CN114773399A - Metal organic luminescent material and application thereof - Google Patents
Metal organic luminescent material and application thereof Download PDFInfo
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- CN114773399A CN114773399A CN202210528233.3A CN202210528233A CN114773399A CN 114773399 A CN114773399 A CN 114773399A CN 202210528233 A CN202210528233 A CN 202210528233A CN 114773399 A CN114773399 A CN 114773399A
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- deuterated
- substituted
- fluoro
- alkyl
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- 239000000463 material Substances 0.000 title claims abstract description 114
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 239000003446 ligand Substances 0.000 claims description 76
- 125000000217 alkyl group Chemical group 0.000 claims description 37
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 229910052805 deuterium Inorganic materials 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 28
- 125000001153 fluoro group Chemical group F* 0.000 claims description 24
- 125000003118 aryl group Chemical group 0.000 claims description 23
- -1 cyano-substituted phenyl Chemical group 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000001072 heteroaryl group Chemical group 0.000 claims description 20
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 18
- 125000004431 deuterium atom Chemical group 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 150000002367 halogens Chemical class 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
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- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
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- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005401 electroluminescence Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 42
- 238000001308 synthesis method Methods 0.000 description 29
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- 238000001704 evaporation Methods 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- 150000001975 deuterium Chemical group 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 12
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- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical class [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 4
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- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
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- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- PFYPDUUXDADWKC-UHFFFAOYSA-N 2-propan-2-ylpyridine Chemical class CC(C)C1=CC=CC=N1 PFYPDUUXDADWKC-UHFFFAOYSA-N 0.000 description 2
- LTKCZYJPQLAGMP-UHFFFAOYSA-N 6-chlorodibenzofuran-3-carbonitrile Chemical compound ClC1=C2OC3=CC(=CC=C3C2=CC=C1)C#N LTKCZYJPQLAGMP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- HAWDTXJEIQKSLF-UHFFFAOYSA-N FC(C=C1)=CC2=C1C(C=CC=C1Cl)=C1O2 Chemical compound FC(C=C1)=CC2=C1C(C=CC=C1Cl)=C1O2 HAWDTXJEIQKSLF-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
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- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
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- NSJVYHOPHZMZPN-UHFFFAOYSA-N (2-methylphenyl)boronic acid Chemical class CC1=CC=CC=C1B(O)O NSJVYHOPHZMZPN-UHFFFAOYSA-N 0.000 description 1
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- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
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- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- YOLNUNVVUJULQZ-UHFFFAOYSA-J iridium;tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ir] YOLNUNVVUJULQZ-UHFFFAOYSA-J 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000005445 isotope effect Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000003933 pentacenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C12)* 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 125000005592 polycycloalkyl group Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002441 reversible effect Effects 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
- 229910052710 silicon Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention relates to the technical field of organic electroluminescent display, and particularly discloses a metal organic luminescent material and application thereof in an organic electroluminescent device. The metal organic luminescent material provided by the invention is shown as a general formula (I), can be applied to the field of organic electroluminescence, can be used as a phosphorescent luminescent material, and can be applied to an organic electroluminescent device, and the prepared electroluminescent device has the excellent performances of high purity, high efficiency and long service life.
Description
Technical Field
The invention relates to the technical field of organic electroluminescent display, and particularly discloses a metal organic luminescent material and application thereof in an organic electroluminescent device.
Background
Since the first thin-layer OLEDs were implemented by c.w.tang and s.a.vanslyke in 1987, and since the first white OLEDs were produced by j.kido et al in 1993, OLEDs were considered to be the most promising alternative for future solid-state display and illumination, with unprecedented advances in both electroluminescent materials and device structures. Compared with organic electroluminescent fluorescent materials, the phosphorescent transition metal complex can simultaneously utilize singlet excitons and triplet excitons, effectively increase the electroluminescent efficiency of the device, and the theoretical internal quantum efficiency can reach 100%, while the fluorescent OLEDs can only reach 25%. Therefore, phosphorescent OLEDs are an important commercial OLED display technology.
OLEDs are generally composed of a plurality of organic functional layers of several nanometers to several tens of nanometers in order, and mainly include a transparent metal oxide anode, such as Indium Tin Oxide (ITO), and a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), a metal cathode, and the like. The working principle of the OLED can be summarized as the following processes that under the drive of an external direct current power supply, holes and electrons are injected through an anode and a cathode respectively, then the continuous and stable transmission of current carriers is realized through the reversible oxidation-reduction process of materials of a hole transport layer and an electron transport layer, finally the holes and the electrons are injected into a light-emitting layer simultaneously, and further the electroluminescence of the device is realized through the radiation excitation of a light-emitting material. In order to suppress the triplet-triplet annihilation effect (TTA) of the phosphorescent light-emitting material itself, the phosphorescent light-emitting material is usually used as a guest doping material and dispersed in a suitable host material, and the host material also plays a role of carrier transport and an energy donor of the phosphorescent emitter, and the energy of the host material is transferred to the phosphorescent guest. Generally, the main components for determining the performance of phosphorescent devices include device structures and materials of various functional layers, and the performance of the phosphorescent device as a guest phosphorescent light-emitting material is particularly important. Phosphorescent light emitting materials typically satisfy one or more of the following characteristics: (1) has high luminescence quantum yield, and the most part of the spectrum is in the visible range (400-700 nm); (2) the material has good carrier transmission performance; (3) has good film forming property and photo-thermal stability. The heavy metal phosphorescent complex can fully utilize singlet excitons and triplet excitons due to the heavy atom effect, so that the internal quantum efficiency of the heavy metal phosphorescent complex can reach 100% theoretically. The iridium complex becomes a hotspot of the current research because of the characteristics of easy adjustment of luminescent color, high brightness, high efficiency, good thermal stability, short phosphorescence life and the like.
The cyclometalated iridium (III) complexes can be divided into five types according to the difference of the types and coordination modes of the ligands. The iridium complex (lr (can)2 (LX;) containing the auxiliary ligand coordination mode has been widely noticed because the synthesis conditions are simple, and the HOMO/LUMO energy level can be adjusted by modifying the main ligand and the auxiliary ligand structure, so as to improve the injection and transport capabilities of carriers and change the photoelectric properties of the complex. Green phosphorescent iridium (III) complexes are the earliest class of phosphorescent materials developed. The best known green-emitting iridium (III) complexes are Ir (ppy)3, (ppy)2Ir (acac) and derivatives thereof (tpy)2Ir (acac) based on 2-phenylpyridine ring metal ligands reported by M.E. Thompson et al, and the emission main peak of such complexes is located between 510-520nm, and the color coordinates are located around (0.32, 0.64), which are standard green emission. Green-emitting iridium (III) complexes based on other cyclometallated ligands are also continually being synthesized. The green phosphorescent dopant material is one of the essential elements for solid state display, and further development of such high-performance iridium (III) complexes is still an important research direction in the industry.
At present, organometallic complexes having phosphorescent emission and organic electroluminescent devices are reported, and various organometallic complex phosphorescent materials are also disclosed in the patent. For example, EP 3825320 a1 discloses a class of Ir complexes containing dibenzofuran ligands, which have serious problems of low phosphorescence efficiency, stability and lifetime, thus hindering the possibility of commercialization. Therefore, the structural improvement of the compound is carried out to develop a new iridium (III) complex with better performance as a phosphorescent luminescent material, and the commercial application is promoted, which has important significance.
Disclosure of Invention
The invention aims to develop a metal organic luminescent material, in particular to a novel organic electrophosphorescent luminescent material containing a metal iridium complex, which is applied to an organic electroluminescent device, and the prepared electroluminescent device has the excellent performances of high purity, high efficiency and long service life.
Specifically, in a first aspect, the present invention provides a metal organic light emitting material having a structure represented by general formula (i):
wherein, the first and the second end of the pipe are connected with each other,
n is 1, 2 or 3; m is 0, 1, 2, 3 or 4; k is 0, 1, 2 or 3; p is 0 or 1;
y is selected from O, S, Se, SO2NR ', CR', SiR ', R' is C1～C6A chain alkyl group;
X1、X2、X3、X4、X5、X6、X7and X8Each independently selected from C or N;
R1、R2each independently selected from hydrogen atom, deuterium atom, halogen, cyano, C1～C20Chain alkyl, C3～C20Cycloalkyl, C1～C20Alkoxy radical, C6～C60Aryloxy group, C1～C20Alkylsilyl group, C6～C60Aryl radical, C3～C60Heteroaryl, C1～C20Deuterated chain alkyl, C3～C20Deuterated cycloalkyl, C1～C20Deuterated alkoxy, C6～C60Deuterated aryloxy group C1～C20Deuterated alkylsilyl, C6～C60Deuterated aryl, C3～C60Deuterated heteroaryl, fluoro-C1～C20Chain alkyl, fluoro C3～C20A cycloalkyl group, a,Fluoro C1～C20Alkoxy, fluoro C6～C60Aryloxy, fluoro C1～C20Alkylsilyl, fluoro C6～C60Aryl, fluoro C3～C60Heteroaryl, cyano-substituted C6～C60Any one of aryl groups; or, when R1Or R2When there are plural, two adjacent R1Or R2Can be connected into a ring;
R13selected from deuterium atom, halogen, cyano, C6～C60Aryl radical, C6～C60A deuterated aryl group;
l is a monovalent bidentate anionic ligand in which the bonding atoms M, N are each independently selected from a nitrogen atom, a carbon atom.
As a preferred embodiment of the present invention, the metal organic light emitting material has a structure represented by general formula (I-1):
wherein, the first and the second end of the pipe are connected with each other,
n is 1, 2 or 3; m is 0, 1, 2, 3 or 4; k is 0, 1, 2 or 3; p is 0 or 1;
y is selected from O, S, Se, CR ', SiR ' and R ' is C1～C6A chain alkyl group;
X3、X4、X5、X6、X7and X8Each independently selected from C or N;
R1、R2each independently selected from hydrogen atom, deuterium atom, halogen, cyano, C1～C20Chain alkyl, C3～C20Cycloalkyl radical, C1～C20Alkoxy radical, C6～C60Aryloxy radical, C1～C20Alkylsilyl group, C6～C60Aryl radical, C3～C60Heteroaryl group, C1～C20Deuterated chain alkyl, C3～C20Deuterated cycloalkyl, C1～C20Deuterated alkoxy, C6～C60Deuterated aryloxy group C1～C20Deuterated alkylsilyl, C6～C60Deuterated aryl, C3～C60Deuterated heteroaryl, fluoro-C1～C20Chain alkyl, fluoro C3～C20Cycloalkyl, fluoro C1～C20Alkoxy, fluoro C6～C60Aryloxy, fluoro C1～C20Alkylsilyl, fluoro C6～C60Aryl, fluoro C3～C60Heteroaryl, cyano-substituted C6～C60Any one of aryl groups; or, when R1Or R2When there are plural, two adjacent R1Or R2Can be connected into a ring;
R13selected from deuterium atom, cyano group, C6～C60Aryl radical, C6～C60A deuterated aryl group;
l is a monovalent bidentate anionic ligand in which the bonding atoms M, N are each independently selected from a nitrogen atom, a carbon atom.
As a preferred embodiment of the present invention, in the general formula (I) and the general formula (I-1), L is a group represented by the following formula (L):
wherein R is3～R10Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted deuterated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 30 carbon atomsAny of a deuterated aryl of atoms, a substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl of 1 to 20 carbon atoms, a substituted or unsubstituted arylalkylsilyl having 6 to 20 carbon atoms; and/or, R3～R10Two adjacent to each other may form a fused ring structure by bridging; and/or the presence of a gas in the gas,
R3～R10when having a substituent group, the substituent group is selected from deuterium atom, halogen, cyano group, C1～C30Alkyl of (C)1～C30Deuterated alkyl of (D), C3～C20Cycloalkyl of (C)3～C20Heterocycloalkyl of (C)6～C60Aryl of, C3～C60Heteroaryl of (1), C1～C20And (3) one or a combination of more of the above-mentioned silane groups.
Preferably, in the group of formula (L), R3～R10Each independently selected from the group consisting of hydrogen atom, deuterium atom, halogen, cyano, alkyl having 1 to 5 carbon atoms, deuterated alkyl having 1 to 5 carbon atoms, substituted or unsubstituted phenyl; when the phenyl group has a substituent group, the substituent group is selected from deuterium atom and C1～C5Alkyl of (C)1～C5Deuterated alkyl, C1～C5And (3) an alkylsilyl group.
Further preferably, said L is selected from the group consisting of:
as a preferred embodiment of the present invention, in the general formula (I) and the general formula (I-1), said n is 1;
y is selected from O, S, Se;
R1selected from H, deuterium atom, C1～C5Alkyl group of (A) or (B),C1～C5Deuterated alkyl, C3～C6Cycloalkyl, phenyl, deuterated phenyl of (a);
m is 0 or 1;
R2selected from H, deuterium atom, halogen, cyano, trifluoromethyl, C1～C5Alkyl of (C)1～C5Deuterated alkyl, phenyl, deuterated phenyl, fluorophenyl, cyano-substituted phenyl, halogen atoms and cyano-substituted phenyl;
k is 0 or 1 or 2 or 3; when k is 2 or 3, two adjacent R2The fused ring structure can be formed by bridging, and can be a five-membered ring or a six-membered ring, preferably, the five-membered ring is a five-membered heterocyclic ring containing an O atom, the six-membered heterocyclic ring is a benzene ring, the five-membered heterocyclic ring can be further connected with a benzo group, and the benzo ring can be substituted by a deuterium atom;
R13selected from deuterium atom, deuterated phenyl, phenyl and cyano;
p is 0 or 1.
In the present invention, C representsa～CbThe expression (b) represents that the group has the number of carbon atoms of a to b, and generally the number of carbon atoms does not include the number of carbon atoms of the substituent unless otherwise specified. In the present invention, unless otherwise specified, the expressions of chemical elements generally include the concept of chemically identical isotopes, such as the expression "hydrogen", the concept of chemically identical "deuterium" and "tritium", and the concept of carbon (C) includes12C、13C, etc., will not be described in detail.
Heteroaryl in this specification refers to an aromatic cyclic group containing a heteroatom, typically selected from N, O, S, P, Si and Se.
In this specification C6～C60Aryl radical, C3～C60Unless otherwise specified, the heteroaryl group is an aromatic group satisfying a pi conjugated system, and includes both monocyclic rings and fused rings. The monocyclic ring means that at least one phenyl group is contained in the molecule, and when at least two phenyl groups are contained in the molecule, the phenyl groups are independent of each other and are linked by a single bondIllustratively phenyl, biphenylyl, terphenylyl, and the like; the condensed ring means that at least two benzene rings are contained in the molecule, but the benzene rings are not independent of each other, but common ring sides are condensed with each other, illustratively, naphthyl, anthryl, phenanthryl and the like; monocyclic heteroaryl means that the molecule contains at least one heteroaryl group, and when the molecule contains one heteroaryl group and other groups (e.g., aryl, heteroaryl, alkyl, etc.), the heteroaryl and other groups are independent of each other and are linked by a single bond, illustratively pyridine, furan, thiophene, etc.; the fused ring heteroaryl group means a fused group of at least one phenyl group and at least one heteroaryl group, or a fused group of at least two heteroaryl groups, illustratively quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, and the like.
In the present specification, substituted or unsubstituted C6～C60Aryl is preferably C6～C30And an aryl group, exemplified by an aryl group in the group consisting of a phenyl group, a naphthyl group, an anthryl group, a benzanthryl group, a phenanthryl group, a benzophenanthryl group, a pyrenyl group, a chrysenyl group, a pyrenyl group, a tetracenyl group, a pentacenyl group, a benzopyrenyl group, a biphenyl group, an idophenyl group, a terphenyl group, a quaterphenyl group, a fluorenyl group, a spirobifluorenyl group, a phenanthrenyl group, a dihydropyrenyl group, a tetrahydropyrenyl group, a cis-or trans-indenofluorenyl group, a trimeric indenyl group, an isotridecyl group, a spirotrimeric indenyl group, and a spiroisoindenylidene group. C of the invention6～C60The aryl group may be a combination of the above groups bonded by a single bond and/or condensed.
In the present specification, substituted or unsubstituted C3～C60Heteroaryl is preferably C3～C30The heteroaryl group may be a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, or the like. Preferred examples of the heterocyclic ring in the present invention include furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole or indolocarbazole. Hair brushMing's C3～C60The heteroaryl group may be a combination of the above groups bonded by a single bond and/or fused.
In the present specification, alkyl is not particularly specified, and includes straight-chain alkyl and branched-chain alkyl as well as the concept of cycloalkyl. Examples thereof include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, adamantyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, pentafluoroethyl, 2, 2, 2-trifluoroethyl and the like.
In the present specification, cycloalkyl includes monocycloalkyl and polycycloalkyl, and there may be mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
In the present specification, the term "C" means C1～C20Examples of alkoxy groups are: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like, among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutyloxy, isopentyloxy, more preferably methoxy, are preferred.
In the present specification, the term "C" means C6～C60The aryloxy group of (A) may include the above-mentioned substituted or unsubstituted C6～C60Specific examples of the group formed by linking each group in the aryl group to oxygen are given above, and are not described herein.
In the present specification, examples of the halogen include: fluorine, chlorine, bromine, iodine, and the like.
As a preferred embodiment of the present invention, the metal organic light emitting material is selected from compounds represented by the following structural formula:
the invention provides a novel metal organic luminescent material containing metal iridium, which can be used as a phosphorescent luminescent material. The phosphorescent material provided by the invention can effectively solve the problems of the commonly used phosphorescent material in the aspects of color purity, luminous efficiency, service life and the like, and an organic electroluminescent device prepared by using the phosphorescent material provided by the invention has excellent performances of high efficiency and long service life.
Specifically, the iridium-containing metal complex material containing deuterium atoms provided by the invention has the following advantages: on one hand, due to the heavy atom effect, after the deuterium atoms are introduced into the luminescent material, the spin-orbit coupling effect of the luminescent molecules is increased, so that the jumping capability among electron systems in the molecules is increased, the generation of phosphorescence is facilitated, and the quantum efficiency of the molecule is increased; by introducing deuterium atoms, the infrared spectrum of the luminescent molecular iridium complex moves to a low field, so that energy dissipation in the excitation process is reduced, and the quantum efficiency is improved. On the other hand, the deuterated iridium complex has lower internal energy than non-deuterated iridium complexes, and the spin-orbit coupling effect of luminescent molecules is enhanced, so that phosphorescence is facilitated, and the quantum efficiency of the luminescent molecules is increased. Because the bond length of the carbon-deuterium bond is short, the bond energy is large, and the energy of the luminescent material is reduced, so that the stability and the service life of the luminescent device are obviously enhanced.
In a second aspect, the invention provides an application of the metal organic light emitting material in the preparation of an organic electroluminescent device.
Preferably, the metal organic light emitting material is used as a phosphorescent light emitting material in an organic electroluminescent device;
further preferably, the metal organic light emitting material is used as a dye material of a host material in an organic electroluminescent device.
In particular, the application is applicable to organic electronic devices including organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, sheet-type scanners, or electronic paper. Most preferably as an organic electroluminescent device.
Further preferably, the metal organic luminescent material is used as a dye material of a host material in an organic electroluminescent device. The material of the invention is used as a dye doped in an organic electroluminescent device to emit light, and the electroluminescent device prepared by utilizing the phosphorescent material of the invention has the superior performances of high purity, high brightness and high efficiency.
In a third aspect, the present invention provides an organic electroluminescent device comprising a light-emitting layer comprising the metal-organic light-emitting material according to the present invention.
Furthermore, the metal organic light-emitting material provided by the invention is used as a dye material of a light-emitting layer, and such organic electroluminescent devices show superior performances of high purity, high brightness and high efficiency.
Preferably, the light-emitting layer includes a host material and a dye material, and the dye material includes the metal organic light-emitting material according to the present invention.
Furthermore, the organic electroluminescent device provided by the invention comprises a substrate, and an anode layer, a plurality of light-emitting unit layers and a cathode layer which are sequentially formed on the substrate; the light-emitting unit layer comprises a light-emitting layer and also comprises one or more of a hole injection layer, a hole transport layer, an electron blocking layer and the like, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and a plurality of light-emitting layers are arranged between the hole transport layer and the electron transport layer. Preferably, the luminescent dye material in the luminescent layer is the metal organic luminescent material provided by the invention.
Further preferably, the doping concentration of the metal organic light emitting material in the host material is 3-12%, more preferably 3-9%, and more preferably 3-5%. When the doping concentration of the metal organic light-emitting material in the host material is about 5%, the performance of the device is best. The doping concentration is mass percentage concentration.
In a fourth aspect, the present invention provides a display apparatus comprising said organic electroluminescent device.
In a fifth aspect, the invention provides a lighting device comprising the organic electroluminescent device.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples. The following examples are given to illustrate the present invention and are not intended to limit the scope of the present invention, and other equivalent changes or modifications made without departing from the spirit of the present invention are intended to be included within the scope of the appended claims.
The synthetic routes for the structural formulae of the present invention are described below, and it will be appreciated by those skilled in the art that similar routes can also be used for the synthesis of other routes.
Synthesis of ligands
Synthesis of ligands M1-M5
Synthesis of ligand M1
The synthetic route for ligand M1 is as follows:
the preparation method comprises the following specific steps:
(1) synthesis of Compound M1-1
2-bromo-5-methylpyridine (17.2g,0.1mol), phenylboronic acid (12.2g, 0.1mol), potassium carbonate (27g, 0.2mol), tetrakis (triphenylphosphine) palladium (1.1 g), tetrahydrofuran (400 mL), and water (100 mL) were sequentially added to a 1L three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a nitrogen gas protector, and heated to reflux for 12 hours. After the reaction is finished, separating an organic phase, extracting, drying, carrying out column chromatography, and spin-drying a solvent to obtain 12.6g of a product.
(2) Synthesis of Compound M1-2
M1-1(16.9g,0.1mol), iridium trichloride hydrate (8.8g,0.25mol), 450mL of ethylene glycol monoethyl ether and 150mL of distilled water are sequentially added into a 1L three-neck flask equipped with a mechanical stirring device, a reflux condensing device and a nitrogen protection device, and the mixture is heated to 130 ℃ for refluxing for 24 hours. Then naturally cooling, adding 100mL of distilled water, oscillating, filtering, washing with water and washing with ethanol. Drying in vacuo afforded 22.8g of the product as a yellow solid.
(3) Synthesis of Compound M1
M1-2(28.2g,0.1mol) and 300ml of methylene chloride were sequentially added to a 1L three-necked flask equipped with a nitrogen blanket, followed by stirring thoroughly, then 300ml of a methanol solution of silver trifluoromethanesulfonate (51.2g, 0.2mol) was added, stirred at room temperature for 24 hours, filtered through celite, and the filtrate was spin-dried to obtain 33.3g of a yellowish brown solid.
Referring to the synthesis of ligand M1, the following ligands were synthesized.
Synthesis of ligand M2
Referring to the synthesis method of ligand M1, 2-bromo-5-deuterated methylpyridine is used to replace 2-bromo-5-methylpyridine, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of ligand M1, so that ligand M2 is obtained.
Synthesis of ligand M3
Referring to the synthesis method of the ligand M1, 2-bromo-5-deuterated methylpyridine is used for replacing 2-bromo-5-methylpyridine, 4-deuterated methylphenylboronic acid is used for replacing phenylboronic acid, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the ligand M1, so that the ligand M3 is obtained.
Synthesis of ligand M4
Referring to the synthesis method of the ligand M1, 2-bromo-5-deuterated methylpyridine is used for replacing 2-bromo-5-methylpyridine, deuterated phenylboronic acid is used for replacing phenylboronic acid, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the ligand M1, so that the ligand M4 is obtained.
Synthesis of ligand M5
Referring to the synthesis method of the ligand M1, 4, 5-dideuteromethylpyridine is used for replacing 2-bromo-5-methylpyridine, 4-deuterated methyl-3-biphenylboronic acid is used for replacing phenylboronic acid, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the ligand M1, so that the ligand M5 is obtained.
Synthesis of ligand H1
The synthetic route for ligand H1 is as follows:
the preparation process comprises the following steps:
(1) synthesis of Compound H1-1
Adding 200mL of THF and 4-chlorodibenzofuran (20g, 0.1mol) into a mechanically-stirred 2L three-necked bottle, starting stirring, cooling to-78 ℃ under the protection of nitrogen, dropwise adding 60mL of 2M n-butyllithium, stirring for 1H, adding deuterated methanol, naturally returning to room temperature, adding a saturated ammonium chloride solution and 200mL of ethyl acetate, extracting to obtain an organic phase, drying, carrying out column chromatography, and spin-drying a solvent to obtain H1-1, wherein the total amount of the solid is 16.2 g.
(2) Synthesis of Compound H1-2
In a 1L three-necked flask equipped with mechanical stirring, H1-1(20.3g, 0.1mol), pinacol diboride diborate (25.4g, 0.1mol), DPPF palladium dichloride (0.7g, 0.001mol), potassium acetate (19.6g, 0.2mol), 300mL DMF were added, reacted at 90 ℃ for 10 hours under nitrogen protection, after the reaction was completed, the organic phase was separated, extracted, dried, subjected to column chromatography, and the solvent was dried by spinning to obtain H1-2, which was 25g of solid in total.
(3) Synthesis of Compound H1
In a 1L three-necked flask equipped with mechanical stirring, H1-2(29.5g, 0.1mol), 2-bromo-4-deuteropyridine (15.8g, 0.1mol), potassium acetate (19.6g, 0.2mol), DPPF dichloropalladium (0.7g, 0.001mol), 400mL tetrahydrofuran and 100mL water were added, the mixture was heated to reflux for 12 hours, cooled to room temperature, added with water, extracted with ethyl acetate, the organic layer was separated, washed with brine, the organic phase was separated, extracted, dried, column chromatographed, and the solvent was spin-dried to give H1 as a total of 18g of solid.
Elemental analysis (C)17H9D2NO): theoretical value C, 82.91; h, 4.91; n, 5.69; o, 6.50; found C, 82.89; h, 4.67; and N, 5.68. MS 247.
Synthesis of ligand H2
Referring to the synthesis method of the ligand H1, 6-chloro-3-fluoro dibenzofuran is used to replace 4-chloro dibenzofuran, the appropriate material ratio is selected, and other raw materials and steps are the same as the synthesis method of the ligand H1, so that the ligand H2 is obtained.
Elemental analysis (C)17H8D2FNO): theoretical value C, 76.97; h, 4.56; f, 7.16; n, 5.28; o, 6.03; found C, 77.01; h, 4.55; and N, 5.21. MS 265.
Synthesis of ligand H3
Referring to the synthesis method of ligand H1, 6-chloro-3-cyano dibenzofuran is used to replace 4-chloro dibenzofuran, and the ligand H3 is obtained by selecting a proper material ratio and adopting the same other raw materials and procedures as those of the synthesis method of ligand H1.
Elemental analysis (C)18H8D2N2O): theoretical value C, 79.40; h, 4.44; n, 10.29; o, 5.88; found C, 79.41; h, 4.45; n,10.25。MS＝272。
Synthesis of ligand H4
Referring to the synthesis method of the ligand H1, 6-chloro-3-deuterated methyl dibenzofuran is used for replacing 4-chlorodibenzofuran, a proper material ratio is selected, and other raw materials and steps are the same as the synthesis method of the ligand H1, so that the ligand H4 is obtained.
Elemental analysis (C)18H8D5NO): theoretical value C, 81.79; h, 6.86; n, 5.30; o, 6.05; found C, 81.81; h, 6.85; and N, 5.35. MS-264.
Synthesis of ligand H5
Referring to the synthesis method of the ligand H1, 6-chloro-3-phenyldibenzofuran is used to replace 4-chlorodibenzofuran, the appropriate material ratio is selected, and other raw materials and steps are the same as the synthesis method of the ligand H1, so that the ligand H5 is obtained.
Elemental analysis (C)23H13D2NO): theoretical value C, 85.42; h, 5.30; n, 4.33; o, 4.95; found C, 85.43; h, 5.35; and N, 4.30. MS 323.
Synthesis of ligand H6
Referring to the synthesis method of the ligand H1, 6-chloro-3-deuterated phenyl dibenzofuran is used to replace 4-chlorodibenzofuran, and the ligand H6 is obtained by selecting a proper material ratio and adopting the same other raw materials and steps as those of the synthesis method of the ligand H1.
Elemental analysis (C)23H8D7NO): theoretical value C, 84.12; h, 6.75; n, 4.26; o, 4.87; found C, 84.13; h, 6.65; and N, 4.23. MS 328.
Synthesis of ligand H7
Referring to the synthesis method of the ligand H6, 2-bromo-4-deuterated isopropyl pyridine is used for replacing 2-bromo-4-deuterated pyridine, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the ligand H6, so that the ligand H7 is obtained.
Elemental analysis (C)26H14D7NO): theoretical value C, 84.29; h, 7.61; n, 3.78; o, 4.32; found C, 84.25; h, 7.65; and N, 3.75. MS 370.
Synthesis of ligand H8
Referring to the synthesis method of the ligand H3, 2-bromo-4-deuterated isopropyl pyridine is used for replacing 2-bromo-4-deuterated pyridine, a proper material ratio is selected, and other raw materials and steps are the same as those of the synthesis method of the ligand H3, so that the ligand H8 is obtained.
Elemental analysis (C)21H14D2N2O): theoretical value C, 80.23; h, 5.77; n, 8.91; o, 5.09; found C, 80.21; h, 5.75; and N, 8.85. MS 314.
Synthesis of ligand H9
Referring to the synthesis method of the ligand H2, 1-chloro-7-fluorodibenzofuran is used for replacing 6-chloro-3-fluorodibenzofuran, a proper material ratio is selected, and other raw materials and steps are the same as the synthesis method of the ligand H2, so that the ligand H9 is obtained.
Elemental analysis (C)17H8D2FNO): theoretical value C, 76.97; h, 4.56; f, 7.16; n, 5.28; o, 6.03; found C, 77.03; h, 4.52; n, 5.22. MS 265.
Synthesis of ligand H10
Referring to the synthesis method of ligand H3, 1-chloro-7-cyano dibenzofuran is used to replace 6-chloro-3-cyano dibenzofuran, and the ligand H10 is obtained by selecting a proper material ratio and other raw materials and steps which are the same as those of the synthesis method of ligand H3.
Elemental analysis (C)18H8D2N2O): theoretical value C, 79.40; h, 4.44; n, 10.29; o, 5.88; found C, 79.43; h, 4.44; n, 10.26. MS 272.
Synthesis of ligand H11
Referring to the synthesis method of ligand H6, 1-chloro-7-deuterated phenyl dibenzofuran is used to replace 6-chloro-3-deuterated phenyl dibenzofuran, and the ligand H11 is obtained by selecting a proper material ratio and adopting the same other raw materials and steps as those of the synthesis method of ligand H6.
Elemental analysis (C)23H8D7NO): theoretical value C, 84.12; h, 6.75; n, 4.26; o, 4.87; found C, 84.16; h, 6.63; and N, 4.28. MS 328.
With reference to the above method, other ligand compounds required in the structural formula of the present invention can be prepared by replacing the reagents.
Example 1: synthesis of Compound I-4
The synthetic route is as follows:
the preparation process comprises the following steps:
m1(7.42g, 0.01mol) and H1(2.46g,0.01mol) were sequentially added to a 500mL three-necked flask equipped with mechanical stirring, a reflux condenser and a nitrogen blanket, then 200mL of ethanol was added, the mixture was heated under reflux for 24 hours, the reaction mixture was cooled to room temperature, the resulting yellow solid was filtered, dissolved in dichloromethane, and subjected to column chromatography to obtain 4.6 g of a bright yellow solid.
Elemental analysis (C)41H28D2IrN3O): theoretical value C, 63.63; h, 4.04; ir, 24.84; n, 5.43; o, 2.07; found C,63.71, H,4.08, N, 5.42. MS 775.
Other specific compounds of the present invention were synthesized by the synthesis method of example 1.
Some of the specific compounds and their assay data are listed in Table 1 below, as shown in examples 2-28.
TABLE 1
Device embodiment: green organic electroluminescent device
The application embodiment of the OLED device provided by the invention is as follows:
the embodiment provides a group of OLED green light devices, and the specific structure of the device is as follows: ITO/HI (10nm)/HT01(60nm)/EB (5nm)/DIC-TRZ: 5% the compound provided by the invention (30nm)/HB (10nm)/ET01: QLi (1:1) (30nm)/QLi (1 nm)/Al.
Wherein the structure of each functional layer material molecule is as follows:
preparation of device OLED-1
The compound I-4 prepared by the invention is selected as a phosphorescent light-emitting material, the doping concentration of the phosphorescent light-emitting material is 5%, and an OLED device is prepared by the following specific preparation process:
(1) the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically degreasing in an ethanol mixed solvent (volume ratio is 1:1), baking in a clean environment until moisture is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using a low-energy solar ion beam;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, vacuum evaporating HI on the anode layer film to be used as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 10 nm; then, evaporating a first hole layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 60 nm; then evaporating an electron barrier layer EB with the evaporation rate of 0.1nm/s and the evaporation film thickness of 5 nm;
(3) an EML is evaporated on the hole transport layer in vacuum and used as a light-emitting layer of the device, the EML comprises a main material DIC-TRZ and a dye material I-4, the doping percentage concentration is 5%, an organic light-emitting layer of the device is formed, the evaporation rate is 0.2nm/s, and the total film thickness is 30 nm; then, evaporating 10nm HB to form a hole blocking layer, wherein the evaporation rate is 0.1 nm/s;
(4) and evaporating on the hole blocking layer according to the mass ratio of 1: the ET01: QLi of 1 is used as an electron transport material of an electron transport layer of a device, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
(5) QLi with the thickness of 1nm is sequentially subjected to vacuum evaporation on the electron transport layer to serve as an electron injection layer, an Al layer with the thickness of 150nm serves as a cathode of the device, and the OLED-1 device is obtained after encapsulation.
According to the preparation method of the OLED-1 device, the OLED-2, OLED-3 and OLED-4 devices are prepared by only changing the doping concentration of the dye material I-4 in the host material DIC-TRZ in the step (3) from 5% to 3%, 7% and 9%, respectively.
The performance of the devices OLED-1 to OLED-4 prepared above was tested, and the results of the tests on the performance of each device are shown in Table 2.
TABLE 2
Comparing the detection results of the four light-emitting devices, it can be seen that the performance of the light-emitting device OLED-1 is the best, that is, when the doping concentration is about 5%, the color coordinate is the best, the efficiency is the highest, and the service life is also the highest. Preparing devices OLED-5-OLED-31
According to the preparation method of the OLED-1 device, the dye material I-4 in the step (3) is respectively replaced by the compounds listed in the table 1, and the doping concentrations of the dye material I-4 in the host material DIC-TRZ are both 5%, so that OLED-5-OLED-31 devices are respectively prepared.
Preparation of comparative devices OLED-32 to OLED-35
A compound A, a compound B, a compound C and a compound D shown in the following structural formulas are used as dye materials to replace a dye material I-4 in an OLED-1 device, the doping concentrations in a main material DIC-TRZ are all 5%, and comparative devices OLED-32, OLED-33, OLED-34 and OLED-35 are respectively prepared.
The performance of the devices OLED-1, OLED-5-OLED-31 and the comparative device are tested, and the performance test results of the devices are shown in Table 3.
TABLE 3
From the above results, it can be seen that the compound provided by the present invention, through the design of the compound structure, for example, the deuterium atom, the deuterated phenyl group and the electron withdrawing group are introduced to the substitutable position of the dibenzofuran, and the structural design of the L group, the electron mobility and the stability of the material are improved, and the light emitting efficiency of the corresponding device is improved while the lifetime is significantly improved. Although the oxygen atom on the dibenzofuran and the benzene ring form p-pi conjugation, electrophilic substitution still easily occurs at the ortho position of oxygen, the carbon-hydrogen bond vibration energy level is higher, and if the carbon-deuterium bond with lower energy level is used, the activation energy is improved due to the isotope effect, so that the stability and the luminous efficiency of the material are improved. Therefore, the phosphorescent material provided by the invention can further improve the service life and the luminous efficiency of the conventional phosphorescent material, and an organic electroluminescent device prepared by using the phosphorescent material has the superior performances of long service life and high efficiency.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A metal-organic light emitting material having a structure represented by general formula (i):
wherein, the first and the second end of the pipe are connected with each other,
n is 1, 2 or 3; m is 0, 1, 2, 3 or 4; k is 0, 1, 2 or 3; p is 0 or 1;
y is selected from O, S, Se, SO2NR ', CR', SiR ', R' is C1～C6A chain alkyl group;
X1、X2、X3、X4、X5、X6、X7and X8Each is independently selected from C or N;
R1、R2each independently selected from hydrogen atom, deuterium atom, halogen, cyano, C1～C20Chain alkyl, C3～C20Cycloalkyl radical, C1～C20Alkoxy radical, C6～C60Aryloxy group, C1～C20Alkylsilyl group, C6～C60Aryl radical, C3～C60Heteroaryl, C1～C20Deuterated chain alkyl, C3～C20Deuterated cycloalkyl, C1～C20Deuterated alkoxy, C6～C60Deuterated aryloxy group C1～C20Deuterated alkylsilyl, C6～C60Deuterated aryl, C3～C60Deuterated heteroaryl, fluoro-C1～C20Chain alkyl, fluoro C3～C20Cycloalkyl, fluoro C1～C20Alkoxy, fluoro C6～C60Aryloxy, fluoro C1～C20Alkylsilyl, fluoro C6～C60Aryl, fluoro C3～C60Heteroaryl, cyano-substituted C6～C60Any one of aryl groups; or, when R1Or R2When there are plural, two adjacent R1Or R2Can be connected into a ring;
R13selected from deuterium atom, halogen, cyano, C6～C60Aryl radical, C6～C60A deuterated aryl group;
l is a monovalent bidentate anionic ligand in which the bonding atoms M, N are each independently selected from a nitrogen atom, a carbon atom.
2. The metal-organic light emitting material according to claim 1, wherein the metal-organic light emitting material has a structure represented by general formula (i-1):
wherein, the first and the second end of the pipe are connected with each other,
n is 1, 2 or 3; m is 0, 1, 2, 3 or 4; k is 0, 1, 2 or 3; p is 0 or 1;
y is selected from O, S, Se, CR ', SiR' is C1～C6A chain alkyl group;
X3、X4、X5、X6、X7and X8Each independently selected from C or N;
R1、R2each independently selected from hydrogen atom, deuterium atom, halogen, cyano, C1～C20Chain alkyl, C3～C20Cycloalkyl radical, C1～C20Alkoxy radical, C6～C60Aryloxy group, C1～C20Alkylsilyl group, C6～C60Aryl radical, C3～C60Heteroaryl group, C1～C20Deuterated chain alkyl, C3～C20Deuterated cycloalkyl, C1～C20Deuterated alkoxy, C6～C60Deuterated aryloxy group C1～C20Deuterated alkylsilyl, C6～C60Deuterated aryl, C3～C60Deuterated heteroaryl, fluoro-C1～C20Chain alkyl, fluoro C3～C20Cycloalkyl, fluoro C1～C20Alkoxy, fluoro C6～C60Aryloxy, fluoro C1～C20Alkylsilyl, fluoro C6～C60Aryl, fluoro C3～C60Heteroaryl, cyano-substituted C6～C60Any one of aryl groups; or, when R is1Or R2When there are plural, two adjacent R1Or R2Can be connected into a ring;
R13selected from deuterium atom, cyano, C6～C60Aryl radical, C6～C60A deuterated aryl group;
l is a monovalent bidentate anionic ligand in which the bonding atoms M, N are each independently selected from a nitrogen atom, a carbon atom.
3. The metal-organic light emitting material according to claim 1 or 2, wherein L is a group represented by the following formula (L):
wherein R is3～R10Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 ring carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted deuterated alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted deuterated aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 20 carbon atoms, Any one of substituted or unsubstituted arylalkylsilyl groups having 6-20 carbon atoms; and/or, R3～R10Adjacent two of them may form a parallel ring structure by bridging; and/or the presence of a gas in the atmosphere,
R3～R10when having a substituent group, the substituent group is selected from deuterium atom, halogen, cyano group, C1～C30Alkyl of (C)1～C30Deuterated alkyl of (D), C3～C20Cycloalkyl of (C)3～C20Heterocycloalkyl of (C)6～C60Aryl of (C)3～C60Heteroaryl of (A), C1～C20One or a combination of more of the alkyl silicon groups;
preferably, R3～R10Each independently selected from the group consisting of hydrogen atom, deuterium atom, halogen, cyano, alkyl having 1 to 5 carbon atoms, deuterated alkyl having 1 to 5 carbon atoms, substituted or unsubstituted phenyl; when the phenyl group has a substituent group, the substituent group is selected from deuterium atom and C1～C5Alkyl of (C)1～C5Deuterated alkyl of (D), C1～C5And (3) an alkylsilyl group.
4. The metal-organic light emitting material according to any one of claims 1 to 3, wherein L is selected from the group consisting of:
5. the metal-organic light emitting material according to any one of claims 1 to 4, wherein n is 1;
y is selected from O, S, Se;
R1selected from H, deuterium atom, C1～C5Alkyl of (C)1～C5Deuterated alkyl of (D), C3～C6Cycloalkyl, phenyl, deuterated phenyl of (a);
m is 0 or 1;
R2selected from H, deuterium atom, halogen, cyano, trifluoromethyl, C1～C5Alkyl group of (A) or (B),C1～C5Deuterated alkyl, phenyl, deuterated phenyl, fluorophenyl, cyano-substituted phenyl, halogen atoms and cyano-substituted phenyl;
k is 0 or 1 or 2 or 3; when k is 2 or 3, two adjacent R2The fused ring structure can be formed by bridging, and can be a five-membered ring or a six-membered ring, preferably, the five-membered ring is a five-membered heterocyclic ring containing an O atom, the six-membered ring is a benzene ring, the five-membered heterocyclic ring can be further connected with a benzo group, and the benzo ring can be substituted by a deuterium atom;
R13selected from deuterium atom, deuterated phenyl, phenyl and cyano;
p is 0 or 1.
6. The metal-organic light emitting material according to any one of claims 1 to 5, wherein the metal-organic light emitting material is selected from compounds represented by the following structural formulas:
7. the use of a metal organic light emitting material according to any one of claims 1 to 6 in the preparation of an organic electroluminescent device;
preferably, the metal organic light emitting material is used as a phosphorescent light emitting material in an organic electroluminescent device;
further preferably, the metal organic light emitting material is used as a dye material of a host material in an organic electroluminescent device.
8. An organic electroluminescent device comprising a light-emitting layer comprising the metal organic light-emitting material according to any one of claims 1 to 6;
preferably, the light-emitting layer comprises a host material and a dye material, wherein the dye material comprises the metal organic light-emitting material according to any one of claims 1 to 6;
more preferably, the doping concentration of the metal organic light emitting material in the host material is 3-12%, and more preferably 3-5%.
9. A display device comprising the organic electroluminescent element according to claim 8.
10. A lighting device comprising the organic electroluminescent element according to claim 8.
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| GB2615643A (en) * | 2021-12-27 | 2023-08-16 | Lg Display Co Ltd | Organometallic compound and organic light-emitting diode including the same |
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