which the emitter material resides, causing any or all of the following: reduced emissivity, altered emission linearity, altered emission intensity with angle, altered emitter material stability, altered OLED efficiency, and reduced OLED device roll-off efficiency. Placing the enhancement layer on the cathode side, the anode side, or both sides creates an OLED device that takes advantage of any of the effects described above. In addition to the specific functional layers mentioned herein and illustrated in the various OLED examples shown in the figures, an OLED according to the present disclosure may also include any other functional layers common in OLEDs.
The enhancement layer may comprise a plasmonic material, an optically active super-structured material or a hyperbolic super-structured material. As used herein, a plasmonic material is a material in which the real part of the dielectric constant crosses zero in the visible or ultraviolet region of the electromagnetic spectrum. In some embodiments, the plasmonic material comprises at least one metal. In such embodiments, the metal may include at least one of the following: ag. Al, au, ir, pt, ni, cu, W, ta, fe, cr, mg, ga, rh, ti, ru, pd, in, bi, ca, alloys or mixtures of these materials, and stacks of these materials. Generally, a metamaterial is a medium composed of different materials, wherein the overall effect of the medium is different from the sum of its material portions. In particular, we define an optically active super-structured material as a material having both negative permittivity and negative permeability. On the other hand, hyperbolic metamaterials are anisotropic media in which the permittivity or permeability has different signs for different spatial directions. Optically active and hyperbolic metamaterials are very different from many other photonic structures, such as distributed Bragg reflectors (Distributed Bragg Reflector, "DBRs"), because the medium should exhibit uniformity in the direction of propagation over the length scale of the wavelength of light. Using terms that will be understood by those skilled in the art: the dielectric constant of a metamaterial in the propagation direction can be described by an effective dielectric approximation. Plasmonic and super-structured materials provide a method for controlling light propagation that can enhance OLED performance in a variety of ways.
In some embodiments, the enhancement layer is provided as a planar layer. In other embodiments, the enhancement layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the wavelength-sized features and the sub-wavelength-sized features have sharp edges.
In some embodiments, the outcoupling layer has wavelength-sized features that are periodically, quasi-periodically, or randomly arranged, or sub-wavelength-sized features that are periodically, quasi-periodically, or randomly arranged. In some embodiments, the outcoupling layer may be composed of a plurality of nanoparticles, and in other embodiments, the outcoupling layer is composed of a plurality of nanoparticles disposed over the material. In these embodiments, the outcoupling may be adjusted by at least one of the following means: changing the size of the plurality of nanoparticles, changing the shape of the plurality of nanoparticles, changing the material of the plurality of nanoparticles, adjusting the thickness of the material, changing the refractive index of the material or an additional layer disposed on the plurality of nanoparticles, changing the thickness of the reinforcing layer, and/or changing the material of the reinforcing layer. The plurality of nanoparticles of the device may be formed from at least one of: a metal, a dielectric material, a semiconductor material, a metal alloy, a mixture of dielectric materials, a stack or layering of one or more materials and/or a core of one type of material and a shell coated with another type of material. In some embodiments, the outcoupling layer is composed of at least metal nanoparticles, wherein the metal is selected from the group consisting of: ag. Al, au, ir, pt, ni, cu, W, ta, fe, cr, mg, ga, rh, ti, ru, pd, in, bi, ca, alloys or mixtures of these materials, and stacks of these materials. The plurality of nanoparticles may have additional layers disposed over them. In some embodiments, the polarization of the emission may be adjusted using an outcoupling layer. Changing the size and periodicity of the outcoupling layer may select the type of polarization that preferentially outcouples to air. In some embodiments, the outcoupling layer also serves as an electrode of the device.
In yet another aspect, the present disclosure also provides a consumer product comprising an Organic Light Emitting Device (OLED) having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a compound as disclosed in the above compound section of the disclosure.
In some embodiments, the consumer product comprises an OLED having an anode; a cathode; and an organic layer disposed between the anode and the cathode, wherein the organic layer may comprise a material having the formula Ir (L A* ) m (L B* ) n (L C* ) p Or a compound comprising a first ligand L A The first ligand L A Having the structure of formula I as described herein.
In some embodiments, the consumer product may be one of the following products: flat panel displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, laser printers, telephones, cellular telephones, tablet computers, tablet handsets, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays with a diagonal of less than 2 inches, 3-D displays, virtual or augmented reality displays, vehicles, video walls comprising a plurality of displays tiled together, theatre or gym screens, phototherapy devices, and billboards.
In general, an OLED includes at least one organic layer disposed between and electrically connected to an anode and a cathode. When a current is applied, the anode injects holes and the cathode injects electrons into the organic layer. The injected holes and electrons each migrate toward the oppositely charged electrode. When an electron and a hole are localized on the same molecule, an "exciton" is formed, which is a localized electron-hole pair having an excited energy state. Light is emitted when the exciton relaxes through a light emission mechanism. In some cases, excitons may be localized on an excimer or exciplex. Non-radiative mechanisms (such as thermal relaxation) may also occur, but are generally considered undesirable.
Several OLED materials and configurations are described in U.S. patent nos. 5,844,363, 6,303,238, and 5,707,745, which are incorporated herein by reference in their entirety.
Initial OLEDs used emissive molecules that emitted light ("fluorescence") from a singlet state, as disclosed, for example, in U.S. patent No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission typically occurs in time frames less than 10 nanoseconds.
Recently, OLEDs have been demonstrated that have emissive materials that emit light from a triplet state ("phosphorescence"). Baldo et al, "efficient phosphorescent emission from organic electroluminescent devices (Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices)", nature, volume 395, 151-154, 1998 ("Baldo-I"); and Bardo et al, "Very efficient green organic light emitting device based on electrophosphorescence (Very high-efficiency green organic light-emitting devices based on electrophosphorescence)", applied physical fast report (appl. Phys. Lett.), vol.75, stages 3,4-6 (1999) ("Bardo-II"), incorporated by reference in its entirety. Phosphorescence is described in more detail in U.S. Pat. No. 7,279,704, columns 5-6, which is incorporated by reference.
Fig. 1 shows an organic light emitting device 100. The figures are not necessarily drawn to scale. The device 100 may include a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron blocking layer 130, an emissive layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, a cathode 160, and a blocking layer 170. Cathode 160 is a composite cathode having a first conductive layer 162 and a second conductive layer 164. The device 100 may be fabricated by depositing the layers in sequence. The nature and function of these various layers and example materials are described in more detail in U.S. Pat. No. 7,279,704 at columns 6-10, which is incorporated by reference.
Further examples of each of these layers are available. 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. 2003/0239980, which is incorporated by reference in its entirety. Examples of luminescent and host materials are disclosed in U.S. Pat. No. 6,303,238 to Thompson et al, which is incorporated by reference in its entirety. An example of an n-doped electron transport layer is BPhen doped with Li in a 1:1 molar ratio, 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, that include composite cathodes having a thin layer of metal (e.g., mg: ag) containing an overlying transparent, electrically conductive, sputter-deposited ITO layer. Barrier The theory and use of layers is 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 implanted 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.
Fig. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 215, an emissive layer 220, a hole transport layer 225, and an anode 230. The device 200 may be fabricated by depositing the layers in sequence. Because the most common OLED configuration has a cathode disposed above an anode, and the device 200 has a cathode 215 disposed below an anode 230, the device 200 may be referred to as an "inverted" OLED. Materials similar to those described with respect to device 100 may be used in the corresponding layers of device 200. Fig. 2 provides one example of how some layers may be omitted from the structure of the apparatus 100.
The simple layered structure illustrated in fig. 1 and 2 is provided by way of non-limiting example, and it should be understood that embodiments of the present disclosure may be used in conjunction with a variety of other structures. The specific materials and structures described are exemplary in nature, and other materials and structures may be used. Functional OLEDs may be obtained by combining the various layers described in different ways, or the layers may be omitted entirely based on design, performance, and cost factors. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Although many of the examples provided herein describe the various layers as comprising a single material, it should be understood that combinations of materials may be used, such as mixtures of host and dopant, or more generally, mixtures. Further, the layers may have various sublayers. The names given to the various layers herein are not intended to be strictly limiting. For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as a hole transport layer or a hole injection layer. In one embodiment, an OLED may be described as having an "organic layer" disposed between a cathode and an anode. This organic layer may comprise a single layer, or may further comprise multiple layers of different organic materials as described, for example, with respect to fig. 1 and 2.
Structures and materials not specifically described, such as OLEDs (PLEDs) comprising polymeric materials, such as disclosed in frank (Friend) et al, U.S. patent No. 5,247,190, which is incorporated by reference in its entirety, may also be used. By way of another example, an OLED with a single organic layer may be used. The OLEDs can be stacked, for example, as described in U.S. patent No. 5,707,745 to Forrest et al, which is incorporated by reference in its entirety. The OLED structure may deviate from the simple layered structure illustrated in fig. 1 and 2. For example, the substrate may include an angled reflective surface to improve out-coupling, such as a mesa structure as described in U.S. Pat. No. 6,091,195 to Furster et al, and/or a pit structure as described in U.S. Pat. No. 5,834,893 to Boolean et al, which are incorporated by reference in their entirety.
Any of the layers of the various embodiments may be deposited by any suitable method unless otherwise specified. Preferred methods for the organic layer include thermal evaporation, ink jet (as described in U.S. Pat. Nos. 6,013,982 and 6,087,196, incorporated by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Pat. No. 6,337,102, incorporated by reference in its entirety, furster et al), and deposition by organic vapor jet printing (OVJP, also known as Organic Vapor Jet Deposition (OVJD)), as described in U.S. Pat. No. 7,431,968, incorporated by reference in its entirety. Other suitable deposition methods include spin-coating and other solution-based processes. The solution-based process is preferably carried out under nitrogen or an inert atmosphere. For other layers, the preferred method includes thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (as described in U.S. patent nos. 6,294,398 and 6,468,819, incorporated by reference in their entirety), and patterning associated with some of the deposition methods such as inkjet and Organic Vapor Jet Printing (OVJP). Other methods may also be used. The material to be deposited may be modified to suit the particular deposition method. For example, substituents such as alkyl and aryl groups that are branched or unbranched and preferably contain at least 3 carbons can be used in small molecules to enhance their ability to withstand solution processing. Substituents having 20 carbons or more may be used, and 3 to 20 carbons are a preferred range. A material with an asymmetric structure may have better solution processibility than a material with a symmetric structure because an asymmetric material may have a lower tendency to recrystallize. Dendrimer substituents may be used to enhance the ability of small molecules to undergo solution processing.
Devices fabricated according to embodiments of the present disclosure may further optionally include a barrier layer. One purpose of the barrier layer is to protect the electrodes and organic layers from harmful substances exposed to the environment including moisture, vapors and/or gases, etc. The barrier layer may be deposited on the substrate, electrode, under or beside the substrate, electrode, or on any other portion of the device, including the edge. The barrier layer may comprise a single layer or multiple layers. The barrier layer may be formed by various known chemical vapor deposition techniques and may include a composition having a single phase and a composition having multiple phases. Any suitable material or combination of materials may be used for the barrier layer. The barrier layer may incorporate inorganic compounds or organic compounds or both. Preferred barrier layers comprise a mixture of polymeric and non-polymeric materials, as described in U.S. patent No. 7,968,146, PCT patent application No. PCT/US2007/023098, and PCT/US2009/042829, which are incorporated herein by reference in their entirety. To be considered as a "mixture", the aforementioned polymeric and non-polymeric materials that make up the barrier layer should be deposited under the same reaction conditions and/or simultaneously. The weight ratio of polymeric material to non-polymeric material may be in the range of 95:5 to 5:95. The polymeric material and the non-polymeric material may be produced from the same precursor material. In one example, the mixture of polymeric and non-polymeric materials consists essentially of polymeric silicon and inorganic silicon.
Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of electronic component modules (or units), which may be incorporated into a wide variety of electronic products or intermediate components. Examples of such electronic products or intermediate components include display screens, lighting devices (e.g., discrete light source devices or lighting panels), etc., that may be utilized by end user product manufacturers. The electronics assembly module may optionally include drive electronics and/or a power source. Devices manufactured in accordance with embodiments of the present disclosure may be incorporated into a wide variety of consumer products having one or more electronic component modules (or units) incorporated therein. Disclosed is a consumer product comprising an OLED comprising a compound of the present disclosure in an organic layer in the OLED. The consumer product should include any kind of product that contains one or more light sources and/or one or more of some type of visual display. Some examples of such consumer products include flat panel displays, curved displays, computer monitors, medical monitors, televisions, billboards, lights for interior or exterior illumination and/or signaling, heads-up displays, fully or partially transparent displays, flexible displays, rollable displays, foldable displays, stretchable displays, laser printers, telephones, cellular telephones, tablet computers, tablet phones, personal Digital Assistants (PDAs), wearable devices, laptop computers, digital cameras, video cameras, viewfinders, micro-displays (displays with a diagonal of less than 2 inches), 3-D displays, virtual or augmented reality displays, vehicles, video walls including a plurality of tiled displays, theatre or gym screens, phototherapy devices, and signs. Various control mechanisms may be used to control devices manufactured in accordance with the present disclosure, including passive matrices and active matrices. Many of the devices are intended to be used in a temperature range that is comfortable for humans, such as 18 ℃ to 30 ℃, and more preferably at room temperature (20-25 ℃), but can be used outside this temperature range (e.g., -40 ℃ to +80 ℃).
Further details regarding OLEDs and the definitions described above can be found in U.S. patent No. 7,279,704, which is incorporated herein by reference in its entirety.
The materials and structures described herein may be applied in devices other than OLEDs. For example, other optoelectronic devices such as organic solar cells and organic photodetectors may employ the materials and structures. More generally, organic devices such as organic transistors may employ the materials and structures.
In some embodiments, the OLED has one or more features selected from the group consisting of: flexible, crimpable, collapsible, stretchable and bendable. In some embodiments, the OLED is transparent or translucent. In some embodiments, the OLED further comprises a layer comprising carbon nanotubes.
In some embodiments, the OLED further comprises a layer comprising a delayed fluorescent emitter. In some embodiments, the OLED includes an RGB pixel arrangement or a white plus color filter pixel arrangement. In some embodiments, the OLED is a mobile device, a handheld device, or a wearable device. In some embodiments, the OLED is a display panel having a diagonal of less than 10 inches or an area of less than 50 square inches. In some embodiments, the OLED is a display panel having a diagonal of at least 10 inches or an area of at least 50 square inches. In some embodiments, the OLED is an illumination panel.
In some embodiments, the compound may be an emissive dopant. In some embodiments, the compounds may produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as delayed fluorescence of type E, see, e.g., U.S. application No. 15/700,352, which is incorporated herein by reference in its entirety), triplet-triplet annihilation, or combinations of these processes. In some embodiments, the emissive dopant may be a racemic mixture, or may be enriched in one enantiomer. In some embodiments, the compounds may be homoleptic (identical for each ligand). In some embodiments, the compounds may be compounded (at least one ligand is different from the others). In some embodiments, when there is more than one ligand coordinated to the metal, the ligands may all be the same. In some other embodiments, at least one ligand is different from the other ligands. In some embodiments, each ligand may be different from each other. This is also true in embodiments where the ligand coordinated to the metal may be linked to other ligands coordinated to the metal to form a tridentate, tetradentate, pentadentate or hexadentate ligand. Thus, where the coordinating ligands are linked together, in some embodiments all of the ligands may be the same, and in some other embodiments at least one of the linking ligands may be different from the other ligand(s).
In some embodiments, the compounds may be used as a phosphor-photosensitizing agent in an OLED, where one or more layers in the OLED contain receptors in the form of one or more fluorescent and/or delayed fluorescent emitters. In some embodiments, the compound may be used as a component of an exciplex to be used as a sensitizer. As a phosphorus photosensitizer, the compound must be able to transfer energy to the acceptor and the acceptor will emit energy or further transfer energy to the final emitter. The receptor concentration may be in the range of 0.001% to 100%. The acceptor may be in the same layer as the phosphorus photosensitizer or in one or more different layers. In some embodiments, the receptor is a TADF emitter. In some embodiments, the acceptor is a fluorescent emitter. In some embodiments, the emission may be produced by any or all of the sensitizer, acceptor, and final emitter.
According to another aspect, a formulation comprising a compound described herein is also disclosed.
The OLEDs disclosed herein can be incorporated into one or more of consumer products, electronics assembly modules, and lighting panels. The organic layer may be an emissive layer, and the compound may be an emissive dopant in some embodiments, and the compound may be a non-emissive dopant in other embodiments.
In yet another aspect of the invention, a formulation comprising the novel compounds disclosed herein is described. The formulation may comprise one or more components disclosed herein selected from the group consisting of: a solvent, a host, a hole injection material, a hole transport material, an electron blocking material, a hole blocking material, and an electron transport material.
The present disclosure encompasses any chemical structure comprising the novel compounds of the present disclosure or monovalent or multivalent variants thereof. In other words, the compounds of the invention or monovalent or multivalent variants thereof may be part of a larger chemical structure. Such chemical structures may be selected from the group consisting of: monomers, polymers, macromolecules and supramolecules (also known as supramolecules). As used herein, "monovalent variant of a compound" refers to the same moiety as the compound but with one hydrogen removed and replaced with a bond to the rest of the chemical structure. As used herein, "multivalent variant of a compound" refers to a moiety that is identical to the compound but where more than one hydrogen has been removed and replaced with one or more bonds to the rest of the chemical structure. In the case of supramolecules, the compounds of the present invention may also be incorporated into supramolecular complexes without covalent bonds.
D. Combinations of compounds of the present disclosure with other materials
Materials described herein as suitable for use in particular 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 emissive dopants disclosed herein can be used in combination with a wide variety of hosts, transport layers, barrier layers, implant layers, electrodes, and other layers that may be present. The materials described or mentioned below are non-limiting examples of materials that may be used in combination with the compounds disclosed herein, and one of ordinary skill in the art may readily review the literature to identify other materials that may be used in combination.
a) Conductive dopants:
the charge transport layer may be doped with a conductive dopant to substantially change its charge carrier density, which in turn will change its conductivity. Conductivity is increased by the generation of charge carriers in the host material and, depending on the type of dopant, a change in Fermi level (Fermi level) of the semiconductor can also be achieved. The hole transport layer may be doped with a p-type conductivity dopant, and an n-type conductivity dopant is used in the electron transport layer.
Non-limiting examples of conductive dopants that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: EP01617493, EP01968131, EP2020694, EP2684932, US20050139810, US20070160905, US20090167167, US2010288362, WO06081780, WO2009003455, WO2009008277, WO2009011327, WO2014009310, US2007252140, US2015060804, US20150123047 and US2012146012.
b)HIL/HTL：
The hole injection/transport material used in the present disclosure is not particularly limited, and any compound may be used as long as the compound is generally used as a hole injection/transport material. Examples of materials include (but are not limited to): phthalocyanines or porphyrin derivatives; aromatic amine derivatives; indolocarbazole derivatives; a fluorocarbon-containing polymer; a polymer having a conductive dopant; conductive polymers such as PEDOT/PSS; self-assembled monomers derived from compounds such as phosphonic acids and silane derivatives; metal oxide derivatives, e.g. MoO x The method comprises the steps of carrying out a first treatment on the surface of the p-type semiconducting organic compounds such as 1,4,5,8,9, 12-hexaazatriphenylene hexacarbonitrile; a metal complex; a crosslinkable compound.
Examples of aromatic amine derivatives for the HIL or HTL include, but are not limited to, the following general structures:
Ar 1 to Ar 9 Is selected from: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, naphthalene, anthracene, a flower, phenanthrene, fluorene, pyrene, a,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipine Pyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, furodipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each Ar may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, ar 1 To Ar 9 Independently selected from the group consisting of:
wherein k is an integer from 1 to 20; x is X 101 To X 108 Is C (including CH) or N; z is Z 101 Is NAr 1 O or S; ar (Ar) 1 Having the same groups as defined above.
Examples of metal complexes used in the HIL or HTL include, but are not limited to, the following general formula:
wherein Met is a metal that may have an atomic weight greater than 40; (Y) 101 -Y 102 ) Is a bidentate ligand, Y 101 And Y 102 Independently selected from C, N, O, P and S; l (L) 101 Is an auxiliary ligand; k' is an integer value of 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.
In one aspect, (Y) 101 -Y 102 ) Is a 2-phenylpyridine derivative. In another aspect, (Y) 101 -Y 102 ) Is a carbene ligand. In another aspect, met is selected from Ir, pt, os, and Zn. In another aspect, the metal complex has a chemical structure as compared to an Fc + The minimum oxidation potential in solution of less than about 0.6V for Fc coupling.
Non-limiting examples of HIL and HTL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified with references disclosing those materials as follows: CN, DE, EP EP, JP07-, JP EP, EP JP07-, JP US, US US, WO US, US WO, WO.
c)EBL：
An Electron Blocking Layer (EBL) may be used to reduce the number of electrons and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking such a barrier layer. Furthermore, a blocking layer may be used to limit the emission to a desired area of the OLED. In some embodiments, the EBL material has a higher LUMO (closer to the vacuum level) and/or higher triplet energy than the emitter closest to the EBL interface. In some embodiments, the EBL material has a higher LUMO (closer to vacuum level) and/or higher triplet energy than one or more of the hosts closest to the EBL interface. In one aspect, the compound used in the EBL contains the same molecule or the same functional group as used in one of the hosts described below.
d) A main body:
the light-emitting layer of the organic EL device of the present disclosure preferably contains at least a metal complex as a light-emitting material, and may contain a host material using the metal complex as a dopant material. Examples of the host material are not particularly limited, and any metal complex or organic compound may be used as long as the triplet energy of the host is greater than that of the dopant. Any host material may be used with any dopant so long as the triplet criteria are met.
Examples of metal complexes used as hosts preferably have the general formula:
wherein Met is a metal; (Y) 103 -Y 104 ) Is a bidentate ligand, Y 103 And Y 104 Independently selected from C, N, O, P and S; l (L) 101 Is another ligand; k' is an integer value of 1 to the maximum number of ligands that can be attached to the metal; and k' +k "is the maximum number of ligands that can be attached to the metal.
In one aspect, the metal complex is:
wherein (O-N) is a bidentate ligand having a metal coordinated to the O and N atoms.
In another aspect, met is selected from Ir and Pt. In another aspect, (Y) 103 -Y 104 ) Is a carbene ligand.
In one aspect, the host compound contains at least one selected from the group consisting of: a group consisting of, for example, the following aromatic hydrocarbon cyclic compounds: benzene, biphenyl, triphenylene, tetramethylene, naphthalene, anthracene, flower, phenanthrene, fluorene, pyrene,Perylene and azulene; for example, the following aromatic impuritiesA group consisting of ring compounds: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furandipyridine, benzothiophenopyridine, thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine; and a group consisting of 2 to 10 cyclic structural units which are the same type or different types of groups selected from an aromatic hydrocarbon ring group and an aromatic heterocyclic group and are bonded to each other directly or via at least one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit, and an aliphatic ring group. Each option in each group may be unsubstituted or may be substituted with a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof.
In one aspect, the host compound contains in the molecule at least one of the following groups:
wherein R is 101 Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl,heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, and when it is aryl or heteroaryl, it has a similar definition as Ar mentioned above. k is an integer from 0 to 20 or from 1 to 20. X is X 101 To X 108 Independently selected from C (including CH) or N. Z is Z 101 And Z 102 Independently selected from NR 101 O or S.
Non-limiting examples of host materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: US, WO WO, WO-based US, WO WO, US, US and US,
e) Other emitters:
one or more other emitter dopants may be used in combination with the compounds of the present invention. Examples of other emitter dopants are not particularly limited, and any compound may be used as long as the compound is generally used as an emitter material. Examples of suitable emitter materials include, but are not limited to, compounds that can produce emissions via phosphorescence, fluorescence, thermally activated delayed fluorescence (i.e., TADF, also known as E-delayed fluorescence), triplet-triplet annihilation, or combinations of these processes.
Non-limiting examples of emitter materials that can be used in OLEDs in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN, EB, EP1239526, EP, JP, KR TW, US20010019782, US TW, US20010019782, US US, US US, WO US, US US, WO.
f)HBL：
A Hole Blocking Layer (HBL) may be used to reduce the number of holes and/or excitons that leave the emissive layer. The presence of such a barrier layer in a device may result in substantially higher efficiency and/or longer lifetime than a similar device lacking the barrier layer. Furthermore, a blocking layer may be used to limit the emission to a desired area of the OLED. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than the emitter closest to the HBL interface. In some embodiments, the HBL material has a lower HOMO (farther from the vacuum level) and/or higher triplet energy than one or more of the hosts closest to the HBL interface.
In one aspect, the compound used in the HBL contains the same molecules or the same functional groups as used in the host described above.
In another aspect, the compound used in the HBL contains in the molecule at least one of the following groups:
wherein k is an integer from 1 to 20; l (L) 101 Is another ligand, and k' is an integer from 1 to 3.
g)ETL：
An Electron Transport Layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped. Doping may be used to enhance conductivity. Examples of the ETL material are not particularly limited, and any metal complex or organic compound may be used as long as it is generally used to transport electrons.
In one aspect, the compounds used in ETL contain in the molecule at least one of the following groups:
wherein R is 101 Selected from the group consisting of: hydrogen, deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof, when aryl or heteroaryl, have similar definitions as for Ar described above. Ar (Ar) 1 To Ar 3 Has a similar definition to Ar mentioned above. k is an integer of 1 to 20. X is X 101 To X 108 Selected from C (including CH) or N.
In another aspect, the metal complex used in ETL contains (but is not limited to) the following formula:
wherein (O-N) or (N-N) is a bidentate ligand having a metal coordinated to atom O, N or N, N; l (L) 101 Is another ligand; k' is an integer value from 1 to the maximum number of ligands that can be attached to the metal.
Non-limiting examples of ETL materials that can be used in an OLED in combination with the materials disclosed herein are exemplified below along with references disclosing those materials: CN103508940, EP01602648, EP01734038, EP01956007, JP2004-022334, JP2005149918, JP2005-268199, KR0117693, KR20130108183, US20040036077, US20070104977, US2007018155, US20090101870, US20090115316, US20090140637, US20090179554, US2009218940, US2010108990, US2011156017, US2011210320, US2012193612, US2012214993, US2014014925, US2014014927, US20140284580, US6656612, US8415031, WO2003060956, WO2007111263, WO2009148269, WO2010067894, WO2010072300, WO2011074770, WO2011105373, WO2013079217, WO2013145667, WO2013180376, WO2014104499, WO2014104535,
h) Charge Generation Layer (CGL)
In tandem or stacked OLEDs, CGL plays a fundamental role in performance, consisting of n-doped and p-doped layers for injecting electrons and holes, respectively. Electrons and holes are supplied by the CGL and the electrode. Electrons and holes consumed in the CGL are refilled with electrons and holes injected from the cathode and anode, respectively; subsequently, the bipolar current gradually reaches a steady state. Typical CGL materials include n and p conductivity dopants used in the transport layer.
In any of the above mentioned compounds used in each layer of the OLED device, the hydrogen atoms may be partially or fully deuterated. The minimum number of hydrogen atoms of the deuterated compound is selected from the group consisting of: 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, 99% and 100%. Thus, any of the specifically listed substituents, such as (but not limited to) methyl, phenyl, pyridyl, and the like, can be in their non-deuterated, partially deuterated, and fully deuterated forms. Similarly, substituent classes (e.g., without limitation, alkyl, aryl, cycloalkyl, heteroaryl, etc.) can also be in their non-deuterated, partially deuterated, and fully deuterated forms.
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. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention. The invention as claimed may thus include variations of the specific examples and preferred embodiments described herein, as will be apparent to those skilled in the art. It should be understood that the various theories as to why the present invention works are not intended to be limiting.
E. Experimental data
Synthesis of materials
Synthesis of 4' -chloro-2 ' -fluoro-2-hydroxy- [1,1' -biphenyl ] -3-carbaldehyde
A mixture of (4-chloro-2-fluorophenyl) boric acid (19.43 g,111 mmol), 3-bromo-2-hydroxybenzaldehyde (16 g,80 mmol), palladium acetate (0.284 g, 2.3838 mmol) and SPhos (1.958 g,4.78 mmol) was suspended in toluene (640 ml) and water (128 ml), followed by N 2 Potassium phosphate (50.7 g,239 mmol) was added. Subsequently, the reaction mixture was heated to 95℃and maintained for 3 hours. After cooling, ethyl acetate (200 mL) and water (100 mL) were added with stirring. The organic layer was collected and the aqueous layer was extracted with ethyl acetate (100 mL). All solvents were removed and the residue was used in the next step without further purification.
Synthesis of 7-chlorodibenzo [ b, d ] furan-4-carbaldehyde
To 4' -chloro-2 ' -fluoro-2-hydroxy- [1,1' -biphenyl]To a solution of 3-formaldehyde (33 g,132 mmol) in DMF (200 ml) was added K 2 CO 3 (54.6 g, 399mmol). The reaction mixture was then heated to 70 ℃ and held for 20 hours. After cooling, the suspension was filtered and washed with ethyl acetate (150 mL). Next, the solution was washed with aqueous HCl (0.5M, 100 mL). The organic layer was collected and the solvent was removed. The residue was purified by flash chromatography using 100:0 to 85:15 heptane: purification with ethyl acetate afforded 17g of product.
Synthesis of 4-bromo-2, 6-diisopropyl-N- (2-nitrophenyl) aniline
By N 2 4-bromo-2, 6-diisopropylaniline (15 g,58.6 mmol), 1-bromo-2-nitrobenzene (13.01 g,64.4 mmol), dicyclohexyl (2 ',6' -dimethoxy- [1,1' -biphenyl) and the like were then purified by vacuum distillation]-2-yl) phosphine (1.923 g,4.68 mmol), pd 2 (dba) 3 (1.072g，1.171mmol)、Cs 2 CO 3 (38.2 g,117 mmol) in toluene (195 m 1) was degassed three times. The reaction mixture was stirred at 100 ℃ for 48 hours. The crude mixture was cooled and filtered in the presence of DCM. The residue was purified by flash chromatography using 5 to 7% ethyl acetate/heptane to give the desired compound as a yellow solid.
Synthesis of N- (4-bromo-2, 6-diisopropylphenyl) benzene-1, 2-diamine
To a solution of 4-bromo-2, 6-diisopropyl-N- (2-nitrophenyl) aniline (5.4 g,14.31 mmol) in ethanol (100 ml) was added ammonium chloride (2.71 g,50.1 mmol), water (50 ml) and iron (4.00 g,71.6 mmol). The reaction was heated in an oil bath set at 90 ℃. The reaction mixture was filtered and washed thoroughly with EtOAc. The filtrate was extracted with EtOAc and washed with brine, and the organic layer was dried over sodium sulfate, filtered, and concentrated to a purple oil. The crude product was purified using 75/25/5 to 60/30/10 heptane/DCM/THF to give 5.05g of the desired compound as a violet oil.
Synthesis of 2- (7-chlorodibenzo [ b, d ] furan-4-yl) -1- (3, 5-diisopropyll- [1,1' -biphenyl ] -4-yl) -1H-benzo [ d ] imidazole
To a solution of N1- (3, 5-diisopropyl- [1,1' -biphenyl ] -4-yl) benzene-1, 2-diamine (18.0 g,47.5 mmol) and 7-chlorodibenzo [ b, d ] furan-4-carbaldehyde (10.2 g,43.3 mmol) in DMF (300 mL) was added sodium bisulphite (45.0 g,432 mmol). The reaction mixture was heated at 120 ℃ for 90 hours, cooled to room temperature and diluted with water (500 mL). The solid was collected by filtration and washed with water (200 mL). The solid was washed with DCM (200 mL) and THF (100 mL), and the remaining pale orange solid was dissolved in DCM and purified by flash chromatography (0-100% THF/isohexane) to give 2- (7-chlorodibenzo [ b, d ] furan-4-yl) -1- (3, 5-diisopropyl- [1,1' -biphenyl ] -4-yl) -1H-benzo [ d ] imidazole (11.5 g,20.63mmol,44% yield) as a pale brown solid.
Synthesis of 1- (3, 5-diisopropyl- [1,1' -biphenyl ] -4-yl) -2- (7- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) dibenzo [ b, d ] furan-4-yl) -1H-benzo [ d ] imidazole
A250 mL 4-neck round bottom flask equipped with a thermocouple, stirring bar and condenser was charged with 2- (7-chlorodibenzo [ b, d) ]Furan-4-yl) -1- (3, 5-diisopropyl- [1,1' -biphenyl]-4-yl) -1H-benzo [ d ]]Imidazole (8.00 g,14.41mmol,1.0 eq), bis (pinacolato) diboron (5.49 g,21.6mmol,1.5 eq), potassium pivalate (5.05 g,36.03mmol,2.5 eq), 2- (dicyclohexylphosphino) -2',4',6' -tris (isopropyl) biphenyl (XPhos) (0.41 g,0.86mmol,0.06 eq) and 1, 4-dioxane (72 mL). Nitrogen was sparged into the reaction mixture for 10 minutes. Tris (dibenzylideneacetone) dipalladium (0) (0.40 g,0.43mmol,0.03 eq.) was added, followed by heating the reaction mixture at 85 ℃ for 4 hours. After cooling to room temperature, the reaction mixture was passed throughPad (50 g) was filtered and rinsed with ethyl acetate (600 mL). The filtrate was concentrated under reduced pressure. The crude product was purified by silica gel chromatography eluting with a 0 to 30% ethyl acetate/hexane gradient to give 1- (3, 5-diisopropyl- [1,1' -biphenyl) as a white amorphous solid]-4-yl) -2- (7- (4, 5-tetralin)Methyl-1, 3, 2-dioxaborolan-2-yl) dibenzo [ b, d]Furan-4-yl) -1H-benzo [ d ]]Imidazole (7.50 g,80% yield). />
Synthesis of 2- (7- (4-di-tert-butyl-1, 3, 5-triazin-2-yl) dibenzo [ b, d ] furan-4-yl) -1- (3, 5-diisopropyl- [1,1' -biphenyl ] -4-yl) -1H-benzo [ d ] imidazole
A250 mL 4-neck round bottom flask equipped with a thermocouple, stir bar, and condenser was charged with 1- (3, 5-diisopropyl- [1,1' -biphenyl ] -4-yl) -2- (7- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) dibenzo [ b, d ] furan-4-yl) -1H-benzo [ d ] imidazole (5.00 g,7.73mmol,1.0 eq.), 2, 4-di-tert-butyl-6-chloro-1, 3, 5-triazine (1.94 g,8.51mmol,1.1 eq.), potassium carbonate (2.67 g,19.33mmol,2.5 eq.), 1, 4-dioxane (58 mL), and water (20 mL). Nitrogen was sparged into the reaction mixture for 10 minutes. Tetrakis (triphenylphosphine) palladium (0) (0.45 g,0.39mmol,0.05 eq.) was added and the reaction mixture was then heated at 85 ℃ overnight. After cooling to room temperature, the reaction mixture was poured into ethyl acetate (500 mL) and the layers were separated. The organic layer was washed with saturated brine (100 mL), dried over sodium sulfate and concentrated under reduced pressure. The crude product was purified by silica gel chromatography eluting with a 0 to 15% ethyl acetate/hexanes gradient to give 2- (7- (4, 6-di-tert-butyl-1, 3, 5-triazin-2-yl) dibenzo [ b, d ] furan-4-yl) -1- (3, 5-diisopropyl- [1,1' -biphenyl ] -4-yl) -1H-benzo [ d ] imidazole (4.63 g,84% yield) as a white solid.
Synthesis of 2- (4-fluorophenyl) -4, 5-bis (methyl-d 3) pyridine
To a solution of 2-bromo-4, 5-bis (methyl-d 3) pyridine (8.0 g,41.6 mmol) and (4-fluorophenyl) (l 4-oxyalkyleneborane (6.45 g,52.1 mmol) in DME (210 ml) was added potassium carbonate (11.51g,83 mmol) and water (70.0 ml). The reaction was purged with nitrogen for 15 minutes, followed by the addition of Pd (PPh 3 ) 4 (1.93 g,1.67 mmol). The reaction was heated under nitrogen in an oil bath set at 95 ℃ for 36 hours. The reaction mixture was extracted with EtOAc, then the organic phase was washed 2 times with brine, dried over sodium sulfate, filtered and concentrated to give a purple solid. The purple solid was purified by column chromatography eluting with 50/47.5/2.5 to 50/40/10 DCM/heptane/EtOAc to give 6.8g of white solid as the desired product.
Di-mu-chloro-tetra [ kappa 2 (C2, N) -2- ((4-fluorobenzene-2' -yl) -4, 5-bis (methyl-d) 3 ) -pyridin-1-yl]Synthesis of Diiridium (III)
A500 mL 4-necked flask was charged with iridium (III) chloride hydrate (20.1 g,63.5mmol,1.0 eq.), 2-ethoxyethanol (280 mL), and deionized water (93 mL). Nitrogen was sparged into the reaction mixture for 10 minutes. Addition of 2- (4-fluorophenyl) -4, 5-bis (methyl-d) 3 ) Pyridine (29.0 g,140mmol,2.2 eq.) and the jet was continued for an additional 10 minutes. After heating at 102 ℃ for 2 days, the reaction was cooled to room temperature and the resulting suspension was filtered. The solid was washed with methanol (100 mL) and then dried under vacuum overnight at 50 ℃ to give di- μ -chloro-tetrakis [ κ2 (C2, N) -2- ((4-fluoroben-2' -yl) -4, 5-bis- (methyl-d) as a yellow solid 3 ) Pyridin-1-yl]Diiridium (III) (39.0 g,96% yield).
[ Ir (2- (5- (fluorobenzene-2-yl) -1' -yl) -4, 5-bis (methyl-d) 3 ) Pyridin-1-yl (-1H) 2 (MeOH) 2 ]Synthesis of trifluoromethane sulfonate
Into a 1L single neck flask was charged di- μ -chloro-tetrakis [ κ2 (C2, N) -2- (5- (fluoroben-2-yl) -1' -yl) -4, 5-bis- (methyl-d) 3 ) Pyridin-1-yl]Diiridium (III) (26.5 g,20.7mmol,1.0 eq.) and dichloromethane(345 mL). A solution of silver trifluoromethane sulfonate (11.2 g,43.5mmol,2.1 eq.) in methanol (69 mL) was added and the flask was wrapped with foil to protect from light. The reaction mixture was stirred at room temperature overnight. The reaction mixture was passed through the top containing(40g) Is filtered through silica gel (200 g) and rinsed with methylene chloride (2L). The filtrate was concentrated under reduced pressure and the residue was dried in vacuo at 50 ℃ for 2 hours to give [ Ir (2- (5- (fluoroben-2-yl) -1' -yl) -4, 5-bis (methyl-d) as a yellow solid 3 ) Pyridin-1-yl- (-1H) 2 (MeOH) 2 ]Trifluoromethane sulfonate (22.1 g,65% yield).
Synthesis of examples of the invention
A250 mL 4-neck round bottom flask equipped with a thermocouple, condenser, and stir bar was charged with [ Ir (2- ((5- (fluoroben-2-yl) -1' -yl) -4, 5-bis (methyl-d) 3 ) -pyridin-1-yl (-1H) 2 (MeOH) 2 ]Trifluoromethanesulfonate (4.00 g,4.89mmol,1.0 eq.) 2- (7- (4, 6-di-tert-butyl-1, 3, 5-triazin-2-yl) dibenzo [ b, d) ]-furan-4-yl) -1- (3, 5-diisopropyl- [1,1' -biphenyl]-4-yl) -1H-benzo [ d ]]Imidazole (3.48 g,4.89mmol,1.0 eq), 2, 6-lutidine (0.57 mL,4.89mmol,1.0 eq.) and diglyme (60 mL). After heating at 125 ℃ for 4 hours, the reaction was cooled to room temperature and concentrated under reduced pressure. The residue was triturated with dichloromethane (30 mL), filtered and the solid was washed with methanol (3 x 20 mL). A solution of the solid (about 3.1 g) in dichloromethane (200 mL) was filtered through a pad of silica gel (50 g) containing a pad of basic alumina (100 g) on top, eluting with dichloromethane (1.0L). The filtrate was concentrated under reduced pressure. The residue was dissolved in dichloromethane (130 ml,52 volumes) and precipitated with methanol (260 ml,100 volumes). The suspension was stirred for 30 min, filtered and the solid was washed with methanol (3×20 mL). The solid was dried under vacuum overnight at 50℃to give bis [2- (5- (fluorobenzene) as a yellow solid-2-yl) -1' -yl) -4,5- (methyl-d 3 ) Pyridin-1-yl]- [2- ((7- (4, 6-di-tert-butyl-1, 3, 5-triazin-2-yl) dibenzo [ b, d)]Furan-4-yl) -3 '-yl) -1- (3, 5-diisopropyl- [1,1' -biphenyl]-4-yl) -1H-benzo [ d ]]Imidazol-1-yl]Iridium (III) (1.34 g,21% yield). Based on the DFT data, this compound had 16.7% 3 MLCT and 66.7% 3 LC composition, whereas the comparative compound shown below has 15.8% 3 MLCT and 58.9% 3 LC composition.
All device examples pass through high vacuum @<10 -7 Tray) manufactured by thermal evaporation (VTE). The anode electrode beingIndium Tin Oxide (ITO). Cathode is made of->Is followed by->Al composition of (c). Immediately after manufacture, all devices were enclosed in a nitrogen glove box using an epoxy-sealed glass cover<1ppm H 2 O and O 2 ) And incorporating a desiccant into the package interior.
The organic stack of the device example consists of: starting from the ITO surface, it is in turn the layer (HIL) as hole injection layerIs used as a Hole Transport Layer (HTL)>Is used as Electron Blocking Layer (EBL)>Is used as an emitting layer (EML)>Is mixed with (C)H1 doped with 40 wt.% H2 and 5 wt.% emitter, and +.as Barrier Layer (BL)>H2 as Electron Transport Layer (ETL)>Liq (8-quinolinyl lithium) with 35% ETM. As used herein, HATCN, HTM, EBL, H, H2 and ETM have the following structures: />
After fabrication, the device was tested to measure EL and JVL. For this purpose, the sample was measured at 10mA/cm using a 2 channel Keysight B2902A SMU 2 Is energized and measured using a Photo Research PR735 spectroradiometer. Collecting the radiation of 380nm to 1080nm (W/str/cm) 2 ) And total integrated photon count. The device is then placed under a large area silicon photodiode for JVL scanning. Using the apparatus at 10mA/cm 2 The lower integrated photon count converts the photodiode current into a photon count. Scanning the voltage from 0 to 200mA/cm 2 Is set in the above-described voltage range. The EQE of the device is calculated using the total integrated photon count. All results are summarized in table 1. Voltage, LE, EQE, PE and LT of inventive example (device 1) 97％ Is reported as relative numbers normalized to the results of comparative example (device 2).
Table 1: at 10mA/cm 2 Inventive and comparative example device data measured at current densities of (c).
| Emitter body | Peak WL (nm) | FWHM(nm) | Voltage (relative value) | EQE (relative value) |
| Examples of the invention | 531 | 27 | 1.00 | 1.00 |
| Comparative example | 525 | 58 | 1.00 | 1.00 |
As the device results in table 1 show, the inventive examples exhibited significantly narrower line shapes (27 nm FWHM) while maintaining comparable performance in other respects. In general, the FWHM of phosphorescent emitter complexes is relatively broad. Achieving a narrow FWHM is a constantly pursuing goal. The narrower the FWHM, the better the color purity for display applications. As background information, an ideal line shape is a single wavelength (single line). This improvement is beyond any value attributable to experimental error, and the observed improvement is significant and unexpected.
Claims (15)
1. Comprises a first ligand L A The compound of (C), the L A Has the structure of formula I:
wherein:
part a is a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic and polycyclic fused ring systems is independently a 5-or 6-membered carbocyclic or heterocyclic ring;
k is selected from the group consisting of: direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) And Si (R) α )(R β )；
Z 1 And Z 2 Each independently is C or N;
X 1 to X 8 Each independently is C or N;
y is selected from the group consisting of: BR, BRR', NR, PR, P (O) R, O, S, se, C =O,
C＝S、C＝Se、C＝NR'、C＝CR'R"、S＝O、SO 2 CR, CRR ', siRR ', and GeRR ';
R 1 、R 2 and R is 3 Each independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
at least one R 2 Or R is 3 Is a 5-or 6-membered heterocycle, which is substituted or unsubstituted, or is a moiety comprising a substituent selected from the group consisting of: COR (continuous operation reactor) R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R ' substituted or unsubstituted dibenzoborole, substituted or unsubstituted carbazole, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, Ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially or fully fluorinated alkyl, partially or fully fluorinated alkenyl, partially or fully fluorinated cycloalkyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate groups, and combinations thereof;
each R is α 、R β 、R R 、R R '、R、R'、R"、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof;
L A coordinated to a metal M selected from the group consisting of: ir, rh, re, ru, os, pt, pd, ag, au and Cu;
the metal M can be coordinated with other ligands;
L A can be conjugated with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;
wherein any two substituents may join or fuse to form a ring;
With the proviso that if R 3 The substituents being heterocyclic, other R 3 The substituent is not F or CN;
with the proviso that if part A is imidazole or pyridine, R 2 The substituent is not carbazole;
with the proviso that L A Does not compriseWherein X is O or S; and is also provided with
With the proviso that the compound is not
2. Compound 1 according to claim 1, wherein Z 1 Is N, and Z 2 Is C; or Z is 1 Is C and Z 2 Is N; or Z is 1 Is C and Z 2 Is C; and/or
Wherein X is 1 To X 8 Each is C, or X 1 To X 8 At least one of which is N; and/or wherein Y is selected from the group consisting of: o, S, BR, NR, CRR ', siRR' and Se.
3. The compound of claim 1, wherein part a is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, triazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinoline, isoquinoline, quinazoline, benzofuran, aza-benzofuran, benzoxazole, aza-benzoxazole, benzothiophene, aza-benzothiophene, benzothiazole, benzoselenophene, aza-benzoselenophene, indene, aza-indene, indole, aza-indole, benzimidazole, aza-benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthrene, aza-phenanthrene, anthracene, aza-anthracene, phenanthridine, fluorene, and aza-fluorene.
4. The compound of claim 1, wherein at least one R 1 Is a cyclic moiety selected from the group consisting of: cycloalkyl, aryl or heteroaryl, which may be further substituted; and/or at least one R 2 Is a substituent selected from the group consisting of: 5-or 6-membered heterocycle, COR R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R ' substituted or unsubstituted dibenzoboroles, substituted or unsubstituted carbazole, substituted or unsubstituted oxazoles, substituted or unsubstituted benzoxazoles, substituted or unsubstituted thiazoles, substituted or unsubstituted benzothiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially or fully fluorinated alkyl, partially or fully fluorinated alkenyl, partially or fully fluorinated cycloalkyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, and combinations thereof; and/or
Wherein at least one R 3 Is a substituent selected from the group consisting of: 5-or 6-membered heterocycle, COR R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R ' substituted or unsubstituted dibenzoboroles, substituted or unsubstituted carbazole, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially or fully fluorinated alkyl, moietyA partially or fully fluorinated alkenyl group, a partially or fully fluorinated cycloalkyl group, a partially or fully fluorinated aryl group, a partially or fully fluorinated heteroaryl group, a cyano-containing alkyl group, a cyano-containing alkenyl group, a cyano-containing cycloalkyl group, a cyano-containing aryl group, a cyano-containing heteroaryl group, an isocyanate group, and combinations thereof.
5. The compound of claim 1, wherein the ligand L A Selected from the group consisting of:
wherein:
X 9 to X 17 Each independently is C or N;
when present, X 9 To X 13 At least one of which is N;
Y A selected from the group consisting of: BR, BRR ', NR, PR, P (O) R, O, S, se, C = O, C = S, C =se, c=nr ', c=cr ' R ", s= O, SO 2 CR, CRR ', siRR ', and GeRR ';
R 4 represents a single substitution to a maximum allowable number of substitutions, or no substitution;
R W represents a single substitution to a maximum allowable number of substitutions;
each R is 4 Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroarylA group, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof;
each R is W Independently selected from the group consisting of: substituted or unsubstituted 5-or 6-membered heterocycle, COR R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R ' substituted or unsubstituted dibenzoboroles, substituted or unsubstituted carbazole, substituted or unsubstituted oxazoles, substituted or unsubstituted benzoxazoles, substituted or unsubstituted thiazoles, substituted or unsubstituted benzothiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially or fully fluorinated alkyl, partially or fully fluorinated alkenyl, partially or fully fluorinated cycloalkyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, and combinations thereof.
6. The compound of claim 1, wherein the ligand L A Selected from the group consisting of:
wherein:
Y A selected from the group consisting of: BR, BRR', N, NR, PR, P (O) R, O, S, se, S = O, SO 2 SiRR 'and GeRR';
R AA 、R BB and R is CC Each represents a single substitution to a maximum allowable number of substitutions, or no substitution;
each R is AA 、R BB 、R CC And R is NN Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof;
R BB and R is CC At least one selected from the group consisting of:
R WW 、
wherein:
X AA and X BB Each independently is C or N;
Y B selected from the group consisting of: BR, NR, O, S, se, CRR ', siRR ' and GeRR ';
R S is monosubstituted to the maximum allowable number of substitutions, or unsubstituted;
each R is N 、R S And R is O Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof; and is also provided with
R WW Selected from the group consisting of: COR (continuous operation reactor) R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R ' substituted or unsubstituted dibenzoborole, substituted or unsubstituted carbazole, substituted or unsubstituted oxazole, substituted or unsubstituted benzoxazole, substituted or unsubstituted thiazole, substituted or unsubstituted benzothiazole, substituted or unsubstituted imidazole, substituted or unsubstituted benzimidazole, ketone, carboxylic acid, ester, nitrile, isonitrile, sulfinyl, sulfonyl, partially and fully fluorinated alkyl, partially or fully fluorinated alkenyl, partially or fully fluorinated cycloalkyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing arylHeteroaryl groups of cyano groups, isocyanate groups, and combinations thereof.
7. The compound of claim 1, wherein the ligand L A Selected from the group consisting of L Ai (E A )(R K )(R L )(R M ) A group consisting of, wherein i is an integer from 1 to 86, E A Is a moiety selected from E1 to E140, and R K 、R L And R is M Each independently selected from R1 to R50; wherein L is A1 (E 1 )(R 1 )(R 1 )(R 1 ) To L A86 (E 140 )(R 50 )(R 50 )(R 50 ) Has a structure defined as follows:
wherein R1 to R50 have the following structure:
Wherein E1 to E140 have the following structure:
8. the compound of claim 1, wherein the compound has the formula M (L A ) p (L B ) q (L C ) r Wherein L is B And L C Each is a bidentate ligand; and wherein p is 1, 2 or 3; q is 0, 1 or 2; r is 0, 1 or 2;
and p+q+r is the oxidation state of the metal M.
9. The compound of claim 8, wherein the compound has a formula selected from the group consisting of: ir (L) A ) 3 、Ir(L A )(L B ) 2 、Ir(L A ) 2 (L B )、Ir(L A ) 2 (L C ) And Ir (L) A )(L B )(L C ) The method comprises the steps of carrying out a first treatment on the surface of the And wherein L is A 、L B And L C Are different from each other; or Pt (L) A )(L B ) The method comprises the steps of carrying out a first treatment on the surface of the And wherein L is A And L B May be the same or different.
10. The compound of claim 8, wherein L B And L C Each independently selected from the group consisting of:
wherein:
t is selected from the group consisting of: B. al, ga and In;
K 1 ' selected from the group consisting of: single bond, O, S, NR e 、PR e 、BR e 、CR e R f And SiR e R f ；
Y 1 To Y 13 Each independently selected from the group consisting of C and N;
y' is selected from the group consisting of: BR (BR) e 、BR e R f 、NR e 、PR e 、P(O)R e 、O、S、Se、C＝O、
C＝S、C＝Se、C＝NR e 、C＝CR e R f 、S＝O、SO 2 、CR e R f 、SiR e R f And GeR e R f ；
R e And R is f Can be fused or joined to form a ring;
each R is a 、R b 、R c And R is d Independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R is f Each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, seleno alkyl, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is also provided with
R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c And R is d Any two substituents of (a) may be fused or joined to form a ring or to form a multidentate ligand.
11. The compound according to claim 8, wherein the compound has the formula Ir (L A ) 3 Ir (L) A )(L Bk ) 2 Ir (L) A ) 2 (L Bk ) Ir (L) A ) 2 (L Cj-I ) Or Ir (L) A ) 2 (L Cj-II ) Is of a structure of (2);
wherein k is an integer from 1 to 474;
wherein j is an integer from 1 to 1416;
wherein each L Bk Has a structure defined as follows:
wherein each L Cj-I With the basisIs of a structure of (2); and is also provided with
Each L Cj-II With the basisWherein for L Cj-I And L Cj-II Each L of (3) Cj ，R 201 And R is 202 As defined below:
wherein R is D1 To R D246 The structure is as follows:
12. the compound of claim 1, wherein the compound is selected from the group consisting of:
13. the compound of claim 8, wherein the compound has formula II:
wherein:
M 1 is Pd or Pt;
moieties E and F are each independently a single or multiple ring structure comprising 5-and/or 6-membered carbocycles or heterocycles;
Z 1 ' and Z 2 ' each independently is C or N;
K 1 and K 2 Each independently selected from the group consisting of direct bond, O and S, wherein K, K 1 And K 2 At least one of which is a direct bond;
L 1 、L 2 and L 3 Each independently selected from the group consisting of: direct bond, BR, BRR', NR,
PR、P(O)R、O、S、Se、C＝O、C＝S、C＝Se、C＝NR、C＝CRR'、S＝O、SO 2 、CR、
CRR ', siRR ', geRR ', alkylene, cycloalkyl, aryl, cycloalkylene, arylene, heteroarylene, and combinations thereof, wherein L 1 And L 2 At least one of which is present;
R E and R is F Each independently represents zero substitution, a single substitution, or up to the maximum allowable number of substitutions for its associated ring;
R、R'、R E and R is F Each independently is hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof; and is also provided with
Where chemically feasible, any two R, R', R 1 、R 2 、R 3 、R E And R is F May be joined or fused together to form a ring.
14. An organic light emitting device, comprising:
an anode;
a cathode; and
An organic layer disposed between the anode and the cathode, wherein the organic layer comprises a first ligand L A The first ligand L A Has the structure of formula I:
wherein:
part a is a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic and polycyclic fused ring systems is independently a 5-or 6-membered carbocyclic or heterocyclic ring;
K is selected from the group consisting of: direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) And Si (R) α )(R β )；
Z 1 And Z 2 Each independently is C or N;
X 1 to X 8 Each independently is C or N;
y is selected from the group consisting of: BR, BRR', NR, PR, P (O) R, O, S, se, C =O,
C＝S、C＝Se、C＝NR'、C＝CR'R"、S＝O、SO 2 CR, CRR ', siRR ', and GeRR ';
R 1 、R 2 and R is 3 Each independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
at least one R 2 Or R is 3 Is a 5-or 6-membered heterocycle, which is substituted or unsubstituted, or is a moiety comprising a substituent selected from the group consisting of: COR (continuous operation reactor) R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R ' substituted or unsubstituted dibenzoboroles, substituted or unsubstituted carbazole, substituted or unsubstituted oxazoles, substituted or unsubstituted benzoxazoles, substituted or unsubstituted thiazoles, substituted or unsubstituted benzothiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially or fully fluorinated alkyl, partially or fully fluorinated alkenyl, partially or fully fluorinated cycloalkyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, and combinations thereof;
Each R is α 、R β 、R R 、R R '、R、R'、R"、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof;
L A coordinated to a metal M selected from the group consisting of: ir, rh, re, ru, os, pt, pd, ag, au and Cu;
the metal M can be coordinated with other ligands;
L A can be conjugated with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;
wherein any two substituents may join or fuse to form a ring;
with the proviso that if R 3 The substituents being heterocyclic, other R 3 The substituent is not F or CN;
the limitation is thatIf part A is imidazole or pyridine, R 2 The substituent is not carbazole;
with the proviso that L A Does not compriseWherein X is O or S; and is also provided with
With the proviso that the compound is not
15. A consumer product comprising an organic light emitting device, the organic light emitting device comprising:
An anode;
a cathode; and
An organic layer disposed between the anode and the cathode, wherein the organic layer comprises a first ligand L A The first ligand L A Has the structure of formula I:
wherein:
part a is a monocyclic or polycyclic fused ring system, wherein each ring of the monocyclic and polycyclic fused ring systems is independently a 5-or 6-membered carbocyclic or heterocyclic ring;
k is selected from the group consisting of: direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) And Si (R) α )(R β )；
Z 1 And Z 2 Each independently is C or N;
X 1 to X 8 Each independently is C or N;
y is selected from the group consisting of: BR, BRR', NR, PR, P (O) R, O, S, se, C =O,
C＝S、C＝Se、C＝NR'、C＝CR'R"、S＝O、SO 2 CR, CRR ', siRR ', and GeRR ';
R 1 、R 2 and R is 3 Each independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
at least one R 2 Or R is 3 Is a 5-or 6-membered heterocycle, which is substituted or unsubstituted, or is a moiety comprising a substituent selected from the group consisting of: COR (continuous operation reactor) R 、CHO、COOR R 、NO 2 、SF 3 、SiF 3 、PF 4 、SF 5 、OCF 3 、SCF 3 、SeCF 3 、SOCF 3 、SeOCF 3 、SO 2 F、SO 2 CF 3 、SeO 2 CF 3 、OSeO 2 CF 3 、OCN、SCN、SeCN、NC、 + N(R R ) 3 、(R R ) 2 CCN、(R R ) 2 CCF 3 、CNC(CF 3 ) 2 、BR R R R ' substituted or unsubstituted dibenzoboroles, substituted or unsubstituted carbazole, substituted or unsubstituted oxazoles, substituted or unsubstituted benzoxazoles, substituted or unsubstituted thiazoles, substituted or unsubstituted benzothiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially or fully fluorinated alkyl, partially or fully fluorinated alkenyl, partially or fully fluorinated cycloalkyl, partially or fully fluorinated aryl, partially or fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing alkenyl, cyano-containing cycloalkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, and combinations thereof;
Each R is α 、R β 、R R 、R R '、R、R'、R"、R 1 、R 2 And R is 3 Independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, boron, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroarylAryl, acyl, carbonyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, germanyl, and combinations thereof;
L A coordinated to a metal M selected from the group consisting of: ir, rh, re, ru, os, pt, pd, ag, au and Cu;
the metal M can be coordinated with other ligands;
L A can be conjugated with other ligands to form tridentate, tetradentate, pentadentate or hexadentate ligands;
wherein any two substituents may join or fuse to form a ring;
with the proviso that if R 3 The substituents being heterocyclic, other R 3 The substituent is not F or CN;
with the proviso that if part A is imidazole or pyridine, R 2 The substituent is not carbazole;
with the proviso that L A Does not compriseWherein X is O or S; and provided that the compound is not +.>
Applications Claiming Priority (22)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63/332,165 | 2022-04-18 | ||
| US63/350,150 | 2022-06-08 | ||
| US63/351,049 | 2022-06-10 | ||
| US17/844,331 | 2022-06-20 | ||
| US63/353,920 | 2022-06-21 | ||
| US63/354,721 | 2022-06-23 | ||
| US63/356,191 | 2022-06-28 | ||
| US63/392,731 | 2022-07-27 | ||
| US63/406,019 | 2022-09-13 | ||
| US63/407,981 | 2022-09-19 | ||
| US63/408,357 | 2022-09-20 | ||
| US63/408,686 | 2022-09-21 | ||
| US63/417,746 | 2022-10-20 | ||
| US63/382,134 | 2022-11-03 | ||
| US18/058,461 | 2022-11-23 | ||
| US63/385,730 | 2022-12-01 | ||
| US63/385,994 | 2022-12-05 | ||
| US63/476,204 | 2022-12-20 | ||
| US63/481,143 | 2023-01-23 | ||
| US18/177,178 | 2023-03-02 | ||
| US18/297,781 | 2023-04-10 | ||
| US18/297,781 US20230337522A1 (en) | 2022-04-18 | 2023-04-10 | Organic electroluminescent materials and devices |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116903663A true CN116903663A (en) | 2023-10-20 |
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ID=88353790
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310416987.4A Pending CN116903663A (en) | 2022-04-18 | 2023-04-18 | Organic electroluminescent material and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116903663A (en) |
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