CN116903672A - Organic electroluminescent material and device - Google Patents
Organic electroluminescent material and device Download PDFInfo
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- CN116903672A CN116903672A CN202310430429.3A CN202310430429A CN116903672A CN 116903672 A CN116903672 A CN 116903672A CN 202310430429 A CN202310430429 A CN 202310430429A CN 116903672 A CN116903672 A CN 116903672A
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- 239000000463 material Substances 0.000 title abstract description 117
- 150000001875 compounds Chemical class 0.000 claims abstract description 230
- 239000003446 ligand Substances 0.000 claims abstract description 126
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 239000013598 vector Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000005281 excited state Effects 0.000 claims abstract description 20
- 125000001424 substituent group Chemical group 0.000 claims description 66
- 125000003118 aryl group Chemical group 0.000 claims description 57
- -1 amino, silyl Chemical group 0.000 claims description 55
- 125000001072 heteroaryl group Chemical group 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 44
- 229910052717 sulfur Inorganic materials 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 40
- 238000006467 substitution reaction Methods 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- 229910052760 oxygen Inorganic materials 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 31
- 239000012044 organic layer Substances 0.000 claims description 29
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 28
- 229910052805 deuterium Inorganic materials 0.000 claims description 25
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 22
- 125000003342 alkenyl group Chemical group 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 20
- 125000000304 alkynyl group Chemical group 0.000 claims description 18
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 18
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 17
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 17
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
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- 125000004104 aryloxy group Chemical group 0.000 claims description 15
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- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims description 15
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 15
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- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 13
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- 229910000085 borane Inorganic materials 0.000 claims description 11
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 10
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 claims description 9
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- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 8
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
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- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 3
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- 238000004378 air conditioning Methods 0.000 claims 2
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- 230000007704 transition Effects 0.000 abstract description 18
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- 239000002019 doping agent Substances 0.000 description 26
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- 239000000203 mixture Substances 0.000 description 18
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- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Natural products C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 13
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 125000005842 heteroatom Chemical group 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 238000004770 highest occupied molecular orbital Methods 0.000 description 11
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 150000003384 small molecules Chemical class 0.000 description 11
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 10
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 10
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- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 150000004696 coordination complex Chemical class 0.000 description 9
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 8
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 7
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- 238000000151 deposition Methods 0.000 description 7
- 125000000623 heterocyclic group Chemical group 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
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- 238000002347 injection Methods 0.000 description 7
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- 239000000243 solution Substances 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- WIUZHVZUGQDRHZ-UHFFFAOYSA-N [1]benzothiolo[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3SC2=C1 WIUZHVZUGQDRHZ-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
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 6
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 6
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- 125000004122 cyclic group Chemical group 0.000 description 6
- 230000003111 delayed effect Effects 0.000 description 6
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 6
- 239000011368 organic material Substances 0.000 description 6
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 6
- 125000003367 polycyclic group Chemical group 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
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- OBZNQOXNXVLYRM-UHFFFAOYSA-N 8,14-dioxa-1-borapentacyclo[11.7.1.02,7.09,21.015,20]henicosa-2,4,6,9(21),10,12,15,17,19-nonaene Chemical compound C1=CC=CC=2OC=3C=CC=C4OC=5C=CC=CC5B(C34)C12 OBZNQOXNXVLYRM-UHFFFAOYSA-N 0.000 description 2
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- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
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- 229910052770 Uranium Inorganic materials 0.000 description 1
- FBVBNCGJVKIEHH-UHFFFAOYSA-N [1]benzofuro[3,2-b]pyridine Chemical compound C1=CN=C2C3=CC=CC=C3OC2=C1 FBVBNCGJVKIEHH-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
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- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- QPJFIVIVOOQUKD-UHFFFAOYSA-N dipyrazino[2,3-f:2,3-h]quinoxaline Chemical group C1=CN=C2C3=NC=CN=C3C3=NC=CN=C3C2=N1 QPJFIVIVOOQUKD-UHFFFAOYSA-N 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
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- 125000002757 morpholinyl group Chemical group 0.000 description 1
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- 150000002829 nitrogen Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 1
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- 229910052763 palladium Inorganic materials 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
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 125000004585 polycyclic heterocycle group Chemical group 0.000 description 1
- 150000004033 porphyrin derivatives Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 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
- 238000012552 review 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
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-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
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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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0086—Platinum compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Abstract
The present application relates to organic electroluminescent materials and devices. Provides a formula M (L 1 )(L 2 ) x (L 3 ) y Which acts as an OLED emitter and has a peak wavelength emission energy. In the formula M (L) 1 )(L 2 ) x (L 3 ) y Wherein M is a metal atom; l (L) 1 、L 2 And L 3 Is a bidentate ligand; x is 1 or 2; y is 0 or 1; m (L) 1 ) 3 、M(L 2 ) 3 And M (L) 3 ) 3 Respectively have T 1 (L 1 )、T 1 (L 2 ) And T 1 (L 3 ) Is a first triplet excited state energy of (a); wherein T is 1 (L 1 )<T 1 (L 2 ) And when L is present 3 At the time T 1 (L 2 )≤T 1 (L 3 ). The compound has an energy gap parameter T of at least 0.13eV 1 (L 2 )‑T 1 (L 1 ) The method comprises the steps of carrying out a first treatment on the surface of the And is also provided withThe calculated angle between the rod axis and the transition dipole moment TDM vector is less than 20 degrees. Also provided are M (L) 1 * )(L 2 ) x (L 3 ) y Wherein the compound is defined herein.
Description
Cross reference to related applications
The present application continues to apply for portions of co-pending U.S. patent application Ser. No. 18/058,461, filed 11/23/2022, and U.S. patent application Ser. No. 18/177,178, filed 3/2023, the contents of which are incorporated herein by reference. The present application is based on 35U.S. C. ≡119 (e) requirement U.S. provisional application No. 63/481,143 submitted by 23.1.2023, U.S. provisional application No. 63/476,204 submitted by 20.12.2022, U.S. provisional application No. 63/385,994 submitted by 5.12.2022, U.S. provisional application No. 63/385,730 submitted by 1.12.2022, U.S. provisional application No. 63/382,134 submitted by 3.11.2022, U.S. provisional application No. 63/417,746 submitted by 20.10.20.2022, U.S. provisional application No. 63/408,686 submitted by 21.9.21.2022, U.S. provisional application No. 63/408,357 submitted by 9.20.2022 U.S. provisional application No. 63/407,981 filed on 9 and 19 of 2022, U.S. provisional application No. 63/406,019 filed on 9 and 13 of 2022, U.S. provisional application No. 63/392,731 filed on 7 and 27 of 2022, U.S. provisional application No. 63/356,191 filed on 6 and 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 and U.S. provisional application No. 63/332,165 filed on 18 of 2022 and 4, the entire contents of all of the above-referenced applications are incorporated herein by reference.
Technical Field
The present disclosure relates generally to 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
In one aspect, the present disclosure provides a compound of formula M (L 1 )(L 2 ) x (L 3 ) y Is a compound of (a). The compound is capable of functioning as an emitter in an organic light emitting device at room temperature and has a peak wavelength emission energy. For a compound having formula M (L 1 )(L 2 ) x (L 3 ) y Is a compound of formula (I):
m is a metal having an atomic mass of at least 40;
L 1 、L 2 and L 3 Is independently a bidentate ligand;
x is 1 or 2;
y is 0 or 1;
1+x+y is the oxidation state of the metal M;
L 1 、L 2 and L 3 Any of the followingA plurality of ligands engageable to form a tetradentate or hexadentate ligand;
if M is Ir, then the compound is a face (fac) complex;
the compound has a rod-like axis having a rod-like parameter (R R )；
The compound has a Transition Dipole Moment (TDM) vector forming an angle with the rod-like axis;
the calculated angle between the rod axis and the TDM vector is less than 20 degrees;
wherein ligand L 1 、L 2 And L 3 Each having a first triplet excited state energy T 1 (L 1 )、T 1 (L 2 )、T 1 (L 3 ) It is defined as corresponding to the trimodal compound M (L 1 ) 3 、M(L 2 ) 3 And M (L) 3 ) 3 Emits energy at a peak wavelength of (1), where T 1 (L 1 )<T 1 (L 2 ) And when y is 1, T 1 (L 2 )≤T 1 (L 3 )；
The compound has an energy gap parameter T of at least 0.13eV 1 (L 2 )-T 1 (L 1 ) The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with
One of the following is true:
(i) Peak emission wavelength is lower than 540nm, and R R Greater than 0.50; or (b)
(ii) A peak emission wavelength of at least 540nm, and R R Greater than 0.83.
In another aspect, the present disclosure provides a compound of formula M (L 1 * )(L 2 ) x (L 3 ) y Is a compound of (a).
In yet another aspect, the present disclosure provides a formulation comprising formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y Is a compound of (a).
In yet another aspect, the present disclosure provides an OLED having an organic layer, the organic layer comprisingThe organic layer comprises a compound of formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y Is a compound of (a).
In yet another aspect, the present disclosure provides a consumer product comprising an OLED having an organic layer comprising formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y 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.
FIG. 3 shows example compounds labeled with Transition Dipole Moment (TDM) vectors, rod axes, and angles therebetween.
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 "selenyloxy" 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" (germyl) refers to-Ge (R) s ) 3 A group wherein each R s May be the same or different.
The term "borane" refers to-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, siliconAlkyl, 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, phenalene, 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, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, seleno, 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, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, and combinations thereof.
In some cases, more preferably the general substituent is 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 2015,71,1425-30 and Azrote (Atzrodt) et al, germany application chemistry (Angew. Chem. Int. Ed.) (reviewed) 2007,46,7744-65, which is incorporated by reference in its entirety, describes the deuteration of methylene hydrogen in benzylamine and the efficient pathway of replacement of 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
The compounds described herein are the result of efforts to develop highly horizontally aligned emitter compounds in which complex T from ancillary ligands 1 The contribution of the emission (i.e., emission from the first triplet excited state) remains as close to zero as possible while the emissive ligand is intentionally elongated and parallel to the Transition Dipole Moment (TDM) vector of the emissive ligand. A highly horizontally aligned compound means that it has a very low Vertical Dipole Ratio (VDR). To date, there are no known examples of correlating very low VDR values of organometallic complex emitter compounds with emissions from their ancillary ligands. Furthermore, there are no known examples of methods and techniques to eliminate or minimize secondary ligand emissions.
The compounds and properties described herein improve the exclusive use of new molecular shape-based descriptors as guidelines to achieve low VDR dopants. The design principles presented herein based on molecular shape rely on the alignment of the relevant TDM of the dopant with the direction of structural elongation of the dopant. In the design of a compound dopant, emission from ancillary ligands is typically ignored. However, the collective combination of emission and ancillary ligands is known to produce compounds in which the significant contribution of emission may come from ancillary ligands, which may produce higher than expected VDR values. Thus, in addition to molecular shape-based descriptors, the compounds described herein attempt to increase the energy gap parameter that describes the difference in emission energy between the ancillary ligand and the emissive ligand. For larger values of the bandgap parameter, the emitter from one or more ancillary ligands is not possible.
In one aspect, the present disclosure provides a compound of formula M (L 1 )(L 2 ) x (L 3 ) y Is a compound of (a). M (L) 1 )(L 2 ) x (L 3 ) y Can act as an emitter in an organic light emitting device at room temperature and has a peak wavelength emission energy. For a compound having formula M (L 1 )(L 2 ) x (L 3 ) y Is a compound of formula (I):
m is a metal having an atomic mass of at least 40;
L 1 、L 2 and L 3 Is independently a bidentate ligand;
x is 1 or 2;
y is 0 or 1;
1+x+y is the oxidation state of the metal M;
L 1 、L 2 and L 3 Any of which may be joined to form a tetradentate or hexadentate ligand;
if M is Ir, then the compound is a face (fac) complex;
the compound has a rod-like axis with a rod-like parameter R R ；
The compound has a TDM vector forming an angle with the rod-like axis;
the calculated angle between the rod axis and the TDM vector is less than 20 degrees;
wherein ligand L 1 、L 2 And L 3 Each having a first triplet excited state energy T 1 (L 1 )、T 1 (L 2 )、T 1 (L 3 ) It is defined as corresponding to the trimodal compound M (L 1 ) 3 、M(L 2 ) 3 And M (L) 3 ) 3 Emits energy at a peak wavelength of (1), where T 1 (L 1 )<T 1 (L 2 ) And when y is 1, T 1 (L 2 )≤T 1 (L 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And is also provided with
The compound has an energy gap parameter T of at least 0.13eV 1 (L 2 )-T 1 (L 1 )。
In the formula M (L) 1 )(L 2 ) x (L 3 ) y In some embodiments of the compounds of (2) the peak emission wavelength is below 540nm and the rod-like parameter R R Greater than 0.50. In some such embodiments, the rod parameter R R Greater than 0.60. In some such embodiments, the rod parameter R R Greater than 0.70. In some such embodiments, the rod parameter R R Greater than 0.80. It is to be understood that R R Always +.1.00, and the above examples apply to formula M (L) throughout this disclosure 1 )(L 2 ) x (L 3 ) y Is a compound of (a).
In the formula M (L) 1 )(L 2 ) x (L 3 ) y In some embodiments of the compounds of (2), the peak emission wavelength is at least 540nm, and the rod-like parameter R R Greater than 0.83. In some such embodiments, the rod parameter R R Greater than 0.85. In some such embodiments, the rod parameter R R Greater than 0.90. It is to be understood that the above embodiments apply to the formula M (L 1 )(L 2 ) x (L 3 ) y Is a compound of (a).
In the formula M (L) 1 )(L 2 ) x (L 3 ) y In some embodiments of the compounds of (2), one of the following is true:
(i) Peak emission wavelength lower than 540nm, and rod-like parameter R R Greater than 0.50; or (b)
(ii) A peak emission wavelength of at least 540nm, and a rod-like parameter R R Greater than 0.83.
In another aspect, the present disclosure provides a compound of formula M (L 1 * )(L 2 ) x (L 3 ) y Is a compound of (a). M (L) 1 * )(L 2 ) x (L 3 ) y Can act as an emitter in an organic light emitting device at room temperature and has a peak wavelength emission energy. For a compound having formula M (L 1 * )(L 2 ) x (L 3 ) y Is a compound of formula (I):
m is a metal having an atomic mass of at least 40;
L 1 * 、L 2 and L 3 Is independently a bidentate ligand;
x is 1 or 2;
y is 0 or 1;
1+x+y is the oxidation state of the metal M;
L 1 * 、L 2 and L 3 Any of which may be joined to form a tetradentate or hexadentate ligand;
if M is Ir, then the compound is a face (fac) complex;
the compound has a rod-like axis with a rod-like parameter R R ；
The compound has a TDM vector forming an angle with the rod-like axis; the calculated angle between the rod axis and the TDM vector is less than 20 degrees;
wherein ligand L 1 * 、L 2 And L 3 Each having a calculated first triplet energy QM_T 1 (L 1 * )、QM_T 1 (L 2 )、QM_T 1 (L 3 ) It is defined as corresponding to the trimodal compound M (L 1 * ) 3 、M(L 2 ) 3 And M (L) 3 ) 3 As calculated using B3LYP exchange-related functional and LACVP-based self-dense functional theory;
wherein QM_T 1 (L 1 * )<QM_T 1 (L 2 ) And whenL 3 Qm_t, when present 1 (L 2 )≤QM_T 1 (L 3 ) Wherein ligand L 1 * Is defined as an emissive ligand, and ligand L 2 And L 3 Defined as ancillary ligands;
wherein the compound has a first triplet energy T which is measured experimentally 1 (M(L 1 * )(L 2 )(L 3 ) Defined as the peak wavelength emission energy of a compound in solution at room temperature;
wherein ligand L 2 Having a first triplet excited state energy T 1 (L 2 ) And if L 3 If present, ligand L 3 Having a first triplet excited state energy T 1 (L 3 ) It is defined as its corresponding trimodal compound M (L 2 ) 3 、M(L 3 ) 3 Emits energy at a peak wavelength of T1 (L 2 )≤T1(L 3 ) The method comprises the steps of carrying out a first treatment on the surface of the And the compound has an energy gap parameter T of at least 0.13eV 1 (L 2 )-T 1 (M(L 1 * )(L 2 )(L 3 ))。
In the formula M (L) 1 * )(L 2 ) x (L 3 ) y In some embodiments of the compounds of (2), one of the following is true:
(i) Peak emission wavelength lower than 540nm, and rod-like parameter R R Greater than 0.50; or (b)
(ii) A peak emission wavelength of at least 540nm, and a rod-like parameter R R Greater than 0.83.
It is to be understood that the formula M (L 1 )(L 2 ) x (L 3 ) y All embodiments and/or features of the compounds of formula (I) are equally or identically applicable to those of formula (I) M (L 1 * )(L 2 ) x (L 3 ) y All examples and/or features of compounds of (2) except that the compound of formula M (L 1 * )(L 2 ) x (L 3 ) y T of the compound of (C) 1 (L 1 * ) Is impractical. In such a caseUnder, use the energy gap parameter T 1 (L 2 )-T 1 (M(L 1 * )(L 2 )(L 3 ) Not T) 1 (L 2 )-T 1 (L 1 )。
FIG. 3 shows compoundsLabeled with TDM vectors, rod axes and angles therebetween.
As used herein, the "peak emission wavelength" of a compound is the wavelength in nanometers related to the peak in the emission spectrum (PL or EL emission), where the peak is that attributed to T 1 The wavelength associated with the highest intensity peak in the entire spectrum of emissions. It should be understood that throughout this disclosure, the terms "peak emission wavelength", "peak emission" and "peak emission energy" are interchangeable.
As used herein, "peak wavelength emission energy" is 1240/peak emission wavelength and is in eV.
In some embodiments, peak emission energy and/or T 1 Energy is defined as the energy at 10% of the peak intensity on the high energy side of the PL or EL spectrum as peak.
As used herein, the "rod-like axis" of a compound is the axis of the main moment of inertia (Principal Moments of Inertia; PMI) associated with the smallest PMI of the compound. In these calculations, I1, I2 and I3 are PMIs of a given 3D structure of a molecule in ascending order (I1. Ltoreq.I2. Ltoreq.I3), and can be calculated using one of a variety of available software, such as the Maestro suite of Schrodinger. It can also be calculated by determining eigenvalues and eigenvectors of an inertial tensor, where the inertial tensor is a matrix I written as:
and its components originate from the 3D structure of the molecule (translated so that the geometric center is at the origin) as follows:
the variable i is used to index atoms of the 3D structure containing the molecule. Atomic mass of atom i is written as m i And the coordinates of atom i are defined as (x i ,y i ,z i ). Eigenvalues give PMI values and eigenvectors give PMI axes (note that, depending on the method used to calculate the eigenvectors, the PMI axes may be transposes of the reported vectors).
Stick-like parameter R R Is defined as its proximity to the value (0, 1) in the NPR metric space and can be written quantitatively as:
wherein the normalized dominant moment ratio (Normalized Principal moments Ratio; NPR) metric space is composed of molecular 3D descriptors to give coordinates (NPR 1, NPR 2), whereinAnd->
In calculating NPR1 and NPR2, noise will be present based on molecular configuration. To minimize this noise, the lowest energy configuration is utilized, where energy is defined as the total energy from some electronic structural calculators, such as the energy from a DFT calculation using B3LYP as a functional and 6-31G as a basis set using Gaussian16 software.
After determining M (L 1 )(L 2 ) x (L 3 ) y The energy gap parameters between the ligands in the compounds of the invention and the compounds themselvesT 1 (L 2 )-T 1 (ML 1 L 2 L 3 ) When the ligand L 1 、L 2 And L 3 Is respectively assigned a first triplet excited state energy T 1 (L 1 )、T 1 (L 2 )、T 1 (L 3 ) Which is defined as its peak wavelength emission energy corresponding to the tri-homoleptic dopant compound. For example, given examples the compounds of the invention Ir (L A )(L B )(L C ) Ligand L A Is a first triplet excited state energy T of 1 (L A ) Will be composed of the compound Ir (L A ) 3 Determining ligand L B Is a first triplet excited state energy T of 1 (L B ) Will be composed of the compound Ir (L B ) 3 Determining, and ligand L C Is a first triplet excited state energy T of 1 (L C ) Will be composed of the compound Ir (L C ) 3 And (5) determining. The energy gap parameter T is then calculated using these energies using the Arrhenius equation (Arrhenius equation) 1 (L 2 )-T 1 (L 1 )：
Wherein the energy of a given ligand varies by ΔE L ＝E L -E min And (2) andk B is the boltzmann constant (Boltzmann constant) (for eV, this is about 8.617333E-5 eV/K), and T is the temperature (300K). The denominator is only used to normalize the overall distribution to a sum of 1.
As compounds Ir (L) A )(L B ) 2 In which Ir (L) A ) 3 Having a peak emission wavelength of 520nm, which corresponds approximately to the peak wavelength emission energy of 2.3846 eV. For Ir (L) A ) 3 With Ir (L) B ) 3 With an energy gap of at least 0.13eV (to minimize the energy from ligand L B Is an emission of (2), ir (L) B ) 3 Must have a peak wavelength emission energy of 2.3846+0.13= 2.5146eV, which is equal to a peak emission wavelength of approximately 493 nm. This will then yield a predicted emission from each ligand as follows:
in other words, more than 99% of the emissions will come from ligand L A 。
In some embodiments of the compounds of the present disclosure, M is selected from the group consisting of: ir, rh, re, ru, os, pt, pd, ag, au and Cu. In some embodiments, M is Ir. In some embodiments, M is Pt or Pd.
In some embodiments, L 2 And L 3 Are all present and different. In some embodiments, L 2 And L 3 Are all present and identical. In some embodiments, L 2 Exist and L 3 Is not present.
In some embodiments, the bandgap parameter is at least 0.15eV. In some embodiments, the bandgap parameter is at least 0.20eV. In some embodiments, the bandgap parameter is at least 0.25eV.
In some embodiments, the peak emission wavelength is below 540nm. In some embodiments, the peak emission wavelength is below 530nm. In some embodiments, the peak emission wavelength is at least 540nm. In some embodiments, the peak emission wavelength is at least 550nm.
In some embodiments, the stick parameter is greater than 0.60. In some embodiments, the stick parameter is greater than 0.65. In some embodiments, the stick parameter is greater than 0.70. In some embodiments, the stick parameter is greater than 0.75. In some embodiments, the stick parameter is greater than 0.80. In some embodiments, the stick parameter is greater than 0.83. In some embodiments, the stick parameter is greater than 0.87. In some embodiments, the stick parameter is greater than 0.90.
In some embodiments, the calculated angle between the rod axis and the TDM vector is less than 17.5 degrees.
In some embodiments, the calculated angle between the rod axis and the TDM vector is less than 15 degrees. In some embodiments, the calculated angle between the rod axis and the TDM vector is less than 12.5 degrees. In some embodiments, the calculated angle between the rod axis and the TDM vector is less than 10 degrees.
The angle between TDM and the rod-like axis can be calculated as follows:
1) A projection t of the TDM vector from the complex space to the real space is obtained.
2) The rod-like axis is equivalent to the PMI axis corresponding to the lowest PMI. This axis is defined by the corresponding PMI eigenvector p.
3) The angle between TDM and the appropriate PMI eigenvector is then defined as:
in the case of the formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y In some embodiments of the compounds of (2), the first ligand L 1 Or L 1 * Has the following characteristics ofIs a structure of (a). In formula Ia and formula Ib:
K 1 is a direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) Or Si (R) α )(R β )；
X a 、X b And X 1 To X 10 Is independently C or N;
x bonded to ring A 7 To X 10 One of which is C;
Y 1 and Y 2 Independently selected from the group consisting of: BR'.、BR'R”、NR'、PR'、P(O)R'、O、S、Se、C＝O、C＝S、C＝Se、C＝NR'、C＝CR'R”、S＝O、SO 2 CR ' R ", siR ' R", and GeR ' R ";
R A 、R B and R is C Independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
each R α 、R β 、R'、R"、R A 、R B And R is C Independently hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with
Any two substituents may be joined or fused to form a ring.
In some embodiments, when the compound has the formula M (L 1 )(L 2 ) 2 Or M (L) 1 * )(L 2 ) 2 When L 1 Or L 1 * Has the following characteristics of And the rod-like parameter is greater than 0.65. In some such embodiments, the rod-like parameter is greater than 0.70, or greater than 0.75, or greater than 0.80.
In some embodiments of the compounds having formula Ia or formula Ib, K 1 Is a direct bond. In some embodiments, K 1 Is O or S. In some embodiments, K 1 Is O.
In some embodiments of compounds having formula Ia or formula Ib, each R', R ", R A 、R B And R is C Is hydrogen or a substituent selected from the group consisting of: deuterium, fluorine, alkyl, cycloalkyl, heteroalkyl, alkoxy, aryloxy, amino, silyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, aryl, heteroaryl, nitrile, isonitrile, thio, germyl, and combinations thereof.
In some embodiments of the compounds having formula Ia or formula Ib, X 7 To X 10 Is C. In the formulaIn some embodiments of Ia or Ib, X 3 To X 6 Is C. In some embodiments of formula Ia or formula Ib, X 3 To X 10 Is C.
In some embodiments of the compounds having formula Ia or formula Ib, X 7 To X 10 At least one of which is N. In some embodiments of the compounds having formula Ia or formula Ib, X 3 To X 6 At least one of which is N. In some embodiments of the compounds having formula Ia or formula Ib, X 3 Is N. In some embodiments of the compounds having formula Ia or formula Ib, X 4 Is N. In some embodiments of the compounds having formula Ia or formula Ib, X 5 Is N. In some embodiments of the compounds having formula Ia or formula Ib, X 6 Is N.
In some embodiments of the compounds having formula Ia or formula Ib, X 7 To X 10 At least one of which is N.
In some embodiments of compounds having formula Ia or formula Ib, Y 2 Selected from the group consisting of: o, S and Se. In some embodiments of formula Ia or formula Ib, Y 2 Is O.
In some embodiments of compounds having formula Ia or formula Ib, Y 2 Selected from the group consisting of: BR ', NR ' and PR '. In some embodiments of compounds having formula Ia or formula Ib, Y 2 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 of compounds having formula Ia or formula Ib, Y 2 Selected from the group consisting of: CR 'R', BR 'R', siR 'R' and GeR 'R'.
In some embodiments of the compounds having formula Ia or formula Ib, X 1 And X 2 Are all C.
In some embodiments of the compounds having formula Ia or formula Ib, X a And X b Are all C.
In some embodiments of the compounds having formula Ib, X a 、X b 、X 1 And X 2 One of which is N. Some of the embodiments in formula IbIn the example, X a 、X b 、X 1 And X 2 Is C.
In some embodiments of compounds having formula Ia or formula Ib, Y 1 Is NR'. In some such embodiments, R' is aryl or heteroaryl. In some such embodiments, R' is phenyl. In some such embodiments, wherein R' is phenyl, at least one of the positions ortho to the bond to N is substituted with alkyl, cycloalkyl, aryl, or heteroaryl. In some such embodiments, wherein R' is phenyl, the position para to the bond to B is substituted with aryl or heteroaryl. In some such embodiments, wherein R' is phenyl, the position para to the bond to B is substituted with phenyl.
In some embodiments of the compounds disclosed herein, ligand L 1 Or L 1 * Selected from the group consisting of the structures of the following list 1:
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wherein:
K 1 is a direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) Or Si (R) α )(R β )；
X a 、X b And X 1 To X 14 Is independently C or N;
Y 1 and Y 2 Independently selected from the group consisting of: BR ', BR' R ", NR ', PR', P (O) R ', O, S, se, C = O, C = S, C =se, c=nr", c=cr' R ", s= O, SO 2 CR ', CR ' R ', siR ' R ', and GeR ' R ';
R A 、R B 、R C and R is AA Each of which independently represents a substitution of a single substitution to a maximum allowable number, orNo substitution;
each R α 、R β 、R'、R"、R A 、R B 、R C And R is AA Independently represents hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with
Any two substituents may be joined or fused to form a ring.
In some embodiments, K 1 Is a direct bond.
In some embodiments, two adjacent R' s C Bonding to form X 3 -X 4 、X 4 -X 5 Or X 5 -X 6 A fused aryl or heteroaryl moiety. In some such embodiments the aryl or heteroaryl moiety is a polycyclic fused ring system. In some such embodiments, the aryl or heteroaryl moiety is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthridine, and fluorene.
In some embodiments, ligand L 1 Or L 1 * Selected from the group consisting of the structures of the following list 2:
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wherein:
K 1 is a direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) Or Si (R) α )(R β )；
Y 1 、Y 2 And Y 3 Independently selected from the group consisting of: BR ', BR' R ", NR ', PR', P (O) R ', O, S, se, C = O, C = S, C =se, c=nr", c=cr' R ", s= O, SO 2 CR ', CR ' R ', siR ' R ', and GeR ' R ';
R A 、R B 、R C 、R AA and R is CC Independently represents a single substitution to a maximum allowable number of substitutions, or no substitution;
each R α 、R β 、R'、R"、R A 、R B 、R C 、R AA And R is CC Independently represents hydrogen or a substituent selected from the group consisting of the general substituents defined herein; and is also provided with
Any two substituents may be joined or fused to form a ring.
In some embodiments, when the compound has the formula M (L 1 )(L 2 ) 2 Or M (L) 1 * )(L 2 ) 2 When L 1 Or L 1 * The structure is not as follows:
wherein X is S or O; r is R 1 Is H, CH 3 Or I; and R is 2 Is H or F.
In some embodiments, when the compound has the formula M (L 1 )(L 2 ) 2 Or M (L) 1 * )(L 2 ) 2 When L 1 Or L 1 * Not selected from one of the following structures:/>
in some embodiments, K 1 Is a direct bond.
In some such embodiments, two adjacent R B Or two adjacent R C Or two adjacent R CC To form an aryl or heteroaryl moiety fused to the ring from which it originates. In some such embodiments, two adjacent R C To form an aryl or heteroaryl moiety fused to the ring from which it originates. In some such embodiments, two adjacent R CC To form an aryl or heteroaryl moiety fused to the ring from which it originates. In some such embodiments, two adjacent R B Or two adjacent R C Or two adjacent R CC To form an aryl or heteroaryl polycyclic fused ring system fused to the ring from which it originates. In some such embodiments, the aryl or heteroaryl moiety is selected from the group consisting of: benzene, pyridine, pyrimidine, pyridazine, pyrazine, imidazole, pyrazole, pyrrole, oxazole, furan, thiophene, thiazole, naphthalene, quinazoline, benzofuran, benzoxazole, benzothiophene, benzothiazole, benzoselenophene, indene, indole, benzimidazole, carbazole, aza-carbazole, dibenzofuran, aza-dibenzofuran, dibenzothiophene, aza-dibenzothiophene, quinoxaline, phthalazine, phenanthridine, and fluorene.
In some embodiments, L 2 And L 3 Each independently selected from the group consisting of the structures of the following list 3:
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wherein:
t is selected from the group consisting of: B. al, ga and In;
K 1 ' is a direct bond or is selected from the group consisting of: NR (NR) e 、PR e O, S and Se; y is Y 1 To Y 13 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 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;
R 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 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 comprising ligands of list 3, at least one R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e And R is f Including electron withdrawing groups. Is comprised ofIn some embodiments of the ligands of Listing 3, at least one R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e And R is f Is an electron withdrawing group. In some embodiments, the electron withdrawing group generally comprises one or more highly electronegative elements such as, but not limited to, fluorine, oxygen, sulfur, nitrogen, chlorine, and bromine.
In some embodiments comprising ligands of list 3, at least one R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e And R is f An electron withdrawing group comprising or selected from the group consisting of the following EWG list: F. CF (compact flash) 3 、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 、(R) 2 CCN、(R) 2 CCF 3 、CNC(CF 3 ) 2 BRR', substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted 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 alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, />
Each of which 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, the electron withdrawing group is a pi-electron deficient electron withdrawing group. 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 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 unsubstitutedSubstituted thiazoles, substituted or unsubstituted benzothiazoles, substituted or unsubstituted imidazoles, substituted or unsubstituted benzimidazoles, ketones, carboxylic acids, esters, nitriles, isonitriles, sulfinyl, sulfonyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate, nitrile, />
Each of which 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' . More detailed information about pi-electron deficient electron withdrawing groups can be found in U.S. provisional application No. 63/417,746 filed on day 10, 20, 2022 and U.S. provisional application No. 63/481,143 filed on day 23, 2023, which are incorporated herein by reference.
In some embodiments, the electron withdrawing group is selected from the group consisting of:
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in some embodiments, the electron withdrawing group is selected from the group consisting of:
in some embodiments, the electron withdrawing group is selected from the group consisting of:
in some embodiments comprising ligands of list 3, L 2 Is of the formula IIK 1 ' is a direct bond, and at least one R a Or R is b Is an electron withdrawing group. In some embodiments of formula II, Y 2 R at a Is an electron withdrawing group. In some embodiments of formula II, Y 2 R at a Is an electron withdrawing group selected from the group consisting of EWG lists. In some embodiments of formula II, Y 2 R at a Selected from the group consisting of: F. CN and CF 3 。
In some embodiments comprising ligands of list 3, Y 7 R at b Is an electron withdrawing group. In some embodiments comprising ligands of list 3, Y 7 R at b Is an electron withdrawing group selected from the group consisting of EWG lists. In some embodiments comprising ligands of list 3, Y 7 R at b Selected from the group consisting of: F. CN and CF 3 。
In some embodiments comprising ligands of Listing 3, exactly one R a Is not hydrogen.
In some embodiments comprising ligands of Listing 3, exactly one R b Is not hydrogen.
In some embodiments, L 2 And L 3 Each independently selected from the group consisting of the structures of list 4 below:
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wherein:
R a '、R b '、R c '、R d ' and R e ' each independently represents zero substitution, mono 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 Any two of the' can be fused or joined toForming a ring or forming a multidentate ligand. In some embodiments, L 2 Selected from L as defined in List 5 below B1 To L B475 A group consisting of:
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in ligand L comprising Listing 5 2 In some embodiments of (2), M is Ir and x is 2. In some such embodiments, L 2 Selected from the group consisting of L B325 To L B475 A group of groups.
In ligand L comprising Listing 5 2 In some embodiments of (2), M is Ir, and x is 1 and y is 1. In some such embodiments, L 2 Selected from the group consisting of L B325 To L B475 A group of groups.
At inclusion of list 5Ligand L 2 In some embodiments of L 3 Selected from the group consisting of L B1 To L B475 A group of groups. In ligand L comprising Listing 5 2 In some embodiments of L 3 Selected from the group consisting of L B325 To L B475 A group of groups.
In some embodiments, the compound comprises at least one deuterium atom.
In some embodiments, the compound comprises at least 10 deuterium atoms.
In some embodiments, the compound has a formula selected from the group consisting of: ir (L) A )(L B ) 2 、Ir(L A * )(L B ) 2 、Ir(L A * )(L B )(L C ) And Ir (L) A )(L B )(L C ). In some embodiments, L A Or L A * Independently selected from the group consisting of list 1, list 2, and structures of formula Ia or formula Ib, L B Selected from list 3, list 4, list II, and list 5 (L Bk ) And L is a group of structures of C Selected from the group consisting of structures of list 3, list 4, formula II, and list 5. When both are present, L B And L C Different.
In some embodiments, L A Or L A * Independently selected from the group consisting of structures of List 1, and L B Selected from the group consisting of the structures of list 5. In some embodiments, L A Or L A * Independently selected from the group consisting of structures of List 2, and L B Selected from the group consisting of the structures of list 5. In some embodiments, L A Or L A * Selected from formula Ia and formula Ib, and L B Selected from the group consisting of the structures of list 5.
In some embodiments, the compound has a formula selected from the group consisting of: ir (L) A )(L Bk ) 2 、Ir(L A * )(L Bk ) 2 、Ir(L A * )(L Bk )(L C ) And Ir (L) A )(L Bk )(L C )。
In some embodiments, the compound is selected from the group consisting of the structures of list 6:
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in some embodiments, a compound having the formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y The compound of the structure of (c) 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, deuterated percentages have their ordinary meaning and include percentages of atoms of possible hydrogen (e.g., positions of hydrogen or deuterium) that are replaced by deuterium atoms.
In the case of a compound having the formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y In some embodiments of the heteroleptic compounds of (2), ligand L A Having a first substituent R I Wherein the first substitutionRadical R I With a ligand L 1 Or L 1 * The first atom a-I furthest from the metal M among all the atoms in (a). In addition, ligand L 2 Having a second substituent R, if present II Wherein the second substituent R II With a ligand L 2 The first atom a-II furthest from the metal M among all the atoms in (a). In addition, ligand L 3 Having a third substituent R, if present III Wherein the third substituent R III With a ligand L 3 The first atom a-III furthest from the metal M among all the atoms in (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 substituent R representing a metal M and a first substituent R I A value D of the linear distance between the first atoms a-I 1 。V D2 Represents the direction from the metal M to the first atom a-II and the vector V D2 Having a substituent R representing a metal M and a second substituent R II A value D of the linear distance between the first atoms a-II 2 。V D3 Represents the direction from the metal M to the first atom a-III, and the vector V D3 Having a substituent R representing a metal M and a third substituent R III A value D of the linear distance between the first atoms a-III 3 。
In such heteroleptic compounds, spheres are defined having a radius R centered at the metal M and the radius R is that which allows the spheres to enclose compounds in which not substituents R I 、R II And R is III The smallest radius of all atoms of the 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, the compound has a transition dipole moment axis, and the transition dipole moment axis is aligned with vector V D1 、V D2 And V D3 The angle between the transition dipole moment axis and the vector V is determined D1 、V D2 And V D3 At least one angle 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 angle 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 angle 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 angle 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 angle 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 angles therebetween being 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 angles therebetween being 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 angles therebetween being 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 in between 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 in between 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 in between 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 compounded compounds, the compounds have a VDR of 0.30 or less. In some embodiments of such compounded compounds, the compounds have a VDR of 0.25 or less. In some embodiments of such compounded compounds, the compounds have a VDR of 0.20 or less. In some embodiments of such compounded compounds, the compounds have a VDR of 0.15 or less.
The meaning of the term transition dipole moment axis of a compound and the perpendicular dipole ratio of the compound will be readily understood by those of ordinary skill in the art. However, the meaning of these terms can 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.
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 as disclosed in the above compound section of the present disclosure.
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 formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y Is a compound of (a).
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 triphenylene comprising a benzo-fused thiophene or a benzo-fused furan, wherein any substituents in the host are non-fused independently selected from the group consisting ofAnd (3) combining substituent groups: 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-boranaphtho [3,2,1-de ] anthracene, triazine, borane, silane groups, aza-triphenylene, aza-carbazole, 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-boranaphtho [3,2,1-de ] anthracene).
In some embodiments, the subject may be selected from the group of subjects consisting of:
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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 comprise two hosts: a first body and a second body. In some embodiments, the first body is a hole transporting body and the second body is an electron transporting body. 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 formula M (L 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y Is a compound of (a).
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 formula M (L) 1 )(L 2 ) x (L 3 ) y Or M (L) 1 * )(L 2 ) x (L 3 ) y Is a compound of (a).
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, vol.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 molar ratio of 1:1, as disclosed in U.S. patent application publication No. 2003/0230980, which is incorporated by reference in its entirety. Examples of cathodes are disclosed in U.S. Pat. Nos. 5,703,436 and 5,707,745, which are incorporated by reference in their entirety, that include composite cathodes having a thin layer of metal (e.g., mg: ag) containing an overlying transparent, electrically conductive, sputter-deposited ITO layer. The theory and use of barrier 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, which are incorporated by reference in their entirety), organic vapor deposition (OVPD) (as described in U.S. Pat. No. 6,337,102, which is incorporated by reference in its entirety), 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, which is 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 limitedAnd 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:
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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, benzene, phenanthrene, fluorene, pyrene, and the like,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: 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; from 2 to 10 ring structures The cyclic structural unit is a group selected from the same type or different types of groups of an aromatic hydrocarbon ring group and an aromatic heterocyclic group and is 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 complexA body. 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.
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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:
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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, phenalene, phenanthrene, fluorene, pyrene,Perylene and azulene; a group consisting of aromatic heterocyclic compounds such as: dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzo Imidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranopyridine, 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:
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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 0 to 20 or an integer 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,
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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.
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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, heteroarylAryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino and combinations thereof, when aryl or heteroaryl, have similar definitions as for Ar 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,
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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 amount of deuterated hydrogen in the 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.
Experimental data
All device examples pass through high vacuum @<10 -7 Tray) thermal evaporation (VTE) manufacture. The anode electrode beingIndium Tin Oxide (ITO). Cathode is made of->Is followed by->Al composition of (c). Immediately after fabrication, all devices were enclosed in a nitrogen glove box using an epoxy-sealed glass cover<1ppm of H 2 O and O 2 ) And incorporating a moisture absorbent into the package interior.
The organic stack of the device example consists of: starting from the ITO surface, in turnIs used as a Hole Injection Layer (HIL),>the hole transport material HTM of (2) acts as a Hole Transport Layer (HTL), -, and->Is used as an Electron Blocking Layer (EBL),>is doped with 30 wt.% H2 and 5 wt.% emitter as an emission layer (EML), -H1>H2 of (2) as Barrier Layer (BL)>Liq (8-quinolinolato lithium) with 35% ETM as Electron Transport Layer (ETL). As used herein, HATCN, HTM, EBL, H, H2 and ETM have the following structures:
after fabrication, the device was tested to measure electroluminescent (EL and JVL) characteristics. 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 intensity (W/str/cm) of 380nm to 1080nm 2 ) And total integrated photon count. The device is then placed under a large area silicon photodiode for JVL scanning. At 10mA/cm using the device 2 The lower integrated photon count converts the photodiode current into a photon count. Scanning voltage is 0 to equal 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 the following table, wherein at 10mA/cm 2 The EQE for the current density of (c) is reported as a relative value normalized to the result of the comparative example (device 2).
As a compound satisfying the above criteria, a compound having the formula M (L 1 )(L 2 ) 2 An example of the benefits of the compounds of (a) we will come from figure 3 (compound a)External Quantum Efficiency (EQE) of the compound of (2) and compound of (B +)>And Compound C->External Quantum Efficiency (EQE) of (a) was compared.
The data are summarized in the following table.
As a compound satisfying the above criteria, a compound having the formula M (L 1 )(L 2 ) 2 We come from compound D as an additional example of the benefits of the compounds of (a)External Quantum Efficiency (EQE) of a compound of (2) and compound EAnd Compound F->External Quantum Efficiency (EQE) of (a) was compared.
The data are summarized in the following table.
EQE is directly related to the degree of alignment of the emitter compounds. Within the family of compounds, the higher the aligned emitter compounds, the higher the EQE will be. The comparison compounds were all within the same household and had similar parameters based on molecular shape. The only significant difference therebetween is the magnitude of the energy gap parameter. We achieve a significant improvement in EQE values by increasing the value of the energy gap parameter. The EQE of the compounds of the present invention was normalized to its corresponding comparative compound. It will be appreciated that every 1% improvement in EQE is considered significant, and based on the above information, it can be seen that the improvement in EQE for these compounds exceeds any value attributable to experimental error and indeed truly significant.
Claims (15)
1. Formula M (L) 1 * )(L 2 ) x (L 3 ) y Wherein:
m is a metal having an atomic mass of at least 40;
L 1 * 、L 2 and L 3 Is independently a bidentate ligand;
x is 1 or 2;
y is 0 or 1;
1+x+y is the oxidation state of the metal M;
L 1 * 、L 2 and L 3 Any of which are capable of being joined to form a tetradentate or hexadentate ligand;
if M is Ir, then the compound is a face (fac) complex;
the compound has a rod-like axis with a rod-like parameter R R ；
The compound has a TDM vector forming an angle with the rod-like axis; the calculated angle between the rod axis and the TDM vector is less than 20 degrees;
wherein the ligand L 1 * 、L 2 And L 3 Each having a calculated first triplet energy QM_T 1 (L 1 * )、QM_T 1 (L 2 )、QM_T 1 (L 3 ) Defined as the corresponding tri-homoleptic compound M (L 1 * ) 3 、M(L 2 ) 3 And M (L) 3 ) 3 Is a triplet excited state energy;
wherein QM_T 1 (L 1 * )<QM_T 1 (L 2 ) And when L 3 Qm_t, when present 1 (L 2 )≤QM_T 1 (L 3 ) Wherein ligand L 1 * Is defined as an emissive ligand, and ligand L 2 And L 3 Defined as ancillary ligands;
wherein the compound has a first triplet energy T which is experimentally measured 1 (M(L 1 * )(L 2 )(L 3 ) Defined as the peak wavelength emission energy of the compound in solution at room temperature;
Wherein the ligand L 2 Having a first triplet excited state energy T 1 (L 2 ) And if L 3 If present, ligand L 3 Having a first triplet excited state energy T 1 (L 3 ) Defined as the corresponding trimodal compound M (L 2 ) 3 、M(L 3 ) 3 Emits energy at a peak wavelength in solution at room temperature, where T1 (L 2 )≤T1(L 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The compound has an energy gap parameter T of at least 0.13eV 1 (L 2 )-T 1 (M(L 1 * )(L 2 )(L 3 ) A) is provided; and one of the following is true:
(i) The peak emission wavelength is lower than 540nm, and the rod-like parameter R R Greater than 0.50; or (b)
(ii) The peak emission wavelength is at least 540nm, and the rod-like parameter R R Greater than 0.83.
2. The compound of claim 1, wherein L 2 And L 3 The same or different; and/or wherein the bandgap parameter is at least 0.15eV; and/or wherein the calculated angle between the rod axis and the TDM vector is less than 17.5 degrees.
3. The compound of claim 1, wherein the first ligand L 1 * Having the formula Ia
Or formula Ib->Is of a structure of (2);
wherein:
K 1 is a direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) Or Si (R) α )(R β )；
X a 、X b 、X 1 To X 10 Is independently C or N;
x bonded to ring A 7 To X 10 One of which is C;
Y 1 and Y 2 Independently selected from the group consisting of: BR ', BR' R ", NR ', PR'
P(O)R'、O、S、Se、C＝O、C＝S、C＝Se、C＝NR'、C＝CR'R"、S＝O、SO 2 、CR'R"、
SiR 'R' and GeR 'R';
R A 、R B and R is C Independently represents a single substitution to the maximum allowable substitution, or no substitution; each R is α 、R β 、R'、R"、R A 、R B And R is C Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and is also provided with
Any two substituents can be joined or fused to form a ring.
4. A compound according to claim 3, K 1 Is a direct bond; and/or X 3 To X 10 Each of which is C or X 3 To X 10 At least one of which is N; and/or wherein Y 2 Selected from the group consisting of: o, S, BR ', NR' and Se.
5. The compound of claim 1, wherein ligand L 1 * Selected from the group consisting of:
wherein:
K 1 is a direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) Or Si (R) α )(R β )；
X a 、X b 、X 1 To X 14 Is independently C or N;
Y 1 and Y 2 Independently selected from the group consisting of: BR ', BR ' R ", NR ', PR ', P (O) R ', O, S, se, C = O, C = S, C =se, c=nr ', c=cr ' R", s= O, SO 2 CR ', CR ' R ', siR ' R ', and GeR ' R ';
R A 、R B 、R C and R is AA Independently represents a single substitution to the maximum allowable substitution, or no substitution;
each R is α 、R β 、R'、R"、R A 、R B 、R C And R is AA Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and is also provided with
Any two substituents can be joined or fused to form a ring.
6. The compound of claim 1, wherein the ligand L 1 * Selected from the group consisting of:
wherein:
K 1 is a direct bond, O, S, N (R) α )、P(R α )、B(R α )、C(R α )(R β ) Or Si (R) α )(R β )；
Y 1 、Y 2 And Y 3 Independently selected from the group consisting of: BR ', BR ' R ", NR '
PR'、P(O)R'、O、S、Se、C＝O、C＝S、C＝Se、C＝NR"、C＝CR'R"、S＝O、SO 2 、
CR ', CR ' R ', siR ' R ', and GeR ' R ';
R A 、R B 、R C 、R AA and R is CC Independently represents a single substitution to the maximum allowable substitution, or no substitution;
each R is α 、R β 、R'、R"、R A 、R B 、R C 、R AA And R is CC Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, seleno, and combinations thereof; and is also provided with
Any two substituents can be joined or fused to form a ring.
7. The compound of claim 1, wherein L 2 And L 3 Each independently selected from the group consisting of:
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wherein:
t is selected from the group consisting of: B. al, ga and In;
K 1 ' is a direct bond or is selected from the group consisting of: NR (NR) e 、PR e O, S and Se;
Y 1 to Y 13 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 Capable of being fused or joined to form a ring;
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;
R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e and R is f Each of which is independently hydrogen or a substituent selected from the group consisting of: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, seleno, 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) can be fused or joined to form a ring or form a multidentate ligand.
8. The compound of claim 7, wherein at least one R a1 、R b1 、R c1 、R d1 、R a 、R b 、R c 、R d 、R e And R is f An electron withdrawing group selected from the group consisting of: F. CF (compact flash) 3 、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 、(R) 2 CCN、(R) 2 CCF 3 、CNC(CF 3 ) 2 BRR', substituted or unsubstituted dibenzoborole, 1-substituted carbazole, 1, 9-substituted carbazole, substituted 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 alkyl, partially and fully fluorinated aryl, partially and fully fluorinated heteroaryl, cyano-containing alkyl, cyano-containing aryl, cyano-containing heteroaryl, isocyanate,
Each of R, R e And R is f Independently hydrogen or a substituent selected from the group consisting of: deuterium, halogen, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aralkyl, alkoxy, aryloxy, amino, silyl, germanyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carboxylic acid, ether, ester, nitrile, isonitrile, thio, seleno, sulfinyl, sulfonyl, phosphino, and combinations thereof:
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' 。
9. The compound of claim 7, wherein L 2 Is a compound of the formula II,K 1 ' is a direct bond, and at least one R a Or R is b Is an electron withdrawing group.
10. The compound of claim 7, wherein L 2 And L 3 Each independently selected from the group consisting of:
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wherein:
R a '、R b '、R c '、R d ' and R e ' each independently represents zero substitution, mono 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: deuterium, halo, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, borane, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitrile, thio, sulfinyl, sulfonyl, phosphino, and combinations thereof; and is also provided with
R a '、R b '、R c '、R d ' and R e Any two of the' can be fused or joined to form a ring or to form a multidentate ligand.
11. The compound of claim 7, wherein L 2 Selected from the group consisting of B1 To L B475 A group consisting of:
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and/or wherein L 3 Selected from the group consisting of L B1 To L B475 A group of groups.
12. The compound of claim 1, wherein M is Ir and x is 2; or wherein M is Ir, x is 1, and y is 1.
13. The compound of claim 1, wherein the compound is selected from the group consisting of:
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14. an organic light emitting device OLED comprising:
an anode;
a cathode; a kind of electronic device with high-pressure air-conditioning system
An organic layer disposed between the anode and the cathode, wherein the organic layer comprises
M(L 1 * )(L 2 ) x (L 3 ) y Wherein:
m is a metal having an atomic mass of at least 40;
L 1 * 、L 2 and L 3 Is independently a bidentate ligand;
x is 1 or 2;
y is 0 or 1;
1+x+y is the oxidation state of the metal M;
L 1 * 、L 2 and L 3 Any of which are capable of being joined to form a tetradentate or hexadentate ligand;
if M is Ir, then the compound is a face (fac) complex;
the compound has a rod-like axis with a rod-like parameter R R ；
The compound has a TDM vector forming an angle with the rod-like axis; the calculated angle between the rod axis and the TDM vector is less than 20 degrees;
wherein the ligand L 1 * 、L 2 And L 3 Each having a calculated first triplet energy QM_T 1 (L 1 * )、QM_T 1 (L 2 )、QM_T 1 (L 3 ) Defined as the corresponding tri-homoleptic compound M (L 1 * ) 3 、M(L 2 ) 3 And M (L) 3 ) 3 Is a triplet excited state energy;
wherein QM_T 1 (L 1 * )<QM_T 1 (L 2 ) And when L 3 Qm_t, when present 1 (L 2 )≤QM_T 1 (L 3 ) Wherein ligand L 1 * Is defined as an emissive ligand, and ligand L 2 And L 3 Defined as ancillary ligands;
wherein the compound has a first triplet energy T which is experimentally measured 1 (M(L 1 * )(L 2 )(L 3 ) Defined as the peak wavelength emission energy of the compound in solution at room temperature;
wherein the ligand L 2 Having a first triplet excited state energy T 1 (L 2 ) And if L 3 If present, ligand L 3 Having a first triplet excited state energy T 1 (L 3 ) Defined as the corresponding trimodal compound M (L 2 ) 3 、M(L 3 ) 3 Emits energy at a peak wavelength in solution at room temperature, where T1 (L 2 )≤T1(L 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The compound has an energy gap parameter T of at least 0.13eV 1 (L 2 )-T 1 (M(L 1 * )(L 2 )(L 3 ) A) is provided; and one of the following is true:
(i) The peak emission wavelength is lower than 540nm, and the rod-like parameter R R Greater than 0.50; or (b)
(ii) The peak emission wavelength is at least 540nm, and the rod-like parameter R R Greater than 0.83.
15. A consumer product comprising an organic light emitting device, the organic light emitting device comprising:
an anode;
a cathode; a kind of electronic device with high-pressure air-conditioning system
An organic layer disposed between the anode and the cathode, wherein the organic layer comprises formula M (L 1 * )(L 2 ) x (L 3 ) y Wherein:
m is a metal having an atomic mass of at least 40;
L 1 * 、L 2 And L 3 Is independently a bidentate ligand;
x is 1 or 2;
y is 0 or 1;
1+x+y is the oxidation state of the metal M;
L 1 * 、L 2 and L 3 Any of which are capable of being joined to form a tetradentate or hexadentate ligand;
if M is Ir, then the compound is a face (fac) complex;
the compound has a rod-like axis with a rod-like parameter R R ；
The compound has a TDM vector forming an angle with the rod-like axis; the calculated angle between the rod axis and the TDM vector is less than 20 degrees;
wherein the ligand L 1 * 、L 2 And L 3 Each having a calculated first triplet energy QM_T 1 (L 1 * )、QM_T 1 (L 2 )、QM_T 1 (L 3 ) Defined as the corresponding tri-homoleptic compound M (L 1 * ) 3 、M(L 2 ) 3 And M (L) 3 ) 3 Is a triplet excited state energy;
wherein QM_T 1 (L 1 * )<QM_T 1 (L 2 ) And when L 3 Qm_t, when present 1 (L 2 )≤QM_T 1 (L 3 ) Wherein ligand L 1 * Is defined as an emissive ligand, and ligand L 2 And L 3 Defined as ancillary ligands;
wherein the compound has a first triplet energy T which is experimentally measured 1 (M(L 1 * )(L 2 )(L 3 ) Defined as the peak wavelength emission energy of the compound in solution at room temperature;
wherein the ligand L 2 Having a first triplet excited state energy T 1 (L 2 ) And if L 3 If present, ligand L 3 Having a first triplet excited state energy T 1 (L 3 ) Defined as the corresponding trimodal compound M (L 2 ) 3 、M(L 3 ) 3 Emits energy at a peak wavelength in solution at room temperature, where T1 (L 2 )≤T1(L 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The compound has an energy gap parameter T of at least 0.13eV 1 (L 2 )-T 1 (M(L 1 * )(L 2 )(L 3 ) A) is provided; and one of the following is true:
(i) The peak emission wavelength is lower than 540nm, and the rod-like parameter R R Greater than 0.50; or (b)
(ii) The peak emission wavelength is at least 540nm, andstick-like parameter R R Greater than 0.83.
Applications Claiming Priority (21)
| 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 | ||
| 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 | ||
| US18/297,777 US20230345811A1 (en) | 2022-04-18 | 2023-04-10 | Organic electroluminescent materials and devices |
| US18/297,777 | 2023-04-10 |
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